WO2014156344A1

WO2014156344A1 - Polyester resin aqueous dispersion and bonding agent composition incorporating same

Info

Publication number: WO2014156344A1
Application number: PCT/JP2014/053140
Authority: WO
Inventors: 達也粟田; 忠彦三上
Original assignee: 東洋紡株式会社
Priority date: 2013-03-26
Filing date: 2014-02-12
Publication date: 2014-10-02
Also published as: CN105008457B; TWI585174B; CN105008457A; JP6424621B2; JPWO2014156344A1; KR102018902B1; TW201444937A; KR20150138149A

Abstract

Provided are a polyester resin aqueous dispersion composition and a bonding agent composition incorporating same. The polyester resin aqueous dispersion composition demonstrates excellent adhesion to a variety of substrates such as textiles, paper, and plastic films while demonstrating exceptional resistance to water (including soapy water) and a variety of solvents. The polyester resin aqueous dispersion composition contains polyesters (A) and (B) of a particular specification, and a curing agent (C). The modulus of elasticity at 120°C of an 8-μm-thick thin film fabricated using the polyester resin aqueous dispersion composition is 1 MPa to 1 kPa.

Description

Aqueous polyester resin dispersion and adhesive composition using the same

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

Until now, organic solvents have been used in large quantities in the fields of paints, inks, coating agents, adhesives, and various treatment agents such as textile products and paper. Recently, environmental pollution caused by these organic solvents, deterioration of the working environment, etc. As a result, organic solvent emission regulations have been strengthened year by year, both domestically and internationally. In response to such a trend, as a measure for reducing the use of organic solvents, there is an increasing trend of making water-based in many applications.

As a method of already dispersing or solubilizing the polyester resin in water, a method in which a hydrophilic raw material is copolymerized and introduced into the molecular skeleton, for example, a raw material containing a sulfonic acid metal base or a polyalkylene glycol is used alone or in combination. A method of copolymerization is known (for example, Patent Document 1). However, in any method, in order to impart excellent solubility or dispersibility in water, it is necessary to use a large amount of the hydrophilic raw material, and the hydrophilic group remains in the obtained thin film. There was a problem in terms of water resistance of the thin film.

As an attempt to solve this problem, a carboxylic acid is added to a polyester resin to make a copolymer polyester resin having a high acid value, and neutralized with ammonia or a low-boiling amine to neutralize the carboxylic acid, which is a hydrophilic group. A method of forming a salt and dispersing or solubilizing a polyester resin in water is known (for example, Patent Document 2). If it is a thin film obtained by this method, ammonia and low boiling point amine neutralizing carboxylic acid are volatilized at the time of thin film production, and the carboxylic acid neutralized salt which is a hydrophilic group does not remain in the thin film. The water resistance of the obtained thin film can be increased.

Japanese Examined Patent Publication No. 47-40873 JP 2008-223093

However, the thin film obtained by the aqueous dispersion copolyester resin produced by the methods disclosed in Patent Documents 1 and 2 is not smoother than the thin film obtained by the copolyester resin dissolved in the solvent. However, sufficient water resistance and solvent resistance have not been obtained.

Furthermore, in the case of an interlayer adhesive resin that adheres two types of base materials, a method in which the base material 1 is usually stored for a long time in a state where the adhesive is applied, and is used by being attached to the base material 2 at the time of use. Therefore, non-curable resins are generally used. However, the adhesive layer using a non-curable resin has problems such as poor adhesive strength, solvent resistance, and water resistance.

There are also two-component curable adhesives in which an isocyanate-based crosslinking agent is blended with a hydroxyl group-containing resin, but after the curing agent is blended with the resin and applied to the base material (base material 1), the reaction between the resin and the curing agent occurs. Before finishing, the next base material (base material 2) must be pasted, and there is a problem that the method of use is limited because it cannot be stored for a long time with the adhesive applied to the base material 1. .

Furthermore, in the case of such an adhesive, since the blended isocyanate reacts with water over time, there is a problem that the stability in the state of the blended liquid is poor.

In addition, in order to solve the above problem, there is an adhesive formed by blending a block isocyanate system. After the curing agent is blended in the resin and applied to the base material (base material 1), the next base material (base material) When pasting 2), the block component of the isocyanate-based curing agent does not dissociate unless it is applied at a high temperature for a long period of time, resulting in poor productivity.

The object of the present invention is to increase the molecular weight rather than a complete curing reaction by reacting a polyester resin with a small amount of a curing agent when applied to the substrate 1, and to store for a long time in a state where the adhesive is applied to the substrate 1. It is possible to provide an adhesive that has good laminating properties when bonded to the substrate 2, adhesive properties after lamination, solvent resistance, and good water resistance.

Although the present invention uses a water-dispersed copolymer polyester resin, it has good adhesion to various substrates such as cloth, paper, or plastic film, and is resistant to various solvents. It aims at providing the adhesive agent excellent in soap water resistance.

In order to achieve the above-mentioned problems, the present inventors have intensively studied and have proposed the following invention. That is, this invention is the polyester resin aqueous dispersion composition, adhesive composition, and laminated body shown below.

Polyester resin aqueous dispersion containing polyester resin (A), polyester resin (B) and curing agent (C), satisfying any of the following (1) to (3), and satisfying (4) below Composition.
(1) The 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 the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. The polyester resin (A) has a glass transition temperature higher than the glass transition temperature of the polyester resin (B). (2) The polyester resin (A) is an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C. or higher. It is a mixture of crystalline polyester resin (A2) having a glass transition temperature of 0 ° C. or lower. The weighted average value of glass transition temperatures of (A1) and (A2) is 5 to 50 ° C., and the weighted average value of acid value is 10 to 400 eq. / T, the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less, and the polyester resin (A1) and the polyester resin ( A weighted average value of the glass transition temperature of 2) is higher than the glass transition temperature of the polyester resin (B). (3) A thin film having a thickness of 8 μm was prepared from the aqueous polyester resin dispersion composition, and the thin film was completely dried. (4) When a polyester resin (A) or polyester resin (B) contained later has a glass transition temperature of 5 to 50 ° C. (4) When a thin film having a thickness of 8 μm is produced with an aqueous polyester resin dispersion composition The elastic modulus of the thin film at 120 ° C. is 1 MPa to 1 kPa

Moreover, it is preferable that a hardening | curing agent (C) is a carbodiimide type hardening | 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) with respect to 100 parts by mass of the polyester resin (A).

An adhesive composition containing the polyester resin aqueous dispersion composition.

The adhesive composition as described above, which is used for laminating a film and a film or paper.

Furthermore, the laminated body laminated | stacked by the said adhesive composition.

A polyester resin aqueous dispersion composition containing a polyester resin satisfying any of the following (1) to (3) and a curing agent (C) is applied to the substrate 1, and the film thickness is 8 μm and elasticity at 120 ° C. A method for producing a laminate in which a thin film having a rate of 1 MPa to 1 kPa is prepared, and then a base material 2 is bonded.
(1) The 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 the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. The polyester resin (A) has a glass transition temperature higher than the glass transition temperature of the polyester resin (B). (2) The polyester resin (A) is an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C. or higher. It is a mixture of crystalline polyester resin (A2) having a glass transition temperature of 0 ° C. or lower. The weighted average value of glass transition temperatures of (A1) and (A2) is 5 to 50 ° C., and the weighted average value of acid value is 10 to 400 eq. / T, the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less, and the polyester resin (A1) and the polyester resin ( The weighted average value of the glass transition temperature of 2) is higher than the glass transition temperature of the polyester resin (B). (3) The glass transition temperature of the polyester resin (A) or polyester resin (B) contained after the thin film is completely dried. At least one of 5 to 50 ° C.

Since 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, the water resistance, solvent resistance, soap water resistance and adhesiveness are improved. An excellent adhesive resin composition can be easily formed.

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

<Polyester resin (A)>
The polyester resin (A) used in the present invention has a chemical structure obtained by polycondensation of a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound. It is preferable to copolymerize polyester, hydroxycarboxylic acid or lactone. In the case of a polyester having a chemical structure obtained by polycondensation of a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound, a polyvalent carboxylic acid compound and It is preferable that at least one of the polyhydric alcohol compounds is a copolyester resin composed of two or more kinds of components. The polycarboxylic acid compound and the polyhydric alcohol compound are preferably copolyester resins mainly composed of a dicarboxylic acid component and a glycol component. Here, mainly means that the total of the dicarboxylic acid component and the glycol component accounts for 50 mol% or more on a molar basis with respect to the total of all acid components and all alcohol components constituting the polyester resin (A) used in the present invention. Point to. The total of the dicarboxylic acid component and the glycol component is preferably 70 mol% or more, more preferably 85 mol% or 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 more preferably an aromatic dicarboxylic acid. The copolymerization amount of the aromatic dicarboxylic acid component is 40 mol% or more, preferably 45 mol% or more, more preferably 50 mol% or more, further preferably 55 mol%, when the total amount of the carboxylic acid components is 100 mol%. That's it. If it is less than 40 mol%, the mechanical strength of the resulting coating film may be lowered, and in that case, it is not practical.

Specific examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, orthophthalic acid, and naltalenedicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid include, but are not limited to, succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These dicarboxylic acid components can be used alone or in combination of two or more. Other polyvalent carboxylic acid components include aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid and tetrahydrophthalic acid. An unsaturated alicyclic such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, and the like can also be used. Further, if necessary, trimellitic acid, trimesic acid, pyromellitic acid, and other tri- and tetracarboxylic acids and anhydrides thereof may be included.

As the glycol component, an aliphatic glycol is preferable. The copolymerization amount of the aliphatic glycol component is 40 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, when the total amount of the glycol components is 100 mol%. is there. When it is less than 40 mol%, the glass transition temperature (hereinafter also referred to as Tg) of the resulting coating film may be high, and may not be suitable for use as an adhesive.

Specifically, aliphatic glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol (hereinafter 2MG). 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol , Polytetramethylene glycol and the like, but are not limited thereto. These glycol components can be used alone or in combination of two or more. Other glycols include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanediol, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogenation An ethylene oxide adduct and a propylene oxide adduct of bisphenol A can also be used. In addition to these, a small amount of triol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and tetraol may be contained if necessary.

The acid value of the polyester resin (A) is preferably in the range of 10 to 400 eq / t. More preferably, it is 11 to 360 eq / t, still more preferably 12 to 320 eq / t, and most preferably 13 to 280 eq / t. If the acid value exceeds 400 eq / t, hydrolysis of the polyester resinous dispersion may be promoted, and long-term storage stability may deteriorate. If the acid value is less than 10 eq / t, the adhesive agent layer obtained from the polyester resin aqueous dispersion composition of the present invention may be poor in solvent resistance and water resistance because it cannot sufficiently react with the curing agent. is there.

Since the polyester resin (A) is dispersed in water, it is preferable to introduce a hydrophilic polar group into the resin skeleton. Examples of the polar group include a sulfonic acid metal base, a carboxyl group, and a phosphoric acid group, but a sulfonic acid metal base and a carboxyl group are more preferable, and further, dispersibility and long-term stability of the resulting aqueous dispersion are excellent. Sulfonate metal base is most preferred. Moreover, these polar groups may be used alone or in combination as required.

The method of introducing the sulfonic acid metal base is not particularly limited, and examples thereof include copolymerization of a dicarboxylic acid or glycol containing a sulfonic acid metal base during polymerization of the polyester resin (A). The dicarboxylic acid containing a sulfonic acid metal base is a dicarboxylic acid containing an alkali metal salt or an alkaline earth metal salt of sulfonic acid, specifically, sodium 5-sulfonatoisophthalate, 5-sulfonatoisophthalate. Examples include potassium acid, sodium 4-sulfonaphthalene-2,7-dicarboxylate, and sodium 5- [4-sulfophenoxy] isophthalate, but are not limited thereto. The glycol containing a sulfonic acid metal base is a glycol containing an alkali metal salt or an alkaline earth metal salt of sulfonic acid, specifically, a sodium salt of 2-sulfo-1,4-butanediol, 2 , 5-dimethyl-3-sulfo-2,5-hexanediol sodium salt, and the like. These dicarboxylic acids or glycols containing a sulfonic acid metal base can be used alone or in combination of two or more.

When the sulfonic acid metal base is introduced as a hydrophilic group, the sulfonic acid-derived functional group concentration in the polyester resin (A) is 70 to 400 eq / t in order to satisfy both water dispersibility and water resistance. preferable. More preferably, it is 90 to 320 eq / t, and particularly preferably 110 to 290 eq / t. When the functional group concentration derived from sulfonic acid is less than 70 eq / t, sufficient dispersion stability may not be ensured, and when it exceeds 400 eq / t, the water resistance of the film may be lowered.

Carboxyl groups can also be introduced as hydrophilic groups other than sulfonic acid metal salts. The method of introducing a carboxyl group is a method in which a polyester resin is polymerized and then post-added with a polyvalent carboxylic acid anhydride under normal pressure and nitrogen atmosphere to give an acid value, or an oligomer before the polyester is made high molecular weight There is a method in which a polycarboxylic acid anhydride is added to a product in a state, and then the molecular weight is increased by a polycondensation reaction under reduced pressure to give an acid value. The former method is preferable because the target acid value is easily obtained. Specific examples of the polyvalent carboxylic acid anhydride include trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, maleic anhydride, 1,8-naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride , Cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol bisanhydro trimellitate, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl Examples include, but are not limited to, -3-cyclohexene-1,2-dicarboxylic acid anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and the like. These polyvalent carboxylic acid anhydrides can be used alone or in combination of two or more.

When the carboxyl group is introduced as a hydrophilic group, the functional group concentration (acid value) derived from the carboxylic acid in the polyester resin (A) is preferably 10 to 400 eq / t. More preferably, it is 100 to 320 eq / t, still more preferably 120 to 320 eq / t, and particularly preferably 150 to 280 eq / t. When the functional group concentration derived from carboxylic acid is less than 10 eq / t, sufficient dispersion stability may not be ensured. When it exceeds 400 eq / t, not only the water resistance of the film is lowered, but also the molecular chain There is a possibility that the hydrolysis of the water accelerates. In particular, when no sulfonic acid metal salt is introduced, 100 eq / t or more is preferable in order to ensure water dispersibility and water resistance.

The polyester resin (A) can be produced by a known method. For example, the above dicarboxylic acid and diol components are esterified at 150 to 250 ° C. and then polycondensed at 230 to 300 ° C. under reduced pressure. By doing so, the target polyester resin can be obtained. When a hydrophilic polar group is introduced, it is preferable to add a monovalent inorganic salt such as sodium acetate or potassium acetate as a polymerization stabilizer. Moreover, you may add compounds, such as a hindered phenol or a hindered amine type, as a heat stabilizer.

<Polyester resin (B)>
Like the polyester resin (A), the polyester resin (B) used in the present invention comprises a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound. It is preferable to copolymerize polyester, hydroxycarboxylic acid or lactone having a chemical structure obtained by polycondensation. In the case of a polyester having a chemical structure obtained by polycondensation of a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound, a polyvalent carboxylic acid compound and It is preferable that at least one of the polyhydric alcohol compounds is a copolyester resin composed of two or more kinds of components. The polycarboxylic acid compound and the polyhydric alcohol compound are preferably copolyester resins mainly composed of a dicarboxylic acid component and a glycol component. Here, mainly means that the total of the dicarboxylic acid component and the glycol component accounts for 50 mol% or more on a molar basis with respect to the total of all acid components and all alcohol components constituting the polyester resin (B) used in the present invention. Point to. The total of the dicarboxylic acid component and the glycol component is preferably 70 mol% or more, more preferably 85 mol% or more, preferably 95 mol% or more, and may be 100 mol%.

The manufacturing method of a polyester resin (B) can take a well-known method similarly to the said polyester resin (A). For example, the target polyester resin can be obtained by esterifying the above dicarboxylic acid and diol components at 150 to 250 ° C. and then polycondensing at 230 to 300 ° C. under reduced pressure. When a hydrophilic polar group is introduced, it is preferable to add a monovalent inorganic salt such as sodium acetate or potassium acetate as a polymerization stabilizer. Moreover, you may add compounds, such as a hindered phenol or a hindered amine type, as a heat stabilizer.

Like the polyester resin (A), the polyester resin (B) preferably has a hydrophilic polar group introduced into the resin skeleton in order to disperse in water. Examples of the polar group include a sulfonic acid metal base, a carboxyl group, and a phosphoric acid group, but a sulfonic acid metal base and a carboxyl group are more preferable, and further, dispersibility and long-term stability of the resulting aqueous dispersion are excellent. Sulfonate metal base is most preferred. Moreover, these polar groups may be used alone or in combination as required. The preferable introduction amount of the functional group is the same as that of the polyester resin (A).

The composition and composition ratio of the polyester resin (A) and the polyester resin (B) used in the present invention are calculated from the integral ratio of ¹ H-NMR measured by dissolving the polyester resin (A) in a solvent such as deuterated chloroform. Can be sought.

The aqueous polyester resin dispersion composition used in the present invention must satisfy one of the following (1) to (3) and satisfy the following (4).

<Polyester resin aqueous dispersion composition satisfying (1)>
The 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 the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. It is preferable that the glass transition temperature of (A) is 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. More preferably, it is 11 to 360 eq / t, still more preferably 12 to 320 eq / t, and most preferably 13 to 280 eq / t. If the acid value exceeds 400 eq / t, hydrolysis of the polyester resinous dispersion may be promoted, and long-term storage stability may deteriorate. If the acid value is less than 10 eq / t, the adhesive agent layer obtained from the polyester resin aqueous dispersion composition of the present invention may be poor in solvent resistance and water resistance because it cannot sufficiently react with the curing agent. is there.

The glass transition temperature of the polyester resin (A) used in the present invention is preferably in the range of 5 to 50 ° C. The temperature is more preferably 7 to 45 ° C, further 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 of the present invention is good, but the tackiness tends to increase. On the other hand, when the glass transition temperature exceeds 50 ° C., when the substrate 2 is bonded, the laminating property may be deteriorated and bonding may not be possible. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease.

The polyester resin (B) used in the present invention is preferably an amorphous polyester resin. Moreover, it is preferable that a glass transition temperature is 25 degrees C or less. More preferably, it is 15 degrees C or less, More preferably, it is 10 degrees C or less, Most preferably, it is 5 degrees C or less. The lower limit is not particularly limited, but is usually −30 ° C. or higher, preferably −25 ° C. When glass transition temperature exceeds 25 degreeC, when bonding with the base material 2, a laminate property may fall and it may become unable to adhere | attach. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease. The acid value is preferably in the range of 0 to 20 eq / t, more preferably 0 to 15 eq / t, still 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 to increase the elastic modulus of the adhesive layer, which may deteriorate the laminating property.

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

The blending ratio (mass ratio) of the polyester resin (A) and the polyester resin (B) is preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight for the polyester resin (B) with respect to 100 parts by weight of the polyester resin (A). More preferred is part by mass, and even more preferred is 18 to 50 parts by mass. If the amount of the polyester resin (B) is too large, the resulting polyester resin aqueous dispersion has good adhesiveness and the like, but tends to increase tackiness. If it is in the said range, since tackiness will also become favorable, it is more preferable. On the other hand, if the blending amount of the polyester resin (B) is too small, the laminating property may be deteriorated when the substrate 2 is bonded to the substrate 2 and may not be bonded. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease.

The blending of the polyester resin (A) and the polyester resin (B) consists of a polyester resin aqueous dispersion prepared using the polyester resin (A) and a polyester resin aqueous dispersion prepared using the polyester resin (B). You may mix, and you may perform water dispersion in the state which mixed the polyester resin (A) and the polyester resin (B). Other polyester resins or aqueous dispersions may be mixed as long as the performance of the present invention is not impaired.

<Polyester resin aqueous dispersion composition 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, and (A1) and (A2) The weight average value of the glass transition temperature is 5 to 50 ° C., the weight average value of the acid value is 10 to 400 eq / t, and the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. The weighted average value 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 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. When it is a mixture of two or more kinds of polyester resins, it contains the polyester resin (A1) and polyester resin (A2) described later, and the weighted average value of the glass transition temperatures of the polyester resin (A1) and the polyester resin (A2) is It is preferably 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 higher, more preferably 55 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower. When the glass transition temperature is less than 50 ° C., the tackiness of the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention is large, which may cause a problem in use. The acid value is preferably in the range of 5 to 400 eq / t, more preferably 10 to 360 eq / t, still 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 polyester resin dispersion is promoted, and long-term storage stability may be deteriorated. When the acid value is less than 10 eq / t, it is impossible to sufficiently react with the curing agent, and therefore the solvent resistance and water resistance of the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention may be inferior. is there.

<Polyester resin (A2)>
The polyester resin (A2) is preferably a crystalline polyester resin. When amorphous, the tackiness of the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention is large, which may cause problems in use. The glass transition temperature is preferably 0 ° C. or lower, more preferably −5 ° C. or lower, preferably −30 ° C. or higher, more preferably −20 ° C. or higher. When the glass transition temperature exceeds 0 ° C., the melting point becomes high, and good laminating properties may not be exhibited during bonding. The acid value is preferably in the range of 5 to 400 eq / t, more preferably 10 to 360 eq / t, still 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 polyester resin dispersion is promoted, and long-term storage stability may be deteriorated. When the acid value is less than 10 eq / t, it is impossible to sufficiently react with the curing agent, and therefore the solvent resistance and water resistance of the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention may be inferior. is there.

The crystalline polyester resin as used in the present invention means that a temperature is raised from −100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and a clear melting peak is formed in the temperature raising process. A non-crystalline polyester resin is heated at a rate of 20 ° C./min from −100 ° C. to 250 ° C. using a differential scanning calorimeter (DSC). Points that do not show a peak.

When the polyester resin (A1) and the polyester resin (A2) are used in combination, the weighted average value of the glass transition temperature of the polyester resin (A) is preferably in the range of 5 to 50 ° C. The temperature is more preferably 7 to 45 ° C, further 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 tackiness tends to increase. On the other hand, when the glass transition temperature exceeds 50 ° C., when the substrate 2 is bonded, the laminating property may be deteriorated and bonding may not be possible. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease.

The weighted average value of the glass transition temperature can be calculated by the following formula.
Weight 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) × polyester resin (A2) Part by mass] / [part by mass of polyester resin (A1) + part by mass of polyester resin (A2)]
Moreover, the glass transition temperature of the polyester resin (A) in the case of using together 3 or more types of polyester resins can also be calculated | required by the weighted average of each polyester resin.

When the polyester resin (A1) and the polyester resin (A2) are used in combination, the weighted average value of the acid value of the polyester resin (A) is preferably in the range of 10 to 400 eq / t. More preferably, it is 11 to 360 eq / t, still more preferably 12 to 320 eq / t, and most preferably 13 to 280 eq / t. If the acid value exceeds 400 eq / t, hydrolysis of the polyester resinous dispersion may be promoted, and long-term storage stability may deteriorate. If the acid value is less than 10 eq / t, the adhesive agent layer obtained from the polyester resin aqueous dispersion composition of the present invention may be poor in solvent resistance and water resistance because it cannot sufficiently react with the curing agent. is there.

The weighted average value of the acid value can be calculated by the following formula.
Weighted average value of acid value of polyester resin (A) = [acid value of polyester resin (A1) × mass part of polyester resin (A1) + acid value of polyester resin (A2) × mass part of polyester resin (A2)] / [Mass part of polyester resin (A1) + Mass part of polyester resin (A2)]
Moreover, the acid value of the polyester resin (A) in the case of using together 3 or more types of polyester resins can also be calculated | required by the weighted average of each polyester resin.

A preferable blending ratio (mass ratio) of the polyester resin (A1) and the polyester resin (A2) is preferably polyester resin (A1) / polyester resin (A2) = 90/10 to 10 to 90, and 80/20 to 20/80. Is more preferable, 70/30 to 30/70 is more preferable, and 60/40 to 40/60 is particularly preferable.

The polyester resin (A1) and the polyester resin (A2) are blended into an aqueous polyester resin dispersion prepared using the polyester resin (A1) and an aqueous polyester resin dispersion prepared using the polyester resin (A2). You may mix, and you may perform water dispersion in the state which mixed the polyester resin (A1) and the polyester resin (A2). Other polyester resins or aqueous dispersions may be mixed as long as the performance of the present invention is not impaired.

The polyester resin (B) used in the present invention is preferably an amorphous polyester resin. Moreover, it is preferable that a glass transition temperature is 25 degrees C or less. More preferably, it is 15 degrees C or less, More preferably, it is 10 degrees C or less, Most preferably, it is 5 degrees C or less. The lower limit is not particularly limited, but is usually −30 ° C. or higher, preferably −25 ° C. When glass transition temperature exceeds 25 degreeC, when bonding with the base material 2, a laminate property may fall and it may become unable to adhere | attach. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease. The acid value is preferably in the range of 0 to 20 eq / t, more preferably 0 to 15 eq / t, still 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 to increase the elastic modulus of the coating film, which may deteriorate the laminating property.

It is preferable that the weighted average value of the glass transition temperatures of the polyester resin (A1) and the polyester resin (A2) is higher than the glass transition temperature of the polyester resin (B). By making the weighted average value of the glass transition temperatures of the polyester resin (A1) and the polyester resin (A2) higher than the glass transition temperature of the polyester resin (B), an effect of improving the laminating property can be expected.

<Polyester resin aqueous dispersion composition satisfying (3)>
A thin film (film thickness: 8 μm) prepared using the polyester resin aqueous dispersion composition according to the present invention is heat-treated at 200 ° C. for 5 minutes (hereinafter also referred to as absolutely dry), and is contained in the thin film after being completely dried. At least one of the glass transition temperatures of the polyester resin (A) or the polyester resin (B) is preferably in the range of 5 to 50 ° C. The temperature is more preferably 7 to 45 ° C, further 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 tackiness tends to increase. On the other hand, when the glass transition temperature exceeds 50 ° C., when the substrate 2 is bonded, the laminating property may be deteriorated and bonding may not be possible. Furthermore, water resistance, solvent resistance, and soap water resistance tend to decrease.

When two or more types of compatible polyester resins are used, the average glass transition temperature after the compatibility is set as the glass transition temperature of the polyester resin.

<Polyester resin aqueous dispersion composition satisfying (4)>
When a thin film having a thickness of 8 μm is produced from the aqueous polyester resin dispersion composition according to the present invention, the elastic modulus at 120 ° C. of the thin film is preferably 1 MPa to 1 kPa.

A thin film of the aqueous polyester resin dispersion composition according to the present invention is obtained by applying the aqueous polyester resin dispersion composition to a non-corona surface of a polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 μm) with a hand coater. After drying at about 1 minute for about 1 minute to obtain a laminate having a thin film with a thickness of 8 μm, the thin film is obtained by peeling it from the polypropylene film.

Next, the elastic modulus (Er) of the thin film is measured using a dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement Control Co., Ltd. at 10 Hz and a temperature rising rate of 4 ° C./min. The value of the elastic modulus 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 further preferably in the range of 0.8 MPa to 100 kPa. When the elastic modulus exceeds 1 MPa, the thin film may have poor laminating properties and may not be bonded. When the elastic modulus is less than 1 kPa, the flow of the thin film increases, and good adhesion may not be obtained.

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

<Curing agent (C)>
Although the hardening | curing agent (C) used for this invention is not specifically limited, It is preferable that it is a carbodiimide type hardening | curing agent. By using a carbodiimide-based curing agent, when applied to the substrate 1, the polyester resin (A) and / or polyester resin (B) is not completely cured with the polyester resin (A) and / or polyester resin (B). It is considered that the curing reaction is small enough to increase the molecular weight of B). Thereby, long-term storage after application of the substrate 1 becomes possible, and it is considered that the laminating property when adhering to the substrate 2, adhesion after adhesion, solvent resistance, and water resistance are improved. In addition, a melamine compound, a blocked isocyanate, a water-dispersed isocyanate curing agent, an epoxy compound, an aziridine compound, an oxazoline compound, a metal ion, and the like may be used in combination as long as the effects of the present invention are not impaired. A preferable blending amount of the curing agent (C) is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and further preferably 3 to 25 parts by weight with respect to 100 parts by weight of the polyester resin (A). 5 to 20 parts by mass is particularly preferable. When the amount is less than 0.5 parts by mass, the solvent resistance and soap water resistance tend to decrease. When the amount exceeds 40 parts by mass, a large amount of unreacted curing agent is present in the coating film, resulting in a decrease in tackiness and adhesiveness. It may cause.

<Polyester resin aqueous dispersion composition>
The polyester resin aqueous dispersion composition according to the present invention is an aqueous dispersion containing a polyester resin (A), a polyester resin (B), and a curing agent (C). When the aqueous polyester resin dispersion according to the present invention is produced, the polyester resin chains (A) and the polyester resin (B) can be dissolved or swollen using an organic solvent (hereinafter also referred to as a good solvent) between the polyester molecular chains. After loosening the entanglement, water dispersion can be produced by adding water. If necessary, an organic solvent in which the polyester resin (A) and the polyester resin (B) are not dissolved or swollen (hereinafter also referred to as a poor solvent) may be added.

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, but is preferably 40 to 160 ° C, and preferably 50 to 140 ° C. More preferably, it is 60 to 120 ° C., more preferably 70 to 100 ° C. If the temperature is lower than 40 ° C., the polyester resin (A) and the polyester resin (B) are not sufficiently dissolved or swelled, so that the entanglement between the molecular chains cannot be sufficiently solved. This is because there is an increased risk of causing deterioration.

The good solvent for the polyester resin (A) and the polyester resin (B) is not particularly limited, but methyl ethyl ketone, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1 , 3-dioxolane, 1,2-hexanediol, methyl cellosolve, n-butyl cellosolve, t-butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, triethylene glycol monobutyl ether It is done. Of these, methyl ethyl ketone, butyl cellosolve, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like are preferable.

Examples of the poor solvent for the polyester resin (A) and the polyester resin (B) include methanol, ethanol, 1-propanol, isopropyl alcohol, and hexane. Of these, ethanol and isopropyl alcohol are particularly preferable. Here, the poor solvent is preferably used in a range of 0 to 70% by weight with respect to the good solvent. More preferably, it is 5 to 50%. If a poor solvent of 70% or more is used, the resin may aggregate and settle.

The good solvent and / or the poor solvent can be removed as necessary after the aqueous dispersion is obtained. When removing, it is preferable to use the organic solvent having a boiling point of less than 100 ° C.

When preparing an aqueous dispersion of a polyester resin into which carboxyl groups have been introduced, polar groups such as carboxyl groups on the surface of the particles are partly or wholly covered with a basic substance in order to stabilize the dispersed resin particles. It is preferable to add.

Examples of basic substances that can be used for neutralization include amines represented by triethylamine and the like, or ammonia, sodium hydroxide, potassium hydroxide, and the like. Use of ammonia or volatile amines is preferred in order to eliminate the concern of remaining in the polyester resin composition after drying and the resulting decrease in water resistance.

Only typical examples of volatile amines are exemplified: monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, Triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, and N, N-dimethylpropanolamine And various amines. Particularly preferred is triethylamine. These volatile amines can be used alone or in combination of two or more.

The particle diameter of the polyester resin phase contained in the aqueous polyester resin dispersion composition of the present invention is very important because it greatly affects the appearance and storage stability of the coating film, and is preferably 30 to 250 nm. More preferably, it is 40 to 200 nm, still 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 forming property is lowered, so that the appearance and performance of the obtained film may be deteriorated. If the thickness is less than 30 nm, the film-forming property tends to be remarkably improved. Therefore, fusion and aggregation between the dispersed particles are likely to occur, and as a result, the possibility of causing thickening and poor dispersion is increased. Here, the particle diameter refers to the average particle diameter of the polyester resin (A) and the polyester resin (B) when using two types of polyester resins, the polyester resin (A) and the polyester resin (B). Furthermore, when three types of polyester resins of polyester resin (A1), polyester resin (A2) and polyester resin (B) are used in combination, polyester resin (A1), polyester resin (A2) and polyester resin (B) Refers to the average particle size. Moreover, when using 4 or more types of polyester resins, the average particle diameter of all the polyester resins currently used is pointed out.

In the aqueous polyester resin dispersion according to the present invention, the coarse particles of 1 μm or more are 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. If it exceeds 1% by mass, a precipitate may be generated over time (long-term storage), resulting in poor storage stability, and may cause unevenness during coating and drying.

The polyester resin aqueous dispersion concentration of the polyester resin aqueous dispersion according to the present invention is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, and most preferably 20%. It is in the range of ~ 33% by mass. When the resin solid content concentration exceeds 45% by mass, the solution viscosity becomes high and aggregation between the resin particles tends to occur, so that the dispersion stability may be greatly lowered. Moreover, if it is less than 5 mass%, it is hard to say that it is practical from both a manufacturing surface and a use surface.

<Anti-blocking agent (D)>
The polyester resin aqueous dispersion composition according to the present invention preferably contains an antiblocking agent. The blending amount is not particularly limited, but is preferably 0 to 20 parts by weight, more preferably 1 to 16 parts by weight, more preferably 3 to 14 parts by weight with respect to 100 parts by weight of the polyester resin (A) as a range that does not adversely affect the adhesive performance. Part is more preferable, and 5 to 12 parts by mass is particularly preferable. The blocking inhibitor (D) can be used alone or in combination of two or more.

The aqueous polyester resin dispersion composition according to the present invention is an emulsifier within a range that does not affect the performance other than the polyester resin (A), the polyester resin (B), the curing agent (C), and the anti-blocking agent (D). Alternatively, additives or the like used in ordinary aqueous adhesives such as a plasticizer, a dispersant, a thickener, a solvent, an antifoaming agent, a preservative, and an antiblocking agent can be appropriately blended as necessary.
<Coating solution>
The coating liquid comprises the polyester resin aqueous dispersion composition of the present invention and, if necessary, an antiblocking agent (D), an emulsifier, a plasticizer, a dispersant, a thickener, a solvent, an antifoaming agent, an antiseptic, and the like. It is prepared by appropriately blending additives and the like used for ordinary aqueous adhesives.

<Adhesive layer>
An adhesive layer can be produced using the polyester resin aqueous dispersion composition according to the present invention. The adhesive layer can be obtained by applying the coating liquid on the substrate 1 and then performing a drying treatment. The coating amount of the aqueous polyester resin dispersion is preferably adjusted so that the thickness is 3 to 30 μm. The thickness of the thin film is preferably 3 to 30 μm, more preferably 5 to 20 μm, still 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 efficient production becomes difficult.

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 preferably in the range of 0.8 MPa to 100 kPa. Further preferred. When the elastic modulus exceeds 1 MPa, when the base material 1 and the base material 2 are bonded to each other, the laminating property may be deteriorated and adhesion may not be possible. When the elastic modulus is less than 1 kPa, when the base material 1 and the base material 2 are bonded together, the flow of the adhesive layer becomes large, and good adhesiveness may not be obtained.

The drying conditions of the coating liquid are not particularly limited, but are preferably 40 to 250 ° C, more preferably 60 to 200 ° C, and further preferably 80 to 150 ° C. If it is less than 40 degreeC, drying time will take time and it is not rational as industrial production. Moreover, there is a possibility that the coating liquid is not completely dried. On the other hand, if it exceeds 250 ° C., a high-performance drying furnace is required, which is not desirable. The drying method is not limited, but known methods such as a hot air drier, induction heating, near infrared heating, far infrared heating, indirect heating can be applied.

After the coating liquid is applied to the substrate 1 and dried and cured to form an adhesive layer, the substrate 2 is bonded to the adhesive layer, thereby providing good solvent resistance, adhesiveness, and water resistance. A laminate having a soap water resistance can be obtained. Although it does not specifically limit as the base material 1 and the base material 2, The base fabric etc. which were processed into the plastic film, the processed paper or unprocessed paper, or fixed thickness etc. are mentioned. Examples of the plastic film include, but are not limited to, poval film, PET film, polyolefin film, polyester film, polyvinyl chloride film, polyurethane fill, and the like. And glass fiber.

In addition, the said base material 1 and the base material 2 may be the same kind, and may differ. 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 using the following examples and comparative examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” simply means “parts by mass”. The characteristics of the polyester resin (A), the polyester resin (B), the polyester resin aqueous 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 performing ¹ H-NMR analysis using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian. .

2. Reduced viscosity ηsp / c (unit: dl / g)
0.10 g of the polyester resin was dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscosity tube.

3. Number average molecular weight Gel Permeation Chromatography of Polyester Resin (A) at a column temperature of 35 ° C. and a flow rate of 1 ml / min using a gel permeation chromatograph 150c manufactured by Waters with tetrahydrofuran as an eluent and a differential refractometer as a detector. The number average molecular weight in terms of polystyrene was obtained. As the column, Showa Denko Co., Ltd. shodex KF-802, KF-804, KF-806 connected in series was used.

4). Crystal melting point and glass transition temperature Using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc., 5 mg of a sample (polyester resin or completely dried film) was sealed in an aluminum presser lid type container, The temperature was measured from 100 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min, and the maximum peak temperature of heat of fusion was determined as the crystalline melting point. In addition, the glass transition temperature is determined by the temperature at the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope from the peak rising portion to the peak apex under the same conditions as in the measurement apparatus. It was. In the present invention, absolutely dry means that a thin film produced using the aqueous polyester resin dispersion composition is heat-treated at 200 ° C. for 5 minutes.

5. Ionic group concentration 5-1. A 0.2 g sample of the carboxyl group concentration (polyester resin) was precisely weighed and dissolved in 20 ml of chloroform. Then, titration was performed with 0.01 N potassium hydroxide (ethanol solution) to obtain a potassium hydroxide equivalent for the polyester resin, and the amount was calculated in terms of eq / ton units. In addition, phenolphthalein was used as an indicator.
5-2. Sodium sulfonate base concentration The sodium concentration was measured by atomic absorption, and the sodium sulfonate base concentration was calculated and converted to eq / t units.

6). Particle diameter and dispersion coefficient The particle diameter and dispersion coefficient of the aqueous polyester resin dispersion were measured. For the measurement, a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter Counter LS13 320) was used. Then, the particle distribution was prepared on a volume basis by this apparatus, the average diameter and the dispersion coefficient were obtained, and the value of the average diameter was taken as the particle diameter.

7). A polyester resin aqueous dispersion was placed in a glass bottle with a viscosity of 140 cc, and the viscosity meter model BL (TOKIMEC INC.) No. 1 or No. Two rotors were used. Measurement was performed at a rotational speed of 60 rpm for 1 minute, and the viscosity of the aqueous polyester resin dispersion was measured.

8. A 120 ° C elastic modulus coating solution is applied to the non-corona surface of a polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 µm) with a hand coater and dried at 120 ° C for 1 minute to have a thin film with a thickness of about 8 µm A laminate was obtained. The thin film was peeled off from the polypropylene film and measured using a dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement Control Co., Ltd. at 10 Hz and a temperature rising rate of 4 ° C./min. The Er value at 120 ° C. obtained by the measurement was in the range of 1 MPa to 1 kPa, and the others were marked with “X”. In Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed so that the film thicknesses were as shown in Table 3, respectively.

9. Polyester resin aqueous dispersion composition storage stability test The polyester resin aqueous dispersion composition was placed in a 140 cc glass bottle, left in an incubator at 40 ° C., and stored for 30 days. After a predetermined number of days, the solution was taken out from the incubator, the solution viscosity was measured by the method described above, and compared with the value measured immediately after preparation of the coating solution. The case where there was no change was indicated as ◯, and the case where the system was solidified was indicated as ×.

10. The coating liquid was applied to the coated coating film stability test substrate 1 with a hand coater and dried at 120 ° C. for 1 minute to obtain a laminate having a thin film having a thickness of about 8 μm. Two of the same laminates were prepared, one of which was laminated on the substrate 2 at a roll temperature of 120 ° C., a pressure of 4 N / cm, and a speed of 1 m / min, and cut to a width of 1 × 1 cm to prepare a test sample 1 The test sample 1 was evaluated for adhesion, solvent resistance (MEK resistance, ethyl acetate resistance, toluene resistance), soap water resistance, and water resistance. The other laminate was covered with a non-corona surface of a polyester film (Toyobo Co., Ltd. 5107, thickness 25 μm) on this laminate and stored for 4 weeks in an environment of 25 ° C. and 60% humidity. After storage, in the same manner as described above, the substrate 2 was laminated at a roll temperature of 120 ° C., a pressure of 4 N / cm, and a speed of 1 m / min, and cut to a width of 1 × 1 cm to obtain a test sample 2. The adhesion, solvent resistance (MEK resistance, ethyl acetate resistance, toluene resistance), soap water resistance, and water resistance of Test Sample 2 were evaluated and compared with the performance before storage (Test Sample 1). The case where there was no change in the evaluation was rated as “◯”, and the case where the test sample 2 had an inferior item was rated as “×”. As the substrate 1, a polyester film (E5107 manufactured by Toyobo Co., Ltd., thickness: 25 μm) was used, and the coating solution was applied to the non-corona surface. As the base material 2, a loose leaf note (manufactured by Kokuyo, No-A836AH) made of high-quality paper and having a thickness of 100 g / m ² was used. In Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed so that the film thicknesses were as shown in Table 3, respectively.

11. Tackiness
The coating liquid is applied to the non-corona surface of the substrate 1 (polyester film (Toyobo Co., Ltd. E5107, thickness 25 μm)) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film having a thickness of about 8 μm. A laminate was obtained. The thin film surfaces are rubbed together by hand in an environment of 25 ° C., ◎ if there is no thin film tack, ○ if there is a slight tack, ○ in the range that does not cause problems in use, polyester resin with tack The case where the adhesion between the compositions did not occur was Δ, and the case where there was tack and the polyester resin compositions were sticking was indicated as x. In Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed so that the film thicknesses were as shown in Table 3, respectively.

12 Adhesiveness
The coating liquid is applied to the non-corona surface of the substrate 1 (polyester film (Toyobo Co., Ltd. E5107, thickness 25 μm)) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film having a thickness of about 8 μm. A laminate was obtained. Laminate this laminate and base material 2 (loose leaf notebook of 100 g / m ² thick paper made of fine paper (manufactured by KOKUYO, No-A836AH)) at a roll temperature of 120 ° C., a pressure of 4 N / cm, and a speed of 1 m / min. A test sample was prepared by cutting to a width of 1 × 1 cm. The test sample was peeled off by hand and the base material was broken.

13. MEK resistance
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in MEK at room temperature (about 25 ° C.) for 1 hour, then taken out from the solution, dried, and then peeled off by hand to break the material. What to do is marked with ○, and others are marked with ×.

14 Acetone resistance
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in acetone at room temperature (about 25 ° C.) for 1 hour, then taken out from the solution, dried, and then peeled off by hand to break the substrate. What to do is marked with ○, and others are marked with ×.

15. Ethyl acetate resistance
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in ethyl acetate at room temperature (about 25 ° C.) for 1 hour, then taken out from the solution, dried, and then peeled off by hand to make the base material Those to be broken were marked with ○, and others were marked with ×.

16. Toluene resistance
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in toluene at room temperature (about 25 ° C.) for 1 hour, then taken out from the solution and dried, and then peeled off by hand to break the material. What to do is marked with ○, and others are marked with ×.

17. Soap-resistant
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in 20% by mass soap water at 70 ° C. for 1 hour, then taken out from the solution, rinsed with water, dried, The case where the base material broke due to peeling was marked with ◯, and the others were marked with x.

18. water resistant
A test sample was prepared in the same manner as in (12. Adhesion section), immersed in water at 25 ° C. for 30 minutes, then taken out from the solution, dried, peeled off by hand, and the base material broke. Other than that, it was set as x.

Example of polyester resin (A) Synthesis of polyester resin (a-1) In a reaction can equipped with a stirrer, a thermometer, a heater, a cooling device, and a condenser for distillation, 138 parts by mass of dimethyl terephthalate, isophthalate 136 parts by mass of dimethyl acid sodium, 11 parts by mass of sodium 5-sulfonatoisophthalate, 108 parts by mass of ethylene glycol, 120 parts by mass of 2,2-dimethyl-1,3-propanediol and 1 part by mass of tetrabutyl titanate, up to 230 ° C. The ester exchange reaction was carried out over 4 hours while raising the temperature. After completion of the transesterification reaction, the pressure in the system was reduced to 10 torr over 60 minutes while the temperature was raised to 240 ° C., and the pressure was further reduced to 1 torr or less under vacuum to carry out a polycondensation reaction at 240 ° C. for 60 minutes. Thereafter, the polycondensation reaction was terminated by flowing nitrogen into the system and breaking the vacuum. After completion of the reaction, the polyester resin was taken out and cooled to obtain polyester resin a-1. As a result of NMR analysis, the obtained polyester resin has a carboxylic acid component in a molar ratio of terephthalic acid / isophthalic acid / 5-sodium sulfonate sodium phthalate = 50 / 47.5 / 2.5, and a glycol component in a molar ratio. Ethylene glycol / 2,2-dimethyl-1,3-propanediol = 50/50. The measurement results are shown in Table 1 together with other resin physical properties.

388 parts by mass of dimethyl terephthalate was added to a reaction vessel equipped with a polyester resin (a-10) synthesis stirrer, condenser and thermometer.
Charge 388 parts by weight of dimethyl isophthalate, 554 parts by weight of 2-methyl-1,3-propanediol, 275 parts by weight of 1,5-pentanediol, and 0.41 part by weight of tetrabutyl titanate. From 160 ° C. to 230 ° C. for 4 hours. Over the course of the transesterification reaction. Next, the pressure in the system was gradually reduced, the pressure was reduced to 5 mmHg over 20 minutes, and a polycondensation reaction was performed at 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. The mixture was cooled to 220 ° C. under a nitrogen stream, and 27 parts by mass of trimellitic anhydride was added to react for 30 minutes. As a result of NMR compositional analysis, the copolymerized polyester (a-1) obtained had an acid component molar ratio of terephthalic acid / isophthalic acid / trimellitic acid = 50/50/3, and a glycol component molar ratio of 2 -Methyl-1,3-propanediol / 1,5-pentanediol = 65/35. The measurement results are shown in Table 1 together with other resin physical properties.

Synthetic polyester resins (a-2) to (a-9) In the same manner as in the synthetic example of polyester resin (a-1), the polyester resins (a-2) to (a- 9) was synthesized. The measurement results of the resin physical properties are shown in Table 1.

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

Production of Polyester Resin Aqueous Dispersion (b-1) A three-necked separable flask equipped with a thermometer, condenser and stirring blade was charged with 300 parts by weight of polyester resin (a-1) and 100 parts by weight of n-butyl cellosolve. Dissolved at ° C. Subsequently, after cooling to 90 degreeC, 600 mass parts warm water was added over 30 minutes, and the polyester resin aqueous dispersion whose solid content concentration is 30 mass% was obtained. The resin physical property measurement results of the obtained polyester resin aqueous dispersion are shown in Table 2.

In the same manner as in the production example of the aqueous polyester resin dispersion (b-1), the polyester resins (a-2) to (a-9) were used, and the compositions described in Table 2 were used. b-2) to (b-9) were produced. Solvents listed in Table 2 were used. Resin physical properties were measured in the same manner as the aqueous polyester resin dispersion (b-1). The results are shown in Table 2.

Production of polyester resin aqueous dispersion (b-10) 100 parts by weight of polyester resin (a-10), 40 parts by weight of n-butyl cellosolve and 2.7 parts by weight of triethylamine were added, followed by stirring at 80 ° C. for 1 hour. Dissolved. Subsequently, 193 parts by mass of ion exchange water was gently added to obtain an aqueous polyester resin dispersion (b-10). Table 2 shows the measurement results of the resin physical properties.

Production of aqueous polyester resin dispersion (b-11) Polyester resin aqueous dispersion (b-11) was prepared using polyester resin (a-11) in the same manner as in the production example of aqueous polyester resin dispersion (b-10). Manufactured. Table 2 shows the measurement results of the resin physical properties.

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

As the blocking inhibitor (D), Nopco (registered trademark) LB-550 manufactured by San Nopco Co., which is a special ester compound, was used.

Example 1
40 parts by mass of an aqueous polyester resin dispersion (b-3), 40 parts by mass of an aqueous polyester resin dispersion (b-9), 20 parts by mass of an aqueous polyester resin dispersion (b-5), and 2 parts by mass of carbodilite SV-02 Then, 2 parts by mass of Nopco LB-550 was mixed to prepare a coating solution. This coating solution is applied to the non-corona surface of a polyester film (E5107 manufactured by Toyobo Co., Ltd., thickness 25 μm) as a base material 1 with a hand coater and dried at 120 ° C. for 3 minutes to form a thin film (coating film) of about 8 μm. A laminated body having was obtained. The glass transition temperature of the polyester resin contained in the thin film after absolutely dried was 15 ° C. As a laminate and a substrate 2, KOKUYO loose leaf (No-A836AH) was laminated at a roll temperature of 120 ° C., a pressure of 4 N, and a speed of 1 m / min to obtain a test sample. This test sample was cut to a width of 1 × 1 cm and evaluated for adhesion, solvent resistance (MEK resistance, acetone resistance, ethyl acetate resistance, toluene resistance), soap water resistance, and water resistance. These evaluation results are shown in Table 3. In addition, this coating solution is applied to the non-corona surface of a polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 μm) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film (coating film) of about 8 μm. A laminate was obtained. When this laminate was used to evaluate the elastic modulus at 120 ° C., the elastic modulus was 383 kPa. Further, this coating solution is applied to the non-corona surface of a polyester film (E5107 manufactured by Toyobo Co., Ltd., thickness 25 μm) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film (coating film) of about 8 μm. A laminate was obtained. The tackiness was evaluated using this laminate. These evaluation results are also shown in Table 3.

Examples 2 to 11
In the same manner as in Example 1, the same evaluation was performed by changing to the blending components and film thicknesses shown in Table 3. These evaluation results are shown together in Table 3.

Comparative Examples 1 to 4
Similar to Example 1, the same evaluation was performed using different blending components. These evaluation results are shown together in Table 3.

As is clear from Table 3, despite the use of an aqueous polyester resin dispersion, it has good adhesion to various substrates such as cloth, paper, and plastic film, and is stable in the state of a coating solution. It can be seen that an adhesive composition excellent in solvent properties, solvent resistance to various solvents, soap water resistance, and water resistance can be obtained.

A polyester resin adhesive composition that has long-term storage stability when applied to the substrate 1 and is excellent in adhesion, solvent resistance, soap water resistance and water resistance can be easily formed. The contribution to the is great.

Claims

Polyester resin aqueous dispersion containing polyester resin (A), polyester resin (B) and curing agent (C), satisfying any of the following (1) to (3), and satisfying (4) below Composition.
(1) The 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 the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. The polyester resin (A) has a glass transition temperature higher than the glass transition temperature of the polyester resin (B). (2) The polyester resin (A) is an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C. or higher. It is a mixture of crystalline polyester resin (A2) having a glass transition temperature of 0 ° C. or lower. The weighted average value of glass transition temperatures of (A1) and (A2) is 5 to 50 ° C., and the weighted average value of acid value is 10 to 400 eq. / T, the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less, and the polyester resin (A1) and the polyester resin ( A weighted average value of the glass transition temperature of 2) is higher than the glass transition temperature of the polyester resin (B). (3) A thin film having a thickness of 8 μm was prepared from the aqueous polyester resin dispersion composition, and the thin film was completely dried. (4) When a polyester resin (A) or polyester resin (B) contained later has a glass transition temperature of 5 to 50 ° C. (4) When a thin film having a thickness of 8 μm is produced with an aqueous polyester resin dispersion composition The elastic modulus of the thin film at 120 ° C. is 1 MPa to 1 kPa
The aqueous polyester resin dispersion composition according to claim 1, wherein the curing agent (C) is a carbodiimide curing agent.
The polyester resin aqueous solution according to claim 1 or 2, comprising 10 to 100 parts by mass of the polyester resin (B) and 0.5 to 40 parts by mass of the curing agent (C) with respect to 100 parts by mass of the polyester resin (A). Dispersion composition.
An adhesive composition containing the aqueous polyester resin dispersion according to any one of claims 1 to 3.
The adhesive composition according to claim 4, which is used for laminating a film and a film or paper.
A laminate laminated with the adhesive composition according to claim 4 or 5.
A polyester resin aqueous dispersion composition containing a polyester resin satisfying any of the following (1) to (3) and a curing agent (C) is applied to the substrate 1, and the film thickness is 8 μm and elasticity at 120 ° C. A method for producing a laminate in which a thin film having a rate of 1 MPa to 1 kPa is prepared, and then a base material 2 is bonded.
(1) The 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 the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less. The polyester resin (A) has a glass transition temperature higher than the glass transition temperature of the polyester resin (B). (2) The polyester resin (A) is an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C. or higher. It is a mixture of crystalline polyester resin (A2) having a glass transition temperature of 0 ° C. or lower. The weighted average value of glass transition temperatures of (A1) and (A2) is 5 to 50 ° C., and the weighted average value of acid value is 10 to 400 eq. / T, the polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C. or less, and the polyester resin (A1) and the polyester resin ( The weighted average value of the glass transition temperature of 2) is higher than the glass transition temperature of the polyester resin (B). (3) The glass transition temperature of the polyester resin (A) or polyester resin (B) contained after the thin film is completely dried. At least one of 5 to 50 ° C.