WO2014156344A1 - Dispersion aqueuse de résine de polyester et composition d'agent liant l'incorporant - Google Patents

Dispersion aqueuse de résine de polyester et composition d'agent liant l'incorporant Download PDF

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Publication number
WO2014156344A1
WO2014156344A1 PCT/JP2014/053140 JP2014053140W WO2014156344A1 WO 2014156344 A1 WO2014156344 A1 WO 2014156344A1 JP 2014053140 W JP2014053140 W JP 2014053140W WO 2014156344 A1 WO2014156344 A1 WO 2014156344A1
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Prior art keywords
polyester resin
glass transition
transition temperature
aqueous
thin film
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PCT/JP2014/053140
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English (en)
Japanese (ja)
Inventor
達也 粟田
忠彦 三上
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東洋紡株式会社
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Priority to CN201480012822.XA priority Critical patent/CN105008457B/zh
Priority to JP2014530986A priority patent/JP6424621B2/ja
Priority to KR1020157016581A priority patent/KR102018902B1/ko
Publication of WO2014156344A1 publication Critical patent/WO2014156344A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline

Definitions

  • the present invention relates to an aqueous polyester resin dispersion and an adhesive composition using the same.
  • 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.
  • 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.
  • 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.
  • 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.
  • the adhesive layer using a non-curable resin has problems such as poor adhesive strength, solvent resistance, and water resistance.
  • 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.
  • 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.
  • this invention is the polyester resin aqueous dispersion composition, adhesive composition, and laminated body shown below.
  • 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.
  • 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).
  • the polyester resin (A) is an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C. or higher.
  • 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
  • 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).
  • a thin film having a thickness of 8 ⁇ m was prepared from the aqueous polyester resin dispersion composition, and the thin film was completely dried.
  • curing agent (C) is a carbodiimide type hardening
  • An adhesive composition containing the polyester resin aqueous dispersion 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.
  • 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 ⁇ m and elasticity at 120 ° C.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • a polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound are preferably copolyester resins mainly composed of a dicarboxylic acid component and a glycol component.
  • 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.
  • aromatic dicarboxylic acid examples include, but are not limited to, terephthalic acid, isophthalic acid, orthophthalic acid, and naltalenedicarboxylic acid.
  • aliphatic dicarboxylic acid examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • polyester resin (A) is dispersed in water, it is preferable to introduce a hydrophilic polar group into the resin skeleton.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • polyvalent carboxylic acid anhydride examples 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.
  • 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.
  • the functional group concentration derived from carboxylic acid is less than 10 eq / t, sufficient dispersion stability may not be ensured.
  • 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.
  • 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.
  • 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.
  • 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.
  • a hindered phenol or a hindered amine type as a heat stabilizer.
  • 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.
  • a polyvalent carboxylic acid compound and an alcohol component composed of a divalent or higher polyhydric alcohol compound are preferably copolyester resins mainly composed of a dicarboxylic acid component and a glycol component.
  • 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).
  • 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.
  • 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.
  • the polyester resin (B) preferably has a hydrophilic polar group introduced into the resin skeleton in order to disperse in water.
  • 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.
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 polyester resin (A2) is preferably a crystalline polyester resin.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)]
  • 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
  • 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)]
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • the polyester resin (B) reacts with the curing agent to increase the elastic modulus of the coating film, which may deteriorate the laminating property.
  • 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).
  • a thin film (film thickness: 8 ⁇ m) 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.
  • 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.
  • the glass transition temperature exceeds 50 ° C.
  • the laminating property may be deteriorated and bonding may not be possible.
  • water resistance, solvent resistance, and soap water resistance tend to decrease.
  • the average glass transition temperature after the compatibility is set as the glass transition temperature of the polyester resin.
  • 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 ⁇ m) 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 ⁇ m, the thin film is obtained by peeling it from the polypropylene film.
  • a polypropylene film Toyobo Co., Ltd., P2161, thickness 50 ⁇ m
  • 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.
  • the elastic modulus exceeds 1 MPa, the thin film may have poor laminating properties and may not be bonded.
  • 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) used for this invention is not specifically limited, It is preferable that it is a carbodiimide type hardening
  • 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.
  • 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.
  • 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).
  • 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.
  • 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
  • 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, triethylene glycol monobutyl ether It is done. Of these,
  • the poor solvent for the polyester resin (A) and the polyester resin (B) examples include methanol, ethanol, 1-propanol, isopropyl alcohol, and hexane. Of these, ethanol and isopropyl alcohol are particularly preferable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the coarse particles of 1 ⁇ m 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.
  • 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.
  • it is less than 5 mass% it is hard to say that it is practical from both a manufacturing surface and a use surface.
  • 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).
  • 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.
  • 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.
  • 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 ⁇ m.
  • the thickness of the thin film is preferably 3 to 30 ⁇ m, more preferably 5 to 20 ⁇ m, still more preferably 6 to 15 ⁇ m, and most preferably 7 to 10 ⁇ m. If it is less than 3 ⁇ m, it is difficult to obtain a uniform adhesive layer, and if it exceeds 30 ⁇ m, 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.
  • 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.
  • 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.
  • the substrate 2 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a 120 ° C elastic modulus coating solution is applied to the non-corona surface of a polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 ⁇ m) with a hand coater and dried at 120 ° C for 1 minute to have a thin film with a thickness of about 8 ⁇ m 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”.
  • the coating amount and the drying time were changed so that the film thicknesses were as shown in Table 3, respectively.
  • 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 ⁇ .
  • 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 ⁇ m.
  • 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 ⁇ m) on this laminate and stored for 4 weeks in an environment of 25 ° C. and 60% humidity.
  • 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 substrate 1 a polyester film (E5107 manufactured by Toyobo Co., Ltd., thickness: 25 ⁇ m) was used, and the coating solution was applied to the non-corona surface.
  • 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.
  • the coating amount and the drying time were changed so that the film thicknesses were as shown in Table 3, respectively.
  • the coating liquid is applied to the non-corona surface of the substrate 1 (polyester film (Toyobo Co., Ltd. E5107, thickness 25 ⁇ m)) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film having a thickness of about 8 ⁇ m. A laminate was obtained.
  • the coating liquid is applied to the non-corona surface of the substrate 1 (polyester film (Toyobo Co., Ltd. E5107, thickness 25 ⁇ m)) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film having a thickness of about 8 ⁇ m.
  • 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.
  • 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 ⁇ .
  • 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 ⁇ .
  • 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 ⁇ .
  • 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 ⁇ .
  • 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.
  • 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.
  • polyester resin (A) Synthesis of polyester resin (a-1)
  • 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.
  • 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.
  • 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.
  • 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.
  • the measurement results are shown in Table 1 together with other resin physical properties.
  • 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.
  • polyester resin (a-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.
  • 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.
  • 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.
  • Nopco registered trademark
  • LB-550 manufactured by San Nopco Co., which is a special ester compound
  • 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 ⁇ m) 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 ⁇ m. A laminated body having was obtained.
  • a polyester film E5107 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m
  • the glass transition temperature of the polyester resin contained in the thin film after absolutely dried was 15 ° C.
  • KOKUYO loose leaf No-A836AH
  • 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.
  • this coating solution is applied to the non-corona surface of a polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 ⁇ m) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film (coating film) of about 8 ⁇ m.
  • a laminate was obtained.
  • the elastic modulus was 383 kPa.
  • this coating solution is applied to the non-corona surface of a polyester film (E5107 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m) with a hand coater and dried at 120 ° C. for 1 minute to have a thin film (coating film) of about 8 ⁇ m.
  • a laminate was obtained. The tackiness was evaluated using this laminate.
  • Example 2 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dispersion Chemistry (AREA)

Abstract

L'invention porte sur une composition aqueuse de résine de polyester sous forme de dispersion et sur une composition d'agent liant l'incorporant. La composition aqueuse de résine de polyester sous forme de dispersion présente une excellente adhérence à un grand nombre de substrats tels que des textiles, du papier et des films plastiques tout en présentant une exceptionnelle résistance à l'eau (y compris l'eau savonneuse) et à un grand nombre de solvants. La composition aqueuse de résine de polyester sous forme de dispersion contient des polyesters (A) et (B) particuliers et un agent durcisseur (C). Le module d'élasticité à 120°C d'un film mince ayant une épaisseur de 8 μm fabriqué à l'aide de la composition aqueuse de résine de polyester sous forme de dispersion est de 1 MPa à 1 kPa.
PCT/JP2014/053140 2013-03-26 2014-02-12 Dispersion aqueuse de résine de polyester et composition d'agent liant l'incorporant WO2014156344A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480012822.XA CN105008457B (zh) 2013-03-26 2014-02-12 聚酯树脂水性分散体以及使用其的粘合剂组合物
JP2014530986A JP6424621B2 (ja) 2013-03-26 2014-02-12 ポリエステル樹脂水性分散体およびこれを用いた接着剤組成物
KR1020157016581A KR102018902B1 (ko) 2013-03-26 2014-02-12 폴리에스테르 수지 수성 분산체 및 이것을 이용한 접착제 조성물

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US10676651B2 (en) * 2016-03-09 2020-06-09 Mitsubishi Chemical Corporation Adhesive film and process for producing the same
US20210371581A1 (en) * 2019-01-17 2021-12-02 Toyobo Co., Ltd. Copolymerized polyester and water dispersion
JP2022518899A (ja) * 2019-01-30 2022-03-17 クレイン アンド カンパニー、 インコーポレイテッド セキュリティ文書用の高性能接着剤
WO2023282068A1 (fr) * 2021-07-08 2023-01-12 Dic株式会社 Stratifié et matériau d'emballage

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JP2017008121A (ja) * 2015-06-16 2017-01-12 ユニチカ株式会社 ポリエステル樹脂組成物およびそれを用いて得られる成形体
US10676651B2 (en) * 2016-03-09 2020-06-09 Mitsubishi Chemical Corporation Adhesive film and process for producing the same
US20210371581A1 (en) * 2019-01-17 2021-12-02 Toyobo Co., Ltd. Copolymerized polyester and water dispersion
JP2022518899A (ja) * 2019-01-30 2022-03-17 クレイン アンド カンパニー、 インコーポレイテッド セキュリティ文書用の高性能接着剤
WO2023282068A1 (fr) * 2021-07-08 2023-01-12 Dic株式会社 Stratifié et matériau d'emballage
JPWO2023282068A1 (fr) * 2021-07-08 2023-01-12
JP7290203B2 (ja) 2021-07-08 2023-06-13 Dic株式会社 積層体及び包装材

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TWI585174B (zh) 2017-06-01
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CN105008457B (zh) 2017-06-30
CN105008457A (zh) 2015-10-28
KR102018902B1 (ko) 2019-09-06
JP6424621B2 (ja) 2018-11-21
JPWO2014156344A1 (ja) 2017-02-16

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