WO2017073697A1 - ポリエステル系樹脂、プライマー用ポリエステル系樹脂、ポリエステル系水性液、及びプライマー層付き基材フィルムならびに積層フィルム - Google Patents
ポリエステル系樹脂、プライマー用ポリエステル系樹脂、ポリエステル系水性液、及びプライマー層付き基材フィルムならびに積層フィルム Download PDFInfo
- Publication number
- WO2017073697A1 WO2017073697A1 PCT/JP2016/081965 JP2016081965W WO2017073697A1 WO 2017073697 A1 WO2017073697 A1 WO 2017073697A1 JP 2016081965 W JP2016081965 W JP 2016081965W WO 2017073697 A1 WO2017073697 A1 WO 2017073697A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- carboxylic acid
- film
- resin
- polyester resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/195—Bisphenol A
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/052—Forming heat-sealable coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
Definitions
- the present invention relates to a polyester-based resin and a polyester-based aqueous liquid. More specifically, the present invention is excellent in adhesion between both a polyester-based resin substrate and a hard coat layer, in particular, moisture and heat-resistant adhesion, and high in refractive index.
- the present invention relates to a polyester-based resin capable of forming a coating film having a good appearance and a polyester-based aqueous liquid.
- polyester films have been used in various industrial fields such as packaging materials, magnetic cards, and printing materials.
- a thermoplastic polyester such as polyethylene terephthalate (PET) or a copolymer thereof mixed with other resins as necessary is melt-extruded and molded, and then biaxially stretched. Heat-fixed ones are used.
- PET polyethylene terephthalate
- Such a polyester film is excellent in various physical properties such as mechanical strength, heat resistance, chemical resistance, etc., but its surface is highly crystallized, so that it is in close contact with, for example, paints, adhesives, inks, etc. There is a problem of poor sex.
- a primer layer with a film formed by applying an aqueous liquid (solution or dispersion) of a polyester resin to the surface of a polyester film, adhesion to a paint or the like is improved. Improvements are being made.
- a hard coat film in which a hard coat layer is laminated on a polyester film is excellent in hardness and scratch resistance and is used for optical applications, etc.
- the primer layer is also provided between the polyester film and the hard coat layer in this hard coat film. Is provided.
- the film having such a configuration there is a problem in that the iris-like reflection due to the difference between the refractive index of the primer layer and the refractive index of the polyester film and the hard coat layer occurs, which impairs visibility.
- Patent Document 1 a dicarboxylic acid component having a naphthalene skeleton is copolymerized in an amount of 50 mol% or more in the total acid component, and a glycol component having a bisphenol A skeleton is copolymerized in an amount of 50 mol% or more in the total glycol component.
- a coated polyester film in which a coating layer mainly composed of a copolyester resin in which 6000 polyalkylene glycol is copolymerized is disclosed, and interference spots occur when a high refractive index hard coat layer is laminated. It is described that a hard coat film that is inconspicuous and has excellent adhesion can be obtained.
- Patent Document 2 has a specific proportion of four specific structural units including a structural unit formed from a salt of an aromatic dicarboxylic acid having 8 to 12 carbon atoms and a structural unit formed from a bisphenol compound, A polyester resin having a specific reduced viscosity and refractive index is disclosed, and it is described that the aqueous liquid is excellent in dispersibility, the refractive index of the resulting layer is high, and easy adhesion is excellent.
- the polyester resin disclosed in Patent Document 1 is obtained by copolymerizing a component having a sulfonate group for water dispersion, the coating film is whitened or foamed in a high temperature and high humidity environment. There was a problem that the appearance deteriorated.
- the polyester resin disclosed in Patent Document 2 contains a large amount of a bisphenol S skeleton having a sulfonyl group, the adhesion with the hard coat layer is reduced in a high temperature and high humidity environment. There was a problem that the film appearance deteriorated.
- the present invention is excellent in the adhesion between the polyester-based resin substrate and the hard coat layer formed from, for example, the active energy ray-curable resin composition, and has a high refractive index under such a background. Furthermore, it aims at providing the polyester-type resin which is excellent in adhesiveness also in a high-temperature, high-humidity environment, and the appearance of a coating film does not deteriorate, and a polyester-type aqueous liquid.
- the present inventor as a result, in the polyester resin obtained from the polyvalent carboxylic acid component (A) and the polyol component (B), naphthalenedicarboxylic acid (a1) as the polyvalent carboxylic acid. Is contained as a main component, and a glycol compound (b1) having a specific structure as a polyol is contained in a large amount, and a sufficient amount of acidic groups capable of being dispersed in water are further contained to lower the refractive index.
- the present inventors have found that a polyester-based resin that can improve the moisture and heat resistance adhesion and solve the above problems can be obtained.
- the gist of the present invention is a polyester-based resin obtained from a polyvalent carboxylic acid component (A) and a polyol component (B), and naphthalenedicarboxylic acid (a1) with respect to the entire polyvalent carboxylic acid component (A). ) And 50 mol% or more of the glycol compound (b1) having a bisphenol skeleton and containing no sulfur-oxygen bond with respect to the entire polyol component (B). Relates to a polyester-based resin having 10 mgKOH / g or more.
- the present invention also provides a polyester-based resin for a primer made of the polyester-based resin, a polyester-based aqueous liquid in which the polyester-based resin is dissolved or dispersed in an aqueous solvent, a base film with a primer layer, and a laminated film. Is.
- the present invention is characterized by the following (1) to (9).
- the polyol component (B) contains 50 mol% or more of the glycol compound (b1) having no bisphenol skeleton, which does not contain a sulfur-oxygen bond, and the polyester resin has an acid value of 10 mgKOH / g or more.
- Polyester resin is characterized by the following (1) to (9).
- a primer-based polyester resin comprising the polyester-based resin according to any one of (1) to (4).
- the adhesion between both the polyester-based resin substrate and the hard coat layer formed from, for example, the active energy ray-curable resin composition, particularly excellent in heat and moisture resistance, and A polyester-based aqueous liquid capable of forming a coating film having a high refractive index and a good appearance can be obtained. Therefore, it is very useful as a primer for providing a hard coat layer on a polyester resin substrate such as a polyester film.
- carboxylic acid includes carboxylic acid derivatives such as carboxylic acid salts, carboxylic acid anhydrides, carboxylic acid halides, and carboxylic acid esters, in addition to carboxylic acid. These carboxylic acid derivatives are referred to as “ester-forming derivatives”.
- the polyester resin of the present invention is obtained by copolymerizing a copolymer component containing a polyvalent carboxylic acid component (A) and a polyol component (B).
- polyvalent carboxylic acid component (A) The polyvalent carboxylic acid component (A) used in the present invention contains naphthalenedicarboxylic acid (a1) as an essential component.
- naphthalenedicarboxylic acid (a1) include, for example, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
- naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
- ester-forming derivatives of the naphthalenedicarboxylic acid such as naphthalenedicarboxylic acid esters such as dimethyl and dimethyl 2,3-naphthalenedicarboxylic acid and naphthalenedicarboxylic acid anhydrides such as 2,3-naphthalenedicarboxylic acid anhydride.
- 2,6-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid ester are preferable, and dimethyl 2,6-naphthalenedicarboxylate is particularly preferable from the viewpoint of availability.
- the naphthalenedicarboxylic acid (a1) must be contained in an amount of 50 mol% or more, preferably 60 to 95 mol%, particularly preferably 70 to 93, based on the entire polyvalent carboxylic acid component (A). Mol%. If the content of naphthalenedicarboxylic acid (a1) in the polyvalent carboxylic acid component (A) is too small, a sufficient refractive index cannot be obtained, and the object of the present invention cannot be achieved. Moreover, since it can suppress the water dispersibility fall of the polyester-type resin obtained as content of naphthalene dicarboxylic acid (a1) is 95% mol or less, it is more preferable.
- polyvalent carboxylic acid component (A) in addition to the naphthalenedicarboxylic acid (a1), other divalent or higher polyvalent carboxylic acids and ester-forming derivatives of these polyvalent carboxylic acids are further contained. It may be.
- Examples of the polyvalent carboxylic acid component other than naphthalenedicarboxylic acid (a1) that can be used in the present invention include: Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, benzylmalonic acid, diphenic acid, 4,4'-oxydibenzoic acid; Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, thiodipropionic acid , Aliphatic dicarboxylic acids such as diglycolic acid; Alicyclics such as 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
- Dicarboxylic acids such as dicarboxylic acids; and ester-forming derivatives of these dicarboxylic acids. These may be used alone or in combination of two or more. Among these, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and ester-forming derivatives of these dicarboxylic acids are preferably used, particularly preferably aromatic dicarboxylic acids and ester-forming derivatives thereof, in terms of refractive index. More preferred are terephthalic acid, isophthalic acid, diphenic acid, 4,4'-oxydibenzoic acid and esters of these dicarboxylic acids.
- the content ratio of the polyvalent carboxylic acid component other than naphthalenedicarboxylic acid (a1) in the polyvalent carboxylic acid component (A) is suitably within a range of 50 mol% or less with respect to the entire polyvalent carboxylic acid component (A). It may be set, and is preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%. When the content of other polyvalent carboxylic acid is too large, there is a tendency that a sufficient refractive index cannot be obtained.
- a small amount of a trivalent or higher polyvalent carboxylic acid can be used.
- the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, Examples include trimesic acid.
- a polyvalent carboxylic acid component (A) has a function as a chain extender, a function as a hydrophilicity-imparting agent, and a function of forming a reaction point with a crosslinking agent described later in a polyester resin.
- the carboxylic acid anhydride (a2) having two or more such carboxylic acid anhydride structures may be any one having at least two carboxylic acid anhydride structures.
- carboxylic acid anhydride (a2) examples include, for example, 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic anhydride), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, 2,2 ', 3,3 Aromatic carboxylic acids such as '-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic anhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride Anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5 dioxot)
- tetracarboxylic dianhydrides are preferred because they are less likely to cause gelation during resin production.
- 1,2,4,5-benzenetetracarboxylic dianhydride pyromellitic anhydride
- An acid anhydride or the like is particularly preferably used.
- the content ratio of the carboxylic acid anhydride (a2) in the polyvalent carboxylic acid component (A) is preferably 3 to 20 mol%, particularly preferably 4 to 4%, based on the entire polyvalent carboxylic acid component (A). 18 mol%, more preferably 5 to 15 mol%, particularly preferably 6 to 12 mol%. If the content ratio is too low, the water dispersibility of the resulting polyester resin tends to decrease. If the content ratio is too high, gelation occurs during the manufacturing process, or the moisture and heat resistance adhesion with the hard coat layer decreases. Tend to.
- a polyvalent carboxylic acid having a sulfonate group it is preferable not to use a polyvalent carboxylic acid having a sulfonate group from the viewpoint of heat and moisture resistance.
- a small amount of a polyvalent carboxylic acid having a sulfonate group may be contained. It is preferably at most mol%, particularly preferably at most 5 mol%, further preferably at most 3 mol%, particularly preferably at most 1 mol%.
- the polyvalent carboxylic acid having a sulfonate group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, dimethyl 5-sulfoisophthalate, sulfoterephthalic acid, 4-sulfonaphthalene-2, Examples include 6-dicarboxylic acid and alkali metal salts thereof.
- One kind selected from these polycarboxylic acids having a sulfonate group may be used, or two or more kinds may be used in combination. From the viewpoint of availability, 5-sulfoisophthalic acid, dimethyl 5-sulfoisophthalate and alkali metal salts thereof are preferable.
- the polyol component (B) used in the present invention contains, as an essential component, a glycol compound (b1) that does not contain a sulfur-oxygen bond and has a bisphenol skeleton.
- glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond examples include bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol AP, bisphenol BP, bisphenol P, bisphenol PH, and bisphenol.
- Z 4,4'-dihydroxybenzophenone and their ethylene oxide, propylene oxide adducts and the like. These may be used alone or in combination of two or more.
- those having no carbon-oxygen double bond such as a carbonyl group are preferably used from the viewpoint of moisture and heat resistance adhesion, and bisphenol A, bisphenol E, bisphenol F, bisphenol AP, bisphenol are also used from the viewpoint of refractive index.
- a BP and bisphenol PH ethylene oxide 2 to 3 mol adduct is particularly preferable, and an ethylene oxide 2 mol adduct of bisphenol A is more preferable.
- the glycol component (b1) not containing a sulfur-oxygen bond and having a bisphenol skeleton is contained in an amount of 50 mol% or more in the polyol component (B), preferably 55 to 100 mol%, Particularly preferred is 65 to 95 mol%, and more preferred is 75 to 90 mol%. If the content of the glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond with respect to the entire polyol component (B) is too low, a sufficient refractive index cannot be obtained, and the wet heat resistance is reduced. The object of the present invention cannot be achieved.
- the glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond in order to further improve the refractive index, those having a fluorene ring, such as bisphenoxyethanol fluorene, can be used as the glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond.
- the content of the glycol compound having a fluorene ring, not containing a sulfur-oxygen bond, and having a bisphenol skeleton is preferably 40 mol% or less, particularly in the polyol component (B). It is preferably 30 mol% or less, more preferably 15 mol% or less, and particularly preferably not contained.
- the polyol component (B) in addition to the glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond, it may further contain another divalent or higher polyol component.
- Examples of the polyol component (B) other than the glycol compound (b1) having a bisphenol skeleton that does not contain a sulfur-oxygen bond that can be used in the present invention include: Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2-methyl-1,3-propanediol 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentane
- aliphatic glycol diols such as ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1, Use 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, which are alicyclic diols. It is preferably an aliphatic diol, and particularly preferably ethylene glycol, 1,6-hexanediol or neopentyl glycol.
- the trihydric or higher polyhydric alcohol can also be used.
- examples of the trihydric or higher polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1 3,6-hexanetriol, adamantanetriol and the like.
- the polyol component (B) includes a glycol compound (b1) having no bisphenol skeleton and other polyol components (others) as a polyol component (B) from the viewpoint of reactivity when producing a polyester-based resin. It is preferable to use a dihydric or higher alcohol.
- the content ratio of the polyol component other than the glycol compound (b1) having no bisphenol skeleton and containing no sulfur-oxygen bond is 0 to 50 mol% in the polyol component (B). It is preferably 5 to 35 mol%, more preferably 10 to 25 mol%. If the content of polyol components other than the glycol compound (b1) having a bisphenol skeleton that does not contain a sulfur-oxygen bond is too large, a sufficient refractive index cannot be obtained or the heat-and-moisture adhesion to the hard coat layer decreases. Tend.
- the polyester-based resin of the present invention is obtained by copolymerizing a copolymer component including the polyvalent carboxylic acid component (A) and the polyol component (B), and has, for example, two or more carboxylic acid anhydride structures.
- a hydroxyl group-containing prepolymer obtained by copolymerizing a polyvalent carboxylic acid component (A) and a polyol component (B) excluding the carboxylic acid anhydride (a2) is chain extended with the carboxylic acid anhydride (a2). can do.
- the mixing ratio (molar ratio) of the polyvalent carboxylic acid component (A) excluding the carboxylic acid anhydride (a2) and the polyol component (B) is such that the polyol is 1 mol of the polyvalent carboxylic acid component (A).
- the component (B) is preferably 1.05 to 1.3 mol, particularly preferably 1.06 to 1.2 mol, and further preferably 1.07 to 1.15 mol.
- This mixture is charged into a suitable reactor and heated to 170 to 260 ° C., whereby the esterification reaction or transesterification reaction proceeds while distilling off water or methanol as a by-product, and a hydroxyl group-containing prepolymer is obtained. A polymer is produced.
- a polyester resin can be obtained by subjecting the hydroxyl group-containing prepolymer to chain extension by a ring-opening addition reaction using a carboxylic acid anhydride (a2).
- the reaction can be allowed to proceed even at room temperature.
- the reaction is preferably carried out at 150 to 210 ° C, more preferably 165 to 200 ° C. Therefore, a solvent is not necessarily required for the above reaction, but if the viscosity of the reaction product at such a temperature is too high, an appropriate solvent can be used as appropriate to facilitate stirring.
- solvents examples include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, xylene, mesitylene, and pseudocumene, and amide solvents such as dimethylformamide and dimethylacetamide.
- ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
- aromatic solvents such as benzene, toluene, xylene, mesitylene, and pseudocumene
- amide solvents such as dimethylformamide and dimethylacetamide.
- an esterification catalyst a transesterification catalyst, other polymerization catalyst, and the like can be appropriately blended.
- tetrabutoxy titanium can be used.
- the polyester resin of the present invention is obtained by the above-described method.
- the weight-average molecular weight of the polyester resin thus obtained is preferably 5,000 to 50,000, particularly preferably 7,000 to 40,000, and more preferably 9,000 to 30,000. If the weight-average molecular weight of the polyester resin is too large, the initial adhesion with the polyester resin substrate or the hard coat layer tends to be lowered, or water dispersion tends to be difficult. Moreover, when a weight average molecular weight is too small, there exists a tendency for wet heat-resistant adhesiveness with a hard-coat layer to fall.
- the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and column: TSKgel SuperMultipore HZ-M (exclusion limit molecular weight: 2) on high performance liquid chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation). ⁇ 10 6 , Theoretical plate number: 16,000 plate / line, Filler material: Styrene-divinylbenzene copolymer, Filler particle size: 4 ⁇ m).
- the glass transition temperature (Tg) of the polyester resin used in the present invention is preferably 60 to 140 ° C., particularly preferably 75 to 130 ° C., and further preferably 80 to 125 ° C. If the glass transition temperature is too high, the moisture and heat resistance adhesion to the hard coat layer is reduced, or when the resin aqueous liquid is applied to the polyester film, drying or cracking occurs when the polyester film with the resin coating is stretched, haze is generated. Tend to occur. On the other hand, if the glass transition temperature is too low, the wet heat and heat adhesion with the refractive index and the hard coat layer tend to decrease.
- the glass transition temperature (Tg) of the polyester resin is measured using a differential scanning calorimeter DSC Q20 manufactured by TA Instruments.
- the acid value of the polyester resin of the present invention needs to be 10 mgKOH / g or more, preferably 10 to 40 mgKOH / g, particularly preferably 15 to 35 mgKOH / g, more preferably 17 to 32 mgKOH / g, particularly It is preferably 18 to 30 mg KOH / g. If the acid value is too low, the water dispersibility is deteriorated, and the heat and heat resistance adhesion with the hard coat layer is deteriorated due to insufficient crosslinking points with the crosslinking agent, so that the object of the present invention cannot be achieved. Moreover, when an acid value is too high, hydrophilicity will become high and there exists a tendency for wet heat-resistant adhesiveness with a hard-coat layer to fall easily.
- the acid value of the polyester resin is determined by neutralization titration based on JIS K0070 by dissolving 0.5 g of a polyester resin in a 7/3 (toluene / methanol (volume ratio)) mixed solvent of toluene and methanol. It is.
- the acid value of the polyester resin means the content of carboxyl groups in the resin.
- the acid value of the polyester resin of the present invention within the above range, for example, it is preferable to contain a carboxylic acid group in the side chain of the polyester resin, and in particular, a carboxyl group derived from pyromellitic acid in the side chain. It is preferable to contain an acid group.
- the refractive index of the polyester resin of the present invention is preferably 1.58 or more, particularly preferably 1.60 to 1.65, and further preferably 1.61 to 1.64. If the refractive index is too high, the wet heat resistance is lowered, or cracks are generated at the time of application of the aqueous resin liquid to the polyester film, drying or stretching of the polyester film with the resin film, and haze tends to occur. On the other hand, when the hardness is too low, iris reflection caused by the difference between the refractive index of the polyester film and the hard coat layer occurs when the hard coat is laminated, and the visibility tends to be lowered.
- the refractive index in the present invention is a refractive index with respect to the D line (589 nm) at 20 ° C., and is measured using an Abbe refractive system DR-M4 manufactured by Atago Co., Ltd.
- antioxidants such as hindered phenols, heat stabilizers, glass fibers, inorganic / organic fillers, colorants, flame retardants, softeners, dispersants, wetting
- An agent, an emulsifier, a gelling agent, an antifoaming agent, other thermoplastic resins, and the like can be blended to such an extent that the effects of the present invention are not impaired and used as a polyester resin composition.
- the polyester-based aqueous liquid of the present invention is obtained by dissolving or dispersing a polyester-based resin obtained as described above in an aqueous solvent.
- dissolution or dispersion in an aqueous solvent is referred to as “water dissolution or dispersion”.
- a method in which a polyester resin is neutralized with a neutralizing agent and dissolved or dispersed in an aqueous solvent to obtain a polyester aqueous solution is preferable.
- the neutralizing agent is not particularly limited as long as it can neutralize the carboxyl group of the polyester resin, and examples thereof include metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ethylamine, Diethylamine, triethylamine, propylamine, isopropylamine, iminobispropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, diethanolamine, triethanolamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, amino And organic amines such as ethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine; and ammonia.
- metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide
- neutralizing agents it is preferable that they have a boiling point of 150 ° C. or less in terms of water resistance of the resulting coating that is easy to evaporate by drying.
- ammonia, diethylamine, and triethylamine are preferable from the viewpoint of high versatility, low boiling point, and easy volatilization during drying, and triethylamine and ammonia are particularly preferable from the viewpoint of particularly excellent dispersion stability of the polyester resin.
- aqueous solvent examples include water or water mixed with an appropriate hydrophilic organic solvent.
- hydrophilic organic solvent examples include ketones such as acetone; alcohols such as methanol, ethanol, and isopropyl alcohol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monotertiary butyl ether.
- the thing which can be mixed with water is mentioned.
- the ratio with respect to the whole polyester-type aqueous liquid is set suitably.
- the ratio of the hydrophilic organic solvent to the entire aqueous liquid is not limited to the above range.
- One kind selected from these aqueous solvents may be used, or two or more kinds may be used in combination.
- a crosslinking agent in the polyester-based aqueous liquid from the viewpoint of improving adhesion.
- a crosslinking agent may be a compound containing a functional group reactive with the functional group contained in the polyester resin, for example, containing a functional group reactive with a hydroxyl group or a carboxyl group in the polyester resin. Is used.
- the cross-linking agent may be a compound containing a functional group reactive with the functional group contained in the polyester resin, for example, a compound having an epoxy group, an oxazoline group, a carbodiimide group, an amino group, or an isocyanate group. , Aziridine compounds, melamine compounds, and the like. Among them, a carbodiimide group, a compound having an isocyanate group, and a melamine compound are preferable.
- Examples of the compound having an epoxy group include bisphenol A / epichlorohydrin type epoxy resin, sorbitol polyglycidyl ether (for example, “Denacol EX-611”, “Denacol EX-612”, “Denacol EX-” manufactured by Nagase ChemteX Corporation).
- Examples of the compound having an oxazoline group include addition-polymerizable 2-oxazolines (for example, 2-isopropenyl-2-oxazoline) having a substituent having an unsaturated carbon-carbon bond at the 2-position carbon position and other unsaturated groups.
- Examples include commercially available products such as “Epocross WS-500”, “Epocross WS-700”, “Epocross K-2010E”, “Epocross K-2020E” manufactured by Nippon Shokubai Co., Ltd. “Epocross K-2030E” and the like.
- the compound having a carbodiimide group may be any compound containing at least two carbodiimide groups.
- Carbodilite V-02 “Carbodilite V-02-L2”, “Carbodilite SV-” manufactured by Nisshinbo Chemical Co., Ltd. 02 ”,“ Carbodilite V-10 ”,“ Carbodilite V-04 ”,“ Carbodilite V-06 ”,“ Carbodilite E-01 ”,“ Carbodilite E-02 ”,“ Carbodilite E-04 ”and the like.
- Examples of the compound having an amino group include hexamethylenediamine and triethanolamine.
- Examples of the compound having an isocyanate group include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene.
- Isocyanate compounds such as diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate and their blocked isocyanate compounds, “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210” ( Self-emulsifying type such as “Elastolone BN-77” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Water-dispersible polyisocyanate compound and the like. Among these, a water dispersion type and a blocked isocyanate compound are preferable.
- the aziridine compound may be any compound containing at least two aziridine groups, and examples thereof include “Chemite PZ-33” and “Chemite DZ-22E” (manufactured by Nippon Shokubai Co., Ltd.).
- melamine compounds include hexamethoxymethylol melamine, “Nikarak MW-30M”, “Nikarak MW-30”, “Nikarak MW-22”, “Nikarak MS-11”, “Nikarak” manufactured by Sanwa Chemical Co., Ltd. MS-011, “Nicarax MX-730”, “Nicarax MX-750”, “Nicarax MX-706”, “Nicarax MX-035” and other methylated melamine resins, “Nicarax MX-45”, “Nicarac MX-” Mixed etherified melamine resin such as "410".
- crosslinking agent one kind selected from these may be used, or two or more kinds may be used in combination.
- the content of the cross-linking agent can be appropriately selected depending on the amount of functional groups contained in the polyester-based resin, the molecular weight of the polyester-based resin, and the purpose of use.
- the active ingredient weight ratio of the polyester-based resin / cross-linking agent is It is preferably 45/55 to 90/10, particularly preferably 50/50 to 80/20, and further preferably 60/40 to 75/25.
- the ratio of the cross-linking agent is too large, the refractive index and the wet heat resistance with the hard coat layer tend to be lowered, and when the ratio is too small, the wet heat resistance with the hard coat layer tends to be lowered.
- an anionic surfactant, a nonionic surfactant, etc. can be mix
- By blending the surfactant it is possible to improve the wettability to the polyester resin substrate when the polyester aqueous liquid is applied to a polyester resin substrate such as a polyester film.
- an appropriate one can be used, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, Examples thereof include alkylsulfosuccinate and dodecylbenzenesulfonate.
- One kind selected from these surfactants may be used, or two or more kinds may be used in combination.
- polyester-based aqueous liquid of the present invention may further contain an antistatic agent, a filler, an ultraviolet absorber, a lubricant, a colorant and the like, if necessary.
- the solid content concentration of the polyester-based aqueous liquid of the present invention is appropriately adjusted so as to ensure good dispersibility of the polyester-based resin and form a good film by coating film formation. % By weight is preferred, and 5 to 20% by weight is particularly preferred.
- polyester-based aqueous liquid is applied to, for example, a polyester-based resin substrate such as a polyester film and dried by heating to form a coating (primer layer) to obtain a substrate film with a primer layer.
- the base film with a primer layer may be further subjected to stretching.
- polyester film As the polyester film as the base film, any conventionally known appropriate film can be used.
- polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and other copolymer components are copolymerized therewith.
- the film which consists of a copolymer etc. can be mentioned.
- the polyester film may be either unstretched or stretched, but it is preferable to use a stretched film, and it is particularly desirable to use a biaxially stretched film.
- an unstretched polyester film can be obtained by melting a raw material polyester, extruding it into a sheet, and cooling it with a cooling drum. Moreover, after extending
- Appropriate techniques can be adopted for coating and forming a polyester-based aqueous liquid on a polyester film.
- a polyester-based aqueous liquid on one or both sides of an unstretched film or a uniaxially stretched film by an appropriate method such as kiss coating, reverse coating, gravure coating, die coating, etc., and heating and drying to form a film
- the film can be stretched to form a biaxially stretched film.
- a polyester-based aqueous liquid can be applied to the secondary stretched film by an appropriate method, followed by heat drying to form a film.
- the coating amount of the polyester aqueous liquid at this time is appropriately set.
- the thickness of the dry coating film is preferably 0.01 to 5 ⁇ m, particularly preferably 0.01 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m, Particularly preferred is 0.05 to 0.15 ⁇ m.
- the base material film with a primer layer thus obtained is excellent in initial and wet heat-resistant adhesion between a polyester resin base material and a hard coat layer formed from, for example, an active energy ray-curable resin composition, and has high refraction. It is very useful as a material for forming a coating such as a primer layer having a high rate. Therefore, the substrate film with a primer layer has good visibility even when used for optical applications.
- the polyester-based resin of the present invention thus obtained has excellent initial and wet heat-resistant adhesion between the polyester-based resin substrate and a hard coat layer formed from, for example, an active energy ray-curable resin composition, It is very useful as a material for forming a film such as a primer layer having a high refractive index (that is, a polyester resin for primer).
- the substrate film with a primer layer of the present invention is, for example, a label sheet or a printing sheet, particularly a film for hard coating, such as various films that are used by providing a printing layer or a hard coating layer on the film or sheet. It is useful as a sheet.
- the substrate film with a primer layer of the present invention has good visibility even when used for optical applications, and is useful as a protective film for optical members and a substrate film for ITO films.
- Table 1 shows the composition and properties of the obtained polyester resin.
- the numerical value of each compound in the column of the polyvalent carboxylic acid component (A) and the polyol (B) represents the mole fraction of the compound with respect to the component (A) or the component (B).
- polyester resins [I-2] and [I-3] were produced in the same manner as in Example 1 except that the copolymerization component and the ratio thereof were changed.
- polyester resins [I′-1] to [I′-4] were produced in the same manner as in Example 1 except that the copolymerization component and the ratio thereof were changed.
- NDCM dimethyl 2,6-naphthalenedicarboxylate
- PMAn a2: pyromellitic anhydride
- SIPM sodium dimethyl 5-sulfoisophthalate
- BisA-EO (b1) Bisphenol A ethylene oxide 2-mole adduct
- BisS-EO Bisphenol S ethylene oxide 2-mole adduct
- NPG Neopentyl glycol EG: Ethylene glycol
- a cross-linking agent was blended in the ratio shown in Table 2 into the polyester aqueous liquid prepared above to prepare a polyester aqueous liquid.
- the obtained polyester-based aqueous liquid was coated with a bar coater No. 1 on a PET film (Toray Industries, Lumirror T60, thickness 100 ⁇ m). 6 and dried at 150 ° C. for 3 minutes to form a primer layer having a thickness of 0.5 ⁇ m.
- the numerical values in the column of parts by weight of the polyester resin and the crosslinking agent represent values converted into the solid content of the polyester resin and the effective component amount of the crosslinking agent.
- UV-7610B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- ethyl acetate 35 parts
- photopolymerization initiator Irgacure-184
- Ciba Specialty Chemicals manufactured by Ciba Specialty Chemicals
- Adhesion (after wet heat resistance test) A film having a primer layer and a hard coat layer laminated thereon was cut into a size of 5 cm ⁇ 13 cm in the same manner as in the evaluation of initial adhesion, and was immersed in boiling water for 6 hours. The film was then wiped off and allowed to stand at room temperature for 1 hour, and then subjected to a cross-cut and tape peel test in the same manner as the initial adhesion evaluation. After the tape peeling test, the adhesion evaluation was performed based on the number of remaining hard coat layers. The evaluation criteria are as follows, and ⁇ and ⁇ are considered to have good adhesion. A: 95/100 or more (remaining number / measured number) ⁇ : 90/100 or more, less than 95/100 ⁇ : 70/100 or more, less than 90/100 ⁇ : less than 70/100
- the crosslinking agents II-1 to II-3 shown in Table 2 are as follows.
- II-1 Melamine-based cross-linking agent “Nicalak MW-30M” (manufactured by Sanwa Chemical Co., Ltd.)
- II-2 Block isocyanate-based crosslinking agent “Elastolon BN-77” (Daiichi Kogyo Seiyaku Co., Ltd.)
- II-3 Carbodiimide crosslinking agent “Carbodilite V-04” (Nisshinbo Chemical Co., Ltd.)
- polyester resins of Examples 1 to 3 have a high refractive index, and the coating film formed using the polyester aqueous solution of Examples 4 to 7 is used at the initial stage. It can be seen that both the adhesion with the hard coat layer is excellent after the test, and the coating film appearance after the wet heat resistance test is excellent.
- the polyester-based aqueous liquids of Comparative Examples 5 and 6 are formed using the polyester-based resins of Comparative Examples 1 and 2 that do not satisfy the content of the polyol component (b1) having a specific structure.
- the resulting coating film was inferior in adhesion to the hard coat layer after the moisture and heat resistance test and in the appearance of the coating film.
- the coating film formed using the polyester-type aqueous liquid of the comparative example 7 which uses the polyester-type resin of the comparative example 3 whose acid value is below a specific value is the coating-film external appearance after a wet heat test. It was inferior.
- a comparative example using the polyester resin of Comparative Example 4 using a glycol component having a bisphenol skeleton containing a sulfur-oxygen bond instead of the polyol component (b1) having a specific structure as the polyol component was inferior in adhesion to the hard coat layer after the moisture and heat resistance test and the coating film appearance.
- the polyester resin of the present invention can be suitably used as a primer for a polyester film on which a hard coat layer or the like is laminated.
- it has excellent adhesion between both polyester resin substrate and hard coat layer, especially wet heat and heat resistance, and can form a film with a high refractive index and good appearance, thus suppressing iris reflection. Therefore, it can be suitably used as a primer for a protective film or an ITO film, particularly for applications requiring visibility and design.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
また、上記特許文献2に開示されたポリエステル樹脂は、スルホニル基を有するビスフェノールS骨格を多量に含有しているため、高温高湿度環境下において、ハードコート層との密着性が低下したり、塗膜外観が悪化するという問題があった。
(1)多価カルボン酸成分(A)とポリオール成分(B)から得られるポリエステル系樹脂であって、前記多価カルボン酸成分(A)は、ナフタレンジカルボン酸(a1)を50モル%以上含有し、かつ、前記ポリオール成分(B)は、硫黄-酸素結合を含まない、ビスフェノール骨格を有するグリコール化合物(b1)を50モル%以上含有し、ポリエステル系樹脂の酸価が10mgKOH/g以上であるポリエステル系樹脂。
(2)前記多価カルボン酸成分(A)が、カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a2)を含有する、前記(1)記載のポリエステル系樹脂。
(3)ポリエステル系樹脂が、前記カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a2)を除く前記多価カルボン酸成分(A)と前記ポリオール成分(B)から得られる水酸基含有プレポリマーを、前記カルボン酸無水物(a2)で鎖延長させてなるものである、前記(2)記載のポリエステル系樹脂。
(4)屈折率が1.58以上である、前記(1)~(3)のいずれか1つに記載のポリエステル系樹脂。
(5)前記(1)~(4)のいずれか1つに記載のポリエステル系樹脂からなる、プライマー用ポリエステル系樹脂。
(6)前記(1)~(4)のいずれか1つに記載のポリエステル系樹脂が、水性溶媒に溶解又は分散されてなる、ポリエステル系水性液。
(7)架橋剤を含有する、前記(6)記載のポリエステル系水性液。
(8)基材フィルム上に、前記(7)記載のポリエステル系水性液中のポリエステル系樹脂が架橋剤により架橋されてなるプライマー層を有する、プライマー層付き基材フィルム。
(9)前記(8)記載のプライマー層付き基材フィルムのプライマー層上に、活性エネルギー線硬化性樹脂組成物が硬化してなるハードコート層を有する、積層フィルム。
本発明のポリエステル系樹脂は、多価カルボン酸成分(A)及びポリオール成分(B)を含む共重合成分を共重合して得られるものである。
本発明で用いられる多価カルボン酸成分(A)は、ナフタレンジカルボン酸(a1)を必須成分として含有する。
これらの中でも、入手のしやすさの点から2,6-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸エステルが好ましく、特に好ましくは2,6-ナフタレンジカルボン酸ジメチルである。
テレフタル酸、イソフタル酸、ベンジルマロン酸、ジフェン酸、4,4′-オキシジ安息香酸等の芳香族ジカルボン酸;
マロン酸、ジメチルマロン酸、コハク酸、グルタル酸、アジピン酸、トリメチルアジピン酸、ピメリン酸、2,2-ジメチルグルタル酸、アゼライン酸、セバシン酸、フマル酸、マレイン酸、イタコン酸、チオジプロピオン酸、ジグリコール酸等の脂肪族ジカルボン酸;
1,3-シクロペンタンジカルボン酸、1,2-シクロヘキサンジカルボン酸、1,3-シクロペンタンジカルボン酸、1,4-シクロヘキサンジカルボン酸、2,5-ノルボルナンジカルボン酸、アダマンタンジカルボン酸等の脂環族ジカルボン酸;等の二価カルボン酸及びこれら二価カルボン酸のエステル形成性誘導体があげられる。
これらは単独でもしくは2種以上併せて用いることができる。
これらの中でも、脂肪族ジカルボン酸、芳香族ジカルボン酸及びこれらジカルボン酸のエステル形成性誘導体を用いることが好ましく、特に好ましくは芳香族ジカルボン酸及びこれらのエステル形成性誘導体であり、屈折率の点で更に好ましくはテレフタル酸、イソフタル酸、ジフェン酸、4,4′-オキシジ安息香酸及びこれらジカルボン酸のエステルである。
1,2,4,5-ベンゼンテトラカルボン酸二無水物(無水ピロメリット酸)、3,3′,4,4′-ベンゾフェノンテトラカルボン酸二無水物、4,4′-オキシジフタル酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,2,5,6-ナフタレンテトラカルボン酸二無水物、エチレングリコールビストリメリテート二無水物、2,2′,3,3′-ジフェニルテトラカルボン酸二無水物、2,2′,3,3′-ジフェニルスルホンテトラカルボン酸無水物、チオフェン-2,3,4,5-テトラカルボン酸二無水物等の芳香族カルボン酸無水物;
1,2,3,4-シクロブタンテトラカルボン酸二無水物、5-(2,5ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、5-(2,5-ジオキソテトラヒドロフリル)-3-シクロヘキセン-1,2-ジカルボン酸無水物、シクロペンタンテトラカルボン酸二無水物等の脂環族カルボン酸無水物;
エチレンテトラカルボン酸二無水物、1,2,3,4-ブタンテトラカルボン酸二無水物、1,2,3,4-ペンタンテトラカルボン酸二無水物等の脂肪族カルボン酸無水物;等が挙げられる。
これらは単独で、もしくは2種以上を併せて用いることができる。
本発明で用いられるポリオール成分(B)は、硫黄-酸素結合を含まない、ビスフェノール骨格を有するグリコール化合物(b1)を必須成分として含有する。
エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,3-プロパンジオール、2,4-ジメチル-2-エチルヘキサン-1,3-ジオール、2-メチル-1,3-プロパンジオール、2,2-ジメチル-1,3-プロパンジオール(ネオペンチルグリコール)、2-エチル-2-ブチル-1,3-プロパンジオール、2-エチル-2-イソブチル-1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチル-1,5-ペンタンジオール、2,2,4-トリメチル-1,6-ヘキサンジオール等の脂肪族ジオール;
1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、スピログリコール、トリシクロデカンジメタノール、アダマンタンジオール、2,2,4,4-テトラメチル-1,3-シクロブタンジオール等の脂環族ジオール;
4,4′-チオジフェノール、4,4′-メチレンジフェノール、4,4′-ジヒドロキシビフェニル、o-,m-及びp-ジヒドロキシベンゼン、2,5-ナフタレンジオール、p-キシレンジオール及びそれらのエチレンオキサイド、プロピレンオキサイド付加体等の芳香族ジオール;等の二価アルコールが挙げられる。
これらは単独でもしくは2種以上併せて用いることができる。
本発明のポリエステル系樹脂は、上記多価カルボン酸成分(A)及びポリオール成分(B)を含む共重合成分を共重合してなるものであり、例えば、カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a2)を除く多価カルボン酸成分(A)、ポリオール成分(B)を共重合して得られる水酸基含有プレポリマーを、カルボン酸無水物(a2)で鎖延長させる方法により製造することができる。
かくして、上述の方法により本発明のポリエステル系樹脂が得られる。
なお、上記の重量平均分子量は、標準ポリスチレン分子量換算による重量平均分子量であり、高速液体クロマトグラフィー(東ソー社製、「HLC-8320GPC」)に、カラム:TSKgel SuperMultipore HZ-M(排除限界分子量:2×106、理論段数:16,000段/本、充填剤材質:スチレン-ジビニルベンゼン共重合体、充填剤粒径:4μm)の2本直列を用いることにより測定されるものである。
上記ポリエステル系樹脂のガラス転移温度(Tg)は、TAインスツルメント社製の示差走査熱量計DSC Q20を用いて測定されるものである。
上記ポリエステル系樹脂の酸価は、ポリエステル系樹脂0.5gを7/3(トルエン/メタノール(体積比))のトルエンとメタノールの混合溶媒に溶解し、JIS K0070に基づき中和滴定により求められるものである。
なお、本発明において、ポリエステル系樹脂の酸価とは、樹脂中におけるカルボキシル基の含有量を意味するものである。
なお、本発明における屈折率とは、20℃におけるD線(589nm)に対する屈折率であり、アタゴ社製のアッベ屈折系DR-M4を用いて測定されるものである。
本発明のポリエステル系水性液は、上記のようにして得られたポリエステル系樹脂が水性溶媒に溶解又は分散されてなるものである。以下、水性溶媒に溶解又は分散させることを「水溶解又は水分散」と表記する。
通常、ポリエステル系樹脂を中和剤で中和して水性溶媒に溶解又は分散させ、ポリエステル系水性液とする方法が好ましい。
なお、ポリエステル系樹脂基材及びハードコート層との初期及び耐湿熱密着性の点からは、界面活性剤を添加しない方が好ましい。
また、この未延伸のポリエステルフィルムを一軸方向または二軸方向に延伸した後、熱固定し、更に必要に応じて熱弛緩処理を施すことで一軸延伸フィルムまたは二軸延伸フィルムを得ることができる。
ポリエステル系樹脂の重量平均分子量、ガラス転移温度、酸価、屈折率の測定に関しては、前述の方法にしたがって測定した。
〔ポリエステル系樹脂[I-1]の製造〕
ナフタレンジカルボン酸ジメチル(a1)240.8部(0.986モル)、ビスフェノールAのエチレンオキサイド2モル付加物(b1)311.5部(0.986モル)、ネオペンチルグリコール15.4部(0.148モル)、触媒としてテトラブトキシチタン0.1部をエステル交換反応器に仕込み、窒素雰囲気下、200℃から265℃まで1時間かけて昇温し、メタノールの溜出が終了するまで265℃でエステル交換反応を行った。
次いで、195℃まで冷却した後、無水ピロメリット酸(a2)32.3部(0.148モル)を仕込み、195℃で1時間反応を行い、ポリエステル系樹脂[I-1]を得た。
得られたポリエステル系樹脂の組成および物性を表1に示す。
なお、表1中、多価カルボン酸成分(A)及びポリオール(B)の欄における各化合物の数値は、成分(A)又は成分(B)に対する化合物のモル分率を表す。
〔ポリエステル系樹脂[I-2]、[I-3]の製造〕
表1に示すとおり、共重合成分及びその割合を変更する以外は実施例1と同様の操作を行って、ポリエステル系樹脂[I-2]、[I-3]を製造した。
〔ポリエステル系樹脂[I’-1]~[I’-4]の製造〕
表1に示すとおり、共重合成分及びその割合を変更する以外は実施例1と同様の操作を行って、ポリエステル系樹脂[I’-1]~[I’-4]を製造した。
NDCM(a1):2,6-ナフタレンジカルボン酸ジメチル
PMAn(a2):無水ピロメリット酸
SIPM:5-スルホイソフタル酸ジメチルナトリウム
BisS-EO:ビスフェノールSのエチレンオキサイド2モル付加物
NPG:ネオペンチルグリコール
EG:エチレングリコール
〔ポリエステル系水性液の調製〕
実施例1~3、比較例1~4で得られたポリエステル系樹脂[I-1]~[I-3]、[I’-1]~[I’-4]について、ポリエステル系樹脂21部、水265部、n-ブチルセロソルブ12部、25%アンモニア水2部を反応器に仕込み、95℃に昇温し攪拌しながら溶解させ、固形分濃度7%のポリエステル系水性液を調製した。
上記で調製したポリエステル系水性液に、表2に示す割合で架橋剤を配合し、ポリエステル系水性液を調製した。得られたポリエステル系水性液をPETフィルム(東レ社製、ルミラーT60、厚み100μm)上にバーコーターNo.6にて塗布し、150℃で3分間乾燥させて、厚み0.5μmのプライマー層を形成した。
なお、表2中、ポリエステル系樹脂及び架橋剤の重量部の欄における数値は、ポリエステル系樹脂の固形分量及び架橋剤の有効成分量に換算した値を表す。
評価基準は以下の通りであり、◎及び○を密着性良好とした。
◎:95/100以上(残存個数/測定個数)
○:90/100以上、95/100未満
△:70/100以上、90/100未満
×:70/100未満
初期密着性の評価と同様の方法にしてプライマー層、ハードコート層を積層したフィルムを5cm×13cmの大きさにカットし、これを6時間沸騰水に浸漬させた。その後フィルムの水気をふき取り、室温で1時間静置後、初期密着性の評価と同様の方法にしてクロスカット、テープ剥離試験を行った。テープ剥離試験後に、ハードコート層が残存した個数により密着性評価を行った。
評価基準は以下の通りであり、◎及び○を密着性良好とした。
◎:95/100以上(残存個数/測定個数)
○:90/100以上、95/100未満
△:70/100以上、90/100未満
×:70/100未満
初期密着性の評価と同様の方法にしてプライマー層、ハードコート層を積層したフィルムを5cm×13cmの大きさにカットし、これを6時間沸騰水に浸漬させた。その後フィルムを沸騰水から取り出し、フィルムの水気をふき取り、室温で1時間静置後の塗膜外観を目視にて評価した。
評価基準は以下の通りであり、◎及び○を塗膜外観良好とした。
◎:沸騰水浸漬前と変化無し
○:僅かに塗膜が白化した
△:やや強く塗膜が白化した
×:著しく塗膜が白化した
II-1:メラミン系架橋剤「ニカラックMW-30M」(三和ケミカル社製)
II-2:ブロックイソシアネート系架橋剤「エラストロンBN-77」(第一工業製薬社製)
II-3:カルボジイミド系架橋剤「カルボジライトV-04」(日清紡ケミカル社製)
また、酸価が特定値以下である比較例3のポリエステル系樹脂を用いてなる、比較例7のポリエステル系水性液を用いて形成してなる塗膜は、耐湿熱試験後の塗膜外観に劣るものであった。
さらに、ポリオール成分として、特定の構造を有するポリオール成分(b1)の代わりに、硫黄-酸素結合を含む、ビスフェノール骨格を有するグリコール成分を用いた比較例4のポリエステル系樹脂を用いてなる、比較例8のポリエステル系水性液を用いて形成してなる塗膜は、耐湿熱試験後のハードコート層との密着性および塗膜外観に劣るものであった。
Claims (9)
- 多価カルボン酸成分(A)とポリオール成分(B)から得られるポリエステル系樹脂であって、前記多価カルボン酸成分(A)は、ナフタレンジカルボン酸(a1)を50モル%以上含有し、かつ、前記ポリオール成分(B)は、硫黄-酸素結合を含まない、ビスフェノール骨格を有するグリコール化合物(b1)を50モル%以上含有し、ポリエステル系樹脂の酸価が10mgKOH/g以上であるポリエステル系樹脂。
- 前記多価カルボン酸成分(A)が、カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a2)を含有する、請求項1記載のポリエステル系樹脂。
- ポリエステル系樹脂が、前記カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a2)を除く前記多価カルボン酸成分(A)と前記ポリオール成分(B)から得られる水酸基含有プレポリマーを、前記カルボン酸無水物(a2)で鎖延長させてなるものである、請求項2記載のポリエステル系樹脂。
- 屈折率が1.58以上である、請求項1~3のいずれか1項に記載のポリエステル系樹脂。
- 請求項1~4のいずれか1項に記載のポリエステル系樹脂からなる、プライマー用ポリエステル系樹脂。
- 請求項1~4のいずれか1項に記載のポリエステル系樹脂が、水性溶媒に溶解又は分散されてなる、ポリエステル系水性液。
- 架橋剤を含有する、請求項6記載のポリエステル系水性液。
- 基材フィルム上に、請求項7記載のポリエステル系水性液中のポリエステル系樹脂が架橋剤により架橋されてなるプライマー層を有する、プライマー層付き基材フィルム。
- 請求項8記載のプライマー層付き基材フィルムのプライマー層上に、活性エネルギー線硬化性樹脂組成物が硬化してなるハードコート層を有する、積層フィルム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187011952A KR20180075521A (ko) | 2015-10-28 | 2016-10-27 | 폴리에스테르계 수지, 프라이머용 폴리에스테르계 수지, 폴리에스테르계 수성액, 및 프라이머층을 구비한 기재 필름 및 적층 필름 |
CN201680062760.2A CN108350155B (zh) | 2015-10-28 | 2016-10-27 | 聚酯系树脂、底漆用聚酯系树脂、聚酯系水性液、和带底漆层的基材薄膜以及层叠薄膜 |
JP2016565521A JPWO2017073697A1 (ja) | 2015-10-28 | 2016-10-27 | ポリエステル系樹脂、プライマー用ポリエステル系樹脂、ポリエステル系水性液、及びプライマー層付き基材フィルムならびに積層フィルム |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-211407 | 2015-10-28 | ||
JP2015211407 | 2015-10-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017073697A1 true WO2017073697A1 (ja) | 2017-05-04 |
Family
ID=58630568
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/081965 WO2017073697A1 (ja) | 2015-10-28 | 2016-10-27 | ポリエステル系樹脂、プライマー用ポリエステル系樹脂、ポリエステル系水性液、及びプライマー層付き基材フィルムならびに積層フィルム |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPWO2017073697A1 (ja) |
KR (1) | KR20180075521A (ja) |
CN (1) | CN108350155B (ja) |
TW (1) | TW201730235A (ja) |
WO (1) | WO2017073697A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110944840A (zh) * | 2017-08-24 | 2020-03-31 | 东洋纺株式会社 | 陶瓷生片制造用脱模膜 |
WO2022230231A1 (ja) * | 2021-04-28 | 2022-11-03 | 関西ペイント株式会社 | 水性塗料組成物及び複層塗膜形成方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112512809B (zh) * | 2018-08-03 | 2023-08-25 | 三菱化学株式会社 | 层叠体 |
CN111647149B (zh) * | 2020-07-07 | 2022-08-02 | 安徽永利新材料科技有限公司 | 耐磨、耐化学品性能优的粉末用聚酯树脂及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04103657A (ja) * | 1990-08-22 | 1992-04-06 | Toyobo Co Ltd | 制振材料用粘弾性樹脂組成物 |
JPH09324148A (ja) * | 1996-06-04 | 1997-12-16 | Toyobo Co Ltd | 水系塗料用組成物及びそれを用いた耐蝕性金属板 |
JP2009126035A (ja) * | 2007-11-22 | 2009-06-11 | Toyobo Co Ltd | 被覆ポリエステルフィルム、およびそれを用いたハードコートフィルム |
WO2014024570A1 (ja) * | 2012-08-10 | 2014-02-13 | 東レ株式会社 | 積層ポリエステルフィルム |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5869567A (en) * | 1996-03-08 | 1999-02-09 | Unitika Ltd. | Polyester resin aqueous dispersion and process for preparing the same |
JP3469033B2 (ja) * | 1996-03-08 | 2003-11-25 | ユニチカ株式会社 | ポリエステル樹脂水分散体及びその製造方法 |
KR100532820B1 (ko) * | 2000-07-11 | 2005-12-02 | 간사이 페인트 가부시키가이샤 | 도공 필름 및 그 적층 방법 |
JP5560530B2 (ja) * | 2007-05-30 | 2014-07-30 | 東洋紡株式会社 | 共重合ポリエステル樹脂 |
JP5420915B2 (ja) * | 2009-01-14 | 2014-02-19 | ユニチカ株式会社 | ポリエステル樹脂塗布熱可塑性樹脂フィルム、およびそれを用いてなる包装袋 |
JP4547644B1 (ja) * | 2009-05-22 | 2010-09-22 | 東洋紡績株式会社 | 光学用易接着性ポリエステルフィルム |
JP5415251B2 (ja) * | 2009-12-28 | 2014-02-12 | ユニチカ株式会社 | ポリエステル樹脂水性分散体、およびその製造方法、ならびにそれから得られる樹脂被膜 |
CN102803339B (zh) * | 2010-04-23 | 2014-10-29 | 日华化学株式会社 | 非结晶性聚酯树脂、静电荷像显像用调色剂用粘结树脂和非结晶性聚酯树脂的制造方法 |
WO2011148914A1 (ja) * | 2010-05-26 | 2011-12-01 | 日本合成化学工業株式会社 | ポリエステル系樹脂、ポリエステル系樹脂の製法、およびポリエステル系樹脂水性液 |
WO2013133451A1 (ja) * | 2012-03-09 | 2013-09-12 | 帝人デュポンフィルム株式会社 | 透明導電性フィルム基材用積層体 |
-
2016
- 2016-10-27 CN CN201680062760.2A patent/CN108350155B/zh active Active
- 2016-10-27 JP JP2016565521A patent/JPWO2017073697A1/ja active Pending
- 2016-10-27 KR KR1020187011952A patent/KR20180075521A/ko not_active Application Discontinuation
- 2016-10-27 WO PCT/JP2016/081965 patent/WO2017073697A1/ja active Application Filing
- 2016-10-28 TW TW105135030A patent/TW201730235A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04103657A (ja) * | 1990-08-22 | 1992-04-06 | Toyobo Co Ltd | 制振材料用粘弾性樹脂組成物 |
JPH09324148A (ja) * | 1996-06-04 | 1997-12-16 | Toyobo Co Ltd | 水系塗料用組成物及びそれを用いた耐蝕性金属板 |
JP2009126035A (ja) * | 2007-11-22 | 2009-06-11 | Toyobo Co Ltd | 被覆ポリエステルフィルム、およびそれを用いたハードコートフィルム |
WO2014024570A1 (ja) * | 2012-08-10 | 2014-02-13 | 東レ株式会社 | 積層ポリエステルフィルム |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110944840A (zh) * | 2017-08-24 | 2020-03-31 | 东洋纺株式会社 | 陶瓷生片制造用脱模膜 |
CN110944840B (zh) * | 2017-08-24 | 2022-04-01 | 东洋纺株式会社 | 陶瓷生片制造用脱模膜 |
WO2022230231A1 (ja) * | 2021-04-28 | 2022-11-03 | 関西ペイント株式会社 | 水性塗料組成物及び複層塗膜形成方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201730235A (zh) | 2017-09-01 |
JPWO2017073697A1 (ja) | 2018-08-16 |
KR20180075521A (ko) | 2018-07-04 |
CN108350155B (zh) | 2021-03-19 |
CN108350155A (zh) | 2018-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5493938B2 (ja) | 成型用積層ポリエステルフィルム | |
CN108350155B (zh) | 聚酯系树脂、底漆用聚酯系树脂、聚酯系水性液、和带底漆层的基材薄膜以及层叠薄膜 | |
JP4956384B2 (ja) | 表示画面用保護フィルムおよびその製造方法 | |
JP6866634B2 (ja) | プライマー層付き基材フィルム及びプリズムシート | |
JP5493940B2 (ja) | 積層ポリエステルフィルム | |
JP6513374B2 (ja) | ポリエステル系樹脂、ポリエステル系樹脂水性液、及びポリエステル系樹脂組成物 | |
JP5210602B2 (ja) | 両面粘着シートおよびその製造方法ならびにその使用方法 | |
JP6690537B2 (ja) | プライマー組成物、及びこれを用いてなるポリエステル系水性液、プライマー層、プライマー層付き基材フィルム、積層フィルム、プリズムシート、並びにポリエステル系樹脂の製造方法 | |
JP7088324B2 (ja) | プライマー組成物及びこれを用いてなる水性液、プライマー層付き基材フィルム並びにプリズムシート | |
JP6063612B2 (ja) | 積層フィルム | |
JP6513381B2 (ja) | ポリエステル系樹脂組成物、及びポリエステル系水性液 | |
JP5203073B2 (ja) | タッチパネル用上部電極 | |
JP5203072B2 (ja) | タッチパネル用上部電極 | |
JP6613171B2 (ja) | ポリエステル系樹脂、ポリエステル系樹脂水性液、及び合成樹脂含有基材用プライマー | |
JP6658219B2 (ja) | プライマー用ポリエステル系樹脂、プライマー用ポリエステル系水性液、プライマー層付きポリエステル系フィルム、積層フィルム、ならびにプライマー用ポリエステル系樹脂の製造方法 | |
JP5210580B2 (ja) | 両面粘着シートおよびその製造方法ならびにその使用方法 | |
JP2017109489A (ja) | 積層フィルム | |
JP6988647B2 (ja) | ポリエステル系樹脂、プライマー組成物、水性液、プライマー層付き基材フィルム及びプリズムシート | |
JP5410698B2 (ja) | 透明導電性ポリエステルフィルム複合体、ならびにタッチパネル用電極 | |
JP6988646B2 (ja) | 不飽和基含有ポリエステル系樹脂、プライマー組成物、水性液、プライマー層付き基材フィルム及びプリズムシート | |
JP7139746B2 (ja) | 不飽和基含有ポリエステル系樹脂、プライマー組成物、プライマー層付き基材フィルム及びプリズムシート |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2016565521 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16859926 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20187011952 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16859926 Country of ref document: EP Kind code of ref document: A1 |