WO2016208655A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2016208655A1 WO2016208655A1 PCT/JP2016/068609 JP2016068609W WO2016208655A1 WO 2016208655 A1 WO2016208655 A1 WO 2016208655A1 JP 2016068609 W JP2016068609 W JP 2016068609W WO 2016208655 A1 WO2016208655 A1 WO 2016208655A1
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- WIPO (PCT)
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- polyester
- primer layer
- primer
- film
- carboxylic acid
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Classifications
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- 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
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- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- 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
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- 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
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- 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
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- 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
- C09D5/002—Priming paints
Definitions
- the present invention relates to a primer composition containing a polyester-based resin, and more specifically, a primer composition having excellent adhesion between both a base film and a coating layer and excellent stability when used as an aqueous liquid. It is about things.
- polyester film thermoplastic polyesters such as polyethylene terephthalate (PET) and copolymers thereof are necessary. Accordingly, a mixture obtained by mixing and extruding another resin is biaxially stretched and heat-set after being melt-extruded and molded.
- PET polyethylene terephthalate
- Such a polyester film is excellent in various physical properties, but has a problem that its surface is highly crystallized and therefore has poor adhesion to a coating layer provided on the film.
- a prism layer as one of the coating layers.
- an active energy ray curable resin composition is introduced into a prism type, and the active energy ray curable resin composition is irradiated with the active energy ray curable resin composition sandwiched between the prism type and the polyester film.
- a method of forming a prism layer formed by curing the active energy ray-curable resin composition on a polyester film by curing the resin composition and removing the prism mold In the case of such a method, it is necessary to use a solvent-free active energy ray-curable resin in order to form a prism pattern precisely.
- the solventless resin has a lower permeation and swelling effect on the primer layer laminated on the polyester film than the solvent-based resin, and the layer formed by curing the active energy ray-curable resin composition and the primer layer. Adhesiveness is likely to be insufficient.
- the primer described in Patent Document 1 has low flexibility of the resulting primer layer, and the acid value of the polyester resin is low, so that crosslinking when crosslinked with a crosslinking agent is insufficient.
- the acid value of the polyester resin is low, so that crosslinking when crosslinked with a crosslinking agent is insufficient.
- the solventless active energy ray-curable resin used for forming the prism layer described above tends to have insufficient adhesion due to the low penetration and swelling effects on the primer layer.
- the present invention under such a background, adhesion between both the base film and the coating layer, in particular, both the polyester film and the prism layer formed by curing the solventless active energy ray-curable resin composition. It is an object of the present invention to provide a primer composition that is excellent in stability and also excellent in stability when used as an aqueous liquid.
- the inventors of the present invention have obtained a copolymer component containing a polyvalent carboxylic acid component (A) and a polyol component (B) in a primer composition containing a polyester resin.
- a polyester resin obtained by copolymerization wherein the content ratio of the linear polyol excluding ethylene glycol with respect to the entire polyol component (B) is 70 mol% or more, and the acid value is 10 mgKOH / g or more.
- a linear polyol other than ethylene glycol is used as a main component so that the flexibility of the resin and the compatibility with the coating layer are excellent in balance. It is presumed that excellent adhesion between the material and the coating layer can be obtained.
- linear polyols when ethylene glycol is used as the main component, the flexibility of the resin is reduced, and depending on the type of coating layer, not only does it have poor affinity, but also the cohesion is strong. Therefore, there is a problem that water dispersibility is lowered.
- a solvent-free active energy ray-curable resin composition used for forming a coating layer, particularly, for example, a prism layer is cured by using a linear polyol excluding ethylene glycol as a main component.
- a primer composition having excellent adhesion to the layer and excellent stability when used as an aqueous liquid.
- the gist of the present invention is a polyester resin obtained by copolymerizing a copolymer component containing a polyvalent carboxylic acid component (A) and a polyol component (B), and ethylene glycol with respect to the entire polyol component (B).
- the present invention relates to a primer composition comprising a polyester resin in which the content ratio of the polyol (b1) having a straight-chain structure excluding is 70 mol% or more and the acid value is 10 mgKOH / g or more.
- the primer composition containing the polyester-based resin has a primer layer formed by crosslinking with a crosslinking agent, a substrate film with a primer layer having the primer layer on the substrate film, and a hard coat layer.
- a laminated film, a prism sheet having a prism layer, a polyester aqueous solution in which a primer composition containing the polyester resin is dissolved or dispersed in an aqueous solvent, and a method for producing a polyester resin are also provided. is there.
- the “film” in the present invention includes a sheet.
- the present invention is characterized by the following (1) to (10).
- the primer composition according to (1) or (2) above which contains a carboxylic acid anhydride (a1) having two or more carboxylic acid anhydride structures as the polyvalent carboxylic acid component (A).
- the base film with a primer layer which has a primer layer as described in said (5) on a base film.
- a method for producing a polyester-based resin, wherein the hydroxyl group-containing prepolymer comprising (B) is chain-extended with a carboxylic acid anhydride (a1) having two or more carboxylic acid anhydride structures.
- the primer composition of the present invention is excellent in adhesion between both the base film and the coating layer, and in particular, a solvent-free active energy ray curable resin composition used for forming a polyester film and a prism layer, for example. Excellent adhesion to the cured layer. Furthermore, since the polyester-based resin contained in the primer composition of the present invention is excellent in stability when used as an aqueous liquid, it can be stored in an aqueous liquid state and has excellent handleability.
- carboxylic acid includes carboxylic acid salts, carboxylic acid anhydrides, carboxylic acid halides, carboxylic acid esters, and the like.
- polyester resin contained in the primer composition of the present invention is obtained by copolymerizing a copolymer component containing a polyvalent carboxylic acid component (A) and a polyol component (B).
- the polyvalent carboxylic acid component (A) used in the present invention may be a divalent or higher polyvalent carboxylic acid, and preferably contains at least a divalent carboxylic acid.
- Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, benzylmalonic acid, diphenic acid, 4,4'-oxydibenzoic acid, naphthalenedicarboxylic acid, dimethyl sodium 5-sulfoisophthalate; 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,
- aromatic dicarboxylic acid and alicyclic dicarboxylic acid are preferably used in terms of adhesion and stability of aqueous liquid, and particularly preferably aromatic dicarboxylic acid from the viewpoint of excellent adhesion.
- Isophthalic acid is preferred.
- the content ratio of the divalent carboxylic acid is preferably 70 to 98 mol%, particularly 75 to 97 mol%, more preferably 80 to 96 mol%, particularly with respect to the whole polyvalent carboxylic acid component (A). Is preferably 85 to 95 mol%. If the content is too low, the water resistance tends to decrease or gelation occurs during the production process, and if it is too high, water dispersion tends to be difficult.
- any one of the above aromatic dicarboxylic acids is the main component, and other divalent carboxylic acids. It is preferable to use 1 or more types together.
- isophthalic acid as a main component and terephthalic acid in combination.
- the main component means that it is usually contained in an amount of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more based on the whole polyvalent carboxylic acid component (A).
- the other divalent carboxylic acid used in combination is added to the entire polyvalent carboxylic acid component (A).
- the content is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and even more preferably 10 to 20 mol%.
- the divalent carboxylic acid used in combination with the main component aromatic dicarboxylic acid is contained.
- a trivalent or higher polyvalent carboxylic acid can be used for the purpose of increasing the branching point in the polyester resin.
- the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, and adamantanetricarboxylic acid. Examples thereof include acids and 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.
- carboxylic acid anhydride (a1) having two or more such carboxylic acid anhydride structures those having at least two carboxylic acid anhydride structures may be used.
- carboxylic acid anhydride (a1) 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 anhydrides such as diphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfone tetracarboxylic anhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride object, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5 dio
- tetracarboxylic dianhydride is preferable from the viewpoint of mild reactivity and hardly causing gelation at the time of resin production.
- aromatic tetracarboxylic dianhydride is preferable from the viewpoint of adhesion.
- 2,4,5-benzenetetracarboxylic dianhydride (pyromellitic anhydride) is preferred.
- the content ratio of the carboxylic acid anhydride (a1) in the polyvalent carboxylic acid component (A) is preferably 2 to 30 mol%, particularly 3 to 25 mol% based on the entire polyvalent carboxylic acid component (A). It is preferable that the amount be 4 mol%, more preferably 4 to 20 mol%, and especially 5 to 15 mol%. If the content is too low, it is difficult to disperse water when the produced polyester resin is dispersed in an aqueous solvent, or the crosslinking point with the crosslinking agent is insufficient, and the adhesion and water resistance tend to decrease. is there.
- the polyol component (B) used in the present invention needs to contain 70 mol% or more of the linear polyol (b1) excluding ethylene glycol with respect to the entire polyol component (B), preferably 75 mol. % Or more, particularly preferably 80 mol% or more, more preferably 85 mol% or more.
- the content of the polyol (b1) having a linear structure excluding ethylene glycol with respect to the entire polyol component (B) is too small, the adhesion with the coating layer is lowered and the object of the present invention cannot be achieved.
- the upper limit of the content of the polyol (b1) having a linear structure excluding ethylene glycol is usually 100 mol%, preferably 98 mol% or less, particularly preferably 95% or less, and further preferably 90 mol% or less.
- linear structure polyol (b1) excluding ethylene glycol examples include diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples include 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, polytetramethylene glycol and the like.
- diethylene glycol 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferably used, and particularly preferably diethylene glycol, because it has moderate flexibility and excellent adhesion. And 1,5-pentanediol.
- polyol component (B) used by this invention other polyols (b2), such as the following dihydric alcohol and trihydric or more polyhydric alcohol, besides the linear structure polyol (b1) except ethylene glycol. ).
- polyols (b2) include ethylene glycol, propylene glycol, dipropylene glycol, 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, 1,3-butane
- An aliphatic diol having a branched structure such as diol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecane dimethanol
- trihydric or higher polyhydric alcohol examples include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantanetriol and the like. It is done.
- polys (b2) are preferably used from the viewpoint of the stability of the aqueous liquid, and among them, it is preferable to use an aliphatic polyol having a branched structure, particularly preferably neopentyl, from the viewpoint of adhesion.
- an aliphatic polyol having a branched structure particularly preferably neopentyl, from the viewpoint of adhesion.
- Glycol 2-methyl-1,3-propanediol, more preferably neopentyl glycol.
- the content of the other polyol (b2) is 2 to 30 with respect to the entire polyol component (B). It is preferably a mol%, particularly preferably 5 to 25 mol%, more preferably 10 to 20 mol%. If the content is too large, the adhesion tends to decrease, and if it is too small, the stability of the aqueous liquid tends to decrease.
- the polyol component (B) when only the polyol (b1) having a linear structure excluding ethylene glycol is used as the polyol component (B), two or more divalent carboxylic acids of the polyvalent carboxylic acid component (A) are used in combination.
- the linear polyol (b1) excluding ethylene glycol and the other polyol (b2) are used in combination as the polyol component (B)
- the divalent carboxylic acid of the polyvalent carboxylic acid component (A) is 1 It is preferable to use the species alone.
- the polyester resin used in the present invention is obtained by copolymerizing a copolymer component containing the polyvalent carboxylic acid component (A) and the polyol component (B).
- a carboxylic acid anhydride (a1) A method of chain-extending a hydroxyl group-containing prepolymer obtained by copolymerizing a polyvalent carboxylic acid component (A) and a polyol component (B) with a carboxylic acid anhydride (a1) having two or more carboxylic acid anhydride structures Can be manufactured.
- the mixing ratio (molar ratio) of the polyvalent carboxylic acid component (A) excluding the carboxylic acid anhydride (a1) 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 1.02 to 1.35 mol, particularly preferably 1.05 to 1.3 mol, and more preferably 1.08 to 1.2 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-based 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 (a1).
- 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 10,000 to 40,000, and more preferably 15,000 to 30,000. If the weight-average molecular weight of the polyester-based resin is too large, it is difficult to disperse the produced polyester-based resin in an aqueous solvent, and if it is too small, an aqueous liquid obtained by dispersing the resin in an aqueous medium. Storage stability, adhesion with a coating layer when a primer layer is formed on a substrate film using an aqueous liquid, and heat and humidity resistance tend to be reduced.
- 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 / piece, 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 ⁇ 15 to 60 ° C., particularly preferably 0 to 50 ° C., and further preferably 25 to 45 ° C. If the glass transition temperature is too high, the adhesiveness is reduced, or the polyester aqueous film is coated on a base film such as a polyester film. Tend to occur. On the other hand, if the glass transition temperature is too low, heat resistance and blocking resistance 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 used in the present invention needs to be 10 mgKOH / g or more, preferably 10 to 150 mgKOH / g, particularly preferably 25 to 100 mgKOH / g, more preferably 35 to 85 mgKOH / g. It is. When the acid value is too low, the water dispersibility is lowered or the adhesion with the coating layer is lowered, and the object of the present invention cannot be achieved. Even if the acid value is too high, the water resistance of the primer layer and the adhesion to the coating layer tend to be lowered.
- the acid value of the polyester resin is determined by neutralization titration based on JIS K0070.
- the primer composition of the present invention in addition to the above polyester-based resin, the primer composition of the present invention, if necessary, hindered phenol-based antioxidants, heat stabilizers, glass fibers, inorganic / organic fillers, colorants, flame retardants, Softeners, dispersants, wetting agents, emulsifiers, gelling agents, antifoaming agents, other thermoplastic resins, and the like can be blended to such an extent that the effects of the present invention are not impaired.
- the polyester-based aqueous liquid of the present invention is obtained by dissolving or dispersing the primer composition containing the polyester-based resin 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-based resin contained in a primer composition is neutralized with a neutralizing agent and dissolved or dispersed in an aqueous solvent to obtain a polyester-based aqueous liquid is preferable.
- the neutralizing agent is not particularly limited as long as it can neutralize the carboxyl group of the polyester resin contained in the primer composition.
- the neutralizing agent is not particularly limited as long as it can neutralize the carboxyl group of the polyester resin contained in the primer composition.
- organic amines such as N-dimethylethanolamine, aminoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine; and ammonia.
- One kind selected from these neutralizing agents may be used, or two or more kinds may be used in combination.
- 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 and triethylamine are preferable, and ammonia is particularly preferable because of its high versatility, low boiling point, and ease of volatilization during drying.
- 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.
- ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monotertiary butyl ether, and isopropyl alcohol are preferably used.
- 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 (C) in the polyester-based aqueous liquid from the viewpoint of improving adhesion.
- the crosslinking agent (C) may be a compound containing a functional group reactive with the functional group contained in the polyester resin.
- a functional group reactive with the carboxyl group in the polyester resin may be used.
- the containing compound is used.
- crosslinking agent (C) examples include compounds having an epoxy group, an oxazoline group, a carbodiimide group, an amino group, or an isocyanate group, a metal compound, an aziridine compound, and a melamine compound.
- 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 having a substituent having an unsaturated carbon-carbon bond at the 2-position carbon position (for example, 2-isopropenyl-2-oxazoline) and other non-polymerizable groups.
- Examples include commercially available products such as copolymers with saturated monomers, “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 having at least two carbodiimide groups as functional groups or cyanamide groups having tautomerism in the molecule.
- Carbodilite manufactured by Nisshinbo Chemical Co., Ltd. “V-02”, “Carbodilite V-02-L2”, “Carbodilite SV-02”, “Carbodilite V-04”, “Carbodilite V-10”, “Carbodilite E-03A”, “Carbodilite E-02”, “ Carbodilite E-04 “and the like.
- Carbodilite V-04 ",” Carbodilite E-04 "and the like having a tetramethylxylylene skeleton are preferable.
- 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 block isocyanate compounds thereof, “Aquanate 100”, “Aquanate 110”, “Aquanate 210” (manufactured by Nippon Polyurethane Co., Ltd.), Self-emulsifying water-dispersed polyisocyanate such as “Elastolon BN-77” (Daiichi Kogyo Seiyaku Co., Ltd.) Compounds, and the like. Among these, water-dispersed “Elastolon BN-77” having an aromatic ring is preferable.
- metal compounds include metal alkoxides such as tetraethyl titanate, tetraethyl zirconate, and aluminum isopropionate, and aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and the like.
- metal alkoxides such as tetraethyl titanate, tetraethyl zirconate, and aluminum isopropionate
- aluminum iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and the like.
- metal chelate compound of ethylenediaminetetraacetic acid coordination compound such as acetic acid-ammonium complex salt, ammonium-carbonate complex salt and the like.
- 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 (C) As a crosslinking agent (C), only 1 type chosen from these may be used, and 2 or more types may be used together.
- a crosslinking agent having an aromatic ring more preferably a compound having an aromatic ring and a carbodiimide group or an isocyanate group, and particularly a compound having an aromatic ring and a carbodiimide group.
- a compound having a tetramethylxylylene skeleton and a carbodiimide group is particularly preferable.
- the primer layer is preferably thin from the viewpoint of cost and transparency, but the adhesiveness tends to decrease when the thickness is thin. The use of agents is particularly effective.
- the content of the crosslinking agent (C) can be appropriately selected depending on the amount of the functional group contained in the polyester resin, the molecular weight of the polyester resin, and the purpose of use, but is usually based on 100 parts by weight of the polyester resin.
- the amount is preferably 1 to 70 parts by weight, particularly 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight. If the content is too large or too small, the adhesion tends to decrease.
- the amount is preferably 15 to 1000 parts by weight, particularly 20 to 500 parts by weight, more preferably 30 to 350 parts by weight, especially 40 to 250 parts by weight, based on 100 parts by weight of the polyester resin. Part.
- the molar ratio of the functional group amount in the polyester resin to the functional group amount in the crosslinking agent is usually preferably 1 / 0.5 to 1/2, particularly 1 / 0.6 to 1. /1.5, more preferably 1 / 0.8 to 1 / 1.2 equivalent.
- a compound having a carbodiimide group is used as the crosslinking agent (C)
- it is preferably contained in a relatively larger amount than usual from the viewpoint of improving the adhesion to the coating layer.
- the molar ratio of groups to carbodiimide groups is preferably 1 / 0.3 to 1/30, in particular 1 / 0.5 to 1/15, more preferably 1/1 to 1/12, in particular 1 /1.5 to 1/10 is preferable.
- the amount of unreacted carbodiimide groups in the primer layer (after crosslinking) is 0 to 3 mmol from the viewpoint of improving the adhesion with the coating layer.
- / G more preferably 0.1 to 2.5 mmol / g, particularly preferably 0.2 to 2.2 mmol / g, particularly preferably 0.3 to 2 mmol / g.
- an anionic surfactant, a nonionic surfactant, etc. can be mix
- the surfactant 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.
- the polyester-based aqueous liquid may further contain an antistatic agent, a filler, an ultraviolet absorber, a lubricant, a colorant, and the like as necessary.
- the solid content concentration of the polyester-based aqueous liquid is appropriately adjusted so as to ensure good dispersibility of the polyester-based resin, and is preferably 5 to 30% by weight, for example. It should be noted that the coating is appropriately diluted so as to obtain a desired film thickness, and is used, for example, by adjusting the solid content concentration to 1 to 10% by weight.
- polyester resins such as polyethylene naphthalate, polyethylene-2,6-naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyethylene, polypropylene, polymethylpentene, and the like.
- Polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; polyamides such as nylon 6 and nylon 6, 6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene Vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, Ethyl Li methacrylate, polyethyl acrylate, acrylic resins such as polybutyl acrylate; polystyrene, polycarbonate, polyarylate, monolayer, or multilayer body is selected from a synthetic resin film or sheet of polyimide and the like.
- a polyester film is preferably used in terms of transparency, chemical resistance, heat resistance, mechanical strength, cost, and the like.
- the polyester film may be either an unstretched one or a stretched one, but a stretched film is preferably used, and a biaxially stretched film is particularly preferred.
- a known general method can be used, and examples thereof include a method of applying a kiss coat, a reverse coat, a gravure coat, a die coat, etc. on one or both sides of a base film.
- the thickness of the primer layer after heat drying (after crosslinking) is preferably 0.01 to 2 ⁇ m, particularly 0.02 to 0.5 ⁇ m, more preferably 0.03 to 0.3 ⁇ m, especially It is preferably 0.05 to 0.15 ⁇ m.
- a laminated film and a prism sheet can be obtained by providing a coating layer on the primer layer of the substrate film with a primer layer and using the coating layer as a hard coat layer or a prism layer.
- the material for forming the coating layer include acrylic resins, epoxy resins, urethane resins and active energy ray-curable resin compositions that are generally used as coating materials.
- a functional resin composition is preferred.
- ⁇ Laminated film> Specifically, by applying an active energy ray-curable resin composition on the primer layer of the base material film with the primer layer and irradiating and curing the active energy ray, the primer of the base material film with the primer layer A laminated film having a hard coat layer formed by curing the active energy ray-curable resin composition on the layer can be obtained.
- a prism layer can be formed on the primer layer of the substrate film with a primer layer to obtain a prism sheet.
- the prism layer is preferably a prism layer formed by curing an active energy ray-curable resin composition, and particularly preferably a prism layer formed by curing a solventless active energy ray-curable resin composition. is there.
- an active energy ray curable resin composition is introduced into a prism type, The active energy ray-curable resin composition is sandwiched between the primer layer side of the substrate film with a primer layer (particularly, the polyester film) and the active energy ray is irradiated to cure the resin composition and remove the prism type.
- a primer layer particularly, the polyester film
- the application method of the active energy ray-curable resin composition is not particularly limited, and for example, spray, shower, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, Examples include wet coating methods such as screen printing and ink jet printing.
- rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price.
- the thickness of the hard coat layer is usually 0.5 to 15 ⁇ m, preferably 1 to 10 ⁇ m, particularly 2 to 7 ⁇ m.
- the thickness of the prism layer is preferably 5 to 50 ⁇ m, particularly 10 to 40 ⁇ m, more preferably 15 to 35 ⁇ m, and particularly preferably 20 to 30 ⁇ m.
- Example 1 [Production of polyester resin [I-1] and aqueous liquid thereof]
- a reaction vessel equipped with a thermometer, a stirrer, a rectifying column, and a nitrogen introduction tube 327.5 parts (1.971 mol) of isophthalic acid as a polyvalent carboxylic acid component and 198.7 parts of diethylene glycol (b1) as a polyol component (1 .872 mol), 30.8 parts (0.296 mol) of neopentyl glycol (b2) and 0.3 part of tetrabutyl titanate (511 ppm based on all copolymerization components) as a catalyst,
- the temperature was raised over time, and an esterification reaction was carried out at 260 ° C.
- polyester-based resin [I-1] 25 parts of the obtained polyester-based resin [I-1], 72.5 parts of water, and 2.5 parts of 25% aqueous ammonia are charged into a reactor, heated to 90 ° C., dissolved with stirring, A polyester aqueous solution (water dispersion) having a partial concentration of 25% was prepared.
- polyester resins [I-2] to [I-4], [I′-1] to [I′-2] and aqueous solutions thereof] As shown in Table 1, polyester resins [I-2] to [I-4], [I′-1] were obtained in the same manner as in Example 1 except that the copolymerization component and the blending ratio thereof were changed. ⁇ [I'-2] and their aqueous liquids were prepared.
- polyester-based resin [I′-3] 25 parts were charged into a reactor, heated to 90 ° C. and dissolved with stirring, and a polyester-based aqueous liquid having a solid content concentration of 25% ( A water dispersion) was prepared.
- Weight average molecular weight GPC measurement was performed using HLC-8320 manufactured by Tosoh Corporation, and it was determined from polystyrene conversion.
- Glass transition temperature (Tg) Measurement was performed using a differential scanning calorimeter DSC Q20 manufactured by TA Instruments.
- IPA isophthalic acid
- TPA terephthalic acid
- SIPM dimethyl sodium 5-sulfoisophthalate
- PMAn pyromellitic anhydride
- DEG diethylene glycol
- PG 1,5-pentanediol
- 1.6HG 1,6-hexanediol
- NPG neo Pentyl glycol
- a crosslinking agent having the kind and blending amount shown in Table 2 below was added, and diluted with deionized water to a solid content of 3% to prepare a coating liquid.
- the prepared coating solution was coated on a PET film (Lumirror T60, manufactured by Toray Industries, Inc., 100 ⁇ m thick) with a bar coater so that the film thickness after drying was as shown in Table 2 below, and dried at 150 ° C. for 3 minutes. As a result, a primer layer was formed.
- a solvent-free ultraviolet curable resin composition UV-9895AS for prism formation (manufactured by Kazumi Special Materials Technology Co., Ltd.) was applied to the bar coater No. 1 on the primer layer. 4 is applied, followed by irradiation with ultraviolet light at 450 mJ / cm 2 using a metal halide lamp having an irradiation intensity of 80 W / cm set at a height of 13 cm from the coating surface, thereby producing an ultraviolet curable resin composition. Curing was performed to form a resin layer having a thickness of 20 ⁇ m.
- crosslinking agents II-1 and II-2 shown in Table 2 are as follows.
- II-1 Cross-linking agent having a carbodiimide group “Carbodilite V-04” (Nisshinbo Chemical Co., Ltd.)
- II-2 Cross-linking agent having an isocyanate group “Elastolon BN-77” (Daiichi Kogyo Seiyaku Co., Ltd.)
- the primer composition of the present invention can be suitably used as a primer for a substrate film.
- the obtained base film with a primer layer is excellent in adhesiveness with a coating layer formed by curing an active energy ray-curable resin composition, for example, a label sheet, a printing sheet, a hard coat film, It is useful as a sheet in which a coating layer is provided on a film such as a prism sheet, and particularly useful as a prism sheet.
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Abstract
Description
しかしながら、近年、コーティング層を形成するコーティング剤等の組成は多様化しており、その種類によってはプライマー層とコーティング層との密着性が十分でない場合があり、密着性のさらなる向上が求められている。
直鎖ポリオールの中でも、エチレングリコールを主成分とした際は樹脂の柔軟性が低下し、またコーティング層の種類によってはそれとの親和性に欠けるため密着性に乏しくなるだけでなく、凝集力が強くなるため水分散性が低下するといった問題がある。そのため、本発明においては、エチレングリコールを除く直鎖ポリオールを主成分とすることにより、コーティング層、特には、例えばプリズム層の形成に用いられる無溶剤系活性エネルギー線硬化性樹脂組成物が硬化してなる層との密着性に優れ、かつ水性液とした際の安定性にも優れたプライマー組成物を得ることができるものである。
なお、本発明における「フィルム」とは、シートを包含するものである。
(1)多価カルボン酸成分(A)とポリオール成分(B)とを含む共重合成分を共重合してなるポリエステル系樹脂であって、前記ポリオール成分(B)全体に対するエチレングリコールを除く直鎖構造のポリオール(b1)の含有割合が70モル%以上であり、酸価が10mgKOH/g以上であるポリエステル系樹脂を含有するプライマー組成物。
(2)前記ポリオール成分(B)として、分岐構造を有する脂肪族ポリオールを含有する、前記(1)に記載のプライマー組成物。
(3)前記多価カルボン酸成分(A)として、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(a1)を含有する、前記(1)または(2)に記載のプライマー組成物。
(4)前記(1)~(3)のいずれか1つに記載のプライマー組成物が、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。
(5)前記(4)に記載のポリエステル系水性液が架橋剤(C)を更に含有し、該架橋剤(C)によりポリエステル系樹脂が架橋されてなるプライマー層。
(6)基材フィルム上に前記(5)に記載のプライマー層を有するプライマー層付き基材フィルム。
(7)前記基材フィルムがポリエステルフィルムである、前記(6)に記載のプライマー層付き基材フィルム。
(8)前記(6)または(7)に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。
(9)前記(6)または(7)に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、無溶剤系活性エネルギー線硬化性樹脂組成物が硬化してなるプリズム層を有するプリズムシート。
(10)前記(1)に記載のポリエステル系樹脂の製造方法であって、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(a1)を除く多価カルボン酸成分(A)とポリオール成分(B)からなる水酸基含有プレポリマーを、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(a1)で鎖延長させてなるものであるポリエステル系樹脂の製造方法。
なお、本発明において、「カルボン酸」との用語は、カルボン酸塩、カルボン酸無水物、カルボン酸ハロゲン化物、カルボン酸エステルなどを含むものである。
本発明のプライマー組成物に含有される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なるものである。
本発明で用いられる多価カルボン酸成分(A)は、二価以上の多価カルボン酸であればよく、少なくとも二価カルボン酸を含むことが好ましい。
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、ナフタレンジカルボン酸、5-スルホイソフタル酸ジメチルナトリウム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;
等が挙げられる。
なかでも本発明においては、イソフタル酸を主成分とし、テレフタル酸を併用することが好ましい。
ここで、主成分とは、多価カルボン酸成分(A)全体に対して、通常50重量%以上、好ましくは60重量%以上、より好ましくは70重量%以上含有することを意味する。
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。
本発明で用いられるポリオール成分(B)は、エチレングリコールを除く直鎖構造のポリオール(b1)をポリオール成分(B)全体に対して70モル%以上含有することが必要であり、好ましくは75モル%以上、特に好ましくは80モル%以上、更に好ましくは85モル%以上である。ポリオール成分(B)全体に対するエチレングリコールを除く直鎖構造のポリオール(b1)の含有量が少なすぎると、コーティング層との密着性が低下し本発明の目的を達成できない。エチレングリコールを除く直鎖構造のポリオール(b1)の含有量の上限は通常100モル%であり、好ましくは98モル%以下、特に好ましくは95%以下、更に好ましくは90モル%以下である。
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、ビスフェノールS,ビスフェノールA、ビスフェノールフルオレン、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-キシレンジオール等の芳香族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;
等の二価アルコールが挙げられる。
かかる含有割合が多すぎると、密着性が低下する傾向があり、少なすぎると水性液の安定性が低下する傾向がある。
本発明に用いられる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(a1)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、カルボン酸無水物構造を2つ以上有するカルボン酸無水物(a1)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。
なお、上記ポリエステル系樹脂の酸価はJIS K0070に基づき中和滴定により求められるものである。
本発明のプライマー組成物には、上記ポリエステル系樹脂以外に、必要に応じて、ヒンダードフェノール系等の酸化防止剤、熱安定剤、ガラス繊維、無機・有機充填剤、色料、難燃剤、軟化剤、分散剤、湿潤剤、乳化剤、ゲル化剤、消泡剤、他の熱可塑性樹脂等を、本発明の効果を損なわない程度に配合することができる。
本発明のポリエステル系水性液は、上記のポリエステル系樹脂を含有するプライマー組成物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、プライマー組成物に含有される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。
特に、プライマー層の厚みはコストや透明性の点から薄い方が好ましいものの、厚みが薄いと密着性が低下する傾向にあるため、インラインコーティングによるナノオーダーの薄膜形成時等には上述の好ましい架橋剤の使用が特に有効である。
特に、架橋剤(C)としてカルボジイミド基を有する化合物を用いる場合においては、コーティング層との密着性を向上させる点からは、通常、架橋剤として含有させる量よりも比較的多く含有させることが好ましく、ポリエステル系樹脂100重量部に対して、15~1000重量部であることが好ましく、特には20~500重量部、更には30~350重量部であることが好ましく、殊には40~250重量部であることが好ましい。
特に、架橋剤(C)としてカルボジイミド基を有する化合物を用いる場合においては、コーティング層との密着性を向上させる点からは、通常よりも比較的多く含有させることが好ましく、ポリエステル系樹脂中のカルボキシル基とカルボジイミド基のモル比は、1/0.3~1/30であることが好ましく、特には1/0.5~1/15、更には1/1~1/12、殊には1/1.5~1/10であることが好ましい。
なお、基材及びコーティング層との密着性および耐水性の点からは、界面活性剤を添加しない方が好ましい。
なかでも、透明性、耐薬品性、耐熱性、機械的強度及びコスト等の点からポリエステルフィルムが好ましく用いられる。
上記ポリエステルフィルムは、未延伸のものと、延伸したもののいずれでもよいが、延伸フィルムを用いることが好ましく、特に二軸延伸フィルムを用いることが好ましい。
コーティング層を形成する材料としては、コーティング材料として一般的に用いられているアクリル系樹脂、エポキシ樹脂、ウレタン樹脂や、活性エネルギー線硬化性樹脂組成物等が挙げられるが、なかでも活性エネルギー線硬化性樹脂組成物が好ましい。
具体的には、上記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を塗工し、活性エネルギー線を照射して硬化することにより、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を得ることができる。
また、プライマー層付き基材フィルムのプライマー層上にプリズム層を形成し、プリズムシートを得ることができる。
プリズム層としては、活性エネルギー線硬化性樹脂組成物が硬化してなるプリズム層であることが好ましく、特に好ましくは、無溶剤系の活性エネルギー線硬化性樹脂組成物が硬化してなるプリズム層である。
プリズム層が活性エネルギー線硬化性樹脂組成物が硬化してなるプリズム層である場合のプリズム層の形成方法としては、例えば、活性エネルギー線硬化性樹脂組成物をプリズム型に導入し、プリズム型とプライマー層付き基材フィルム(特には、ポリエステルフィルム)のプライマー層側とで活性エネルギー線硬化性樹脂組成物を挟み込んだ状態で活性エネルギー線を照射し、樹脂組成物を硬化させ、プリズム型を取り除くことにより、基材フィルム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プリズム層を形成する方法が挙げられる。
〔ポリエステル系樹脂[I-1]及びその水性液の製造〕
温度計、攪拌機、精留塔、窒素導入管の付いた反応缶に、多価カルボン酸成分としてイソフタル酸327.5部(1.971mol)、ポリオール成分としてジエチレングリコール(b1)198.7部(1.872mol)、ネオペンチルグリコール(b2)30.8部(0.296mol)、触媒としてテトラブチルチタネート0.3部(全共重合成分に対して511ppm)を仕込み、内温200~260℃まで2時間かけて昇温し、260℃で3時間エステル化反応を行った。その後、内温170℃まで下げ、ピロメリット酸無水物(a1)43.0部(0.197mol)を添加し1時間鎖延長反応を行い、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を表1に示す。
〔ポリエステル系樹脂[I-2]~[I-4]、[I’-1]~[I’-2]及びそれらの水性液の製造〕
表1に示すとおり、共重合成分及びその配合割合を変更した以外は実施例1と同様の操作を行って、ポリエステル系樹脂[I-2]~[I-4]、[I’-1]~[I’-2]及びそれらの水性液を製造した。
〔ポリエステル系樹脂[I’-3]の製造及びその水性液の製造〕
温度計、攪拌機、精留塔、窒素導入管の付いた反応缶に、多価カルボン酸成分としてイソフタル酸297.5部(1.791mol)、5-スルホイソフタル酸ジメチルナトリウム52.5部(0.177mol)、ポリオール成分としてジエチレングリコール(b1)216.3部(2.038mol)、ネオペンチルグリコール(b2)33.8部(0.325mol)、触媒としてテトラブチルチタネート0.3部(全共重合成分に対して511ppm)を仕込み、内温200~260℃まで2時間かけて昇温し、260℃で2時間エステル化反応を行った。その後、触媒としてテトラブチルチタネート0.3部仕込み、1hPaまで減圧し、1時間重縮合反応を行い、ポリエステル系樹脂[I’-3]を得た。
東ソー社製のHLC-8320を用いてGPC測定を行い、ポリスチレン換算から求めた。
TAインスツルメント社製の示差走査熱量計DSC Q20を用いて測定した。
ポリエステル系樹脂0.5gを7/3(トルエン/メタノール)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た。
調製した25wt%ポリエステル系樹脂水性液を室温で保管し、水性液が調製から分散状態を維持している期間により水性液の安定性を評価した。評価基準は以下の通りである。
◎:1ヶ月以上分散状態を維持した。
○:1週間~1ヶ月未満で水性液の流動性が失われた。または、沈殿が生じた。
×:1週間未満で水性液の流動性が失われた。または、沈殿が生じた。
IPA:イソフタル酸
TPA:テレフタル酸
SIPM:5-スルホイソフタル酸ジメチルナトリウム
PMAn:ピロメリット酸無水物
DEG:ジエチレングリコール
1.5PG:1,5-ペンタンジオール
1.6HG:1,6-ヘキサンジオール
NPG:ネオペンチルグリコール
EG:エチレングリコール
上記で調製したポリエステル系水性液に、下記表2に示す通りの種類、配合量の架橋剤を添加し、固形分3%となるように脱イオン水で希釈し、塗液を調製した。調製した塗液を、乾燥後の膜厚が下記表2に示す通りになるようにPETフィルム(東レ社製、ルミラーT60、厚み100μm)上にバーコーターにて塗布し、150℃で3分間乾燥させることで、プライマー層を形成した。
◎:35/36以上(残存個数/測定個数)
○:30/36以上、34/36以下
△:20/36以上、29/36以下
×:19/36以下
II-1:カルボジイミド基を有する架橋剤「カルボジライトV-04」(日清紡ケミカル社製)
II-2:イソシアネート基を有する架橋剤「エラストロンBN-77」(第一工業製薬社製)
Claims (10)
- 多価カルボン酸成分(A)とポリオール成分(B)とを含む共重合成分を共重合してなるポリエステル系樹脂であって、前記ポリオール成分(B)全体に対するエチレングリコールを除く直鎖構造のポリオール(b1)の含有割合が70モル%以上であり、酸価が10mgKOH/g以上であるポリエステル系樹脂を含有するプライマー組成物。
- 前記ポリオール成分(B)として、分岐構造を有する脂肪族ポリオールを含有する、請求項1記載のプライマー組成物。
- 前記多価カルボン酸成分(A)として、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(a1)を含有する、請求項1または2記載のプライマー組成物。
- 請求項1~3のいずれか1項記載のプライマー組成物が、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。
- 請求項4記載のポリエステル系水性液が架橋剤(C)を更に含有し、該架橋剤(C)によりポリエステル系樹脂が架橋されてなるプライマー層。
- 基材フィルム上に請求項5記載のプライマー層を有するプライマー層付き基材フィルム。
- 前記基材フィルムがポリエステルフィルムである、請求項6記載のプライマー層付き基材フィルム。
- 請求項6または7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。
- 請求項6または7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、無溶剤系活性エネルギー線硬化性樹脂組成物が硬化してなるプリズム層を有するプリズムシート。
- 請求項1記載のポリエステル系樹脂の製造方法であって、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(a1)を除く多価カルボン酸成分(A)とポリオール成分(B)からなる水酸基含有プレポリマーを、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(a1)で鎖延長させてなるものであるポリエステル系樹脂の製造方法。
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