JP2011184688A - Undercoat agent for plastic film with active energy ray-cured coating, and plastic film with active energy ray-cured coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an undercoat agent formable of an undercoat layer with high productivity, the undercoat layer well adhering to both of a cured film made of an active energy ray-curable material and a plastic film. <P>SOLUTION: The undercoat agent for a plastic film with an active energy ray-cured coating contains: a polyester resin (A) having a content of a carboxylate anion group of 0.3 to 1.5 mmol/g; a (meth)acrylate compound (B) having at least one carboxylate anion group; and a compound (C) having at least three aziridinyl groups. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention mainly relates to an undercoat agent used for closely bonding an active energy ray cured film and a plastic film.

  Plastic films made of thermoplastic resins such as polyester, polystyrene, and polyolefin are used in various industrial applications. In particular, polyester films are applied to various products because of their excellent mechanical strength and transparency.

  By the way, since a plastic film may be hard to adhere | attach with cured films, such as an ink and an adhesive agent, the improvement of adhesiveness is achieved by surface treatments, such as corona discharge and sandblasting. However, there is a limit to the effect, and there are problems such as a decrease in adhesion over time. Therefore, in this field, an easily adhesive undercoat layer may be provided in advance on the surface of the plastic film.

  However, an undercoat layer that adheres well to a plastic film is inferior in adhesion to a cured layer made of a material that cures with active energy (such as an ultraviolet curable resin such as pentaerythritol triacrylate). It has been empirically known that a good undercoat layer has poor adhesion to a plastic film. Therefore, a practical undercoat agent that is excellent in adhesiveness between both a cured film layer made of an active energy curable material and a plastic film is desired.

  Under such circumstances, as an undercoat agent having excellent adhesion, for example, Patent Document 1 discloses a composition comprising a solvent-soluble saturated polyester resin, a polyisocyanate, and an acrylate compound polymerized with active energy rays as essential components. However, the effect is not enough. In addition, this method requires a long pot life (about 1 to 6 days) in order to form an undercoat layer, so there are concerns about adverse effects on the polyester film as a base material, and it is also difficult in terms of productivity. There is.

Japanese Patent Laid-Open No. 3-121183

  The present invention provides an undercoat layer having excellent adhesion between a cured film made of an active energy ray-curable material and a plastic film (hereinafter simply referred to as adhesion) at a relatively low temperature for a short time. It is an object of the present invention to provide a novel undercoat agent that can be formed in a simple manner.

  As a result of intensive studies, the present inventor has found that the following problems can be solved by the following undercoat agent, and has completed the present invention.

  That is, the present invention relates to a polyester resin (A) having a carboxylate anion group content of 0.3 to 1.5 mmol / g, a compound (B) having an active energy ray polymerizable functional group and a carboxylate anion group, and An undercoat agent for a plastic film with an active energy ray-cured film containing the compound (C) having at least three aziridinyl groups; an undercoat layer comprising the undercoat agent on at least one surface of the plastic film, and active energy ray curing The present invention relates to a plastic film with an active energy ray-cured film, wherein the film layers are laminated in this order.

  The undercoat layer made of the undercoat agent of the present invention adheres well to both a cured film made of an active energy ray-curable material and a plastic film (particularly a polyester film). In addition, there is an unexpected effect that the adhesion is hardly lowered even under high temperature and high humidity.

  In addition, the undercoat layer can be obtained at a relatively low temperature and in a short time, so that it is particularly suitable for a thin plastic film, has low energy cost, and is excellent in productivity.

  Therefore, the undercoat agent can be used for various plastic films having an active energy ray cured film, such as a film for plate making, a film for packaging, a film for optical parts, a film for semiconductor processing tape, plastic fibers and sheets, and plastic molding. Suitable for the production of body etc.

  The undercoat agent according to the present invention comprises a polyester resin (A) having a carboxylate anion group content of 0.3 to 1.5 mmol / g (hereinafter referred to as component (A)), an active energy ray polymerizable functional group. And a compound (B) having a carboxylate anion group (hereinafter referred to as “component (B)”) and a compound (C) having at least three aziridinyl groups (hereinafter referred to as “component (C)”).

  The undercoat agent is characterized in that the components (A) to (C) are integrally crosslinked through a reaction between a carboxylate anion group and an aziridinyl group to form an undercoat layer. As a result, it is considered that the desired effect is achieved.

As the component (A), various known resins can be used without particular limitation as long as they are polyester resins having a carboxylate anion group (—COO ⁻ ). Further, the content of carboxylate anion group is 0.3 to 1.5 mmol / g, preferably 0.4 to 1.3 mmol / g. In addition, carboxylate anion group content means the millimol number of the carboxylate anion group contained in 1 g (nonvolatile matter conversion) of (A) component, and is a calculated value.

  Specific examples of the component (A) include dicarboxylic acids (a1) (hereinafter referred to as component (a1)), diols (a2) (hereinafter referred to as component (a2)), and triols (a3) used as necessary. ) (Hereinafter referred to as component (a3)) and a product obtained by neutralizing a reaction product of tricarboxylic acid (a4) (hereinafter referred to as component (a4)) is preferable.

  Specific examples of the component (a1) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, orthophthalic acid, diphenylmethane-4,4′-dicarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Aliphatic (unsaturated) dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, maleic acid, fumaric acid, succinic acid, citraconic acid; hexahydrophthalic acid , 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; monoalkyl esters or dialkyl esters thereof (both alkyl groups having about 1 to 3 carbon atoms); As for, its anhydride and the like can be mentioned. As the component (a1), the aromatic dicarboxylic acid contains at least one selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, and phthalic anhydride, particularly in terms of adhesion. It is preferable. Moreover, content of aromatic dicarboxylic acid in (a1) component is about 30-100 mol% normally.

  Specific examples of the component (a2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Aliphatic diols such as pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol; cyclohexanedimethanol, cyclohexanediol, water Aliphatic diols such as ethylene oxide adducts of bisphenol A added; aromatic diols such as catechol, resorcinol, xylylene glycol, bishydroxyethoxybenzene; other diols such as polyethylene glycol and polypropylene glycol Ruki glycol, and the like.

  The component (a3) is an optional component used for introducing a crosslinked structure or a branched structure into the component (A). By using this component, the carboxylate anion group content can be set to a relatively high value. It becomes easy. Specific examples thereof include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol and the like. Tetraols such as erythritol, sorbitol, pentaerythritol and dipentaerythritol may be used in combination.

  The component (a4) is an essential component used for imparting the carboxylate anion group content to the component (A), and specific examples thereof include trimellitic acid, trimellitic anhydride, trimesic acid, and the like. It is done. For the same purpose, a tetracarboxylic acid such as pyromellitic acid or pyromellitic anhydride may be used in combination.

  The amount of component (a1) to component (a4) used is not particularly limited, and is appropriately determined in consideration of the content of the carboxylate anion group and the like. Usually, when the total of the component (a1) and the component (a2) is 100 parts by weight, the component (a1) is about 30 to 70 parts by weight, and the component (a2) is about 70 to 30 parts by weight. Moreover, when using (a3) component, the quantity is about 0.5-5 weight part normally with respect to a total of 100 weight part of (a1) component and (a2) component. Moreover, the usage-amount of (a4) component is about 0.5-10 weight part normally with respect to a total of 100 weight part of (a1) component and (a2) component.

  The dehydration condensate obtained by reacting the component (a1), the component (a2) and, if necessary, the component (a3) can be obtained according to various known polyester production methods. Specifically, for example, the components may be reacted sequentially or simultaneously at about 160 to 250 ° C. for about 1 to 10 hours. A reaction product of the dehydration condensate and the component (a4) (hereinafter referred to as unneutralized polyester resin) can also be obtained at the same reaction temperature and reaction time. Both esterification reactions can be carried out under normal pressure or reduced pressure, and various known organic solvents and esterification catalysts can be used for both esterification reactions.

  Organic solvents include ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, methoxypropyl acetate, methyl cellosolve Examples thereof include ester organic solvents such as acetate and cellosolve acetate; ether organic solvents such as dioxane, diethyl ether and tetrahydrofuran; aprotic polar organic solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide.

  Examples of the esterification catalyst include antimony trioxide, tetrapropyl titanate, tetrabutyl titanate, tetrastearyl titanate, dibutyltin dilaurate, dibutyltin dichloride, zinc oxide, cobalt octylate, and the amount used is usually (a1). It is about 0 to 5 weight% with respect to the total weight of a component-(a4) component.

  Examples of basic compounds used for neutralizing unneutralized polyester resins include ammonia; volatilization of monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethylamine, diethylamine, monobutylamine, cyclohexylamine, aniline, arylamine, alkanolamine, and the like. Amines; alkali metal compounds such as sodium hydroxide and potassium hydroxide. Among these, it is preferable to use volatile amines, particularly triethylamine, because the undercoat layer can be obtained in a shorter time. The usage-amount of a basic compound is a ratio of about 80-300 mol% normally with respect to all the carboxyl groups which unneutralized polyester resin has.

  The component (A) thus obtained has a glass transition temperature of usually about 0 to 80 ° C., preferably about 10 to 60 ° C. from the viewpoint of adhesion and the like. The number average molecular weight (polystyrene conversion value by gel permeation chromatography) is usually about 3,000 to 20,000, preferably about 5,000 to 18,000.

As the component (B), various known compounds can be used without particular limitation as long as they are compounds having an active energy ray-polymerizable functional group and a carboxylate anion group (—COO ⁻ ). Specific examples of the polymerizable functional group include one selected from the group consisting of a (meth) acryloyl group, an allyl group, an allyl ether group, an ethenyl group, and a vinyl ether group. In particular, the component (B) having a (meth) acryloyl group is preferable because it is easily available.

  Specific examples of the component (B) include neutralized monocarboxy mono (meth) acrylates (B-1) (hereinafter referred to as component (B-1)), neutralized monocarboxy poly (meth) acrylates. Product (B-2) (hereinafter referred to as component (B-2)) and neutralized product of (meth) acryloyl group-containing polyester (B-3) (hereinafter referred to as component (B-3), (B) -1) component, and one selected from the group consisting of (except for those corresponding to component (B-2)). The basic compound used for each neutralized product is the same as that used for the preparation of the component (A). For the same reason as described above, volatile amines, particularly triethylamine, are preferred. Moreover, the neutralization method is based on various known means.

  Examples of the monocarboxymono (meth) acrylates constituting the component (B-1) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acryloyloxyethyl succinate, and (meth) acryloyl. And oxybenzoic acid.

  Examples of the monocarboxy poly (meth) acrylates constituting the component (B-2) include polycarboxylic acids (b1) (hereinafter referred to as the component (b1)) and various hydroxyl group-containing (meth) acrylate compounds (b2). (Hereinafter referred to as the component (b2)). As the component (b1), for example, adipic acid, phthalic acid, (anhydrous) maleic acid, (anhydrous) succinic acid and the like are preferable. As the component (b1), the same components as the component (a1) and / or the component (a4) can be used. Specific examples of the component (b2) include glycerol di (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and the like. The monocarboxypoly (meth) acrylates may be, for example, commercially available products such as “Aronix M-510” and “Aronix M-520” (both manufactured by Toagosei Co., Ltd.).

  (B-3) Examples of the (meth) acryloyl group-containing polyester constituting the component include a hydroxyl group possessed by a dehydration condensate of the component (b1) and the polyol (b3) (hereinafter referred to as the component (b3)). And those obtained by reacting the component (B-1). In this case, as the component (b1), for example, adipic acid, phthalic acid, (anhydrous) maleic acid, (anhydrous) succinic acid and the like are preferable. Moreover, as (b2) component, the same thing as said (a2) component and / or (a3) component can be used, For example, glycerol, polyethyleneglycol, etc. are preferable. Moreover, as this (B-1) component, (meth) acrylic acid is preferable, for example. The (meth) acryloyl group-containing polyesters may be, for example, commercially available products such as “Aronix M-7100” and “Aronix M-8560” (both manufactured by Toagosei Co., Ltd.).

  In addition, as the component (B), for example, neutralized products of monovinyl monocarboxyl compounds such as vinyl benzoic acid, JP-A-1-268709, JP-A-8-301977, and JP-A-11-181021 are described. A neutralized product of the compound can be used.

  Although the physical property of (B) component is not specifically limited, When adhesiveness etc. are considered, carboxylate anion group content is about 0.1-14 mmol / g normally, Preferably it is 1-7 mmol / g. In addition, the said content means the millimol number of the carboxylate anion group contained in (B) component 1g (nonvolatile content conversion), and is a calculated value.

  Moreover, when adhesiveness etc. are considered, content of the active energy ray polymeric functional group in (B) component is about 50-500 eq / g normally, Preferably it is 80-300 eq / g. In addition, the said content means the equivalent (number) of the polymerizable functional group contained in 1g (nonvolatile content conversion) of (B) component, and is a calculated value.

  The component (C) is a component that reacts with both the component (A) and the component (B), and various known compounds can be used without particular limitation as long as the compound has at least three aziridinyl groups in the molecule. In view of adhesion, availability, etc., those represented by the following general formula (1) are particularly preferable.

(In Formula (1), X ¹ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylol group having 1 to 3 carbon atoms. R ¹ represents hydrogen or a methyl group. R ² and R ³ represent Each represents hydrogen or an alkyl group having 1 to 6 carbon atoms.)

  Examples of the compound represented by the formula include glycerol-tris [2-propyl- (1-aziridinyl)] propionate, trimethylolpropane-tris (1-aziridinylpropionate), tetramethylolmethane. -Tri- (β-aziridinyl propionate), trimethylolpropane tris (β-aziridinyl propionate), glyceryl tris (β-aziridinyl propionate) and the like.

  As the component (C) other than the general formula (1), there are other four functional groups such as tetraaziridinyl metaxylenediamine, tetraaziridinylmethylparaxylenediamine, and tetramethylpropanetetraaziridinylpropionate. Examples thereof include aziridine compounds and hexafunctional aziridine compounds described in JP-A No. 2003-104970.

  In addition, with (C) component, neopentyl glycol di (β-aziridinyl propionate), 4,4′-isopropylidenediphenol di (β-aziridinyl propionate), 4,4′-methylene Bifunctional aziridine compounds such as diphenoldi (β-aziridinylpropionate); aziridine, 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine Monofunctional aziridine compounds such as can be used in combination.

  The undercoat agent of the present invention can further contain a polyisocyanate curing agent (D) (hereinafter referred to as “component (D)”). As the component (D), aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate and other diisocyanate compounds (D) such as diisocyanate compounds (D), (D) component dimers, trimers and the like.

  The trimer includes a diisocyanate nurate (D-1) represented by the following general formula (2) and / or a diisocyanate adduct (D-2) represented by the general formula (3). included. By using these, the curing rate and hardness of the undercoat film can be suitably increased without impairing the stability (non-gelling property) of the undercoat agent.

(In formula (2), R ⁴ represents any one of an aromatic diisocyanate residue, an aliphatic diisocyanate residue, and an alicyclic diisocyanate residue.)

(In formula (3), R ⁵ represents an alkyl group having 1 to 3 carbon atoms or a functional group represented by OCN—R ⁶ —HN—C (═O) —O—CH ₂ —, and R ⁶ represents Represents an aromatic diisocyanate residue, an aliphatic diisocyanate residue, or an alicyclic diisocyanate residue.)

  Content of (A) component-(D) component in the undercoat agent of this invention is not specifically limited. For example, regarding the component (A) and the component (B), the content of the component (B) relative to 100% by weight (in terms of non-volatile content) of the component (A) is usually 0.5 to 30 from the viewpoint of adhesion and the like. % By weight, preferably 1 to 20% by weight. Further, regarding the relationship between the components (A) to (C), the amount of each used is xmol of the carboxylate anion group of the component (A) and the carboxylate anion of the component (B) from the viewpoint of adhesion and the like. When the group is ymol and the aziridinyl group of the component (C) is zmol, (x + y) / z is usually about 0.05 to 3, preferably 0.2 to 2.5. The The amount of component (D) used is not particularly limited, but is usually about 0 to 30% by weight, preferably 5 to 100% by weight (in terms of nonvolatile content) of components (A) to (C). 15% by weight.

  The undercoat agent of the present invention can be made into a non-aqueous undercoat agent using the organic solvent (preferably a ketone organic solvent) as a diluent solvent. The nonvolatile content is not particularly limited, but is usually 10 to 50% by weight in consideration of convenience of use.

  The undercoat agent of the present invention includes a leveling agent, an antiskid agent, an antiseptic agent, a rust inhibitor, a pH adjuster, an antioxidant, a pigment, a dye, a lubricant, an inorganic filler (colloidal silica, zinc oxide, calcium carbonate, barium sulfate). , Titanium oxide, kaolin, aluminum hydroxide, etc.), additives such as light stabilizers, ultraviolet absorbers, aziridinyl group ring-opening catalysts (paratoluenesulfonic acid, etc.) and the like may be blended.

  The plastic film with an active energy ray cured film of the present invention (hereinafter sometimes simply referred to as a laminated film) includes an undercoat layer comprising the undercoat agent of the present invention on at least one surface of the plastic film, and an active energy ray cured film layer. Are laminated in this order.

  Examples of the plastic film include a polystyrene film, a polycarbonate film, a polyester film, an ABS film, a polyvinyl chloride film, a polyester film, a polyolefin film, and a triacetyl cellulose film, and these are subjected to a surface treatment such as corona discharge. May be. Since the undercoat agent of the present invention is cured at a relatively low temperature, it can be suitably used even for a polyester film, particularly a polyethylene terephthalate (PET) film, which is generally inferior in heat resistance.

The undercoat layer is obtained by applying the undercoat agent of the present invention to the plastic film and drying it. Examples of the coating means include a roll coater, a reverse roll coater, a gravure coater, a knife coater, and a bar coater. The coating amount is usually about 0.01 to 10 g / m ² as a dry nonvolatile content. The film thickness is not particularly limited, but is usually about 0.1 to 10 μm. The drying temperature is usually from room temperature to about 150 ° C., and the drying time is usually from about 10 seconds to 3 minutes.

  The active energy ray-cured coating layer is obtained by applying various known active energy ray-curable materials on the undercoat layer by the above means and irradiating the active energy rays. The thickness of the cured film layer is not particularly limited, but is usually about 1 to 75 μm.

  The active energy ray curable material may be any of a monomer type, an oligomer type, and a polymer type. Specific examples include the component (B); the component (b2); 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, and cyclopentanyl (meth) acrylate. , Mono (meth) acrylates such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobonyl (meth) acrylate; 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate such as ethylene oxide modified di (meth) acrylate of bisphenol A Acrylates: trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( Examples thereof include compounds having at least three (meth) acryloyl groups such as (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and glycerol tri (meth) acrylate. An oligomer such as polyurethane poly (meth) acrylate and the polyester poly (meth) acrylate; a non-copolymer type material such as an acrylic resin having a plurality of polymerizable functional groups such as (meth) acryloyl groups and hydroxyl groups in the molecule. These may be a mixture of two or more.

  Among the active energy ray-curable materials, examples of the polymer type material include acrylic resins having a plurality of polymerizable functional groups such as (meth) acryloyl groups and hydroxyl groups in the molecule. As the acrylic resin, for example, a reaction product obtained by adding a carboxyl group-containing (meth) acrylic compound to a polymer obtained from a polymerizable compound containing an epoxy group-containing vinyl compound (JP 2009-286972 A, etc.) Browse) can be used. Examples of the epoxy group-containing vinyl compound include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether, and other polymerizable compounds include chain alkyl groups such as methyl methacrylate and ethyl methacrylate. Examples include (meth) acrylic acid esters. Examples of the carboxyl group-containing (meth) acrylic compound include acrylic acid and methacrylic acid. The physical properties of the reaction product are not particularly limited, but the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is about 9,000-60,000, and the (meth) acryl equivalent is about 210-780 g / eq. The acid value is about 0.1 to 5 mgKOH / g.

  In addition, various known polymerization initiators may be blended in the active energy ray-curable material. Specific examples include benzophenone-based polymerization initiators such as benzophenone, benzoylbenzoic acid, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, methyl benzoylbenzoate, phenylbenzophenone, trimethylbenzophenone and hydroxybenzophenone; phenoxydichloro Acetophenone polymerization initiators such as acetophenone, butyldichloroacetophenone, diethoxyacetophenone, hydroxymethylphenylpropanone, isopropylphenylhydroxymethylpropanone, hydroxycyclohexylphenylketone, hydroxycyclohexylphenylketone; thioxanthone, chlorothioxanthone, methylthioxanthone, isopropylthioxanthone , Dichlorothioxanthone, diethyl Okisanton, like thioxanthone type polymerization initiators such as diisopropyl thioxanthone. In addition, the said organic solvent and additive may be mix | blended with the said material.

Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the supply source of ultraviolet rays include a high-pressure mercury lamp and a metal halide lamp, and the supply amount is usually about 100 to 2,000 mJ / cm ² . Examples of the electron beam supply method include scanning electron beam irradiation and curtain electron beam irradiation method, and the irradiation energy is usually about 10 to 200 kGy.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these. In each example, parts and% are based on weight unless otherwise specified.

Production Example 1
<Manufacture of (A) component>
In a reaction vessel equipped with a stirrer, a cooler, a thermometer and a nitrogen gas introduction tube, 480 parts of terephthalic acid, 432 parts of isophthalic acid, 54 parts of azelaic acid, 256 parts of ethylene glycol, 355 parts of 1,6-hexanediol and glycerin 23 parts were charged and the reaction system was heated with stirring to melt them. Next, while removing water produced by the dehydration condensation reaction, the reaction system was gradually heated from 160 ° C. to 200 ° C. over 3 hours, and further kept at 200 ° C. for 1 hour. Next, 0.16 part of antimony trioxide was added. Next, a vacuum decompression apparatus was connected to the reaction vessel, and a reduced pressure polycondensation reaction was performed at 235 ° C. and 2.8 kPa for 1 hour. Subsequently, the reduced pressure state was released, the reaction system was cooled to 150 ° C., 207 parts of trimellitic anhydride was charged into the reaction system, and the temperature was kept for 1 hour. Next, 466 parts of methyl isobutyl ketone and 466 parts of methyl ethyl ketone were added and dissolved uniformly. Thus, the non-volatile content is 60%, the carboxylate anion group content (calculated from the raw material charge weight) is 1.3 mmol / g, and the glass transition temperature (product name “DSC6200” manufactured by Seiko Instruments Inc.) The measured value by. The same applies hereinafter. ) Is a polyester resin having a number average molecular weight of 5,000 at 17 ° C. and a number-average molecular weight (gel permeation chromatography device (product name “HLC-8220GPC”: manufactured by Tosoh Corporation), hereinafter the same). A solution of A-1) was obtained.

Production Examples 2-6, Comparative Production Example 1
A solution of polyester resins (A-2) to (A-6) and (A) was obtained in the same manner as in Production Example 1, except that the composition was changed to the composition shown in Table 1.

In Table 1, each symbol has the following meaning.
TPA: terephthalic acid IPA: isophthalic acid AZE: azelaic acid CHDA: cyclohexanedicarboxylic acid EG: ethylene glycol 1,6HG: 1,6 hexanediol NPG: neopentyl glycol BEPD: 2-butyl-2-ethyl-1,3-propane Diol CHDM: Cyclohexanedimethanol Gly: Glycerin TMP: Trimethylolpropane TMAn: Trimellitic anhydride C: Carboxylate anion group content (mmol / g)
Tg: Glass transition temperature (° C)
Mn: Number average molecular weight

<Preparation of undercoat agent>
Example 1
To 100 parts of the polyester resin (A-1) solution obtained in Production Example 1 (60% non-volatile content), 1.2 parts of 2-carboxyethyl acrylate and 6.2 parts of triethylamine (TEA) were used as the component (B). Added and mixed. Next, 13.4 parts of trimethylolpropane tris- (β-aziridinyl propionate) as component (C) was added to the solution, diluted with 178 parts of methyl ethyl ketone, and an undercoat agent having a nonvolatile content of 25%. Got.

Examples 2-27, Comparative Examples 1-14
An undercoat agent was obtained in the same manner as in Example 1 except that the raw material type and the amount used were changed to those shown in Table 2 (both had a nonvolatile content of 25%).

Example 28
After adding 6 parts of component (B) and 6.2 parts of TEA shown in Table 1 to 100 parts of solution of component (A-1) (nonvolatile content 60%), the solution shown in Table 1 is shown in Table 1 (C) 13.8 parts of component and 18.7 parts of isophorone diisocyanate as component (D) were added and diluted with 230.6 parts of methyl ethyl ketone to obtain an undercoat agent having a nonvolatile content of 25%.

<Preparation of active energy ray-curable resin composition>
70 parts of commercially available polyester acrylate (trade name “Aronix M-9050” manufactured by Toagosei Co., Ltd.), 30 parts of 1,6-hexanediol acrylate (trade name “HDDA” manufactured by Daicel Cytec Co., Ltd.), Hikari Mix well 5 parts of the initiator (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1 part of the silicone leveling agent (trade name “BYK340” manufactured by Big Chemie Japan Co., Ltd.). Then, an ultraviolet curable composition was prepared.

<Preparation of laminated film>
The undercoat agent according to Example 1 was applied to a commercially available PET film (trade name “Lumirror T60” manufactured by Toray Industries, Inc.) with a bar coater so that the dry film thickness was 1 μm, and dried at 120 ° C. for 30 seconds. I let you. Next, the ultraviolet curable resin composition was applied to the undercoat surface with a bar coater so that the film thickness after curing was 5 μm. Next, a laminated film was produced by passing the coated film under the high-pressure mercury lamp (80 W, mercury lamp height 10 cm, transport speed 10 m / min) three times in the air. A laminated film was similarly prepared for the undercoat agents of Examples 2-28 and Comparative Examples 1-14.

Example 29
The undercoat agent according to Example 2 was applied to Lumirror T60 with a bar coater so that the dry film thickness was 1 μm, and dried at 120 ° C. for 30 seconds. Next, an ultraviolet curable resin (trade name “BS700”, manufactured by Arakawa Chemical Industries, Ltd.) mainly composed of dipentaerythritol polyacrylate is diluted with ethyl acetate as an ultraviolet curable resin on the undercoat surface. A solution obtained by adding 5 parts of Irgacure 184 to the resulting solution (non-volatile content 80% by weight) was applied with a bar coater so that the film thickness after curing was 5 μm, and then the film was dried at 80 ° C. for 30 seconds. Next, a laminated film was produced under the conditions described above.

<Initial adhesion>
In accordance with JIS 5400, a 100 mm square of 1 mm square was formed on the laminated film according to Example 1, and then an adhesive tape was applied, which was rapidly peeled off in the vertical direction. Next, the adhesion was evaluated according to the following criteria based on the remaining amount of the cured film. The adhesion was evaluated in the same manner for the laminated films of other examples and comparative examples.
6: 90% or more remains
5: 80% or more and less than 90% remain
4: 70% or more and less than 80% remain
3: More than 60% and less than 70% remain
2: 50% or more and less than 60% remain
1: Less than 50% remains

<Durable adhesion>
After the laminated film according to Example 1 was left in a constant temperature and humidity chamber (60 ° C., 95% RH) for 4 days, the adhesion of the cured film was evaluated according to the following criteria by the same method as the initial adhesion. The adhesion was evaluated in the same manner for the laminated films of other examples and comparative examples.
6: 90% or more remaining 5: 80% or more but less than 90% remaining 4: 70% or more but less than 80% remaining 3: 60% or more but less than 70% remaining 2: 50% or more but less than 60% remaining 1:50 <% Remains

In Table 2, each symbol has the following meaning.
β-CEA: 2-carboxyethyl acrylate (trade name “β-CEA”: manufactured by Daicel Cytec Co., Ltd., carboxylate anion group content 6.5 mmol / g, acryloyl group content 144 eq / g)
M-510: Acid-modified acrylate oligomer (trade name “Aronix M-510”: manufactured by Toagosei Co., Ltd., carboxylate anion group content 1.6 mmol / g)
M-520: Acid-modified acrylate oligomer (trade name “Aronix M-520”: manufactured by Toagosei Co., Ltd., carboxylate anion group content 0.43 mmol / g)
M-7100: Polyester acrylate oligomer (trade name “Aronix M-7100”: manufactured by Toagosei Co., Ltd., carboxylate anion group content 0.18 mmol / g)
M-8560: Polyester acrylate oligomer (trade name “Aronix M-8560”: manufactured by Toagosei Co., Ltd., carboxylate anion group content 0.19 mmol / g)
M-306: Pentaerythritol triacrylate (trade name “Aronix M-306”, manufactured by Toagosei Co., Ltd., carboxylate anion group content 0 mmol / g)
HEA: hydroxyethyl acrylate

PZ-33: Commercially available triaziridine-based crosslinking agent (trimethylolpropane tris (β-aziridinyl propionate): trade name “PZ-33”: manufactured by Nippon Shokubai Co., Ltd.)
TAZO: Commercially available triaziridine-based crosslinking agent (tetramethylolmethane-tri- (β-aziridinylpropionate)): trade name “TAZO”: manufactured by Mutual Yakuhin Co., Ltd.)
EX-622: Commercially available epoxy-based crosslinking agent (trade name “Denacol EX-622”: manufactured by Nagase ChemteX Corporation)
V-7: Commercially available carbodiimide crosslinking agent (trade name “Carbodilite V-07”: manufactured by Nisshinbo Industries, Inc.)

Claims (14)

A polyester resin (A) having a carboxylate anion group content of 0.3 to 1.5 mmol / g, an active energy ray-polymerizable functional group and a compound (B) having a carboxylate anion group, and at least 3 aziridinyl groups An undercoating agent for a plastic film with an active energy ray-cured film, which comprises a compound (C) having two. Component (A) is obtained by neutralizing a reaction product of a dehydration condensate composed of dicarboxylic acids (a1), diols (a2), and triols (a3) used as necessary, and tricarboxylic acids (a4). The undercoat agent according to claim 1, wherein The undercoat agent according to claim 1 or 2, wherein the component (a1) contains an aromatic dicarboxylic acid. (A) The undercoat agent in any one of Claims 1-3 whose glass transition temperature of a component is 0-80 degreeC. The number average molecular weight of (A) component is 3,000-20,000, The undercoat agent in any one of Claims 1-4. (B) The undercoat agent in any one of Claims 1-5 whose active energy ray polymeric functional group of a component is a (meth) acryloyl group. Component (B) is a neutralized product of monocarboxymono (meth) acrylates (B-1), a neutralized product of monocarboxypoly (meth) acrylates (B-2), and a (meth) acryloyl group-containing polyester. The undercoat agent according to any one of claims 1 to 6, which is one selected from the group consisting of a neutralized product (B-3). (B) The undercoat agent in any one of Claims 1-7 whose content of the carboxylate anion group in a component is 0.1-14 mmol / g. The undercoat agent according to claim 1, wherein the component (C) is represented by the general formula (1).
(In Formula (1), X ¹ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylol group having 1 to 3 carbon atoms. R ¹ represents hydrogen or a methyl group. R ² and R ³ represent Each represents hydrogen or an alkyl group having 1 to 6 carbon atoms.) The undercoat agent according to any one of claims 1 to 9, wherein the content of the component (B) with respect to 100% by weight (in terms of nonvolatile content) of the component (A) is 0.5 to 30% by weight. In the case where the carboxylate anion group of the component (A) is xmol, the carboxylate anion group of the component (B) is ymol, and the aziridinyl group of the component (C) is zmol, (x + y) / z is 0.05 to 3 The undercoat agent according to any one of claims 1 to 10, which is 0.0. Furthermore, the undercoat agent in any one of Claims 1-11 containing a polyisocyanate type hardening | curing agent (D). The plastic film with an active energy ray cured film which the undercoat layer which consists of an undercoat agent in any one of Claims 1-12, and an active energy ray cured film layer are laminated | stacked in this order on the at least single side | surface of a plastic film. The plastic film with an active energy ray cured film according to claim 13, wherein the plastic film is a polyethylene terephthalate film.