KR101812998B1 - An undercoat agent for a plastic film with a cured thin film which is set by the radiation of actinic-energy-ray and a plastic film with a cured thin film which is set by the radiation of actinic-energy-ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an undercoating agent capable of forming a cured film formed from an active energy ray-curable material and an undercoat layer closely adhering to both sides of a plastic film.
(A) a polyester resin (A) having a carboxylate anion group content of 0.3 to 1.5 mmol / g, a (meth) acrylate compound (B) having at least one carboxylate anion group and an aziridinyl group at least 3 Is used as the undercoating film for a plastic film.

Description

TECHNICAL FIELD [0001] The present invention relates to a plastic film comprising an undercoat agent for a plastic film and an active energy ray-curable film containing an active energy ray-curable film, and a plastic film with a cured thin film which is set by the actinic-energy-ray}

The present invention relates to an undercoat agent mainly used to adhere a plastic film layer to an active energy radiation cured film layer.

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

However, since the plastic film may be difficult to adhere to the cured film such as ink or adhesive, adhesion of the plastic film is improved by surface treatment such as corona discharge or sandblast. However, there is a limit to the effect, and there is a problem that the adhesion is deteriorated over time. Therefore, in the art, an undercoat layer having a reverse adhesion (adhesion) is provided in advance on the surface of a plastic film.

However, the undercoat layer closely adhered to the plastic film has poor adhesion to the cured layer formed from a material (such as ultraviolet curable resin such as pentaerythritol triacrylate) that is cured by an active energy ray, and on the contrary, A good undercoat layer is known to have poor adhesion to plastic films. As a result, a practical undercoat excellent in adhesiveness to both the cured coating layer of the photo-curing material and both of the plastic film is desperate.

Under such circumstances, for example, Patent Document 1 discloses a composition comprising, as an essential component, a solvent-soluble saturated polyester resin, a polyisocyanate, and an acrylate compound polymerized with an active energy ray as an undercoat agent having such excellent adhesion, The effect is not enough. In addition, since a long pot life (about 1 to 6 days) is required in order to form an undercoat layer in this method, the polyester film as a base material adversely affects not only productivity but also productivity.

Patent Document 1: JP-A-3-121183

The present invention relates to a cured film which is formed from an active energy ray-curable material and which is capable of forming an undercoat layer having excellent adhesiveness (hereinafter, simply referred to as simply adhesion property) to both of the cured film and the plastic film at a relatively low temperature in a short period of time. And to provide an undercoating agent.

As a result of intensive studies, the inventors of the present invention have found that the following undercoating agent can solve the above-mentioned problems and accomplish 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 aziridinyl group An undercoat layer formed from the undercoating agent and an active energy ray-cured coating layer formed on the at least one side of the plastic film, the active energy ray- And a plastic film comprising an active energy ray cured coating formed by laminating in order.

The undercoat layer formed from the undercoating agent of the present invention closely adheres to both the cured coating formed from the active energy ray-curable material and the plastic film (especially the polyester film). In addition, there is also an unexpected effect that the adhesiveness does not deteriorate even in a high temperature and high humidity environment.

In addition, since the undercoat layer can be obtained at a relatively low temperature in a short time, it is not only suitable for a plastic film of a thin film but also has a low energy cost and excellent productivity.

Therefore, the undercoating agent can be used for various plastic films having an active energy rays hardening film, such as plate-making films, packaging films, films for optical parts, films for semiconductor processing tapes, ≪ / RTI >

The undercoating 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 carboxyl (B) (hereinafter referred to as component (B)) having at least three anion groups and a compound (C) having at least three aziridinyl groups (hereinafter referred to as component (C)).

The undercoating agent is characterized in that the components (A) to (C) are subjected to a cross-linking reaction integrally through a reaction between a carboxylate anion group and an aziridinyl group to form an undercoat layer. As a result, The effect of which is shown in Fig.

As the component (A), any known polyester resin having a carboxylate anion group (-COO ^- ) can be used without any particular limitation. The content of the carboxylate anion group is 0.3 to 1.5 mmol / g, preferably 0.4 to 1.3 mmol / g, and if it is out of the range, the adhesion is not good. On the other hand, the carboxylate anion group content is a calculated value that refers to the number of millimoles (mmol) of the carboxylate anion groups contained in 1 g of the component (A) (in terms of the nonvolatile component).

Specific examples of the component (A) include dicarboxylic acids (a1) (hereinafter referred to as component (a1)), diol (a2) (hereinafter referred to as component (a2) (Hereinafter referred to as a component (a4)) and a tricarboxylic acid (a4) (hereinafter referred to as a component (a4)) are neutralized.

Specific examples of the component (a1) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, orthophthalic acid and diphenylmethane-4,4'-dicarboxylic acid; aromatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, (Unsaturated) dicarboxylic acids such as succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, sebacic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, maleic acid, fumaric acid and citraconic acid; Alicyclic dicarboxylic acids such as hexane dicarboxylic acid and 1,2-cyclohexane dicarboxylic acid; alkyl esters or dialkyl esters thereof (all having about 1 to 3 carbon atoms in the alkyl group); And anhydrous compounds. As the component (a1), it is preferable that the aromatic dicarboxylic acid contains at least one member selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate and phthalic anhydride from the viewpoint of adhesion and the like. The content of the aromatic dicarboxylic acid in the component (a1) is usually about 30 to 100 mol%.

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, , Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and 2-methyl-1,3-propanediol; aliphatic diols such as cyclohexanedimethanol, cyclohexanediol, Alicyclic diols such as ethylene oxide adducts of ethylene oxide, ethylene oxide adducts of ethylene oxide and ethylene oxide adducts of ethylene oxide, ethylene oxide adduct of ethylene oxide and ethylene oxide adduct of ethylene oxide, ethylene oxide adduct of ethylene oxide and ethylene oxide adduct of ethylene oxide, And the like.

The component (a3) is an optional component used for introducing a crosslinking structure or a branched structure into the component (A), and by using this, it becomes easy to set the carboxylate anion group content to a relatively high value. Specific examples thereof include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol and 1,2,4-butanetriol. In addition, tetraols such as erythritol, sorbitol, pentaerythritol, and dipentaerythritol can 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, and trimethic acid. In addition, tetracarboxylic acids such as pyromellitic acid and pyromellitic anhydride can be used in combination for the same purpose.

The amount of the components (a1) to (a4) to be used is not particularly limited and is appropriately determined in consideration of the content of the carboxylate anion groups and the like. The amount of the component (a1) is about 30 to 70 parts by weight, and the amount of the component (a2) is about 70 to 30 parts by weight, when the total of the components (a1) and (a2) is 100 parts by weight. When the component (a3) is used, the amount thereof is usually about 0.5 to 5 parts by weight based on 100 parts by weight of the total of the components (a1) and (a2). The amount of the component (a4) used is usually about 0.5 to 10 parts by weight based on 100 parts by weight of the total of the components (a1) and (a2).

The dehydrating condensation product 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. Concretely, for example, each component may be reacted sequentially or simultaneously at about 160 to 250 ° C for about 1 to 10 hours. A reaction product of the dehydrated condensate and the component (a4) (hereinafter referred to as an un-neutralized polyester resin) can also be obtained at the same reaction temperature and reaction time. The esterification reaction can be carried out under atmospheric pressure or reduced pressure, and various known organic solvents or esterification catalysts can be used in the esterification reaction.

Examples of the organic solvent include ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, , Ester organic solvents such as methyl cellosolve acetate and cellosolve acetate, ether organic solvents such as dioxane, diethyl ether and tetrahydrofuran, organic solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide Nonpolar polar organic solvents and the like.

Examples of the esterification catalyst include antimony trioxide, tetrapropyl titanate, tetrabutyl titanate, tetra stearyl titanate, dibutyl tin dilaurate, dibutyl tin dichloride, zinc oxide, and cobalt octyl. is about 0 to 5% by weight based on the total weight of the components (a1) to (a4).

Examples of the alkaline compound used for neutralization of the neutralized polyester resin include ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethylamine, diethylamine, monobutylamine, cyclohexylamine, aniline, Volatile amines such as arylamine and alkanolamine; and alkali metal compounds such as sodium hydroxide and potassium hydroxide. Of these, use of volatile amines, particularly triethylamine, is preferable from the viewpoint that an undercoat layer can be obtained in a shorter time. The amount of the alkaline compound to be used is usually about 80 to 300 mol% with respect to all the carboxyl groups possessed by the non-neutralized polyester resin.

The component (A), which can be obtained as described above, usually has a glass transition temperature of about 0 to 80 캜, preferably about 10 to 60 캜, from the viewpoint of adhesion and the like. In addition, the number average molecular weight (polystyrene conversion value by gel permeation chromatography) is usually about 3,000 to 20,000, and preferably about 5,000 to 18,000.

As the component (B), any known compound may be used without particular limitation, as long as it is a compound having an active energy-ray-polymerizable functional group and a carboxylate anion group (-COO ^- ). Specific examples of the polymerizable functional group include a group selected from the group consisting of a (meth) acryloyl group, an allyl group, an aryl ether group, an ethenyl group, and a vinyl ether group. Particularly, the component (B) having a (meth) acryloyl group is preferable from the viewpoint of availability.

Specific examples of the component (B) include a neutralized product of a monocarboxy mono (meth) acrylate (B-1) (hereinafter referred to as a component (B-1)), a neutralized product of a monocarboxy poly (meth) 3) (hereinafter referred to as (B-3)) component (B-2) (hereinafter referred to as component (B-2)) and neutralized product 1) component, and the component (B-2) are excluded). The basic compound used in each of the neutralizers is the same as that used for the preparation of the component (A), and for the same reasons, volatile amines, especially triethylamine, are preferred. In addition, the neutralization method is based on various known means.

(Meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acryloyloxyethyl, succinic acid (meth) acryloyloxyethyl, And benzoic acid benzoic acid.

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

Examples of the (meth) acryloyl group-containing polyesters constituting the component (B-3) include polyesters having a dehydration condensation product of the component (b1) and the polyol (b3) And the component (B-1) is reacted with a hydroxyl group. In this case, examples of the component (b1) include adipic acid, phthalic acid, (maleic anhydride) and (anhydrous) succinic acid. The component (b2) may be the same as the component (a2) and / or the component (a3), for example, glycerin or polyethylene glycol. As the component (B-1), for example, (meth) acrylic acid is preferable. The above-mentioned (meth) acryloyl group-containing polyesters may be commercially available products such as "Aronix M-7100" and "Aronix M-8560" (all manufactured by Toagosei Co., Ltd.).

In addition, examples of the component (B) include neutralized monovinyl monocarboxylic compounds such as vinylbenzoic acid, and compounds disclosed in Japanese Patent Application Laid-Open Nos. 1-268709, 8-301977, 11-181021 And the like can be used.

The physical properties of the component (B) are not particularly limited, but the carboxylate anion group content is usually about 0.1 to 14 mmol / g, preferably 1 to 7 mmol / g, in view of adhesiveness and the like. Incidentally, the above-mentioned content is a calculated value which refers to the number of millimoles of carboxylate anion groups contained in 1 g of component (B) (converted to nonvolatile components only).

In view of adhesion and the like, the content of the active energy ray polymerizable functional group in the component (B) is usually about 50 to 500 eq / g, preferably 80 to 300 eq / g. Incidentally, the above-mentioned content is a calculated value referring to the equivalent (number) of the polymerizable functional groups contained in 1 g of the component (B) (converted only into the non-volatile component).

The component (C) is a component which reacts with both the component (A) and the component (B), and any known compound can be used without particular limitation, provided that the compound has at least three aziridinyl groups in the molecule. In view of adhesiveness and availability, it is particularly preferable to be one represented by the following formula (1).

(In the 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 each represent hydrogen or an alkyl group having 1 to 6 carbon atoms.

Examples of the compound represented by Formula 1 include glycerol tris [2-propyl- (1-aziridinyl)] propionate, trimethylolpropane tris (1-aziridinylpropionate), tetramethylol methane Tri- (? - aziridinyl propionate), trimethylolpropane tris (? - aziridinyl propionate) and glyceryl tris (? - aziridinyl propionate).

In addition, quaternary functional aziridine compounds such as tetraaziridinyl methaxylenediamine, tetraaziridinylmethylparaxylenediamine and tetramethylpropane tetraaziridinyl propionate, and hexafunctional aziridine compounds such as 6-functional aziridine compounds described in JP-A No. 2003-104970 Aziridine compounds and the like.

On the other hand, in addition to the component (C), neopentyl glycol di (β-aziridinyl propionate), 4,4'-isopropylidenediphenol di (β-aziridinyl propionate) Bifunctional aziridine compounds such as methylene diphenol di (β-aziridinyl propionate), aziridine, 2-methyl aziridine, 2-ethyl aziridine, 2,2- Aziridine, and 2-phenyl aziridine can be used in combination.

Further, the undercoating agent of the present invention may further contain a polyisocyanate-based curing agent (D) (hereinafter referred to as component (D)). Examples of the component (D) include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylene diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate; Diisocyanate compounds (D) such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diisocyanate; (D) Dimer, trimer, etc. of the component.

The trimer may include a diisocyanate nylate (D-1) represented by the following formula (2) and / or a diisocyanate adduct (D-2) represented by the following formula (3). By using these, the curing rate and hardness of the undercoat coating can be preferably increased without impairing the stability (non-gellability) of the undercoating agent.

(In the above formula (2), R ⁴ represents an aromatic diisocyanate residue, an aliphatic diisocyanate residue or an alicyclic diisocyanate residue.)

(Wherein 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 -

R ⁶ represents an aromatic diisocyanate residue, an aliphatic diisocyanate residue or an alicyclic diisocyanate residue.)

In the undercoating agent of the present invention, the content of the component (B) relative to 100 wt% of the component (A) (in terms of the nonvolatile component) is not particularly limited, but is generally from 0.5 to 30 wt% %, Preferably 1 to 20 wt%.

The content of the component (A) to the component (C) is not particularly limited, but from the viewpoint of adhesion and the like, x mol of the carboxylate anion group of the component (A) and y mol of the carboxylate anion group of the component (B) (X + y) / z is in the range of usually about 0.05 to 3, preferably 0.2 to 2.5 when the aziridinyl group of the component (C) is represented by z mol. The amount of the component (D) to be used is not particularly limited, but is usually about 0 to 30% by weight based on 100% by weight of the total of the components (A) to (C) 5 to 15% by weight.

The undercoating agent of the present invention can be prepared as a non-aqueous (non-water-soluble) undercoat agent by applying the organic solvent (preferably a ketone-based organic solvent) as a diluting solvent. The nonvolatile component is not particularly limited, but is usually 10 to 50% by weight from the viewpoint of ease of use.

The undercoating agent of the present invention may contain additives such as leveling agents, anti-slip agents, preservatives, waterproofing agents, pH adjusters, antioxidants, pigments, dyes, lubricants, inorganic fillers (colloidal silica, zinc oxide, calcium carbonate, barium sulfate, Aluminum hydroxide, etc.), a light stabilizer, an ultraviolet absorber and the like, and an aziridinyl ring-opening catalyst (para-toluenesulfonic acid, etc.).

The plastic film containing the active energy rays ray-cured coating of the present invention (hereinafter, simply referred to as a laminated film) has an undercoat layer and an active energy ray ray-cured coating layer, which are determined on the at least one side of the plastic film by the undercoat of the present invention, Are stacked 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. It may be processed. Since the undercoating agent of the present invention is cured at a relatively low temperature, a polyester film, in particular, a polyethylene terephthalate (PET) film, which is generally considered to have poor heat resistance, can be preferably used.

The undercoat layer can be obtained by applying the undercoating agent of the present invention to the plastic film and drying the undercoat layer. Examples of application 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 non-volatile component. The film thickness is not particularly limited, but is usually about 0.1 to 10 mu m. Further, the drying temperature is usually about room temperature to 150 ° C, and the drying time is usually about 10 seconds to 3 minutes.

The active energy ray cured coating layer can be obtained by applying an active energy ray-curable material to the undercoat layer by any of the known methods by the above means and irradiating the active energy ray. The thickness of the cured coating layer is not particularly limited, but is usually about 1 to 75 μm.

The active energy ray-curable material may be a monomer type, an oligomer type, a polymer type, or the like. Specific examples include the component (B), the component (b2), the component (b2), and the component (b2) (Meth) acrylates such as cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isobornyl (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A Di (meth) acrylates such as ethylene oxide modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, glycerol tri (meth) acrylate, etc. (Meth) acryloyl groups, and the like; oligomers such as polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, and the like A material having a non-conjugated polymer such as an acrylic resin having a plurality of functional groups and hydroxyl groups in the molecule, and these may be a mixture of two or more kinds.

Examples of the aggregate-type material in the active energy ray-curable material include an acrylic resin having a polymerizable functional group such as a (meth) acryloyl group and a plurality of hydroxyl groups in the molecule. As the acrylic resin, there may be mentioned, for example, a reaction product (see JP-A-2009-286972) produced by addition reaction of a carboxyl group-containing (meth) acrylic compound to an aggregate obtained from a polymerizable compound containing an epoxy group- Can be used. Examples of the epoxy group-containing vinyl compound include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and other polymerizable compounds such as methyl methacrylate, ethyl methacrylate (Meth) acrylate esters having a chain-type alkyl group. Examples of the carboxyl group-containing (meth) acrylic compound include acrylic acid and methacrylic acid. Although the physical properties of the reaction product are not particularly limited, the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is about 9,000 to 60,000, the (meth) acrylic equivalent is about 210 to 780 g / eq, To about 5 mg KOH / g.

The active energy ray-curable material may be blended with various known polymerization initiators. Specific examples thereof include benzophenone-based polymerization initiators such as benzophenone, benzoylbenzoic acid, o -benzoylbenzoic acid methyl ester, p -dimethylamino benzoic acid ester, methyl benzoylbenzoate, phenylbenzophenone, trimethylbenzophenone and hydroxybenzophenone; Acetophenone type polymerization initiators such as dichloroacetophenone, butyldichloroacetophenone, diethoxyacetophenone, hydroxymethylphenylpropanone, isopropylphenylhydroxymethylpropanone, hydroxycyclohexylphenylketone, and hydroxycyclohexylphenylketone; Thioxanthone polymerization initiators such as thioxanthone, chlorothioxanthone, methylthioxanthone, isopropylthioxanthone, dichlorothioxanthone, diethylthioxanthone and diisopropylthioxanthone, and the like can be used. . In addition, the organic solvent and the additive may be added to the material.

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

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, parts and percentages are by weight unless otherwise specified.

Manufacturing example  One

≪ Preparation of component (A) >

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 23 parts of glycerin were placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas introducing tube, The reaction system was heated to dissolve them. Subsequently, the reaction system was gradually heated from 160 DEG C to 200 DEG C for 3 hours while removing the water produced by the dehydration condensation reaction, and was further maintained at 200 DEG C for 1 hour. Then, 0.16 part of antimony trioxide was added. Then, a vacuum decompression device was provided in the reaction vessel, and a polycondensation reaction was carried out under reduced pressure at 235 DEG C and 2.8 kPa for 1 hour. Thereafter, the reduced pressure state was released, the reaction system was cooled to 150 DEG C, 207 parts of anhydrous trimellitic acid was added to the reaction system, and the mixture was kept warm for 1 hour. Then, 466 parts of methyl isobutyl ketone and 466 parts of methyl ethyl ketone were added to dissolve uniformly. Thus, the nonvolatile component was 60%, the carboxylate anion group content (calculated from the purchased weight of the raw material) was 1.3 mmol / g and the glass transition temperature (product name: DSC6200: manufactured by Seiko Instruments Inc.) (The same meaning as the following) means the value in terms of polystyrene according to a number average molecular weight (gel permeation chromatography apparatus (product name: "HLC-8220GPC": book) (A-1) solution having a weight average molecular weight of 5,000.

Manufacturing example  2 to 6, Comparative Manufacturing Example  One

Solutions of polyester resins (A-2) to (A-6) and (A) were prepared in the same manner as in Production Example 1, except that the composition of Table 1 was changed.

(A) Others (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (end)
(a1)
TPA 480 479 476 475 478 478 IPA 432 402 400 475 402 402 244 AZE 54 87 86 87 87 CHDA 591

(a2)

EG 256 256 264 254 279 279 79 1,6-HG 355 354 361 354 354 NPG 395 133 BEPD 82 CHDM 459 (a3)
Gly 23 23 TMP 13 11 (a4) TMAn 207 119 86 79 66 38 33 C 1.3 0.89 0.68 0.55 0.44 0.31 0.29 Tg 17 19 20 67 23 23 44 Mn 5,000 10,000 10,000 10,000 15,000 15,000 18,000

In Table 1, the symbols have the following meanings.

TPA: terephthalic acid

IPA: isophthalic acid

AZE: Azera phosphoric acid

CHDA: Cyclohexanedicarboxylic acid

EG: ethylene glycol

1,6-HG: 1,6-hexanediol

NPG: neopentyl glycol

BEPD: 2-butyl-2-ethyl-1,3-propanediol

CHDM: Cyclohexanedimethanol

Gly: glycerin

TMP: trimethylol propane

TMAn: Anhydrous trimellitic acid

C: carboxylate anion group content (mmol / g)

Tg (占 폚): glass transition temperature

Mn: number average molecular weight

< Undercoat  Preparation>

Example  One

1.2 parts of 2-carboxyethyl acrylate as a component (B) and 6.2 parts of triethylamine (TEA) were added to 100 parts of the solution of the polyester resin (A-1) obtained in Production Example 1 (nonvolatile component 60% Respectively. Next, 13.4 parts of trimethylolpropane tris (β-aziridinyl propionate) as a component (C) was added to the solution, and the solution was diluted with 178 parts of methyl ethyl ketone to obtain an undercoat composition having a nonvolatile component of 25% .

Example  2 to 27, Comparative Example  1 to 14

An undercoating agent was obtained in the same manner as in Example 1 except that the kinds and amounts of raw materials shown in Table 2 were changed (all nonvolatile components were 25%).

Example  28

6 parts of the component (B) shown in Table 1 and 6.2 parts of TEA were added to 100 parts (nonvolatile component 60%) of the solution of the component (A-1) , 18.7 parts of isophorone diisocyanate as a component (D), and 230.6 parts of methyl ethyl ketone were diluted to obtain an undercoating agent having a nonvolatile component of 25%.

< Active energy ray  Preparation of curable resin composition &gt;

70 parts of a commercially available polyester acrylate (trade name: Aronix M-9050: manufactured by TOAGOSU SEIYU K.K.), 1,6-hexanediol acrylate (trade name: HDDA: Dicer Cytech Co., , 5 parts of a photoinitiator (trade name: Irgacure 184, manufactured by Chiba Specialty Chemicals Co., Ltd.) and 1 part of a silicone leveling agent (trade name: BYK340: manufactured by Vick Chemical Co., To prepare an ultraviolet ray curable composition.

&Lt; Fabrication of laminated film &

The undercoating agent obtained in Example 1 was applied to a commercially available PET film (trade name: &quot; Lumirra T60 &quot;: manufactured by Toray Industries, Inc.) with a bar coater so as to have a film thickness of 1 mu m after drying and dried at 120 DEG C for 30 seconds . Then, the above ultraviolet-curable resin composition was coated on the undercoat side with a bar coater so that the film thickness after curing was 5 占 퐉. Then, the coated film was passed through the atmosphere three times under a high-pressure mercury lamp (80 W, mercury lamp height: 10 cm, conveying speed: 10 m / min) to produce a laminated film. The undercoating agents of Examples 2 to 28 and Comparative Examples 1 to 14 were also formed as described above to produce a laminated film.

Example  29

The undercoating agent prepared in Example 2 was applied to a laminate T60 using a bar coater so as to have a dry film thickness of 1 占 퐉 and dried at 120 占 폚 for 30 seconds. Then, on the undercoat side, dipentaerythritol poly (Nonvolatile component 80% by weight) obtained by diluting an ultraviolet-curable resin (trade name: BS700, manufactured by Arakawa Chemical Industries, Ltd.) having an acrylate as a main component diluted with ethyl acetate was added with 5 parts of Irgacure 184 , And the coating was applied with a bar coater so that the film thickness after curing was 5 mu m, and then the film was dried at 80 DEG C for 30 seconds. Subsequently, a laminated film was produced under the above-mentioned conditions.

&Lt; Initial adhesion &

In accordance with JIS 5400, a 1-mm mass was formed on a laminate film prepared in Example 1 on a substrate ranch in an amount of 100 sheets, and then an adhesive tape was stuck thereon and rapidly peeled off in the vertical direction. Then, the adherence of the cured film to the remaining amount was evaluated according to the following criteria. The laminated films of other examples and comparative examples were also evaluated in the same manner as above.

6: 90% or more remains

5: 80% to less than 90% remain

4: 70% or more and less than 80% remain

3: 60% to less than 70% remain

2: 50% to less than 60% remain

1: Less than 50% remains

&Lt; Durability &gt;

The laminated film prepared in Example 1 was allowed to stand in a constant temperature and humidity bath (60 DEG C, 95% RH) for 4 days, and then the adhesion of the cured film was evaluated by the following criteria in the same manner as the adhesion evaluation described above. The adhesion of the laminated films of other examples and comparative examples was also evaluated in the same manner as described above.

6: 90% or more remains

5: 80% to less than 90% remain

4: 70% or more and less than 80% remain

3: 60% to less than 70% remain

2: 50% to less than 60% remain

1: Less than 50% remains

(A) Others (B) Others (C) Others

(D)
Initial contact My cram
Cling A-1 A-2 A-3 A-4 A-5 A-6 end
B-1 B-2 B-3 M-306 HEA PZ-33 TAZO EX-622 V-07 β-CEA M-510 M-520 M-7100 M-8560 Example 1 100 6 19.2 0.67 5 5 Example 2 100 6 13.8 0.67 6 6 Example 3 100 6 11.0 0.67 6 6 Example 4 100 6 9.4 0.67 6 6 Example 5 100 6 7.9 0.67 6 6 Example 6 100 6 6.2 0.67 5 5 Example 7 100 6 20.3 0.67 6 6 Example 8 100 6 12.3 0.67 5 5 Example 9 100 6 12.0 0.67 5 5 Example
10 100 6 12.0 0.67 5 5 Example
11 100 1.2 13.4 0.67 6 6 Example
12 100 1.2 12.1 0.67 6 6 Example
13 100 1.2 11.8 0.67 6 6 Example
14 100 1.2 11.8 0.67 6 6 Example
15 100 1.2 11.8 0.67 6 6 Example
16 100 6 27.6 0.33 6 6 Example
17 100 12 28.8 0.67 6 6 Example
18 100 12 15.9 0.67 6 6 Example
19 100 18 15.9 0.67 6 6 Example
20 100 6 20.3 0.67 6 6 Example
21 100 6 13.8 0.67 6 6 Example
22 100 6 12.0 0.67 6 6 Example
23 100 6 12.0 0.67 6 6 Example
24 100 6 6.9 1.33 6 6 Example
25 100 6 3.1 2.67 5 4 Example
26 100 6 41.3 0.22 6 6 Example
27 100 6 55.0 0.16 5 5 Example
28 100 6 13.8 0.67 18.7 6 6 Example
29 100 6 13.8 0.67 6 6 Comparative Example 1 100 6 5.9 0.67 2 One Comparative Example 2 6 5.9 0.67 One One Comparative Example 3 6 5.9 0.67 One One Comparative Example 4 6 5.9 0.67 One One Comparative Example 5 100 6 0 - One One Comparative Example 6 100 6 0 - One One Comparative Example 7 100 6 0 - One One Comparative Example 8 100 6 0 - One One Comparative Example 9 100 1.2 11.7 0.67 4 3 Comparative Example
10 100 6 11.7 0.67 3 2 Comparative Example
11 100 6 11.7 0.67 3 2 Comparative Example
12 100 11.7 0.67 One One Comparative Example
13 100 6 18.1 0.67 One One Comparative Example
14 100 6 35.2 0.67 One One

In Table 2, symbols have the following meanings.

β-CEA: carboxylate anion group content: 6.5 mmol / g, acryloyl group content: 144 eq / g) (trade name "β-CEA" manufactured by Daicel-Cytec Corporation)

M-510: Acid-modified acrylate oligomer (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., content of carboxylate anion group: 0.18 mmol / g)

M-8560: polyester acrylate oligomer (trade name: ARONIX M-8560, manufactured by TOAGOSEI CO., LTD., Content of carboxylate anion group: 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: commercial triaziridine crosslinking agent (trimethylolpropane tris (? -Aziridinyl propionate): trade name: "PZ-33" manufactured by Nippon Shokubai Co., Ltd.)

TAZO: commercially available triaziridine crosslinking agent (tetramethylol methane tri (? -Aziridinyl propionate): trade name: TAZO: manufactured by Sogo Kako Co., Ltd.)

EX-622: commercially available epoxy cross-linking agent (trade name &quot; Denacor EX-622 &quot; manufactured by Nagase &

V-07: commercially available carboxyimide crosslinking agent (trade name &quot; CarboxyLite V-07 &quot;: manufactured by Nisshinbo Industries,

Claims (14)

(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 a compound having at least three aziridinyl groups ( C). &Lt; / RTI &gt;
(A1), diol (a2) and triol (a3) formed from a dicarboxylic acid (a1) and a diol (a2) And the reaction product of the terephthalic acid (a4) and the dehydrated condensate formed from the tricarboxylic acid (a4) is neutralized.
The undercoating agent according to claim 2, wherein the component (a1) contains an aromatic dicarboxylic acid.
The undercoat agent according to claim 1 or 2, wherein the component (A) has a glass transition temperature of 0 to 80 ° C.
The undercoat agent according to claim 1 or 2, wherein the number average molecular weight of the component (A) is from 3,000 to 20,000.
The undercoat agent according to claim 1 or 2, wherein the active energy-polymerizable functional group of the component (B) is a (meth) acryloyl group.
The composition according to claim 1 or 2, wherein the component (B) is a neutralized product of monocarboxy mono (meth) acrylates (B-1), a neutralized product of monocarboxy poly (meth) And a neutralized product of a (meth) acryloyl group-containing polyester (B-3).
The undercoating agent according to claim 1 or 2, wherein the content of the carboxylate anion group in the component (B) is 0.1 to 14 mmol / g.
The undercoat agent according to claim 1 or 2, wherein the component (C) is a compound represented by the following formula (1)
[Chemical Formula 1]

(In the 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 each represent hydrogen or an alkyl group having 1 to 6 carbon atoms.
The undercoat agent according to claim 1 or 2, wherein the content of the component (B) relative to 100 wt% of the component (A) (in terms of the nonvolatile component) is 0.5 to 30 wt%.
The positive resist composition as claimed in claim 1 or 2, wherein x mol of the carboxylate anion group of the component (A), y mol of the carboxylate anion group of the component (B), and z mol of the aziridinyl group of the component (C) , Wherein (x + y) / z is 0.05 to 3.0.
The undercoating agent according to claim 1 or 2, further comprising a polyisocyanate-based curing agent (D).
An active energy ray curable coating comprising an active energy ray cured coating layer formed by laminating an undercoat layer and an active energy ray cured coating layer formed from the undercoating agent of claim 1 or 2 on at least one surface of a plastic film in this order.
14. The plastic film according to claim 13, wherein the plastic film is a polyethylene terephthalate film.