KR20120030972A - Non-aqueous 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

PURPOSE: A non-aqueous undercoat agent is provided to manufacture an undercoat layer capable of bonding with a plastic film and an active energy ray-cured layer well in relatively short time, and to have excellent drying properties. CONSTITUTION: A non-aqueous undercoat agent comprises an active energy ray-cured film. The active energy ray-cured film comprises a branched polyester resin containing hydroxy group, a compound containing an active energy ray-polymerizable functional group and hydroxy group, and polyisocyanate having at least three kinds of isocyanate. The branched polyester resin is a dehydration condensation product selected from dicarboxylic acids, diols and triols, and hydroxyl value is 10-40 mg KOH/g.

Description

Non-aqueous 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}

The present invention provides a plastic comprising a non-aqueous undercoat agent used as an undercoat layer of a laminated film comprising an active energy ray-curable coating layer and a plastic film layer, and an active energy ray-curing coating prepared using the undercoat agent. It is about a film.

Plastic films made from thermoplastic resins such as polystyrene films, polycarbonate films, polyester films and the like have been provided for various industrial uses. In particular, polyester films are excellent in mechanical strength, transparency and the like, and are used in various products.

However, the plastic film may be difficult to adhere to a cured film (hereinafter referred to as an active energy ray cured film) made from a material cured by an active energy ray such as pentaeritritol triacrylate (PETA). . In order to improve adhesiveness, surface treatment, such as corona discharge or sand blast, may be performed, for example. However, there is a limit in improving the adhesiveness and there is a problem such that the adhesiveness decreases over time, so that an undercoat layer of easily adhesiveness may be provided in advance on the surface of the plastic film.

The conventional undercoat layer generally used polyester resin, acrylic resin, etc. as a raw material, and polyisocyanate etc. as a crosslinking agent (for example, refer patent document 1, patent document 2). However, since a raw material and a crosslinking agent are generally aqueous solution or water dispersion, it may be difficult to manufacture an undercoat film in a short time. Moreover, in general, problems such as poor moisture resistance of the undercoat layer and deterioration in adhesion over time have also been pointed out.

(Patent Document 1) JP10100349 A

(Patent Document 2) WO2004 / 065120 A

SUMMARY OF THE INVENTION An object of the present invention is a non-aqueous under which can produce an undercoat film having excellent adhesion between the cured film produced from an active energy ray-curable material and a plastic film (hereinafter, referred to as “adhesiveness”) and having good moisture resistance as well as a relatively short time. It is to provide a coating agent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the following undercoat agent discovered that the said subject could be solved, and completed this invention.

That is, this invention is active energy containing the branched polyester resin (A) which has a hydroxyl group, the compound (B) which has an active-energy-ray-polymerizable functional group, and a hydroxyl group, and the polyisocyanate (C) which has at least 3 types of isocyanate groups. An undercoat agent for a plastic film containing a precured film; The at least one surface of a plastic film relates to the plastic film containing the undercoat layer formed from the said undercoat agent, and an active-energy-ray-cured film formed by laminating | stacking in this order.

According to the undercoat agent of the present invention, an undercoat layer that adheres well to both the cured film and the plastic film (particularly, the polyester film) formed from the active energy ray-curable material can be produced in a relatively short time. In addition, the undercoat layer is excellent in moisture resistance, and the extent to which the adhesive force decreases with time is small. Furthermore, since the undercoat agent of this invention hardens in a short time at comparatively low temperature, and is excellent in dryness, it is suitable also for the plastic film and thin plastic film which are inferior in heat resistance.

Accordingly, the undercoat agent produces various plastic films having an active energy ray-curable coating, for example, a film for making, a film for packaging, a film for optical parts, a film for semiconductor processing tape, etc. Suitable for

The undercoat agent which concerns on this invention has the branched polyester resin (A) which has a hydroxyl group (henceforth (A) component), the compound (B) which has an active energy ray polymerizable functional group, and a hydroxyl group (hereinafter, (B ) And a non-aqueous composition containing polyisocyanate (C) (hereinafter referred to as (C) component) having at least three kinds of isocyanate groups.

A) component has a hydroxyl group in a molecule | numerator, and it does not specifically limit if it is a polyester resin which is a branched molecular structure, Various well-known things can be used. Specifically, dicarboxylic acids (a1) (hereinafter referred to as component (a1)), diols (a2) (hereinafter referred to as component (a2)) and triols (a3) used hereinafter as required (hereinafter, (a3) The dehydration condensate formed from)) 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 and naphthalene acid; Aliphatic (unsaturated) such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azeline acid, sebacic acid, undecanoic acid, dodecaneic acid, tridecanoic acid, maleic acid, fumaric acid and citraconic acid ) Dicarboxylic acids; Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid; Alkyl esters or dialkyl esters (all have about 1-3 carbon atoms in the alkyl group); These anhydrides etc. are mentioned. It is preferable to contain aromatic dicarboxylic acid from a viewpoint of adhesiveness, moisture resistance, etc. as (a1) component, Especially, it consists of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalic acid, naphthalene acid, dimethyl naphthalene acid, and phthalic anhydride It is preferable to include at least 1 sort (s) selected from the group. In addition, content of the aromatic dicarboxylic acid in (a1) component is about 30-100 mol% normally from a viewpoint of adhesiveness with a polyester film.

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-pentanediol Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1,3-propanediol; Alicyclic diols such as cyclohexanedimethanol, cyclohexanediol, and ethylene oxide adducts of hydrogenated bisphenol A; Aromatic diols such as catechol, resorcinol, xylene glycol, bis hydroxyethoxybenzene, and ethylene oxide adducts of bisphenol A; Examples of the diols other than these include polyalkylene glycols such as polyethylene glycol and polypropylene glycol having a degree of polymerization of 4 or more.

(a3) A component is a component used in order to introduce a branched structure into (A) component. In the present specification, the branched structure is meant to include a crosslinked structure. Specific examples of the component (a3) include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, and the like. In addition, tetraols, such as erythritol, sorbitol, pentaerythritol, and dipentaerythritol, can be used together.

Although the usage-amount of (a1) component-(a4) component is not specifically limited, Usually, when the sum total of (a1) component and (a2) component is 100 mol, about 30-70 mol% of (a1) component, (a2) The component is about 70-30 mol%. In addition, (a3) component is about 0.5-5 mol% normally with respect to a total of 100 mol of (a1) component and (a2) component.

The dehydrated condensate that can be obtained can be obtained according to various known polyester production methods. In addition, the conditions of the dehydration condensation reaction is not particularly limited, but the reaction may be carried out at atmospheric pressure or under reduced pressure. Moreover, various well-known esterifications, such as antimony trioxide, tetra propyl titanate, tetra butyl titanate, tetra stearyl titanate, dibutyl tin dilaurate, dibutyl tin dichloride, zinc oxide, and cobalt octylate, respond to an esterification reaction. A catalyst can be used and the usage-amount is about 0 to 5 weight% normally with respect to the total weight of (a1) component-(a3) component.

Although the physical property of (A) component thus obtained is not specifically limited, For example, it is the range whose hydroxyl value (JISK15571) is about 10-40 mg KOH / g normally, Preferably it is 15-30 mg KOH / g. When the hydroxyl value is 10 mg KOH / g or more, the curability becomes good, the crosslinking density of the undercoat layer is improved, and the moisture resistance is good. Moreover, adhesiveness becomes favorable because a hydroxyl value becomes 40 mg KOH / g or less. Furthermore, a hydroxyl value can be adjusted with the usage-amount of the said (a3) component.

In addition, the glass transition temperature of the component (A) is usually about 0 to 60 ° C, preferably about 10 to 50 ° C, from the viewpoint of adhesion and moisture resistance, and the number average molecular weight (polystyrene equivalent value by gel permeation chromatography). This is usually about 5,000 to 22,000, preferably about 8,000 to 20,000.

As long as the component (B) is a compound having an active energy ray polymerizable functional group and a hydroxyl group, various known ones can be used without particular limitation. Since the component (B) has an active energy ray polymerizable functional group in the molecule, it contributes to the adhesion between the active energy ray cured coating layer and the undercoat layer, and also has a hydroxyl group in the molecule. It is thought to contribute to the adhesion between the plastic film layer and the undercoat layer by injecting into the undercoat layer.

Specifically as an active energy ray polymerizable functional group, 1 type chosen from the group which consists of a (meth) acryloyl group, an allyl group, an aryl ether group, an ethenyl group, a vinyl ether group, etc. are mentioned. Among them, a (meth) acryloyl group which has a high polymerization rate and can produce an undercoat layer in a short time is preferable.

Specific examples of the component (B) include monohydroxy mono (meth) acrylates (B-1) (hereinafter referred to as component (B-1)) and monohydroxypoly (meth) acrylates (B-2). (Hereinafter, it is called (B-2) component) and 1 type chosen from the group which consists of polyhydroxy poly (meth) acrylates.

As (B-1) component, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are mentioned, for example. Moreover, as (B-2) component, trimethylol propane di (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol tetra penta (meth) acrylate, etc. are mentioned, for example. Moreover, as (B-3) component, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc. are mentioned, for example. Among these, the component (B-2) and the component (B-3) are preferable from the viewpoints of adhesion and moisture resistance.

Component (C) is a component that can react with both (A) component and (B) component, and as a result of the crosslinking reaction of components (A) to (C) integrally with a hydroxyl group and an isocyanate, It is thought that the undercoat layer which produces an effect can be obtained.

As a specific example of (C) component, the diisocyanate nurate (C-1) (henceforth a component (C-1)) represented by following General formula (1), and the diisocyanate represented by following General formula (2) are represented, for example. Adduct body (C-2) (henceforth a (C-2) component) is mentioned.

<Formula 1>

(R ¹ represents any of aromatic diisocyanate residue, aliphatic diisocyanate residue and alicyclic diisocyanate residue.)

<Formula 2>

(R ² represents an alkyl group having 1 to 3 carbon atoms or a functional group which may be represented by OCN—R ³ —HN—C (═O) —O—CH ₂ —. In the above formula or R ³ in R ² , respectively Independently any of aromatic diisocyanate residue, aliphatic diisocyanate residue and alicyclic diisocyanate residue.)

The said diisocyanate residue means the remaining group except an isocyanate group in the aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate which comprise (C-1) component or (C-2) component.

Examples of the aromatic diisocyanate include tridiisocyanate, α, α, α ', α'-tetramethyl xylene diisocyanate, diphenyl methane diisocyanate, naphthalene diisocyanate, xylene diisocyanate and the like. Moreover, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate etc. are mentioned as aliphatic diisocyanate. Examples of the alicyclic diisocyanate include dicyclohexyl methane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tri diisocyanate and the like.

As a commercial item of the said (C) component, for example, the colonate 2030, the colonate L, the colonate HX (all are manufactured by Nippon Polyurethane Industry Co., Ltd.), the colonate HL (made by Nippon Polyurethane Industry Co., Ltd.), Take Nate D110N (Mitsui Chemical Co., Ltd. product) etc. are mentioned.

Moreover, as (C) component (henceforth a (C-3) component) other than (C-1) component and (C-2) component, for example, a biuret type polyisocyanate, a lysine triisocyanate, a 6 functional poly Isocyanate (product name Duranate MHG80B, Asahi Kasei Chemicals Co., Ltd. product) etc. can also be used.

As (C) component, it is preferable in order of (C-1) component, (C-2) component, and (C-3) component from a dryness, adhesiveness, and moisture resistance of an undercoat layer. Moreover, the said aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate can be used as a dilution component with (C) component.

The undercoat agent of this invention can contain various well-known urethanized catalyst (D) (henceforth (D) component) for the purpose of raising the hardenability of an undercoat agent, and obtaining an undercoat layer faster. Specific examples of the component (D) include organic metal catalysts such as dibutyl tin dilaurate and dioctyl tin dilaurate and bismuth octylate, and amine catalysts such as organic amines such as triethyl amine or triethylene and salts thereof. .

The undercoat agent of this invention is used normally as a solution of various well-known organic solvent (E) (henceforth (E) component). Specific examples of the component (E) include ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester organic solvents (methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate). , Acid ethyl, butyl propionate, methoxy propyl acetate, methyl cellosolve acetate, cellosolve acetate, etc.), ether organic solvents (dioxane, diethyl ether, tetrahydrofuran, etc.), aprotic polar organic solvents (N- Methyl pyrrolidone, dimethyl formamide, dimethyl acetamide, etc.), aromatic hydrocarbon-based organic solvents (Sorbetso 100, Sorbetso 150 (all manufactured by EXXON Chemical Co., Ltd.), toluene, xylene, etc. are mentioned. In the case of using a ketone organic solvent, in addition to prolonging the pot life of the undercoat agent, the undercoat layer has good dryness, and is excellent in adhesion and moisture resistance. It is preferable because the cured film can be formed in a relatively short time.

The content of the (A) component and the (B) component of the undercoat agent of the present invention is not particularly limited, but from the viewpoint of adhesiveness and moisture resistance, the two components may be formed in terms of 100 parts by weight (in terms of non-volatile content) It is preferable to use content of B) component about 0.5-30 weight part normally, Preferably it is 1 to 10 weight part.

As for content of (C) component, when x mol of hydroxyl group of (A) component, y mol of hydroxyl group of (B) component, and z mol of isocyanate group of (C) component, z / (x + y) is 0.5 normally It is preferable that it is the range of about -5, especially 1.0-3.0. In the said range, hardening | curing property of an undercoat agent, adhesiveness, moisture resistance, etc. become especially favorable.

Content of (D) component is about 0.1-5 weight part normally with respect to 100 weight part (solid content conversion) of (A) component, Preferably it is 0.3-3 weight part. When it is content of the said range, the curability, adhesiveness, moisture resistance, etc. of an undercoat agent become especially favorable.

Although the usage-amount of (E) component is not specifically limited, The range in which the non volatile matter concentration of an undercoat agent is about 10-50 weight% normally, Preferably it is 20-40 weight%.

In addition, the undercoat agent of the present invention is an additive as a leveling agent, an anti-slip agent, 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.). ), A light stabilizer, an ultraviolet absorber, the following photopolymerization initiator and the like can be blended.

The plastic film (hereinafter also referred to simply as laminated film) containing the active energy ray-curable coating of the present invention comprises an undercoat layer and an active energy ray-curable coating layer composed of the undercoat agent of the present invention on at least one side of the plastic film. It is formed by stacking in order.

As a plastic film, the film manufactured from thermoplastic resins, such as a polystyrene film, a polycarbonate film, a polyester film, an ABS film, a polyvinyl chloride film, a polyolefin film, a triacetyl cellulose film, is mentioned, for example. In addition, these may be surface-treated, such as corona discharge. Among these, a polyester film, especially a polyethylene terephthalate (PET) film, is preferable from a viewpoint of adhesiveness, moisture resistance, etc.

An undercoat layer can be obtained by the process of apply | coating the undercoat agent of this invention to the said plastic film, and drying it. Examples of the application means include a roll coater, reverse roll coater, gravure coater, knife coater, bar coater and the like. The coating amount is usually about 0.01 to 10 g / m ² as a dry nonvolatile component. In addition, the film thickness is not particularly limited, but is usually about 0.1 to 10 μm. Furthermore, drying temperature is about room temperature-150 degreeC normally, specifically room temperature-120 degreeC, and drying time is about 10 second-about 3 minutes normally.

The active energy ray-cured coating layer can be obtained by applying an active energy ray-curable material onto the undercoat layer by the above means by various known methods and irradiating active energy rays. Moreover, although the film thickness of a cured coating layer is not specifically limited, Usually, it is about 1-75 micrometers.

As the active energy ray-curable material, a monomer type, an oligomer type, a polymer type or the like can be used. As a specific example, the said (B) component; The above component (b-2); 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dish Mono (meth) acrylates such as clofentenyl (meth) acrylate and isobonyl (meth) acrylate; 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, diethylene glycoldi (meth) acrylate, neopentyl glycol Di (meth) acrylates such as di (meth) acrylate; Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerytate Compounds having at least three (meth) acryloyl groups, such as lititol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and glycerol tri (meth) acrylate; Oligomers, such as a polyurethane poly (meth) acrylate and the said polyester poly (meth) acrylate, are mentioned and can use 2 or more types together.

In addition, the active energy ray-curable material may be blended with various known photopolymerization initiators. Specifically, benzophenone type polymerization initiators, such as benzophenone, benzoyl benzoic acid, p-dimethyl amino benzoic acid ester, methyl benzoyl benzoic acid, phenyl benzophenone, trimethyl benzophenone, and hydroxy benzophenone; Acetphenone-based polymerization initiators such as phenoxydichloroacetphenone, butyldichloroacetphenone, diethoxyacetphenone, hydroxy methyl phenyl propane, isopropyl phenyl hydroxy methyl propanone and hydroxy cyclohexyl phenyl ketone; Thioxanthone-based polymerization initiators such as thioxanthone, chlorothioxanthone, methyl thioxanthone, isopropyl thioxanthone, dichlorothioxanthone, diethyl thioxanthone and diisopropyl thioxanthone; 2 or more types can be used together.

In addition, the said (E) component or an additive can be mix | blended with the said active energy ray hardening material.

Examples of active energy rays include ultraviolet rays and electron beams. As a supply source of an ultraviolet-ray, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned, for example, The supply quantity is about 100-2,000 mJ / cm <^2> normally. Moreover, as a supply system of an electron beam, a scanning electron beam irradiation, a curtain type electron beam irradiation method, etc. are mentioned, for example, The irradiation energy is about 10-200 kGy normally.

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 addition, in each case, a part and% are a basis of weight unless there is particular notice.

Production Example 1 Preparation of (A) Component

In a reaction vessel equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction tube, 479 parts of terephthalic acid, 422 parts of isophthalic acid, 87 parts of azeline acid, 256 parts of ethylene glycol, 221 parts of 1,6-hexanediol, 148 parts of neopentyl glycol, and trimethyl 7 parts of olpropane were added, and the reaction system was heated under stirring to dissolve them. Then, the mixture was gradually heated from 160 to 200 ° C. for 3 hours while removing the water produced by the dehydration condensation reaction, and further maintained at 200 ° C. for 1 hour. Then 0.16 parts of antimony trioxide was added. Then, a vacuum decompression device was installed in the reaction vessel, and polycondensation reaction was carried out at 235 ° C. and 2.8 kPa under reduced pressure for 1 hour. Then, 512 parts of methyl isobutyl ketones and 768 parts of methyl ethyl ketones were added, and it melt | dissolved uniformly. In this way, the nonvolatile content is 50%, the hydroxyl value is 21 mgKOH / g, and the glass transition temperature (measured by the product name DSC6200, Seiko Instruments Co., Ltd., hereinafter means the same.) Is 31 ° C and the number average molecular weight. (The polystyrene conversion value by a gel permeation chromatography apparatus (product name HLC-8220GPC Doso Co., Ltd. product is called. It is the same below.) The polyester resin (A-1) solution which is 10,000 was produced.

<Production Examples 2 to 11 and Comparative Production Example 1>

Each solution of the branched polyester resins (A-2) to (A-11) in the same manner as in Production Example 1 except that the kind and the amount of the components (a1) to (a3) were changed to the compositions shown in Table 1, and A solution of non-branched polyester resin (A-12) was obtained. In addition, in Table 1, the usage-amount unit of each component is negative.

Preparation Example 1 Production Example 2 Production Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Preparation Example 11 Comparative Preparation Example 1 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 (a1) TPA 479 479 480 544 402 492 376 348 477 479 328 IPA 402 402 432 391 603 413 282 414 401 402 328 AZE 87 87 54 84 89 320 87 87 SEB 231 HHPA 255 CHDA 664 (a2) EG 256 256 256 300 166 287 251 238 269 256 178 182 1,6HD 221 221 355 215 348 353 354 NPG 148 148 61 313 215 283 PG 209 2MPD 1,4BD 213 DEG 148 CHDM 212 BisA Eo
additive 762 (a3) GLY 23 23 23 TMP 7 7 3 7 7 7 13 10 OHV 21 16 30 13 12 11 30 8 31 45 12 5 Tg 31 33 19 35 58 65 -5 26 16 17 31 70 Mn 10000 13000 10000 19000 16000 17000 10000 22000 7000 4000 19000 23000

In Table 1, each symbol has the following meaning

TPA: Terephthalic Acid

IPA: isophthalic acid

AZE: Azaline acid

SEB: Sebacic acid

HHPA: Hexahydrophthalic anhydride

CHDA: 1,4-cyclohexanedicarboxylic acid

EG: ethylene glycol

1,6-HG: 1,6-hexanediol

NPG: Neopentylglycol

PG: Propylene Glycol

2MPD: 2-methyl1,3-propanediol

1,4BD: 1,4-butanediol

DEG: Diethylene Glycol

CHDM: 1,4-cyclohexanedimethanol

BisA Eo Additive: Ethylene Oxide Additive of Bisphenol A

Gly: Glycerin

TMP: trimethylolpropane

OHV: hydroxyl value (mg KOH / g)

Tg: glass transition temperature (℃)

Mn: number average molecular weight

<Preparation of undercoat agent>

Example 1

To 100 parts of the branched polyester resin (A-1) obtained in Production Example 1, 1.5 parts of pentaerythritol triacrylate (trade name "Biscoto # 300": Osaka Organic Chemical Industry Co., Ltd.) was used as (B) component. Add and mix. Subsequently, 8.9 parts of hydrated foam (brand name: Nippon Polyurethane Industry Co., Ltd.) of hexamethylene diisocyanate (brand name: Japan Polyurethane Industry Co., Ltd.) as a (C) component was added to the said solution, and (D) component dioctyl tin 0.25 parts of dilaurate (brand name "Neostan U-810": Ildong Chemical Co., Ltd.) was added, and diluted with 131 parts of methyl ethyl ketone as (E) component to obtain an undercoat having a nonvolatile content of 25%.

Examples 2 to 26, Comparative Examples 1 to 5

The undercoat agent was obtained by the same method as Example 1 except having changed into the raw material type and the usage-amount shown in Table 2 (the non volatile matter of any undercoat agent is 25%).

<Preparation of active energy ray curable resin composition>

UV-curable resin composition by mixing 100 parts of tripropylene glycol diacrylate (trade name "TPGDA": manufactured by Daicel Cytec Co., Ltd.) and 5 parts of photoinitiator (trade name "Irugakyua 184" manufactured by Chiba Japan Co., Ltd.) Was prepared.

<Production of laminated film>

The undercoating agent of Example 1 was applied to a commercial PET film (trade name "Lumera T60", 75 µm thick, manufactured by Toray Corporation) with a bar coater so that the film thickness after drying was 1 µm, and dried at 120 ° C for 30 seconds. Thereafter, the ultraviolet curable resin composition was immediately applied to the undercoat surface with a bar coater so that the thickness became 10 μm after curing. Then, the laminated | multilayer film was produced by passing the film after application | coating three times under the high pressure mercury lamp (80W, mercury lamp height 10cm, conveyance speed 10m / min) in air | atmosphere. Similarly, the laminated | multilayer film was produced about the undercoat agent of another Example and a comparative example.

Initial adhesion

In accordance with JIS 5600, 100 mm of 1 mm masses were formed on the laminated film of Example 1 in the form of a checkerboard scale, and then an adhesive tape was attached and this was quickly removed in the vertical direction. Subsequently, initial adhesiveness was evaluated according to the following criteria with the remaining amount of the cured film. It evaluated also the laminated | multilayer film of another Example and a comparative example. These results are shown in Table 2.

6: 90 masses or more remained.

5: 80 mass or more and less than 90 mass remained.

4: 70 masses or more and less than 80 masses remained.

3: More than 60 masses and less than 70 masses remained.

2: 50 mass or more and less than 60 mass remained.

1: Less than 50 masses remained.

Moisture Resistance

After leaving the laminated film prepared in Example 1 for 4 days in a constant temperature and humidity chamber (60 degreeC, 95% RH), the moisture resistance of the cured film was evaluated in accordance with the method and the criteria similar to the said initial stage adhesiveness evaluation. These results are shown in Table 2.

(A)
ingredient (B) component (C) component z / (x + y) (D) component Evaluation results V300 M400 V295 ^{(* 2)} HX D110N U810 U600 Early
Adhesion Moisture resistance Example 1 A-1 100 1.5 8.9 2.0 0.25 6 6 Example 2 A-2 100 1.5 7.3 2.0 0.25 6 6 Example 3 A-3 100 1.5 11.9 2.0 0.25 6 6 Example 4 A-4 100 1.5 6.3 2.0 0.25 6 6 Example 5 A-5 100 1.5 5.6 2.0 0.25 6 6 Example 6 A-6 100 1.5 5.3 2.0 0.25 5 5 Example 7 A-7 100 1.5 12.0 2.0 0.25 4 4 Example 8 A-8 100 1.5 4.2 2.0 0.25 4 4 Example 9 A-9 100 1.5 12.4 2.0 0.25 5 5 Example 10 A-10 100 1.5 17.4 2.0 0.25 4 3 Example 11 A-11 100 1.5 5.6 2.0 0.25 4 3 Example 12 A-1 100 1.5 4.4 1.0 0.25 6 6 Example 13 A-1 100 1.5 13.3 3.0 0.25 6 6 Example 14 A-1 100 1.5 17.9 4.0 0.25 6 6 Example 15 A-1 100 1.5 1.3 0.3 0.25 4 3 Example 16 A-1 100 1.5 26.5 6.0 0.25 4 3 Example 17 A-1 100 0.5 7.7 2.0 0.25 6 6 Example 18 A-1 100 3 10.8 2.0 0.25 6 6 Example 19 A-1 100 5 13.3 2.0 0.25 6 6 Example 20 A-1 100 10 16.7 2.0 0.25 4 4 Example 21 A-1 100 1.5 8.6 2.0 0.25 6 6 Example 22 A-1 100 1.5 15.7 2.0 0.25 6 6 Example 23 A-1 100 1.5 8.9 2.0 One 6 6 Example 24 A-1 100 1.5 8.9 2.0 0.5 6 6 Example 25 A-1 100 1.5 8.9 2.0 0.1 6 6 Example 26 A-1 100 1.5 8.9 2.0 0.25 5 5 Comparative Example 1 A-1 100 7.0 2.0 0.5 One One Comparative Example 2 A-12 ^{(* 1)} 100 1.5 3.6 2.0 0.5 One One Comparative Example 3 A-1 100 1.5 0.0 0.5 One One Comparative Example 4 0 1.5 1.4 2.0 0.5 One One Comparative Example 5 A-1 100 1.5 7.0 2.0 0.5 2 2

In Table 2, each symbol has the following meaning.

M400 ： dipentaerythritol penta and hexa acrylate

V295 ： trimethylolpropane triacrylate (product name "Screw coat # 295" Osaka Organic Chemical Industry Co., Ltd. product)

D110N: Commercial isocyanate type crosslinking agent (trimethylolpropane xylene diisocyanate): Brand name "Takenate D110N": Mitsui Chemicals Co., Ltd. product

U600 ： Octyl acid bismuth (brand name "Neostan U600" Nitto Kasei Co., Ltd. product)

In Table 2, (* 1) and (* 2) are the comparative examples which do not correspond to the (A) component and (B) component of this invention, respectively.

Claims (12)

It includes an active energy ray cured film containing a branched polyester resin (A) having a hydroxyl group, a compound (B) having an active energy ray polymerizable functional group and a hydroxyl group, and a polyisocyanate (C) having at least three kinds of isocyanate groups. Undercoat agent for plastic film to make.
The undercoat agent according to claim 1, wherein the component (A) is a dehydration condensate selected from the group consisting of dicarboxylic acids (a1), diols (a2) and triols (a3).
The undercoat agent according to claim 1 or 2, wherein the component (a1) contains an aromatic dicarboxylic acid.
The undercoat agent according to any one of claims 1 to 3, wherein the hydroxyl value of the component (A) is 10 to 40 mg KOH / g.
The undercoat agent of any one of Claims 1-4 whose glass transition temperature of the said (A) component is 0-60 degreeC.
The undercoat agent according to any one of claims 1 to 5, wherein the number average molecular weight of the component (A) is 5, 000 to 22,000.
The undercoat agent according to any one of claims 1 to 6, wherein the active energy ray polymerizable functional group of the component (B) is a (meth) acryloyl group.
The undercoat agent according to any one of claims 1 to 7, wherein the undercoat agent further comprises a urethanization catalyst (D).
The hydroxyl group of the component (A) is x mol, the hydroxyl group of the component (B) is y mol and the isocyanate group of component (C) is z mol. x + y) is an undercoat agent characterized by the above-mentioned.
The undercoat agent according to claim 8 or 9, wherein the content of the component (D) is 0.1 to 5 parts by weight with respect to 100 parts by weight (in terms of non-volatile content) of the component (A).
A plastic film comprising, on at least one side of the plastic film, an undercoat layer formed from the undercoat agent of any one of claims 1 to 10 and an active energy ray cured film formed by laminating in this order an active energy ray cured coating layer. .
12. The plastic film of claim 11, wherein the plastic film is a polyester film.