TW201224076A - Non-aqueous primer with active energy ray-cured coating for plastic film and plastic film with active energy ray-cured coating - Google Patents

Abstract

The present invention provides a non-aqueous novel primer capable of forming a primer layer within a shorter period of time. The primer layer has an excellent moisture tolerance and adhesion with both a plastic film and a cured coating consisting of the active energy ray-curable material. The present invention uses a composition as a primer, in which the composition comprises: (A) the branched polyester resin with a hydroxyl group; (B) a compound with an active energy ray-polymerizable functional group and a hydroxyl group; and (C) a polyisocyanate ester with at least three isocyanate groups.

Description

201224076 VI. Description of the Invention: [Technical Field] The present invention relates to a non-aqueous primer and a plastic film with an active energy ray hardening film which is used as an undercoat layer of a laminated film. The laminated film has an active energy ray hardening film layer plastic film layer, and the plastic film with the active energy ray hardening film is formed by using the primer. [Prior Art] A plastic film composed of a thermoplastic resin such as a polystyrene film, a polycarbonate film or a polyester film is provided for various industrial uses. In particular, the polyester film is applied to a wide variety of products because of its excellent mechanical strength and transparency. However, ...:, the plastic film and the hardened film composed of the material hardened by the active energy ray (hereinafter referred to as 麁 method M pure denier β, 丄一,

The previous base coat was treated with enamel. However, the adhesion of the adhesion is delayed over time, and the surface of the L film is provided with an undercoat layer which is easily adhered. In the case of a resin such as a polyester resin or an acrylic resin, 201224076 is used as a main component, and a polyisocyanate or the like is used as a crosslinking agent (for example, as a reference, Patent Document 1 or Patent Document 2). However, since the main agent or the cross-linking agent is generally an aqueous solution or an aqueous dispersion, it may sometimes be difficult to obtain an undercoat film in a short period of time. Further, in general, the undercoat layer is also pointed out to have problems such as poor moisture resistance and a decrease in adhesion with time. [Prior Art Document] (Patent Document) Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei 10-100349. Patent Document 2: International Publication No. WO2004/065120 [Draft of the Invention] [Problems to be Solved by the Invention] The problem is to provide a non-aqueous primer which is capable of forming an undercoat film in a relatively short period of time, and the primer film is adhered to both the hardened film and the plastic enamel composed of the active energy ray-curable material. The properties (hereinafter simply referred to as adhesion) are excellent, and the moisture resistance is also good. [Technical means for solving the problem] The inventors of the present invention have intensively studied and found that the above problem can be solved by the undercoating agent having the following constitution. That is, the present invention relates to a non-aqueous primer for a plastic film having an active energy ray hardening film 201224076, which comprises: (A) a branched polyester resin having a hydroxyl group, and (B) an active energy ray polymerizable property. a functional group and a transbasic compound, and (C) a polyisocyanate having at least 3 isocyanate groups; and the present invention relates to a plastic film having an active energy ray hardening film, which is at least a plastic film The following layer is sequentially laminated on one surface: an undercoat layer ' and an active energy ray-hardened film layer composed of a non-aqueous primer for a plastic film having an active energy ray-hardened film. [Efficacy] According to the primer of the present invention, it is possible to obtain an undercoat layer and a hardened film and a plastic film (especially a polyester film) composed of an active energy ray-curable material in a relatively short period of time. Both are well sealed. Further, the undercoat layer is excellent in moisture resistance, and the degree of decrease in adhesion with time is small. Further, since the primer of the present invention can be cured in a short period of time at a relatively low temperature and is excellent in drying property, it is also suitable for a plastic film having poor heat resistance or a plastic film of a film. Therefore, the primer is suitable for the production of various plastic films having an active energy ray-cured film, and is suitable for, for example, production of a film for a plate making, a film for packaging, a film for an optical component, a film for a semiconductor processing tape, and the like. Manufacture of plastic fibers or plastic sheets, plastic moldings, etc. 201224076 [Embodiment] The primer of the present invention is a non-aqueous composition comprising: (A) a branched polyester resin having a hydroxyl group (hereinafter referred to as (a) forming/knife), and (B) having active energy A compound having a linear polymerizable functional group and a hydroxyl group (hereinafter referred to as a component (8)) and (c) a polyisocyanate having at least three isocyanato groups (hereinafter referred to as a component (c)). The component (A) is not particularly limited as long as it is a polyester resin having a radical in the molecule and having a branched molecular structure, and various conventional materials can be used. Specifically, it is preferably selected from (al) diterpenic acid (hereinafter referred to as (al) component), (a2) glycol (hereinafter referred to as (^) component), and & U3) triol (hereinafter referred to as A dehydrated condensate composed of the component (a3). Specific examples of the component (a 1 ) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, diphenylmethane-4,4,dicarboxylic acid, and naphthoic acid. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecane II Aliphatic (unsaturated) dicarboxylic acids such as acid, maleic acid, fumaric acid, succinic acid, citraconic acid; M-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid An alicyclic dicarboxylic acid; a monoalkyl or dialkyl ester of these acids (the number of carbon atoms of the alkyl group is about 1 to 3, such as an anhydride of these acids, etc. (al) component, from the close

6 S 201224076 From the viewpoint of properties or moisture resistance, it is preferable to contain an aromatic diacid, and the aromatic dicarboxylic acid is particularly preferably selected from the group consisting of terephthalic acid 'p-benzene-formic acid dimethyl vinegar. At least one of a group consisting of phthalic acid, dimethyl phthalate, and cholic acid: dimethyl naphthalate and phthalic anhydride. Further, the content of the aromatic dicarboxylic acid in the 'al component' is preferably from about <% to (10) mol% from the viewpoint of adhesion to the mulched film. Specific examples of the component (a2) include ethylene glycol, diethyl alcohol, triethylene glycol, and dimethylamine, propylene glycol, 1,3-butanediol, and butyl alcohol. , 15-pentanediol, 1,6-hexanediol, neopentyl glycol, decyl 1,5-pentane-alcohol, 2-methyl-1,3-propylene glycol and other aliphatic diols, Methanol, net p-co-hexanol, hydrogenated bisphenol A, epoxy epoxide adduct, etc. 瑷炷 _ _ # # # # 衣 私 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇Methanol, bis (base acetylene) lean m rolled soil), aromatic diol such as ethylene oxide adduct of bisphenol A _. kg _ ' ° the polymerization degree other than the yeast one is 4 The above polyalkylene glycol such as polyethylene glycol or polypropylene glycol. The knives are used in order to impart a branching structure to the component (A). Further, in the present specification, the "branched structure" - the shackle 3 has a "crosslinked structure". Specific examples of the component (...) include glycerin, di-methylpropane, trihydroxydecylethane, 1,2,6-hexanediol, 1,2,4-butadiene J. In addition, it can be used together with (a3) component 201224076: tetrahydric alcohol such as erythritol, sorbitol, pentaerythritol, dipentaerythritol. (The amount of aO component to (a3) component is not particularly limited. Usually, the 'U1' component in the case where the (al) component and the (a2) component are combined to be 1 〇〇 mol is about 3 〇 to 70 mol / 〇, and the (a2) component is 70 to 30 mol %. Further, the component (a3) is usually about 5 to 5 mol% relative to the (al) component and the (a2) component in total, and the component (a1) to (a3) is composed of (a1) component to (a3) component. The dehydrated condensate thus formed can be obtained by various conventional methods for producing a vinegar. Further, the conditions of the dehydration condensation reaction are not particularly limited, and the reaction can be carried out under normal pressure or under reduced pressure. In the reaction, various conventional esterification catalysts can be used: trifluorochemical, tetrapropyl titanate, tetrabutyl titanate. Tetrastrate titanate, dibutyltin dilaurate, dibutyltin dichloride, zinc oxide, cobalt octoate, etc., the amount of these esterification catalysts is usually relative to the (al) component ~ (a3) component The physical properties of the component (A) thus obtained are not particularly limited, and for example, the hydroxyl group (JIS K-1557-1) is usually in the range of about 10 to 40 mgKOH/g. In the range of about 15 to 30 mg KOH/g, it is preferable that the valence of the hydroxyl group is 10 mg KOH/g or more, so that the curability is good 201224076, the crosslinking density of the undercoat layer is improved, and the moisture resistance is improved. When the valence of the hydroxyl group is 4 〇 mg K 〇 H / g or less, the adhesion can be improved. Further, the valence of the hydroxy group can be adjusted by the amount of the component (a3) used. From the viewpoint of the glass transition temperature of the component (A), it is usually about 〇6〇5, and is preferably about 1 〇5 (about rc, the number average molecular weight (according to the polystyrene value of the gel permeation chromatography). ) It is better to pass around 5〇〇〇~22000, and it is better to be around 8〇〇〇~20000. (Β), any compound having an active energy ray-polymerizable functional group and a trans group may be used, and various S-known substances may be used without particular limitation. (Β) component 'may be due to active energy ray polymerization in the molecule S The energy base contributes to the adhesion between the active energy ray hardening film layer and the undercoat layer, and may have a base group in the molecule, so it may be combined with the component (C) described later to be combined with the bottom. In the coating, it contributes to the adhesion between the plastic film layer and the undercoat layer. As the active energy ray-polymerizable functional group, specifically, it may be selected from the group consisting of (fluorenyl) acrylonitrile and propylene At least one of the group consisting of a propyl group, a propyl ether group, a vinyl group, and a vinyl group. Among them, a (meth) acrylonitrile group is preferred because it is fast and can obtain an undercoat layer in a short time.

9 S 201224076 As a specific example of the component (B), it can be exemplified by a single antelope

Mono(meth)acrylates (B_i) (hereinafter referred to as (B_^) into eight K monohydroxy poly(meth)acrylates (Β_2) (knife/, r is called (Β-2) component And a poly-hydroxy (indenyl) acrylate (b_3) (referred to as a component (B-3)) in the group of one to (as a component (B-1)', for example, V Τ %) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate (meth) acrylate 4-(butyl) and the like. Further, examples of the (Β_2) component include trimethylolpropane bis(indenyl) acrylate, glycerin di(methyl 1) internal acid vinegar, and dipentaerythritol penta(meth)acrylic acid g. Further, examples of the component (B-3) include pentaerythritol di(meth)acrylate and dipentaerythritol tetra(meth)acrylate. Among them, the (B_2) component and the component are preferred from the viewpoints of adhesion or moisture resistance. The component (C) is a component capable of reacting with both the component (A) and the component (B). It is possible that the components (A) to (8) are crosslinked by a reaction of a trans group and an isocyanate, and the result is Get the primer that works as expected. Specific examples of the component (C) include a diisocyanate trimer (c_1) represented by the following formula (1) (hereinafter referred to as (c_n component)' and a formula represented by the following formula (2) Diisocyanate adduct (c_2)

10 S 201224076 (hereinafter referred to as (C-2) component [Chemical Formula 1] 〇 OCN-

Nc〇 N- I R1 (1)

Nc〇 (wherein R represents an aromatic acid vinegar residue, and a diisocyanuric acid residue, an aliphatic diiso-half, or any one of the ester residues of the formula 2); -C ( = 〇) 1 3 ?h2 r3~nco R — c — C Η 2 — Ο — c CH, °) -NH-R3_Nc〇(2) 〇-c (=〇) —NH—R3 —Nc〇 (wherein R2 represents a functional group having a ruthenium of 1 to 3 or a functional group represented by 〇CN-R3-HN-C(= 〇>) 〇ου * _ 0_CH2_. And R2 in 'R3, respectively, independent of the dry 荽 不 香 香 香 二 diisocyanate residue, aliphatic isopropyl vinegar residue, > 5 fat aid -V _ X 丞 and 曰% diisocyanate residues Any one). In addition, the term "diisocyanate residue" means a group of diisocyanate, aliphatic diisocyanate, and an alicyclic ring which constitute a component of (c·1), or a component (C_2). The diisocyanate (tetra) is a group remaining after the isocyanate group is removed.

11 S 201224076 As aromatic 旌__ β, - isocyanate, for example, toluene diisocyanate, ^,,, α,, - tetramethyl phthalic acid diisocyanate, dimercene diisocyanate, bannaphthalene Isocyanate, diterpene diisocyanate, and the like. Further, examples of the lipid di-isocyanate include hexamethylene diisocyanate and trimethicone hexamethylene diisocyanate lysine disodium lactic acid. In addition, you go to Bu /, 乍 is a month B ring diisocyanate, can be cited: bishexyl decane-isocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene Diisocyanate, hydrogenated hydrazine diisocyanate, and the like. — As a commercial item of the above component (c), for example,

Coronate 2030, Coronate L, coronate Ηχ (all manufactured by Japan Gas Glue Industrial Co., Ltd.), c〇ronate hl (manufactured by Sakamoto Polyurethane Industry Co., Ltd.), Takenate D110N (manufactured by Mitsui Chemicals Co., Ltd.) )Wait. Further, as the (C-1) component and the component (C) other than the component (C-2) (hereinafter referred to as (C-3) component), for example, a biuret type polyisocyanate or an amine can be used. Acid triisocyanate or a hexafunctional polyisocyanate (product name "Duranate MHG-80B", manufactured by Asahi Kasei Chemicals Co., Ltd.). As the component (C), '(C-1) component, (c-2) component, (C-3) are sequentially selected from the viewpoints of drying property, adhesion, and moisture resistance of the undercoat layer.

12 S 201224076 The ingredients are preferred. Further, the above-mentioned aromatic diisocyanate-isoxamic acid vinegar may be used as the component (c), and an aliphatic diisocyanate or an alicyclic group may be used. The primer of the present invention may contain various conventional (D) urethane-e) catalysts for the purpose of improving the hardenability of the primer and obtaining the undercoat layer in a shorter period of time (hereinafter referred to as (d) & points). Specific examples of the component (9) include dibutyltin dilaurate, dioctyltin dilaurate or octoate organic metal catalyst, and amine amines such as triethylamine and diethylenediamine. Media. The primer of the present invention is usually used in the form of a solution of various conventional organic solvents (8) (hereinafter referred to as (E) components). Specific examples of the component (e) include a ketone organic solvent [propionamidine, ethylidene ethyl hydrazine, methyl isobutyl ketone, cyclohexanone, etc.] 'ester organic solvent [acetic acid " Vinegar, isopropyl acetate, butyl vinegar acetate, vinegar acetate, ethyl formate, butyl citrate, methoxyacetic acid acetate, methyl sarbuta acetate, 赛路苏 acetate, etc. Ether-based organic solvent [d1〇xane, diethyl ether, tetrahydrofuran, etc.], aprotic polar organic solvent [N-methylpyrrolidone, dimethyl decylamine] diroxalylamine Etc., an aromatic hydrocarbon-based organic solvent [S〇lvess〇#1〇〇, (all manufactured by ExxonMobil Chemical Co., Ltd.), 甲笨, dimethyl styrene, etc.]. Among these, when a ketone organic solvent is used, 201224076 can also improve the drying property of the undercoat layer in addition to extending the life of the primer, and can be formed in a relatively short period of time. The adhesion or the sclerosing film which is excellent in the surface is preferable. / % β; The weight of the enthalpy is not particularly limited, and from the viewpoints of adhesion or moisture resistance, the two formations are preferably used in the following ranges: 1 相对 with respect to the (A) component ( The content of the component (8) is usually about 0.1 to 3 parts by weight, preferably 5% by weight, based on parts by weight (in terms of non-volatile components). ▲In the case where the hydroxyl group of the component (A) is set to the component of the component (8)

When the isocyanate group of the y mole and (C) component is ζmol, (the content of the C component is usually Z/(X+mG.5~5, especially Η:·〇) The range of the primer is set to be within this range, and the curability, adhesion, or wettability of the primer is particularly good. VIII) 100 parts by weight of the (Α) component (converted to non- In the case of the volatile forming tool J, the amount of the component (D) is usually about 1 to 5 parts by weight, preferably about 3 parts by weight, and the amount of the primer is set to be the content of the primer. Hardness, adhesion, or moisture can be particularly good. (Ε) The amount of the component used is in the range of the concentration of the volatile component, but the range of the primer is not 20~-weight. OK. 0 Reset % Left ^ is preferably 14 1 201224076 Further, in the primer ▲ just in the present invention, the following additives can also be formulated: leveling agent, anti-slip agent, anti-oxidant, pigment, dye, slippery Agent, inorganic filler (colloidal gas 彳 ^ emulsified hair, rolled zinc, calcium carbonate, barium sulfate, titanium oxide, kaolin, gas oxime, emulsified aluminum, etc.), light stabilizer, UV a line absorber, a photopolymerization initiator, etc., which will be described later. The plastic film of the present invention having an active fried denier b 1 line hardened film (hereinafter sometimes referred to simply as a laminated film), a and at least a plastic film The undercoat layer composed of the primer of the present invention, & 1 θ ' Μ, and the active energy ray-hardened film layer are sequentially laminated on one surface. Examples of the plastic film include polyphenylene. a film made of a thermoplastic resin such as an ethylene film, a polycarbonate film, a poly S film, an ABS film, a polyvinyl chloride film, a polycarbon film, or a cellulose triacetate film, and these films can also be subjected to electric discharge. Among these films, from the viewpoint of adhesion or wetness, it is preferable to use a poly(p-type film), and particularly preferably a polyethylene terephthalate (PET) film. By applying the primer of the present invention to the plastic film and drying it, the "painting means can be exemplified by a roll coater, a reverse roll coater, a gravure coater, and a knife coater. , bar coater, etc. The amount of brushing is usually dry and non-volatile ingredients are 〇〇1~1〇 left Right. Further, the film thickness is not particularly limited, but it is usually about 〇~ι〇. Moreover, the drying temperature is usually room temperature ~15 〇 (^ about

15 S 201224076 It is about room temperature ~120 °C. The drying time is usually about 1 〇 to ~3 minutes. The active energy ray-hardening film layer is obtained by applying various conventional active energy ray-curable materials to the undercoat layer by the above-mentioned means and irradiating the active energy enthalpy. The film thickness of the hardened 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. Specifically, the above (Β) component; the above (b2) component; (meth)acrylic acid 2-ethylhexyl acrylate, (meth) isopropyl isodecyl ester, (mercapto) acrylic acid Isooctyl ester, benzyl (meth) acrylate, cyclopentyl (meth) acrylate cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (fluorenyl) acrylate Mono(meth)acrylates such as esters; 1,3-butanediol di(meth)acrylate, 1,4-butanediol bis(indenyl)acrylate, 1,6-hexanediol di(曱) Di(meth) acrylates such as acrylate, diethylene glycol di(meth) acrylate, neopentyl glycol bis(indenyl) acrylate; trishydroxypropyl propane tris(fluorenyl) acrylate Ethylene oxide modified trihydroxymercaptopropane tri(meth) acrylate, propylene oxide modified dimethylolpropane tri(decyl) acrylate, dipentaerythritol hexa(meth) acrylate, two Trihydroxymercaptopropane tetra(meth)acrylate vinegar, glycerol tri(meth)acrylate, etc. have at least 3 (A 201224076 base) C The acyl compound; Yue ester polyamine poly (Yue-yl) acrylic acid vinegar, the polyester poly (meth) acrylate oligomer and the like, and also two or more kinds. Further, in the active energy ray-curable material, various conventional photopolymerization initiators may be blended. Specific examples thereof include benzophenone, benzoic acid, and p-dimethylamine benzoate, methyl benzophenone, phenyl benzophenone, and trimethyl benzophenone. a dimercapto ketone polymerization initiator such as hydroxybenzophenone; phenoxydichloroacetophenone, butyl diacetophenone, diethoxyacetophenone, hydroxymethylphenylpropionate, Isopropyl phenyl group, fluorenyl, hexyl phenyl (tetra) phenethyl (tetra) polymerization initiator; thioxanthone, thioxanthone, methyl (tetra) ketone, isopropyl (tetra) oxime, A thioxanthone-based polymerization initiator such as di-(tetra) ketone, diethyl hydrazine or diisopropyl thioxanthone may be used in combination of two or more. Further, in addition to the active energy ray-curable material, the component (E) or the additive may be formulated. The active energy ray ' can be exemplified by ultraviolet rays or electron beams. The source of the ultraviolet: for example, a high-pressure mercury lamp or a metal mascara lamp can be cited, and the irradiation amount is usually about 100 to 2 〇〇〇 mW. Further, examples of the supply method of the beamlet include scanning electron beam irradiation, electron beam irradiation, and the like, and the irradiation energy is usually H) to 200 kGy.

17 S 201224076 or so. [Examples] Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the parts and % in each case are all based on weight unless otherwise specified. [Production Example 1] <Production of component (A)> In a reaction vessel equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction tube, 479 parts of terephthalic acid, 402 parts of isophthalic acid, and hydrazine were fed. 87 parts of diacid, 256 parts of ethylene glycol, 221 parts of 1,6-hexanediol, 148 parts of neopentyl glycol, and 7 parts of trimethylolpropane were heated under stirring to melt the reaction system. Then, while removing the water generated in the dehydration condensation reaction, the reaction system was gradually heated from 160 ° C to 2000 over 3 hours, and further kept at 200 ° for 1 hour. Then, 0.16 parts of antimony trioxide was added. Next, a vacuum pressure reducing device was connected to the reaction vessel, and the condensation condensation reaction was carried out at 235 ° C and 28 kPa for 1 hour. Next, 512 parts of methyl isobutyl ketone and 768 parts of methyl ethyl ketone were added and uniformly dissolved. Thus, a solution of the polyester resin (A-1) can be obtained. The non-volatile component of the polyester resin (A-1) is 50%, the hydroxyl value is 21 mgK〇H/g, and the glass transition temperature (by 18 201224076) The measured value measured by the product name "DSC6200" (manufactured by Sakamoto Seiko Instruments Co., Ltd.) is the same as 31 C, the number average molecular weight (by gel permeation chromatography device (product name "HLC") -822〇GPC", manufactured by Sakamoto Tosoh Co., Ltd.) The measured value of polystyrene is the same as the above) is 1〇000° [Production Examples 2 to 11 and Comparative Manufacturing Example i] The type of the component (a) and the amount of the component (a; 3) were changed as shown in Table 1, and the same procedure as in the production example was carried out to obtain a branched polyester resin (A-2) to (A- 11) each solution, and a solution of the non-branched polyester resin (A_2). In addition, the unit of the amount of each component used in the table is a part. [Table 1]

19 S 201224076 Comparative Manufacturing Example 1 A-12 328 〇〇(N m <N 00 r-H 762 *〇o 23000 Manufacturing Example 11 A-11 <N s V〇00 Bu CO oo <N 212 〇( N 19000 Manufacturing Example 10 A-10 479 S inch SS 256 m (N JO Bu 4000 Manufacturing Example 9 A-9 477 〇269 mv〇7000 Manufacturing Example 8 A-8 348 inch 231 238 215 00 v〇CS 22000 Manufacturing Example 7 A-7 376 1_____ (N 〇〇CN 320 CN CO m <N 沄up 10000 Manufacturing Example 6 A-6 492 m * 1 s 287 r « ΓΛ 〇17000 Manufacturing Example 5 A-5 402 S Ό v〇v 〇209 : m (N 卜 < N 00 * Ti 16000 Manufacturing Example 4 A-4; 544 < 3 cn 300 sm cn κη ro 19000 Manufacturing Example 3 A-3 480 <N rj 256 355 m <N沄2 10000 Manufacturing Example 2 A-2 479 s inch j 256 cs CN ΓΛ ΓΛ 13000 Manufacturing Example 1 A-1 479 s inch 256 T-*H 04 fN OO inch 卜 oJ 10000 TPA IPA AZE SEB HHPA CHDA 〇ω QK v〇NPG 〇iX 2MPD -1 1,4BD DEG CHDM BisA EO adduct GLY TMP OHV 00 Mn N C3 20 201224076 In Table 1, each symbol is as follows: TPA: terephthalic acid IPA: isophthalic acid AZE: sebacic acid SEB: sebacic acid HHPA: hexahydrophthalic anhydride CHDA: 1,4 -cyclohexanedicarboxylic acid EG: ethylene glycol 1,6HD: 1,6-hexanediol NPG: neopentyl glycol PG: propylene glycol 2MPD: 2-mercapto-1,3-propanediol 1,4BD : 1, 4_butanediol DEG: diethylene glycol CHDM : 1,4-cyclohexane dimethanol

Bis A EO adduct: ethylene oxide adduct of bisphenol A GLY : glycerol TMP : trihydroxymethyl propane OHV : hydroxyl value (mgKOH / g)

Tg: glass transition temperature (°C) Μη: number average molecular weight <modulation of primers> [Example 1] 21 201224076 A solution 100 of the branched polyester resin (A_丨) obtained in Production Example 1 Adding pentaerythritol triacrylate (trade name "ViSC〇at #300", 5 parts manufactured by Osaka Organic Chemical Industry Co., Ltd. as component (B), and then adding "C〇ronate" to the solution HX" (trimer of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.)) 8.9 parts as component (c), and added dioctyltin dilaurate (trade name: rNe〇stann U_81〇) , manufactured by Nitto Chemical Co., Ltd.) G.25 is a component (D), and is diluted with methyl ethyl ketone and 13 parts of bismuth (E), and a non-volatile component of 25% is obtained. [Examples 2 to 26, Comparative Examples 1 to 5] A primer was obtained in the same manner as in Example i except that the amount of the raw material used in Table 2 was changed. The non-volatile components of the paint are 25%.) <Active energy line Preparation of Chemical Resin Composition> Tripropylene glycol diacrylate (trade name: factory tpgda), DA leg-CYTEC Co., Ltd.) (10) part of photoinitiator ("trade name "IRGACURE184", Japan Ciba 5 parts of the product are sufficiently mixed to prepare an ultraviolet curable resin composition. <Production of laminated film> Commercially available PET film (trade name "Lumirr〇rT6〇"^75_ 曰On the basis of the coating machine, the primer of the coating method of Example 22 201224076 was coated with a bar coater, and the dried film thickness was 1 μm, and dried at 120 ° C for 30 seconds. The ultraviolet curable resin composition was applied to the undercoat surface by a bar coater, and the film thickness after hardening was 1 μm. Next, 'in the atmosphere, a high pressure mercury lamp (8〇w, The height of the mercury lamp was 10 cm 'transport speed was 丨〇m/min.) The coated film was passed three times to form a laminated film. The primers of the other examples and comparative examples were also formed in the same manner to form a laminate. Membrane. <Initial Adhesion> According to the standard of IIS 5600, in the laminated film of the embodiment, 10 (M solid 1 mm square) is formed in a checkerboard pattern, and the tape is adhered and rapidly peeled off in the vertical direction. Then, according to the residual amount of the hardened film, The initial adhesion was evaluated by the following criteria. The laminate films of the other examples and comparative examples were also evaluated in the same manner. The results are shown in Table 2. 6 Residual 90 squares or more. • Residual 80 squares Above and less than 9 squares. 4 · Residual 70 squares or more and less than one square. 3. Remaining 60 squares or more and less than 7 squares. 2 · Residual 50 squares or more and less than 6 squares. 1 : Residual less than 50 squares β <moisture resistance>

After the laminated crucible of Example 1 was placed in a constant temperature and humidity chamber (6 〇t, 95% rh) for 4 days, the adhesion of the hardened film was evaluated based on the same method as the initial adhesion evaluation I 23 201224076. Sex. These results are shown in Table 2. [Table 2] (A) Component (B) Component (C) Component z/(x+y) (D) Component Evaluation Result V300 Μ400 V295 (·2) HX D110N U810 U600 Initial Adhesive 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 Implementation 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 Π 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 1 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 1 1 Comparative Example 2 A-12(.1) 100 1·5 3.6 2.0 0.5 1 1 Flavor Example 3 A-1 100 1.5 0.0 0.5 1 1 Comparative Example 4 0 1.5 1.4 2.0 0.5 1 1 case 5 A-1 100 1.5 7.0 2.0 0.5 2 2

S 24 201224076 In Table 2, each symbol has the following meaning. M400: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name "Aronix M-400", manufactured by Toagosei Co., Ltd.) V295: trihydroxymercaptopropane triacrylate (trade name "viscoat#295", Manufactured by Osaka Organic Chemical Industry Co., Ltd.) D11 ON : Commercially available isocyanate crosslinking agent (trimethylolpropane xylene diisocyanate, trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc.) U600: bismuth octoate (The product name is "Neostann U-600", manufactured by Nitto Kasei Co., Ltd.). Further, (*1) and (*2) in Table 2 are respectively associated with the components (A) and (B) of the present invention. Not the same comparative example. [Simple diagram description] None [Main component symbol description] None

S 25

Claims (1)

201224076 VII. Patent application scope: 1. A non-aqueous primer for plastic film with active energy ray hardening film, which has 3 (A) branched polyester resin with trans-base, (b) active energy a compound having a linear polymerizable functional group and a hydroxyl group, and (c) a polyisocyanate having at least three isocyanate groups. 2. A non-aqueous primer for a plastic film having an active energy ray hardening film as described in claim 1, wherein the component (A) is (a) diteric acid, (a2) glycol And (a3) a dehydrated condensate composed of a triol. 3. The non-aqueous primer for a plastic film having an active energy ray hardening film according to the first or second aspect of the patent application, wherein the (al) component contains an aromatic dicarboxylic acid. 4. The non-aqueous primer for a plastic film having an active energy ray hardening film according to the first or second aspect of the invention, wherein the component (A) has a hydroxyl group content of from 1 to 40 mgKOH/g. 5. The non-aqueous primer for a plastic film having an active energy ray hardening film according to the first or second aspect of the patent application, wherein the glass transition temperature of the component (A) is 0 to 60 °C. S 26 201224076 6. The non-aqueous primer for a plastic film having an active energy ray hardening film according to the first or second aspect of the invention, wherein the component (A) has a number average molecular weight of 5,000 to 22,000. 7. A non-aqueous primer for a plastic film with an active energy ray hardening film as described in claim 1 or 2, wherein the active energy ray-polymerizable functional group of the component (B) is (methyl) ) acrylonitrile. 8. The non-aqueous primer for a plastic film having an active energy ray hardening film according to the first or second aspect of the invention, which further comprises (D) an amine phthalate catalyst. 9. A non-aqueous primer for a plastic film having an active energy ray hardened skin, as described in claim 1 or 2, wherein the light base of the component (A) is X-mole, When the hydroxyl group of the component (B) is y mole and the isocyanate group of the component (C) is z mole, z/(x+y) is 0.5 to 5. 10' is a non-aqueous primer for a plastic film with an active energy ray hardening film as described in claim 8 of the claim, wherein the component (10) is replaced with (a non-volatile component) The content of the component (D) is 0.1 to 5 parts by weight. 11 申'^主蜜jt I • 咕 利 范围 范围 范围 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶 塑胶201224076 parts by weight (calculated as non-volatile components), the content of the component (D) is 0.1 to 5 parts by weight. 12. A plastic film with an active energy ray hardening film, which is formed by sequentially laminating the following layers on at least one side of the plastic film: as claimed in any one of claims 1 to 11 An undercoat layer composed of a non-aqueous primer for a plastic film having an active energy ray-hardened film and an active energy ray-hardened film layer. 13_ The plastic film with an active energy ray hardened film as described in claim 12, wherein the plastic film is a polyester film. S 28 201224076 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 201224076 Seventh First "No.1 privilege"mn; j year;.!>fe Patent application scope: L__ill 1 · One with A nonaqueous primer for a plastic film of an active energy ray-hardening film, comprising: (A) a branched polyester resin having a hydroxyl group, (B) a compound having an active energy ray polymerizable functional group and a hydroxyl group, and (C) A polyisocyanate having at least 3 isocyanate groups. 2- A non-aqueous primer for a plastic film with an active energy ray hardening film as described in claim 1, wherein the component (A) is an (al) dicarboxylic acid or a (a2) glycol. And (a3) a dehydrated condensate composed of a triol. 3. A non-aqueous primer for a plastic film with an active energy ray hardening film as described in the second paragraph of the patent application, wherein the (al) component contains an aromatic oxime. 4. As described in claim 1 A non-aqueous primer for a plastic film with an active energy ray hardening film, wherein the (A) component has a hydroxyl value of 10 to 40 mgKOH/g 〇 5. The active energy ray hardening is described in the first item of the patent application. The non-aqueous primer for the plastic film of the film 'the glass transition temperature of the component (A) is 0 to 60 ° C. The non-aqueous primer for a plastic film having an active energy ray hardened film according to the first aspect of the invention, wherein the amount of the component (A) is an average molecular weight of 5000 to 22,000. 7. The non-aqueous primer for a plastic film with an active energy ray hardening film according to claim 1, wherein the active energy ray-polymerizable functional group of the component (B) is a (fluorenyl) acrylonitrile group. . The non-aqueous primer for a plastic film with an active energy ray hardening film according to any one of the items 1 to 7, wherein the (D) aminate catalyst. 9. The non-aqueous primer for a plastic film having an active energy ray hardening film according to claim 8, wherein the base of the component (A) is X-mole or (B) When the hydroxyl group is y mole and the isocyanate group δ of the component (c) is z mole, z/(X+y) is 〇·5 to 5. The content of the (D) component in the active energy ray hardened skin with respect to the (Α) component is 10. The non-aqueous primer for the plastic film of the film according to the eighth aspect of the patent application, The parts by weight (calculated as non-volatile components) 〇·1 to 5 parts by weight. Π. A kind of active energy ray-hardened pecan shed AI plastic y plastic film, which is laminated on at least one side of the plastic film. The layer is formed by you. The patent application scope is 27th 201224076 1 item The primer layer comprising a non-aqueous primer for a plastic film having an active energy ray-hardening film according to any one of the items 10, and an active energy ray-curable film layer. 1 2. A plastic film with an active energy ray hardened film as described in claim 1 wherein the plastic film is a polyester film. 28