TWI577733B - Active energy ray hardening resin composition - Google Patents

Description

Active energy ray-curable resin composition

The present invention relates to an active energy ray-curable resin composition, and more particularly, relates to a fast curing rate, imparting damage resistance, abrasion resistance, stain resistance, flex resistance, workability, and transparency, and An active energy ray-curable resin composition of a coating film having a high hardness.

As a building member such as a floor slab or a wall material, or as a cabinet for home appliances such as furniture, kitchen products, and refrigerators, it is used in wood systems such as wood, plywood, laminated timber, particle board, and hard board. The surface of the base material made of the material or the surface of the base material made of a metal material such as iron or aluminum is decorated with a decorative decorative sheet. In addition, in recent years, a decorative sheet is attached to an exterior portion such as a door sash of an automobile or an interior portion such as an instrument panel, instead of directly applying a hard coating material (for example, Patent Document 1). Such a decorative sheet requires a high level of balance to have damage resistance, abrasion resistance, stain resistance, transparency, and the like, in addition to the decorative property.

In order to impart the above characteristics to the decorative sheet, it is widely applied to the surface of the thermoplastic resin film as a substrate, and is formed by containing A coating film formed by a coating of a curable resin composition.

As the coating material, a polyfunctional acrylate and/or a polyfunctional urethane acrylate containing dipentaerythritol hexaacrylate or pentaerythritol tetraacrylate, and an active energy ray-curable resin composition containing polyisocyanate are often used. Coating material (for example, Patent Document 2), but the coating film made of the above coating material has a poor balance between the bending resistance, the scratch resistance, and the abrasion resistance, and when the bending resistance is good, the scratch resistance or the resistance is resistant. The wear and tear is not sufficient. Further, since the coating material has a slow curing rate, it is necessary to suppress the linear velocity at a low level when the decorative sheet coated with the coating material on the surface of the substrate is produced by wire production. In the case where the UV curability is not good, there is a method of improving the UV illuminance, but there is a problem that the film is deformed by the radiant heat of the UV lamp.

A composition containing a polymer having a decane bond and an acrylic polyol resin (for example, Patent Document 3) or a poly-polymer is proposed as a curable coating material to which a coating film having improved scratch resistance or abrasion resistance is provided. A composition of a copolymer of a dimethyloxane moiety and a polymer chain portion of a vinyl polymer (for example, Patent Document 4). However, these coatings have a slow curing rate, and the resulting coating film is insufficient in stain resistance.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-118061

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-216812

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-268195

[Patent Document 4] Japanese Patent No. 3999111

An object of the present invention is to provide an active energy ray-curable resin which has a high curing rate and is excellent in scratch resistance, abrasion resistance, stain resistance, flex resistance, workability, transparency, and high hardness. Composition.

The present inventors have found that the above object can be attained by combining a resin composition of a polyether (meth) acrylate having a specific number of (meth) acryloxy group modified with ethanolamine and a polyisocyanate. Further, it has been found that when the resin composition is further blended with fine particles, the hardness of the coating film is further improved.

That is, the present invention is an active energy ray-curable resin composition characterized by containing (A) having the following formula (1):

(Here, R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) propylene fluorenyloxy groups, and the number of (meth) propylene fluorenyl groups in R1 is in R2 An ethanolamine-modified polyether (meth)acrylate having a total of (3) or more of (meth)acryloxyloxy groups, (B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) The photopolymerization initiator has a ratio (a/b) of the number (a) of the hydroxyl groups of the component (A) to the number (b) of the isocyanate groups of the component (B) in the range of 0.5 to 1.2.

Since the resin composition of the present invention has a high curing rate, the composition is applied to a thermoplastic resin film as a substrate and cured to produce a laminate, which can increase the speed of the manufacturing line, which lowers the manufacturing cost. . Moreover, the coating film obtained from the composition of the present invention is excellent in scratch resistance, abrasion resistance, stain resistance, flex resistance, workability, and transparency. Further, when fine particles are further blended in the resin composition, The hardness of the film will increase. Therefore, the laminate having the coating film can be suitably used as a building member such as a floor panel or a wall material, a household appliance such as a refrigerator, an exterior part such as a door and window of an automobile, an interior part such as an instrument panel, or the like. Decorative sheet for surface protection or decoration.

1‧‧·coating film

2‧‧‧ anchor coating

3‧‧‧ thermoplastic resin film

4‧‧‧ adhesive layer

5‧‧‧ thermoplastic resin film

Fig. 1 is a schematic view showing an example of a laminate of the present invention.

(A) Ethanolamine modified polyether (meth) acrylate

The component (A) in the composition of the present invention is an ethanolamine-modified polyether (meth) acrylate having the following formula (1).

In the above formula, each of R1 and R2 has one or more (A a polyether (meth) acrylate residue of a propylene methoxy group, the total number of (meth) propylene fluorenyl groups in R1 and the number of (meth) propylene methoxy groups in R 2 is 3 or more Preferably, it is 3 to 9, more preferably 4. In the above formula (1), when the total number of (meth)acryloxy groups in R1 and the number of (meth)acryloxy groups in R2 are 2 or less in total, the coating film is resistant to abrasion and abrasion. And poor pollution resistance. R1 and R2 may be the same or different from each other, and it is preferred that R1 and R2 are the same.

Component (A) has the function of capturing oxygen radicals. In general, a compound containing a (meth) propylene oxime functional group, when hardened by radical polymerization, is susceptible to polymerization by oxygen radicals in the air, particularly on the surface of the coating film. The hardening reaction by oxygen radicals becomes slower. In order to sufficiently harden the surface and increase the irradiation time of the active energy ray, the speed of the manufacturing line is lowered, and the inside of the coating film is less affected by oxygen radicals, the hardening reaction is excessively performed, and the coating film becomes brittle, therefore, The bending resistance is deteriorated. Since the component (A) has a specific structure of the above formula (1), the composition of the present invention is not hindered by oxygen radicals, so that the curing reaction rate is fast, and scratch resistance and abrasion resistance are obtained. A coating film excellent in stain resistance, flex resistance, workability, and transparency. The component (A) has an ethanolamine residue, and it is considered that hydrogen of a methylene group adjacent to the nitrogen atom in the ethanolamine residue is removed to generate a radical, and the oxygen radical is bound thereto and captured.

The component (A) can be produced, for example, by reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with ethanolamine at room temperature. This reaction is highly active at normal temperature and does not require a catalyst. Also, in order to prevent The gelation is preferably carried out by adding a solvent or the like to lower the apparent concentration.

R1-OC(=O)-CH=CH ₂ (3)

R2-OC(=O)-CH=CH ₂ (4) Here, R1 and R2 are as defined above.

In addition, when the component (A) is produced by the above method, a plurality of side reactants are produced in addition to the target component (A) of the main product, and in the coating material field, the component is usually used in a state in which the by-products are contained ( A).

Examples of the compound represented by the above formulas (3) and (4) include TPGDA (trade name) (tripropylene glycol diacrylate) manufactured by Daicel-Cytec Co., Ltd., and OTA 480 (trade name) (glycerol propoxy triacrylate). Ester), and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

The above OTA 480 has a compound of the following formula (5).

Particularly preferred as the component (A) is a compound having the following formula (2).

When the component (A) is a compound having the above formula (2), the obtained composition has good storage stability, and the obtained coating film is resistant to bending, workability, transparency, ternary formability, and damage resistance. The balance between sex, abrasion resistance and stain resistance is very good. Further, in general, in a production line of a laminate obtained by coating a base film with a coating material, when the laminate is wound by a roll, in order to prevent the laminate from sticking to each other, it is usually provided on the coating film. The separator, but when the component (A) is a compound of the above formula (2), the hardening reaction is very fast, and therefore there is an advantage that a separator is not required.

(B) Polyisocyanate

Component (B) is a compound having two or more isocyanate groups (-N=C=O) in one molecule. Specific examples thereof include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of methylphenyl diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. Fosone Trimethylolpropane adduct of diisocyanate, trimeric isocyanate of methyl phenyl diisocyanate, trimeric isocyanate of hexamethylene diisocyanate, trimeric isocyanate of isophorone diisocyanate and hexamethylene A polyisocyanate such as a biuret of a diisocyanate; and a urethane cross-linking agent such as a blocked isocyanate of the above polyisocyanate. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethyl benzoate may be added as needed.

Among these, from the viewpoints of the flexural resistance and the ternary formability of the coating film and the storage stability of the coating material, it is preferred to have three or more isocyanate groups in one molecule, and the following may be suitably used. a trimer of hexamethylene diisocyanate represented by the formula (6) and having an isocyanate ring structure or a trimer of hexamethylene diisocyanate represented by the following formula (7) and being trimethylolpropane Compound. These have the structural characteristics that the isocyanate group exists at the positions separated from each other at the front end of the hexamethylene chain, and therefore, the obtained coating film has elasticity, and is excellent in scratch resistance and abrasion resistance.

The resin composition of the present invention is hardened by the reaction of the hydroxyl group of the component (A) with the isocyanate group of the component (B). In order to sufficiently produce hardening, the resin composition of the present invention has a ratio (a/b) of the number of hydroxyl groups (a) of the component (A) to the number of isocyanate groups (b) of the component (B) of 0.5 to 1.2. Good is in the range of 0.7~1.1. When the above ratio is less than the above lower limit, the obtained coating film is inferior in bending resistance and three-dimensional formability. When the above ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance to aqueous contaminants such as water-based magic inks.

Further, the resin composition of the present invention may further contain a (meth) acrylate compound (A') other than the component (A). By containing In the fraction (A'), the characteristics of the coating film can be appropriately adjusted in accordance with the use of the laminate. When the component (A') is contained, the total number of hydroxyl groups (a) of the component (A) and the number of hydroxyl groups (a') of the component (A') (a+a') and the isocyanate group of the component (B) The ratio of the number (b) ((a+a')/b) is in the range of 0.5 to 1.2, preferably 0.7 to 1.1. When the above ratio is less than the above lower limit, the obtained coating film is inferior in bending resistance and three-dimensional formability. When the above ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance to aqueous contaminants such as water-based magic inks. Further, the component (A') may or may not have a hydroxyl group. The blending ratio of the component (A) to the component (A') can be appropriately determined depending on the use of the laminate. When the sum of the amount of the component (A) and the amount of the component (A') is 100% by mass, the component (A) is usually 10 to 100% by mass and the component (A') is 90 to 0% by mass, preferably a component. (A) 50 to 100% by mass and component (A') 50 to 0% by mass.

Examples of the (meth) acrylate-based compound (A') include a polyurethane (meth) acrylate, a polyester (meth) acrylate, and a (meth) acrylate polyacrylate. (meth) propylene methoxy group such as epoxy acrylate, polyalkylene glycol poly(meth) acrylate, and polyether (meth) acrylate containing prepolymer or oligomer; ) methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , isodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenyl celecoxime (A) Acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-propenyloxyethyl hydrogen phthalate Ester, dimethylaminoethyl (meth)acrylate, (methyl) propyl a compound containing one (meth) propylene oxime group such as triethyl oleic acid ethyl ester and trimethyl methoxy methoxy methacrylate; diethylene glycol di(meth) acrylate, neopentyl glycol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(methyl)propene oxime Oxypolyvinyloxyphenyl)propane and 2,2'-bis(4-(methyl)propenyloxypolyoxyphenyl)propane and the like containing 2 (meth)acryloxyloxy groups a compound containing three (meth)acryloxyl groups such as trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate; pentaerythritol tetra(methyl) a compound containing four (meth) propylene fluorenyl groups such as acrylate; a compound containing six (meth) acryloxy groups such as dipentaerythritol hexaacrylate; and the like, one or two or more kinds thereof may be used. .

In the present specification, the number of hydroxyl groups per unit amount of the component (A) and the component (A') is determined based on JIS-K-1557-1:2007. That is, by acetylating each of the hydroxyl groups of the component (A) and the component (A') by using an acetamidine reagent (pyridine solution of acetic anhydride), the excess acetamidine reagent is used. The water was hydrolyzed, and the produced acetic acid was obtained by a method of titrating a potassium hydroxide solution by using a potentiometric automatic titration apparatus Model AT-610 of Kyoto Electronics Industry Co., Ltd., and determining the above number. Further, the number of isocyanate groups per unit amount of the component (B) is determined based on JIS-K-7301:1995. That is, by reacting the isocyanate group of the component (B) with di-n-butylamine, the excess di-n-butylamine is used, and the potential difference automatic titrator AT-610 of Kyoto Electronics Industry Co., Ltd. is used to The above method is determined by the method of aqueous solution titration.

(C) Photopolymerization initiator

The component (C) is a radical polymerization type photopolymerization initiator, and a known one can be used. Examples thereof include a triazine-based compound, an acetophenone-based compound, a biimidazole compound, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, an anthraquinone-based compound, and an alkylphenone-based compound. A photopolymerization initiator such as a mercapto phosphine oxide compound, a titanocene compound, an oxime ester compound, a fluorenyl phenyl acetate compound, a hydroxyketone compound, or an amino benzoate compound. These may be used individually or in combination of 2 or more types. Among these, the reaction mechanism is a radical generating type which is removed by hydrogen, and a benzophenone type compound is preferable, and specific examples thereof include benzophenone and benzoic acid methyl-o-benzene. Methionate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone , 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6 - Trimethylbenzophenone and the like.

The blending amount of the component (C) can be appropriately selected depending on the kind of other components or the desired thickness of the coating film, and generally, in the case of the component (A), 100 parts by mass or the presence of the component (A') The amount is from 0.5 to 10 parts by mass based on 100 parts by mass of the total of the component (A) and the component (A'). For example, when the component (A) is a compound of the above formula (2), the component (B) is a compound of the above formula (6), and the component (C) is benzophenone, when the thickness of the coating film is 0.5 to 30 μm, When the amount of the component (C) is 4 to 10 parts by mass and the thickness of the coating film is 30 μm to 500 μm with respect to 100 parts by mass of the component (A), It is 0.5 to 8 parts by mass based on 100 parts by mass of the component (A). When the thickness of the coating film is thin, the amount of the component (C) is generally large, and the thinner the film, the more likely it is to cause the hardening inhibition by oxygen radicals.

(F) microparticles

The resin composition of the present invention preferably contains 1 part by mass based on 100 parts by mass of the component (A) or 100 parts by mass of the component (A) and the component (A'). ~50 parts by mass of particles having a particle diameter of 1 nm to 300 nm. The component (F) functions to increase the hardness of the coating film obtained from the resin composition of the present invention. The component (F) is an inorganic fine particle or an organic fine particle.

Examples of the inorganic fine particles include vermiculite (cerium oxide); metal oxide fine particles such as alumina, zirconia, titania, zinc oxide, cerium oxide, indium oxide, tin oxide, indium tin oxide, cerium oxide, cerium oxide, and the like. Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal fine particles; metal sulfide fine particles; metal nitride fine particles and the like.

Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, a vinyl resin, an amine compound, and a cured resin of formaldehyde.

These may be used alone or in combination of two or more.

Further, for the purpose of improving the dispersibility of the fine particles in the coating material or increasing the hardness of the obtained coating film, a decane coupling agent such as vinyl decane or amino decane may be used as the surface of the fine particles; Coupling agent; aluminate coupling agent; having (meth) acrylonitrile, vinyl, allyl, etc. An organic compound having a reactive functional group such as an ethylenically unsaturated bond group or an epoxy group; or a surface treatment agent such as a fatty acid or a fatty acid metal salt.

Among these, in order to obtain a coating film having a higher hardness, fine particles of vermiculite or alumina are preferable, and fine particles of vermiculite are more preferable. As a commercial product of the smectite granules, Snowtex (trade name) of Nissan Chemical Industry Co., Ltd., and Quatron (trade name) of Fuso Chemical Industry Co., Ltd., etc. are mentioned.

The particle diameter of the component (F) must be 300 nm or less in order to impart transparency to the obtained coating film. Further, when the particle diameter is coarse, the hardness of the obtained coating film tends to be insufficient. It is preferably 200 nm or less, more preferably 120 nm or less. On the other hand, the lower limit of the particle diameter is not particularly limited, and generally obtained particles are at most about 1 nm even fine.

Furthermore, in this specification, the particle diameter of the microparticles is laser diffraction using Nikkiso Co., Ltd. In the particle diameter distribution curve measured by the scattering particle size analyzer MT3200II (trade name), the particle diameter accumulated by 50% by mass of the particles is small.

Further, the blending amount of the component (F) is 100 parts by mass based on 100 parts by mass of the component (A) or 100 parts by mass of the component (A) and the component (A'). It is 1 to 50 parts by mass. The hardness improvement effect of the coating film cannot be obtained in 1 part by mass or less. When the amount is 50 parts by mass or more, the bending resistance is lowered. It is preferably 3 to 25 parts by mass.

(D) solvent

The composition of the present invention may contain a solvent as needed for dilution. The solvent is compatible with the components (A), (A'), (B), (C) and (E), There is no particular limitation on those which do not react with the components (A), (A'), (B), (C), (E) and (F), or catalyze self-reaction of these components. For example, a known one such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate or diacetone alcohol can be used. In particular, a solvent containing 40% by mass or more, more preferably 80% by mass or more, based on 1-methoxy-2-propanol is preferred, and the following thermoplastic resin film (3) coated with the above composition is This is especially true in the case of a resin film having low solvent resistance such as a polyester resin film to be stretched. In general, the polyester resin film which is not stretched is excellent in three-dimensional formability and flex resistance, and has excellent surface gloss. Therefore, it is widely used as a base film of a decorative film, but has poor solvent resistance. Therefore, when the solvent-containing composition is applied to the polyester resin film which is not stretched as the base film, the obtained decorative film loses the surface gloss, or the base film may swell depending on the case, and the decorative film cannot be decorated. The problem with the film. When the solvent contains 40% by mass or more of 1-methoxy-2-propanol, the above problem does not occur.

The amount of the solvent can be appropriately adjusted in such a manner as to be suitable for viscosity in accordance with the thickness of the coating device or the coating film. In the case of the component (A'), the component (A') is usually 150 to 250 parts by mass based on 100 parts by mass of the total of the component (A) and the component (A').

(E) UV reactive fluorine-based surface modifier

The composition of the present invention may further contain an ultraviolet-reactive fluorine-based surface modifier (E) in order to prevent the coating from collapsing, or the fingerprint resistance, stain resistance, and adhesion of the coating film. Ultraviolet reactive fluorine-based surface modifier (E), A compound having a fluorine-containing group, a hydrophilic group, a lipophilic group, and an ultraviolet-ray reactive group is preferred, and a commercially available example of the component (E) is Megafac RS-75 (trade name) of DIC Corporation. The amount of the component (E) is preferably 0.1 in terms of 100 parts by mass of the component (A) or 100 parts by mass of the component (A) and the component (A') in the case where the component (A') is present. ~5 parts by mass, more preferably 0.2 to 2.0 parts by mass. When it is more than 5 parts by mass, the surface hardness may be lowered.

Moreover, the resin composition of the present invention may contain an antioxidant, a weather-resistant stabilizer, a light-resistant stabilizer, a UV absorber, a heat stabilizer, an antistatic agent, a surfactant, and the like, without impairing the effects of the present invention. One or two or more kinds of additives such as a coloring agent, an infrared shielding agent, a leveling agent, a shake imparting agent, and a filler.

The resin composition of the present invention can be obtained by mixing and stirring the above components (A), (B), (C), preferably (F), and other optional components.

The resin composition thus obtained is active energy ray-curable, and is applied to the surface of the thermoplastic resin film (3) as a substrate, and is cured by irradiation with an active energy ray such as ultraviolet rays, visible rays, or electron beams. A laminate of the coating film (1) excellent in scratch resistance, abrasion resistance, stain resistance, and flex resistance. Or by a substrate excellent in solvent resistance, for example, a 2-axis extended polyethylene terephthalate film having a surface subjected to release treatment, the above composition is coated and dried. After the coating film (1) is formed by hardening, it is laminated with the thermoplastic resin film (3) by a method such as thermal lamination or dry lamination, whereby a laminate having the coating film (1) can be obtained.

Moreover, since the resin composition of the present invention has a fast curing reaction, the linear velocity at the time of applying the composition to the substrate to produce a laminate can be improved, and thus the production cost can be reduced.

The thickness of the coating film (1) is preferably 0.5 μm or more. When it is thinner, the damage resistance may be insufficient. On the other hand, the upper limit of the thickness of the coating film is not particularly limited. However, a coating film which is thicker than necessary is only a factor of cost increase, so even if it is thick, it is at most 60 μm.

Thermoplastic resin film (3)

A thermoplastic resin film (3) in which a coating film (1) composed of the above resin composition is laminated to form a laminate can be used, and any thermoplastic resin film can be used. For example, a polyvinyl chloride resin; a non-crystalline, low crystalline or crystalline polyester; a polyolefin such as polypropylene or polyethylene; acrylonitrile. Butadiene. Styrene copolymer resin (ABS resin) or styrene. Ethylene. Butadiene. Styrene copolymer, styrene. Ethylene. Butadiene. a styrene resin such as a hydride of a styrene copolymer; an unstretched film of a thermoplastic resin such as polyamine, acryl, polycarbonate, or polyurethane, a uniaxially stretched film, and a biaxial extension film. Preferably, a stretch-free film of a polyvinyl chloride resin or a non-crystalline polyester resin or a stretched crystalline polyester film can be used. Further, in order to impart high gloss to the laminate, the thermoplastic resin film (3) preferably has a high surface gloss itself and is preferably transparent. Specifically, it is preferably a non-stretched film of a non-crystalline polyester resin and an extended-processed polyester film, particularly preferably a polyethylene terephthalate or a diol copolymerized polyethylene terephthalate. Diester, acid copolymerized polyethylene terephthalate And a polyester resin such as polyethylene naphthalate or a biaxially stretched polyester film formed by any combination of the above.

The non-stretching film of the above non-crystalline polyester resin may, for example, SET329 FZ26401 {trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film of Riken technos Co., Ltd., two axes Examples of the extended polyester film include Lumirror (trade name) of Toray Co., Ltd., Embed S25 (trade name) of Unitika Co., Ltd., Melinex (705) #75 (trade name) of Teijin Co., Ltd., and Toyobo Co., Ltd. A4300 (trade name) of the company.

The thickness of the thermoplastic resin film (3) is usually 10 μm to 100 μm, preferably 15 to 50 μm. When the thickness is thinner than the lower limit, the laminate may be wrinkled. When the thickness is thicker than the upper limit, the laminate may be rebounded during lapping forming, or the processing speed of the coating process or the lamination process may have to be suppressed. Low level.

The coating film (1) formed of the above composition may be laminated to the thermoplastic resin film (3) by directly applying the above composition to the thermoplastic resin film (3) or by interposing an anchor coating layer (2). The layer is coated. dry. Hardening; or by coating a substrate with excellent solvent resistance, for example, a 2-axis extended polyethylene terephthalate film whose surface is subjected to release treatment, coating the above composition and drying. After the coating film (1) is formed by hardening, it is thermally laminated or dry-bonded, and the thermoplastic resin film (3) is bonded directly or via a layer of the anchor coating layer (2).

Anchor coating (2)

The above laminate may have an anchor coat layer (2) between the coating film (1) and the thermoplastic resin film (3). By providing the anchor coating layer (2), the adhesion strength between the coating film (1) and the thermoplastic resin film (3) can be improved.

As the anchor coating agent for forming the anchor coating layer (2), as long as it is well dissolved in 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl A known solvent such as a ketone, ethyl acetate or acetone, and a sufficient anchor effect is not particularly limited, and a polyester type, an acrylic type, a polyurethane type, an amine group can be used. Conventional applications such as formic acid acrylate and polyester urethane. As a commercial example, Vylon 24SS (trade name) of Toyobo Co., Ltd., AU2141NT of Tokushiki Co., Ltd., etc. are mentioned.

When the anchor coating layer (2) is provided, an anchor coating layer (2) may be preliminarily formed on one side of the thermoplastic resin film (3) by applying an anchor coating agent in a conventional manner, and the anchor coating layer (2) is laminated thereon. A coating film (1) made of the above composition.

The thickness of the anchor coating layer (2) is usually about 0.1 to 5 μm, preferably 0.5 to 2 μm.

The method of applying the above resin composition or anchor coating agent to the thermoplastic resin film (3) is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be exemplified.

Thermoplastic resin film (5)

The above laminate may be laminated with a thermoplastic resin film (3) The thermoplastic resin film (5) (see FIG. 1) may be further laminated on the surface opposite to the surface of the coating film (1) via the adhesive layer (4), or the adhesive layer (6) may be further provided thereon. When the laminate having the coating film (1) is attached to a body (for example, a particle board) having irregularities on the surface, the laminate further has a thermoplastic resin film (5), thereby preventing the above-mentioned unevenness and the like. The surface of the laminate is thus preferred to maintain clearness.

The laminate of the thermoplastic resin film (5) can be formed by, for example, applying an adhesive to a surface opposite to the surface of the coating film (1) on which the thermoplastic resin film (3) is laminated to form an adhesive layer (4). The thermoplastic resin film (5) is bonded thereto by using a heat laminating device of a metal roll-rubber roll thereon. At this time, the metal roll side was brought into contact with the coating film (1). The surface temperature of the metal roll is preferably 120 ° C or higher, more preferably 160 ° C or higher. The upper limit of the surface temperature is about 250 ° C in consideration of the heat resistance of the thermoplastic resin film (3). When a mirror metal roll is used as the above metal roll, the surface of the laminate (the surface of the coating film (1)) can be imparted with higher gloss. When an embossed metal roll is used as the above metal roll, embossing can be applied to the surface of the laminate (the surface of the coating film (1)).

The thickness of the thermoplastic resin film (5) is not particularly limited, but is usually 20 to 1000 μm, preferably 100 to 500 μm. When the laminate is too thin, when the laminate is attached to the object, the unevenness of the surface of the object will be on the surface of the laminate, and the clarity may not be obtained. When the thickness is too thick, the laminate may be bonded to the object. Easy to lower.

As the thermoplastic resin film (5), those mentioned in the above thermoplastic resin film (3) can be used. Also, will have thermoplastic When the laminate of the resin film (5) is attached to the object, it is preferable to heat the end portion or the like to facilitate the bending process. Therefore, the thermoplastic resin film (5) preferably has a glass transition temperature of 60. ~130 °C. Examples of the thermoplastic resin film having such a glass transition temperature include acrylic resin, polyvinyl chloride resin, polyester resin, and acrylonitrile. Butadiene. A film of a styrene copolymer resin.

In particular, the thermoplastic resin film (5) comprises the following resins (α-1) and (α-2): (α-1) wherein the dicarboxylic acid component is terephthalic acid; the diol component is ethylene glycol. 60% by mole or more, less than 90% by mole, and amorphous polyethylene terephthalate system with 10% by mole or more and less than 40% by mole of 1,4-cyclohexanedimethanol The resin (PETG) is 30 to 70% by mass, preferably 40 to 60% by mass; and (α-2) is 90 mol% or more and less than 99 mol% of the dicarboxylic acid component. 1 mol% or more and less than 10 mol% of phthalic acid; the diol component is 70 to 30% by mass of a crystalline polyethylene terephthalate resin of ethylene glycol, preferably 60 to 40% The mass%, where the amount of the resin (α-1) and the amount of the resin (α-2) are 100% by mass in total, and the film formed of the aromatic polyester resin composition has a temperature of 60 to 130 ° C. Since the glass has a high transfer temperature and high rigidity, even if the thickness of the film is thin, it is possible to obtain sharpness, which is suitable for the cost reduction.

The aromatic polyester resin composition may further contain a polybutylene terephthalate resin or a polytrimethylene terephthalate resin, and the dicarboxylic acid component is terephthalic acid and isophthalic acid. And diol component It is another polyester resin such as a polybutylene terephthalate copolymerized resin of tetramethylene glycol. In addition, when the total amount of the resin (α-1), the resin (α-2), and the other polyester resin is 100 parts by mass, the resin may be further contained in an amount of 0.1 to 10 parts by mass in addition to the above. The resin further contained in the above may, for example, be a methacrylate-styrene/butadiene rubber graft copolymer, an acrylonitrile-styrene/butadiene rubber graft copolymer, or an acrylonitrile-styrene/ethylene-propylene copolymer. Rubber graft copolymer, acrylonitrile-styrene/acrylate graft copolymer, methacrylate/acrylate rubber graft copolymer, methacrylate-acrylonitrile/acrylate rubber graft copolymer and thermoplasticity An elastomer resin such as a polyester elastomer. Further, the aromatic polyester-based resin composition may further contain a lubricant, an antioxidant, a weather-resistant stabilizer, a thermal stabilizer, a mold release agent, an antistatic agent, and a surfactant in a range of 0.1 to 5 parts by mass. And other additives. Examples of the lubricant include hydrocarbon waxes such as paraffin wax, polyethylene wax, and polypropylene wax; fatty acid waxes such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; and decyl stearate; Ammonium oxystearate, decyl oleate, decyl succinate, decyl ricinoleate, decyl phthalate, decyl methylene bis-stearate, decyl ethyl bis-stearate Or aliphatic amide amine wax; aliphatic ester wax such as n-butyl stearate or montanoic acid ester wax; aliphatic metal soap wax, urea-formaldehyde wax, and the like. Further, a pigment and an inorganic filler may be further contained. The pigment is not particularly limited, and examples thereof include titanium oxide (white) and carbon black (black). Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, aqueous magnesium citrate, and talc.

Thin by the above aromatic polyester resin composition The film can be produced by any method, for example, a calendering machine film can be used, or an extruder and a T die can be used to form a film. Any of the calendering machines can be used, and examples thereof include an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverse L type 4 roll, and a Z type roll. Any extruder may be used, and examples thereof include a single-shaft extruder, a co-rotating two-axis extruder, and a counter-rotating two-axis extruder. Any of the T-die can be used, and examples thereof include a manifold die, a fishtail die, and a hanger die.

In the case of the laminate shown in Fig. 1, the thermoplastic resin film (3) is preferably a biaxially stretched polyester film or a thermoplastic resin film (5) is a film of the above aromatic polyester resin composition.

The adhesive for forming the adhesive layer (4) and the adhesive layer (6) is not particularly limited as long as sufficient adhesive strength can be obtained, and for example, acrylic, ethylene vinyl acetate or vinyl acetate can be used. A conventional adhesive such as a polyester, a polyurethane, an epoxy resin, a chloroprene rubber or a styrene butadiene rubber. The method of providing the adhesive layer is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating may be mentioned. In this case, any dilution solvent such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate or acetone may be used as needed.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto.

Synthesis Example 1

OTA480 (product name, glycerol propoxy triacrylate of the above formula (5)) manufactured by Daicel-Cytec Co., Ltd. and 2-aminoethanol, which is 1 mol with respect to the former 2 mol The amount of the mixture was placed in a glass beaker and reacted at a temperature of 23 ° C for 72 hours to obtain an ethanolamine-modified polyether acrylate (A-1) having four propylene fluorenyloxy groups having the structure of the above formula (2). The number of hydroxyl groups per unit amount of the component (A-1) was 1.09 mol/kg as measured by the above method.

Synthesis Example 2

In the same manner as in the above Synthesis Example 1, except that the above-mentioned Synthesis Example 1 was used, in the same manner as in the above Synthesis Example 1, tripropylene glycol diacrylate (manufactured by Daicel-Cytec Co., Ltd.) was used instead of OTA480 (manufactured by Daicel-Cytec Co., Ltd.). A propylene oxirane ethanolamine modified polyether acrylate (A-2). The number of hydroxyl groups per unit amount of the component (A-2) was 1.51 mol/kg.

Example 1

100 parts by mass of the component (A-1) of the component (A), and Colonate HX (trade name, polyisocyanate of the above formula (6), manufactured by Japan Polyurethane Co., Ltd. as the component (B) (B-1) 25 parts by mass, 7 parts by mass of benzophenone (C-1) as the component (C), and 200 parts by mass of 1-methoxy-2-propanol as the component (D), and As any other ingredient 0.3 parts by mass of a collapsible prevention agent (Polyflow 75 (trade name) manufactured by Kyoeisha Co., Ltd.) was mixed and stirred to obtain an active energy ray-curable resin composition. Further, the number of isocyanate groups per unit amount of the component (B-1) was 5.12 mol/kg as measured by the above method. Therefore, the ratio (a/b) of the number of hydroxyl groups (a) in 100 parts by mass of the component (A-1) to the number (b) of isocyanate groups in 25 parts by mass of the component (B-1) is 1.09 × 100. /(5.12×25)=109/128=0.85.

A two-axis stretch polyester film "UnitikaS" (trade name, thickness 50 μm) of Unitika Co., Ltd. was used as the thermoplastic resin film (3), and an anchor coating agent (Vylon 24SS (Toyobo Co., Ltd.) was applied to one side thereof. Trade name)) A dry film thickness of 1 μm was obtained to obtain a thermoplastic resin film (3) having an anchor coat layer (2) on one side. The resin composition obtained above was applied onto the anchor coating layer (2), dried, irradiated with ultraviolet rays, and then continuously wound at a line speed of 50 m/min in a series of manufacturing lines to wind the obtained laminate. step. The winding of the rolls can be carried out well without using a separator. The coating of the above resin composition was carried out by using a film meyer bar type coating apparatus so that the thickness of the coating film after drying was 11 μm. Further, the linear velocities in the examples and the comparative examples are the fastest speeds at which the laminate can be stably produced in the production line. The following tests (1) to (7) were carried out on the obtained laminate. The results are shown in Table 1.

Example 2

In addition to the use of Sumijule HT (trade name, polyisocyanate of the above formula (7), per unit amount of Bayer urethane co., Ltd. The number of isocyanate groups: 3.10 mol/kg) (B-2) 42 parts by mass The laminate was produced in the same manner as in Example 1 except that the component (B) was used. The results are shown in Table 1.

Examples 3 to 6 and Comparative Examples 1 to 2

A laminate was produced in the same manner as in Example 1 except that the amount of the component (B) in Example 1 was changed to that shown in Table 1. The results are shown in Table 1.

Comparative example 3

A laminate was produced in the same manner as in Example 6 except that the component (A-2) obtained in Synthesis Example 2 was used instead of the component (A-1). The linear velocity at this time was 50 m/min in the same manner as in Example 6, but a separator was used for winding the roller. The results are shown in Table 1.

Comparative example 4

In the same manner as in Example 1, tripropylene glycol diacrylate (manufactured by Daicel-Cytec Co., Ltd., number of hydroxyl groups per unit: 0 mol/kg) (A-3) was used instead of the component (A-1); A benzoyl ketone photopolymerization initiator (Darocur 1173 [trade name], 2-hydroxy-2-methyl-1-phenyl-propan-1-one) of Ciba Japan Co., Ltd. C-2) A laminate was produced in the same manner as in Example 1 except for the component (C). The linear velocity at this time was 30 m/min. When benzophenone (C-1) is not used as the component (C), the above (C-1) is used because the above (A-3) is used instead of the component (A-1). Slow reason. In the hardening of the above (A-3) and the above (B-1), the above (C-2) is used as the component (C) so as to be carried out at a rapid rate without gelation. The same applies to the following Comparative Examples 5 and 6. In addition, the amount of the component (C) is 5 parts by mass, because if it is 7 parts by mass, it is too much, and gelation occurs. The results are shown in Table 1.

Comparative Example 5

In addition to the first embodiment, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol/kg) (A-4) was used instead of the component (A-1). Further, a laminate was produced in the same manner as in Example 1 except that the ratio of the component (B) was changed so that the ratio (a/b) was 0.85. The results are shown in Table 1. Further, the above (A-4) does not have a hydroxyl group in its structure, but since it contains a component in which a part of the acryloxy group is hydrolyzed, a hydroxyl group exists. The same applies to (A-5) in Comparative Example 6 below.

Comparative Example 6

In addition to Example 1, di-trimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol/kg) (A-5) was used in place of the component ( A-1) A laminate was produced in the same manner as in Example 1 except that the amount of the component (B) was changed so that the ratio (a/b) was 0.85. The results are shown in Table 1.

Comparative Example 7

In addition to Example 1, it was made using Natoco Co., Ltd. A layer was obtained in the same manner as in Example 1 except that "self-healing paint No. 100" (trade name, polydimethyl methoxy oxane graft acrylate-based paint) was used as a resin composition and the dried film thickness was 20 μm. Fit. At this time, the linear velocity is 10 m/min, and a separator must be used for winding the roller. The results are shown in Table 1. Further, the thickness of the coating film in Comparative Example 7 was made thicker than the thickness (11 μm) of Example 1, because the damage resistance-1 and 2 corresponding to the most important characteristics of the above self-healing coating were intended. The result is ◎ compared with the examples. The damage resistance is thicker than the coating film.

Example 7

A laminate was produced in the same manner as in Example 1 except that the thickness of the coating film was changed to 2 μm in Example 1. The linear velocity at this time is 40 m/min. The linear velocity was made slower than that of Example 1, because the influence of oxygen radicals was on the inside of the coating film when the coating film was thin, and as a result, the curing speed of the entire coating film was slowed down. The results are shown in Table 1.

Example 8

A laminate was produced in the same manner as in Example 1 except that the thickness of the coating film was changed to 50 μm in Example 1. The linear velocity at this time is 50 m/min. The results are shown in Table 1.

Example 9

A laminate was produced in the same manner as in Example 1 except that methyl ethyl ketone was used as the component (D) in Example 1. Line speed at this time 50m/min. The results are shown in Table 1.

experiment method (1) Pencil hardness

The hardness of the surface of the coating film was evaluated in accordance with JIS K 5600-5-4 under the condition of a load of 200 g using a pencil {Uni" (trade name) of Mitsubishi Pencil Co., Ltd.

(2) Damage resistance-1

The laminate obtained above was cut into a length of 200 mm × a width of 25 mm, and used as a test piece, which was placed in a vibration tester of JIS L 0849, and the surface of the coating film was a surface. Next, after the steel wire of #0000 was installed in the friction terminal of the Xuezheng testing machine, the load was 1 kg, and the surface of the test piece was rubbed 5 times. The above surface was visually observed and evaluated by the following criteria.

◎: no scars

○: There are 1 to 3 scars

△: There are 4 to 10 scars

×: There are more than 11 scars

(3) Damage resistance-2

The laminate obtained above was cut into a length of 150 mm × a width of 75 mm, and was used as a test piece on a glass plate so that the surface of the coating film was a surface. Using a 4 row copper brush (500 gf load) made by Zhongwu Brush Industry, the surface of the test piece was wiped 10 times back and forth by a single pass of 100 mm. Visual view The above surface was examined and evaluated by the following criteria.

◎: no scars

○: There are 1 to 3 scars

△: There are 4 to 10 scars

×: There are more than 11 scars

(4) Pollution resistance-1

After the surface of the coating film of the laminate obtained above was contaminated with dots by an oily red magic ink, the contaminated portion was covered with a watch glass and allowed to stand at room temperature for 24 hours. Next, the contaminated portion was wiped with Kimwipe (trade name) sufficiently saturated with isopropyl alcohol until the Kimwipe was free from new adhesion, and after washing, the above portion was visually observed and evaluated by the following criteria.

◎: no pollution

○: Only a little pollution remains.

△: Residual pollution

×: Residual significant pollution

(5) Pollution resistance-2

After the surface of the coating film of the laminate obtained above was contaminated with dots by aqueous red magic ink, the contaminated portion was covered with a watch glass and left at room temperature for 24 hours. Next, the contaminated part was thoroughly washed with running water, and then Kimwipe (trade name) containing tap water was used, and the Kimwipe was wiped until there was no new adhesion, and after washing, the above portion was visually observed. Benchmark to evaluate.

◎: no pollution

○: Only a little pollution remains.

△: Residual pollution

×: Residual significant pollution

(6) Flexibility

The laminate obtained above was cut into a size of 100 mm × 50 mm, and the double-sided tape No. 500A made by Nitto Denko was attached to an aluminum plate having a thickness of 0.3 mm to form a surface of the coating film as a test piece. Using a bending test apparatus of JIS K 5600-5-1 model 1 equipped with a mandrel having a diameter of 2 mm, the test piece was bent at 180° at an equal speed in such a manner that the coating film surface became the outer side for 2 seconds. After the end of the bending, the 30 mm portion of the center of the bent portion was examined for the presence or absence of cracking (cracking) of the coating film, and was evaluated by the following criteria.

◎: no cracks

○: There is 1 crack

△: There are 2~3 cracks

×: There are more than 4 cracks

(7) Appearance

The laminate obtained above was cut into a size of 100 mm × 100 mm, and placed on a smooth glass plate arranged horizontally so that the surface of the coating film became the upper side. The curled portions at the four corners of the laminate were measured at a vertical distance from the glass plane, and the average value thereof was determined and evaluated based on the following criteria.

◎: less than 2mm

○: 2 mm or more and less than 5 mm

△: 5mm or more, less than 10mm

×: 10mm or more

As is apparent from Table 1, the composition of the present invention can produce a laminate having a coating film composed of the composition at a high linear velocity, and the coating film is resistant to damage, staining, and folding. Excellent in sex and appearance. On the other hand, the composition of Comparative Examples 1 and 2 having a ratio (a/b) outside the range of the present invention was inferior in any of the obtained coating films such as scratch resistance, stain resistance and flex resistance. As the component (A), the composition of Comparative Example 3 in which the number of (meth)acrylomethoxy groups was smaller than the range of the present invention was poor, and the obtained coating film was inferior in damage resistance and stain resistance. As the component (A), the composition of Comparative Examples 4 to 6 which did not have an ethanolamine residue was used, and the curing rate was slow, so the linear velocity was slow. Further, the obtained coating film is inferior in any of the scratch resistance, the stain resistance, the flex resistance, and the appearance. As a resin composition, Comparative Example 7 in which a polydimethylsiloxane was grafted with an acrylate-based paint of a self-healing coating was used, and the coating film was poor in stain resistance. Further, as is apparent from the comparison between Example 7 and Example 8, the linear velocity was high in the case where the thickness of the coating film was thick, and the thickness of the coating film was thicker than that in Example 1 in Comparative Example 7, but the curing rate was slow. Therefore the line speed is slow.

Example 10

In addition to Example 1, SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film, thickness 100 μm, manufactured by Riken technos Co., Ltd., and surface according to JIS-7105 was used. A laminate was produced in the same manner as in Example 1 except that the thermoplastic resin film (3) was used as the thermoplastic resin film (3) and the anchor coating agent was not used. The linear velocity at this time is 50 m/min. Right place The resulting laminate was subjected to the above tests (1) to (7). Further, the 60° glossiness of the surface of the coating film (1) was measured in accordance with JIS-7105-1981. The results are shown in Table 2.

Example 11

In the same manner as in Example 10 except that a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 50:50 (volume ratio) was used as the component (D). Laminated body. The results are shown in Table 2.

Reference example 1

The laminate was produced in the same manner as in Example 10 except that methyl ethyl ketone was used as the component (D). However, the thermoplastic resin film (3) as a substrate was swollen, and a laminate could not be obtained. .

As shown in Table 2, when the thermoplastic resin film (3) as the substrate is a polyester film having no extension, when methyl ethyl ketone is used as the solvent (D), the base film is swollen and the laminate cannot be obtained ( Reference example 1). However, when a solvent (D) containing 40% by mass or more of 1-methoxy-2-propanol (D-2) is used, the base film is not swollen, and the gloss of the base film is not lowered, and a laminate can be obtained. (Examples 10 and 11).

Example 12

A two-axis stretch polyester film "E5101 (trade name)" (thickness: 25 μm) of Toyobo Co., Ltd. was used as the thermoplastic resin film (3), and a one-side coating device using a gravure printing method was used to coat the Toyobo Co., Ltd. The anchor coating agent "Vylon 24SS (trade name)" of the company has a dry film thickness of 1 μm, and a thermoplastic resin film (3) having an anchor coating (2) on one side is obtained. On the anchor coating layer (2), the active energy ray-curable resin composition obtained in Example 1 was applied and dried, and irradiated with ultraviolet rays, followed by continuous operation at a linear velocity of 50 m/min in a series of production lines. The laminate is wound by a roll. The winding of the rolls can be carried out well without using a separator. The coating of the above resin composition was carried out by using a coating apparatus using a film Meyer wire rod method, and the thickness of the coating film after drying was 11 μm.

On the thermoplastic resin film (3) of the laminate obtained above, a polyester-based hot-melt adhesive "AD-170-20 (trade name)" of Tokushiki Co., Ltd. was applied to make the thickness after drying 2.5 μm, which is attached to the following using a mirror metal roll-rubber roll thermal laminating device A thermoplastic resin film (5) was obtained, and a laminate having the structure shown in Fig. 1 was obtained. At this time, the metal roll side was brought into contact with the coating film (1), and the surface temperature of the metal roll was set to 190 °C. The above tests (1) to (7) and the following tests (8) to (10) were carried out on the laminate obtained in the above manner. Further, the 60° glossiness of the surface of the coating film (1) was measured in accordance with JIS-7105-1981. The results are shown in Table 3.

Production of thermoplastic resin film (5)

44 parts by mass of PETG resin "Cadence GS1 (trade name)" from Eastman Chemical Company, and crystalline polyethylene terephthalate resin "WK-801 (trade name)" (dicarboxylic acid) of Wankai New Materials Co., Ltd. Acid component: a mixture of 90% by mole or more of terephthalic acid, less than 99% by mole and 1 mole% of isophthalic acid, less than 10% by mole; diol component: ethylene glycol) 41 parts by mass 15 parts by mass of the polybutylene terephthalate resin "Toraycon 1200M (trade name)" of Toray Co., Ltd., and Kaneace FM-40 (trade name) of Kaneka Co., Ltd. 0.5 parts by mass of the lubricant "Loxiol G78 (trade name)" of Cognis Japan Co., Ltd., and the titanium oxide (white pigment) "Tipaque CR-60-2 (trade name)" of Ishihara Sangyo Co., Ltd. 12 quality The resin composition consisting of a part is melt-extruded into a film shape by a two-axis extruder equipped with a vacuum vent hole and a T-die connected to the extruder, and is made of a mirror-finished roll made of metal and rubber. The cooling roller holds the molten film to be cooled and solidified to obtain a thermoplastic resin film (5)

Example 13

In addition to the use of Sumijule HT (trade name, polyisocyanate of the above formula (7), the number of isocyanate groups per unit amount: 3.10 mol/kg) (B-2) 42 A laminate was produced in the same manner as in Example 12 except for the component (B). The results are shown in Table 3.

Examples 14 to 17 and Comparative Examples 8 to 9

A laminate was produced in the same manner as in Example 12 except that the amount of the component (B) was changed to that shown in Table 3 in Example 12. The results are shown in Table 3.

Comparative Example 10

A laminate was produced in the same manner as in Example 17 except that the component (A-2) obtained in Synthesis Example 2 was used instead of the component (A-1). The linear velocity at this time was 50 m/min as in Example 17, but a separator was used for winding the roller. The results are shown in Table 3.

Comparative Example 11

In addition to Example 12, tripropylene glycol diacrylate (manufactured by Daicel-Cytec Co., Ltd., number of hydroxyl groups per unit: 0 mol/kg) (A-3) was used in place of the component (A-1), and used. Phenyl ketone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2)5 from Ciba Japan Co., Ltd. The amount of mass as a component A laminate was produced in the same manner as in Example 12 except for (C). The linear velocity at this time was 30 m/min. When the benzophenone (C-1) is not used as the component (C), the above (A-1) substitution component (A-1) is used, and the (C-1) curing rate is slow. The curing of the above (A-3) and the above (B-1) is carried out at a rapid rate without gelation, and the above (C-2) is used as the component (C). The same applies to the following Comparative Examples 12 and 13. In addition, when the amount of the component (C) is 5 parts by mass, the amount of the component (C) is too large, and gelation occurs. The results are shown in Table 3.

Comparative Example 12

In addition to Example 12, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol/kg) (A-4) was used instead of the component (A-1). Further, a laminate was produced in the same manner as in Example 12 except that the ratio (a/b) was changed to 0.85. The results are shown in Table 3. Further, the above (A-4) does not have a hydroxyl group in its structure, but since it contains a component in which a part of the acryloxy group is hydrolyzed, a hydroxyl group exists. The same applies to (A-5) in Comparative Example 13 below.

Comparative Example 13

In addition to Example 12, di-trimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol/kg) (A-5) was used in place of the component ( A-1), and the amount of the component (B) was changed, and the laminate was produced in the same manner as in Example 12 except that the ratio (a/b) was 0.85. The results are shown in Table 3.

Example 18

A laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was changed to 2 μm in Example 12. The linear velocity at this time is 40 m/min. The linear velocity was slower than that of Example 12. When the coating film was thin, the influence of oxygen radicals was on the inside of the coating film, and as a result, the curing speed of the entire coating film became slow. The results are shown in Table 3.

Example 19

A laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was changed to 50 μm in Example 12. The linear velocity at this time is 50 m/min. The results are shown in Table 3.

Example 20

A laminate was produced in the same manner as in Example 12 except that in Example 12, methyl ethyl ketone was used as the component (D). The linear velocity at this time is 50 m/min. The results are shown in Table 3.

Example 21

In the present embodiment, an example of the component (A') is added in addition to the component (A). 50 parts by mass of the component (A-1) was used as the component (A), and 50 parts by mass of the component (A-4) was used as the component (A'). Further, a laminate was produced in the same manner as in Example 12 except that the active energy ray-curable resin composition was obtained using the components (B) to (E) shown in Table 3. The results are shown in Table 3.

Example 22

A laminate was produced in the same manner as in Example 21 except that the blending amount of the component (E) was 2.0 parts by mass. The results are shown in Table 3.

experiment method (8) Solvent friction test

The laminate obtained above was cut out to a size of 100 mm × 100 mm, and the surface of the coating film (1) was rubbed 10 times with a Kimwipe (trade name) containing methyl ethyl ketone, and the gloss or clarity of the portion was visually observed. Whether there is a change in sex is assessed by the following criteria.

○: no change in surface gloss or clarity

×: Surface gloss or clarity changes

(9) Glycerol test

The laminate obtained above was cut into a size of 100 mm × 100 mm, and immersed in glycerin adjusted to 100 ° C for 30 seconds, and then the gloss or clarity of the surface of the coating film (1) was visually observed to be changed, and evaluated by the following criteria.

○: no change in surface gloss or clarity

×: Surface gloss or clarity changes

(10) scratch resistance (nail)

The laminate obtained above was cut into a size of 120 mm × 60 mm, and placed on the glass plate with the coating film (1) placed thereon, while pressing with the left hand. The surface of the coating film (1) was scratched with a right-handed nail, and the damage was visually evaluated by the following reference.

◎: no scars can be observed at all

○: almost no scars were observed

△: A little scar was observed.

×: Significantly observed scars

As is clear from Table 3, the laminate having the coating film (1) composed of the active energy ray-curable resin composition of the present invention has high gloss, and is resistant to damage, staining, flexing, and appearance. The characteristics are also good. On the other hand, the laminate of Comparative Example 8 in which the ratio (a/b) was not lower than the lower limit of the present invention was poor in bending resistance, and the laminate of Comparative Example 9 which was larger than the upper limit of the present invention was resistant to contamination by water-based pollutants. Bad sex. As the component (A), a laminate of Comparative Example 10 in which the number of (meth)acryloxy groups was less than the range of the present invention was used, and the damage resistance, the solvent friction test, and the glycerin test were poor. In Comparative Examples 11 to 13 in which the component (A) was used without the ethanolamine residue, the curing rate of the resin composition was slow, and thus the linear velocity was slow. Further, the obtained laminate was inferior in any of the scratch resistance, the stain resistance, the flex resistance, the appearance, the solvent friction test, the glycerin test, and the scratch resistance test.

Example 23

In addition to Example 12, SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film, thickness 100 μm, surface according to JIS-7105, manufactured by Riken technos Co., Ltd. was used. In the same manner as in Example 12, the laminate was produced and evaluated in the same manner as in Example 12, except that the 60° gloss was measured at 90% in the case of 1981 and the anchor coating treatment was used as the thermoplastic resin film (3). The results are shown in Table 4.

Example 24

A laminate was produced in the same manner as in Example 23 except that a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 50:50 (volume ratio) was used as the component (D). The results are shown in Table 4.

Reference example 2

The laminate was produced in the same manner as in Example 23 except that methyl ethyl ketone was used as the component (D). However, the thermoplastic resin film (3) was swollen, and a laminate could not be obtained.

As shown in Table 4, when the thermoplastic resin film (3) is a polyester film having no extension, when the methyl ethyl ketone is used as the solvent (D), the thermoplastic resin film (3) is swollen and the laminate cannot be obtained ( Reference example 1). but When the solvent (D) containing 40% by mass or more of 1-methoxy-2-propanol (D-2) is used, the thermoplastic resin film (3) does not swell, and the thermoplastic resin film (3) The gloss is not lowered, and a laminate can be obtained.

Example 25

70 parts by mass of the component (A-1) as the component (A), and dipentaerythritol hexaacrylate as the component (A') (manufactured by Nippon Kayaku Co., Ltd., the number of hydroxyl groups per unit amount: 0.63 mol/ (a-4) 30 parts by mass of Colonate HX (trade name, polyisocyanate of the above formula (6)) (B-1) 22 manufactured by Japan Polyurethane Co., Ltd. as component (B) Parts by mass, 5 parts by mass of benzophenone (C-1) as component (C), Darocur 1173 of Ciba Japan Co., Ltd. (trade name, phenylalkylketone photopolymerization initiator, 2-hydroxy-2) -2 parts by mass of -methyl-1-phenyl-propan-1-one) (C-2), 8 parts by mass of high-purity colloidal cerium oxide (F-1) having an average particle diameter of 80 nm as component (F), And 200 parts by mass of 1-methoxy-2-propanol (D-1) as the component (D) was stirred to obtain an active energy ray-curable resin composition.

Further, the number of isocyanate groups per unit amount of the component (B-1) was determined to be 5.12 mol/kg as measured by the above method. Therefore, the ratio of 70 parts by mass of the component (A-1) to the number of hydroxyl groups (a) of 30 parts by mass of the component (A-2) and the number of isocyanate groups (b) of 22 parts by mass of the component (B-1) ( a/b), Department (1.09×70+0.63×30)/(5.12×22)=0.85.

The two-axis stretch polyester film "Emblet S25" (trade name, thickness 25 μm) of Unitika Co., Ltd. was used as the thermoplastic resin film (3), and the anchor coating agent was applied to one side thereof (Vylon 24SS of Toyobo Co., Ltd.) (trade name)) A dried film thickness of 1 μm was obtained to obtain a thermoplastic resin film (3) having an anchor coat layer (2) on one side. The resin composition obtained above was applied onto the anchor coating layer (2), dried, irradiated with ultraviolet rays, and then continuously wound at a line speed of 50 m/min in a series of manufacturing lines to wind the obtained laminate. step. The winding of the rolls can be carried out well without using a separator. The coating of the above resin composition was carried out by using a coating apparatus using a film Meyer wire rod method, and the thickness of the coating film after drying was 11 μm. Further, the linear velocities in the examples and the comparative examples are the fastest speeds at which the laminate can be stably produced in the production line. The above test (1) to (7) and the following test (11) were carried out on the obtained laminate. The results are shown in Table 5.

Example 26

In addition to the use of Sumijule HT (trade name, polyisocyanate of the above formula (7), the number of isocyanate groups per unit amount: 3.10 mol/kg) (B-2) 36 A laminate was produced in the same manner as in Example 25 except for the component (B). The results are shown in Table 5.

Examples 27 to 30 and Comparative Examples 14 to 15

Except in Example 25, the amount of the component (B) was changed as shown in Table 5. A laminate was produced in the same manner as in Example 25 except for the above. The results are shown in Table 5.

Example 31

In the same manner as in Example 25, 100 parts by mass of the component (A-1) was used as the component (A), 25 parts by mass of the component (B-1) was used as the component (B), and 7 parts by mass of the component (C-1) was used. A laminate was produced in the same manner as in Example 25 except for the component (C). The results are shown in Table 6.

Comparative Example 16

In Example 31, 100 parts by mass of the component (A-2) obtained in Synthesis Example 2 was used instead of the component (A-1), and 35 parts by mass of the component (B-1) was used as the component (B). Example 31 A laminate was produced in the same manner. The linear velocity at this time was 50 m/min as in Example 31, but a separator was used for winding the roller. The results are shown in Table 6.

Comparative Example 17

In the same manner as in Example 31, tripropylene glycol diacrylate (manufactured by Daicel-Cytec Co., Ltd., number of hydroxyl groups per unit: 0 mol/kg) (A-3) was used instead of the component (A-1), and benzene was used. Alkyl ketone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2), Ciba Japan Co., Ltd. A laminate was produced in the same manner as in Example 31 except for the component (C). The linear velocity at this time was 30 m/min. Do not use benzophenone (C-1) as component (C) because When the above component (A-3) is used instead of the component (A-1), the above (C-1) has a slow curing rate. The curing of the above (A-3) and the above (B-1) is carried out at a rapid rate without gelation, and the above (C-2) is used as the component (C). The same applies to the following Comparative Examples 18 and 19. Further, the amount of the component (C) is 5 parts by mass, because 7 parts by mass is too large, and gelation occurs. The results are shown in Table 6.

Comparative Example 18

In addition to Example 31, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol/kg) (A-4) was used instead of the component (A-1). Further, a laminate was produced in the same manner as in Example 31 except that the ratio (a/b) was changed to 0.85. The results are shown in Table 6. Further, the above (A-4) does not have a hydroxyl group in its structure, but since it contains a component in which a part of the acryloxy group is hydrolyzed, a hydroxyl group exists. The same applies to (A-5) in Comparative Example 19 below.

Comparative Example 19

In addition to Example 31, di-trimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol/kg) (A-5) was used in place of the component ( A-1), and the amount of the component (B) was changed, and the ratio (a/b) was changed to 0.85, and a laminate was produced in the same manner as in Example 31. The results are shown in Table 6.

Example 32

A laminate was produced in the same manner as in Example 31 except that the thickness of the coating film was changed to 2 μm in Example 31. The linear velocity at this time is 40 m/min. The linear velocity was slower than that of Example 31 because the effect of oxygen radicals was on the inside of the coating film when the coating film was thin, and as a result, the curing speed of the entire coating film became slow. The results are shown in Table 6.

Example 33

A laminate was produced in the same manner as in Example 31 except that the thickness of the coating film was changed to 50 μm in Example 31. The linear velocity at this time is 50 m/min. The results are shown in Table 6.

Example 34

A laminate was produced in the same manner as in Example 31 except that methyl ethyl ketone (D-2) was used as the component (D). The results are shown in Table 6.

Examples 35 to 37 and Reference Examples 3 to 4

The laminate was produced in the same manner except that the blending amount of the component (F-1) was changed to the amount shown in Table 7 in Example 25. The results are shown in Table 7.

Example 38

Except in Example 36, using high-purity colloidal cerium oxide (F-2) having an average particle diameter of 20 nm as the component (F), all were produced in the same manner. Make a layer. The results are shown in Table 7.

Example 39

A laminate was produced in the same manner except that in Example 36, a high-purity colloidal cerium oxide (F-3) having an average particle diameter of 150 nm was used as the component (F). The results are shown in Table 7.

Example 40

A laminate was produced in the same manner except that in Example 36, a high-purity colloidal cerium oxide (F-4) having an average particle diameter of 250 nm was used as the component (F). The results are shown in Table 7.

Reference example 5

A laminate was produced in the same manner except that in Example 36, a high-purity colloidal cerium oxide (F-5) having an average particle diameter of 400 nm was used as the component (F). The results are shown in Table 7.

Examples 41, 42

In the same manner as in Example 25 except that the blending amount of the component (A) and the component (B) was changed to the amounts shown in Table 8, the laminate was produced in the same manner. The linear velocity at this time is 50 m/min. The results are shown in Table 8.

Example 43

In addition to Example 42, further use of DIC Corporation The laminate was produced in the same manner as the component (E) in an amount of 0.5 parts by mass of Megafac RS-75 (trade name) (E-1). The linear velocity at this time is 50 m/min. The results are shown in Table 8.

Example 44

In the same manner as in Example 43, except that the blending amount of the component (E-1) was changed to 2.0 parts by mass, the laminate was produced in the same manner. The linear velocity at this time is 50 m/min. The results are shown in Table 8.

experiment method (11) Haze

The coating film (1) side of the laminate was measured as an incident surface in accordance with JIS K 7105.

As is apparent from Tables 5 to 8, the composition of the present invention can produce a laminate having a coating film composed of the composition at a high linear velocity, and the coating film is resistant to damage, contamination, and abrasion. Excellent flexibility, appearance and transparency.

On the other hand, the compositions of Comparative Examples 14 and 15 which were outside the range of the present invention (a/b) were inferior in any of the obtained coating films such as scratch resistance, stain resistance and flexural resistance.

When the number of (meth)acryloxyloxy groups was less than the range of the present invention, the composition of Comparative Example 16 as the component (A) was found to have poor damage resistance and stain resistance.

Only the composition of Comparative Examples 17 to 19 which did not have an ethanolamine residue as the component (A) had a slow curing rate, and thus the linear velocity was slow. Again, the income Any of the scratch resistance, stain resistance, flex resistance, and appearance of the coating film is poor.

In Reference Example 3 in which the component (F) was not used, the pencil hardness was insufficient.

The reference example 4 in which the blending amount of the component (F) was more than the preferred range of the present invention was poor in bending resistance.

In Reference Example 5 in which the particle diameter of the component (F) was larger than the preferred range of the present invention, the transparency (haze) was poor.

Example 45

In addition to Example 31, SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film, thickness 100 μm, surface according to JIS-) manufactured by Riken technos Co., Ltd. was used. A laminate was produced in the same manner as in Example 31 except that the anchor coating agent was used as the thermoplastic resin film (3) as measured in 7105-1981. The linear velocity at this time is 50 m/min. The above tests (1) to (7) were carried out on the obtained laminate. Further, the 60° glossiness of the surface of the coating film (1) was measured in accordance with JIS-7105-1981. The results are shown in Table 9.

Example 46

In addition to Example 45, a mixed solvent of 1-methoxy-2-propanol (D-1): methyl ethyl ketone (D-2) = 50:50 (mass ratio) was used as the component (D). A laminate was produced in the same manner as in Example 45 except for the above. The results are shown in Table 9.

Reference example 6

In the same manner as in Example 45 except that methyl ethyl ketone (D-2) was used as the component (D), the laminate was produced in the same manner as in Example 45, but the thermoplastic resin film (3) as a substrate was used. Swelling, the laminate cannot be obtained.

As shown in Table 9, when the thermoplastic resin film (3) as the substrate is a non-extended amorphous polyester film, when methyl ethyl ketone is used as the solvent (D), the base film is swollen and cannot be obtained. Laminate (Reference Example 6). However, when 40% by mass or more of 1-methoxy-2-propanol (D-2) is used as the solvent (D), the base film does not swell and the gloss of the base film does not decrease, and the obtained film can be obtained. Laminates (Examples 45 and 46).

1‧‧·coating film

2‧‧‧ anchor coating

3‧‧‧ thermoplastic resin film

4‧‧‧ adhesive layer

5‧‧‧ thermoplastic resin film

Claims (15)

An active energy ray-curable resin composition characterized by containing (A) having the following formula (1): (Here, R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) propylene fluorenyloxy groups, and the number of (meth) propylene fluorenyl groups in R1 is in R2 An ethanolamine-modified polyether (meth)acrylate having a total of (3) or more of (meth)acryloxyloxy groups, (B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) The photopolymerization initiator has a ratio (a/b) of the number (a) of the hydroxyl groups of the component (A) to the number (b) of the isocyanate groups of the component (B) in the range of 0.5 to 1.2. The composition of claim 1, wherein the component (A) is represented by the following formula (2): Expressed as a compound. An active energy ray-curable resin composition characterized by containing (A) having the following formula (1): (Here, R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) propylene fluorenyloxy groups, and the number of (meth) propylene fluorenyl groups in R1 is in R2 An ethanolamine-modified polyether (meth)acrylate having a total of (3) or more of (meth)acryloxyloxy groups, and a (meth)acrylate compound other than the (A') component (A), B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) a photopolymerization initiator, and the number of hydroxyl groups (a) of the component (A) and the number of hydroxyl groups of the component (A') The ratio of (a+a') to the number (b) of isocyanate groups ((a+a')/b) of the component (B) is in the range of 0.5 to 1.2. The composition of claim 3, wherein the component (A) is represented by the following formula (2): Expressed as a compound. The composition according to any one of claims 1 to 4, wherein the component (B) is a polyisocyanate having three isocyanate groups in one molecule. The composition of claim 1 or 2 further contains (D) a solvent, and the amount of the component (D) is 150 to 250 parts by mass based on 100 parts by mass of the component (A). The composition of claim 3 or 4 further comprising (D) a solvent, and the amount of the component (D) is 150 to 250 by mass based on 100 parts by mass of the total of the component (A) and the component (A'). Share. The composition of claim 6, wherein the component (D) is a solvent containing 40% by mass or more of 1-methoxy-2-propanol. If the composition of claim 1 or 2 is further contained (E) The ultraviolet-reactive fluorine-based surface modifier, and the amount of the component (E) is 0.1 to 5 parts by mass based on 100 parts by mass of the component (A). The composition of claim 3 or 4 further comprising (E) a UV-reactive fluorine-based surface modifier, and the amount of the component (E) is 100 relative to the total of the component (A) and the component (A'). The mass fraction is 0.1 to 5 parts by mass. The composition of claim 1 or 2 further contains (F) fine particles having a particle diameter of 1 nm to 300 nm, and the amount of the component (F) is 1 to 50 parts by mass based on 100 parts by mass of the component (A). The composition of claim 3 or 4 further comprising (F) fine particles having a particle diameter of 1 nm to 300 nm, and the amount of the component (F) is 100 in total with respect to the component (A) and the component (A'). The mass fraction is 1 to 50 parts by mass. A coating comprising the composition of any one of claims 1 to 12. A laminate which is laminated on a single side of a thermoplastic resin film (3) with a coating film (1) composed of the coating material of claim 13 with or without an anchor coating (2). The laminate of claim 14 is provided on the surface of the thermoplastic resin film (3) on which the coating film (1) is not laminated, and has a thermoplastic resin film (5) via the adhesive layer (4).