WO2014083644A1

WO2014083644A1 - Active-energy-ray-curable resin composition

Info

Publication number: WO2014083644A1
Application number: PCT/JP2012/080777
Authority: WO
Inventors: 清水　基弘; 耕平中島; 茂一伊藤; 仁美猪俣; 智志塩田
Original assignee: リケンテクノス株式会社
Priority date: 2012-11-28
Filing date: 2012-11-28
Publication date: 2014-06-05
Also published as: TWI577733B; TW201430052A

Abstract

A composition according to the present invention comprises (A) a specific ethanolamine-modified polyether (meth)acrylate, (B) a polyisocyanate having at least two isocyanate groups per molecule and (C) a photopolymerization initiator, wherein the ratio of the number (a) of hydroxy groups in the component (A) to the number (b) of isocyanate groups in the component (B) (i.e., (a/b)) falls within the range from 0.5 to 1.2.

Description

Active energy ray-curable resin composition

The present invention relates to an active energy ray-curable resin composition, and more specifically, has a high curing rate, excellent scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, transparency, and hardness. The present invention relates to an active energy ray-curable resin composition that provides a high coating film.

Conventionally, base materials made of woody materials such as wood, plywood, laminated timber, particle board, hardboard, as building materials such as flooring and wall materials, or as cabinets for household appliances such as furniture, kitchen products, refrigerators, etc. A decorative sheet made by pasting a decorative sheet on the surface or the surface of a base material made of a metal material such as iron or aluminum is used. In recent years, it has been proposed to apply a decorative sheet instead of directly applying a hard coat paint to an exterior part such as a door sash of an automobile or an interior part such as an instrument panel (for example, a patent) Reference 1). Such a decorative sheet is required to have a good balance of not only decorativeness but also scratch resistance, abrasion resistance, stain resistance, transparency and the like at a high level.

In order to impart the above properties to a decorative sheet, it is widely performed to form a coating film made of a paint containing a curable resin composition on the surface of a thermoplastic resin film serving as a base material.

As the paint, a paint containing an active energy ray-curable resin composition containing a polyfunctional acrylate such as dipentaerythritol hexaacrylate or pentaerythritol tetraacrylate and / or a polyfunctional urethane acrylate and a polyisocyanate is often used ( For example, Patent Document 2), a coating film made of the above-mentioned paint has a poor balance between bending resistance and scratch resistance and wear resistance, and if the bending resistance is improved, scratch resistance and abrasion resistance are not sufficient. . Moreover, the said coating material has a slow curing speed, Therefore When manufacturing the decorative sheet | seat with which the coating material was apply | coated to the base-material surface by line production, it is necessary to suppress a line speed low. When the UV curability is poor, there is a method of increasing the UV illuminance, but there is a problem that the film is deformed by the radiant heat of the UV lamp.

As a curable coating that gives a coating film with improved scratch resistance and abrasion resistance, a composition containing a polymer having a siloxane bond and an acrylic polyol resin (for example, Patent Document 3), a polydimethylsiloxane portion and a vinyl monomer There has been proposed a composition containing a copolymer having a polymer chain moiety (for example, Patent Document 4). However, these paints have a slow curing rate, and the resulting coating film has insufficient stain resistance.

Japanese Patent Laid-Open No. 2003-118061 JP-A-11-216812 Japanese Patent Laid-Open No. 11-268195 Japanese Patent No. 3999411

The object of the present invention is an active energy ray curing that has a high curing rate, excellent scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, transparency, and can obtain a coating film with high hardness. It is providing a functional resin composition.

The present inventors have found that a resin composition in which a polyether (meth) acrylate modified with ethanolamine and having a specific number of (meth) acryloyloxy groups is combined with a polyisocyanate can achieve the above object. Further, it has been found that when finer particles are added to the resin composition, the hardness of the coating film is further increased.

That is, the present invention
(A) The following formula (1):

(Where R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more,
(B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) a photopolymerization initiator, the number of hydroxyl groups (a) in component (A) and the number of isocyanate groups in component (B) ( An active energy ray-curable resin composition having a ratio (a / b) to b) in the range of 0.5 to 1.2.

The resin composition of the present invention has a high curing speed. Therefore, when a laminate is produced by applying this composition to a thermoplastic resin film as a base material and curing it, the speed of the production line can be increased. This leads to a reduction in manufacturing costs. Moreover, the coating film obtained from the composition of this invention is excellent in scratch resistance, abrasion resistance, stain resistance, bending resistance, workability, and transparency. In addition, when finer particles are added to the resin composition, the hardness of the coating film is further increased. Therefore, the laminated body having this coating film is used for surface protection and decoration of building materials such as floor materials and wall materials, home appliances such as refrigerators, exterior parts such as automobile door sashes, and interior parts such as instrument panels. Can be suitably used as a decorative sheet.

It is a schematic diagram which shows an example of the laminated body of this invention.

(A) Ethanolamine-modified polyether (meth) acrylate 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, R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 The total number of groups is 3 or more, preferably 3 to 9, and more preferably 4. In the above formula (1), when the sum of the number of (meth) acryloyloxy groups in R1 and the number of (meth) acryloyloxy groups in R2 is 2 or less, the scratch resistance, abrasion resistance and contamination resistance of the coating film Inferior to sex. R1 and R2 may be the same or different from each other, but R1 and R2 are preferably the same.

Component (A) functions to capture oxygen radicals. In general, when a (meth) acryloyloxy functional group-containing compound is cured by radical polymerization, the radical polymerizable compound is susceptible to polymerization inhibition by oxygen radicals in the air, and particularly on the surface of the coating film, a curing reaction is caused by oxygen radicals. Become slow. If the irradiation time of the active energy rays is increased so that the surface is sufficiently cured, the speed of the production line is reduced, and the influence of oxygen radicals is relatively small inside the coating film. Becomes fragile, and therefore has poor bending resistance. Since the component (A) has the specific structure of the above formula (1), the composition of the present invention is not inhibited by oxygen radicals. Therefore, the curing reaction rate is high, and scratch resistance, abrasion resistance, A coating film excellent in stain resistance, bending resistance, workability, and transparency can be obtained. Component (A) has an ethanolamine residue, a hydrogen is generated by extracting hydrogen of a methylene group adjacent to the nitrogen atom in the ethanolamine residue, and an oxygen radical is bound and trapped there. It is done.

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 room temperature and does not require a catalyst. In order to prevent gelation, it is preferable to add a solvent or the like to lower the apparent concentration.
R1-O—C (═O) —CH═CH ₂ (3)
R2-O—C (═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, many kinds of side reaction products are generated in addition to the target component (A) which is the main product. Usually, these by-products are used.

As the compounds represented by the above formulas (3) and (4), for example, TPGDA (trade name) (tripropylene glycol diacrylate) and OTA 480 (trade name) (glycerin propoxytriacrylate) manufactured by Daicel-Cytec Corporation, In addition, dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. may be mentioned.

The OTA480 is a compound having the following formula (5).

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

When the component (A) is a compound having the above formula (2), the resulting composition has good storage stability, and the resulting coating film has bending resistance, workability, transparency, and three-dimensional formability. The balance of scratch resistance, abrasion resistance and stain resistance is very good. Also, in general, in a production line for producing a laminate obtained by applying a paint to a base film, a separator is placed on a coating film in order to prevent the laminates from blocking each other when the laminate is wound around a roll. However, when the component (A) is a compound of the above formula (2), the curing reaction is very fast, so there is an advantage that it is not necessary to use a separator.

(B) The polyisocyanate component (B) is a compound having two or more isocyanate groups (—N═C═O) in one molecule. Specifically, methylene bis-4-cyclohexyl isocyanate, trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol propane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, hexa Examples thereof include polyisocyanates such as isocyanurate of methylene diisocyanate, isocyanurate of isophorone diisocyanate and biuret of hexamethylene diisocyanate, and urethane crosslinking agents such as block type isocyanates of the above polyisocyanate. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate and dibutyltin diethylhexoate may be added as necessary.

Among these, those having three or more isocyanate groups in one molecule are preferable from the viewpoint of the bending resistance and three-dimensional formability of the coating film and the storage stability of the paint, and particularly represented by the following formula (6). A hexamethylene diisocyanate trimer having an isocyanate ring structure, or a hexamethylene diisocyanate trimer represented by the following formula (7) and a trimethylolpropane adduct. It can be suitably used. These have a structural feature that isocyanate groups are present at positions away from each other at the end of the hexamethylene chain, and thus the resulting coating film is elastic and excellent in scratch resistance and abrasion resistance.

The resin composition of the present invention is cured by the reaction between the hydroxyl group in component (A) and the isocyanate group in component (B). The resin composition of the present invention has a ratio (a / b) of the number of hydroxyl groups (a) in component (A) to the number of isocyanate groups (b) in component (B) (a / b) so that curing can occur sufficiently. It is in the range of 5 to 1.2, preferably 0.7 to 1.1. When the ratio is less than the lower limit, the resulting coating film is inferior in bending resistance and three-dimensional formability. When the ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance against aqueous contaminants such as aqueous magic.

In addition, the resin composition of the present invention comprises a (meth) acrylate compound (A ′) other than the component (A).
May further be included. By including the component (A ′), the properties of the coating film can be appropriately adjusted according to the use of the laminate. When the component (A ′) is included, the total number (a + a ′) of the number of hydroxyl groups (a) of the component (A) and the number of hydroxyl groups (a ′) of the component (A ′) and the isocyanate group of the component (B) The ratio ((a + a ′) / b) to the number (b) of is in the range of 0.5 to 1.2, preferably 0.7 to 1.1. When the ratio is less than the lower limit, the resulting coating film is inferior in bending resistance and three-dimensional formability. When the ratio is larger than the above upper limit, the resulting coating film is poor in stain resistance against aqueous contaminants such as aqueous magic. In addition, the component (A ′) may or may not have a hydroxyl group. The compounding ratio of the component (A) and the component (A ′) can be appropriately determined according to 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, The component (A) is preferably 50 to 100% by mass and the component (A ′) is preferably 50 to 0% by mass.

Examples of the (meth) acrylate compound (A ′) include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate and (Meth) acryloyloxy group-containing prepolymer or oligomer such as polyether (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) Acrylate, phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoro Compounds containing one (meth) acryloyloxy group such as ethyl (meth) acrylate and trimethylsiloxyethyl 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- (meth) acryloyloxypolyethyleneoxyphenyl) pro And compounds containing two (meth) acryloyloxy groups such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) acrylate and trimethylolethanetri ( Compounds containing 3 (meth) acryloyloxy groups such as (meth) acrylate; compounds containing 4 (meth) acryloyloxy groups such as pentaerythritol tetra (meth) acrylate; (meth) such as dipentaerythritol hexaacrylate The compound etc. which contain six acryloyloxy groups can be mentioned, These can use 1 type (s) or 2 or more types.

In this specification, the number of hydroxyl groups per unit amount of each of component (A) and component (A ′) was determined based on JIS-K-1557-1: 2007. That is, each hydroxyl group of component (A) and component (A ′) is acetylated with an acetylating reagent (acetic anhydride in pyridine), then excess acetylating reagent is hydrolyzed with water, and the resulting acetic acid is converted into Kyoto. The above number was determined by titration with an ethanol solution of potassium hydroxide using a potentiometric automatic titrator AT-610, manufactured by Denki Kogyo Co., Ltd. The number of isocyanate groups per unit amount of component (B) was determined based on JIS-K-7301: 1995. That is, by reacting the isocyanate group of component (B) with dinormal butylamine, and then titrating excess dinormal butylamine with an aqueous hydrochloric acid solution using an automatic potentiometric titrator AT-610 type manufactured by Kyoto Electronics Industry Co., Ltd. The above number was determined.

(C) The photopolymerization initiator component (C) is a radical polymerization type photopolymerization initiator, and known ones can be used. For example, triazine compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds And photopolymerization initiators such as oxime phenylacetate compounds, hydroxyketone compounds and aminobenzoate compounds. These can be used alone or in combination of two or more. Among these, benzophenone compounds are preferable because the reaction mechanism is a radical generation type by hydrogen abstraction. Specifically, benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis ( Diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone and 2, Examples include 4,6-trimethylbenzophenone.

The compounding quantity of a component (C) can be suitably selected with the kind of other component, and desired coating-film thickness, Generally, with respect to 100 mass parts of component (A), or a component (A ') When present, the amount is about 0.5 to 10 parts by mass with respect to 100 parts by mass in total of component (A) and 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, the coating thickness is 0.5 to When the thickness is 30 μm, the amount of the component (C) is 4 to 10 parts by mass with respect to 100 parts by mass of the component (A), and when the coating thickness is 30 to 500 μm, the component (A) 100 0.5 to 8 parts by mass with respect to parts by mass. The reason why the amount of the component (C) is generally larger when the thickness of the coating film is thinner is that the thinner the film, the more easily the influence of curing inhibition by oxygen radicals occurs.

(F) Fine particles The resin composition of the present invention comprises fine particles having a particle size of 1 nm to 300 nm based on 100 parts by mass of component (A), or component (A) and component (A ′) when component (A ′) is present. It is preferably contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass in total of A ′). Component (F) serves to increase the hardness of the coating film obtained from the resin composition of the present invention. As the component (F), both inorganic fine particles and organic fine particles can be used.
Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal fine particles; metal sulfide fine particles; metal nitride fine particles;
Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde.
These can be used alone or in combination of two or more.
In addition, for the purpose of increasing the dispersibility of the fine particles in the paint or increasing the hardness of the resulting coating film, the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Coupling agent; Organic compound having an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group and allyl group and reactive functional group such as epoxy group; Surface treatment agent such as fatty acid and fatty acid metal salt You may use what was processed.
Of these, silica and aluminum oxide fine particles are preferable, and silica fine particles are more preferable in order to obtain a coating film with higher hardness. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

The particle diameter of the component (F) needs to be 300 nm or less in order to impart transparency of the resulting coating film. Moreover, when the particle diameter is coarse, the hardness of the obtained coating film tends to be insufficient. Preferably it is 200 nm or less, More preferably, it is 120 nm or less. On the other hand, there is no particular lower limit of the particle diameter, but normally available particles are at most about 1 nm even if they are fine.

In the present specification, the particle diameter of the fine particles is a cumulative particle diameter distribution curve of 50 measured using a laser diffraction / scattering particle size analyzer MT3200II (trade name) manufactured by Nikkiso Co., Ltd. The particle diameter is mass%.

Moreover, the compounding quantity of a component (F) is with respect to 100 mass parts of components (A), or when a component (A ') exists, with respect to a total of 100 mass parts of a component (A) and a component (A'). 1 to 50 parts by mass. If it is 1 part by mass or less, the effect of improving the hardness of the coating film cannot be obtained. If it is 50 parts by mass or more, the bending resistance is lowered. The amount 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 components (A), (A ′), (B), (C) and (E), and components (A), (A ′), (B), (C), ( There is no particular limitation as long as it does not react with E) and (F) or catalyze the self-reaction of these components. For example, known compounds such as 1-methoxy-2-propanol, n-butyl acetate, toluene and methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, diacetone alcohol and the like can be used. Of these, a solvent containing 40% by mass or more, more preferably 80% by mass or more of 1-methoxy-2-propanol is preferable, and the thermoplastic resin film (3) described below is coated with the above composition. This is especially true in the case of a resin film having low solvent resistance such as a stretched polyester resin film. In general, unstretched polyester-based resin films are widely used as base films for decorative films because they are excellent in three-dimensional formability and bending resistance and surface gloss, but are poor in solvent resistance. Therefore, when a composition containing a solvent is applied to an unstretched polyester resin film as a base film, the surface gloss of the resulting decorative film is lost, or in some cases the base film swells and a decorative film is obtained. There is a problem of disappearing. If 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 so as to have a suitable viscosity according to the coating apparatus and the thickness of the coating film. Usually, 150 to 250 parts by mass with respect to 100 parts by mass of component (A) or, when component (A ′) is present, with respect to 100 parts by mass of component (A) and component (A ′) in total. It is.

(E) UV-reactive fluorine-based surface modifier The composition of the present invention is a UV-reactive fluorine-based surface modifier for preventing paint repellency and for preventing fingerprint resistance, stain resistance and blocking of the coating film. Agent (E) may further be included. The ultraviolet-reactive fluorine-based surface modifier (E) is preferably a compound having a fluorine-containing group, a hydrophilic group, a lipophilic group, and an ultraviolet-reactive group. Mega-Face RS-75 (trade name) is available. The amount of component (E) is based on 100 parts by weight of component (A) or, if component (A ′) is present, based on a total of 100 parts by weight of component (A) and component (A ′), The amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2.0 parts by mass. If the amount is more than 5 parts by mass, the surface hardness may decrease.

Further, the resin composition of the present invention is an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, within a range not impairing the effects of the present invention. One type or two or more types of additives such as a colorant, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be included.

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

The resin composition thus obtained is active energy ray-curable, and this is applied to the surface of the thermoplastic resin film (3) as a base material and irradiated with active energy rays such as ultraviolet rays, visible rays, and electron beams. When cured, a laminate having a coating film (1) excellent in scratch resistance, abrasion resistance, contamination resistance and bending resistance is obtained. Alternatively, after the coating composition (1) is formed by applying, drying and curing the above composition to a substrate having excellent solvent resistance, for example, a biaxially stretched polyethylene terephthalate film having a release treatment applied to the surface, thermal lamination is performed. By laminating with the thermoplastic resin film (3) by a method such as dry lamination, a laminate having the coating film (1) is obtained.

Further, since the resin composition of the present invention has a fast curing reaction, it is possible to increase the line speed when the composition is applied to a substrate to produce a laminate, and thus the manufacturing cost can be reduced. .

The thickness of the coating film (1) is preferably 0.5 μm or more. If it is thinner than this, scratch resistance may be insufficient. On the other hand, there is no upper limit on the thickness of the coating film. However, since an unnecessarily thick coating film only increases the cost, the thickness is 60 μm at most.

Thermoplastic resin film (3)
Any thermoplastic resin film can be used as the thermoplastic resin film (3) where the coating film (1) made of the resin composition is laminated to form a laminate. For example, polyvinyl chloride resin, non-crystalline, low crystalline or crystalline polyester, polypropylene, polyolefin such as polyethylene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer Styrene resin such as hydrogenated styrene / ethylene / butadiene / styrene copolymer, unstretched film of thermoplastic resin such as polyamide, acrylic, polycarbonate, polyurethane, uniaxially stretched film and biaxially stretched film it can. Preferably, a non-stretched film of a polyvinyl chloride resin or an amorphous polyester resin or a stretched crystalline polyester film is used. Moreover, when it is going to provide high glossiness to a laminated body, it is preferable that a thermoplastic resin film (3) itself has high surface glossiness, and it is preferable that it is transparent. Specifically, a non-stretched film of an amorphous polyester resin and a stretched polyester film are preferable. Polyester resins such as polyethylene terephthalate, glycol copolymerized polyethylene terephthalate, acid copolymerized polyethylene terephthalate, and polyethylene naphthalate, or these resins A biaxially stretched polyester film comprising any combination is particularly preferred.

Examples of the non-stretched film of the non-crystalline polyester resin include SET329 FZ26401 {trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film} manufactured by Riken Technos Co., Ltd. Mention of Lumirror (trade name) of Co., Ltd., Emblet S25 (trade name) of Unitika Co., Ltd., Melinex (705) # 75 (trade name) of Teijin Ltd. and A4300 (trade name) of Toyobo Co., Ltd. it can.

The thickness of the thermoplastic resin film (3) is usually 10 μm to 100 μm, preferably 15 to 50 μm. If it is thinner than the above lower limit, wrinkles may enter the laminated body. If it is thicker than the above upper limit, the laminated body will be bounced during lapping molding, and the processing speed of coating and laminating must be kept low. It may disappear.

Lamination of the coating film (1) composed of the above composition onto the thermoplastic resin film (3) is applied directly to the thermoplastic resin film (3) or via an anchor coat (2) layer described later. A coating film (1) by applying, drying and curing the above composition to a substrate excellent in solvent resistance, for example, a biaxially stretched polyethylene terephthalate film having a release treatment applied to the surface by drying and curing ) Can be performed by bonding directly to the thermoplastic resin film (3) or via the anchor coat (2) layer by a method such as thermal lamination or dry lamination.

Anchor coat (2)
The laminate may have an anchor coat (2) between the coating film (1) and the thermoplastic resin film (3). By providing the anchor coat (2), the adhesive strength between the coating film (1) and the thermoplastic resin film (3) can be increased.

As an anchor coating agent for forming the anchor coat (2), it is well soluble in known solvents such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetone and the like. As long as a sufficient anchor effect can be obtained, there is no particular limitation, and conventional ones such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used. Commercially available examples include Byron 24SS (trade name) manufactured by Toyobo Co., Ltd., AU2141NT manufactured by Tokushi Co., Ltd., and the like.

When the anchor coat (2) is provided, the anchor coat (2) is formed on one surface of the thermoplastic resin film (3) by applying an anchor coat agent by a conventional method. The anchor coat (2) A coating film (1) comprising the above composition can be laminated on the substrate.

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

The method for applying the resin composition or the anchor coating agent to the thermoplastic resin film (3) is not particularly limited, and a known web application method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

Thermoplastic resin film (5)
In the laminate, the thermoplastic resin film (5) is further laminated via an adhesive layer (4) on the surface opposite to the surface on which the coating film (1) of the thermoplastic resin film (3) is laminated. (Refer to FIG. 1), and an adhesive layer (6) may be further provided thereon. When the laminate having the coating film (1) is attached to an adherend (for example, a particle board) having irregularities on the surface, the irregularities are laminated when the laminate further has a thermoplastic resin film (5). It is preferable that it can be prevented from reaching the surface of the film, and therefore, vividness can be maintained.

The lamination of the thermoplastic resin film (5) is performed, for example, by applying an adhesive on the surface opposite to the surface on which the coating film (1) of the thermoplastic resin film (3) is laminated, and then applying the adhesive layer (4). The thermoplastic resin film (5) can be formed thereon by using a metal roll-rubber roll heat laminating apparatus. At this time, the metal roll side is 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 surface metal roll is used as the metal roll, high gloss can be imparted to the surface of the laminate (the surface of the coating film (1)). When an embossed metal roll is used as the metal roll, embossing can be imparted 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. If it is too thin, when the laminate is affixed to the adherend, the irregularities on the surface of the adherend may reach the surface of the laminate, and may not provide sharpness. If it is too thick, Bonding workability to the adherend tends to be lowered.

As the thermoplastic resin film (5), those mentioned for the thermoplastic resin film (3) can be used. In addition, when the laminate having the thermoplastic resin film (5) is attached to the adherend, it is preferable to heat the end portions and the like to facilitate the bending process. For this reason, the thermoplastic resin film (5) The glass transition temperature is preferably 60 to 130 ° C. Examples of the thermoplastic resin film having such a glass transition temperature include films of acrylic resin, polyvinyl chloride resin, polyester resin, and acrylonitrile / butadiene / styrene copolymer resin.

Among them, the thermoplastic resin film (5) has the following resins (α-1) and (α-2):
(Α-1) Amorphous polyethylene terephthalate in which the dicarboxylic acid component is terephthalic acid, and the glycol component is composed of 60 mol% or more and less than 90 mol% of ethylene glycol and 10 mol% or more and less than 40 mol% of 1,4-cyclohexanedimethanol. Resin (PETG) 30 to 70% by mass, preferably 40 to 60% by mass, and (α-2) dicarboxylic acid component is 90 to 99% by mol of terephthalic acid and 1 to 10% by mol of isophthalic acid A crystalline polyethylene terephthalate resin having a glycol component of ethylene glycol of 70 to 30% by mass, preferably 60 to 40% by mass,
Wherein the total amount of the resin (α-1) and the resin (α-2) is 100% by mass, and the film made of the aromatic polyester resin composition is a glass of 60 to 130 ° C. It has a transition temperature and has high rigidity, so that even if the thickness of the film is reduced, sharpness can be obtained, which is preferable because it leads to cost reduction.

The aromatic polyester resin composition further comprises a polybutylene terephthalate resin, a polytrimethylene terephthalate resin, a polytrimethylene terephthalate resin, a polybutylene terephthalate copolymer in which the dicarboxylic acid component is terephthalic acid and isophthalic acid, and the glycol component is tetramethylene glycol. Other polyester resins such as resins may be included. Further, when the total amount of the resin (α-1), the resin (α-2), and the other polyester-based resin is 100 parts by mass, a further resin other than the above is added in an amount of 0.1 to 10 parts by mass. It may be included in the range. Examples of the further resin include methacrylic acid ester-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / ethylene-propylene rubber graft copolymer, acrylonitrile-styrene / Mention may be made of elastomer resins such as acrylic ester graft copolymers, methacrylic ester / acrylic ester rubber graft copolymers, methacrylic ester-acrylonitrile / acrylic ester rubber graft copolymers and thermoplastic polyester elastomers. The aromatic polyester resin composition further contains 0.1 to 5 mass of additives such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent and a surfactant. It may be included in the range of parts. 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, composite stearic acid, and oleic acid, stearamide, and oxystearic acid. Aliphatic amide waxes such as amide, oleic acid amide, erucyl amide, ricinoleic acid amide, behenic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, aliphatic esters such as stearic acid n-butyl and montanic acid ester wax And waxes, aliphatic metal soap waxes, urea-formaldehyde waxes and the like. Further, a pigment and an inorganic filler can be further contained. There is no restriction | limiting in particular in the said pigment, For example, a titanium oxide (white), carbon black (black), etc. are mentioned. Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, hydrous magnesium silicate, and talc.

The film comprising the aromatic polyester resin composition can be produced by any method, for example, can be formed using a calendar processing machine, or can be formed using an extruder and a T die. You can also Any calendar processing machine can be used, and examples thereof include an upright three roll, an upright four roll, an L four roll, an inverted L four roll, and a Z roll. Any extruder can be used, and examples thereof include a single-screw extruder, a same-direction rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. Any T die can be used, and examples thereof include a manifold die, a fishtail die, and a coat hanger die.

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

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. For example, acrylic, ethylene vinyl acetate, acetic acid Conventional adhesives such as vinyl, polyester, polyurethane, epoxy resin, chloroprene rubber and styrene butadiene rubber can be used. The method in particular of providing an adhesive bond layer is not restrict | limited, A well-known web application | coating method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. At this time, any diluent solvent such as 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Synthesis example 1
Daicel Cytec Co., Ltd. OTA480 (product name, glycerin propoxytriacrylate of formula (5) above) and 2-aminoethanol were charged into a glass beaker in an amount of 1 mol of the latter to 2 mol of the former, The reaction was carried out at a temperature of 23 ° C. for 72 hours to obtain an ethanolamine-modified polyether acrylate (A-1) having four acryloyloxy groups having the structure of the above formula (2). The number of hydroxyl groups per unit amount of component (A-1) was 1.09 mol / kg as measured by the method described above.

Synthesis example 2
In Synthesis Example 1, two samples were used in the same manner as in Synthesis Example 1 except that tripropylene glycol diacrylate (manufactured by Daicel-Cytec) was used instead of OTA480 (manufactured by Daicel-Cytec). An ethanolamine-modified polyether acrylate (A-2) having an acryloyloxy group was synthesized. The number of hydroxyl groups per unit amount of component (A-2) was 1.51 mol / kg.

Example 1
100 parts by mass of component (A-1) as component (A), Coronate HX (trade name, polyisocyanate of formula (6) above) (B-1) 25 manufactured by Nippon Polyurethane Industry Co., Ltd. as component (B) Anti-repellent agent (Kyoeisha Co., Ltd.) as other optional components of 10 parts by mass, 7 parts by mass of benzophenone (C-1) as component (C), and 200 parts by mass of 1-methoxy-2-propanol as component (D) An active energy ray-curable resin composition was obtained by mixing and stirring together with 0.3 part by mass of manufactured Polyflow 75 (trade name). The number of isocyanate groups per unit amount of component (B-1) was 5.12 mol / kg as measured by the method described above. Therefore, the ratio (a / b) of the number of hydroxyl groups (a) in 100 parts by mass of component (A-1) to the number of isocyanate groups (b) in 25 parts by mass of component (B-1) is 1.09 × 100. /(5.12×25)=109/128=0.85.

Unitika's biaxially stretched polyester film “Unitika S” (trade name, thickness 50 μm) is used as the thermoplastic resin film (3), and an anchor coating agent (Toyobo Co., Ltd. Byron 24SS (trade name)) is used on one side. Was applied to a dry film thickness of 1 μm to obtain a thermoplastic resin film (3) having an anchor coat (2) on one side. The process of applying the resin composition obtained above on the anchor coat (2), drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll is a series of production lines, 50 m / min line Performed continuously at speed. The roll could be wound well without using a separator. The resin composition was applied using a film Mayer bar type coating apparatus so that the coating thickness after drying was 11 μm. In addition, the line speed in an Example and a comparative example is the fastest speed which can manufacture a laminated body stably in a production line. The obtained laminates were subjected to the following tests (1) to (7). The results are shown in Table 1.

Example 2
As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) Was used in the same manner as in Example 1 except that 42 was used in an amount of 42 parts by mass. The results are shown in Table 1.

Examples 3 to 6 and Comparative Examples 1 and 2
A laminate was produced in the same manner as in Example 1 except that the amount of component (B) in Example 1 was changed as shown in Table 1. The results are shown in Table 1.

Comparative Example 3
In Example 6, 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 in place of the component (A-1). The line speed at this time was 50 m / min as in Example 6, but a separator was required for winding onto the roll. The results are shown in Table 1.

Comparative Example 4
In Example 1, instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used. (C) is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd. A laminate was produced in the same manner as in Example 1 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min. The reason why benzophenone (C-1) was not used as component (C) was that when (A-3) was used instead of component (A-1), the curing rate was slow in (C-1). It is. The component (C-2) was used as the component (C) so that the curing of the component (A-3) and the component (B-1) proceeded at a high speed without gelation. The same applies to Comparative Examples 5 and 6 below. The amount of component (C) is 5 parts by mass because 7 parts by mass is too large and gelation occurs. The results are shown in Table 1.

Comparative Example 5
In Example 1, 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 component (A-1). In addition, a laminate was manufactured 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. The above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed. The same applies to (A-5) in Comparative Example 6 below.

Comparative Example 6
In Example 1, instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. In addition, a laminate was manufactured 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 Example 1, “self-healing paint No. 100” (trade name, polydimethylsiloxane graft acrylate-based paint) manufactured by NATCO Co., Ltd. was used as the resin composition, and the dry film thickness was 20 μm. A laminate was obtained in the same manner as in Example 1. The line speed at this time was 10 m / min, and a separator was required for winding onto a roll. The results are shown in Table 1. The film thickness in Comparative Example 7 was made thicker than the thickness in Example 1 (11 μm) because the results of scratch resistance-1 and 2 corresponding to the most important characteristics of the self-healing paint were This is for comparison with the example. The scratch resistance is better when the coating thickness is thicker.

Example 7
In Example 1, a laminate was produced in the same manner as in Example 1 except that the coating thickness was 2 μm. The line speed at this time was 40 m / min. The reason why the line speed is slower than that of Example 1 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 1.

Example 8
In Example 1, a laminate was produced in the same manner as in Example 1 except that the coating thickness was 50 μm. The line speed at this time was 50 m / min. The results are shown in Table 1.

Example 9
In Example 1, a laminate was produced in the same manner as in Example 1 except that methyl ethyl ketone was used as the component (D). The line speed at this time was 50 m / min. The results are shown in Table 1.

Test Method (1) Pencil Hardness According to JIS K 5600-5-4, the hardness of the coating film surface was evaluated using a pencil {"Uni" (trade name) of Mitsubishi Pencil Co., Ltd.} under a 200 g load condition.

(2) Scratch resistance-1
The laminate obtained above was cut into a size of 200 mm in length and 25 mm in width to obtain a test piece, which was placed in a JIS L 0849 Gakushin tester so that the coating surface would be the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin Tester, a load of 1 kg was placed, and the surface of the test piece was rubbed 5 times. The surface was visually observed and evaluated according to the following criteria.
◎: No scratch ○: 1 to 3 scratches △: 4 to 10 scratches ×: 11 or more scratches

(3) Scratch resistance-2
The laminate obtained above was cut into a size of 150 mm length × 75 mm width to make a test piece, which was placed on a glass plate so that the coating film surface was the surface. Using a four-row brass brush (load: 500 gf) manufactured by Nakaya Brush Industry, the surface of the test piece was rubbed 10 times at a distance of 100 mm in one way. The surface was visually observed and evaluated according to the following criteria.
◎: No scratch ○: 1 to 3 scratches △: 4 to 10 scratches ×: 11 or more scratches

(4) Pollution resistance-1
After the surface of the coating film of the laminate obtained above was spot-contaminated with oily red magic, the contaminated part was covered with a watch glass and left at room temperature for 24 hours. Subsequently, the contaminated portion was cleaned by wiping until the wiping of the kimwipe was completely removed using a Kimwipe (trade name) sufficiently containing isopropyl alcohol, and the above portion was visually observed and evaluated according to the following criteria. .
◎: No contamination ○: Slight contamination remains △: Contamination remains significantly ×: Contamination remains significantly

(5) Pollution resistance-2
After the surface of the coating film of the laminate obtained above was spot-contaminated with aqueous red magic, the contaminated part was covered with a watch glass and allowed to stand at room temperature for 24 hours. Next, after thoroughly washing the contaminated part with running water, using a Kimwipe (trade name) sufficiently containing tap water, wiping and cleaning until the Kimwipe is no longer dirty, and then visually observing the above part. The evaluation was based on the following criteria.
◎: No contamination ○: Slight contamination remains △: Contamination remains significantly ×: Contamination remains significantly

(6) Bending resistance The laminate obtained above was cut into a size of 100 mm × 50 mm, and this was cut into a double-sided tape No. 2 manufactured by Nitto Denko. Using 500 A, a test piece was prepared by adhering to an aluminum plate having a thickness of 0.3 mm so that the coating film surface was the surface. Using a JIS K 5600-5-1 type 1 bending test apparatus to which a mandrel having a diameter of 2 mm is attached, the test piece is turned to 180 ° at an even speed over 2 seconds so that the coating surface is on the outside. Bent. After the end of bending, the presence or absence of cracks in the coating film was confirmed for the central 30 mm portion of the bent portion, and evaluated according to the following criteria.
◎: No crack ○: One crack △: Two to three cracks ×: Four or more 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 coating film surface was on the upper side. The curls at the four corners of the laminate were measured at a vertical distance from the glass plane, the average value was determined, and evaluated according to the following criteria.
◎: Less than 2 mm ○: 2 mm or more and less than 5 mm △: 5 mm or more and less than 10 mm ×: 10 mm or more

As can be seen from Table 1, the composition of the present invention can produce a laminate having a coating film comprising the composition at a high line speed, and the coating film has scratch resistance and stain resistance. Excellent bending resistance and appearance. On the other hand, the compositions of Comparative Examples 1 and 2 having a ratio (a / b) outside the scope of the present invention are inferior in any of scratch resistance, stain resistance and bending resistance of the resulting coating film. The composition of Comparative Example 3 using a component (A) having a smaller number of (meth) acryloyloxy groups than the range of the present invention is inferior in scratch resistance and stain resistance of the resulting coating film. The compositions of Comparative Examples 4 to 6 using the component (A) having no ethanolamine residue had a slow curing speed and therefore a slow line speed. Further, the obtained coating film was inferior in any of scratch resistance, stain resistance, bending resistance and appearance. In Comparative Example 7 in which a polydimethylsiloxane graft acrylate paint, which is a self-healing paint, was used as the resin composition, the coating film was poor in stain resistance. Further, as is clear from the comparison between Example 7 and Example 8, the thicker coating film can increase the line speed, but in Comparative Example 7, the coating film thickness is higher than that of Example 1. Despite the increase in thickness, the cure rate was slow and therefore the line speed was slow.

Example 10
In Example 1, as the thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 μm, conforming to JIS-7105-1981 on the surface. A laminate was produced in the same manner as in Example 1 except that the 60 ° gloss (90%) measured in this manner was used and no anchor coat agent was used. The line speed at this time was 50 m / min. The obtained laminates were subjected to the tests (1) to (7). Further, the 60 ° gloss of the surface of the coating film (1) was measured according to JIS-7105-1981. The results are shown in Table 2.

Example 11
A laminate was produced 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). The results are shown in Table 2.

Reference example 1
In Example 10, a laminate was produced in the same manner as in Example 10 except that methyl ethyl ketone was used as component (D). However, the thermoplastic resin film (3) as a base material swelled, and the laminate was produced. Could not get.

As shown in Table 2, when the thermoplastic resin film (3) as the substrate is an unstretched polyester film, when methyl ethyl ketone is used as the solvent (D), the substrate film swells to obtain a laminate. (Reference Example 1). However, when a solvent containing 1% by mass 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 is not lowered. A laminate was obtained (Examples 10 and 11).

Example 12
A biaxially stretched polyester film “E5101 (trade name)” (thickness 25 μm) of Toyobo Co., Ltd. is used as the thermoplastic resin film (3), and an anchor coating agent “Byron 24SS (trade name) of Toyobo Co., Ltd. is used on one side thereof. Was applied using a gravure coating device so as to have a dry film thickness of 1 μm to obtain a thermoplastic resin film (3) having an anchor coat (2) on one side. A series of steps of applying the active energy ray-curable resin composition obtained in Example 1 on the anchor coat (2), drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll The line was run continuously at a line speed of 50 m / min. The roll could be wound well without using a separator. The resin composition was applied using a film Mayer bar type coating apparatus so that the coating thickness after drying was 11 μm.

On the thermoplastic resin film (3) of the laminate obtained above, a polyester hot melt adhesive “AD-170-20 (trade name)” manufactured by Tokushi Co., Ltd. has a thickness of 2.5 μm after drying. Then, the thermoplastic resin film (5) obtained as described below is bonded using a mirror metal roll-rubber roll thermal laminator to obtain a laminate having the structure shown in FIG. It was. At this time, the metal roll side was in contact with the coating film (1), and the surface temperature of the metal roll was set to 190 ° C. For the laminate thus obtained, the above test (1
) To (7) and the following tests (8) to (10) were conducted. Further, the 60 ° gloss of the surface of the coating film (1) was measured according to 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)” of Eastman Chemical Company, Inc. Crystalline polyethylene terephthalate resin “WK-801 (trade name)” (Dicarboxylic acid component: mixture of terephthalic acid 90 mol% or more and less than 99 mol% and isophthalic acid 1 mol% or more and less than 10 mol%; glycol component: ethylene glycol) 41 parts by mass, polybutylene terephthalate resin “Toraycon 1200M” manufactured by Toray Industries, Inc. (Trade name) ”15 parts by weight, Kaneka Co., Ltd. core-shell type acrylic rubber“ Kane Ace FM-40 (trade name) ”2 parts by weight, Cognis Japan Co., Ltd. lubricant“ Roxyol G78 (trade name) ”0.5 Parts by weight, and titanium oxide (white pigment) “Taipe” from Ishihara Sangyo Co., Ltd. "CR-60-2 (trade name)" 12 parts by mass of a resin composition is melt-extruded into a film form from a twin-screw extruder with a vacuum vent and a T-die connected to the extruder. A thermoplastic resin film (5) was obtained by being cooled and solidified by being sandwiched between a mirror cooling roll made of rubber and a cooling roll made of rubber.

Example 13
As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) Was used in the same manner as in Example 12 except that 42 was used in an amount of 42 parts by mass. 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 component (B) in Example 12 was changed as shown in Table 3. 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 in place of the component (A-1). The line speed at this time was 50 m / min as in Example 17, but a separator was required for winding on the roll. The results are shown in Table 3.

Comparative Example 11
In Example 12, instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used. (C) is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd. A laminate was produced in the same manner as in Example 12 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min. The reason why benzophenone (C-1) was not used as component (C) was that when (A-3) was used instead of component (A-1), the curing rate was slow in (C-1). It is. The component (C-2) was used as the component (C) so that the curing of the component (A-3) and the component (B-1) proceeded at a high speed without gelation. The same applies to Comparative Examples 12 and 13 below. The amount of component (C) is 5 parts by mass because 7 parts by mass is too large and gelation occurs. The results are shown in Table 3.

Comparative Example 12
In 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 component (A-1). Further, a laminate was produced in the same manner as in Example 12 except that the amount of component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 3. The above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed. The same applies to (A-5) in Comparative Example 13 below.

Comparative Example 13
In Example 12, instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. Further, a laminate was produced in the same manner as in Example 12 except that the amount of component (B) was changed so that the ratio (a / b) was 0.85. The results are shown in Table 3.

Example 18
In Example 12, a laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was 2 μm. The line speed at this time was 40 m / min. The reason why the line speed is slower than in Example 12 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 3.

Example 19
In Example 12, a laminate was produced in the same manner as in Example 12 except that the thickness of the coating film was 50 μm. The line speed at this time was 50 m / min. The results are shown in Table 3.

Example 20
In Example 12, a laminate was produced in the same manner as in Example 12 except that methyl ethyl ketone was used as the component (D). The line speed at this time was 50 m / min. The results are shown in Table 3.

Example 21
In this example, component (A ′) was added in addition to component (A). As component (A), 50 parts by mass of component (A-1) was used, and as component (A ′), 50 parts by mass of component (A-4) was used. Furthermore, 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 amount of component (E) was 2.0 parts by mass. The results are shown in Table 3.

Test method (8) Solvent rubbing test The laminate obtained above was cut into a size of 100 mm × 100 mm, and the surface of the coating film (1) was scrubbed using Kimwipe (trade name) sufficiently containing methyl ethyl ketone. The presence or absence of a change in gloss or sharpness of the portion after 10 reciprocating wipes was visually observed and evaluated according to the following criteria.
○: No change in surface gloss or sharpness ×: Change in surface gloss or sharpness

(9) Glycerin test Changes in gloss and sharpness of the surface of the coating film (1) after 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. The presence or absence of was visually observed and evaluated according to the following criteria.
○: No change in surface gloss or sharpness ×: Change in surface gloss or sharpness

(10) Scratch resistance (claw)
The laminate obtained above is cut into a size of 120 mm × 60 mm and placed on a glass plate so that the coating film (1) is on top. The surface was rubbed and the scratch resistance was visually evaluated according to the following criteria.
◎: Scratches are not recognized at all ○: Scratches are hardly observed △: Scratches are slightly observed ×: Scratches are remarkably recognized

As can be seen from Table 3, the laminate having the coating film (1) made of the active energy ray-curable resin composition of the present invention has high gloss and has scratch resistance, stain resistance, and bending resistance. Moreover, characteristics such as appearance are also good. On the other hand, the laminate of Comparative Example 8 in which the ratio (a / b) is less than the lower limit of the present invention is inferior in bending resistance, and the laminate of Comparative Example 9 having a ratio (a / b) larger than the upper limit of the present invention is resistant to contamination by aqueous contaminants. Inferior to sex. As the component (A), the laminate of Comparative Example 10 in which the number of (meth) acryloyloxy groups is less than the range of the present invention is inferior to scratch resistance, solvent rubbing test and glycerin test. In Comparative Examples 11 to 13 using a component (A) that does not have an ethanolamine residue, the curing rate of the resin composition was slow, and therefore the line speed was slow. Further, the obtained laminate was inferior to any of scratch resistance, stain resistance, bending resistance, appearance, solvent rubbing test, glycerin test, and scratch resistance test.

Example 23
In Example 12, as a thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 μm, surface JIS-7105-1981 A laminate was manufactured and evaluated in the same manner as in Example 12 except that a 60 ° gloss (measured in accordance with 90%) and not subjected to anchor coating treatment was used. 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
A 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) swelled and a laminate could not be obtained.

As shown in Table 4, when the thermoplastic resin film (3) is an unstretched polyester film, when methyl ethyl ketone is used as the solvent (D), the thermoplastic resin film (3) swells to obtain a laminate. (Reference Example 1). However, when a solvent (D) containing 1% by mass of 1-methoxy-2-propanol (D-2) is used, the thermoplastic resin film (3) does not swell and the thermoplastic resin film (3 It was possible to obtain a laminate without reducing the gloss of *

Example 25
70 parts by weight of component (A-1) as component (A)
30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) as component (A ′)
Coronate HX (trade name, polyisocyanate of the above formula (6)) (B-1) 22 parts by mass as a component (B) manufactured by Nippon Polyurethane Industry Co., Ltd.
5 parts by mass of benzophenone (C-1) as component (C)
Ciba Japan Co., Ltd. Darocur 1173 (trade name, alkylphenone photopolymerization initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) 2 parts by mass,
8 parts by mass of high-purity colloidal silica (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 component (D) were stirred. Thus, an active energy ray-curable resin composition was obtained.
The number of isocyanate groups per unit amount of component (B-1) was 5.12 mol / kg as measured by the method described above. Therefore, the ratio of the number of hydroxyl groups (a) in 70 parts by mass of component (A-1) and 30 parts by mass of component (A-2) to the number of isocyanate groups (b) in 22 parts by mass of component (B-1) (a / B)
It is (1.09 * 70 + 0.63 * 30) / (5.12 * 22) = 0.85.

A biaxially stretched polyester film “Embret S25” (trade name, thickness 25 μm) manufactured by Unitika Ltd. is used as the thermoplastic resin film (3), and an anchor coating agent (byron 24SS (trade name) manufactured by Toyobo Co., Ltd.) is used on one side thereof. ) Was applied to a dry film thickness of 1 μm to obtain a thermoplastic resin film (3) having an anchor coat (2) on one side. The process of applying the resin composition obtained above on the anchor coat (2), drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll is a series of production lines, 50 m / min line Performed continuously at speed. The roll could be wound well without using a separator. The resin composition was applied using a film Mayer bar type coating apparatus so that the coating thickness after drying was 11 μm. In addition, the line speed in an Example and a comparative example is the fastest speed which can manufacture a laminated body stably in a production line. The obtained laminates were subjected to the above tests (1) to (7) and the following test (11). The results are shown in Table 5.

Example 26
As a component (B), Sumidur HT of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of the above formula (7), number of isocyanate groups per unit amount: 3.10 mol / kg) (B-2) Was used in the same manner as in Example 25 except that 36 was used in an amount of 36 parts by mass. The results are shown in Table 5.

Examples 27-30 and Comparative Examples 14-15
A laminate was produced in the same manner as in Example 25 except that the amount of component (B) in Example 25 was changed as shown in Table 5. The results are shown in Table 5.

Example 31
In Example 25, 100 parts by mass of the component (A-1) as the component (A), 25 parts by mass of the component (B-1) as the component (B), and 7 parts by mass of the component (C-1) as the component (C). A laminate was produced in the same manner as in Example 25 except that it was used. The results are shown in Table 6.

Comparative Example 16
In Example 31, except that 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). A laminate was manufactured in the same manner as in Example 31. The line speed at this time was 50 m / min as in Example 31, but a separator was required for winding on the roll. The results are shown in Table 6.

Comparative Example 17
In Example 31, instead of component (A-1), tripropylene glycol diacrylate (manufactured by Daicel-Cytec, number of hydroxyl groups per unit amount: 0 mol / kg) (A-3) was used. (C) is an alkylphenone photopolymerization initiator (Darocur 1173 (trade name), 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (C-2) from Ciba Japan Co., Ltd. A laminate was produced in the same manner as in Example 31 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min. The reason why benzophenone (C-1) was not used as component (C) was that when (A-3) was used instead of component (A-1), the curing rate was slow in (C-1). It is. The component (C-2) was used as the component (C) so that the curing of the component (A-3) and the component (B-1) proceeded at a high speed without gelation. The same applies to Comparative Examples 18 and 19 below. The amount of 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 Example 31, instead of component (A-1), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (A-4) was used. In addition, a laminate was manufactured in the same manner as in Example 31 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 6. The above (A-4) does not have a hydroxyl group in structure, but a hydroxyl group exists because it contains a component in which a part of the acryloyloxy group is hydrolyzed. The same applies to (A-5) in Comparative Example 19 below.

Comparative Example 19
In Example 31, instead of component (A-1), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (A-5) was used. In addition, a laminate was manufactured in the same manner as in Example 31 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 6.

Example 32
In Example 31, a laminate was produced in the same manner as in Example 31 except that the thickness of the coating film was 2 μm. The line speed at this time was 40 m / min. The reason why the line speed is slower than in Example 31 is that when the coating film is thin, the influence of oxygen radicals reaches the inside of the coating film, and as a result, the curing speed of the entire coating film becomes slow. The results are shown in Table 6.

Example 33
In Example 31, a laminate was produced in the same manner as in Example 31 except that the coating thickness was 50 μm. The line speed at this time was 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) in Example 31. The results are shown in Table 6.

Examples 35 to 37, Reference Examples 3 to 4
A laminate was produced in the same manner as in Example 25 except that the amount of component (F-1) was changed to the amount shown in Table 7. The results are shown in Table 7.

Example 38
A laminate was produced in the same manner as in Example 36 except that high-purity colloidal silica (F-2) having an average particle diameter of 20 nm was used as the component (F). The results are shown in Table 7.

Example 39
A laminate was produced in the same manner as in Example 36, except that high-purity colloidal silica (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 as in Example 36 except that high-purity colloidal silica (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 as in Example 36 except that high-purity colloidal silica (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 and 42
In Example 25, a laminate was produced in the same manner except that the amounts of component (A) and component (B) were changed to the amounts shown in Table 8. The line speed at this time was 50 m / min. The results are shown in Table 8.

Example 43
A laminate was produced in the same manner as in Example 42 except that 0.5 part by mass of MegaFac RS-75 (trade name) (E-1) manufactured by DIC Corporation was used as the component (E). The line speed at this time was 50 m / min. The results are shown in Table 8.

Example 44
A laminate was produced in the same manner as in Example 43, except that the amount of component (E-1) was changed to 2.0 parts by mass. The line speed at this time was 50 m / min. The results are shown in Table 8.

Test method (11) Haze According to JIS K 7105, the coating film (1) side of the laminate was measured as the incident surface.

As can be seen from Tables 5 to 8, the composition of the present invention can produce a laminate having a coating film comprising the composition at a high line speed, and the coating film has scratch resistance, Excellent contamination, bending resistance, appearance and transparency.
On the other hand, the compositions of Comparative Examples 14 and 15 whose ratio (a / b) is outside the scope of the present invention are inferior in any of the scratch resistance, stain resistance and bending resistance of the resulting coating film.
The composition of Comparative Example 16 using a component (A) having a smaller number of (meth) acryloyloxy groups than the range of the present invention is inferior in scratch resistance and stain resistance of the resulting coating film.
The compositions of Comparative Examples 17 to 19 using only those having no ethanolamine residue as the component (A) had a slow curing speed and therefore a slow line speed. Further, the obtained coating film was inferior in any of scratch resistance, stain resistance, bending resistance and appearance.
In Reference Example 3 in which the component (F) is not used, the pencil hardness is insufficient.
Reference Example 4 in which the amount of component (F) is greater than the preferred range of the present invention is inferior in bending resistance.
Reference Example 5 in which the particle diameter of the component (F) is larger than the preferred range of the present invention is inferior in transparency (haze).

Example 45
In Example 31, as the thermoplastic resin film (3), SET329 FZ26401 (trade name, cyclohexanedimethanol copolymerized polyethylene terephthalate (PETG resin) film manufactured by Riken Technos Co., Ltd., thickness 100 μm, conforming to JIS-7105-1981 on the surface. And a laminate was produced in the same manner as in Example 31 except that the 60 ° gloss (90%) was used and no anchor coat agent was used. The line speed at this time was 50 m / min. The obtained laminates were subjected to the tests (1) to (7). Further, the 60 ° gloss of the surface of the coating film (1) was measured according to JIS-7105-1981. The results are shown in Table 9.

Example 46
Example 45 is the same as Example 45 except that 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. The results are shown in Table 9.

Reference Example 6
In Example 45, a laminate was produced in the same manner as in Example 45 except that methyl ethyl ketone (D-2) was used as the component (D). The thermoplastic resin film (3) as a base material was produced. It swelled and a laminate could not be obtained.

As shown in Table 9, when the thermoplastic resin film (3) as the base material is an unstretched amorphous polyester film, when methyl ethyl ketone is used as the solvent (D), the base film swells and is laminated. A body could not be obtained (Reference Example 6). However, when a solvent containing 1% by mass 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 is not lowered. A laminate was obtained (Examples 45 and 46).

1: Coating film 2: Anchor coat 3: Thermoplastic resin film 4: Adhesive layer 5: Thermoplastic resin film

Claims

(A) The following formula (1):

(Where R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more,
(B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) a photopolymerization initiator, the number of hydroxyl groups (a) in component (A) and the number of isocyanate groups in component (B) ( An active energy ray-curable resin composition having a ratio (a / b) to b) in the range of 0.5 to 1.2.
Component (A) is represented by the following formula (2):

The composition of Claim 1 which is a compound represented by these.
(A) The following formula (1):

(Where R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more,
(A ′) (meth) acrylate compounds other than component (A),
(B) a polyisocyanate having two or more isocyanate groups in one molecule, and (C) a photopolymerization initiator, the number of hydroxyl groups (a) in component (A) and the number of hydroxyl groups in component (A ′) ( The ratio ((a + a ′) / b) of the total (a + a ′) of a ′) to the number of isocyanate groups (b) in component (B) is in the range of 0.5 to 1.2. An active energy ray-curable resin composition.
Component (A) is represented by the following formula (2):

The composition of Claim 3 which is a compound represented by these.
The composition according to any one of claims 1 to 5, wherein the component (B) is a polyisocyanate having three isocyanate groups in one molecule.
6. The solvent according to claim 1, further comprising (D) a solvent, wherein the amount of the component (D) is 150 to 250 parts by mass with respect to 100 parts by mass of the component (A). Composition.
6. The method according to claim 3, further comprising (D) a solvent, wherein the amount of component (D) is 150 to 250 parts by mass with respect to a total of 100 parts by mass of component (A) and component (A ′). The composition according to item.
The composition according to claim 6 or 7, wherein the component (D) is a solvent containing 40% by mass or more of 1-methoxy-2-propanol.
(E) An ultraviolet-reactive fluorine-based surface modifier is further included, and the amount of component (E) is 0.1 to 5 parts by mass with respect to 100 parts by mass of component (A). 9. The composition according to any one of 6 and 8.
(E) An ultraviolet reactive fluorine-based surface modifier is further included, and the amount of component (E) is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of component (A) and component (A ′). The composition according to any one of claims 3 to 5, 7 and 8.
(F) The composition further comprises fine particles having a particle diameter of 1 nm to 300 nm, and the amount of component (F) is 1 to 50 parts by mass with respect to 100 parts by mass of component (A). 10. The composition according to any one of 8 or 9.
(F) Fine particles having a particle diameter of 1 nm to 300 nm are further included, and the amount of the component (F) is 1 to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (A ′). Item 11. The composition according to any one of Items 3 to 5, 7, 8, or 10.
A paint comprising the composition according to any one of claims 1 to 12.
The laminated body by which the coating film (1) which consists of a coating material of Claim 13 was laminated | stacked on one side of the thermoplastic resin film (3) through the anchor coat layer (2) or not.
The laminated body of Claim 14 which has a thermoplastic resin film (5) through the adhesive bond layer (4) in the surface in which the coating film (1) is not laminated | stacked of a thermoplastic resin film (3).