JP2021020414A - Laminate film for decoration of three-dimensional molded article - Google Patents

Abstract

To provide a laminate film for the decoration of a three-dimensional molded article having excellent appearance and strength.SOLUTION: A laminate film for the decoration of a three-dimensional molded article has a substrate film layer (A), a clear coating layer (B), a design layer (C), and an adhesive layer (D). The design layer (C) is a layer formed in such a manner that a resin composition containing a monomer/oligomer (C1) having an unsaturated double bond is UV-cured.SELECTED DRAWING: None

Description

The present invention relates to a laminated film for decorating a three-dimensional molded product.

In molded products obtained from various materials such as plastics, metals, and the like, the surface is generally decorated for the purpose of imparting design to the surface and protecting the surface.

As one of such decoration methods, a film decoration method using a laminated film as described in Patent Documents 1 and 2 is known. In this method, a layer for decorating a molded product is created as a film, and this is attached onto the molded product for decoration. Such a laminated film is composed of a plurality of different layers according to functions, and it is generally practiced that a design layer is provided for the purpose of obtaining designability.

In such a three-dimensional molded product decorative laminated film, a problem of appearance deterioration called dusty skin is likely to occur due to stress during molding. Further, when a flat pigment such as aluminum or mica is used as a bright material in the design layer as in the method described in Patent Document 3, there is a problem that the orientation of the flat pigment is disturbed due to stress during molding and the appearance is deteriorated. was there.

Further, although the clear coating film layer has been UV-cured so far, the design layer has not been UV-cured.

JP-A-2015-145103 JP-A-2017-7109 International Publication No. 2016/080423

An object of the present invention is to solve the above-mentioned problems and to provide a three-dimensional molded product decorative laminated film having excellent appearance and strength.

The present invention is a three-dimensional molded product decorative laminated film having a base film layer (A), a clear coating layer (B), a design layer (C) and an adhesive layer (D), and the design layer ( C) is a three-dimensional molded product decorative laminated film, which is a layer formed of a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond.

The design layer (C) further preferably contains 0.05 to 4.0% by weight of isocyanate.
The isocyanate is preferably a blocked isocyanate.
It is preferable that the design layer (C) further contains a flat pigment.
The design layer (C) may be composed of a plurality of layers.

The clear coating layer (B) is formed by an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). It is preferable that the material is
The laminated film for decoration of the three-dimensional molded product preferably has an elongation of 30 to 500% in a temperature range of 40 to 130 ° C. as a laminated film.

The laminated film for decorating a three-dimensional molded product of the present invention prevents orientation disorder during molding of a bright material to improve the appearance, and is also excellent in strength such as weather resistance and impact resistance.

It is a schematic diagram which shows an example of the laminated structure of the laminated film for decoration of a three-dimensional molded product of this invention. It is a schematic diagram which shows an example of the laminated structure of the laminated film for decoration of a three-dimensional molded product of this invention. It is a figure which shows concretely the reading method at the time of reading Tg from a chart in the method of measuring Tg in this invention. It is a graph which showed the elongation change by the temperature of a film, and the molding temperature range.

Hereinafter, the present invention will be described in detail.
(Three-dimensional molded product decorative laminated film)
The laminated film for decorating a three-dimensional molded product of the present invention is a film used for decorative molding of a three-dimensional molded product. That is, a film having a design property is adhered to various molded bodies to give the molded body a design property or a surface protection function.
At that time, it is deformed into a shape along the surface of the three-dimensional shape and brought into close contact with each other.
Any known method can be used as such a method of adhering, and examples thereof include a method of deforming and adhering by a method such as vacuum forming or compressed air forming. Further, a method of deforming a laminated film for decorative molding into the shape of the outer wall surface of the mold in the mold and then performing injection molding can be mentioned.

In the present invention, it is intended to suppress a decrease in design due to stress generated during decorative molding of such a three-dimensional molded product, shrinkage during curing, and the like. That is, a design layer having a high crosslink density is formed by curing a monomer / oligomer having an unsaturated double bond by energy ray curing. As a result, it is possible to prevent deterioration of the appearance by making it difficult to generate a physical force.

With such a configuration, it is possible to obtain a three-dimensional molded product decorative laminated film having remarkably superior performance in terms of design.

The laminated film for decoration of a three-dimensional molded product of the present invention
(A) Base film layer,
(B) Clear coating film layer (C) Design layer and
(D) It has an adhesive layer.

Of the above layers, the adhesive layer (D) needs to be the outermost layer, and the design layer (C) is a clear coating film layer (B) made of an energy ray-curable coating film and an adhesive layer (D). It exists between and.

Examples of the layer structure of the three-dimensional molded product decorative laminated film capable of obtaining the above-mentioned effects include those shown in FIGS. 1 and 2.
The three-dimensional molded product decorative laminated film shown in FIG. 1 includes an adhesive layer (D), a design layer (C), a clear coating film layer (B) composed of an energy ray-curable coating film, and a release layer (E). And the base film layer (A) are laminated in this order.

The film having such a structure is adhered to the three-dimensional molded product by the adhesive layer (D), and the base film layer (A) is peeled off after the decorative molding to perform decoration. As a result, a decorative layer consisting of three layers, an adhesive layer (D), a design layer (C), and a clear coating film layer (B) composed of an energy ray-curable coating film, is formed on the three-dimensional molded product. is there.

The three-dimensional molded product decorative laminated film shown in FIG. 2 is a film in which an adhesive layer (D), a design layer (C), a base film layer (A), and a clear coating film layer (B) are laminated in this order. is there. In such a film, the base film layer (A) is not peeled off, and a decorative layer including the layer is formed on the three-dimensional molded product.

(Design layer (C))
The design layer (C) is a layer for imparting a design appearance to a three-dimensional molded product in a three-dimensional molded product decorative laminated film, and is a layer having a design property such as a coloring material or a bright pigment. It is preferable to have.
The design layer (C) of the present invention is formed of a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond.
When the laminated film for decorating a three-dimensional molded product of the present invention is used, the film is deformed into the shape of the three-dimensional molded product. Therefore, when a constant force is applied to the resin, strain is generated and internal stress is generated. Due to such internal stress, the pigment in the design layer (C) is disturbed, dusty skin is formed, and the appearance is deteriorated. Therefore, by blending a monomer / oligomer (C1) having an unsaturated double bond and forming a crosslinked chain after molding, these problems caused by stress are improved.

As the monomer / oligomer (C1) having an unsaturated double bond, any known compound can be used, and for example, the following compounds can be used.

Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethylene glycol. Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , 1,10-Decandiol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate and the like. Among them, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and the like can be preferably used.

Examples of (meth) acrylates having 3 functional groups include trimethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and trimethylolpropane propylene oxide-modified tri (meth) acrylate. Includes meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin propoxytri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate and the like. Of these, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and the like can be preferably used.

Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, and pentaerythritol propylene oxide-modified tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate and the like. Among them, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be preferably used.

Examples of (meth) acrylates having 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Dipentaerythritol penta (meth) acrylate, ditrimethylolpropanpenta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanehexa (meth) acrylate, dipenta Examples thereof include polyfunctional (meth) acrylates such as hexa (meth) acrylates, which are modified caprolactones of erythritol. Only one kind of these monomers may be used, or two or more kinds thereof may be used in combination.

Examples of the (meth) acrylic oligomer include epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate-based prepolymer can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a bisphenol type epoxy resin or a novolak type epoxy resin having a relatively low molecular weight to esterify it. The urethane acrylate can be generally obtained by reacting a polyester polyol, a polyether polyol, or a polycarbonate polyol with an isocyanate monomer or a prepolymer, and reacting an acrylate monomer having a hydroxyl group with a product obtained.
Only one kind of these (meth) acrylic oligomers may be used, two or more kinds thereof may be used in combination, or the above-mentioned polyfunctional (meth) acrylate-based monomer may be used in combination.

As the monomer / oligomer (C1) having an unsaturated double bond, a commercially available product such as UV 1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can also be used.

The design layer preferably contains the monomer / oligomer (C1) having an unsaturated double bond in a proportion of 1 to 30% by weight. By containing it in such a ratio, the above-mentioned effects can be suitably exhibited. The lower limit of the blending amount is more preferably 2% by weight, further preferably 5% by weight. The upper limit of the blending amount is more preferably 20% by weight, further preferably 10% by weight.

(Photoactivant)
In the design layer, in addition to the compound (C1) described above, a photoactivator can be used as a photoreaction initiator. Examples of the photoactivator include a radical generator that generates radicals and a photoacid generator that generates an acid by light.

The photoactivator is preferably a compound that produces an acid upon irradiation with energy rays. As the photoactivator that produces an acid by irradiation with energy rays, a compound that produces a strong acid by irradiation with energy rays can be used without particular limitation. The photoactivator that can be used in the present invention is not particularly limited, but generally known compounds that generate sulfonic acid by irradiation with an onium salt and energy rays can be used. Examples of the onium salt include a diallyl iodonium salt, a triarylsulfonium salt and a triarylselenium salt, and suitable counter anions include tetrafluoroborate, trifluoromethanesulfonate, hexafluoroantimonate and hexa. Examples include compounds such as fluoroarsenate and hexafluorophosphate. Examples of compounds that generate sulfonic acid by irradiation with energy rays include β-ketosulfone compounds, ester compounds of nitrobenzyl alcohol and aryl sulfonic acid, ester compounds of oxime and aryl sulfonic acid, and N-hydroxyamide or imide. Examples thereof include an ester compound with sulfonic acid and an ester compound with benzoin and sulfonic acid. The photoactivator (B) may be used alone or in combination of two or more.

As the photoactivator, for example, PIR 03N manufactured by Sanyo Chemical Industries, Ltd. can be used.

The content of the photoactivator is preferably 0.05 to 5.0% by weight.
When the number of design layers is two or more, the content of the layer containing the photoactivator is preferably 0.05 to 5.0% by weight.

The design layer (C) of the present invention may further contain the isocyanate compound (C2) in an amount of 0.05% by weight to 4.0% by weight based on the weight of the entire design layer.
When the isocyanate compound (C2) is blended, the design property is not deteriorated even when a physical force is generated in the design layer due to stretching, stress, shrinkage during curing, etc. during decorative molding of the three-dimensional molded product. It is a thing. By blending a small amount of a curing agent, it is possible to cope with stretching during three-dimensional molding without impairing the performance as a decorative molded product, and further, it also has an effect of reducing stress during stretching. .. On the other hand, from the viewpoint of reducing curing shrinkage during thermosetting and ensuring stretching characteristics, the amount of the curing agent used is extremely small as compared with the amount used in a general coating composition. Is preferable.

The design layer containing the isocyanate compound (C2) is preferably a crosslinked structure formed by thermosetting. Thereby, the above-mentioned effect can be obtained more efficiently.
When the design layer (C) contains the isocyanate compound (C2), it is preferable that the design layer (C) is cured by the isocyanate compound (C2) in the process of film production. Thereby, the above-mentioned curing of the present invention can be obtained more preferably.
Further, by forming the crosslinked structure, it is possible to impart strength such as weather resistance and impact resistance to the design layer as well as aesthetics.

If the amount of the isocyanate compound (C2) is less than 0.05% by weight, the performance of the decorative molded product may not be satisfied, and if it is more than 4.0% by weight, the orientation of the pigment may be disturbed due to stress during molding. It is not preferable because it may occur.

The content of the isocyanate compound (C2) is preferably 0.07 to 3.0% by weight, more preferably 0.1 to 2.0% by weight.

The isocyanate compound (C2) is not particularly limited as long as it is a compound having one or more isocyanate groups. For example, examples of monoisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, lauryl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, and tolyrene isocyanate. For example, polyisocyanate includes tolylene diisocyanate, 4,4. Aromatic ones such as ′ -diphenylmethane diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate; aliphatic ones such as hexamethylene diisocyanate; alicyclic ones such as isophorone diisocyanate; the monomer and its bullet type, nurate Examples include multimers such as type and adduct type. Of these, it is preferable to use the HDI nurate type and the allophanate type from the viewpoint of ensuring stretchability after curing. Examples of commercially available products include R-271 (NPAU), Crosnate UV (Dainichiseika Kogyo), D-178N (Mitsui Chemicals), Sumijour N-3400 (Sumitomo Bayer Urethane) and the like.

The isocyanate compound (C2) contained in the design layer may be a blocked isocyanate compound blocked by a sealing agent.
As a result, the reactivity of isocyanate can be suppressed, the storage stability can be improved, and the handling in the reaction process can be facilitated.

Examples of the encapsulant include monohydric alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenolcarbinol, methylphenylcarbinol; ethylene glycol. Cellosolves such as monohexyl ether and ethylene glycol mono2-ethylhexyl ether; polyether-type both-terminal diols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol phenol; ethylene glycol, propylene glycol and 1,4-butanediol Diols such as; polyester-type double-ended polyols obtained from dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid; phenols such as parat-butylphenol and cresol; dimethylketooxime, methylethylketo Oxims such as oxime, methylisobutylketooxym, methylamylketooxym, and cyclohexanone oxime; lactams typified by ε-caprolactam and γ-butyrolactam; and the like can be mentioned. Among them, it is preferable to use Duranate 17B-60PX, TPA-B80E (Asahi Kasei) or the like as commercially available products.

In addition to the above components, the design layer (C) of the present invention preferably contains a bright material (C3) and a hydroxyl group-containing resin (C4). Any known hydroxyl group-containing resin (C4) can be used, but from the viewpoint of obtaining processability and good coating film physical properties, the hydroxyl group-containing urethane resin (C4-1) should be used. Is preferable.

(Glow material (C3))
The effect of the present invention becomes more remarkable when the design layer (C) contains a bright material (C3). That is, it is also effective from the viewpoint of solving the problem of deterioration of the appearance due to the disordered orientation of the bright material.
The bright material (C3) is not particularly limited, and aluminum, glass, inorganic pigments, organic pigments and the like can be used. More specifically, metal pigments using coated aluminum, aluminum flakes, copper, zinc, nickel, tin, metal such as aluminum oxide or metallic bright materials such as alloys; mica such as interference mica and white mica. Pigments and the like can be mentioned. Among them, it is preferable to use a flat pigment such as aluminum or mica in order to improve the appearance.

The design layer contains 0.5 to 60 parts by weight of (C3) in 100 parts by weight of the total solid content weights ((C2) + (C3) + (C4)) of (C2) to (C4). It is preferable to use the one contained so as to be in the range.

The design layer (C) further contains a hydroxyl group-containing resin (C4). The hydroxyl group-containing resin (C4) is not particularly limited, and examples thereof include vinyl chloride resin, acrylic resin, urethane resin, polyester resin, and the like, and two or more of these are mixed and used. You may. Of these, urethane resin (C4-1) is particularly preferable.

The hydroxyl group-containing resin (C4) preferably has a hydroxyl value of 1 to 100 mgKOH. This is because the reaction with the above-mentioned isocyanate compound (C2) can be satisfactorily generated by setting the content within such a range.
Hereinafter, the urethane resin (C4-1) that can be suitably used as the hydroxyl group-containing resin (C4) of the present invention will be specifically described.

(Urethane resin (C4-1))
The urethane resin (C4-1) is not particularly limited, but the weight average molecular weight Mw is preferably 10,000 or more and 200,000 or less, and more preferably 30,000 or more and 150,000 or less. When the weight average molecular weight Mw is less than 10,000, the flexibility of the design layer (C) is lowered, and when the weight average molecular weight Mw exceeds 200,000, the colored coating composition is produced and the film is coated. Becomes difficult.

The polyurethane resin (C4-1) preferably has a Tg: −30 ° C. to 30 ° C. If the Tg is less than -30 ° C, there may be a problem that the tackiness (blocking) of the coating film after coating and drying is lowered, and if it exceeds 30 ° C, molding defects due to the coating film hardness UP and the product It may cause a problem of deterioration of low temperature physical properties.

In the present specification, Tg means a value measured by the following steps with a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)). That is, a step of raising the temperature from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min (step 1), a step of lowering the temperature from 150 ° C. to -50 ° C. at a temperature lowering rate of 10 ° C./min (step 2), and raising. It is a value obtained from the chart at the time of raising temperature in step 3 in the step (step 3) of raising the temperature from −50 ° C. to 150 ° C. at a temperature rate of 10 ° C./min. That is, the temperature indicated by the arrow in the chart shown in FIG. 3 was defined as Tg.

(Other ingredients)
Further, the thermosetting resin composition used for forming the design layer (C) has other components such as an ultraviolet absorber (UVA), a light stabilizer (HALS), a pigment, a surface conditioner, and a defoamer. Other components such as a conductive filler and a solvent may be contained.

The composition for forming the design layer (C) may be one to which an aluminum aggregation inhibitor is added. In this case, it is preferable that the action of the aluminum aggregation inhibitor can suppress the aggregation failure between the aluminum and the resin. Specifically, as the aluminum coagulation inhibitor, Dyanal RE360 (manufactured by Mitsubishi Rayon Co., Ltd.) or the like can be used.

Further, the design layer (C) may contain a coloring pigment that does not correspond to the bright material, instead of the bright material (C3). Further, the bright material (C3) and the coloring pigment may be used in combination.

The design layer (C) of the three-dimensional molded product decorative laminated film of the present invention may be a single layer, but may be various other layers.
When the design layer (C) has two or more design layers, it is formed by UV curing a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond in only one layer. It may be a layer, or it may be a layer formed by UV curing a resin composition containing a monomer / oligomer (C1) in which a plurality of layers have unsaturated double bonds.

When the number of design layers is two or more, the above-mentioned photoactivator may be added to only one layer or to a plurality of layers.

When the design layer (C) has two or more layers, a design in which the first design layer is a layer containing a mica pigment and the second design layer is a layer containing a white pigment can be mentioned. it can.

When the design layer (C) has two or more design layers, the resin composition containing the monomer / oligomer (C1) having an unsaturated double bond is UV-cured at least for the layer containing the flat pigment. It is preferable to form by allowing.
Further, as described in detail below, the design layer (C) may have a function as an adhesive layer (D). In this case, it is preferable to use a resin containing an adhesive resin.

Hereinafter, layers other than the design layer (C) will be described in detail.
(Base film layer (A))
The base film layer (A) also functions as a carrier film when producing the laminated film of the present invention. That is, it is used as a base material for forming each layer during the production of the three-dimensional molded product decorative laminated film of the present invention.

The film forming the base film layer (A) is not particularly limited, and is conventionally known such as a soft vinyl chloride film, a non-stretched polypropylene film, a non-stretched polyester film, a polycarbonate film, an acrylic resin film, and a fluorine film. Film is mentioned. Among these, a film formed of polyester and / or polyolefin is preferable, and a non-stretched polyester film is more preferable from the viewpoint of energy saving and low temperature processability. The thickness of the base film layer (A) is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm. If it is out of this range, it is not preferable in terms of function as a carrier film and economic efficiency in energy ray curing.

(Clear coating film layer (B))
The clear coating film layer (B) used in the present invention is for protecting the surface, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film, and is known. It can be a coating film layer.
Among them, it is preferably formed by an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2) and a polymerization initiator (B3). .. As a result, stretching during use is facilitated, and deep drawing can be easily performed, so that the three-dimensional shape can be easily followed. It also has the advantage that blocking is less likely to occur.

Further, in the active energy ray-curable coating composition, (B1) is added to 100 parts by weight of the total weight of the solid content of (B1) and the solid content of (B2) ((B1) + (B2)). It contains 50 to 99 parts by weight and (B2) so as to be within the range of 1 to 50 parts by weight, and the total amount of the solid content weight of (B1) and the solid content weight of (B2) ((B1) + (B2). )) It is preferable to contain (B3) in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight. As a result, it is possible to have blocking resistance and deep drawing property (stretchability) before curing. Further, it can have high scratch resistance, surface hardness, chemical resistance and impact resistance after curing.
Hereinafter, (B1) to (B3) will be described in detail.

(Polyurethane acrylate (B1))
Polyurethane acrylate (B1) is a compound having a urethane bond in the molecule and a (meth) acrylate group in the molecule. By using this, the stretchability at the time of performing decorative molding is improved, and since it can easily cope with deep drawing, the follow-up to the three-dimensional shape becomes good.

The polyurethane acrylate (B1) is not particularly limited, and any known polyurethane acrylate can be used. For example
i) A compound obtained by equivalently reacting a compound having two or more isocyanate groups in the molecule with a compound having one or more hydroxyl groups and one or more double bonding groups in the molecule.
ii) A compound having two or more isocyanato groups in the molecule is reacted with a condensate of the polyol and a monobasic acid and / or a polybasic acid and / or an acid anhydride thereof, and then 1 in the molecule. A compound obtained by reacting a compound having one or more hydroxyl groups with one or more double bonding groups.
iii) Obtained by reacting a polyol with a compound having two or more isocyanate groups in the molecule, and then reacting a compound having one or more hydroxyl groups and one or more double bonding groups in the molecule. Compounds,
And so on.

In the above i) to iii), examples of the compound having one or more hydroxyl groups and one or more double bond groups in the molecule include 2-hydroxy (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Examples of 4-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like, and commercially available products include the Praxel F (M) A series (trade name of Daicel Chemical Co., Ltd.). Further, in the above ii) to iii), examples of the polyhydric alcohol include polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane and the like, and commercially available products include the praxeldiol series (trade name of Daicel Chemical Co., Ltd.). ), Plaxel triol series (trade name of Daicel Chemical Co., Ltd.), etc.

The polyol is not particularly limited, and known acrylic polyols, polyester polyols, polycarbonate polyols and the like can be used. Further, various low molecular weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, and neopentyl glycol can also be used as needed.

The polyol preferably has a polycarbonate diol skeleton at a ratio of polycarbonate concentration: 0.5 to 75 wt% (ratio to the total amount of polyurethane acrylate (B1)). By using a material having a polycarbonate diol skeleton, toughness is exhibited, and there is an advantage that it is possible to prevent swelling during decorative molding and to maintain the appearance of the design (prevention of cracking).
The polycarbonate diol is more preferably 2 to 70% by weight.

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and is, for example, an aromatic compound such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, or metaxylylene diisocyanate. Aliphatic compounds such as hexamethylene diisocyanate; Aliphatic compounds such as isophorone diisocyanate; monomers thereof and multimers such as bullet type, nurate type, adduct type and the like.

Commercially available products of the above polyisocyanates include Duranate 24A-90PX (NCO: 23.6%, trade name, manufactured by Asahi Kasei Corporation), Sumijour N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate D165N- 90X (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), Sumijour N-3300, Sumijour N-3500 (trade name, manufactured by Sumitomo Bayer Urethane), Duranate THA-100 (trade name, manufactured by Asahi Kasei), etc. Can be mentioned. Further, if necessary, blocked isocyanates having these blocks can be used.

The polyurethane acrylate (B1) may have a urea bond in part.
In order to have a urea bond, a polyamine compound may be partially used in the synthesis of polyurethane acrylate. The polyamine compound that can be used is not particularly limited, and for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylene. Diamine, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylene diamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, Aliphatic polyamines such as (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine, piperazine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1 , 4-Cyclohexanediamine, Isophoronediamine (IPDA), Methylenebiscyclohexane 2,4'-and / or 4,4'-diamine, alicyclic polyamines such as norbornandiamine; phenylenediamine, xylylenediamine, 2,4- Aromatic diamines such as tolylene diamine, 2,6-tolylene diamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane; And diamine diamine obtained by converting the carboxyl group of dimer acid into an amino group, dendrimer having a primary or secondary amino group at the terminal, and the like can be mentioned.

The polyurethane acrylate (B1) preferably has a double bond equivalent of 130 to 600 g / eq, and more preferably 150 to 300 g / eq. If the double bond equivalent is less than 130 g / eq, there is a possibility that the cured film may be inferior in crack resistance and impact resistance. If the double bond equivalent exceeds 600 g / eq, problems such as inferior scratch resistance, surface hardness, and chemical resistance may occur.

The polyurethane acrylate (B1) preferably has a weight average molecular weight of 3000 to 20000. If the weight average molecular weight is less than 3000, a problem of poor blocking resistance may occur. When the weight average molecular weight exceeds 200,000, the compatibility between the obtained polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond contained in the clear coating composition is lowered. In addition, when the weight average molecular weight exceeds 200,000, the viscosity of the clear coating composition tends to increase. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition is significantly reduced, which may cause a problem that the processability is deteriorated. There is. In this specification, the weight average molecular weight was measured by the method described later.

The polyurethane acrylate (B1) preferably has a urethane concentration of 300 to 2000 g / eq. When the urethane concentration is less than 300 g / eq, the compatibility between the obtained polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond contained in the clear coating composition is lowered. In addition, when the urethane concentration is less than 300 g / eq, the viscosity of the clear coating composition tends to increase. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition is significantly reduced, which may cause a problem that the processability is deteriorated. There is. If the urethane concentration exceeds 2000 g / eq, there may be a problem that the blocking resistance and the impact resistance are inferior.

The polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g / eq. When the urea concentration is less than 500 g / eq, the compatibility between the obtained polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond contained in the clear coating composition is lowered. In addition, when the urea concentration is less than 500 g / eq, the viscosity of the clear coating composition tends to increase. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition is significantly reduced, which may cause a problem that the processability is deteriorated. There is. If the urea concentration exceeds 1000 g / eq, there may be a problem that the blocking resistance is inferior.

The polyurethane acrylate (B1) may be modified with fluorine and / or silicone. That is, the polyurethane acrylate (B1) may be synthesized by the above-mentioned method using a monomer containing fluorine or a silicone unit, or the polyurethane acrylate (B1) obtained by the above-mentioned method has. The functional group may be reacted with a compound having fluorine and / or silicone.

(Monomer / oligomer having unsaturated double bond (B2))
As the monomer / oligomer (B2) having an unsaturated double bond, any known monomer / oligomer can be used, and for example, the same compound (C1) as described above can be used.

(Polymerization initiator (B3))
The clear coating composition may further contain a polymerization initiator (B3) in addition to the polyurethane acrylate (B1) and the monomer / oligomer having an unsaturated double bond (B2). Examples of the polymerization initiator (B3) include, but are not limited to, an electromagnetic ray polymerization initiator in which polymerization is initiated by an electromagnetic ray such as ultraviolet rays (UV) or an electron beam, and a radical polymerization initiator for thermosetting. ..

Specifically, examples of the electromagnetic beam polymerization initiator include benzoin compounds such as benzoin methyl ether; anthraquinone compounds such as 2-ethylanthraquinone; benzophenone compounds such as benzophenone; sulfide compounds such as diphenyl sulfide; Thioxanthone compounds such as 2,4-dimethylthioxanthone; acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone; phosphinoxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphinoxide; Examples thereof include a polymerization initiator for ultraviolet (UV) curing such as Irgacure (registered trademark) -184 and Irgacure-819 (both manufactured by BASF). As the polymerization initiator, one kind or two or more kinds of these compounds can be used.

Examples of the thermosetting radical polymerization initiator include t-amylperoxy-2-ethylhexanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and trigonox (registered trademark) 121-50. Organic peroxides and the like (manufactured by Kayaku Akzo Corporation) can be mentioned. As the organic peroxide as the radical polymerization initiator for thermosetting, one kind or two or more kinds may be used.

(Amount of (B1) to (B3) blended)
In 100 parts by weight of the solid content weight of (B1) and the total solid content weight of (B2) ((B1) + (B2)), 50 to 99 parts by weight of (B1) and 1 to 50 parts by weight of (B2). It is contained so as to be within the range of parts by weight, and (B3) is 0 with respect to 100 parts by weight of the total amount of the solid content weight of (B1) and the solid content weight of (B2) ((B1) + (B2)). It is preferably contained so as to be within the range of 5 to 20 parts by weight.

If the content of the polyurethane acrylate (B1) is less than 50 parts by weight, the blocking resistance is lowered, which is not preferable. If the content of the polyurethane acrylate (B1) exceeds 99 parts by weight, scratch resistance and surface hardness become insufficient, which is not preferable. The lower limit is more preferably 55 parts by weight or more, and further preferably 65 parts by weight or more. The upper limit is more preferably 98 parts by weight or less, and further preferably 95 parts by weight or less.

If the content of the monomer / oligomer (B2) having an unsaturated double bond is less than 1 part by weight, scratch resistance and surface hardness become insufficient, which is not preferable. If the content of the monomer / oligomer (B2) having an unsaturated double bond exceeds 50 parts by weight, the blocking resistance is lowered, which is not preferable. The lower limit is more preferably 2 parts by weight or more, and further preferably 5 parts by weight or more. The upper limit is more preferably 45 parts by weight or less, and further preferably 35 parts by weight or less.

If the content of the polymerization initiator (B3) is less than 0.5 parts by weight, the clear layer cannot be sufficiently cured, and the obtained clear has scratch resistance, surface hardness, chemical resistance, and impact resistance. There is a possibility that the physical properties of the coating film cannot be obtained. When the content of the polymerization initiator (B3) exceeds 20 parts by weight, the unreacted polymerization initiator (B3) remains in the clear coating film, and the clear coating film is deteriorated by outdoor sunlight or the like. , Weather resistance may deteriorate.

The clear coating composition preferably contains 0.5 to 20 parts by weight of a monomer having a thiol group and / or an amine group.
The monomer having a thiol group and / or an amine group is not particularly limited, and examples thereof include commonly used thiol compounds and amine compounds.

Examples of the amine compound include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine and diethylenetriamine: 1,2- and 1,3-cyclobutanediamine, 1, Alicyclic polyamines such as 2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4'-and / or 4,4'-diamine, norbornanediamine: phenylenediamine , Xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoludiamine, aromatic amines such as 4,4-bis- (sec-butyl) diphenylmethane: and the carboxy group of dimer acid. Diamine diamine converted to an amino group, a dendrimer having an amino group at the terminal, and a polyamine having an amine as a repeating structure can also be used, but are not limited thereto.

Examples of the thiol compound include 1,4-bis (3-mercaptobutylyloxy) butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, 4-t-butyl-1,2-benzenedithiol, and bis. -(2-Mercaptoethyl) sulfide, 4,4'-thiodibenzenethiool, benzenedithiol, glycoldimercaptoacetate, glycoldimercaptopropionate, ethylenebis (3-mercaptopropionate), polyethylene glycol dimercaptoacetate , Polyethylene glycol di- (3-mercaptopyropionate), 2,2-bis (mercaptomethyl) -1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithian, bisphenofluorenbis ( Ethoxy-3-mercaptopropionate), 4,8-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecandiol, 2-mercaptomethyl-2-methyl-1,3-propanedithiol , 1,8-Dimercapto-3,6-dioxaoctane, thioglycerol Bismercapto-acetate and other bifunctional thiols: Trimethylolpropane (trimethercaptopropionate) (TMPTMP), Trimethylolpropane Tris (3-mercaptobuty) Rate), trimethylolpropanetris (3-mercaptopropionate), trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptoacetate), tris (3-mercaptopropyl) isocyanurate, 1 , 3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,2,3-trimercaptopropane, and Trifunctional thiols such as tris (3-mercaptopropionate) triethyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione: poly (mercaptopropylmethyl) siloxane (PMPMS) ), 4-Mercaptomethyl-3,6-dithia-1,8-octanedithiol pentaerythritol tetrakis (3-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto). Propionate), Pentaerythritol Tetraquis (3) -Contains, but is not limited to, polyfunctional thiols such as mercaptobutyrate).

The clear coating layer (B) used in the three-dimensional molded product decorative laminated film of the present invention is as described above, but more preferably, the polyurethane acrylate (B1) has a double bond equivalent: 130. ~ 600g / eq
Molecular weight Mw: 3000-2000000
Urethane concentration: 300-2000 g / eq,
It is preferably formed by the coating composition. It is preferable to use one that satisfies these properties. By forming the clear coating film layer (B) with such a clear coating composition, it is possible to provide blocking resistance, high scratch resistance, surface hardness, chemical resistance, and to impart good impact resistance. It is preferable in that respect. Further, the polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g / eq.

The weight average molecular weight in the present specification was measured using HLC-82220 GPC manufactured by Tosoh Corporation. The measurement conditions are as follows.
Column: TSKgel Super Multipore HZ-M 3 development Solvent: Tetrahydrofuran Column inlet oven 40 ° C.
Flow rate: 0.35 ml / min.
Detector: RI
Standard polystyrene: Tosoh Corporation PS oligomer kit

(Other ingredients)
In the clear coating composition, in addition to the above-mentioned polyurethane acrylate (B1), monomer / oligomer having an unsaturated double bond (B2), and polymerization initiator (B3), a compound usually added as a coating material is included in the clear coating composition. It may be contained as another component. Examples of other components include ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins and cross-linking agents, pigments, surface conditioners, defoamers, conductive fillers, solvents and the like.

Further, a solvent may be used for mixing each component contained in the clear coating composition and adjusting the viscosity. Examples of the solvent include ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, aromatic hydrocarbon-based, and other conventionally known organic solvents used in paints. The solvent may be used alone or in combination of two or more. When the above solvent is used, if a volatile substance remains on the laminated film, the volatile substance may volatilize when decorating the base material, resulting in pinholes or swelling. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

Further, the clear coating composition preferably further contains 0.5 to 60 parts by weight of an inorganic / organic filler having an average primary particle diameter of 100 nm or less. Thereby, blocking resistance, high scratch resistance, and surface hardness can be improved. The lower limit of the blending amount is more preferably 1% by weight, and the upper limit is more preferably 50% by weight.

Examples of the inorganic filler include silica, fine powder glass, alumina, calcium carbonate, kaolin, clay, sepiolite (magnesium silicate), talc (magnesium silicate), mica (aluminum silicate), zonotrite (calcium silicate), aluminum borate, and hydro. Talsite, wollastonite (calcium silicate), potassium titanate, titanium oxide, barium sulfate, magnesium sulfate, magnesium hydroxide, ittoria, ceria, silicon carbide, boron carbide, zirconia, aluminum nitride, silicon nitride, or a combination of these. Examples thereof include a fused mixture, or a non-metallic inorganic material so-called ceramic filler obtained through molding, firing, or the like. Among them, silica, alumina, zirconia, or a eutectic mixture thereof is preferable from the viewpoint of price and effect.

Examples of the organic filler include beads made of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins.
Also, as commercially available products, organosilica sol MIBK-ST, MEK-ST-UP, MEK-ST-L, MEK-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.), SIRMIBK15ET% -H24, SIRMIBK15ET% -H83, ALMIBK30WT%- H06 (CIK Nanotech) or the like can be used.

The clear coating composition may contain 0.5 to 20% by weight (solid content ratio in the coating material) of the polyisocyanate compound having an isocyanate group. By blending a polyisocyanate compound, moldability (stretchability) and scratch resistance can be imparted, which is preferable. The lower limit of the blending amount is more preferably 2% by weight, and the upper limit is more preferably 18% by weight.

(Adhesive layer (D))
The adhesive layer (D) is used for adhering the laminated film to the surface of the base material when decorating the base material with the laminated film.

The adhesive contained in the adhesive layer (D) is not particularly limited as long as it is a conventionally known adhesive, and examples thereof include Byron UR-3200 (manufactured by Toyobo Co., Ltd.) and UR-1361ET (manufactured by Toagosei). Can be done.
The adhesive may be formed by applying and drying the adhesive, or may be formed by laminating an adhesive sheet.

The adhesive layer (D) is selected from the group consisting of urethane resin, acrylic resin, olefin resin, vinyl chloride / vinegar resin, epoxy resin and butyral resin, and at least one adhesive resin having a softening temperature of 20 to 100 ° C. is used. It is more preferable that it is contained.

By forming such an adhesive layer (D), suitable adhesive performance with the base material described in detail below can be obtained, and appropriate deformation occurs in the vacuum forming process so that the adhesive layer (D) is in close contact with the base material. It is desirable to use the various resins described above in terms of obtaining adhesion.

As the resin type described above, it is necessary to select one having good adhesiveness to the molded product as the base material. That is, it is preferable to appropriately select and use a resin having good adhesiveness to the base material from the above-mentioned resins. For example, it is preferable to use an olefin resin when the base material is polypropylene resin, an acrylic resin or vinyl chloride / vinegar resin when the base material is ABS, and a urethane resin having a polycarbonate skeleton when the base material is polycarbonate.

The adhesive layer (D) contains an adhesive resin having a softening temperature of 20 to 100 ° C. That is, even with the above-mentioned resin, if the softening temperature is less than 20 ° C, the tack on the surface becomes large and the film is likely to be blocked, which is not preferable. If the temperature exceeds 100 ° C, it is good at the time of vacuum forming. The object of the present invention cannot be achieved because the deformation cannot be achieved. The lower limit of the softening temperature is more preferably 25 ° C., and even more preferably 30 ° C. The upper limit of the softening temperature is more preferably 90 ° C., and even more preferably 80 ° C.

In the present specification, the softening temperature of the adhesive layer (D) is a value measured by the method described in detail in the following examples.

Further, when the adhesive resin is an amorphous polymer, the weight average molecular weight is in the range of 5,000 to 150,000. When the adhesive resin has a crystalline structure, the softening temperature is the melting temperature, so that the fluidity is ensured above the softening temperature (melting temperature), but in the case of an amorphous polymer, it is above the softening temperature. It is necessary to ensure fluidity. Therefore, the weight average molecular weight Mw needs to be in the range of 5,000 to 150,000.

When the weight average molecular weight Mw is less than 5,000, the film-forming property is inferior when forming a film, and when the weight average molecular weight Mw exceeds 150,000, the permeability to the substrate during molding is inferior and adhesion can be ensured. It will be difficult.
The lower limit is more preferably 6000 and even more preferably 8000. The upper limit is more preferably 130000 and even more preferably 100000.
The weight average molecular weight of the adhesive resin is a value measured by the method described in detail in the following examples.

Further, in order to improve the adhesiveness, the adhesiveness at the molding temperature, that is, the softening temperature is required, which is measured by the inclined ball tack test (JIS Z0237) and the rolling ball tack test (PSTC-6). In order to obtain sufficient adhesiveness, it is preferably 300 mm or less, more preferably 250 mm or less in the rolling ball tack test.

The adhesive layer (D) may be a mixture of two or more adhesive resins satisfying the above-mentioned properties. In order to obtain the properties required in the present invention, it may be desirable to combine two or more kinds.

The thickness of the adhesive layer (D) is preferably 0.004 to 0.1 mm. If it is out of this range, it is not preferable in that the adhesion to the molded base material is lowered and the coating and drying properties are deteriorated. The lower limit is more preferably 0.01 mm, and the upper limit is more preferably 0.06 mm.

The adhesive layer (D) preferably contains a curing agent. When a curing agent is contained, it is preferable to use polyisocyanate as the curing agent. The polyisocyanate that can be used is not particularly limited, and for example, those exemplified as being usable in the formation of the clear coating film layer (B) can be used.
When a curing agent is used, it is preferable to use an adhesive resin having a functional group reactive with the curing agent. Specifically, it preferably has a hydroxyl group. In this case, the hydroxyl value is preferably 1 to 100 mgKOH / g. The lower limit is more preferably 2 mgKOH / g, and even more preferably 5 mgKOH / g. The upper limit is more preferably 80 mgKOH / g, and even more preferably 50 mgKOH / g. If the hydroxyl value is low, a sufficient crosslinked film cannot be obtained, and if the hydroxyl value is high, the film after cross-linking is inferior in stretchability, or the reaction with isocyanate is insufficient and unreacted hydroxyl value remains, resulting in water resistance. There is a possibility that the performance such as is inferior.

The amount of polyisocyanate as a curing agent should be appropriately determined by the OH equivalent of the resin in the adhesive layer (D) and the NCO equivalent of the polyisocyanate, and the ratio is about 1: 0.8 to 1: 1.2. It is preferable to mix with. The total amount of the adhesive layer (D) is preferably 0.5 parts by weight to 10 parts by weight.

The adhesive layer (D) may have the function of the design layer (C). That is, by blending various design components such as pigments with the adhesive layer (D), it is possible to obtain an adhesive layer (Dd) having a function as a design layer. By doing so, the multilayer structure can be reduced by one layer, which is preferable in that the cost can be reduced.

In this case, the adhesive layer (Dd) having a function as a design layer is the above-mentioned "layer formed by a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond". There may be. Further, the "layer formed by the resin composition containing the monomer / oligomer (C1) having an unsaturated double bond" may contain 0.05 to 4.0% by weight of the isocyanate compound (C2). Often, it may be thermosetting in the film manufacturing process.

The adhesive layer (Dd) having a function as a design layer can be a layer formed by applying the colored coating composition and then drying it. Further, the adhesive layer (D) is an adhesive layer (Dd) having a function as a design layer, and at the same time, a design layer (C) is formed separately from the adhesive layer (D) to obtain designability by two or more layers. There may be. In this case, among the design layers composed of the multi-layer coating film, even if it is "a layer formed by a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond", the layer on the side that is not so. It may be.

The adhesive layer (D) may contain components other than the above-mentioned adhesive resin, curing agent, and component for imparting design, as long as the object of the invention is not impaired. Such compounding components include ultraviolet absorbers (UVA), light stabilizers (HALS), curing catalysts, antioxidants, surface conditioners, leveling agents, sagging agents, thickeners, defoamers, and conductive materials. Examples thereof include fillers and solvents.

Further, a solvent may be used for mixing each component contained in the adhesive layer (D) and adjusting the viscosity. Examples of the solvent include ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, aromatic hydrocarbon-based, and other conventionally known organic solvents used in paints. The solvent may be used alone or in combination of two or more. When the above solvent is used, if a volatile substance remains on the laminated film, the volatile substance may volatilize and cause pinholes or swelling when decorating the base material. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

(Release layer (E))
The laminated film for decorating a three-dimensional molded product of the present invention may further have a release layer (E).
Any known release layer (E) can be used as the release layer (E) in the present invention, and can be formed by, for example, a silicone-based release agent or the like.
The peel strength between the release layer (E) and the clear coating film layer (B) is preferably 0.05 to 8.0 N / 25 mm, and more preferably 0.1 to 5.0 N / 25 mm. If it is less than 0.05 N / 25 mm, the base film layer (A) is peeled off during film production and decorative molding, resulting in poor workability. If it exceeds 8.0 N / 25 mm, the post-molded film is separated. When peeling, peeling may be difficult.

(When the layer formed by the clear coating film layer (B) has irregularities)
In the present invention, the layer formed by the clear coating film layer (B) may have irregularities. Such a laminated film for decorating a three-dimensional molded product is a technique published by the present inventors as International Publication No. 2016/136638.
Hereinafter, the technique will also be briefly described below.

In this embodiment, the base film layer (A) has an uneven pattern on at least one side. The uneven pattern is not particularly limited, and can be formed by a known processing method such as embossing, hairline processing, chemical etching, kneading mat processing, coating mat processing, and resin layer separation.

The uneven pattern in the present invention is visually recognized, and by providing the uneven pattern, it has a visual effect in a design sense. Specifically, by passing a film while heating between a metal roll and a rubber roll with various patterns embossed on the surface, leather-like, wood-grain, and silk-like irregularities are formed, and the surface has a hairline. By using a processed film, a hairline metal-like design can be expressed, and by using a film with various matte processing, a metal-like design with an adjusted matte feeling and a low-gloss printed pattern design can be expressed. Can be expressed.

Using the base film layer (A) as described above, the clear coating film layer (B) is applied onto the surface having the uneven pattern to form a film, and then the base film layer (A) is used during use. ) Is peeled off to obtain a clear coating film layer (B) having an uneven pattern on the surface.

(Elongation at break)
The three-dimensional molded product decorative laminated film of the present invention preferably has a breaking elongation of 30 to 500% at 40 to 130 ° C. before curing. That is, by having such a breaking elongation in the above temperature range, it is possible to easily cope with deep drawing. It is possible to keep the value within such a numerical range by preparing the components of each layer forming the film. In the present invention, "having a breaking elongation of 30 to 500% at 40 to 130 ° C." means that a temperature range showing a breaking elongation of 30 to 500% is within 40 to 130 ° C. and molding is performed at that temperature. This means that sufficient stretchability can be obtained.

FIG. 4 shows a state of "having a breaking elongation of 30 to 500% at 40 to 130 ° C.". That is, the one shown by the solid line in FIG. 4 has a breaking elongation of 30 to 500% within the range of 40 to 130 ° C., but the one shown by the broken line is out of the range.

The elongation at break was measured at a tensile speed of 50 mm / min under a temperature condition of 80 ° C. using an Autograph AG-IS manufactured by Shimadzu Corporation in a state of containing the base film (A), and any layer was measured. It is a value obtained by measuring the elongation at the time of breaking.

(Manufacturing method of laminated film)
For each layer other than the base film layer (A) constituting the three-dimensional molded product decorative laminated film of the present invention, a coating composition in which the components constituting each layer is dissolved in a solvent is prepared, and the base film layer is used. It can be formed by applying and drying on (A).

The coating method for forming each of the above layers is not particularly limited, but for example, spray coating by spray, an applicator, a die coater, a bar coater, a roll coater, a comma coater, a roller brush, a brush, a spatula, or the like is used. And apply. After applying the colored paint solution by the above coating method, it can be formed by heating and drying in order to remove the solvent in the colored paint solution. Further, when the design layer (C) is formed, it may be heated to cause curing of the isocyanate compound after heat drying.

Further, as described above, the adhesive layer (D) may be adhered by a laminating method instead of a method of coating and drying. That is, a film formed by the adhesive layer (D) may be prepared and formed by laminating the film.

(how to use)
When the base material is decorated with the three-dimensional molded product decorative laminated film of the present invention, it may be performed in the same manner as a conventionally known method, and is not particularly limited. That is, the base film layer (A) is peeled off from the laminated film as necessary, and the laminated film is pressure-bonded so that the adhesive layer faces the surface of the base material and the laminated film adheres to the surface of the base material. Let me decorate. Then, energy beam irradiation is performed to cure each layer to obtain a coating film. In the present invention, energy ray curing is caused in the design layer (C), but when energy ray irradiation is required in other layers as well, it is not necessary to separately effect these, and once. Multiple layers can be cured at the same time by irradiation with energy rays.

Further, the laminated film of the present invention can also be used as a laminated film for decorating a three-dimensional molded product for vacuum forming. In the above vacuum forming, adhesion is performed under vacuum conditions such that the distance between the base material and the film is 70 kPa or less at the time of molding. It is preferable to perform molding at such a degree of vacuum in that air does not enter between the adhesive layer (D) and the molded body, and high-adhesion decoration can be performed.

Further, it is preferable that the molding for decoration is performed by selecting the temperature at which the elongation of the laminated film is 30 to 500% from the temperature range of 40 to 130 ° C. As a result, since the laminated film can preferably cope with high elongation, good vacuum forming can be performed.

The base material that can be suitably decorated by the laminated film of the present invention is not particularly limited, but is, for example, an automobile exterior such as a bumper, a front under spoiler, a rear under spoiler, a side under skirt, a side garnish, and a door mirror. Examples include parts, instrument panels, center consoles, automobile interior parts such as door switch panels, housings for mobile phones and audio products, refrigerators, fan heaters, home appliances such as lighting fixtures, and vanities.

Hereinafter, the present invention will be described with reference to Examples. In the examples,% in the blending ratio means% by weight unless otherwise specified. The present invention is not limited to the examples shown below.

(Synthesis example Polyurethane acrylate synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow pipe, and a material inlet was prepared.
While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight by quantification of terminal functional groups = 1,000) 200.0 g, 1, 80.0 g of 4-butanediol and 120.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mgKOH / g) were charged. Then, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the inside of the system became uniform, 314.2 g of 4,4'-methylenebis-cyclohexyldiisocyanate was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyltin laurylene as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption of 2,270 cm- ¹ by the free isocyanate group measured by infrared absorption spectrum analysis disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin solution containing polyurethane. The viscosity of the obtained resin solution was 200 dPa · s / 20 ° C., the solid content was 45%, and the double bond equivalent was 600 g / eq. The weight average molecular weight of polyurethane measured by GPC was 44,000. The polyurethane acrylate obtained in this synthetic example will be hereinafter referred to as "polyurethane acrylate (B1)".

[Manufacturing example of laminated film]
<Adjustment of base film>
When there was a release layer, a fluorine-based release agent was applied to one surface of the base film forming the coating film layer to form the release layer.

<Adjustment of clear paint solution>
Put polyurethane acrylate (B1) and monomer (B2) in a container equipped with a stirrer, add MEK in an amount that makes the final paint NV = 40% while stirring, and further add a polymerization initiator (B3). The mixture was stirred for 1 minute to obtain a clear paint solution.

<Adjustment of colored paint solution>
Put the monomer (C1), isocyanate (C2), brightener (C3), urethane resin (C4) and photoactivator in a container equipped with a stirrer, and stir to make the final paint NV = 35%. MIBK was added and stirred for 30 minutes to obtain a colored paint solution.

<Adhesive paint solution adjustment>
Each resin was put into a container equipped with a stirrer, MEK in an amount such that the final paint became NV = 30% was put in while stirring, and the mixture was stirred for 30 minutes to obtain an adhesive paint solution.

<Preparation of laminated film 1>
The above clear paint solution is applied to the base film (A) using an applicator so that a clear coating layer (B) having a dry film thickness (hereinafter, dry film thickness) of 20 μm can be obtained. , 80 ° C. was dried for 15 minutes to form a clear coating film layer (B). In the following, a film in which the clear coating film layer (B) is formed on the base film layer (A) is referred to as a (A + B) layer film. Next, the colored paint solution is applied on the clear coating layer (B) of the (A + B) layer film using an applicator so that a design layer (C) having a dry film thickness of 20 μm can be obtained, and then , 80 ° C. for 15 minutes to form a design layer (C).
Subsequently, an adhesive paint solution is applied on the design layer (C) using an applicator so that an adhesive layer (D) having a dry film thickness of 20 μm can be obtained, dried at 80 ° C. for 15 minutes, and bonded. The agent layer (D) was formed.

<Preparation of laminated film 2>
The above clear paint solution is applied to the base film (A) using an applicator so that a clear coating layer (B) having a dry film thickness (hereinafter, dry film thickness) of 20 μm can be obtained. , 80 ° C. for 15 minutes to form a clear coating layer (B).
In the following, a film in which the clear coating film layer (B) is formed on the base film layer (A) is referred to as a (A + B) layer film.
Next, the colored paint solution is applied using an applicator on the side of the (A + B) layer film opposite to the clear coating layer (B) so that the design layer (C) having a dry film thickness of 20 μm can be obtained. Then, it was dried at 80 ° C. for 15 minutes to form a design layer (C).
Subsequently, an adhesive paint solution is applied on the design layer (C) using an applicator so that an adhesive layer (D) having a dry film thickness of 20 μm can be obtained, dried at 80 ° C. for 15 minutes, and bonded. The agent layer (D) was formed.

[Production example of a molded product decorated with a laminated film]
The base material (molded product) was placed on a vertical elevating table equipped in a double-sided vacuum forming apparatus (trade name: NGF-0709, manufactured by Fuse Vacuum Co., Ltd.) consisting of an upper and lower box. Then, the laminated film obtained above was set in the sheet clamp frame on the upper part of the molding base material (molded product) of the double-sided vacuum forming apparatus. Subsequently, the pressure inside the upper and lower boxes is reduced to 1.0 kPa, and the laminated film is heated to 90 ° C. using a near-infrared heater to raise the molded base material to raise the molded base material. And the laminated film were pressure-bonded, and then 200 kPa of compressed air was introduced only into the upper box and held for 35 seconds.
The upper and lower boxes were opened to atmospheric pressure to obtain a decorative molded body decorated with a laminated film.
Further, from the clear coating layer (B) side of the decorative molded product, ultraviolet rays having a light amount of 2000 mJ / cm ² are irradiated using a high-pressure mercury lamp of 120 W / cm to clear the clear coating layer (B). Was cured to obtain a UV (ultraviolet) cured molded product.

The raw materials used in the table are as follows.
NovaClear SG007 (Mitsubishi Chemical): A-PET Sheet Teflex FT-3 (Teijin Film Solution): Easy-to-form biaxially stretched polyester film UV 1700B (Nippon Synthetic Chem Industry): Urethane acrylate oligomer Lucillin TPO (BASF): 2, 4,6-trimethylbenzoyludiphenyl-phosphine oxide M-402 (Toa Synthetic): DPHA
Alpaste 65-388 Aluminum (Toyo Aluminum): Aluminum Paste PIR 03N (Sanyo Kasei): Photoactivator E-1321 (Toa Synthetic): PVC, Vinegar Bipolymer Resin Xp012N35 (Mitsui Chemicals): Modified Olefin Resin MAU-2600 (Dainichiseika Kogyo): PC-based urethane resin D-178NL curing agent (Mitsui Chemicals): Isocyanate
Sumijour N-3400 (Sumitomo Bayer Urethane): Isocyanate The OH group-containing polycarbonate polyurethane used to form the design layer is a resin that does not have unsaturated double bonds.

The obtained laminated film and molded product were evaluated according to the following criteria. The results are shown in the table.

(Elongation)
The measurement was carried out at a tensile speed of 50 mm / min under a temperature condition of 80 ° C. using an Autograph AG-IS manufactured by Shimadzu Corporation including a base material.
Elongation was determined when either layer broke.

(Moldability)
It was confirmed by TOM molding using a double-sided vacuum forming machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd.
⊚: Can be molded by following the high stretched part on the base material ○: Can be molded by following the medium stretched part on the base material △: Can be molded by following the low stretched part on the base material ×: Cannot be molded

(Adhesion)
Go board cellophane tape (registered trademark) peeling test 2mm 100 Muscat ○: No peeling △: ~ 50% peeling ×: ~ 100% peeling

(water resistant)
After immersion at 40 ° C. for 240 hours, the appearance (wrinkles, cracks) was confirmed.
Go board cellophane tape peeling test 2mm 100 Muscat ○: No peeling △: ~ 50% peeling ×: ~ 100% peeling

(Impact resistance after molding)
Using a DuPont impact resistance tester, a weight weighing 500 g was dropped from a height of 20 cm, and cracks in the coating film were confirmed.
○: No cracks △: Slight cracks in the coating film ×: Significant cracks in the coating film

(Non-adhesive)
Five pieces of gauze were layered on the surface of the coating film, a weight of 500 g was placed on the surface, and the mixture was left at 70 ° C. for 2 hours.
◎: No change in the coating film ○: Slight change in the appearance of the coating film (texture marks)
Δ: The appearance of the coating film clearly changed (texture marks)
X: The appearance of the coating film changes significantly (texture marks)

The softening point was confirmed by TMA (needle insertion mode).
<Analyzer>
SII Nanotechnology Co., Ltd.
"TMA / SS7100C"
<Analysis conditions>
Load 10mN
Temperature rise 5 ° C / min
As for the measurement temperature range, the melting point and glass transition temperature were confirmed by DSC, and the measurement was started from around 0 ° C. for a clearly soft sample, and the measurement was started from room temperature for other samples.

The molecular weight was confirmed by GPC.
<Analyzer>
Tosoh Corporation
"High-speed GPC HLC-8220 GPC"
<Analysis conditions>
Eluent THF (containing antioxidant)
Flow rate 0.35 ml / min
Injection volume 10 μl
Temperature control part 40 ℃
Detector RI
Standard polystyrene: The calculated molecular weight is converted to polystyrene.

From the table, it was shown that the laminated film of the present invention had excellent performance in all the evaluation items.

The laminated film for decorating a three-dimensional molded product of the present invention can be suitably used when performing three-dimensional decoration having a three-dimensional shape surface on various molded bodies.

Claims (8)

A three-dimensional molded product decorative laminated film having a base film layer (A), a clear coating film layer (B), a design layer (C), and an adhesive layer (D).
The design layer (C) is a three-dimensional molded product decorative laminated film, which is a layer formed of a resin composition containing a monomer / oligomer (C1) having an unsaturated double bond. The laminated film for decorating a three-dimensional molded product according to claim 1, wherein the design layer (C) further contains an isocyanate compound (C2) in an amount of 0.05 to 4.0% by weight. The laminated film for decorating a three-dimensional molded product according to claim 2, wherein the isocyanate compound (C2) is a blocked isocyanate. The laminated film for decorating a three-dimensional molded product according to claim 1, 2, or 3, wherein the design layer (C) is thermosetting in the film manufacturing process. The laminated film for decorating a three-dimensional molded product according to claim 1, 2, 3 or 4, wherein the design layer (C) further contains a flat pigment. The laminated film for decoration of a three-dimensional molded product according to claim 1, 2, 3 or 4, wherein the design layer (C) is composed of a plurality of layers. The clear coating layer (B) was formed by an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). The laminated film for decorating a three-dimensional molded product according to claim 1, 2, 3, 4, 5 or 6. The laminated film for decorating a three-dimensional molded product according to claim 1, 2, 3, 4, 5 or 6, wherein the laminated film has an elongation of 30 to 500% in a temperature range of 40 to 130 ° C.