JP6352595B2 - Method for producing decorative film and energy ray curable inkjet ink - Google Patents

Description

  The present invention relates to a method for producing a decorative film capable of easily obtaining a decorative film exhibiting excellent stretchability at room temperature.

In recent years, from the viewpoint of environmental problems such as VOC, a solvent-free energy ray curable ink jet printing method has attracted attention (for example, Patent Document 1).
Using such a printing method, for example, a base material and a base material are formed on a three-dimensional three-dimensional molded product such as a housing such as a home appliance, a mobile phone, a digital camera, or a tablet PC, and an automobile interior part. The use of a decorative film having a decorative layer has been studied. Specifically, an insert that forms a three-dimensional three-dimensional molded product decorated with a decorative film on the surface by injection molding a molten resin or the like into a three-dimensional three-dimensional molded film of a decorative film. Decoration to a three-dimensional three-dimensional molded article has been studied using a construction method or a TOM method in which a decorative film is stretched and adhered to a three-dimensional three-dimensional molded article.
However, a decorative layer formed from a conventional energy beam curable inkjet composition (hereinafter sometimes referred to simply as curable ink) does not have sufficient stretchability and follows the mold during molding. As a result, there is a problem that a satisfactory image quality cannot be obtained due to the phenomenon that the decorative layer does not fully extend and cracks occur.
With respect to such a problem, Patent Document 2 discloses a curable ink containing a reactive oligomer. According to such a composition, the stretchability of the decorative layer can be improved.

Japanese Patent No. 3619778 JP 2004-131725 A

However, even a decorative layer formed using such a composition with improved stretchability has a problem of low stretchability at room temperature.
This invention is made | formed in view of the said problem, and it aims at providing the manufacturing method of the film for decorating which can obtain easily the film for decorating which shows the drawability excellent at normal temperature. To do.

  As a result of repeated researches to solve the above problems, the inventors of the present invention have achieved the stretchability of the decorative layer by the light source of the exposure light used for curing the coating film formed using the energy ray curable inkjet composition. It has been found that the stretchability of the decorative layer tends to decrease when exposure light having an emission spectrum in the low wavelength region is used, and the present invention has been completed.

  In order to solve the above-mentioned problems, the present invention is an application for forming a coating film by applying an energy ray-curable inkjet ink composition having a polymerization initiator, a polymerizable compound and an ultraviolet absorber on a substrate by an inkjet method. The wavelength region of the wavelength less than 380 nm (hereinafter sometimes referred to simply as a short wavelength region) and the wavelength region within the wavelength range of 380 nm to 420 nm (hereinafter simply referred to as a long wavelength region) with respect to the process and the coating film. And irradiating with exposure light having an emission spectrum to form a decorative layer by irradiating with exposure light having an emission spectrum, and the ultraviolet absorber has a light transmittance of a wavelength of 380 nm. Provided is a method for producing a decorative film characterized by containing only an ultraviolet absorber (hereinafter sometimes referred to simply as a short wavelength ultraviolet absorber) of 30% or less. .

  According to this invention, the film for decorating which shows the extending | stretching outstanding at normal temperature can be easily obtained by including only a short wavelength ultraviolet absorber as said ultraviolet absorber.

  The present invention has a polymerization initiator, a polymerizable compound, and an ultraviolet absorber, and includes only an ultraviolet absorber having a light transmittance of 30% or less as a wavelength of 380 nm as the ultraviolet absorber. A line curable inkjet composition is provided.

  According to the present invention, by including only the short wavelength ultraviolet absorber as the ultraviolet absorber, by using such a curable ink, excellent stretching at room temperature regardless of the type of exposure light used for curing. It is possible to easily obtain a decorative film exhibiting properties.

  In the present invention, the ultraviolet absorber having a light transmittance of 380 nm or less is preferably 30% or less, and the light transmittance of a wavelength of 420 nm is preferably 10% or more. This is because the inside of the coating film can be sufficiently cured.

  In the present invention, it is preferably for curing with exposure light having an emission spectrum in a wavelength region of a wavelength of less than 380 nm and a wavelength region within a wavelength range of 380 nm to 420 nm. This is because the effects of the present invention can be more effectively exhibited.

  The present invention produces an effect that a method for producing a decorative film capable of easily obtaining a decorative film exhibiting excellent stretchability at room temperature can be provided.

It is process drawing which shows an example of the manufacturing method of the film for decorating of this invention.

The present invention relates to a method for producing a decorative film and an energy ray curable inkjet composition used therefor.
Hereinafter, the manufacturing method of the film for decorating of this invention and an energy-beam curable inkjet composition are demonstrated.

A. First, the curable ink of the present invention will be described.
The curable ink of the present invention includes a polymerization initiator, a polymerizable compound, and an ultraviolet absorber, and includes only an ultraviolet absorber having a light transmittance of 380 nm or less as the ultraviolet absorber. It is a feature.

According to the present invention, by including only the short-wavelength ultraviolet absorber as the ultraviolet absorber, a decorative film that exhibits excellent stretchability at room temperature can be easily obtained regardless of the type of exposure light source used for curing. Can get to.
Here, the reason why the above-described effect is exhibited by including only the short wavelength ultraviolet absorber as the ultraviolet absorber is presumed as follows.

That is, when the coating film of the curable ink formed on the substrate is irradiated with exposure light having an emission spectrum in the short wavelength region, the exposure light in the short wavelength region is mainly on the surface of the coating film. It is absorbed and curing proceeds selectively on the surface of the coating film. For this reason, the decoration layer formed when the coating film is cured has a hard layer formed on the surface thereof. As a result, when a decorative film including such a decorative layer is stretched, a hard layer on its surface is cracked, and sufficient stretching becomes difficult.
On the other hand, by including only the short wavelength ultraviolet absorber as the ultraviolet absorber, it becomes possible to selectively absorb the exposure light in the low wavelength region as described above, and a hard layer is formed on the surface. Can be suppressed.

Therefore, even when a light source having an emission spectrum in a short wavelength region such as a metal halide lamp is used as exposure light irradiated on the coating film to form a decoration layer, a hard layer is formed on the surface. This can be suppressed, and the occurrence of cracks and the like during stretching can be suppressed. For this reason, it is possible to obtain a decorative film having excellent stretchability even at room temperature.
In addition, in any case of a light source having an emission spectrum in a short wavelength region such as a metal halide lamp and a light source having an emission spectrum mainly in a long wavelength region such as an ultraviolet LED, formation of a hard layer on the surface was suppressed. A decorative layer can be formed. That is, even when the type of exposure light source is different, a decorative layer having the same stretchability can be formed. Therefore, even when a facility having a light source having an emission spectrum in a short wavelength region such as a metal halide lamp and a facility having a light source mainly having an emission spectrum in a long wavelength region such as an ultraviolet LED are mixed, A decorative layer having the same stretchability can be stably formed without changing the ink components for each facility.
From such a thing, the film for decorating which has the extending | stretching outstanding at normal temperature can be easily obtained by including only a short wavelength ultraviolet absorber as said ultraviolet absorber.

The curable ink of the present invention has a polymerization initiator, a polymerizable compound, and an ultraviolet absorber.
Hereinafter, each component of the curable ink of the present invention will be described in detail.

1. Ultraviolet absorber The ultraviolet absorber in the present invention contains only an ultraviolet absorber having a light transmittance of 380 nm of 30% or less.
In addition, the ultraviolet absorber in the present invention is not particularly limited as long as it is generally used as an ultraviolet absorber. For example, a colorant, a polymerizable compound, a polymerization initiator, and other various types. It is preferable not to include those having other uses other than the ultraviolet absorption use such as additives added for the above use.

Note that including only the short wavelength ultraviolet absorber means that the ultraviolet light absorber has a transmittance of light of wavelength 380 nm larger than 30% and absorbs exposure light in the long wavelength region of wavelength 380 nm to 420 nm (hereinafter, referred to as “ultraviolet absorber”). It may simply be a long-wavelength ultraviolet absorber).
Here, substantially not containing a long-wavelength ultraviolet absorber means that the long-wavelength ultraviolet absorber is not contained in an amount that inhibits curing of the coating film by exposure light in the long-wavelength region, Specifically, it means that the content of the short wavelength ultraviolet absorber in the ultraviolet absorber is 95% by mass or more, among which 99% by mass or more is preferable, in particular, 100% by mass. % Is preferred. It is because the effect of the present invention can be more effectively exhibited when the content is within the above range.

The transmittance of light having a wavelength of 380 nm of the short wavelength ultraviolet absorber is not particularly limited as long as it is 30% or less, but is preferably 20% or less, particularly 10% or less. Preferably there is. When the transmittance is within the above-described range, exposure light in a short wavelength region can be effectively absorbed, and the influence of the type of light source used for curing the coating film can be reduced. Because.
The light transmittance means the ratio (%) of the light intensity at the time of emission with respect to the light intensity at the time of incidence of light of each wavelength that passes through the short wavelength ultraviolet absorber, and is a short wavelength with a concentration of 1%. An ultraviolet absorbent solution (solvent toluene) is prepared, and is measured by a double beam photometry method using a 10 mm wide glass cell and a xenon lamp as a light source. More specifically, it can be obtained by a method using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation) and using toluene as a reference.

  The transmittance of light with a wavelength of 320 nm of the short wavelength ultraviolet absorber is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less. When the transmittance is within the above-described range, exposure light in a short wavelength region can be effectively absorbed, and the influence of the type of light source used for curing the coating film can be reduced. Because.

  The transmittance of light having a wavelength of 420 nm of the short wavelength ultraviolet absorber is preferably 10% or more, more preferably 40% or more, and particularly preferably 60% or more. It is because the inside of a coating film can fully be hardened because the said transmittance | permeability is in the above-mentioned range.

  Specific examples of the short wavelength ultraviolet absorber include Tinuvin 120 (2,5-di-tert-butyl-4-hydroxybenzoate 2,4-di-tert-butylphenyl), Tinuvin 234 (2 -[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole), tinuvin 326 (2- (5-chloro-2-benzotriazolyl) -6-tert- Butyl-p-cresol), tinuvin 329 (2- (2-hydroxy-5-tert-octylphenyl) benzotriazole), tinuvin 384-2 (benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)- 5- (1,1-dimethylethyl) -4-hydroxy and a mixture of C7-9 side chain and linear alkyl ester), Tinuvin 400 (2- (4,6 Reaction product of bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane [(C10-C16 mainly C12-C13 alkyloxy) methyl] oxirane) Tinuvin 479 (2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine), Tinuvin 928 (2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol), among others. Tinuvin 384-2, Tinuvin 400, Tinuvin 479 and the like are preferable, and Tinuvin 400 is particularly preferable. This is because exposure light in the short wavelength region can be selectively absorbed by the short wavelength ultraviolet absorber, and the exposure light in the long wavelength region is not prevented from being absorbed by the coating film. Moreover, it is because the influence by the kind of light source used for hardening of a decoration layer can be made less.

  The content of the ultraviolet absorber is not particularly limited as long as it can form a decorative layer having excellent stretchability. It is preferably in the range of 1% by mass to 3% by mass, and more preferably in the range of 0.1% by mass to 2% by mass, and particularly in the range of 0.5% by mass to 2% by mass. It is preferable to be within. This is because, if the content is within the above-described range, a decorative layer that is more excellent in stretchability can be formed, and if the content is large, curability decreases.

2. Polymerization initiator The polymerization initiator used in the present invention is capable of polymerizing the polymerizable compound when exposed to exposure light.

The polymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound when exposed to exposure light, and those generally used for curable inks are used. be able to. For example, acylphosphine oxide initiators, α-aminoalkylphenone initiators, thioxanthone initiators, aminocarbonyl initiators, ketone initiators, and the like can be used.
In the present invention, among them, acylphosphine oxide initiators, α-aminoalkylphenone initiators, and thioxanthone initiators can be preferably used. In particular, acylphosphine oxide initiators and thioxanthone initiators are preferably used. be able to.

  Examples of the acylphosphine oxide initiator include 4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6- Tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide, 4-isopropylbenzoyldiphenylphosphine oxide, 1-methylcyclohexanoylbenzoyldiphenylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, , 4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoylphenylphosphinic acid isopropyl ester, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. It is done. These may be used alone or in combination. Moreover, as a commercial item, DAROCURE TPO etc. by Ciba company is mentioned.

  Examples of the α-aminoalkylphenone initiator include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone-1,2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-2-one and the like. These may be used alone or in combination. Examples of commercially available products include IRGACURE 369 and IRGACURE 907 manufactured by Ciba.

  Examples of the thioxanthone initiator include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Examples include 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. These may be used alone or in combination. Moreover, as a commercial item, KAYACURE DETX-S made from Nippon Kayaku Co., Ltd., Chivacure ITX made from a double bond chemical company, etc. are mentioned.

Examples of the aminocarbonyl-based initiator include 4,4′-bis (diethylamino) benzophenone, ethyl-4-dimethylaminobenzoate, and isoamyl p- (dimethylamino) benzoate.
Examples of the ketone initiator include 2,4-diethylthioxanthen-9-one and / or 2-isopropylthioxanthone.

The content of the polymerization initiator is not particularly limited as long as it can form a decorative layer having a desired stretchability. For example, the content of the polymerization initiator is 5% by mass to 20% by mass in the curable ink. It is preferably within the range, and in particular, it is preferably within the range of 5% by mass to 15% by mass, and particularly preferably within the range of 7% by mass to 12% by mass. This is because when the content is within the above-described range, the sensitivity is excellent, other components can be sufficiently contained, and the curability can be excellent.
In the case where both an acylphosphine oxide initiator and a thioxanthone initiator are used in combination as the polymerization initiator, the content of the acylphosphine oxide initiator is in the range of 5% by mass to 15% by mass. It is preferable that it is within the range of 6% by mass to 12% by volume, and preferably within the range of 7% by mass to 10% by mass. Further, the content of the thioxanthone-based initiator is preferably in the range of 0.1% by mass to 5% by mass, preferably in the range of 0.5% by mass to 4% by mass, and 1% by mass. It is preferable that it is in the range of% to 3% by mass. This is because by making the content of the acylphosphine oxide-based initiator higher than that of the thioxanthone-based initiator, the curable ink can be made excellent in color developability.

3. Polymerizable compound The polymerizable compound in the present invention has one or more ethylenically unsaturated double bonds.
As such a polymerizable compound, for example, a monofunctional monomer having one ethylenically unsaturated double bond, a polyfunctional monomer having 2 or more ethylenically unsaturated double bonds, a polyfunctional oligomer, or the like is used. Can do. In the present invention, these can be used in combination.

Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, stearyl carbitol (meth) acrylate, glycidyl ( (Meth) acrylate, allyl (meth) acrylate, isooctyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate Etc.
Also, vinyl monomers such as N-vinyl pyrrolidone, N-vinyl cabrolactone, vinyl imidazole, vinyl pyridine, styrene, phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) Acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, baracyl phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic acid ester monomers such as acrylate, benzyl (meth) acrylate, orthophenylphenoxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylate, acryloylmorpholine Can be mentioned.

  Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. , Polytetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 3-methyl -1,5-pentanediol di (meth) acrylate, neobendyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, hydroxypivalic acid neobendyl glycol di (meta) Acrylate, bisphenol A polyethoxydiol di (meth) acrylate, bisphenol A polypropoxydiol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol brobantri (Meth) acrylate, pentaerythritol tri (meth) acrylate, glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipe Can be mentioned data hexa (meth) acrylate.

  Moreover, as said polyfunctional oligomer, the bifunctional oligomer which has two ethylenically unsaturated double bonds, such as a urethane acrylate oligomer, a polyester acrylate oligomer, an epoxy acrylate oligomer, etc. which are described in Unexamined-Japanese-Patent No. 2010-70754 etc., for example. Can be used.

The monofunctional monomer content is not particularly limited as long as the decorative layer can have desired physical properties, but is in the range of 50% by mass to 95% by mass in the curable ink. In particular, it is preferably in the range of 60% by mass to 95% by mass, and more preferably in the range of 70% by mass to 90% by mass.
The total content of the polyfunctional monomer and oligomer is not particularly limited as long as the decorative layer can have desired physical properties, but is 0.1 mass in the curable ink. % To 5% by mass, preferably 1% to 5% by mass, and particularly preferably 1% to 4% by mass. It is because it can be made excellent in sclerosis | hardenability and toughness, maintaining a drawability because the said content is in the above-mentioned range.

4). Other Components The curable ink of the present invention contains a polymerization initiator, a polymerizable compound, and an ultraviolet absorber, but usually contains a colorant. If necessary, leveling agents, antifoaming agents, antioxidants, pH adjusting agents, charge imparting agents, bactericides, antiseptics, deodorants, charge adjusting agents, wetting agents, anti-skinning agents, fragrances, plastics You may mix | blend well-known general additives, such as an agent, as an arbitrary component.

  As the colorant used in the present invention, those generally used for curable inks can be used, and for example, pigments and the like can be used.

  Organic pigments and inorganic pigments can be used as the pigment.

  Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine organic pigments, quinacridone organic pigments, perylene organic pigments, dioxazine organic pigments, nickel azo pigments, isoindolinones. Organic pigments, pyranthrone organic pigments, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, etc. Examples of solid solution pigments and other pigments include carbon black.

  When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214; I. Pigment Red 5, 7, 9, 12, 48, 49, 52, 53, 57, 97, 112, 122, 123, 149, 168, 177, 180, 184, 192, 202, 206, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254; I. Pigment orange 16, 36, 43, 51, 55, 59, 61, 64, 71; C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50; C.I. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64; C.I. I. Pigment green 7, 36, 58; I. Pigment brown 23, 25, 26, and the like.

  Specific examples of the inorganic pigment include barium sulfate, iron oxide, zinc oxide, barium carbonate, barium sulfate, silica, clay, talc, titanium oxide, calcium carbonate, synthetic mica, alumina, zinc white, lead sulfate, yellow lead, Examples include zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and inorganic solid solution pigments.

The average dispersed particle diameter of the pigment is not particularly limited as long as the desired color can be developed. It varies depending on the type of pigment used, but the pigment has good dispersion stability and sufficient coloring power. From the viewpoint of obtaining, the median diameter (D50) in the curable ink is preferably in the range of 5 nm to 200 nm, and more preferably in the range of 30 nm to 150 nm. If the median diameter is less than or equal to the above upper limit value, nozzle clogging of the ink-jet head is unlikely to occur, a highly reproducible and homogeneous image can be obtained, and the resulting printed matter can be of high quality. is there. This is because when the median diameter is not more than the above lower limit, the light resistance may be lowered.
The average dispersed particle diameter of the pigment can be obtained by preparing a measurement sample obtained by diluting a curable ink with ethyl diglycol acetate about 50 times and measuring it by a dynamic scattering light method. Specifically, it can be measured using a laser diffraction / scattering particle size analyzer Microtrac particle size analyzer UPA150 (manufactured by Nikkiso Co., Ltd.) at a measurement temperature of 25 ° C.

  The content of the colorant is not particularly limited as long as a desired image can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of the colorant, it is preferably in the range of 0.5% by mass to 25% by mass in the curable ink, and more preferably in the range of 0.5% by mass to 15% by mass. It is preferably within the range, and particularly preferably within the range of 1% by mass to 10% by mass. This is because when the content is in the above-described range, the balance between the dispersion stability of the colorant and the coloring power can be improved.

When a pigment is used as the colorant, the pigment is usually used together with a pigment derivative or a pigment dispersant. This is because the pigment can be excellent in dispersibility.
Examples of such pigment derivatives include pigment derivatives having a dialkylaminoalkylsulfonic acid amide group and pigment derivatives having a dialkylaminoalkyl group.
Examples of the pigment dispersant include ionic or nonionic surfactants and anionic, cationic or nonionic polymer compounds. Among these, a polymer compound containing a cationic group or an anionic group is preferable from the viewpoint of dispersion stability. Examples of commercially available pigment dispersants include SOLSPERS manufactured by Lubrizol, DISPERBYK manufactured by BYK Chemie, EFKA manufactured by Fuka Additives, and the like. The contents of the pigment derivative and the pigment dispersant are each preferably in the range of 0.05% by mass to 5% by mass in the curable ink.

As the leveling agent, those generally used for curable inks for the purpose of adjusting the surface tension can be used.
Examples of such leveling agents include silicone compounds having a polydimethylsiloxane structure. This is because it is easy to finely adjust the liquid properties such as the surface tension of the curable ink by using the silicone compound. Among the silicone compounds, a silicone compound having an ethylenically unsaturated double bond in the molecule is preferable. This is because it is possible to form a decorative layer with excellent adhesion and to easily adjust the stretchability of the decorative layer.

Examples of such a silicone compound having an ethylenically unsaturated double bond include BYK-300, BYK-302, BYK-306, BYK-307 manufactured by BYK Chemie, which are described in JP-A-2010-70754. BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK -375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570; manufactured by Degussa TEGO-Rad2100, TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2600, TEGO-Rad2600, TE O-Rad2700: Kyoeisha Chemical Co., Ltd. granol 100, granol 115, granol 400, granol 410, granol 435, granol 440, granol 450, B-1484, polyflow ATF-2, KL-600, UCR-L72, UCR-L93 Etc.
Further, the content of the leveling agent is not particularly limited as long as it can achieve a desired viscosity. For example, 0.02% by mass to 2.5% by mass in the curable ink. Can be within the range.

5. Curable ink The viscosity of the curable ink of the present invention is not particularly limited as long as it can be ejected using an inkjet device, but is preferably in the range of 9 mPa · s to 15 mPa · s, In particular, it is preferably in the range of 10 mPa · s to 14 mPa · s, and particularly preferably in the range of 10.5 mPa · s to 13 mPa · s. This is because, when the viscosity is within the above-described range, the curable ink in the present invention can be excellent in dischargeability.
In addition, the said viscosity shows a viscosity in 40 degreeC. The viscosity can be obtained by measuring with a falling ball viscometer (AMVn manufactured by Anton Paar). The temperature at this time can be set to 40 ° C., and the density can be set to 1.05 g / cm ² .

The stretchability of the curable ink of the present invention is not particularly limited as long as desired decoration can be performed, but it is preferably 150% or more, and more preferably 200% or more. In particular, it is preferably 250% or more. This is because by having the above-described stretchability, it is possible to decorate the three-dimensional solid molded product with high accuracy.
In addition, since it becomes easy to decorate a three-dimensional solid molded article as the extensibility is excellent, there is no particular upper limit, but it is usually 350% or less from the viewpoint of the strength of the decorative layer.
The stretchability of the curable ink refers to the stretchability of the decorative layer obtained by curing the coating film formed using the curable ink at room temperature.
Such a stretchability measuring method is not particularly limited as long as the stretchability can be measured. Specifically, the substrate has a size of 50 mm × 100 mm and a thickness of about 1 mm. A vinyl chloride sheet MACTAC JT5829R (manufactured by Martini Co., Ltd.) was used, and a curable ink was applied onto this substrate with a bar coater # 6, and then a UV exposure apparatus (B125D-C10-SM-J, manufactured by GS YUASA). ) To prepare a test piece composed of a base material obtained by exposure to 300 mJ / cm ² (λ = 365 nm) and curing the coating film, and a decorative layer having a thickness of 7 mm, and this was tested in a 25 ° C. environment. Attach both ends in the longitudinal direction of the test piece to a tensile tester AGS-1kNX (manufactured by Shimadzu Corporation), pull at a pulling speed of 10 mm / min, and measure the maximum elongation at which the decorative layer does not crack It is possible to use a method of calculating the elongation ratio (length before length / stretching after stretching) × 100 (%).
Further, such stretchability can be adjusted by the type and content of each component such as the polymerizable compound.

The method for preparing the curable ink of the present invention is not particularly limited as long as the above components can be uniformly dispersed or dissolved, and a method generally used for curable ink is used. be able to.
Specifically, first, the colorant, a part of the polymerizable compound, and if necessary, a dispersant are mixed, the mixture is dispersed by a disperser, then the remaining components are added to the mixture, and a stirrer is added. The method of mixing until it becomes uniform can be mentioned.
Examples of the disperser include a disperser; a container drive medium mill such as a ball mill, a centrifugal mill, and a planetary ball mill; a high-speed rotating mill such as a sand mill; and a medium agitation mill such as a stirring tank mill. Examples of the stirrer include a three-one motor, a magnetic stirrer, a dispaper, and a homogenizer. Also, a mixer such as a line mixer may be used.

As a use of the curable ink of the present invention, it can be used for the formation of a decoration layer using an inkjet method, and in particular, has a decoration layer formed on a base material and a base material, and the surface of a member to be decorated It is preferably used for a decorative film that is laminated on the surface, in particular for three-dimensional molding, that is, for decorative purposes that is laminated along the surface of a member to be decorated that has a three-dimensional surface. It is preferably used for a film. In the present invention, in particular, it is preferably used for a three-dimensional molding at normal temperature, that is, used for a decorative film for decorating a member to be decorated by stretching at normal temperature. This is because the effect of the present invention that a decorative film excellent in stretchability at room temperature can be obtained can be more effectively exhibited.
Moreover, in this invention, it is preferable for the hardening by the exposure light which has a light emission spectrum in the wavelength range less than 380 nm and the wavelength range within the range of wavelengths 380 nm-420 nm. This is because the effects of the present invention can be more effectively exhibited.
In addition, the decoration in this invention is a thing which raises the decoration effect of the surface of a to-be-decorated member by laminating the film for decorating, and, specifically, a pattern, a mark on the surface of the to-be-decorated member In addition to those that form letters, those that give gloss and matte are also included.
The decorative layer is formed on the base material for such decoration, and is a layer that imparts gloss and matte in addition to those that form patterns, marks, and characters.

B. Next, the manufacturing method of the film for decorating of this invention is demonstrated.
The method for producing a decorative film according to the present invention is an application in which an energy ray-curable inkjet ink composition having a polymerization initiator, a polymerizable compound and an ultraviolet absorber is applied onto a substrate by an inkjet method to form a coating film. The coating film is cured by irradiating the coating film with exposure light having an emission spectrum in a wavelength region having a wavelength of less than 380 nm and a wavelength region within a wavelength range of 380 nm to 420 nm. And an irradiation step, wherein the ultraviolet absorber includes only an ultraviolet absorber having a light transmittance of 30% or less at a wavelength of 380 nm.

A method for producing such a decorative film of the present invention will be described with reference to the drawings. Drawing 1 is a flowchart showing an example of the manufacturing method of the film for decoration of the present invention. As shown in FIG. 1, the method for producing a decorative film according to the present invention uses an energy ray-curable inkjet ink composition 2 ′ having a polymerization initiator, a polymerizable compound, and an ultraviolet absorber by an inkjet method. By coating on (FIG. 1 (a)), a coating film 2 is formed (FIG. 1 (b)), and then for the coating film 2, a wavelength region having a wavelength of less than 380 nm and a wavelength range of 380 nm to 420 nm The coating film 2 was cured by irradiating exposure light having an emission spectrum in the wavelength region (FIG. 1 (c)) to form a decorative layer 3, and formed on the substrate 1 and the substrate 1. The decorative film 10 having the decorative layer 3 is obtained (FIG. 1 (d)).
In addition, the ultraviolet absorber includes only an ultraviolet absorber having a light transmittance of 380 nm of 30% or less.
1A to 1B are the application steps, and FIGS. 1C to 1D are the irradiation steps.

  According to this invention, the film for decorating which shows the extending | stretching outstanding at normal temperature can be easily obtained by including only the said short wavelength ultraviolet absorber as said ultraviolet absorber.

The manufacturing method of the film for decorating of this invention has the said application | coating process and an irradiation process.
Hereinafter, each process of the manufacturing method of the film for decorating of this invention is demonstrated.

1. Application Step The application step in the present invention is a step in which a curable ink is applied onto a substrate by an ink jet method to form a coating film.
The curable ink may be the same as the content described in the section “A. Energy ray curable inkjet composition”, and the description thereof is omitted here.

In this step, an inkjet method is used as a method for forming a coating film by applying a curable ink on a substrate.
The ink jet method may be any of the ink jet methods such as a piezo method, a thermal method, and an electrostatic method, and among them, an agglomerate is hardly generated and a piezo ink jet method is excellent because of excellent discharge stability. The method is preferred.
Note that a piezoelectric inkjet head (recording head) uses a piezoelectric vibrator as a pressure generating element, and discharges ink droplets by pressurizing and depressurizing a pressure chamber by deformation of the piezoelectric vibrator.

The base material in this step is laminated on the surface of the member to be decorated together with a decorative layer formed by supporting the coating film and curing the coating film.
A thermoplastic resin can be mentioned as a material which comprises such a base material. It is because it can be easily stretched together with the decorative layer by heating. This is because even if the member to be decorated is a three-dimensional solid molded product, it can be easily laminated on the surface of the member to be decorated.
The thermoplastic resin is not particularly limited as long as it exhibits a desired stretchability. For example, acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), acrylic resin, polypropylene, polyethylene Polyolefin resins such as polycarbonate resins, vinyl chloride resins, and the like. Among them, polyolefin resins, polycarbonate resins, and ABS resins are preferable, and polyolefin resins are particularly preferable.
Moreover, the said thermoplastic resin can be used 1 type or in mixture of 2 or more types.

  The substrate may be a single layer or a laminate in which two or more layers are laminated.

  The thickness of the base material is not particularly limited as long as it has a desired stretchability, and varies depending on the type and application of the decorative film produced by the production method of the present invention. In general, it is preferably in the range of 100 μm to 500 μm, more preferably in the range of 250 μm to 500 μm, and particularly preferably in the range of 300 μm to 500 μm. When the thickness is within the above-described range, there is no deformation or the like at the time of carrying out the present step or the irradiation step, and the handleability can be improved. It is because it can be made excellent in stretchability.

The tensile elastic modulus of the substrate is not particularly limited as long as it has a desired stretchability, but is preferably in the range of 1000 MPa to 4000 MPa (initial modulus), and in particular, 2000 MPa to It is preferable to be within the range of 3000 MPa.
This is because, when the tensile elastic modulus is within the above-described range, high rigidity can be imparted to the base material, and thus distortion of the shape during vacuum forming can be suppressed.
The tensile elastic modulus is a tensile elastic modulus at room temperature measured according to JIS K7127, using Type B as a test piece, under a tensile speed of 50 m / min.

If necessary, the base material can be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides. It is because it can be excellent in adhesiveness with the layer formed on the base material.
Examples of the oxidation method include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method. It is done. These surface treatments are appropriately selected depending on the type of material constituting the substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, on the substrate, a treatment such as forming a primer layer may be performed, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

  The thickness of the coating film formed in this step is not particularly limited as long as it can have a desired stretchability, but can be in the range of 1 μm to 20 μm, Especially, it is preferable to exist in the range of 1 micrometer-15 micrometers, and it is especially preferable to exist in the range of 3 micrometers-10 micrometers. This is because, when the thickness is within the above-described range, excellent stretchability at room temperature can be achieved.

  The formation location of the coating film formed in this step is not particularly limited as long as it is on the base material, but is usually formed on the entire surface of one surface of the base material.

2. Irradiation process The irradiation process in this invention is a process of hardening the said coating film by irradiating the said coating film with exposure light, and setting it as a decoration layer.

The exposure light irradiated in this step has an emission spectrum in both the wavelength region of wavelength less than 380 nm and the wavelength region within the wavelength range of 380 nm to 420 nm.
The emission spectrum of such exposure light is not particularly limited as long as it has an emission spectrum in both the short wavelength region and the long wavelength region, but the entire emission spectrum in the wavelength region of 300 nm to 380 nm. Emission spectrum intensity ratio (short wavelength region emission spectrum intensity / short wavelength region emission spectrum intensity), which is the ratio of the intensity (short wavelength region emission spectrum intensity) to the total emission spectrum intensity (long wavelength region emission spectrum intensity) in the wavelength range of 380 nm to 420 nm. The long-wavelength region emission spectrum intensity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 4, and particularly preferably in the range of 1 to 3. . It is because the decoration film which shows the extending | stretching outstanding also at normal temperature can be obtained because the said emission spectrum intensity ratio exists in the above-mentioned range.
The total emission spectrum intensity is obtained by measuring the emission spectrum of the exposure light and integrating the radiance in the wavelength region. Specifically, a method of measuring using a spectral irradiance meter is mentioned, and more specifically, it can be obtained using a spectroradiometer USR-45V (manufactured by USHIO INC.).

  Specific examples of the light source for the exposure light include a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, and an ultrahigh-pressure mercury lamp. In this process, a metal halide lamp (manufactured by GS Yuasa Co., Ltd.) It is preferable to use MAL series). This is because by using the light source, the effect of using the short ultraviolet absorber can be more effectively exhibited. Further, it is used as a light source for a conventional general exposure facility, so that the cost can be reduced.

The total amount of exposure light irradiated to the coating film in this step is not particularly limited as long as it can form a decorative layer having a desired stretchability, but is 50 mJ / cm ^{2 to} 1000 mJ /. can be in the range of cm ^2, preferably in the range of these the ^{50mJ / cm 2 ~500mJ / cm 2} , ^particularly preferably in the range of 50mJ / cm ² ~300mJ / cm 2 . This is because, when the total amount of energy is within the above-described range, the surface is sufficiently cured, blocking is small, and a decorative layer having excellent stretchability can be obtained.

  The thickness and the formation location of the decorative layer formed by this step can be the same as the thickness and the formation location of the coating film.

3. The manufacturing method of the film for decorating The manufacturing method of the film for decorating of this invention has the said application | coating process and an irradiation process, However, You may have another process as needed.
Such other steps include a primer layer formed between the base material and the decoration layer, a protective layer formed on the decoration layer, and a side of the base material opposite to the side on which the decoration layer is formed. A step of forming another layer such as a pressure-sensitive adhesive layer formed on the surface of the film, a release layer formed on the pressure-sensitive adhesive layer, a drying step of drying the solvent when the solvent is contained in the coating film, the decoration Examples include a baking step for heating the layer.
In addition, about such each process etc., since it shall be generally used for manufacture of the film for decorating, description here is abbreviate | omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention more specifically.

1. Preparation of curable ink A polymerization initiator, a polymerizable compound, an ultraviolet absorber, a colorant and an additive were prepared according to the composition described in Table 1 below (Examples 1 to 6, Comparative Examples 1 and 2).
In addition, the numerical value of each component in Table 1 shows the weight part of each component.

Further, isobornyl acrylate, phenoxyethyl acrylate, N-vinylcaprolactam, and aliphatic urethane acrylate (CN996 manufactured by Sartomer) were used as the polymerizable compound.
2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (polymerization initiator 1), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-Morpholinyl) phenyl] -1-butanone (polymerization initiator 2) was used.
As a polymerization inhibitor, phenothiazine was used.
As a colorant, black base (12 parts by weight of NEROX 5600 manufactured by Evonik Degussa, 6.9 parts by weight of BYK-UV9150 manufactured by BYK Chemie, 81.1 parts by weight of ZA-IBXA manufactured by Kyoeisha Chemical Co., D / P = 0.08, P = 12%) was used.
As a leveling agent, silicon polyether acrylate (Degosa TEGO-Rad2300) was used.
2,4-Diethylthioxanthone was used as a photosensitizer.
D / P represents the weight of the active component of the dispersant / the weight of the pigment, and P = 12% represents the content in the solid content of the pigment.

Further, as UV absorbers, TINUVIN 326 (380 nm transmittance 0%, 420 nm transmittance 30%), TINUVIN 384-2 (380 nm transmittance 0%, 420 nm transmittance 100%), TINUVIN 400 (380 nm transmittance 0%, 420 nm transmittance) 100%), TINUVIN479 (380 nm transmittance 0%, 420 nm transmittance 60%), TINUVIN900 (380 nm transmittance 0%, 420 nm transmittance 100%), TINUVIN928 (380 nm transmittance 0%, 420 nm transmittance 100%), TINUVIN120 (380 nm transmittance 100%, 420 nm transmittance 100%) was used.
In addition, the transmittance | permeability of a ultraviolet absorber shows the transmittance | permeability in 380 nm and 420 nm about the toluene solution of 1% ultraviolet absorber, respectively.

2. Evaluation Method The curable inks prepared in Examples and Comparative Examples were evaluated for stretchability and curability. The results are shown in Table 1 below.

(1) Stretchability Using a vinyl chloride sheet MACTAC JT5829R (manufactured by Martini Co., Ltd.) having a size of 50 mm × 100 mm and a thickness of about 1 mm, a curable ink was applied on this substrate with a bar coater # 6. As a UV exposure apparatus, a test piece in which a decorative layer having a thickness of 7 mm was formed on a substrate was prepared by performing exposure once using a UV-LED or a metal halide.
The exposure amount per single UV exposure apparatus as a light source UV-LED and metal halide (total energy amount in 320Nm～390nm) are each set to 100 mJ / cm ² and 115mJ / cm ^2, also metal halide emission spectrum The intensity ratio ((short wavelength region emission spectrum intensity) / (long wavelength region emission spectrum intensity)) was 2.
Then, both ends in the longitudinal direction of the test piece are attached to a tensile tester AGS-1kNX (manufactured by Shimadzu Corporation) in a 25 ° C. environment, and pulled at a pulling speed of 10 mm / min to measure the maximum elongation at which the decorative layer does not crack. The elongation percentage (length after stretching / length before stretching) × 100 (%) was calculated. The results are shown in Table 1.

(2) Curability After applying curable ink to a PVC sheet (MACTAC JT5829R made by Martini Co., Ltd.) with a bar coater # 6, rubbing the surface of the coated surface with a rolling pin until the coating of the curable ink is not tackled. The number of exposures was measured. The UV exposure apparatus and the exposure conditions per time were the same as those used for the evaluation of “(1) Stretchability”. The results are shown in Table 1.

(3) Summary From Table 1, it was confirmed that in the examples, a decorative layer having good stretchability (stretchability of 200% or more is acceptable) can be formed regardless of the exposure apparatus.
Moreover, from the evaluation of curability, it was confirmed that the curability was not affected by the UV absorber because there was no difference in the presence or type of the UV absorber.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Paint film 3 ... Decoration layer 10 ... Film for decorating

Claims (3)

An application step of applying an energy ray-curable inkjet ink composition having a polymerization initiator, a polymerizable compound, and an ultraviolet absorber on a substrate by an inkjet method to form a coating film;
An irradiation step for curing the coating film by irradiating the coating film with exposure light having an emission spectrum in a wavelength region of a wavelength of less than 380 nm and a wavelength region within a wavelength range of 380 nm to 420 nm; ,
Have
As the ultraviolet absorber, including only an ultraviolet absorber having a light transmittance of 30% or less at a wavelength of 380 nm,
The substrate includes a thermoplastic resin;
A method for producing a decorative film, characterized by obtaining a decorative film for three-dimensional molding.   The method for producing a decorative film according to claim 1, wherein a stretchability of the decorative layer at room temperature is 150% or more. The polymerizable compound contains a monofunctional monomer,
The content of the monofunctional monomer is in the range of 60% by mass to 95% by mass in the energy ray curable ink jet ink composition. Film manufacturing method.

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