JP7064088B1 - Laminated film for decorative molding, manufacturing method of the film, and decorative molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film for decorative molding having excellent moldability, wherein the present invention has been made in view of the above background, and is a decorative molded body having excellent chipping resistance, abrasion resistance and chemical resistance. It is an object of the present invention to provide a laminated film for decorative molding capable of forming. SOLUTION: The laminated film for decorative molding having a surface protective layer and a base material layer has a maltens hardness of 100 to 300 N / mm2 measured from the surface protective layer side of the laminated film for decorative molding. The surface protective layer exhibits a sea-island structure having a domain (D) and a matrix (M), and the Kulmvine diameter of the domain (D) is 0.05 to 0.5 μm, and the domain (D) and the matrix (M) are formed. A laminated film for decorative molding, characterized in that the ratio D: M to and D: M is 5 to 44: 95 to 56. [Selection diagram] Fig. 2

Description

The present invention relates to a laminated film for decorative molding having a surface protective layer exhibiting a specific hardness and a sea-island structure, a method for producing the film, and a decorative molded body.

Resin molded products are often used for mobile information terminal devices such as smartphones, notebook computers, home appliances, and interior / exterior parts of automobiles. A surface protective layer such as a hard coat layer is provided on the outermost surface of these resin molded products by spray coating or dipping coating, or by integrating a decorative film having a hard coat layer in advance at the time of molding. It has been done.

In Patent Document 1, a multilayer body having at least one layer each of a layer made of an acrylic resin (A) and a layer made of an aliphatic polycarbonate resin (B) is obtained by co-pressing the two types of resins. It is stated to that effect.
Patent Document 2 describes a vinyl having a carboxyl group and a hydroxyl group, having a solid acid value of 15 to 150 mgKOH / g, a solid content hydroxyl value of 2 to 80 mgKOH / g, and a glass transition temperature of 70 to 140 ° C. Curability for decorative films for thermoforming, which contains a system polymer and a polyisocyanate compound, and the content of the polyisocyanate compound is a content that reacts with the solid content hydroxyl value of 2 to 80 mgKOH / g of the vinyl polymer. The resin composition is disclosed.
Patent Document 3 describes a laminated hard coat film for molding in which a surface protective layer containing a resin is provided on a base film, and has an elongation rate of 10% or more in an atmosphere of 23 ° C. and 50% RH. A laminated hardcourt film for molding is disclosed. The use of an active energy ray-curable resin as a resin contained in the hard coat layer is disclosed.
Patent Document 4 discloses a decorative sheet having a surface protective layer on a substrate, which is obtained by cross-linking and curing a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a specific ratio.

Japanese Unexamined Patent Publication No. 2011-161871 Japanese Unexamined Patent Publication No. 2012-09724 Japanese Unexamined Patent Publication No. 2012-210755 Japanese Unexamined Patent Publication No. 2007-290392

The laminated film for decorative molding is required to have excellent designability because it is also used for the interior and outer layers of automobiles, for example, while it is also required to have excellent moldability capable of three-dimensional molding. In addition, after molding, high scratch resistance and chemical resistance (sunscreen cream resistance, etc.) are required. Furthermore, assuming outdoor use, it is required that it is not easily scratched even if it is hit by sand or stone, and that it is not noticeable even if it is scratched (chipping resistance). By the way, chipping resistance requires resistance to momentary impact, and is a problem that cannot be solved only by balancing simple hardening and softening of the coating film. Also in the above Patent Documents 1 to 4. None of them satisfied all of these characteristics.

The present invention has been made in view of the above background, and is a laminated film for decorative molding having excellent moldability, and can form a decorative molded body having excellent chipping resistance, abrasion resistance, and chemical resistance. It is an object of the present invention to provide a laminated film for decorative molding.

The present invention solves the above-mentioned problems by the surface protective layer side of the laminated film for decorative molding exhibiting a specific Martens hardness and the surface protective layer having islands having a specific Kulmvine diameter in a specific ratio.
That is, the present invention relates to the following [1] to [7].

[1] A laminated film for decorative molding having a surface protective layer and a base material layer.
The Martens hardness measured from the surface protective layer side of the laminated film for decorative molding is 100 to 300 N / mm ² .
The surface protective layer exhibits a sea-island structure having a domain (D) and a matrix (M).
The Kulmvine diameter of the domain (D) is 0.05 to 0.5 μm, and the diameter is 0.05 to 0.5 μm.
The ratio D: M between the domain (D) and the matrix (M) is 5 to 44: 95 to 56.
Laminated film for decorative molding.

[2] A cured product of a (meth) acrylate resin (a) in which the matrix (M) has a hydroxyl group and does not have a photocurable functional group, and an isocyanate-based curing agent (b) that does not have a photocurable functional group. And
The decoration according to [1], wherein the domain (D) is a cured product of an active energy ray-curable component containing a urethane (meth) acrylate (c) and / or a (meth) acrylate having a weight average molecular weight of 400 to 5000. Laminated film for molding.

[3] The laminated film for decorative molding according to [1] or [2], wherein the elongation rate of the surface protective layer when the laminated film for decorative molding is pulled at 140 ° C. is 50 to 200%.

[4] The laminated film for decorative molding according to any one of [1] to [3], wherein the haze specified by JIS K 7361 of the surface protective layer is 5% or less.

[5] A (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group, an isocyanate-based curing agent (b) having no photocurable functional group, and a urethane (meth) acrylate (c). ) And / or a protective agent containing an active energy ray-curable component containing a (meth) acrylate having a weight average molecular weight of 400 to 5000 and an organic solvent.
After coating on the base material layer, drying, and reacting at least a part of the (meth) acrylate resin (a) with the isocyanate-based curing agent (b),
Irradiate with active energy rays to cure the active energy ray-curable component to form a surface protective layer.
[2] The method for producing a decorative molding laminated film according to any one of [2] to [4].

[6] A (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group, an isocyanate-based curing agent (b) having no photocurable functional group, and a urethane (meth) acrylate (c). ) And / or a protective agent containing an active energy ray-curable component containing a (meth) acrylate having a weight average molecular weight of 400 to 5000 and an organic solvent.
After coating on a release film, drying, and reacting at least a part of the (meth) acrylate resin (a) with the isocyanate-based curing agent (b),
Irradiate with active energy rays to cure the active energy ray-curable component to form a surface protective layer.
Next, the surface protective layer is attached to the base material layer via the adhesive layer.
[2] The method for producing a decorative molding laminated film according to any one of [2] to [4].

[7] A decorative molded body comprising the decorated body and the laminated film for decorative molding according to any one of [1] to [4], which covers at least a part of the decorated body. ..

According to the present invention, it is possible to provide a laminated film for decorative molding having excellent moldability that can be applied to various shapes. Further, a decorative molded product using this can provide a decorative molded product having high designability, which is less likely to cause discoloration or whitening even when a chemical comes into contact with the surface thereof and is not easily scratched even in a harsh environment.

Elastic modulus image of SPM measurement of the cross section of the surface protective layer. Analysis image of domain (D) by image processing software.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. The numerical values "A to B" specified in the present specification indicate numerical values A or more and B or less. Further, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acrylate" means acrylate and methacrylate.
Further, the active energy ray-curable component may be abbreviated as a photocurable component.
The weight average molecular weight of the present specification is a value measured by GPC (gel permeation chromatography) manufactured by Toso. Details will be described in the column of Examples.

<Laminate film for decorative molding>
The laminated film for decorative molding of the present invention includes at least a surface protective layer and a base material layer, and has a maltens hardness of 100 to 300 N / mm ² measured from the surface protective layer side and 150 to 250 N / mm ² . Is more preferable. When the Martens hardness is 100 N / mm ² or more, it is less likely to be scratched even when rubbed with steel wool, and when it is 300 N / mm ² or less, the chipping resistance and extensibility are good.
For the Martens hardness, a "Fisherscope H-100C" manufactured by Fisher Instruments Co., Ltd. was used as an ultrafine hardness tester, and a Vikkers indenter (Vickers indenter) was used for the surface protective layer of the laminated film for decorative molding of the present invention. It is a value when a quadrangular pyramid) is pushed in with a force of 3 mN and held for 5 seconds. Further, the pushing depth of the terminal must not exceed the thickness of the surface protective layer. It is preferable that the pressing depth is set to a distance corresponding to 5% to 50% with respect to the thickness of the surface protective layer.
Martens hardness is increased by lowering the molecular weight of urethane (meth) acrylate (c), which will be described later, or by increasing the number of functional groups (acrylate groups) per molecule, and urethane (meth) acrylate (c). It is reduced by increasing the molecular weight such as, or decreasing the number of functional groups per molecule.

<Surface protective layer>
The surface protective layer exhibits a sea-island structure having a domain (D) and a matrix (M). The sea-island structure in the present invention is specified by observing the cross section of the surface protective layer with a scanning probe microscope (hereinafter, may be abbreviated as SPM) and detecting the difference in elastic modulus.
SPM is a microscope that observes the surface state by scanning the surface of a sample while tapping it with a minute probe (cantilever). In addition to general surface shapes such as unevenness, the peak value of the voltage generated during tapping corresponds to the elastic modulus of the measured surface, so the magnitude of the elastic modulus of the surface is used as an image based on the voltage peak value. Can be expressed.
Specifically, the cross section of the surface protective layer is observed using an MFP-3D manufactured by Oxford Instruments Co., Ltd. in a cantilever: AC-160TS, dynamic measurement mode. The measurement range is 2 μm × 2 μm, and the elastic modulus image is observed. As a method for obtaining a cross section to be observed by SPM, the target sample frozen with liquid nitrogen or the like is broken (freeze cutting method), the target sample is cut with a sharp blade such as a razor (microtome method), or cut out with a cutter or the like. There is a method (ion milling method) in which the cross section of the target sample is prepared with abrasive paper and the sample is processed by irradiating the sample with an ion beam using a cross-section polisher device, and the cross section can be obtained by various methods. The ion milling method is most preferable.

By the way, a state in which an inorganic filler or an organic filler is dispersed in a resin is broadly referred to as a sea-island structure. Further, the surface protective layer in the present invention may contain an inorganic filler or an organic filler. However, the inorganic filler and the organic filler are not included in any of the concepts of the matrix (M) and the domain (D) in the present invention. In that respect, the sea-island structure in the present invention is slightly different from the sea-island structure in the general sense.
That is, when observing the cross section of the surface protective layer containing the inorganic filler or the organic filler, unevenness due to the filler is observed. Although it depends on the size of the filler, the observed unevenness is at least 5 nm. Island observed as unevenness of 5 nm or more is not included in the concept of domain (D) in the present invention. The domain (D) in the present invention means an island that is not detected as unevenness but is detected by a difference in elastic modulus.

The surface protective layer in which the sea-island structure is not observed in the unevenness and the sea-island structure is observed due to the difference in elastic modulus is, for example, a (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group. A photocurable component containing an isocyanate-based curing agent (b) having no photocurable functional group, a urethane (meth) acrylate (c) and / or a (meth) acrylate having a weight average molecular weight of 400 to 5000, and an organic solvent. It can be formed by using a protective agent containing and. The reason and mechanism that can be formed have not been clarified, but it is speculated as follows.
That is, when a uniform protective agent is applied to the base material or the release film and dried as described later, the (meth) acrylate resin (a) and the isocyanate-based curing agent (b) react with each other. In the process of forming the matrix (sea), a part of the photocurable component is gradually separated from the uniform protective agent to form a domain (island) precursor that will become a domain (island) in the future. After the reaction between the (meth) acrylate resin (a) and the isocyanate-based curing agent (b) has proceeded to some extent, it is contained in the domain (island) precursor and the matrix (sea) by irradiating with active energy rays. It is considered that by curing the photocurable component, the sea-island structure is not observed in the unevenness, and a surface protective layer in which the sea-island structure is observed is formed due to the difference in elastic modulus.
That is, the photocurable component containing the urethane (meth) acrylate (c) and / or the (meth) acrylate having a weight average molecular weight of 400 to 5000 has an appropriate affinity with the (meth) acrylate resin (a) as a whole. Can form a uniform and transparent protective agent. Since it has a "urethane" bond or a certain molecular weight, it is compatible in the process of the curing reaction between the (meth) acrylate resin (a) and the isocyanate-based curing agent (b). It is speculated that a kind of separation occurs when viewed microscopically, and a domain (island) with almost no difference in elevation is formed from the matrix (sea).

When the surface protective layer exhibits such a peculiar sea-island structure, the compatibility of the photocurable component is lowered in the process of the curing reaction between the (meth) acrylate resin (a) and the isocyanate-based curing agent (b). It is possible to impart a higher degree of moldability, chipping resistance and chemical resistance than when it is not used or when an organic filler is simply blended. When the organic filler is simply blended, diffused reflection of light is likely to occur at the interface between the organic filler and the matrix (sea), but in the case of the sea-island structure in the present invention, the light at the boundary between the domain (island) and the matrix (sea). It is possible to develop high transparency with little diffused reflection.

<Krumbine diameter and ratio of domain (D) to matrix (M)>
The Kulmvine diameter of the domain (D) of the surface protective layer in the present invention is 0.05 to 0.5 μm, and the ratio D: M of the domain (D) to the matrix (M) is 5 to 44: 95 to 56. .. Regarding the ratio of both, paying attention to the ratio of the domain (D), the ratio of the domain (D) may be 5 to 44%.
By setting the Kulmvine diameter of the domain (D) and the ratio of the domain (D) within the above ranges, the effect of achieving both chemical resistance, moldability, and chipping resistance at a high level can be obtained.

The Kulmvine diameter is an average value of the distances between two points connected by the longest straight line crossing each domain (D), preferably 0.05 to 0.3 μm, more preferably 0.08 to 0.15 μm. .. Specifically, for each of the domains (D) confirmed in the range of 2 μm × 2 μm at any three locations, the above-mentioned “distance between two points connected by the longest straight line” is calculated, and the average thereof is calculated. ..
The Kulmvine diameter tends to increase as the weight average molecular weight (hereinafter, Mw) of the urethane (meth) acrylate (c) described later increases. Further, the size can be controlled by changing the composition of the solvent (S) used as the protective agent. Specifically, when a ketone solvent is used, the diameter of the krumbine becomes smaller, and by using an alcohol solvent, the diameter of the krumbine can be greatly adjusted.
As for the Kulmvine diameter, since the boundary surface between the domain (D) and the matrix (M) can be visually recognized in the above-mentioned SPM observation image, this is referred to as Mac-View Ver. It can be measured by image analysis using the analysis software of 4 (Mount Tech).

For the ratio of the domain (D), the elastic modulus image by the above SPM is obtained from Mac-View Ver. It is obtained from the following mathematical formula (1) using the area of the domain (D) and the area of the matrix (M) measured by the analysis software of 4 (Mount Tech).
The area of the domain (D) is the total area of each domain (D) in the observation image, and the area of the matrix (M) is the total area of each domain (D) in the observation image from the area of the observation area. , The total area of the inorganic filler, and the total area of the organic filler are excluded.
When the surface protective layer contains an inorganic filler or an organic filler, their presence is detected as unevenness as described above. The detection of the uneven image is performed at the same time as the elastic modulus image by SPM. Therefore, the area occupied by the domain of the inorganic filler or the domain of the organic filler detected as an uneven image is subtracted from the area of the observation region, and this is the area of the observation region by observing the elastic modulus image, that is, the area of each domain (D). And the area of the matrix (M).
Domain (D) ratio (%) = total area of each domain (D) x 100 / (total area of each domain (D) + area of matrix (M)) ... Formula (1)

The ratio of domains (D) can be adjusted from the size and number of each domain (D). The ratio of the domain (D) is 5 to 44%, preferably 5 to 30%, more preferably 10 to 20%.
The size of each domain (D) can be increased by increasing the Mw of the (meth) acrylate resin (a) described later or increasing the hydroxyl value.

Further, the transparency (haze value) of the surface protective layer is preferably 5% or less, more preferably 3.5% or less, and further preferably 1.5% or less from the viewpoint of enhancing the design of the laminated film for decorative molding. It is preferably less than 0.5%, most preferably less than 0.5%. By setting the Kulmvine diameter and ratio of the domain (D) in the above range, it is possible to suppress light scattering and enhance transparency.

The surface protective layer is formed by using a protective agent. The protective agent preferably contains a plurality of components having an appropriate affinity, and a curing agent and a solvent (s) capable of reacting with at least one of the above components. The above components can be appropriately selected according to the purpose, but among them, a (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group, an isocyanate-based curing agent (b), and a urethane (meth) acrylate. It preferably contains (c) and / or an active energy ray-curable component containing a (meth) acrylate having a weight average molecular weight of 400-5000. In this case, the cured product of the (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group and the isocyanate-based curing agent (b) forms a matrix (M), and urethane (meth) acrylate (meth) acrylate ( c) and / or a cured product of an active energy ray-curable component containing a (meth) acrylate having a weight average molecular weight of 400-5000 forms the domain (D). Hereinafter, each component will be described in detail.

<(Meta) acrylate resin (a) having a hydroxyl group and no photocurable functional group>
The (meth) acrylate resin (a) can be obtained by copolymerizing a (meth) acrylate-based monomer having a hydroxyl group with another (meth) acrylate-based monomer having no hydroxyl group. That is, the (meth) acrylate resin (a) is a copolymer composed of a unit derived from a (meth) acrylate-based monomer having a hydroxyl group and a unit derived from another (meth) acrylate-based monomer.

The (meth) acrylate-based monomer having a hydroxyl group preferably has a hydroxyl group as a primary hydroxyl group.
Since it is a primary hydroxyl group, the reaction with the isocyanate-based curing agent (b) described later proceeds smoothly, and the quality of the laminated film for decorative molding is stabilized. Further, the reaction between the (meth) acrylate resin (a) and the isocyanate-based curing agent (b) tends to be dense, and the phase separation with the urethane (meth) acrylate (c) proceeds smoothly.

Examples of the (meth) acrylate-based monomer having a hydroxyl group include hydroxyalkyl (meth) acrylates and compounds in which ε-caprolactone is added to the hydroxyalkyl (meth) acrylate, and hydroxyalkyl (meth) acrylates are preferable.

Specific examples of hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-. Examples thereof include hydroxyalkyl (meth) acrylates having an alkyl group having 1 to 4 carbon atoms, such as hydroxybutyl (meth) acrylate.
Specific examples of the compound obtained by adding ε-caprolactone to hydroxyalkyl (meth) acrylate include 1 mol adduct of ε-caprolactone of 2-hydroxyethyl (meth) acrylate and 2 mol of ε-caprolactone of 2-hydroxyethyl (meth) acrylate. Examples of the adduct include an ε-caprolactone adduct of a hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms such as a ε-caprolactone 3 mol adduct of 2-hydroxyethyl (meth) acrylate. It is not limited to such an example.
These hydroxyl group-containing monomers may be used alone or in combination. 2-Hydroxyethyl (meth) acrylate is particularly preferable from the viewpoint that the distance between the molecules is relatively short when crosslinked with an isocyanate curing agent and the abrasion resistance and chemical resistance are improved.

Examples of other (meth) acrylate-based monomers having no hydroxyl group include various monomers as shown below.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth). Acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Examples thereof include alkyl (meth) acrylates such as tert-butylhexyl (meth) acrylates, 2-acetoacetoxyethyl (meth) acrylates, and phenoxyethyl (meth) acrylates.
Examples of the monomer having an alicyclic hydrocarbon group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate. Examples thereof include dicyclopentenyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, α-methylglycidyl acrylate, α-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethylacrylate, and 3,4-epoxycyclohexylmethylmethacrylate.

The (meth) acrylate resin (a) is preferably obtained by polymerizing a methacrylate-based monomer among the various monomers described above. In particular, methyl methacrylate, ethyl methacrylate and tert-butyl methacrylate are preferable from the viewpoint of abrasion resistance, moldability and chemical resistance, and ethyl methacrylate and tert- are further preferable from the viewpoint of phase separation from urethane (meth) acrylate (c). Butyl methacrylate is preferable, and ethyl methacrylate, which improves chipping resistance due to its moderate flexibility, is most preferable.

The hydroxyl value of the (meth) acrylate resin (a) is preferably 5 to 190 mgKOH / g, more preferably 55 to 150 mgKOH / g, and even more preferably 70 to 120 mgKOH / g. When it is in a preferable range, it is easier to phase-separate from urethane (meth) acrylate (c) and form a sea-island structure.
The hydroxyl value represents the solid content hydroxyl value and is a value measured according to JIS K1557-1.

The (meth) acrylate resin (a) may have an acid value. Having an acid value promotes the reaction between the hydroxyl group and isocyanate, and can reduce unreacted substances.
When imparting an acid value, the acid value of the (meth) acrylate resin (a) is preferably 20 mgKOH / g or less. This is because having an acid value enhances the compatibility between the (meth) acrylate resin (a) and the urethane (meth) acrylate (c), making it difficult to stably form the sea-island structure.
As a method of imparting an acid value to the (meth) acrylate resin (a), it is obtained by copolymerizing a monomer having an acid value with another monomer. Monomers having an acid value include (meth) acrylic acid, maleic anhydride, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl-hexahydrophthalic acid, and 2- (meth). ) Acryloyloxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like can be mentioned.
The acid value represents the solid content acid value and is a value measured according to JIS K1557-5.

The glass transition temperature of the (meth) acrylate resin (a) is preferably 20 ° C. to 120 ° C. or lower. When the glass transition temperature is 20 ° C. or higher, good scratch resistance and scratch resistance can be obtained, and when the glass transition temperature is 120 ° C. or lower, the moldability is improved. The glass transition temperature of the (meth) acrylate resin (a) is determined by the type and copolymerization ratio of the other (meth) acrylate-based monomer copolymerized with the (meth) acrylate-based monomer having a hydroxyl group.
The glass transition temperature shown here refers to the glass transition temperature measured by differential scanning calorimetry (DSC) with respect to 100% of the solid content of the (meth) acrylate resin (a).

The weight average molecular weight (Mw) of the (meth) acrylate resin (a) is preferably 50,000 to 500,000, more preferably 100,000 to 300,000. When the weight average molecular weight is 50,000 or more, moldability and abrasion resistance are improved, and when it is 500,000 or less, gel formation is prevented and a surface protective layer having good surface smoothness is prevented. Can be obtained.

The polydispersity (Mw / Mn) of the (meth) acrylate resin (a) is preferably 2.3 to 10. When comparing polymers with similar weight average molecular weights, polymers with a small degree of polydispersity contain relatively few low molecular weight components, and polymers with a large degree of polydispersity have relatively many low molecular weight components. included. The polymer may also contain molecules that are not directly involved in the curing reaction. Among the molecules that are not directly involved in the curing reaction, the low molecular weight component acts as a plasticizer, so that the physical properties of the film after curing change greatly depending on the degree of polydispersity. That is, when the polydispersity is 2.3 or more, the crosslink density of the cured coating film is appropriately lowered and the moldability is improved. On the other hand, when the polydispersity is 10 or less, the plasticity of the cured coating film can be appropriately suppressed and the abrasion resistance can be maintained. The polydispersity is more preferably 2.3 to 9, and even more preferably 2.3 to 8.

Examples of the method for polymerizing the (meth) acrylate-based monomer include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. Since the obtained reaction mixture can be used as it is, the obtained reaction mixture can be used as it is. The solution polymerization method is preferable.

Examples of the solvent used for solution polymerization of the (meth) acrylate-based monomer include aromatic solvents such as toluene and xylene; alcohol-based solvents such as n-butyl alcohol, propylene glycol monomethyl ether, diacetone alcohol, and ethyl cellosolve. Solvents; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; dimethylformamide and the like, but the present invention is not limited to these examples. not. The amount of the solvent is preferably appropriately determined according to the concentration of the monomer mixture, the molecular weight of the target (meth) acrylate resin, and the like.
Since the domain size can be adjusted by using a ketone solvent and an alcohol solvent in combination when forming the surface protective layer, it is preferable to use a ketone solvent or an alcohol solvent at the time of synthesis.

Examples of the polymerization initiator include azo compounds and organic peroxides. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile) and 2,2. '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate), 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] And so on. Examples of the azo compound include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate and di (2-ethoxyethyl) peroxydicarbonate. , Tert-Butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate and tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide and dipropionyl peroxide, Examples include diacetyl peroxide.
The present invention is not limited to such examples.

<Isocyanate-based curing agent (b)>
The isocyanate-based curing agent (b) reacts with the hydroxyl group which is a crosslinkable functional group in the (meth) acrylate resin (a) which has the above-mentioned hydroxyl group and does not have a photocurable functional group to form the matrix (M). Used to form. The compounding ratio of the (meth) acrylate resin (a) and the isocyanate-based curing agent (b) is the mol ratio of the isocyanate group in the isocyanate-based curing agent (B) and the hydroxyl group in the acrylic copolymer (A). However, NCO / OH = 0.5 / 1 to 3/1 is preferable, and NCO / OH = 1.01 / 1 to 1.5 / 1 is more preferable. In particular, when the isocyanate group exceeds 1 mol with respect to 1 mol of the hydroxyl group, the cross-linking reaction between the hydroxyl group in the acrylic copolymer (a) and the isocyanate-based curing agent (b) proceeds smoothly, and the phase separation proceeds. A surface protective layer having good chemical resistance and chipping resistance can be obtained. When the isocyanate group is 3 mol or less with respect to 1 mol of the hydroxyl group, an excessive cross-linking reaction is suppressed and the moldability is improved. When the isocyanate group is 0.5 mol or more with respect to 1 mol of the hydroxyl group, the effects of improving the chemical resistance by crosslinking and promoting the phase separation of the domain (D) can be clearly seen.

The isocyanate-based curing agent (b) preferably has two or more isocyanate groups in one molecule, and examples of the skeleton include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates. Above all, it is preferable to use an aliphatic isocyanate-based curing agent from the viewpoint of preventing yellowing of the molded decorative film. The isocyanate-based curing agent (b) may be used alone or in combination of two or more types. Further, a curing agent that reacts with other hydroxyl groups may be used as long as it does not affect the physical properties of the decorative film of the present invention.

Examples of the aromatic isocyanate include 1,3-phenylenediocyanate, 4,'-diphenyldiisocyanate, 1,4-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. , 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4', 4 "-triisocyanate Examples thereof include phenylmethane triisocyanate.

Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylenedi isocyanate, and dodecamethylene diisocyanate. Examples thereof include 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the alicyclic isocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2. , 4-Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like.

These isocyanate-based curing agents further include an adduct of the isocyanate and a polyol compound such as trimethylolpropane, a bullet or isocyanurate of the isocyanate, and further, a polyether polyol, a polyester polyol, or an acrylic polyol known as the isocyanate. It is preferable to use it as an adduct with a polybutadiene polyol, a polyisoprene polyol, or the like.

Among these isocyanate-based curing agents (b), low-yellowing aliphatic or alicyclic isocyanates are preferable from the viewpoint of design, and adducts are preferable from the viewpoint of film strength of the cured film. More specifically, an adduct of hexamethylene diisocyanate (HDI) and an adduct of 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) are preferable. In addition, a mixture of these is also preferably used.

Further, in the present invention, a blocked isocyanate curing agent may be used from the viewpoint of storage stability of the protective agent. As the blocked isocyanate curing agent, those obtained by blocking the above-mentioned unblocked isocyanate curing agent with various blocking agents are used, and as the blocking agent, those that dissociate at a relatively low temperature of about 80 ° C to 120 ° C are used. preferable. When a non-blocking isocyanate curing agent is used, the (meth) acrylic resin (a) having a hydroxyl group and the isocyanate-based curing agent (b) are packaged separately and mixed immediately before use. Is preferably used.

<Active energy ray curable component (photocurable component)>
The photocurable component in the present invention forms the domain (D) and includes a urethane (meth) acrylate (c) and / or a (meth) acrylate having a weight average molecular weight of 400 to 5000.
<Urethane (meth) acrylate (c)>
The urethane (meth) acrylate is a reaction product of a compound having an isocyanate group and a (meth) acrylate having a hydroxyl group, and has a (meth) acryloyl group at the end of the molecule. As the compound having an isocyanate group, a polyfunctional one is used and a (meth) acrylate having one hydroxyl group is reacted, or a compound having a monofunctional isocyanate group is used and a (meth) acrylate having a plurality of hydroxyl groups is reacted. It is preferable to use a urethane (meth) acrylate having a plurality of (meth) acryloyl groups. It can also be extended with diols and diamines. Urethane (meth) acrylate ligomers having a plurality of (meth) acryloyl groups are rapidly cured by active energy such as ultraviolet rays and electron beams due to unsaturated carbon bonds derived from (meth) acrylate. The obtained cured product has a high crosslink density and excellent chemical resistance. When the radically polymerizable crosslinking component is crosslinked by ultraviolet rays or the like, a photopolymerization initiator can be used, and a polymerization accelerator can also be used in combination. When cross-linking with an electron beam, these may not be blended.

The weight average molecular weight (Mw) of the urethane (meth) acrylate (c) is preferably 300 to 4000. When it is 4000 or less, the compatibility with the (meth) acrylate resin (a) is lowered and it becomes easy to form a sea-island structure, and when it is 300 or more, the flexibility of the domain (D) is improved and it is decorated. Even after molding the laminated film for molding, the chemical resistance can be maintained at a high level. This is because the domain (D) is easily deformed along with the shape deformation of the matrix (M).
Urethane (meth) acrylate (c) having a large Mw is a prepolymer having an isocyanate group formed by reacting various diols and diamines with a compound having a relatively low molecular weight isocyanate group, and having a hydroxyl group (meth). ) It can be obtained by reacting with acrylate.

Examples of the diols include diols having a linear aliphatic structure and diols having a branched chain aliphatic structure. Examples of the diamines include diamines having a linear aliphatic structure, diamines having a branched chain aliphatic structure, and diamines having an alicyclic structure.

The hydroxy (meth) acrylates having one hydroxyl group used for forming the urethane (meth) acrylate (c) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3. -Chloropropyl (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (meth) ) Acrylic acid-2-hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerindi (meth) ) Acrylate and the like can be mentioned.

Examples of the hydroxy (meth) acrylates having a plurality of hydroxyl groups used for forming the urethane (meth) acrylate (c) include pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, and dipentaerythritol mono (meth) acrylate. , Dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerin (meth) acrylate and the like.

As the compound having an isocyanate group used for forming the urethane (meth) acrylate (c), those exemplified as the isocyanate-based curing agent (b) having no photocurable functional group can be similarly exemplified.
Further, examples of the isocyanate group-containing compound used for forming the urethane (meth) acrylate (c) include 2-isocyanatoethyl (meth) acrylate, 2- ((meth) acryloyloxy) ethyl isocyanate, 1,1. -A compound having an isocyanate group and a (meth) acryloyl group, such as (bis (meth) acryloyloxymethyl) ethyl isocyanate, can also be exemplified.

<(Meta) acrylate with a weight average molecular weight of 400 to 5000>
(Meta) acrylates (hereinafter, also referred to as oligomers) having a weight average molecular weight of 400 to 5000 can also be used for the formation of the domain (D).
For example, a polyester having a (meth) acryloyl group can be obtained by forming a polyester having a carboxy group and reacting the carboxy group in the polyester with a glycidyl (meth) acrylate. If a polyester having a carboxy group introduced only at the terminal is used, a (meth) acryloyl group can be introduced only at the end. Polyesters with carboxy groups introduced into the ends and side chains can be used to introduce (meth) acryloyl groups into the ends and side chains.
Alternatively, (meth) acrylate having a carboxy group and another (meth) acrylate or the like are copolymerized to obtain a copolymer, and glycidyl (meth) acrylate is reacted with the carboxy group in the copolymer to obtain (meth) acrylate. ) An oligomer having an acryloyl group is obtained, or a copolymer is obtained by copolymerizing glycidyl (meth) acrylate with another (meth) acrylate, and the glycidyl group in the copolymer is reacted with (meth) acrylic acid. Thereby, an oligomer having a (meth) acryloyl group can be obtained.
Alternatively, a (meth) acrylate having a hydroxyl group and no photocurable functional group is copolymerized with another (meth) acrylate to obtain a copolymer, and the hydroxyl group in the copolymer is combined with an isocyanate group ( An oligomer having a (meth) acryloyl group can also be obtained by reacting a compound having a (meth) acryloyl group.

The photocurable component in the present invention is a reaction between a (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group and an isocyanate-based curing agent (b) having no photocurable functional group. During matrix (M) formation
Others (meth) other than the urethane (meth) acrylate (c) and the (meth) acrylate, as long as the phase separation of the urethane (meth) acrylate (c) and the (meth) acrylate having a weight average molecular weight of 400 to 5000 is not impaired. ) An acrylate-based monomer can be contained.

The protective agent preferably contains a photopolymerization initiator in order to promote photopolymerization of the photocurable component. Examples of the photopolymerization initiator include the following.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo {2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2 -Acetphenones such as methylpropane-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other examples include, but are not limited to, phenylglycoxymethyl ester.
More specifically, Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure. Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (BASF), Adecaoptomer N1414, Adecaoptomer N1717 (ADEKA), EsACure1001M LAmBerti), Diazonium Compound Publication, Organic Azido Compounds, Ortho-quinonediazides, Various Onium Compounds including Iodium Compounds, Metal Arene Complexes, Transition Metal Complexes Containing Transition Metals such as Luthenium, Aluminate Complexes, 2,4 , 5-Triarylimidazole dimer, carbon tetrabromide, organic halogen compounds, sulfonium complex or oxosulfonium complex, aminoketone oxime ester compound and the like.

Further, as the photopolymerization initiator, a hydrogen abstraction type radical initiator can be used, and specific examples thereof include aromatic ketones such as acetophenone, benzophenone, benzyl, Michler ketone, thioxanthone, and anthraquinone. , Not limited to these. It is common in the art to use these compounds in combination with tertiary amines, specifically trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, p-dimethylaminophenylalkyl. Esters and the like are mentioned, but not limited to these.

Among these, acetophenones, phosphine oxides and the like can be preferably used as the photopolymerization initiator.

The photopolymerization initiator can be used alone or in combination of two or more, and can be arbitrarily mixed and used depending on the characteristics required for the reaction-cured product and the compound to be cured by the active energy ray. When these photopolymerization initiators are used, the amount used is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the active energy ray-curable component including urethane (meth) acrylate (c) and the like. Is preferable.

Further, a sensitizer can be contained. Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal allene complexes, organic ruthenium complexes, Mihiler ketone derivatives, biimidazole derivatives, etc. However, but not limited to these.

The amount of the active energy ray-curable component containing urethane (meth) acrylate (c) and the like is the active energy ray containing (meth) acrylate resin (a), isocyanate (b), urethane (meth) acrylate (c) and the like. The solid content of the curable component is 25 to 49% by mass, more preferably 30 to 40% by mass, based on 100% by mass of the total solid content. When it is 25% by mass or more, chemical resistance and chipping resistance are improved. On the other hand, when it is 50% by mass or less, the balance of the sea-island structure is good and the formability is improved.

<Solvent (s)>
As the solvent (s) used for the protective agent, a known solvent may be appropriately selected and used, and for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate; acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, etc. Ketones such as acetylacetone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; dimethylsulfoxide and dimethylsulfoamide; water and methanol , Ethanol, isopropanol, alcohols such as propylene glycol monomethyl ether-1-methoxy-2-propanol and the like. These may be used alone or in any combination of two or more. In particular, the size of the domain (D) of the present invention can be controlled by the solvent composition, and it is preferable to use ketones in combination with secondary or tertiary alcohols, and the secondary or tertiary alcohols with respect to ketones. It is more preferable that the mass ratio is 1 to 10. By setting the mass ratio in a preferable range, phase separation between the matrix (M) and the domain (D) is promoted, and a desired sea-island structure can be obtained. Secondary or tertiary alcohols have low reactivity with isocyanate curing agents and can be used as a solvent without affecting the curing reaction.

Protective agents include inorganic fillers, organic fillers, fillers, thixotropic agents, anti-aging agents, antioxidants, antistatic agents, flame retardants, thermal conductivity improvers, plasticizers, anti-sags, anti-sags, as needed. Various additives such as stains, preservatives, disinfectants, defoamers, leveling agents, thickeners, pigment dispersants, and silane coupling agents may be further added. Above all, it is preferable to contain an inorganic filler and / or an organic filler for the purpose of forming irregularities on the surface of the surface protective layer to impart a blocking prevention effect, and for the purpose of imparting strength to the surface protective layer to improve scratch resistance. As described above, the concepts of the matrix (M) and the domain (D) in the present invention do not include the inorganic filler and the organic filler.

Specific examples of the inorganic filler include metal oxides such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, and antimony, hydroxides, sulfates, carbonates, silicates, and the like. Examples include fine particles. As a more detailed example, an inorganic substance containing silica, silica gel, aluminum oxide, aluminum hydroxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminosilicate, talc, mica, glass fiber, glass powder and the like. System particles can be mentioned. The inorganic filler may be used alone or in combination of two or more.

Specific examples of the organic filler include polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, polymethylmethacrylate resin, polystyrene resin, polyamide resin, melamine resin, guanamine resin, phenol resin, urea resin, silicone resin, methacrylate resin, and acrylate. Examples thereof include polymer fine particles such as resin, cellulose powder, nitrocellulose powder, wood powder, used paper powder, shell powder, starch and the like. One kind of organic filler may be used, or two or more kinds may be used in combination.

The above-mentioned inorganic filler and organic filler can be contained in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of the (meth) acrylate resin (a). When the content is 0.1 part by mass or more, the above effect can be expected, and when it is 20 parts by mass or less, the moldability is excellent and the transparency is not impaired.

Inorganic fillers and organic fillers can be prepared by simply mixing them with a dispersant, if necessary, to obtain the desired effects. Even better effects can be obtained by mechanically mixing.

<Laminate film for decorative molding and its manufacturing method>
The laminated film for decorative molding of the present invention has a surface protective layer and a base material layer having a specific Martens hardness, and as described above, the surface protective layer has a specific domain (D) and a matrix (M). It presents a sea-island structure with.

<Base layer>
The base material layer is a design layer, a metal layer (including a vapor-deposited film), and an adhesive layer formed on a film that acts as a support or a film that acts as a support by using a paint for imparting design. , A film provided with a polarizing layer or the like.
The film itself that plays a role as a support includes, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polycarbonate film, a polymethylmethacrylate film, a polyamide film, a polyimide film, a polyvinyl chloride film, and a polychloride. Examples thereof include vinylidene film, polyvinyl alcohol film, polystyrene film, polyacrylonitrile film, and the like, and one or more laminated films can be used. In particular, polyethylene terephthalate film, polycarbonate film, and polymethylmethacrylate film are preferable from the viewpoint of transparency and moldability. These films can also be used alone or in a laminated manner. For example, a PMMA / PC film in which polymethylmethacrylate (PMMA) is co-extruded onto a polycarbonate (PC), or a polycarbonate. It is also possible to use a film in which a film and a polyester film are laminated with an adhesive. A film or a combination thereof can be appropriately selected and used depending on the intended use.

The laminated film for decorative molding of the present invention is produced by applying a protective agent on the base material layer and drying it, and at least a part of the (meth) acrylate resin (a) is the isocyanate-based curing agent (b). ), Then the active energy ray is irradiated to cure the active energy ray curable component, and a surface protective layer can be formed. After irradiation with active energy rays, aging can be carried out to further promote the reaction between the (meth) acrylate resin (a) and the isocyanate-based curing agent (b).

When a film having a softening temperature of 60 to 150 ° C., which serves as a support, is used as the base material layer, the elastic modulus of the film decreases in the heated manufacturing process such as drying and aging of the protective agent, resulting in deformation and deformation. May cause dimensional changes, blocking, etc. Therefore, when a film having a low softening temperature is used, a transfer method may be adopted in which the surface protective layer is transferred onto the substrate layer with an adhesive to form the film.
Specifically, first, a protective agent is applied to the release agent-treated surface of the release film, and the solvent is put into a drying oven to volatilize, age, and cure the solvent to obtain a surface protective layer, and then an adhesive. Is applied onto the surface protective layer or the base material layer to form an adhesive layer, and the surface protective layer and the base material layer are bonded to each other via the adhesive layer. The release film may be peeled off after laminating.

As a method of applying the protective agent to the base material layer or the release film, a known method can be used, specifically, comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like. Can be mentioned.

The films used for the release film include polyethylene terephthalate, polybutylene terephthalate, and the like.
Any one of polyester film made of polyester such as polyethylene naphthalate, polyolefin film made of polyolefin such as polyethylene, polypropylene, polymethylpentene, plastic film such as polycarbonate film and polyvinyl acetate film, paper film such as pulp, or these. A laminated body composed of two or more kinds of material layers can be mentioned, and a film having a release agent treated on the film can be used.

In order to obtain the laminated film for decorative molding of the present invention, it is preferable to dry the protective agent at 50 to 200 ° C., and more preferably 70 to 120 ° C. After drying, it is preferable to age for about 10 minutes to 10 days in an environment of room temperature to 50 ° C. in order to complete the curing reaction of the protective agent resin.

A peelable film may be laminated on the other surface of the base material layer on which the surface protective layer is laminated to prevent scratches. In particular, when a polycarbonate-based base material is used as the base material layer, it is preferable to protect the surface of the base material with a peelable film until immediately before use because it is easily scratched.

The thickness of the base material layer is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 50 to 300 μm. Within the above range, the moldability and scratch resistance of the laminated film for decorative molding are improved.

The thickness of the surface protective layer formed on the base material layer is preferably 1 μm to 20 μm, more preferably 3 μm to 10 μm. When it is 1 μm or more, chemical resistance and abrasion resistance are improved, and when it is 20 μm or less, moldability and chipping resistance are improved.

The thickness of the laminated film for decorative molding may be as long as it can smoothly perform insert molding, in-molding, and press molding. It is preferably in the range of 15 to 1000 μm, more preferably in the range of 50 to 500 μm. When it is in a preferable range, the follow-up of unevenness at the time of molding becomes good, and film breakage and wrinkles are less likely to occur during molding.

When the laminated film for decorative molding is subjected to a tensile test at 140 ° C. measured in accordance with JIS K 7161, the surface protective layer may be cracked, the surface protective layer may be peeled off from the base material layer, or the surface protective layer may be formed. The elongation rate until it breaks is preferably 50% to 200%, more preferably 80% to 200%. When it is 200% or less, twisting due to heat during molding can be reduced, and mold marks due to the mold during molding are less likely to remain on the surface protective layer. When it is 50% or more, it has an appropriate rigidity and the moldability is improved. The elongation rate of the laminated film for decorative molding is a numerical value obtained by determining the magnitude of elongation based on the initial state in which the state before the start of the test is set to 0%.

<Decorative molded body>
Next, the decorative molded body of the present invention will be described. The decorative molded body of the present invention is a molded body whose surface is covered with a laminated film for decorative molding, and the material of the coated molded body (hereinafter, also referred to as a decorated body) is not particularly limited. Known materials can be used.
The surface of the decorative molded body using the laminated film for decorative molding of the present invention is excellent in chemical resistance. It is considered that some of the components are microscopically compatible with the matrix component (M) in order to form the domain (D) in the surface protective layer. From the point of view of the ratio of the observed domain (D), all the active energy ray-curable components including the urethane (meth) acrylate (c) compounded and / or the (meth) acrylate having a weight average molecular weight of 400 to 5000 are domains ( This is because it seems that it has not been used for the formation of D).
At the time of molding, the matrix (M) in the surface protective layer is stretched, and the shape of the domain (D) is slightly changed with the stretching, and the orientation along the surface of the decorated body is increased. Will be. As a result, it is considered that high chemical resistance can be exhibited even after molding.

Examples of materials that can be used as decorative bodies include wood, paper, metal, plastic, fiber reinforced plastic, rubber, glass, minerals, clay, etc., and use one type or a combination of two or more types. Can be done.
Examples of plastics include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, epoxy resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, poly (meth) acrylate, polycarbonate, polyamide, and polyimide. , Polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroloethylene and the like, and can be used alone or in combination of two or more.

Examples of the fiber reinforced plastic include carbon fiber reinforced plastic, glass fiber reinforced plastic, aramid fiber reinforced plastic, polyethylene fiber reinforced plastic and the like, and one type or a combination of two or more types can be used.
Examples of the metal include hot-rolled steel, cold-rolled steel, zinc-plated steel, electrozinc-plated steel, hot-dip zinc-plated steel, alloyed hot-dip zinc-plated steel, zinc-alloyed-plated steel, copper-plated steel, and zinc-nickel-plated steel. Zinc-aluminum plated steel, iron-zinc plated steel, aluminum plated steel, aluminum-zinc plated steel, tin plated steel, etc., aluminum, stainless steel, copper, aluminum alloy, electromagnetic steel, etc., one type or two or more types Can be used in combination. Further, an agent layer or the like may be provided on the surface of the metal.

The laminated film for decorative molding and the decorative body of the present invention are integrated by a known integration method, for example, insert molding, in-mold molding, vacuum forming, compressed air molding, TOM molding, press molding and the like. be able to.

Further, for example, after the laminated film for decorative molding of the present invention is premolded into a desired shape, plastic or fiber reinforced plastic is injection-molded so that the laminated film for decorative molding side becomes the outermost layer, and the decorative molding is performed. You can also get a body.
Alternatively, a molded body is obtained from plastic, fiber reinforced plastic, or metal, and the laminated film for decorative molding of the present invention is premolded on the surface of the molded body, or the laminated film for decorative molding is premolded into a desired shape. The molded body can also be obtained by pasting it so that the surface protective layer side is the outermost layer.

In the decorative molded body of the present invention, the surface protective layer side of the laminated film for decorative molding is located on the outermost layer. The laminated film for decorative molding may be provided with a protective film on the surface of the surface protective layer and the surface of the base material layer to prevent scratches that may occur in each process such as coating, drying, aging, and molding integration. .. When the decorative molded body is used, the protective film is peeled off.

The decorative molded body manufactured by using the laminated film for decorative molding of the present invention as a decorative film includes a metal-like or piano black-like instrument panel decoration panel, a shift gate panel, a door trim, an air conditioner operation panel, a car navigation system, and the like. It is used as an interior part of an automobile, or as an exterior part such as an emblem on the front and rear of an automobile, a center ornament of a tire wheel, and a name plate.
In addition to internal and external parts for automobiles, it protects not only exterior materials such as home appliances, smart keys, smartphones, mobile phones, and laptop computers, but also exterior materials such as helmets and suitcases, and LCD screens such as car navigation systems and LCD TVs. It can be suitably used for exterior materials such as protective sheets and power storage devices, sports equipment such as tennis rackets and golf shafts, building materials such as doors and partitions for houses, and wall materials.

<Example>
Hereinafter, embodiments of the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention at all. In the examples, "part" represents "parts by mass" and "%" represents "% by mass".
Further, in the following examples, the molecular weights of the (meth) acrylate resin (a) and the urethane (meth) acrylate (c) are the weight average molecular weights in terms of polystyrene measured by GPC (gel permeation chromatography), and are measuring devices. Is GPC-8020 (manufactured by Tosoh), eluent is tetrahydrofuran, three columns are TSKgelSuperHM-M (manufactured by Tosoh), column temperature is 40 ° C, flow velocity is 0.6 ml / min, sample concentration is 0. It was measured at 3.3% and an injection volume of 10 μL.
In the present specification, the non-volatile content means a value calculated from the mass of the sample after heating / the mass of the sample before heating when 1 g of the sample is heated at 170 ° C. for 10 minutes. However, in the case of a commercially available product, a value calculated based on a method specified by the manufacturer may be adopted.
The acid value was measured by a potentiometric titration method according to JIS K1557-5, and calculated by solid content acid value [mgKOH / g] = acid value [mgKOH / g] ÷ non-volatile content [%].
The hydroxyl value was measured by potentiometric titration by the A method (acetylation method) according to JIS K1557-1, and calculated by solid content hydroxyl value [mgKOH / g] = hydroxyl value [mgKOH / g] ÷ non-volatile content [%]. ..

[Manufacturing Example 1]
100 parts of methyl ethyl ketone (MEK) was charged in a four-necked flask equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, and the temperature was raised while stirring in a nitrogen atmosphere. When the temperature inside the flask reaches 75 ° C., this temperature is maintained as the synthetic temperature, and 76.8 parts of ethyl methacrylate, 23.2 parts of 2-hydroxyethyl methacrylate and 2,2'-azobis (2,4-dimethylvaleronitrile) are maintained. ) (V65) 0.10 part of the mixture was added dropwise over 2 hours. From 1 hour after the completion of monomer dropping, 50 parts of V65: 0.05 part diluted with 20 parts of MEK was divided into 5 parts and added every hour to continue the reaction. From the non-volatile content measurement, the unreacted monomer in the solution was 5% or less. I confirmed that it became. The reaction was terminated by diluting with 40 parts of propylene glycol monomethyl ether and cooling to obtain a (meth) acrylate resin (a-1) solution having a hydroxyl group having a solid content of about 40%. The (meth) acrylate resin (a-1) having a hydroxyl group had a glass transition temperature of 63 ° C., an acid value of 0 mgKOH / g, a hydroxyl group value of 100 mgKOH / g, and Mw: 200,000.

[Manufacturing Examples 2 to 13]
Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and the amount charged were changed to those shown in Table 1, and (meth) acrylate resins having a hydroxyl group (a-2 to a-7, a-9 to a-13). In addition, a solution of a (meth) acrylate resin (a-8) having no hydroxyl group was obtained.
Two-thirds of the polymerization initiator was dissolved in a monomer solution and dropped into a flask, and after the completion of dropping the monomer solution, one-third was dissolved in a solvent and dropped. The total amount is shown in the table.

The symbols in Table 1 are as follows.
EMA: Ethyl Methacrylate tert-BMA: Tertiary Butyl Methacrylate MMA: Methyl Methacrylate HEMA: 2-Hydroxyethyl Methacrylate HPMA: Hydroxypropyl Methacrylate MAA: Methacrylic Acid V65: 2,2'-Azobis (2,4-dimethylvaleronitrile)
MEK: Methyl Ethyl Ketone PGM: Propylene Glycol Monomethyl Ether

Below, the details of the materials used to prepare the surface protective layer are shown below.
<Isocyanate-based curing agent (b)>
B-1 Asahi Kasei Duranate TSE-100 NCO group content: 12.0%

<Active energy ray curable component>
<Urethane (meth) acrylate (c)>
・ C-1 Mw: 400 3 functional ・ c-2 Mw: 1000 3 functional ・ c-3 Mw: 3000 4 functional ・ c-4 Mw: 200 2 functional ・ c-5 Mw: 14000 2 functional ・ c-6 Mitsubishi Chemical UV-7605B Mw: 1100 6-functional c-7 MIWON Miramer PU610 Mw: 1800 6-functional c-8 Mitsubishi Chemical UV-7630B Mw: 2200 6-functional c-9 MIWON Miramer MU9500 Mw: 3200 10-functional c-10 Mitsubishi Chemical Corporation Shikou UV-7610B Mw: 11000 9-functional c-11 MIWON Miramer SC2152 Mw: 20787 15 functional <weight average molecular weight 400-5000 (meta) Acrylate>
・ C-12 MIWON Miramer PE210 (bisphenol A epoxy diacrylate) Mw: 520 bifunctional ・ c-13 MIWON Miramer EA2280 (modified epoxy diacrylate) Mw: 1580 2 functional ・ c-14 MIWON Miramer PS420 (Polyester acrylate) Mw: 3000 4-functional, c-15 MIWON Miramer PE230 (aliphatic epoxy diacrylate) Mw: 420 2-functional

<Light initiator>
-Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone

<Base layer>
・ F-1 S000 manufactured by Sumika Acrylic Sales Co., Ltd. (polymethylmethacrylate film, thickness 125 μm)
・ F-2 Mitsubishi Gas Chemical Company's Iupiron film FE-2000 (polycarbonate film, thickness 200 μm)
・ F-3 Idemitsu Unitech Pure Thermo AG-301X (polypropylene film, thickness 300 μm)

<Manufacturing of filler dispersion>
[Manufacturing of dispersion (1)]
25 parts by mass of synthetic spherical silica SO-C5 manufactured by Admatex (average particle size 1.3 to 1.7 μm according to the manufacturer's data), 35 parts by mass of methyl ethyl ketone, and 30 parts by mass of 3-methoxy-1-butanol are mixed and dispersed. After stirring, dispersion treatment was performed with a sand mill to prepare a dispersion (1) having a non-volatile content of about 25%. The D50 particle size of the oxide in the obtained dispersion was 1.6 μm. The D50 particle size was measured using "Nanotrack UPA" manufactured by Nikkiso Co., Ltd.

[Manufacturing of dispersion (2)]
Sumitomo Chemical Co., Ltd. Aluminum oxide (average particle size 150 nm) 25 parts by mass, methyl ethyl ketone 35 parts by mass, 3-methoxy-1-butanol 30 parts by mass are mixed, and after stirring with a disper, dispersion treatment is performed with a sand mill to obtain a non-volatile content of about 25. % Dispersion (2) was prepared. The D50 particle size of the metal oxide in the obtained metal oxide dispersion was 150 nm. The D50 particle size was measured using "Nanotrack UPA" manufactured by Nikkiso Co., Ltd.

[Manufacturing of dispersion (3)]
Synthetic spherical silica SO-C5 manufactured by Admatex was manufactured and dispersed in the same manner as the dispersion (1) except that it was changed to "Epostal FS" (melamine resin, average primary particle size: 200 nm) manufactured by Nippon Shokubai. Obtained body (3). The D50 particle size in the obtained filler dispersion was 200 nm.

[Manufacturing of dispersion (4)]
Manufactured in the same manner as the dispersion (1) except that the synthetic spherical silica SO-C5 manufactured by Admatex was changed to "MX-80H3wT" manufactured by Soken Chemical Co., Ltd. (acrylic rate crosslinked product, average primary particle size: 800 nm). This was performed to obtain a dispersion (4). The D50 particle size of the metal oxide in the obtained metal oxide dispersion was 800 nm.

<< Preparation and evaluation of protective agents and laminated films for decorative molding >>
[Example 1]
<Making protective agent>
(Meta) acrylate resin (a-1) solution with a solid content of about 40%: 100 parts, isocyanate curing agent (b-1): 27.5 parts, urethane (meth) acrylate (c-1): 22.5 parts , Photopolymerization initiator corresponding to 5 parts with respect to 100 parts of (c-1): Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone 1.1 Parts, 8 parts of the filler dispersion (1) and 213.7 parts of methyl ethyl ketone (MEK) were stirred and mixed with a disper to obtain a protective agent (X-1) having a non-volatile content of 25%.

<Manufacturing of laminated film Y-1 for decorative molding>
A protective agent (X-1) was applied to the base material layer (F-1) using a bar coater, and dried in an oven at 100 ° C. for 2 minutes to obtain a coating film having a film thickness of 5 μm. After irradiating the coating film with ultraviolet rays at a conveyor speed of 5 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² , 2 lights) (integrated light amount 1000 mJ / cm ² ), the temperature is 40 ° C. It was stored (aged) in an oven for 7 days, and the unreacted product of the (meth) acrylate resin (a-1) and the curing agent (b-1) was reacted to form a surface protective layer. This is referred to as a decorative molding laminated film (Y-1).
With respect to the obtained laminated film for decorative molding before molding, the martens hardness, confirmation of the sea-island structure by the difference in elastic modulus, elongation rate, chipping resistance, scratch resistance, chemical resistance, etc. are evaluated according to the method described later. At the same time, a decorative molded body was produced using the laminated film for decorative molding, and the moldability was evaluated, and the chemical resistance and the like of the produced decorative molded body were evaluated.

<Evaluation of transparency (haze)>
Instead of the base material layer (F-1), the surface protective layer was similarly applied to the peeled surface of the release film (PET film TN-100 manufactured by Toyobo Co., Ltd.) except that the protective agent (X-1) was applied. Formed.
A surface protective layer was isolated from the release film, and the haze value was measured using a haze meter NDH-2000 (manufactured by Tokyo Denshoku Co., Ltd.).

[Examples 2 to 5]
As shown in Table 2, a protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated in the same manner as in Example 1 except that the blending amount of the active energy ray-curable component was changed. ..

[Examples 6-9, 27-36]
As shown in Tables 2 and 4, a protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated in the same manner as in Example 1 except that the types of the active energy ray-curable components were changed. bottom.

[Examples 10 to 12]
As shown in Table 2, the protective agent, the laminated film for decorative molding, and the transparency are the same as in Example 1 except that the blending amounts of the isocyanate-based curing agent (b) and the active energy ray-curable component are changed. An evaluation sample was created and evaluated.

[Examples 13 to 14]
The same as in Example 1 except that the protective agent (X-1) was used and the thickness of the surface protective layer was changed as shown in Table 2, the protective agent, the laminated film for decorative molding, and the sample for transparency evaluation were used. Was created and evaluated.

[Examples 15 to 24]
As shown in Table 3, instead of the (meth) acrylate resin (a-1) solution, the (meth) acrylate resin (a-2) to (a-10) solutions are used, and the isocyanate-based curing agent (b) is used. A protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated in the same manner as in Example 1 except that the blending amount of the active energy ray-curable component was changed.

[Examples 25 to 26]
As shown in Table 3, the same as in Example 1 except that the protective agent (X-3) was used and the base material layers F-2 and F-3 were used instead of the base material layer F-1. , Protective agent, laminated film for decorative molding and sample for transparency evaluation were prepared and evaluated.

[Comparative Examples 1 to 4]
As shown in Table 5, the same as in Example 1 except that the active energy ray-curable component was not blended and the filler dispersions (1) to (4) were blended in place of the filler dispersion (1). Then, a protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated.
An attempt was made to confirm the sea-island structure due to the difference in elastic modulus according to the method described later, but it could not be confirmed.

[Comparative Example 5]
As shown in Table 5, a large amount of the isocyanate-based curing agent b-1 was added to the (meth) acrylate resin (a-1) solution, and the amount of the active energy ray-curable component was changed. In the same manner as in Example 1, a protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated.

[Comparative Example 6]
As shown in Table 5, the same as in Example 1 except that the (meth) acrylate resin (a-1) solution was mixed with a large amount of the isocyanate-based curing agent b-1 and the active energy ray-curable component. Then, a protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated.

[Comparative Examples 7-9]
As shown in Table 5, instead of the (meth) acrylate resin (a-1) solution, the (meth) acrylate resin (a-11) to (a-13) solutions are used, and the isocyanate-based curing agent (b) is used. A protective agent, a laminated film for decorative molding, and a sample for transparency evaluation were prepared and evaluated in the same manner as in Example 1 except that the blending amount of the active energy ray-curable component was changed. Since the (meth) acrylate resin (a-3) does not have a hydroxyl group, the column of NCO / OH in Table 4 is set to "-".
An attempt was made to confirm the sea-island structure due to the difference in elastic modulus according to the method described later, but it could not be confirmed.

[Comparative Example 10]
As shown in Table 5, the protective agent and the laminated film for decorative molding are the same as in Example 1 except that neither the (meth) acrylate resin (a-1) solution nor the isocyanate-based curing agent b-1 is used. And a sample for transparency evaluation was prepared and evaluated.
An attempt was made to confirm the sea-island structure due to the difference in elastic modulus according to the method described later, but it could not be confirmed.

[Comparative Example 11]
As shown in Table 5, the protective agent, the laminated film for decorative molding, and the transparency evaluation were carried out in the same manner as in Example 1 except that the isocyanate-based curing agent b-1 and the active energy ray-curable component were not blended. Samples were created and evaluated.
An attempt was made to confirm the sea-island structure due to the difference in elastic modulus according to the method described later, but it could not be confirmed.

<Evaluation of Martens hardness>
Using the ultra-micro hardness tester "Fisherscope H-100C" manufactured by Fisher Instruments, push the Vikkers indenter (square pyramid) with a force of 3 mN and hold it for 5 seconds on the surface protective layer side of the laminated film for decorative molding. The value was read after it was made to. The pushing depth of the terminal is 0.8 μm.

<Confirmation of sea island structure>
<Measurement of Kulmvine diameter>
A laminated film for decorative molding is cut into 1.5 cm squares, sandwiched between two slide glasses on which thermosetting epoxy resin (G2 manufactured by Gatan) is hung, and the resin is placed on a hot plate at 120 ° C. for 5 minutes. Was cured.
Cut the cured sample into 5 mm squares with a razor, install it on the sample table of the cross section polisher device (SM-09010 manufactured by JEOL Ltd.), set the acceleration voltage of the argon ion beam to 5 kV, and make a cross section for observation. Made.
With respect to the cross section, an SPM device (Oxford Instruments MFP-3D, cantilever: AC-160TS, dynamic measurement mode, Setpoint: 1.4 ∨, Target Elastic: 2 ∨) was used with respect to the cross section of the surface protective layer. Measurements were made in a range of 2 μm × 2 μm at arbitrary three locations, and elastic modulus images and unevenness images (height difference images) were obtained.
For the obtained elastic modulus image (FIG. 1), image analysis software [Mac-View Ver. 4] was taken in, all the domains (D) visible from the image were selected in the manual mode, analysis was performed, and the Kulmvine diameters of all the selected domains (D) were calculated and used as the average value. (Fig. 2)

<Ratio of domain (D)>
If an island with a height difference of more than 5 nm is found in the uneven image (height difference image) obtained by using the SPM device, the area of the island detected by the height difference is calculated from the area of 2 μm × 2 μm. Subtract, and use this value as the reference area.
From the elastic modulus image obtained for the same observation area, all the domains (D) that can be confirmed are selected in the manual mode in the same manner as the measurement of the Kulmvine diameter, and automatic analysis is performed to calculate the total area of the domain (D). Using the reference area as the denominator, the ratio of any one domain (D) is calculated. The observation area was changed, the ratio of the domain (D) was obtained in the range of 2 μm × 2 μm at any three points in total, and the average value was calculated.

<Measurement of elongation>
A laminated film for decorative molding was cut into a width of 10 mm and a length of 20 mm, and a tensile test was performed under the following conditions.
Tensile tester: "Desktop precision universal tester AGS-X" (manufactured by Shimadzu Corporation)
Heating furnace: "Constant temperature tank TCE-N300" (manufactured by Shimadzu Corporation)
Sample width: 10 mm
Temperature: 140 ° C
Tensile speed: 30 mm / min
Distance between chucks: 10 mm
The elongation rate was calculated from the distance between the chucks when an appearance abnormality occurred such as cracks in the surface protective layer, peeling of the surface protective layer from the base material layer, or breakage of the surface protective layer. If the distance between the chucks when the appearance is abnormal is 20 mm, the 10 mm laminated film for decorative molding is further stretched by 10 mm, so the elongation rate is calculated to be 100%.

<Evaluation of chipping resistance>
Cut the laminated film for decorative molding into 3 cm (length) x 5 cm (width), face the base material layer side to the stainless steel plate (4 cm in length x 10 cm in width), and fix the end with double-sided tape with a width of 5 mm. Using (manufactured by Co., Ltd.), 100 g of JIS test silica sand sold by the Japan Powder Association, with an air pressure of 3.0 kg / cm ² from a distance of 30 cm, at an angle of 23 ° C and 90 degrees. It collided with the surface protective layer. After the collision, the laminated film for decorative molding was washed with water and dried, and then the surface of the surface protective layer was visually evaluated for whitening under sunlight, and the substrate layer was exposed at a magnification of 50 times using a microscope. The presence or absence of was observed. S was evaluated as the best, A was good, B was general-purpose usable, C was practical depending on the usage environment, and D was not practical.
S: Although there are scratches, there is no or very little whitening due to scratches.
A: Partially obvious whitening.
B: Overall clear whitening.
C: There is a clear whitening on the whole, and a part of the base material layer is exposed.
D: The base material layer is exposed as a whole.

<Evaluation of abrasion resistance>
Cut the laminated film for decorative molding into a length of 10 cm and a width of 5 cm, and rub steel wool (# 0000) on the surface of the surface protective layer twice with a load of 100 g. It was evaluated from the change (ΔHAZE). S is the best, A is excellent, B is good, C is usable, and D is impractical. The evaluation criteria are as follows.
S: Less than 5 scratches A: 5 or more scratches and less than 10 scratches B: 10 or more scratches and less than 0.5% ΔHAZE C: 10 or more scratches and 0.5% or more ΔHAZE 3. Less than 0% D: 10 or more scratches and 3.0% or more of ΔHAZE

<Evaluation of chemical resistance>
0.5 g of sunscreen cream (NeurogenAultrASherDRY-TOUCHSUNSCREENSPF55 (manufactured by Johnson & Johnson)) was applied to the surface of the surface protective layer of the laminated film for decorative molding, and the mixture was allowed to stand at 80 ° C. for 4 hours. After leaving it to stand, the sunscreen cream was rinsed with water to remove water, and then the appearance of a circle having a diameter of 3 cm centered on the portion where the sunscreen cream was dropped was visually observed.
In addition, SA is preferably used as a protective agent for imparting chemical resistance, B and C can be put into practical use depending on the usage environment of the molded product, and D is not suitable for practical use. The evaluation criteria are as follows.
S: No appearance defects are seen.
A: Traces of the coated area can be seen, but no whitening or surface roughness is observed.
B: Whitening and surface roughness are seen in a part of the coated part.
C: Slight whitening and surface roughness are seen in the entire coated area.
D: Significant whitening and surface roughness are observed throughout the coated area.

<Evaluation of moldability>
[Making decorative molded body]
Placed in a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd., NGF0406-T) in the direction in which the base material layer of the laminated film for decorative molding and the decorative molded body are in contact with each other, and molding is performed under the following conditions. A decorative molded body was produced.
As shown below, three types of aluminum rectangular parallelepipeds with the same area but different heights were used as the decorative molded body, and the laminated film for decorative molding was adhered to the surface of the rectangular parallelepiped 5 cm in length × 5 cm in width. In this state, the decorative molding laminated film was stretched mainly in the height direction, and the five surfaces of the rectangular parallelepiped were covered with the decorative molding laminated film. In the obtained decorative molded body, the surface protective layer is located on the outermost surface on the convex surface side.
Rectangular parallelepiped (1): length 5 cm x width 5 cm x height 1 cm
Rectangular parallelepiped (2): length 5 cm x width 5 cm x height 0.75 cm
Rectangular parallelepiped (3): length 5 cm x width 5 cm x height 0.5 cm

Molding temperature: 120 ° C
Compressed air pressure: 300kPA
Compressed air time: 10 seconds

Based on the presence or absence of cracks in the surface protective layer on the side surface (height portion) of the decorative molded body and the presence or absence of damage to the base material layer, evaluation was made according to the following criteria.
S: In any of the rectangular parallelepipeds (1) to (3), the surface protective layer is not cracked and the base material layer is not damaged.
A: In the case of the rectangular parallelepiped (1), cracks occur in the surface protection layer, but the base material layer is not damaged. In the case of rectangular parallelepipeds (2) and (3), the surface protective layer has no cracks and the base material layer is not damaged.
B: In the case of rectangular parallelepipeds (1) and (2), cracks occur in the surface protective layer, but the base material layer is not damaged. In the case of the rectangular parallelepiped (3), the surface protective layer has no cracks and the base material layer is not damaged.
C: In all cases of rectangular parallelepipeds (1) to (3), cracks occur on a part of the four side surfaces of the surface protective layer, but the base material layer is not damaged.
D: In all cases of rectangular parallelepipeds (1) to (3), cracks occur over the entire four sides of the surface protective layer, or the base material layer is torn.
It should be noted that S, A, and B are easy to mold, C can be put into practical use depending on the shape of the object to be molded, and D is not suitable for practical use.

<Evaluation of chemical resistance of decorative molded body>
Using the rectangular parallelepiped (1) created in the formability evaluation, apply sunscreen cream to the surface of the decorative molded body 5 cm in length × 5 cm in width, and evaluate in the same way as in the case of evaluating the chemical resistance of the laminated film for decorative molding. bottom.

As shown in the examples of Tables 2, 3 and 4, the Martens hardness is in a specific range, and the surface protective layer forming components are partially incompatible with each other to form a domain (D), whereby high transparency is achieved. It has excellent scratch resistance, chemical resistance, extensibility, and chipping resistance while maintaining its properties, and showed performance within the practical range in all evaluation items.
If the Martens hardness and the Kulmvine diameter of the domain (D) and their ratio are within a specific range, the abrasion resistance, moldability, chipping resistance, and chemical resistance are within the practical range, and the chemical resistance of the molded body is high. Retention or improvement was seen.
Examples 2 to 7, 10, 15 to 18, 27 to 30, and 33 to 36, which are in a particularly preferable range, exhibited high performance in terms of chemical resistance and chipping resistance.

Comparative Examples 1 to 4 and 7 to 11 in which the sea-island structure was not recognized by the elastic modulus image were particularly out of the practical range in chemical resistance and chipping resistance, and even if the sea-island structure was recognized by the elastic modulus image, the domain ( Even in Comparative Examples 5 and 6 in which the ratio of D) was out of the range, various performances were out of the practical range.

Claims (6)

A laminated film for decorative molding having a surface protective layer and a base material layer.
The Martens hardness measured from the surface protective layer side of the laminated film for decorative molding is 100 to 300 N / mm ² .
The surface protective layer exhibits a sea-island structure having a domain (D) and a matrix (M), and the matrix (M) has a hydroxyl group and does not have a photocurable functional group (meth) acrylate resin (a) and light. It is a cured product with an isocyanate-based curing agent (b) having no curable functional group, and the domain (D) is a urethane (meth) acrylate (c) and / or a (meth) acrylate having a weight average molecular weight of 400 to 5000. It is a cured product of a polyfunctional active energy ray-curable component containing
The Kulmvine diameter of the domain (D) is 0.05 to 0.5 μm, and the diameter is 0.05 to 0.5 μm.
The ratio D: M between the domain (D) and the matrix (M) is 5 to 44: 95 to 56.
Laminated film for decorative molding. The laminated film for decorative molding according to claim 1 , wherein the elongation rate of the surface protective layer of the laminated film for decorative molding in a tensile test at 140 ° C. is 50 to 200%. The laminated film for decorative molding according to claim 1 or 2 , wherein the haze specified by JIS K 7361 of the surface protective layer is 5% or less. A (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group, an isocyanate-based curing agent (b) having no photocurable functional group, a urethane (meth) acrylate (c) and / Alternatively, a protective agent containing an active energy ray-curable component containing (meth) acrylate having a weight average molecular weight of 400 to 5000 and an organic solvent can be used.
After coating on the base material layer, drying, and reacting at least a part of the (meth) acrylate resin (a) with the isocyanate-based curing agent (b),
Irradiate with active energy rays to cure the active energy ray-curable component to form a surface protective layer.
The method for producing a laminated film for decorative molding according to any one of claims 1 to 3 . A (meth) acrylate resin (a) having a hydroxyl group and no photocurable functional group, an isocyanate-based curing agent (b) having no photocurable functional group, a urethane (meth) acrylate (c) and / Alternatively, a protective agent containing an active energy ray-curable component containing (meth) acrylate having a weight average molecular weight of 400 to 5000 and an organic solvent can be used.
After coating on a release film, drying, and reacting at least a part of the (meth) acrylate resin (a) with the isocyanate-based curing agent (b),
Irradiate with active energy rays to cure the active energy ray-curable component to form a surface protective layer.
Next, the surface protective layer is attached to the base material layer via the adhesive layer.
The method for producing a laminated film for decorative molding according to any one of claims 1 to 3 . A decorative molded body comprising the decorated body and the laminated film for decorative molding according to any one of claims 1 to 3 , which covers at least a part of the decorated body.

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