Resin composition and laminate

Abstract

To provide a resin composition which is excellent in printability, and is excellent in glossiness, weather resistance and adhesion when being formed into a cured product, and a laminate having a resin layer containing a cured product of the resin composition.SOLUTION: A resin composition contains a resin (A) containing 40-90 mass% of a constitutional unit derived from an aromatic group-containing monomer having 9 or more carbon atoms, and a (meth)acrylic resin (B) containing no constitutional unit derived from the aromatic group-containing monomer, wherein the resin (B) has a glass transition temperature of 40-70°C, and a mass ratio (resin (A) / resin (B)) of the resin (A) to the resin (B) is 90 / 10 to 10 / 90.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a laminate. [Background technology]

[0002] A conventional method for decorating the surface of an exterior part of a motorcycle or the like involves attaching a decorative film or decorative sheet to the surface of the exterior part. A protective clear layer is provided on the outermost layer of the decorative film or decorative sheet, which contributes to improving the appearance of the decorative film or decorative sheet (see, for example, Patent Document 1). In recent years, there has been a demand for high added value in decorative films and decorative sheets. As an example, there is a demand for high gloss protective clear layers, which greatly contribute to the appearance. However, a high gloss clear layer cannot be obtained with a clear ink that uses a general acrylic resin. One method for obtaining a high gloss clear layer is to use a high refractive index resin, and for example, the use of polystyrene, a high refractive index material, to obtain a high gloss clear layer has been considered (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-048264 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-348116 Summary of the Invention [Problem to be solved by the invention]

[0004] From the perspective of decorative properties, the protective clear layer is required to have excellent printability during production, and since it is located on the outermost surface, it is also required to have excellent weather resistance. However, it has been revealed that the styrene-based resin-containing clear ink described in Patent Document 2 has poor printability because air bubbles are observed on the surface during printing. In addition, styrene-based resin-containing clear inks have poor weather resistance compared to general acrylic resin-containing clear inks. Furthermore, it has been revealed that clear inks with a high styrene-based resin content are prone to poor adhesion at the interface with the underlying colored ink layer when used, for example, as a protective clear layer. However, there is room for improvement in glossiness of general acrylic resin-containing clear inks.

[0005] The present invention aims to provide a resin composition that has excellent printability and, when cured, has excellent gloss, weather resistance, and adhesion, and a laminate having a resin layer containing a cured product of the resin composition. [Means for solving the problem]

[0006] That is, the present invention includes the following aspects. <1> The resin (A) contains 40% by mass to 90% by mass of structural units derived from aromatic-containing monomers having 9 or more carbon atoms, and a (meth)acrylic resin (B) does not contain structural units derived from aromatic-containing monomers, The resin (B) has a glass transition temperature of 40°C to 70°C, A resin composition, wherein the mass ratio of the resin (A) to the resin (B) (resin (A) / resin (B)) is 90 / 10 to 10 / 90. <2> the mass ratio of the resin (A) to the resin (B) (resin (A) / resin (B)) is 80 / 20 to 80 / 20; <1> The resin composition according to claim 1. <3> The aromatic-containing monomer is a (meth)acrylate-based aromatic-containing monomer. <1> or <2> The resin composition according to claim 1. <4> The aromatic-containing monomer is a (meth)acrylate-based aromatic-containing monomer having a benzyl group. <1> ~ <3> The resin composition according to any one of the above. <5> a substrate and a film laminated on the substrate <1> ~ <4> and a resin layer containing a cured product of the resin composition according to any one of the above items. [Effects of the Invention]

[0007] According to the present invention, there are provided a resin composition which has excellent printability and, when cured, has excellent gloss, weather resistance, and adhesion, and a laminate having a resin layer containing a cured product of the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this disclosure, numerical ranges indicated using "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, unless otherwise specified, the amount of each component in a composition is expressed as the total amount of multiple types of substances when each component contains multiple types of substances. In the present disclosure, (meth)acrylic means one or both of acrylic and methacrylic, and (meth)acrylate means one or both of acrylate and methacrylate.

[0009] <Resin composition> The resin composition of the present disclosure comprises a resin (A) containing 40% by mass to 90% by mass of structural units derived from an aromatic-containing monomer having 9 or more carbon atoms, and a (meth)acrylic resin (B) containing no structural units derived from an aromatic-containing monomer. The resin (B) has a glass transition temperature of 40 to 70°C, and the mass ratio of the resin (A) to the resin (B) (resin (A) / resin (B)) is 90 / 10 to 10 / 90.

[0010] As a result of investigations by the present inventors, it has become clear that the resin composition having the above-mentioned constitution has excellent printability, and when made into a cured product, has excellent gloss, weather resistance and adhesion. The reason why the resin composition of the present disclosure has excellent gloss when cured is thought to be that the aromatic-containing monomer is a high refractive index monomer like styrene. Furthermore, a polymer obtained from the high refractive index monomer produces a high refractive index resin. It has been found that when the aromatic-containing monomer has 9 or more carbon atoms, the resin composition containing resin (A) has better printability than a resin composition containing a styrene-based resin, and also has excellent weather resistance when cured.

[0011] Furthermore, as mentioned above, clear inks containing a high proportion of styrene-based resin to enhance gloss tend to have poor adhesion at the interface with the underlying colored ink layer when used, for example, as a protective clear layer. However, it has been found that the adhesion to the underlying colored ink layer can be improved by using resin (B) that does not contain structural units derived from aromatic-containing monomers and has a glass transition temperature (Tg) of 40°C to 70°C in combination, and by setting the mass ratio of resin (A) to resin (B) (resin (A) / resin (B)) to 90 / 10 to 10 / 90.

[0012] Resin (A) (aromatic-containing monomers with 9 or more carbon atoms) Resin (A) has a structural unit derived from an aromatic-containing monomer having 9 or more carbon atoms. From the viewpoint of copolymerizability with other monomers, the number of carbon atoms in the aromatic-containing monomer is preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less. The aromatic-containing monomer having 9 or more carbon atoms is preferably a (meth)acrylate-based aromatic-containing monomer. When the aromatic-containing monomer is a (meth)acrylate-based aromatic-containing monomer, transparency tends to be improved. Improved transparency also improves gloss. Furthermore, the (meth)acrylate aromatic-containing monomer preferably has a benzyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, or an anthracenyl group, and from the viewpoint of printability, it is more preferable that the (meth)acrylate aromatic-containing monomer has a benzyl group. These aromatic-containing monomers having 9 or more carbon atoms may be used alone or in combination of two or more.

[0013] Resin (A) contains 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more of structural units derived from aromatic-containing monomers having 9 or more carbon atoms. Resin (A) may contain 60% by mass or more, 70% by mass or more, 80% by mass or more, or 85% by mass or more of structural units derived from aromatic-containing monomers having 9 or more carbon atoms. When resin (A) contains 40% by mass or more of structural units derived from aromatic-containing monomers having 9 or more carbon atoms, the gloss of the cured product is excellent. The resin (A) also contains 90% by mass or less of structural units derived from aromatic-containing monomers having 9 or more carbon atoms. When the content of structural units derived from aromatic-containing monomers having 9 or more carbon atoms in the resin (A) is 90% by mass or less, the resin exhibits excellent polymerizability during production. The content of structural units derived from aromatic-containing monomers having 9 or more carbon atoms in the resin (A) is 40% by mass to 90% by mass, preferably 45% by mass to 90% by mass, and more preferably 50% by mass to 90% by mass.

[0014] (Other monomers) The resin (A) may further have a structural unit derived from a monomer other than the aromatic-containing monomer having at least 9 carbon atoms. The other monomer may be used alone or in combination of two or more types. Examples of other monomers include carboxyl group-containing monomers and hydroxyl group-containing monomers. When the resin (A) has at least one of a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer, the resin (A) has excellent curability. The carboxyl group-containing monomer and the hydroxyl group-containing monomer are each preferably a (meth)acrylic monomer.

[0015] Examples of (meth)acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-methyl-3-hydroxybutyl (meth)acrylate, 1,3-dimethyl-3-hydroxybutyl (meth)acrylate, 2,2,4-trimethyl-3-hydroxypentyl (meth)acrylate, 2-ethyl-3-hydroxyhexyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, and pentaerythritol tri(meth)acrylate. Examples of the (meth)acrylic monomer having a carboxy group include (meth)acrylic acid.

[0016] When resin (A) has at least one of a carboxyl group-containing monomer-derived structural unit and a hydroxyl group-containing monomer-derived structural unit, the total content of the carboxyl group-containing monomer-derived structural unit and the hydroxyl group-containing monomer-derived structural unit in resin (A) may be 5% by mass or more, or may be 10% by mass or more. When this content is 5% by mass or more, the curability, weather resistance, and chemical resistance tend to be excellent. Furthermore, the total content of structural units derived from carboxyl group-containing monomers and structural units derived from hydroxyl group-containing monomers in resin (A) may be 20% by mass or less, or 15% by mass or less. When this content is 20% by mass or less, the gloss of the cured product tends to be excellent. The total content of the structural units derived from carboxyl group-containing monomers and the structural units derived from hydroxyl group-containing monomers in the resin (A) may be 5 to 20% by mass, or 10 to 20% by mass.

[0017] Furthermore, alkyl (meth)acrylate monomers may be used as other monomers. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate may be linear, branched, or cyclic.

[0018] From the viewpoint of glossiness when formed into a cured product, the content of structural units derived from alkyl (meth)acrylate monomers in the resin (A) is preferably 0% by mass to 10% by mass, and more preferably 0% by mass to 5% by mass.

[0019] (glass transition temperature) The glass transition temperature of the resin (A) is preferably at least 30° C., and more preferably at least 35° C. When the glass transition temperature of the resin (A) is at least 30° C., the printability tends to be excellent. The glass transition temperature of the resin (A) is preferably 75° C. or lower, more preferably 70° C. or lower, more preferably 60° C. or lower, and particularly preferably 50° C. or lower. When the glass transition temperature of the resin (A) is 75° C. or lower, tack tends to be suppressed when formed into a laminate, and blocking resistance tends to be improved. The glass transition temperature of the resin (A) is preferably 30°C to 75°C. The glass transition temperature of the resin (A) can be measured by a dynamic viscoelasticity measuring device.

[0020] (molecular weight) The weight-average molecular weight of the resin (A) is preferably at least 5,000, more preferably at least 7,000, and even more preferably at least 10,000. When the weight-average molecular weight of the resin (A) is at least 5,000, the resin composition tends to have an appropriate viscosity and excellent printability. The weight average molecular weight of the resin (A) is preferably not more than 30,000, more preferably not more than 25,000, and may be not more than 20,000. When the weight average molecular weight of the resin (A) is not more than 30,000, the resin composition tends to have an appropriate viscosity and excellent printability. The weight average molecular weight of the resin (A) is preferably 5,000 to 30,000.

[0021] The weight-average molecular weight of resin (A) can be determined by gel permeation chromatography using a standard polystyrene conversion method. More specifically, the weight-average molecular weight can be determined using a Tosoh Corporation "HLC-8220" GPC analysis system, two Tosoh Corporation "TSKgel Super Multipore HZ-H" columns connected in series, a differential refractometer (RI) built into the GPC analysis system as a detector, tetrahydrofuran as the mobile phase, a flow rate of 0.35 mL / min, and a column temperature of 40°C.

[0022] [Resin (B)] Resin (B) is not particularly limited as long as it is (meth)acrylic, does not contain structural units derived from aromatic-containing monomers, and has a glass transition temperature of 40°C to 70°C. When the glass transition temperature of resin (B) is 70°C or lower, the cured product has excellent adhesion. When the glass transition temperature of resin (B) is 40°C or higher, the plate release during screen printing is good, resulting in excellent printability.

[0023] The glass transition temperature of the resin (B) is preferably 41° C. or higher. The glass transition temperature of the resin (B) is preferably 68° C. or lower, and more preferably 66° C. or lower. The glass transition temperature of the resin (B) can be measured by a dynamic viscoelasticity measuring device.

[0024] Resin (B) does not contain a structural unit derived from an aromatic-containing monomer, and may be composed of a structural unit derived from a (meth)acrylic monomer, and examples of the (meth)acrylic monomer include a (meth)acrylic monomer having a carboxy group, a (meth)acrylic monomer having a hydroxyl group, and an alkyl (meth)acrylate monomer. The (meth)acrylic monomer having a carboxy group, the (meth)acrylic monomer having a hydroxyl group, and the alkyl (meth)acrylate monomer in resin (B) may be the same as those described for resin (A).

[0025] The total content of the structural units derived from carboxyl group-containing monomers and the structural units derived from hydroxyl group-containing monomers in the resin (B) may be 5% by mass or more, or may be 10% by mass or more. When this content is 5% by mass or more, the resin (B) tends to have excellent curability. Furthermore, the total content of structural units derived from carboxyl group-containing monomers and structural units derived from hydroxyl group-containing monomers in resin (B) may be 20% by mass or less, or 15% by mass or less. When this content is 20% by mass or less, the curability tends to be excellent, and the weather resistance and chemical resistance of the cured product tend to be excellent. The total content of the structural units derived from carboxyl group-containing monomers and the structural units derived from hydroxyl group-containing monomers in the resin (B) may be 5 to 20% by mass, or 10 to 20% by mass.

[0026] The content of structural units derived from alkyl (meth)acrylate monomers in resin (B) is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. Resin (B) may contain structural units derived from alkyl (meth)acrylate monomers in an amount of 70% by mass or more, 80% by mass or more, or 85% by mass or more. When resin (B) contains structural units derived from alkyl (meth)acrylate monomers in an amount of 40% by mass or more, the cured product exhibits excellent adhesion. Furthermore, the resin (B) may contain structural units derived from alkyl (meth)acrylate monomers in an amount of 95% by mass or less, or 90% by mass or less. The content of structural units derived from alkyl (meth)acrylate monomers in the resin (B) is preferably 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.

[0027] The weight average molecular weight of resin (B) is preferably 1,000 or more, more preferably 3,000 or more, and may be 5,000 or more, or even 7,000 or more. When the weight average molecular weight of resin (B) is 1,000 or more, the resin composition tends to have an appropriate viscosity and excellent printability. The weight average molecular weight of resin (B) is preferably 25,000 or less, more preferably 22,000 or less, and may be 20,000 or less, or may be 18,000 or less. When the weight average molecular weight of resin (B) is 25,000 or less, the resin composition tends to have an appropriate viscosity and excellent printability. The weight average molecular weight of the resin (B) is preferably 1,000 to 25,000. The weight average molecular weight of the resin (B) can be measured in the same manner as the weight average molecular weight of the resin (A).

[0028] [Resin (A) and Resin (B)] (mass ratio) In the resin composition of the present disclosure, the mass ratio of resin (A) to resin (B) (resin (A) / resin (B)) is 90 / 10 to 10 / 90. When the mass ratio of resin (A) to resin (B) is 10 or more, the gloss is excellent. When the mass ratio of resin (A) to resin (B) is 90 or less, the adhesion is excellent. Resin (A) / resin (B) is preferably 85 / 15 to 15 / 85, more preferably 80 / 20 to 20 / 80, and even more preferably 80 / 20 to 40 / 60.

[0029] [Other resins] The resin composition of the present disclosure may contain other resins in addition to resin (A) and resin (B). Examples of other resins include resins known in the art. However, from the viewpoint of effectively achieving the effects of the present invention, the proportion of other resins in the entire resin is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0030] In other words, the total content of resin (A) and resin (B) in the entire resin is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0031] [Other ingredients] The resin composition of the present disclosure may contain components other than the resin, such as a crosslinking agent, a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, a surfactant, a colorant, a metallic pigment, and a filler.

[0032] (Crosslinking agent) The crosslinking agent is not particularly limited, but is preferably a polymer of a compound having two or more isocyanate groups in one molecule. Examples of compounds having two or more isocyanate groups in one molecule include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI) and their hydrogenated products, diphenylmethane diisocyanate, hexamethylene diisocyanate (HMDI), and isophorone diisocyanate. Among these, HMDI is preferred from the viewpoint of suppressing yellowing. The crosslinking agent may be used alone or in combination of two or more types.

[0033] When a crosslinking agent is used, the content of the crosslinking agent in the resin composition is preferably an amount such that the crosslinkable groups in the crosslinking agent are 0.8 to 1.1 equivalents relative to the crosslinkable functional groups in the resin (A), for example, 1 to 20% by mass relative to 100 parts by mass of the resin (A).

[0034] (solvent) Examples of the solvent include ketone solvents such as cyclohexanone, isophorone, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and methylcyclohexanone; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbon solvents such as hexane, cyclohexane, octane, mineral spirits, and kerosene; aromatic hydrocarbon solvents such as toluene, xylene, and 1,2,4-trimethylbenzene; and halogenated solvents such as chlorobenzene and dichlorobenzene. The solvents may be used alone or in combination of two or more.

[0035] When using the resin composition for screen printing, it is preferable to use a solvent with an evaporation rate ratio of 0.3 or less. Here, the evaporation rate ratio refers to the relative rate value of each solvent when the evaporation rate of butyl acetate is set to 1. The smaller the evaporation rate ratio of the solvent, the slower the evaporation rate. When the resin composition contains a solvent with an evaporation rate ratio of 0.3 or less, plate drying during screen printing is suppressed, and workability tends to improve.

[0036] (Leveling agent) Examples of leveling agents include fluorine-based leveling agents, silicon-based leveling agents, and acrylic leveling agents. When the resin composition contains a leveling agent, the leveling agent orients on the coating film surface when the resin composition dries, uniformizing the surface tension of the coating film, thereby preventing poor appearance such as unevenness and cissing, and improving wetting with the substrate film. Specific examples of leveling agents include "Polyflow" (an acrylic leveling agent manufactured by Kyoeisha Chemical Co., Ltd.), "Disparlon" (Kusumoto Chemical Co., Ltd.), and "BYK" (BYK Japan). The leveling agents may be used alone or in combination of two or more types.

[0037] (Antifoaming agent) Known antifoaming agents, UV absorbers, and light stabilizers can be used as appropriate. Examples of antifoaming agents include "DOWSIL" (Dow-Toray Co., Ltd., silicone-based antifoaming agent), "Shin-Etsu Silicone" (Shin-Etsu Chemical Co., Ltd.), the TSF451 series, and the TFH450 series (Momentive Performance Materials). Antifoaming agents may be used alone or in combination of two or more. When an antifoaming agent is used, the content of the antifoaming agent is preferably 0.1 to 0.5 parts by mass relative to 100 parts by mass of the resin (A).

[0038] (UV absorbers, light stabilizers) As the ultraviolet absorber and light stabilizer, known ones can be used as appropriate. Examples of ultraviolet absorbers include "Tinuvin 400" (BASF). Examples of light stabilizers include "Tinuvin 770" (BASF). The ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more.

[0039] When an ultraviolet absorber is used, the content of the ultraviolet absorber is preferably 1 to 3 parts by mass per 100 parts by mass of the resin (A). When a light stabilizer is used, the content of the light stabilizer is preferably 1 to 3 parts by mass per 100 parts by mass of the resin (A). When an ultraviolet absorber and a light stabilizer are used in combination, the total amount of the ultraviolet absorber and the light stabilizer is preferably 2 to 6 parts by mass per 100 parts by mass of the resin (A).

[0040] (coloring agent) As the colorant, any known colorant can be used as appropriate, but pigments are preferred.

[0041] (Applications, etc.) The resin (A) composition can be used to form various coating layers, and is preferably used to form a protective clear layer. The method for applying the resin composition is not particularly limited, and can be screen printing, gravure printing, bar coating, knife coating, roll coating, blade coating, die coating, spray coating, electrostatic coating, dip coating, etc.

[0042] <Laminate> The laminate of the present disclosure includes a substrate and a resin layer containing a cured product of the resin composition described above, laminated on the substrate. The laminate may optionally include other components such as a pressure-sensitive adhesive layer or adhesive layer for adhering to an adherend. A printed layer may also be provided between the resin layer and the substrate.

[0043] The material of the substrate is not particularly limited. Examples include resin, metal, ceramic, paper, wood, and combinations thereof. The thickness of the substrate is not particularly limited and can be selected depending on the application. The thickness of the substrate can be, for example, in the range of 20 μm to 500 μm, and preferably in the range of 30 μm to 100 μm.

[0044] Resins that can be used as the substrate include polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, poly(ethylene-tetrafluoroethylene), polycarbonate, polyester, poly(meth)acrylate, polyolefin, polyamide, polyvinyl alcohol, polystyrene, polyurethane, etc. These resins may be used alone or in combination of two or more. When two or more resins are used in combination, they may be mixed or two or more substrates made of different resins may be combined. Among the above, polyvinyl chloride has excellent adhesion to the resin layer, and therefore tends to prevent the resin layer from peeling off from the laminate.

[0045] The resin layer containing the cured product of the resin composition is formed by applying the above-mentioned resin composition to a substrate or a printed layer provided as needed, and curing it. The method for applying the resin composition is not particularly limited, and examples thereof include screen printing, gravure printing, bar coating, knife coating, roll coating, blade coating, die coating, spray coating, electrostatic coating, and dip coating. Among these, screen printing is preferred. The method for curing the resin composition is not particularly limited, and can be performed using hot air drying, an oven, a hot plate, or the like.

[0046] The thickness of the resin layer is not particularly limited and can be selected depending on the application, and can be, for example, in the range of 1 μm to 100 μm, and preferably in the range of 3 μm to 20 μm.

[0047] When the laminate includes a printed layer between the resin layer and the substrate, the method for forming the printed layer is not particularly limited. For example, the printed layer can be formed by applying a resin composition containing a resin, a colorant, a solvent, etc. to the substrate by a method such as screen printing, and optionally undergoing steps such as drying and curing.

[0048] The resin layer in the laminate of the present disclosure has excellent printability, suppresses foaming during coating, and has excellent gloss and weather resistance, making it suitable for use as a film, sticker, or the like to be attached to, for example, a vehicle body or an object installed outdoors. [Example]

[0049] The present invention will be specifically illustrated below with reference to examples, but the present invention is not limited to these examples in any way.

[0050] Example 1 (1) Preparation of the substrate [Base material] An adhesive-treated polyvinyl chloride film (manufactured by Nippon Carbide Industries Co., Ltd., trade name "Haiescal 0010H") was used as the substrate.

[0051] (2) Color ink printing The red ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK911"; the blue ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK391"; the green ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK791"; the yellow ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK247"; the white ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK661"; and the black ink used was Teikoku Ink Mfg. Co., Ltd., product name "VK911". Each color ink was prepared by adding 30 parts by mass of a 50 / 50 volume% mixed solvent of butyl cellosolve acetate (manufactured by Taishin Chemical Co., Ltd.) and Solvesso 100 (manufactured by ExxonMobil Japan LLC) to 70 parts by mass of each ink. The prepared color ink was printed on a substrate to form an ink layer.

[0052] (3) Preparation of resin composition Resin (A1) was synthesized by copolymerizing 86.5 parts by mass of benzyl methacrylate (carbon number 11), 12.5 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by mass of acrylic acid. The weight-average molecular weight (Mw) of the resulting resin (A1) was 12,000, and the glass transition temperature (Tg) was 48°C.

[0053] Resin (B1) was synthesized by copolymerizing 47 parts by weight of methyl methacrylate, 7 parts by weight of n-butyl acrylate, 32 parts by weight of n-butyl methacrylate, 13 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of acrylic acid. The weight-average molecular weight (Mw) of the resulting resin (B1) was 18,000, and the glass transition temperature (Tg) was 50°C.

[0054] A composition was prepared by mixing 80 parts by weight of resin (A1) and 20 parts by weight of resin (B1), adding 0.20 parts by weight of an antifoaming agent, 2.0 parts by weight of an ultraviolet absorber, and 2.0 parts by weight of a light stabilizer. To this composition, 14 parts by weight of an HMDI-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "Coronate HK", solids content 100.0 mass%) and 11 parts by weight of a 50 / 50 volume% mixed solvent of butyl cellosolve acetate (manufactured by Taishin Chemical Co., Ltd.) and Solvesso 100 (manufactured by ExxonMobil Japan LLC) were added as a diluent to prepare the resin composition of Example 1.

[0055] (4) Formation of resin layer The above resin composition was printed on the substrate or on the ink layer serving as a base layer using a semi-automatic screen printer manufactured by Ceria Corporation at a 180 mesh screen to a thickness of 7 μm. The printing conditions were: scan speed: 300 mm / sec, squeegee pressure: 0.2 MPa, squeegee hardness: 70-75°, squeegee depression: 0.5 mm, squeegee angle: 70°, and clearance: 4.00 mm. After coating, the composition was dried by heating in an 80°C atmosphere for 60 minutes using a hot air dryer to form a resin layer. The sample in which the resin layer was formed on the substrate was designated Sample 1, and the sample in which the resin layer was formed on the ink layer was designated Sample 2.

[0056] (5) Evaluation (5-1) Glossiness For Sample 2, the gloss was measured at a light receiving angle of 60° using an all-in-one gloss meter IQ (manufactured by Rhopoint Instruments) in accordance with JIS Z 8741:1997. The measured samples were A4 size sheets, and measurements were taken on the top, middle, and bottom left, center, and right sides, with a total of N=9, and evaluation was based on the average value. The evaluation criteria were as follows. When judging according to the following evaluation criteria, the sample with the lowest gloss among the samples having ink layers of each color was used for evaluation. Specifically, in Example 1, the gloss of the sample having an ink layer of black ink was judged according to the following evaluation criteria. The evaluation results are shown in Table 2.

[0057] -Evaluation criteria- A: Glossiness Gs (60°) is 93.0 or more. B: The gloss level Gs(60°) is 89.5% or more and less than 93.0%. F: Glossiness Gs (60°) is less than 89.5%.

[0058] (5-2) Printability In producing Sample 1, the appearance of the resin composition was observed immediately after printing or immediately after drying, and printability was evaluated. The evaluation criteria were as follows. The evaluation results are shown in Table 2.

[0059] -Evaluation criteria- A: Immediately after drying, there is no problem with the appearance. B: Immediately after drying, there is a citrus peel and foaming. F: Foaming occurs immediately after printing or the screen is not easily separated.

[0060] (5-3) Weather resistance Sample 1 was placed in an accelerated weather resistance tester (Sunshine Weather Meter, S-WOM) for 1000 hours, and then its appearance was observed to evaluate its weather resistance. The evaluation criteria were as follows. The evaluation results are shown in Table 2.

[0061] -Evaluation criteria- A: There is no problem with the appearance. F: Yellowing occurs or gloss is significantly reduced.

[0062] (5-4) Adhesion The release film of Sample 2 was peeled off, and an aluminum substrate was attached. After 48 hours, "Cellotape" (registered trademark) (Nichiban Co., Ltd.) was attached to the resin layer in accordance with JIS K5400:1990, and 100 1 mm grids of this Cellotape (registered trademark) were rapidly peeled off in a 90-degree angle to check the number of peeled areas between the resin layer and the ink layer. The results are shown in Table 2. In Table 2, "100 / 100" means that out of 100 measured samples, not a single peel was observed.

[0063] The evaluation criteria were as follows. In making judgments based on the following evaluation criteria, the sample with the lowest adhesion among the samples having ink layers of each color was used as the evaluation target. The evaluation results are shown in Table 2.

[0064] -Evaluation criteria- A:100 / 100 B: 90 / 100 or more and less than 100 / 100 F: Less than 90 / 100 or peeling outside the grid In Table 2, * indicates that peeling occurred outside the grid.

[0065] Example 2 Samples 1 and 2 were prepared in the same manner as in Example 1, except that resin (B2) was used in which resin (B1) was replaced with 57 parts by mass of methyl methacrylate, 7 parts by mass of n-butyl acrylate, 22 parts by mass of n-butyl methacrylate, 13 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by mass of acrylic acid, and were evaluated in the same manner as in Example 1. Resin (B2) had a weight-average molecular weight (Mw) of 16,000 and a glass transition temperature (Tg) of 65°C.

[0066] Example 3 Samples 1 and 2 were prepared in the same manner as in Example 1, except that resin (B3) was used in place of resin (B1), in which 37 parts by mass of methyl methacrylate, 7 parts by mass of n-butyl acrylate, 42 parts by mass of n-butyl methacrylate, 13 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by mass of acrylic acid were used, and evaluated in the same manner as in Example 1. Resin (B3) had a weight-average molecular weight (Mw) of 18,000 and a glass transition temperature (Tg) of 42°C.

[0067] Example 4 Samples 1 and 2 were prepared in the same manner as in Production Example 1, except that the blending ratio of resin (A1) and resin (B1) (resin (A) / resin (B)) was changed to 60 / 40, and were evaluated in the same manner as in Example 1.

[0068] Example 5 Samples 1 and 2 were prepared in the same manner as in Production Example 1, except that the compounding ratio of resin (A1) to resin (B1) (resin (A) / resin (B)) was changed to 40 / 60, and were evaluated in the same manner as in Example 1.

[0069] Example 6 Samples 1 and 2 were prepared in the same manner as in Production Example 1, except that the compounding ratio of resin (A1) to resin (B1) (resin (A) / resin (B)) was changed to 20 / 80, and were evaluated in the same manner as in Example 1.

[0070] Example 7 Samples 1 and 2 were prepared in the same manner as in Production Example 1, except that the compounding ratio of resin (A1) to resin (B1) (resin (A) / resin (B)) was changed to 10 / 90, and were evaluated in the same manner as in Example 1.

[0071] Example 8 Samples 1 and 2 were prepared in the same manner as in Production Example 1, except that the compounding ratio of resin (A1) to resin (B1) (resin (A) / resin (B)) was changed to 90 / 10, and were evaluated in the same manner as in Example 1.

[0072] Example 9 Samples 1 and 2 were prepared in the same manner as in Example 1, except that resin (A1) was replaced with resin (A2) containing 86.5 parts by mass of benzyl acrylate (having 10 carbon atoms), 12.5 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by mass of acrylic acid, and were evaluated in the same manner as in Example 1. Resin (A2) had a weight-average molecular weight (Mw) of 12,000 and a glass transition temperature (Tg) of 47°C.

[0073] Example 10 Samples 1 and 2 were prepared in the same manner as in Example 1, except that resin (A1) was replaced with resin (A3) containing 86.5 parts by mass of phenyl methacrylate (having 10 carbon atoms), 12.5 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by mass of acrylic acid, and were evaluated in the same manner as in Example 1. Resin (A3) had a weight-average molecular weight (Mw) of 12,000 and a glass transition temperature (Tg) of 38°C.

[0074] Comparative Example 1 In preparing the resin composition of Example 1, resin (A) was not used, and 0.50 parts by mass of an antifoaming agent, 2.0 parts by mass of UVA, and 2.0 parts by mass of HALS were added to 100 parts by mass of resin (B). Samples 1 and 2 were prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[0075] Comparative Example 2 A styrene-based resin (S) was synthesized by copolymerization of 50 parts by mass of styrene monomer, 31.5 parts by mass of methyl methacrylate, 5 parts by mass of n-butyl acrylate, 12.5 parts by mass of 2-hydroxyethyl acrylate, and 1.0 part by mass of acrylic acid. The weight-average molecular weight (Mw) of the resulting styrene-based resin (S) was 13,000, and the glass transition temperature (Tg) was 45°C. Samples 1 and 2 were prepared in the same manner as in Example 1, except that 0.50 parts by mass of an antifoaming agent, 2.0 parts by mass of UVA, and 2.0 parts by mass of HALS were added to 100 parts by mass of the obtained styrene-based resin (S), and were evaluated in the same manner as in Example 1.

[0076] Comparative Example 3 Samples 1 and 2 were prepared in the same manner as in Example 1, except that the resin (A1) was changed to a styrene-based resin (S) (having 8 carbon atoms), and were evaluated in the same manner as in Example 1.

[0077] Comparative Example 4 In preparing the resin composition of Example 1, the resin (B1) was not used, and 0.50 parts by mass of an antifoaming agent, 2.0 parts by mass of UVA, and 2.0 parts by mass of HALS were added to 100 parts by mass of the resin (A1). Samples 1 and 2 were prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[0078] Comparative Example 5 Resin (B-1) was synthesized by copolymerizing 67 parts by weight of methyl methacrylate, 7 parts by weight of n-butyl acrylate, 12 parts by weight of n-butyl methacrylate, 13 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of acrylic acid. The weight-average molecular weight (Mw) of the resulting resin (B-1) was 16,000, and the glass transition temperature (Tg) was 75°C. Samples 1 and 2 were prepared in the same manner as in Example 1 except that resin (B1) was changed to resin (B-1), and were evaluated in the same manner as in Example 1.

[0079] Comparative Example 6 Resin (B-2) was synthesized by copolymerizing 27 parts by weight of methyl methacrylate, 7 parts by weight of n-butyl acrylate, 52 parts by weight of n-butyl methacrylate, 13 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of acrylic acid. The weight-average molecular weight (Mw) of the resulting resin (B-2) was 16,000, and the glass transition temperature (Tg) was 35°C. Samples 1 and 2 were prepared in the same manner as in Example 1 except that resin (B1) was changed to resin (B-2), and were evaluated in the same manner as in Example 1.

[0080] Comparative Example 7 Resin (C) was synthesized by copolymerizing 69.2 parts by weight of benzyl methacrylate, 9.4 parts by weight of methyl methacrylate, 1.4 parts by weight of n-butyl acrylate, 6.4 parts by weight of n-butyl methacrylate, 12.6 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of acrylic acid. The weight-average molecular weight (Mw) of the resulting resin (C) was 13,000, and the glass transition temperature (Tg) was 39°C. Samples 1 and 2 were prepared in the same manner as in Example 1, except that 0.50 parts by mass of antifoaming agent, 2.0 parts by mass of UVA, and 2.0 parts by mass of HALS were added to 100 parts by mass of the obtained resin (C), and were evaluated in the same manner as in Example 1.

[0081] [Table 1]

[0082] [Table 2]

[0083] The results in Table 2 show that the resin compositions of Examples 1 to 10 have excellent printability, and when cured, have excellent gloss, weather resistance, and adhesion. On the other hand, Comparative Example 1, which did not use the resin (A) of the present disclosure, had inferior glossiness compared to the Examples. Comparative Example 2, which used a styrene-based resin (S), had excellent glossiness but did not contain the resin (B) of the present disclosure, and therefore had inferior adhesion compared to the Examples. In Comparative Example 2, foaming was observed during printing, and printability was inferior to that of the Examples. Comparative Example 3 used a styrene-based resin (S) instead of resin (A), and although resin (B) of the present disclosure was also used in combination, printability was inferior to that of the Examples. Comparative Examples 2 and 3, which used a styrene-based resin (S), also had inferior weather resistance compared to the Examples. Comparative Example 4 used the resin (A) of the present disclosure but did not use the resin (B) of the present disclosure, and therefore adhesion was inferior to that of the Examples.

[0084] In Comparative Example 5, the glass transition temperature of the resin (B-1) was higher than 70° C., and therefore the adhesion was inferior to that of the Examples. In Comparative Example 6, the glass transition temperature of the resin (B-2) was lower than 40° C., and therefore the printability was inferior to that of the Examples. Therefore, in Comparative Example 6, the gloss, weather resistance, and adhesion of the cured product could not be evaluated.

[0085] The resin used in Comparative Example 7 contained 40% to 90% by mass of structural units derived from aromatic-containing monomers having 9 or more carbon atoms, and further contained structural units derived from alkyl(meth)acrylate monomers that are expected to function as resin (B), but when this resin was used, the adhesion was inferior to that of the Examples, and the gloss was also lower than that of the Examples. From these results, it can be seen that separating the functions of improving gloss and adhesion and incorporating them separately in resin (A) and resin (B), as in Examples 1 to 10, contributes to the effects of the present invention.

Claims

1. The resin (A) contains 40% by mass to 90% by mass of structural units derived from an aromatic-containing monomer having 9 or more carbon atoms, and a (meth)acrylic resin (B) does not contain any structural units derived from an aromatic-containing monomer, the aromatic-containing monomer is a (meth)acrylate-based aromatic-containing monomer having a benzyl group, The resin (A) further contains a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from a carboxy group-containing monomer, the resin (B) contains a structural unit derived from an alkyl(meth)acrylate monomer, a structural unit derived from a hydroxyl group-containing monomer, and a structural unit derived from a carboxy group-containing monomer, The resin (B) has a glass transition temperature of 40°C to 70°C, A resin composition, wherein the mass ratio of the resin (A) to the resin (B) (resin (A) / resin (B)) is 90 / 10 to 10 / 90.

2. The resin composition according to claim 1, wherein the mass ratio of the resin (A) to the resin (B) (resin (A) / resin (B)) is 80 / 20 to 80 / 20.

3. A laminate comprising: a substrate; and a resin layer laminated on the substrate, the resin layer comprising a cured product of the resin composition according to claim 1 or 2.

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