TW201441032A - Resin laminate - Google Patents

Abstract

Provided is a resin laminate which has high surface hardness, while having high transparency. A resin laminate which comprises: a hard resin layer which is formed from a curable resin composition containing, as an essential component, a polyfunctional (meth)acrylic monomer, and which has a three-dimensional crosslinked structure, while having a thickness of from 25 [mu]m to 250 [mu]m (inclusive); and a base layer which is composed of one or more layers that are formed of a thermoplastic resin. This resin laminate is characterized in that: the hard resin layer has a tensile modulus of 2,000-4,000 MPa and a total light transmittance of 90% or more by itself; the number of moles of the (meth)acryl groups of the curable resin composition per 100 g of the solid content is 0.6-0.9; and the laminate has a pencil hardness of 6H or more.

Description

Resin laminate

The present invention relates to a resin laminate having excellent surface hardness, transparency, and moldability, and particularly relates to a resin laminate which is suitable as a transparent multilayer sheet for a display panel.

A substrate such as a liquid crystal display used in an electronic device such as a digital camera or a mobile phone, or a protective plate for preventing surface damage or contamination such as a liquid crystal display, etc., is made of acrylic or polycarbonate or polyparaphenyl. A laminate made of a thermoplastic resin such as ethylene glycolate. The resin forming the laminates can be used in a wider range of fields than previously used because of its excellent optical properties and comparatively less rupturable properties of the glass. However, thermoplastic resins such as acrylic acid, polycarbonate, and polyethylene terephthalate have disadvantages such as worse surface hardness, abrasion resistance, and scratch resistance than glass.

In order to solve this drawback, the surface modification of the prior resin laminate was started. For example, it is widely practiced to apply a thermosetting resin or an ultraviolet curable resin to the surface of a substrate. The resin laminate after the application of the coating can improve the abrasion resistance and the scratch resistance to some extent, but the surface is hard. The degree is still insufficient, and the surface hardness such as the pencil hardness of the glass is still low, and there is a big problem in practical use.

In the coating technique for further improving the surface hardness of the transparent plastic material, for example, a filler having a high hardness is mixed in the hard coat layer to increase the surface hardness (refer to Patent Document 1, Patent Document 2, and Patent Document 3). Moreover, a similar method has been reviewed, for example, to increase the film thickness of the hard coat layer to alleviate the stress generated, to incorporate inorganic and/or organic crosslinked particles, and to introduce functional groups into the surface of the particles, and the hard coat layer. The resin is partially crosslinked, that is, a method of so-called organic-inorganic mixing (refer to Patent Document 4 and Patent Document 5). Further, attempts have been made to multilayer the hard coat layer to increase the thickness of the entire coating layer to obtain a higher surface hardness (refer to Patent Document 6).

Specifically, for example, the substrate is a polyethylene terephthalate film or a cellulose triacetate film having a higher pencil hardness than the polycarbonate resin, and as a result, a pencil hardness of 4H can be achieved. 6H, which proves its effect, but because only a thin hard coating layer cannot achieve pencil hardness, it needs to have the auxiliary function of the underlying or inorganic material. Therefore, such underlying or inorganic materials may become a factor that hinders transparency, and cannot be applied to a liquid crystal display-like display device.

It has also been attempted to form a double-layered polycarbonate resin having a certain film thickness on a polycarbonate resin substrate, which is obtained by using a polycarbonate resin having a lower pencil hardness, and is obtained by containing a bifunctional urethane acrylate and a polyfunctional compound. A coating film formed of an ultraviolet curable resin having a specific functional group number of an oligomer, a polyfunctional monomer, or a monofunctional monomer. However, the pencil hardness of this technique is at most 4H (refer to Patent Document 7).

Prior technical literature Patent literature

[Patent Document 1] JP-A-2002-107503

[Patent Document 2] JP-A-2002-060526

[Patent Document 3] Report No. WO2010/035764

[Patent Document 4] JP-A-2000-112379

[Patent Document 5] JP-A-2000-103887

[Patent Document 6] JP-A-2000-052472

[Patent Document 7] Patent No. 4646643

Summary of invention

In view of the above problems of the prior art, the present invention provides a resin laminate having both high surface hardness and high transparency.

In order to obtain a resin laminate having high surface hardness and high transparency, the present inventors have found that a hard resin layer composed of a predetermined curable resin composition and a thermoplastic resin are provided. The resin laminate of the formed base material layer can achieve the same at the same time to complete the present invention.

In other words, the present invention has a hard resin layer having a thickness of 25 μm or more and 250 μm or less having a three-dimensional crosslinked structure, which is formed of a curable resin composition of a polyfunctional (meth)acrylic monomer as an essential component. In the resin laminate of the base material layer composed of a single layer or a thermoplastic resin of a plurality of layers or more, the hard resin layer has a tensile modulus of 2,000 to 4,000 MPa, and a total light transmittance. In addition, the resin composition of the solid content of the curable resin composition is from 0.6 to 0.9 per 100 g of the (meth)acrylic group, and the pencil hardness of the laminate is 6H or more.

In the present invention, it is preferred that the hard resin layer and the substrate layer are laminated via an adhesive layer. The adhesive layer is preferably one or more selected from the group consisting of an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. Further, the hard resin layer and the thermoplastic resin layer may be laminated via an easy-adhesion layer. Further, the present invention may be provided with a hard resin layer on both sides of the front and back.

Moreover, in the present invention, the polyfunctional (meth)acryl-based monomer contained in the curable resin composition forming the hard resin layer is preferably a structure having a cage-type sesquioxalin structure. More preferably, it is a polyfunctional (meth)acrylic monomer having a caged sesquiterpene structure, which is represented by the following formula (1) (R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1) (wherein R ¹ to R ⁶ are an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, or a (meth)acrylic group; a methoxyalkyl group, a vinyl group, or a group having an epoxy ring, and may further contain the same group or a different group, but having at least two (meth)acrylic groups in the formula, and n, m, l is the average value, n is the number of 6~14, m is the number of 0~4, l is the number of 0~4, and satisfies the object represented by m≦1).

The resin laminate of the present invention can have a high surface hardness while maintaining transparency. In addition, since it is a resin laminate which is sufficiently resistant to impact or bending, it is excellent in workability such as molding, cutting, and piercing, and can be used as a display panel and a casing having excellent pattern properties.

1‧‧‧hard resin layer

2‧‧‧Binder

3, 3b‧‧‧ thermoplastic resin layer

4‧‧‧Printing layer

5‧‧‧ Pressure-sensitive adhesive layer

Fig. 1 is a schematic explanatory view showing a laminate of a first aspect of the invention.

Fig. 2 is a schematic explanatory view showing a laminate of a second aspect of the invention.

Fig. 3 is a schematic explanatory view showing a laminate of a third aspect of the invention.

The invention will be described in detail below.

<hard resin layer>

The hardened resin composition in which the hard resin layer is formed in the resin laminate of the present invention may contain two or more ethylenically unsaturated bonds in the molecule. The (meth) acrylate of the knot is not particularly limited. That is, the above polyfunctional (meth) acrylate such as a difunctional (meth) acrylate or a trifunctional or higher (meth) acrylate.

Difunctional (meth) acrylates such as ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, hexane diol (meth) acrylate, long chain aliphatic bis (A) Acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, exfoliation Di(meth)acrylate, glycerol (meth)acrylate, triethylene glycol di(meth)acrylate tetraethylene glycol di(meth)acrylate, tetramethyl glycol di(meth)acrylic acid Ester, butanediol di(meth) acrylate, dicyclopentanyl di(meth) acrylate, polyethylene glycol di(meth) acrylate, poly propyl di (meth) acrylate, Triglycerin di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, methoxylated cyclohexyl (Meth)acrylate, acrylated trimeric isocyanate, bis(propyleneoxypentaerythritol) adipate, bisphenol A di(meth)acrylate, tetrabromobisphenol A di(methyl) Acrylate, Phenol S di (meth) acrylate, butanediol di (meth) acrylate, dibutyl phthalate (meth) acrylate, di (meth) acrylate, zinc di (meth) acrylate.

Further, a trifunctional or higher (meth) acrylate such as trimethylolpropane tri(meth) acrylate, trimethylolethane tri(meth) acrylate, glycerol tri(meth) acrylate, Pentaerythritol II Acrylate, pentaerythritol tri(meth)acrylate, alkyl modified pentaerythritol tri(meth)acrylate, tris(meth)acrylate, tris(propyleneoxyethyl)trimeric isocyanate, three ( Methyl propylene oxyethyl) trimer isocyanate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl modified dipentaerythritol tetra (A) Acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate , carboxylic acid modified dipentaerythritol penta (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, Ester hexa(meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Further, in the curable resin composition, a compound having a structure of a curable cage-type sesquioxalin is preferable as the polyfunctional (meth)acryl-based monomer.

Further, the compound having a curable cage-type sesquioxane structure is more preferably a cage-type sesquioxanes resin represented by the general formula (1).

(R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1) (wherein R ¹ to R ⁶ are carbon number 1~ An alkyl group, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group, a group having an oxirane ring, which may be the same group or contain a different group. However, there are at least two (meth)propenyl groups in the formula, n, m, and l are average values, n is a number from 6 to 14, m is a number from 0 to 4, and l is a number from 0 to 4, and satisfies m≦1).

Preferably, the above-mentioned cage-type sesquiterpene resin has a ruthenium atom constituting the cage having an organic functional group having a (meth)acryl group or a reactive functional group formed by a (meth) propylene decoxyalkyl group. The cage type sesame sesquioxane resin which can control the molecular weight distribution and the molecular structure, but may be partially substituted by an alkyl group, a phenyl group or the like, and may not be a completely blocked polyhedral structure, and may be a partially cleaved structure. In the case of a partially cleaved structure, the linked polyoxyl chain may have a (meth)acrylic group.

The hard resin layer formed of the curable resin composition used in the present invention is required to use a solid component of the curable resin composition in an amount of from 0.6 to 0.9 per 100 g of the (meth)acrylic group. Therefore, the thickness needs to be 25 μm or more and 250 μm or less. When the number of moles of (meth)acrylic groups per 100 g is less than 0.6, sufficient pencil hardness cannot be obtained, and when it exceeds 0.9, impact resistance is lowered, and machining such as cutting or perforation is difficult to perform. Further, when the thickness is less than 25 μm, sufficient pencil hardness cannot be obtained, and when the thickness exceeds 250 μm, the total light transmittance is lowered, and there is a problem that transparency necessary for the display cannot be obtained.

The number of moles of the (meth)acrylic group per 100 g of the solid content of the curable resin composition was calculated by the following formula.

(molar number per 100 g of (meth)acrylic group) = (100 / molecular weight) × 1 (meth)acrylic group in the molecule

Further, when a plurality of polyfunctional (meth)acryl-based monomers are used as the curable resin composition, the number of moles of the average (meth)acrylic group calculated by the addition ratio is added, and the filling with cerium oxide or the like is added. The weight of the agent was also included, and the average value of the number of moles of the (meth)acrylic group was calculated.

The hardened resin composition forming the hard resin layer may be a combination of a monofunctional (meth) acrylate in a range in which the molar content of the (meth)acryl group per 100 g of the solid component does not deviate from 0.6 to 0.9. However, when a certain amount or more of a monofunctional (meth) acrylate is added, the surface hardness tends to be lowered. Therefore, it is desirable to have a minimum limit for the purpose of adjusting the viscosity and the like, and it is preferably 30 parts by weight with respect to the curable resin composition. %.

Monofunctional (meth) acrylates such as methacrylate, ethacrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, mercaptoacrylic acid Ester, neopentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, hydrazine Acrylate, isodecyl acrylate, mercapto acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, ten Pentaalkyl acrylate, isotetradecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, n - Alkyl acrylates such as lauryl acrylate, stearin acrylate, propylene morpholine, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl Acrylate, dicyclopentanyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3 -phenoxypropyl acrylate, 1,4-butanediol monoacrylate, 2-hydroxyalkyl propylene decyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6-hexanediol monoacrylate, The neopentyl alcohol monoacrylate, the hydroxyl group-containing acrylate compound, a cyclic ester compound such as ε-caprolactone, an alkyl glycidyl ether, an allyl glycidyl ether, or a glycidyl acrylate. a compound obtained by an addition reaction of a glycidyl group-containing compound with acrylic acid, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, (2-ethyl-2) -methyl-1,3-dioxoalkan-4-yl)methacrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)- Acrylate and the like.

The hardened resin composition used in the present invention can be obtained by copolymerizing these radicals to obtain a (meth)acrylic resin copolymer. In order to improve the physical properties of the (meth)acrylic resin copolymer or to promote radical copolymerization or the like, various additives may be added to the curable resin composition of the present invention. The additive which promotes the reaction, for example, a thermal polymerization initiator, a thermal polymerization promoter, a photopolymerization initiator, a photoinitiation aid, a sharpness agent, and the like. When the photopolymerization initiator or the thermal polymerization initiator is added, the amount thereof may be in the range of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by total of the total of the curable resin composition. When the amount is less than 0.1 part by weight, the hardening is insufficient, the strength and rigidity of the obtained hard resin layer are lowered, and when it exceeds 5 parts by weight, the problem of coloring of the hard resin layer or the like may occur.

The photopolymerization initiator used when the curable resin composition is used as a photocurable composition is, for example, an acetophenone type, a benzoin system, a benzophenone type, a thioxanthone type, or a mercapto phosphine oxide system. Compounds such as. More specifically, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[4-(2-Hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenylglyoxylate methyl ester, 2, 4,6-trimethylphenylnonyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylphenylhydrazino)-phenylphosphine oxide, 1,2-octanedione, 1 -[4-(phenylthio)-2-(0-phenylhydrazinyl)], ethyl ketone, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole 3-yl]-1-(0-acetamidofluorene), 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) )-butanone-1-one, bis-2,6-dimethoxybenzoin-2,4,4-trimethylpentylphosphine oxide, benzophenone, thioxanthone, 2-chloro And thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Further, these may be used alone or in combination of two or more.

After the addition of the radical polymerization initiator, the curable resin composition used in the present invention can be cured by heating or light irradiation to produce a hard resin layer of any shape such as a flat surface or a curved surface. When a hard resin layer of any shape is produced by heating, the molding temperature can be selected from a wide range from room temperature to 200 ° C by selecting a thermal polymerization initiator and an accelerator. At this point, the hard tree can be polymerized and hardened in the mold or on the steel strip to obtain the desired shape. Lipid layer.

Further, when the hard resin layer is produced by light irradiation, it can be obtained by irradiating ultraviolet rays having a wavelength of 10 to 400 nm or visible light having a wavelength of 400 to 700 nm. The wavelength of light used is not particularly limited, but is particularly suitable for near-ultraviolet rays having a wavelength of 200 to 400 nm. Lamps used as sources of ultraviolet light, such as low-pressure mercury lamps (output force: 0.4~4W/cm), high-pressure mercury lamps (40~160W/cm), ultra-high pressure mercury lamps (173~435W/cm), metal halide lamps (80~160W) /cm), pulsed xenon lamp (80~120W/cm), electrodeless discharge lamp (80~120W/cm), etc. These ultraviolet lamps are characterized by their respective spectral distributions and can be selected depending on the type of photoinitiator used.

A method of obtaining a hard resin layer of any shape used in the present invention by light irradiation, for example, by injecting a curable resin composition into a mold having an arbitrary pore shape and consisting of a transparent material such as quartz glass, A method in which a UV lamp is irradiated with ultraviolet rays to carry out polymerization hardening, and then a mold is released from the mold to produce a hard resin layer of a desired shape, or when a mold is not used, the cured resin of the present invention is used, for example, using a squeegee or a roll coater. The composition is applied to a moving steel strip, and is polymerized and cured by the above ultraviolet lamp to produce a sheet-like hard resin layer.

<Substrate layer>

The thermoplastic resin layer (base material layer) used in the present invention preferably has excellent transparency, and is suitable for polyethylene terephthalate (PET), triethylenesulfonyl cellulose (TAC), and polyethylene naphthalate. Glycol ester (PEN), poly Methyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC) A cycloolefin copolymer (COC), a resin film containing a norbornene resin, a polyether oxime, a cellophane, an aromatic polyamine, or the like. These films may be used without stretching or extended processing, but in terms of heat resistance, transparency, weather resistance, solvent resistance, impact resistance, processability, and cost, particularly preferred is polyparaphenylene. Ethylene glycol dicarboxylate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC).

Since the base material layer imparts rigidity to the resin laminate of the present invention, it has sufficient resistance against impact or bending. For example, when the hard resin layer of the present invention is formed of a curable resin composition containing a polyfunctional (meth)acryl-based monomer having a cage-type sesquiterpene structure, it has a pencil hardness of 6H or more. The surface hardness is high, but when the thickness is 250 μm or less in order to ensure transparency, the impact resistance will be insufficient. Therefore, in the present invention, sufficient resistance to impact, bending, or the like can be provided by the base material layer. The base layer may have a total thickness of 0.5 to 2000 μm, preferably 10 to 1000 μm. When the thickness is less than 0.5 μm, sufficient rigidity cannot be obtained, and when it exceeds 2000 μm, processing such as molding, cutting, or punching is difficult.

<Next layer>

In the resin laminate of the present invention, the hard resin layer and the substrate layer can be laminated by any of the adhesive layers (adhesive layers) in the form of a film or a sheet.

The thickness of the adhesive layer is 0.01 to 30 μm, preferably 0.1 to 10 μm. When it is less than 0.01 μm, it is difficult to obtain a sufficient adhesive effect, and when the thickness is 30 μm or more, the laminate may not have sufficient pencil hardness.

Moreover, an adhesive bond, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive can be used as the adhesive layer for the adhesive layer. Such materials as acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ethers Reagent, rubber adhesive, vinyl chloride-vinyl acetate adhesive, styrene-butadiene-styrene copolymer (SBS copolymer) adhesive, hydride (SEBS copolymer) adhesive, ethylene-vinyl acetate copolymerization Ethylene adhesive such as ethylene-styrene copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, etc. The acrylate adhesive or the like is not particularly limited as long as it has good adhesion, transparency, and processability.

<easy layer>

Further, another material constituting the adhesive layer is an easy-to-adhere layer. The easy-adhesion layer is a layer which is chemically easy to be attached to the surface of the resin layer which is difficult to bond, or which is easily and physically treatable. The chemically easy to be used means that a film layer of a resin having a functional group is formed on a substrate layer, and a chemical bond can be formed with the hard resin layer to obtain an adhesive force, and the physical property can be easily followed by the substrate. A resin film layer or an inorganic film layer having irregularities is formed, and an adhesion force to the hard resin layer is obtained by a fixing effect. Materials having chemically and easily achievable energy, such as polyfunctional (meth) acrylates, epoxys, thiol group-containing compounds, etc., which have physical and easily capable materials such as SiO ₂ , SiN, SiC, etc. A vapor deposition film or the like.

Moreover, Fig. 1 shows a first aspect of the resin laminate of the present invention. In the resin laminate shown in Fig. 1, when the adhesive layer 2 is held on both sides of the thermoplastic resin layer (base material layer) 3, the hard resin layer 1 is laminated on both the upper and lower sides. Further, in the resin laminate of the first aspect, the one-sided hard resin layer 1 has a structure in which the printed layer 4 is formed. In this case, the adhesive layer 2 has a function as an adhesive for integrating the hard resin layer 1 and the thermoplastic resin layer 3. Thus, the printed layer 4 is formed on the lower surface of the resin laminate of the present invention to form a pattern, a character, or the like. The printed pattern of the printed layer 4 can be arbitrarily selected, such as wood grain, stone grain, cloth grain, sand grain, geometric pattern, text, full version, metal and the like. Moreover, the adhesive layer 2 may be the aforementioned adhesive layer or easy-adhesion layer.

The printing layer 4 is preferably a resin component having a good phase property with a hard resin layer or a thermoplastic resin layer (base material layer), for example, a polyethylene resin such as a vinyl chloride/vinyl acetate copolymer, a polyamide resin, or a polyester. A resin, an acrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, an alkyd resin, and a chlorinated polyolefin resin. The addition of such a resin component inhibits peeling or peeling off of the printing.

Further, when the printed layer 4 is formed, a coloring agent containing a suitable pigment or dye can be used.

The method of forming the printed layer 4 is, for example, lithography, rotation A printing method such as a gravure printing method or a screen printing method, a coating method such as a roll coating method or a spray printing method, and a flexographic printing method.

The thickness of the printed layer 4 can be appropriately selected depending on the desired surface appearance of the resin laminate, and is generally 0.5 to 30 μm.

Moreover, the second and third embodiments of the resin laminate of the present invention have the structures shown in Figs. 2 and 3 .

In the second embodiment shown in FIG. 2, after the printing layer 4 is formed on the thermoplastic resin 3b, the pressure-sensitive adhesive layer 5 is held on the printing layer 4 side and the printing layer 4 side. The hard resin layer 1 is formed on the side of the printing layer 4, and the thermoplastic resin layer 3 is formed on the side where the printing layer 4 is not formed.

In Fig. 2, the thermoplastic resin 3b to be used is not particularly limited as long as it has transparency, and is preferably polymethyl methacrylate (PMMA).

In the third embodiment shown in Fig. 3, a hard resin layer 1 is formed on the thermoplastic resin 3 via a binder, and after the printing layer 4 is formed on the lower surface of the thermoplastic resin 3, a printed layer is not formed under the thermoplastic resin 3. The thermoplastic resin layer 3 is formed in the case where the pressure-sensitive adhesive layer 4 is held on the thermoplastic resin layer 3 of 4.

The pressure-sensitive adhesive layer 5 used in the embodiment of FIGS. 2 and 3 may be a known pressure-sensitive adhesive. Specifically, for example, a binder such as a natural rubber-based resin, a synthetic rubber-based resin, a polyfluorene-based resin, an acrylic resin, a vinyl acetate-based resin, or a urethane-based resin.

The above-mentioned adhesive can be an unrestricted material having necessary light transmittance, adhesiveness, and weather resistance.

Further, in order to prevent deterioration of the pigment by the layer structure, the binder preferably contains a UV absorber (benzotriazole or the like) having an effect of absorbing ultraviolet rays.

The pressure-sensitive adhesive layer 5 has an average thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm. When it is less than 0.01 μm, sufficient bonding strength cannot be obtained, and the effect of flattening by absorbing the unevenness of the printing layer is reduced. Further, when the laminate is 30 μm or more, sufficient pencil hardness cannot be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION The state of the resin laminate in Figs. 1 and 3 can be imparted to the three-dimensional shape by thermoforming. In Fig. 1 and Fig. 3, the thermoplastic resin layer 3 can be formed by heat, and the hard resin layer 1 can have a sufficient flexibility to follow the shape of the thermoplastic resin layer to form an integrally molded product under the adhesive layer 2. . Thermoforming such as vacuum forming, pressure forming, press forming, and the like.

Further, when the embodiment of the present invention is a layer structure similar to the resin laminate shown in Fig. 2, the pressure-sensitive adhesive layer 5 may be bonded to the A member and the B member which are each formed into a predetermined shape, and The thermoplastic resin layer 3 constituting the B member can be molded by injection molding into a mold having a desired shape in which the A member is filled.

In this case, the printing layers 4 are formed in each of FIGS. 1 to 3, but the printing layer 4 may be omitted, and the lamination manufacturing process may be formed by any printing method between any of the layers.

The injection molded thermoplastic resin is preferably transparent, and is suitable for polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polymethyl methacrylate (PMMA). Polycarbonate Ester (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cyclic olefin copolymer (COC), aromatic polyamide, etc., heat resistance, transparency, weather resistance, resistance From the viewpoints of solvent property, rigidity, and cost, polyethylene terephthalate, polymethyl methacrylate, or polycarbonate is preferably used, and polycarbonate is particularly preferred from the viewpoint of impact resistance.

Example

The invention will now be described in more detail by way of examples. Further, the evaluation methods and symbols used in the present invention are as follows.

1) Pencil hardness: measured in accordance with JIS K 5600.

2) Total light transmittance: measured in accordance with JIS K 7361-1.

3) Film thickness: measured by ID-SX manufactured by Mith.

4) Tensile modulus: measured in accordance with JIS 7127.

5) Machinability: A processing machine (manufactured by Megalo Co., Ltd.) with a mixing blade (2 mm, straight edge), and a processing condition of 20,000 rpm and a conveying speed of 900 mm/min. After the obtained resin laminate was subjected to a cutting process, a cross-sectional microscope observation was carried out, and the object observed as chipping was regarded as ×, and the unobserved object was regarded as ○.

[Example 1] (Making a hard resin layer)

After heating and mixing dipentaerythritol hexaacrylate at 110 ° C: 85 parts by weight, PMMA: 15 parts by weight, and mixing 1-hydroxyl as a photopolymerization initiator Base cyclohexyl phenyl ketone: 2.5 parts by weight of a curable resin composition.

Next, using a roll coater, a curable resin composition having a thickness of 0.15 mm was spread over the peeled PET, and another peeled PET was laminated on the cast curable resin composition. Thereafter, the high-pressure mercury lamp of 30 W/cm was used to harden at an exposure amount of 4000 mJ/cm ² , and after peeling off all of the peeled-treated PET, a sheet-like hard resin layer having a certain thickness was obtained. The tensile modulus and total light transmittance of the obtained hard resin layer were measured, and the results are shown in Table 1.

(Production of resin laminate)

The cationic photocurable adhesive (manufactured by Kyoritsu Chemical Co., Ltd.) having a thickness of 5 μm was applied to polycarbonate (PC-1151, manufactured by Teijin Co., Ltd., 200 mm × 200 mm × thickness: 0.5 mm), and the above-mentioned results were obtained. The hard resin layer was bonded to the entire surface of one side of the polycarbonate, and after pressing, a resin laminate was obtained by irradiating ultraviolet rays on both sides at a ratio of 500 mJ/cm ² using a metal halide lamp. The pencil hardness, workability, and the like of the obtained resin laminate were evaluated, and the results are shown in Table 1.

[Synthesis example]

400 ml of 2-propanol (IPA) as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. After adding 150 ml of IPA and 126.9 g of 3-methylpropoxypropyltrimethoxydecane (MTMS: SZ-6030, manufactured by Toray Island Co., Ltd.) from a dropping funnel, stirring was carried out. While the reaction vessel was being incubated, the MTMS solution of MTMS was added dropwise at room temperature for 30 minutes. After the completion of the MTMS drip, the mixture was stirred for 2 hours without heating. After stirring, the solvent was removed under reduced pressure and dissolved in 500 ml of toluene. The reaction solution was washed with saturated saline until neutral, and then dehydrated with magnesium sulfate. After filtering off the magnesium sulfate and concentrating, 86 g of a cage-type sesquiterpene compound having a methacryl oxime group on all of the ruthenium atoms was obtained. The sesquiterpene is a colorless viscous liquid which is soluble in various organic solvents.

[Embodiment 2]

The caged sesquioxalin compound having a methacryl fluorenyl group on all of the ruthenium atoms obtained in the above synthesis example was mixed: 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, dicyclopentanyl diacrylate: 32 The transparent curable resin composition was obtained by using a weight ratio of urethane oligomer: 1:6 parts by weight and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight.

Next, after the hard resin layer was obtained in the same manner as in Example 1, a resin laminate was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

[Examples 3 to 9 and Comparative Examples 1 to 4]

A hard resin layer and a resin laminate were obtained in the same manner as in Example 1 except that the addition composition of the curable resin composition was the weight ratio shown in Table 1. The evaluation results of the obtained molded articles are combined as shown in Table 1.

The code numbers in the table are as follows.

A: Compound obtained in Synthesis Example 1

B: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)

C: Trimethylolpropane trimethacrylate (photo ester TMP of Kyoeisha Chemical Co., Ltd.)

D: pentaerythritol triacrylate (photochemical acrylate PE-3A manufactured by Kyoeisha Chemical Co., Ltd.)

E: caprolactone modified dipentaerythritol hexaacrylate 1 (KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd.)

F: caprolactone modified dipentaerythritol hexaacrylate 2 (KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd.)

G: Dicyclopentane diacrylate (Kyoeisha Chemical Co., Ltd.) Photopolymer acrylate (DCP-A)

H: Dicyclopentyl dimethacrylate (Nippon Nakamura Chemical Co., Ltd. NK ester DCP)

I: PMMA (Curaray (share) Parapat LW: weight average molecular weight of about 34,000)

J: urethane acrylate oligomer 1 (UF-503 manufactured by Kyoeisha Chemical Co., Ltd.: number average molecular weight of about 8800)

K: urethane acrylate oligomer 2 (NH oligo UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd.: number average molecular weight about 1100)

L: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator, IGFACURE 184 manufactured by BASF Japan)

1‧‧‧hard resin layer

2‧‧‧Binder

3‧‧‧ thermoplastic resin layer

4‧‧‧Printing layer

Claims (7)

A resin laminate comprising a hard resin composition containing a polyfunctional (meth)acrylic monomer as an essential component, and having a three-dimensional crosslinked structure and having a thickness of 25 μm or more and 250 μm or less In the resin laminate of the base material layer composed of a single layer or a thermoplastic resin of a plurality of layers or more, the hard resin layer has a tensile modulus of 2,000 to 4,000 MPa and a total light transmission. The rate of the solid content of the curable resin composition is from 0.6 to 0.9 per 100 g of the (meth)acryl group, and the pencil hardness of the laminate is 6 H or more. The resin laminate of claim 1, wherein the hard resin layer and the substrate layer are laminated via an adhesive layer. The resin laminate according to claim 2, wherein the adhesive layer is selected from the group consisting of an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. It is composed of two or more species. The resin laminate of claim 1 or 2, wherein the hard resin layer and the thermoplastic resin layer are laminated with an easy-to-attach layer. The resin laminate according to any one of claims 1 to 4, wherein the polyfunctional (meth)acrylic monomer contained in the hardened resin composition forming the hard resin layer has a cage-type sesquioxane structure. Things. The resin laminate according to any one of claims 1 to 5, wherein the polyfunctional (meth)acrylic monosystem having a cage-type sesquioxalin structure is represented by the following formula (1) (R ¹ SiO _{3/2) n} (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1) (wherein R ¹ to R ⁶ are an alkyl group having 1 to 6 carbon atoms, a phenyl group) a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group, or a group having an epoxy ring, and may further contain the same group or a different group, but have at least 2 (meth)propenyl group, n, m, l are average values, n represents the number of 6 to 14, m represents the number of 0 to 4, l represents the number of 0 to 4, and satisfies m≦1) Said. The resin laminate according to any one of claims 1 to 6, wherein both sides of the front and back are provided with a hard resin layer.