KR20140114795A - Resin laminate and molding method using the same - Google Patents

Abstract

A resin laminate having high surface hardness and high transparency and a molding method using the same are provided.
[MEANS FOR SOLVING PROBLEMS] At least one hard resin layer having a glass transition temperature of 200 ° C or higher, which is obtained by curing a three-dimensionally crosslinkable hard resin composition containing a polyfunctional (meth) acrylic monomer having a cage silsesquioxane structure, Wherein the hard resin layer has a tensile elastic modulus of 2,000 to 4,000 MPa in a single layer, and the thermoplastic resin layer has a tensile modulus of 2,000 to 4,000 MPa in a single layer. The thermoplastic resin layer has a ratio of a room temperature elastic modulus to a 150 < , The total light transmittance is 90% or more, the pencil hardness of the resin laminate is 6H or more, the ratio of the total thickness of the thermoplastic resin layer to the thickness of the hard resin layer is 0.25 or more and 10 or less, This is a molding method in which a thermoplastic resin is injection-molded by loading into a mold.

Description

[0001] Resin laminate and molding method using the same [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate having a moldable hard coating film and a molding method using the resin laminate, The present invention relates to a resin laminate which can be widely used including a housing and various parts of a personal computer and a portable electronic device in addition to an illumination cover and is suitable for a display face plate among them and has a state of a transparent multilayer sheet and a molding method using the resin laminate.

For example, as a substrate for a liquid crystal display or the like in an electronic device such as a digital camera or a mobile phone, or a protective plate for protecting a surface of a liquid crystal display or the like from scratches or contamination, etc., a thermoplastic resin such as acryl, polycarbonate, or polyethylene terephthalate A laminate produced is used. These resins have excellent optical characteristics and are less likely to be broken than glass, and thus they have been widely used in the fields where conventional glass has been used in recent years. However, thermoplastic resins such as acryl, polycarbonate, and polyethylene terephthalate have drawbacks in that their surface hardness, abrasion resistance, and scratch resistance are lower than those of glass, and scratches easily occur.

In order to overcome such drawbacks, the surface modification of the resin laminate has been studied. For example, it has been widely practiced to coat thermosetting resin or ultraviolet curable resin on the substrate surface. The resin laminate to which these coatings have been applied exhibits some improvement in abrasion resistance and scratch resistance. However, the surface hardness is insufficient and the surface hardness such as pencil hardness is lower than that of glass.

As a coating technique for further improving the surface hardness of the transparent plastic material, attempts have been made to improve the surface hardness by incorporating, for example, a filler of high hardness into the hard coat layer (see Patent Document 1, Patent Document 2, Patent 3). As a similar method, inorganic and / or organic crosslinked particles may be mixed in order to slightly increase the film thickness of the hard coating and relax the generated stress, or functional groups may be introduced into the surface of the particles to partially So-called organic-inorganic hybrid method of crosslinking is studied (see Patent Document 4 and Patent Document 5). Further, attempts have been made to obtain a higher surface hardness by increasing the thickness of the entire coating by layering the hard coat layer (see Patent Document 6).

However, as a concrete example of these methods, the pencil hardness is achieved from 4H to 6H by using a polyethylene terephthalate film or a cellulose triacetate film originally having a pencil hardness higher than that of a polycarbonate resin as a substrate, and the effect is demonstrated , Since hard pencil hardness can not be achieved only with a thin hard coating layer, an auxiliary function of hard ground layer or inorganic material is essential. For this reason, these underlying layers and inorganic materials are factors that hinder transparency and are unsuitable for display devices such as liquid crystal displays.

It is also possible to use a polycarbonate resin which is a resin having a low pencil hardness and a coating film comprising a bifunctional urethane acrylate, a polyfunctional oligomer, a polyfunctional monomer, a monofunctional monomer and an ultraviolet curable resin having a specific functional group number, Attempts have been made to form two layers on a polycarbonate resin substrate in thickness. However, the pencil hardness is 4H at the maximum, which is not sufficient (see Patent Document 7).

Japanese Patent Application Laid-Open No. 2002-107503 Japanese Patent Application Laid-Open No. 2002-060526 WO 2010/035764 brochure Japanese Patent Laid-Open Publication No. 2000-112379 Japanese Patent Application Laid-Open No. 2000-103887 Japanese Patent Application Laid-Open No. 2000-052472 Japanese Patent No. 4626463

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a resin laminate having high surface hardness and high transparency, and a molding method using the same.

The present inventors have made intensive investigations to obtain a resin laminate having excellent transparency while having excellent surface hardness. As a result, they have found that by forming a resin laminate having a light resin layer composed of a predetermined three-dimensionally crosslinkable hard resin composition and a predetermined thermoplastic resin layer, Can be achieved at the same time, and the present invention has been accomplished.

That is, the present invention relates to a hard resin layer comprising at least one hard resin layer having a glass transition temperature of 200 ° C or higher, which is obtained by curing a three-dimensional crosslinked hard resin composition containing a polyfunctional (meth) acrylic monomer having a cage silsesquioxane structure, (E ₁ / E ₂ ) of a room temperature elastic modulus (E ₁ ) and a 150 ° C elastic modulus (E ₂ ) of ₁ to 500 on at least one side of the hard resin layer as a resin laminate having a thermoplastic resin layer , And the hard resin layer has a tensile elastic modulus in a unit of 2,000 to 4,000 MPa and a total light transmittance of 90% or more, and the pencil hardness of the resin laminate is 6H or more and the total thickness (t ₁ ) of the thermoplastic resin layer and the hard water the ratio (t ₁ / t ₂₎ of thickness (t ₂₎ of the resin layer is a resin laminate according to claim 10 or less than 0.25. Here, the term "(meth) acryl" has the meaning of both "methacryl" and "acrylic", and the same applies to the following.

Preferably, the number of moles of the (meth) acrylic group per 100 g of the solid resin component contained in the above-mentioned three-dimensional crosslinkable hard resin composition is 0.6 to 0.9, and the thickness of the obtained hard resin layer is 50 탆 or more and 250 탆 or less .

Preferably, the hard resin layer and the thermoplastic resin layer are laminated via an adhesive layer. Preferably, the adhesive layer is made of a pressure-sensitive adhesive, a pressure-sensitive adhesive, a photo-curing adhesive, a thermosetting adhesive, . Alternatively, the hard resin layer and the thermoplastic resin layer may be laminated through the adhesive layer.

The multifunctional (meth) acrylic monomer having the cage silsesquioxane structure is preferably 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 alkyl groups having ¹ to ⁶ carbon atoms, phenyl groups, (meth) acryl groups, (meth) acryloyloxyalkyl groups, vinyl groups and oxirane rings, And n is an integer of 6 to 14, m is a number of 0 to 4, l is a number of 0 to 4, m ≤ l).

Further, the present invention is a method for molding a resin laminate, characterized in that the resin laminate is thermoformed to give a predetermined shape. Further, the present invention is a molding method characterized by integrating a resin laminate having a hard resin layer and a thermoplastic resin by integrating a resin laminate of a predetermined shape obtained by the above into a mold and injection molding the thermoplastic resin.

(Effects of the Invention)

INDUSTRIAL APPLICABILITY According to the present invention, since a resin laminate having high surface hardness while maintaining transparency and having sufficient resistance against impact or bending can be obtained, it is excellent in workability such as molding, cutting and punching, It can be used as an excellent housing or the like.

Fig. 1 is an explanatory view schematically showing a resin laminate of the first embodiment of the present invention. Fig.
Fig. 2 is an explanatory diagram schematically showing a resin laminate according to a second embodiment of the present invention. Fig.
3 is an explanatory diagram schematically showing a resin laminate of a third embodiment of the present invention.
4 is a side view showing an injection molding machine used in the embodiment of the present invention.
5 is a sectional view of the resin laminate after molding.

Hereinafter, the present invention will be described in detail.

≪ Hard resin layer >

The hard resin layer in the resin laminate of the present invention is formed by curing a three-dimensional crosslinked hard resin composition containing a polyfunctional (meth) acrylic monomer having a cage silsesquioxane structure, and its glass transition temperature is 200 Lt; / RTI >

Among them, the polyfunctional (meth) acrylic monomer having the curable cage silsesquioxane structure is preferably represented by the following 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 alkyl groups having ¹ to ⁶ carbon atoms, a phenyl group, a (meth) acrylic group, a (meth) acryloyloxyalkyl group, a vinyl group and an oxirane ring, And n is an integer of 6 to 14, m is a number of 0 to 4, 1 is a number of 0 to 4, m ≤ l)

That is, the multifunctional (meth) acrylic monomer having the cage silsesquioxane structure can be produced by reacting a reactive functional group comprising an organic functional group having a (meth) acrylic group or a (meth) acryloyloxyalkyl group on the entire silicon atoms constituting the cage It is preferable that the molecular weight distribution and the molecular structure are controlled. However, a part of the functional groups may be substituted by an alkyl group, a phenyl group, etc., and the structure may be a structure in which a part of the polyhedral structure is not completely closed. In the case of a partially cleaved structure, a (meth) acrylic group may be contained in a connected silicon chain.

Further, the three-dimensional crosslinkable hard resin composition of the hard resin layer (1) used in the present invention can be used in combination with (meth) acrylate having two or more ethylenic unsaturated bonds in the molecule. Examples of the polyfunctional (meth) acrylate include bifunctional (meth) acrylates and trifunctional or more (meth) acrylates.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, long chain aliphatic di (meth) (Meth) acrylate, glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di Acrylates such as ethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di Di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylol (Meth) acrylate, acrylate isocyanurate, bis (acryloxy neopentyl glycol) adipate, bisphenol A di (meth) acrylate, methacrylic acid di (Meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, phthalic acid di , Zinc di (meth) acrylate, and the like.

Examples of the (meth) acrylate having three or more functional groups include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, phosphoric tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylol propane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (metha) (Meth) acrylate, urethane (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, alkyltrimethoxysilane, ) Acrylate, ester hexa (meth) acrylate, and the like.

Further, the polyfunctional (meth) acrylate having a cage silsesquioxane structure may be used singly or in combination of two or more.

The hard resin layer (1) comprising the three-dimensional crosslinkable hard resin composition of the present invention preferably has a number of moles of (meth) acrylic groups per 100 g of the solid content of the three-dimensional crosslinkable hard resin composition of 0.6 to 0.9, The thickness is preferably 50 占 퐉 or more and 250 占 퐉 or less. If the number of moles of (meth) acrylic groups per 100 g is less than 0.6, sufficient pencil hardness can not be obtained. If the number of moles is more than 0.9, flexibility is lost and molding becomes difficult and the impact resistance is lowered and mechanical working such as cutting and punching becomes difficult. If the thickness is less than 50 탆, sufficient pencil hardness can not be obtained. If the thickness exceeds 250 탆, the total light transmittance is lowered and transparency necessary for display and the like can not be obtained.

The number of moles of the (meth) acrylic group per 100 g of the solid content of the three-dimensionally crosslinkable hard resin composition is calculated by the following formula.

(Number of moles of (meth) acrylic group per 100 g) = (100 / molecular weight) x number of (meth) acrylic groups in one molecule

When a plurality of polyfunctional (meth) acrylic monomers are used as the three-dimensional crosslinkable hard resin composition, the average (meth) acrylic group number calculated according to the compounding ratio is used, and when a filler such as silica is blended, The average value of the number of moles of the (meth) acrylic group is calculated. (Mol / 100 g) per unit mass of the (meth) acrylic group present in the solid content of the three-dimensionally crosslinkable hard resin composition.

The hard resin layer (1) composed of the three-dimensional crosslinkable hard resin composition forming the hard resin layer is formed in such a range that the number of moles of the (meth) acrylic group per 100 g of the solid content of the three-dimensional crosslinkable hard resin composition does not deviate from the range of 0.6 to 0.9 May be combined with a monofunctional (meth) acrylate. However, since the surface hardness tends to decrease when the monofunctional (meth) acrylate is blended in a certain amount or more, it is preferable to limit the blending amount for the purpose of viscosity adjustment to a minimum, and the three- By weight or less.

Examples of the monofunctional (meth) acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, pentyl acrylate, neopentyl acrylate Acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, Acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, isomyristyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate , Nonadecyl acrylate, eicodecyl acrylate, n-lauryl acrylate, Alkyl acrylates such as acryloylmorpholine, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, phenyl acrylate, benzyl acrylate Hydroxypropyl acrylate, 1,4-butanediol monoacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl acrylate, hydroxyalkyl acryloyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate, cyclic ester such as ε-caprolactone A glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl acrylate; (2-ethyl-2-methyl-1, 3-di (meth) acrylate, a compound obtained by the addition reaction of acrylic acid and acrylic acid, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate, and the like.

Assuming that the resin laminate of the present invention is used as a window glass for an automobile or an airplane, the surface is heated to a high temperature by direct sunlight. In addition, when used as a housing for a personal computer or a portable electronic device, heat is generated inside the device. Therefore, the hard resin layer needs to have heat resistance to prevent deformation due to heat, and the glass transition temperature needs to be 200 ° C or higher. In consideration of the fact that the organic material is contained, the upper limit of the glass transition temperature of the hard resin layer at 450 deg.

The tensile elastic modulus of the light-hard resin layer used in the present invention is 2,000 to 4,000 MPa. When the tensile modulus of elasticity is less than 2,000 MPa, the pencil hardness of the resin laminate is less than 6H, and when it is more than 4,000 MPa, there is a problem that workability such as molding, cutting and punching becomes difficult. In addition, since the hard resin layer used in the present invention is suitable for a display face plate, its total light transmittance must be 90% or more.

The (meth) acrylic resin copolymer can be obtained by radical copolymerization of the three-dimensional crosslinkable hard resin composition used in the present invention. Various additives may be added to the three-dimensionally crosslinkable hard resin composition of the present invention for the purpose of improving physical properties of the (meth) acrylic resin copolymer or promoting radical copolymerization. As an additive for accelerating the reaction, a thermal polymerization initiator, a thermal polymerization promoter, a photopolymerization initiator, a photoinitiator, and a photosensitizer may be exemplified. When a photopolymerization initiator or a thermal polymerization initiator is incorporated, the addition amount thereof is preferably 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 weight of the total amount of the three-dimensionally crosslinkable hard resin composition . If the addition amount is less than 0.1 part by weight, the curing becomes insufficient and the strength and rigidity of the obtained hard resin layer are lowered. On the other hand, if it exceeds 5 parts by weight, there is a possibility that problems such as coloring of the hard resin layer occur. Incidentally, the filler such as silica is not included in the total amount of 100 parts by weight of the three-dimensionally crosslinkable hard resin composition.

As the photopolymerization initiator used when the three-dimensionally crosslinkable hard resin composition is used as the photocurable composition, compounds such as acetophenone, benzoin, benzophenone, thioxanthone, and acylphosphine oxide can be suitably used. More specifically, there can be mentioned 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- -1-one, 2-hydroxy-1- [4- [2-hydroxy- Methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenyl- (4-phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1 - [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2 Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1 -hydroxy-cyclohexyl- -Morpholinophenyl) -butan-1-one, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide , Benzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone, In addition to being used alone, two or more of them may be used in combination.

The three-dimensional crosslinked hard resin composition used in the present invention can be prepared by blending a radical polymerization initiator and curing the composition by heating or light irradiation to produce a hard resin layer in an arbitrary shape such as a plane or a curved surface. When a hard resin layer having an arbitrary shape is produced by heating, the molding temperature may be selected within a wide range from room temperature to around 200 ° C depending on the choice of the thermal polymerization initiator and the accelerator. In this case, a hard resin layer having a desired shape can be obtained by polymerization-curing in a mold or on a steel belt.

When a hard resin layer is produced by light irradiation, it can be obtained by irradiating ultraviolet light having a wavelength of 10 to 400 nm or visible light having a wavelength of 400 to 700 nm. The wavelength of light to be used is not particularly limited, but near-ultraviolet rays having a wavelength of 200 to 400 nm are suitably used. Mercury lamps (output: 0.4 to 4 W / cm), high pressure mercury lamps (40 to 160 W / cm), ultra high pressure mercury lamps (173 to 435 W / cm), metal halide lamps (80 to 160 W / Cm), a pulse xenon lamp (80 to 120 W / cm), and an electrodeless discharge lamp (80 to 120 W / cm). Since these ultraviolet lamps are characterized by their spectral distribution, they are selected according to the type of photoinitiator used.

As a method of obtaining a hard resin layer having an arbitrary shape used in the present invention by light irradiation, a three-dimensional crosslinking type hard resin composition is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass , A method of producing a molded article (hard resin layer) having a desired shape by irradiating ultraviolet rays by the ultraviolet lamp to perform polymerization curing and demolding from a mold. When the mold is not used, for example, the three-dimensional crosslinkable hard resin composition of the present invention is coated on a moving steel belt using a doctor blade or a roll-shaped coater, and polymerization curing is performed by the ultraviolet lamp, And a method for producing a molded article.

Further, when the three-dimensional crosslinkable hard resin composition is cured by the ultraviolet ray irradiation method, since the ultraviolet curing reaction is a radical reaction, the reaction is inhibited by oxygen. Therefore, from the viewpoint of inhibiting reaction inhibition by oxygen in the curing reaction of the three-dimensional crosslinkable hard resin composition, it is preferable to coat the surface of the three-dimensional crosslinkable hard resin composition with a cover layer made of a transparent plastic film . The surface of the three-dimensional cross-linkable hard resin composition is covered with a cover layer, so that the oxygen concentration on the surface of the three-dimensional cross-linkable hard resin composition is preferably 1% or less, more preferably 0.1% or less. In order to reduce the oxygen concentration in this way, it is preferable to adopt a transparent plastic film having no voids on the surface and having a low oxygen permeability. Examples of the material of such a film include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene phthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, vinyl fluoride Based resins, polyamides, polyarylates, cellophane, polyethersulfone, and norbornene-based resins. These plastics can be used singly or in combination of two or more kinds.

Since the plastic film must be able to peel off from the hard resin layer and the thermoplastic resin layer made of the three-dimensional cross-linkable hard resin composition, it is preferable to use the plastic film that has been subjected to the peeling treatment such as silicone coating or fluorine coating on the surface of the plastic film desirable.

In addition, the plastic film can be used as the protective sheet 6. When used as the protective sheet 6, it is preferable to use a polyethylene terephthalate film or a polycarbonate film from the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, strength and cost.

<Thermoplastic resin layer>

The thermoplastic resin layer 3 (3b) used in the present invention is preferably excellent in transparency and is preferably a thermoplastic resin layer made of polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA ), Polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer Various resin films such as a resin, a polyether sulfone, a cellophane and an aromatic polyamide can be suitably used. From the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, hardness, moldability, strength and cost, polyethylene terephthalate, It is preferable to use acrylate or polycarbonate. These films may be unrefrigerated or stretched.

The ratio (E ₁ / E ₂ ) of the modulus of elasticity (E ₁ ) at room temperature of the thermoplastic resin layer used in the present invention to the modulus of elasticity (E ₂ ) at 150 ° C is in the range of 1 to 500. 150 DEG C is a standard temperature of a mold or an injection-molding resin at the time of molding, which will be described later. When the elastic modulus at room temperature is higher than the elastic modulus at this temperature, the shape when molded by springback by the light- It can not be maintained. Therefore, the larger the ratio of the modulus of elasticity at room temperature to the modulus of elasticity at 150 deg. C, the more easily molding at a molding temperature, and the shape can be easily maintained at room temperature. However, when the modulus of elasticity exceeds 500, the pencil hardness of the resin laminate becomes less than 6H, and it is difficult to control the shape at the time of thermoforming. For the measurement of the modulus of elasticity, the thermoplastic resin layer was subjected to dynamic viscoelastic measurement from room temperature to 230 deg. C at a heating rate of 5 deg. C / min to obtain a ratio of room temperature and a storage elastic modulus (E ') at 150 deg. The room temperature referred to in the present invention refers to a temperature of approximately 23 to 27 占 폚 and 25 占 폚 for the measurement of elastic modulus.

The ratio of the total thickness of the thermoplastic resin layer to the thickness of the hard resin layer (thermoplastic resin layer / light-hard resin layer) used in the present invention is 0.25 or more and 10 or less. If the thickness ratio is less than 0.25, there is a problem that workability such as molding, cutting and punching becomes difficult. When it exceeds 10, there is a problem that pencil hardness becomes less than 6H. It is also preferable that the thickness of the thermoplastic resin layer (in the case of a plurality of layers, the total) is 30 占 퐉 to 1000 占 퐉. If it is less than 30 mu m, there is a problem that the hard resin layer cracks or cracks in injection molding. On the other hand, when the thickness exceeds 1000 mu m, the pencil hardness becomes less than 6H, and processing becomes difficult.

The hard resin layer (1) and the thermoplastic resin layer (3) of the resin laminate according to the present invention can be laminated by any one of a film form and a sheet form. The thickness of the binder layer 2 is preferably 0.01 to 30 占 퐉, and more preferably 0.1 to 10 占 퐉. When the thickness is less than 0.01 탆, it is difficult to obtain a sufficient adhesive effect, and when the thickness is 30 탆 or more, the pencil hardness of the resin laminate can not be sufficiently obtained. The binder layer 2 here may be either of the following adhesive layer or the adhesive layer.

<Adhesive Layer>

Examples of the constituent material of the binder layer 2 include an adhesive layer using a pressure-sensitive adhesive, a pressure-sensitive adhesive, a photo-curable adhesive, a thermosetting adhesive and a hot-melt adhesive. Examples of the adhesive layer include an acrylic adhesive, a urethane adhesive, Vinyl alcohol adhesive, polyolefin adhesive, modified polyolefin adhesive, polyvinyl alkyl ether adhesive, rubber adhesive, vinyl chloride-vinyl acetate adhesive, styrene-butadiene styrene copolymer (SBS copolymer) adhesive, hydrogenated product (SEBS copolymer) , Ethylene-vinyl acetate copolymer, and ethylene-styrene copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer Acrylic acid ester adhesives and the like When adhesion, transparency and the good processability is not particularly limited.

&Lt; Adhesive layer &

Another constituent of the binder layer 2 is the adhesive layer. The adhesive layer is a layer on which chemical bonding ability or physical adhesion ability is imparted to the surface of the resin layer which is an adhesive layer. The chemical bonding capability is to form a thin film layer of a resin having a functional group on a base layer and to form a chemical bond with a hard resin layer to obtain adhesion. Physical adhesion is a function of a resin thin film layer or an inorganic thin film layer Thereby obtaining the adhesion with the hard resin layer by the anchor effect. Is as the material chemical having a bonding function polyfunctional (meth) acrylate acids, epoxy, thiol group containing compounds and the like may be mentioned, as the material physical having a bonding function SiO _2, SiN, vapor-deposited film of SiC, or the like, etc. .

Fig. 1 shows a first embodiment as an embodiment of the resin laminate according to the present invention. 1, a hard resin layer 1 is formed on both upper and lower surfaces of a thermoplastic resin layer 3 via a binder layer 2, and a hard resin layer 1 is formed on one side of the thermoplastic resin layer 3, And a protective layer 6 is formed on the outermost surfaces of the front and back surfaces. Each of the binder layers 2 functions as an adhesive layer for integrating the hard resin layer 1 and the thermoplastic resin layer 3 together.

As shown in Fig. 1, the print layer 4 is formed on the lower surface of the resin laminate according to the present invention, so that shapes, characters and the like can be formed. Examples of the print pattern of the print layer 4 include patterns of wood grain, discoloration, texture of a cloth, a flat pattern, a geometric pattern, a character, an entire surface print, and a metallic pattern.

The print layer 4 is preferably blended with a resin component having good compatibility with the hard resin layer or the thermoplastic resin layer. For example, a polyvinyl resin such as a vinyl chloride / vinyl acetate copolymer, a polyamide resin , A polyester 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. By blending these resin components, it is possible to suppress the peeling or separation of printing. Further, at the time of forming the print layer 4, a colorant containing a pigment or a dye of an appropriate color can be used.

Examples of the method for forming the print layer 4 include a coating method such as a printing method such as an offset printing method, a gravure rotary printing method and a screen printing method, a roll coating method, a spray coating method, etc., and a flexo printing method . The thickness of the printed layer 4 is suitably selected so that a desired surface appearance can be obtained in the present laminated sheet, main laminated film product or laminated sheet laminated molded product, and is preferably about 0.5 to 30 탆 .

As the second and third embodiments of the resin laminate of the present invention, for example, the structures shown in Figs. 2 and 3 can be exemplified.

2, the print layer 4 is formed on the upper surface of the thermoplastic resin layer 3, and the upper side of the print layer 4 and the print layer 4 are formed And a thermoplastic resin layer 3b is formed on the side where the print layer 4 is not formed, and a thermosetting resin layer 3b is formed on the side where the print layer 4 is not formed. And a protective sheet 6 is formed on both surfaces thereof.

In Fig. 2, the thermoplastic resin (3) to be used is not particularly limited as long as it is transparent, but polymethyl methacrylate (PMMA) is preferable. When the thermoplastic resin 3 is PMMA, when the thermoplastic resin is thicker than PC, the hard pencil hardness can be made even if the hard resin layer has a thickness close to the lower limit value.

On the other hand, in the third embodiment shown in Fig. 3, the hard resin layer 1 is formed by sandwiching the binder 2 on the upper surface of the thermoplastic resin 3 and the printed layer (not shown) is formed on the lower surface of the thermoplastic resin layer 3 The thermoplastic resin layer 3 on which the printing layer 4 is formed is formed with the thermoplastic resin 3b through the binder layer 2 or the pressure-sensitive adhesive layer 5, And a protective sheet 6 is formed. The resin laminate according to the third embodiment is suitable for machining a shape having a smaller radius of curvature r, for example.

A known pressure-sensitive adhesive can be used as the pressure-sensitive adhesive layer 5 used in the embodiment of Figs. Specifically, for example, a pressure-sensitive adhesive such as a natural rubber resin, a synthetic rubber resin, a silicone resin, an acrylic resin, a vinyl acetate resin, or a urethane resin can be used. These adhesives are not limited to these as long as they can obtain necessary light transmittance, tackiness and weather resistance. Further, depending on the layer structure, it is preferable to include a UV absorber (benzotriazole, etc.) having an effect of absorbing ultraviolet rays in the pressure-sensitive adhesive in order to prevent deterioration of the dye.

The pressure-sensitive adhesive layer 5 preferably has an average thickness of 0.01 to 30 탆, preferably 0.1 to 10 탆. When the thickness is less than 0.01 탆, sufficient adhesive strength can not be obtained, and the effect of flattening the irregularities of the printed layer is lowered. Further, when the thickness is 30 m or more, the pencil hardness of the laminate can not be sufficiently obtained.

Embodiments of the present invention In Figs. 2 and 3, a three-dimensional shape can be imparted by thermoforming in the state of the resin laminate. The thermoplastic resin layer 3 and the thermoplastic resin layer 3b in Figs. 2 and 3 can be formed by heat, and since the hard resin layer 1 has sufficient flexibility, the thermoplastic resin layer 3 and the binder layer 2). Examples of thermoforming include vacuum molding, pressure molding, and press molding.

Further, in the case of the layer structure of the resin laminate shown in Fig. 2 of the embodiment of the present invention, the A part and the B part formed in advance into a predetermined shape are preliminarily bonded via the pressure-sensitive adhesive layer 5 It is also good. That is, the A part having the protective sheet 6, the hard resin layer 1, the pressure-sensitive adhesive layer 5, the print layer 4, and the thermoplastic resin layer 3, the thermoplastic resin layer 3b, And bonding the B part composed of the protective sheet 6 through the pressure-sensitive adhesive layer 5.

Embodiment 3 of the Present Invention In the resin laminate shown in Fig. 3, a C part (a protective sheet 6, a hard resin layer 1, a binder layer 2, a thermoplastic resin layer 3, The thermoplastic resin layer 3b is injected by injection molding and then the protective sheet 6 is set up so that the protective sheet 6 is set So that the B part (thermoplastic resin layer 3b and protective sheet 6) may be formed.

Although the printing layer 4 is formed in each of Embodiments 1 to 3, the printing layer 4 may be omitted, or may be formed by an arbitrary printing method between arbitrary layers in accordance with the laminate manufacturing process do.

As shown in Fig. 3, in the present invention, a resin laminate that has been thermoformed into a predetermined shape as required can be loaded into a mold, and the thermoplastic resin can be integrated with the thermoplastic resin by injection molding. The thermoplastic resin to be injection molded is preferably one having transparency. The thermoplastic resin to be injection-molded is preferably made of polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate Polyolefins such as polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene- Aromatic polyamide and the like can be suitably used. From the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, strength and cost, it is preferable to use polyethylene terephthalate, polymethyl methacrylate or polycarbonate, From the viewpoint of impact resistance, polycarbonate is particularly preferable.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The evaluation method and symbols used in the present invention are as follows.

1) Pencil hardness: Measured according to JIS K 5600.

2) Total light transmittance: Measured according to JIS K 7361-1.

3) Film thickness: Measured using ID-SX manufactured by Mitsutoyo Co., Ltd.

4) Tensile modulus: Measured according to JIS K 7127.

5) Processability: A lutheran blade (Uchiyama Hamano, blade diameter 2 mm, straight blade) was attached to a luther machine (manufactured by Megaro Teknica), and the resin laminate obtained in the example was rotated at a rotation speed of 20,000 rpm, Cutting was performed at a processing condition of 900 mm / min. Microscopic observations were made on the cut surface, and it was found that the fracture (chipping) was observed on the cut surface and the case where it was not observed.

6) Moldability: The molded article obtained after the execution of the following vacuum pneumatic coin molding or injection molding was observed to find that any one of crack, gold, fracture and whitening was observed.

[Synthesis Example 1]

400 ml of 2-propanol (IPA) as a solvent and 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) as a basic catalyst were added to a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer. 150 ml of IPA and 126.9 g of 3-methacryloxypropyltrimethoxysilane (MTMS: SZ-6030, manufactured by Toray Dow Corning Toray Silicone Co., Ltd.) were placed in a dropping funnel, and 30 ml of an IPA solution of MTMS Min. After completion of dropwise addition of MTMS, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 500 ml of toluene. The reaction solution was washed with saturated brine until it became neutral, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered and concentrated to obtain 86 g of a cage silsesquioxane compound having a methacryloyl group on all silicon atoms. The silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

[Example 1]

(Preparation of hard resin layer)

23 parts by weight of a cage silsesquioxane compound having the methacryloyl group obtained in the above Synthesis Example on all silicon atoms, 39 parts by weight of dipentaerythritol hexaacrylate, 32 parts by weight of dicyclopentanyl diacrylate, 6 parts by weight of urethane acrylate oligomer and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed to obtain a transparent three-dimensionally crosslinkable hard resin composition. The number of moles of (meth) acrylic group per 100 g of the resin solid content contained in the three-dimensional crosslinkable hard resin composition was determined to be 0.76 for the resulting three-dimensional crosslinkable hard resin composition, using the above-described formula. Table 1 shows the composition of the three-dimensional crosslinked hard resin composition.

The abbreviations in Table 1 are as follows.

A: The compound obtained in Synthesis Example 1

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

C: trimethylolpropane trimethacrylate (Wright Ester TMP manufactured by Kyoeisha Kagaku Co., Ltd.)

D: Pentaerythritol triacrylate (Light 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: dicyclopentanyl diacrylate (dimethyloltricyclodecane diacrylate) (Light Acrylate DCP-A manufactured by Kyowa Chemical Co., Ltd.)

H: dicyclopentanyl dimethacrylate (NK Ester DCP manufactured by Shin Nakamura Kagaku Co., Ltd.)

I: Polymethyl methacrylate (PMMA (Parapet LW manufactured by Kuraray Co., Ltd., weight average molecular weight: about 34,000)

J: Urethane acrylate oligomer 1 [UF-503 (number average molecular weight: about 8800, manufactured by Kyowa Chemical Co., Ltd.)

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

L: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator, IRGACURE 184, BASF Japan)

Subsequently, a three-dimensional cross-linkable hard resin composition was cast (softened) on PET peeled to a thickness of 0.15 mm using a roll coater, and another peeled PET was laminated on the cast three-dimensionally crosslinkable hard resin composition A high-pressure mercury lamp of 30 W / cm was used to cure at an integrated exposure dose of 4000 mJ / cm &lt; 2 &gt;, and the peeled PET was entirely peeled off to obtain a sheet-like hard resin layer having a predetermined thickness (150 mu m). As a result of measuring the glass transition temperature of the obtained hard resin layer, no measurement was observed up to 300 ° C. The tensile modulus and total light transmittance of the hard resin layer were measured. The results are shown in Table 1.

(Production of resin laminate)

A cationic photo-curing adhesive (manufactured by Kyoritsu Chemical Co., Ltd.) was applied and softened to a thickness of 5 탆 in polycarbonate (PC-1151 manufactured by Teijin Co., Ltd., 200 mm x 200 mm x thickness 0.5 mm) (A part) was obtained by adhering a protective sheet to the hard resin layer by irradiating ultraviolet rays from both sides at a rate of 500 mJ / cm &lt; 2 &gt; with a metal halide lamp after bonding to the entire one surface side of the polycarbonate, . The dynamic viscoelasticity (DMA) was measured at room temperature (25 ° C) to 230 ° C at a heating rate of 5 ° C / min for the polycarbonate used as the thermoplastic resin layer, and the storage elastic modulus (E ₁ ) at room temperature The elastic modulus ratio (E ₁ / E ₂ ) was found from the storage modulus (E ₂ ) at a temperature of 120 ° C to be 1.35.

(Vacuum pressure forming example)

The resin laminate (part A) obtained above was sandwiched from above and below with silicone rubber (thickness 0.8 mm), and the resin laminate (part A) was pressed with a pressure of 5 atm and upper and lower mold temperatures of 150 deg. (A part) was formed with a curved surface shape (height b: 7 mm) having a sectional shape shown in Fig. 5 with a curved surface at four sides (curvature radius a: 8 mm) did. The pencil hardness of the surface of the hard resin layer of the obtained molded product of the resin laminate was 8H. In addition, the processability and moldability of the resin laminate were evaluated. The results are summarized in Table 2.

[Example 2]

(Preparation of hard resin layer)

23 parts by weight of a cage silsesquioxane compound having the methacryloyl group obtained in the above Synthesis Example on all silicon atoms, 39 parts by weight of dipentaerythritol hexaacrylate, 32 parts by weight of dicyclopentanyl diacrylate, 6 parts by weight of urethane acrylate oligomer and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed to obtain a transparent three-dimensionally crosslinkable hard resin composition having the composition shown in Table 1.

Subsequently, a three-dimensionally crosslinkable hard resin composition was cast (softened) on the PET having a size of 200 mm x 200 mm x thickness of 100 m using a roll coater so as to have a thickness of 0.10 mm, The laminate was cast in a three-dimensional crosslinked hard resin composition using PET as a protective sheet and then cured at a total exposure dose of 4000 mJ / cm 2 using a high-pressure mercury lamp of 30 W / cm to obtain a thermoplastic resin A sheet having PET as a resin layer was obtained. A printing layer and a binder layer were provided on the opposite side of the adhesion surface of the obtained thermoplastic resin layer of the obtained sheet to obtain a resin laminate (part C). The glass transition temperature of the hard resin layer in this part C is not observed by measurement up to 300 DEG C, and the tensile modulus and the total light transmittance of each part are as shown in Table 1. [ The elastic modulus ratio (E ₁ / E ₂ ) of PET used as the thermoplastic resin layer is also summarized in Table 1.

(Vacuum pressure forming example)

The resin laminate (C part) was sandwiched from above and below with a silicone rubber (thickness 0.8 mm), and the resin laminate (part C) was pressed for 10 seconds with a pressure drop of 5 atm and upper and lower mold temperatures of 150 to 250 캜, And a pressure holding time of 30 seconds. The pencil hardness of the hard resin layer of the obtained molded product of the resin laminate was 7H. In addition, the processability and moldability of the resin laminate were evaluated. The results are summarized in Table 2.

(Injection Molding Example)

Subsequently, the curved resin laminate (C part) is loaded in the first injection molding die of Fig. 4, and then the second injection molding die is superimposed on the first injection molding die. In this state, (Polycarbonate resin, trade name &quot; HFD1810 &quot; manufactured by SABIC CHEMICAL CO., LTD.) Which had been previously dried at 120 ° C for 24 hours was injection-molded under conditions of a resin temperature of 320 ° C, a mold temperature of 90 ° C to 120 ° C, a pressure of the mold of 300-500kg / , Thereby obtaining an injection-molded article in which a resin laminate (C part) having a hard resin layer as shown in Fig. 3 and a thermoplastic resin (part B) of 500 mu m were integrated.

[Comparative Example 1]

85 parts by weight of dipentaerythritol hexaacrylate and 15 parts by weight of PMMA were heated and kneaded at 110 DEG C and then mixed with 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator to obtain a three-dimensionally crosslinkable hard resin composition .

Subsequently, a hard resin layer was obtained in the same manner as in Example 2, and a resin laminate was prepared and evaluated. The results are shown in Table 2.

[Examples 3 to 8 and Comparative Examples 2 to 6]

In Example 3, Example 7, Comparative Example 2, and Comparative Example 4, in the same manner as in Example 1, Example 4, Example 5, Example 6, Example 8 , And Comparative Example 1, Comparative Example 3, Comparative Example 5 and Comparative Example 6, a hard resin layer and a resin laminate were obtained in the same manner as in Example 2. [ The evaluation results of the obtained molded articles are shown together in Table 2.

[Synthesis Example 2]

4.0 mol (825 g) of dicyclopentanyl acrylate, 3.0 mol (390 g) of 2-hydroxyethyl methacrylate, 3.0 mol (595 g) of 1,4-butanediol diacrylate, 4.0 mol of 1-pentene (889 g) and 2400 mL of toluene were charged into a 10.0 L reactor, 240 mmol of benzoyl peroxide were added at 90 DEG C, and the mixture was reacted for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered, dried and weighed to obtain 615 g of copolymer A (yield: 34%).

The Mw of the obtained copolymer A was 15200, the Mn was 3900 and the Mw / Mn was 3.9. Copolymer A contained 37.8 mol% of the structural units derived from dicyclopentanyl acrylate in total, 29.3 mol% of the total of the structural units derived from 2-hydroxyethyl methacrylate, the structural unit derived from 1,4-butanediol diacrylate 32.9 mol%. Further, the terminal group of the structure derived from 2,4-diphenyl-4-methyl-1-pentene is preferably selected from dicyclopentanyl acrylate, 2-hydroxyethyl methacrylate, 1,4-butanediol diacrylate and 2,4 -Diphenyl-4-methyl-1-pentene in an amount of 9.8 mol% based on the total amount. The ratio of pendant acrylate was 16.5 mol%. Mb was 0.29. Copolymer A was soluble in ethanol, 2-propanol, butanol, toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was observed.

[Synthesis Example 3]

0.24 mol (49.5 g) of dicyclopentanyl acrylate, 2.6 mol (729.4 g) of dimethyloltricyclodecane diacrylate, 0.96 mol (190.1 g) of 1,4-butanediol diacrylate, Dodecyl mercaptan, and 700 ml of toluene were charged into a 3.0 L reactor. The reaction was carried out in the same manner as in Example 1, 72 mmol of benzoyl peroxide were added at 90 占 폚 and reacted for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The resulting polymer was washed with hexane, filtered, dried and weighed to obtain 696.9 g of copolymer B (yield: 63.7 mol%).

The Mw of the obtained copolymer B was 39500, the Mn was 7240, and the Mw / Mn was 5.5. By conducting ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer A contained 4.9 mol% of the structural unit derived from dicyclopentanyl acrylate, 0.20 mol% of dimethyloltricyclodecane diacrylate, The total amount of the structural units derived from the rate was 75.5 mol% and the content of the structural unit derived from 2-hydroxypropyl acrylate was 19.6 mol%. Further, the terminal group of the structure derived from 2,4-diphenyl-4-methyl-1-pentene is preferably dicyclopentanyl acrylate, dimethylol tricyclodecane diacrylate, 2-hydroxypropyl acrylate, -Diphenyl-4-methyl-1-pentene and t-dodecyl mercaptan (hereinafter referred to as the total amount of all the structural units). On the other hand, the terminal group of the structure derived from t-dodecyl mercaptan was present in an amount of 18.6 mol% based on the total amount of all the structural units. The ratio of pendant acrylate was 43.5 mol%.

Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

[Examples 9 to 12]

A light-hard resin layer and a resin laminate were obtained in the same manner as in Example 1 except that the weight ratio shown in Table 3 was used. Table 3 shows the evaluation results of the obtained molded products.

In addition, abbreviations other than the abbreviations already listed in Table 3 are as follows.

M: Copolymer A obtained in Synthesis Example 2

N: Copolymer B obtained in Synthesis Example 3

B: dipentaerythritol hexaacrylate (manufactured by Daicel-Cytec K.K.)

O: trimethylolpropane triacrylate (manufactured by Kyowa Chemical Industry Co., Ltd.)

G: Dimethylol-tricyclodecane diacrylate (dicyclopentanyl diacrylate) (Light Acrylate DCP-A manufactured by Kyoreisha Chemical Co., Ltd.)

P: 1,9-nonanediol diacrylate (manufactured by Kyowa Shinkagaku Co., Ltd.)

Q: dicyclopentanyl acrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd.)

R: Tripapentaerythritol octaacrylate

1: hard resin layer 2: binder layer
3, 3b: thermoplastic resin layer 4: printing layer
5: Pressure-sensitive adhesive layer 6: Protective sheet

Claims (8)

(Meth) acrylic monomer having a cage-type silsesquioxane structure and having a glass transition temperature of 200 ° C or higher and a hard resin layer having a glass transition temperature of 200 ° C or higher, A resin laminate having a thermoplastic resin layer having a ratio of a room temperature elastic modulus (E ₁ ) to an elastic modulus (E ₂ ) at 150 ° C (E ₁ / E ₂ ) of 1 to 500 on at least one side, tensile modulus at 2,000~4,000㎫ groups being as well as the total light transmittance is not less than 90%, and a pencil hardness of the resin laminate of more than 6H, the total thickness of the thermoplastic resin layer (t ₁₎ to the thickness of the rigid resin layer (t ₂₎ the resin laminate wherein the ratio (t ₁ / t ₂₎ is less than or equal to 0.25 10. The method according to claim 1,
Wherein the number of moles of (meth) acrylic groups per 100 g of the solid resin component contained in the three-dimensional crosslinkable hard resin composition is 0.6 to 0.9, and the thickness of the hard resin layer is 50 to 250 탆. 3. The method according to claim 1 or 2,
Wherein a hard resin layer and a thermoplastic resin layer are laminated via an adhesive layer. 3. The method according to claim 1 or 2,
Wherein the adhesive layer is one of a pressure sensitive adhesive, a pressure sensitive adhesive, a photo-curable adhesive, a thermosetting adhesive, or a hot-melt adhesive. 3. The method according to claim 1 or 2,
Wherein the hard resin layer and the thermoplastic resin layer are laminated via the adhesive layer. 3. The method according to claim 1 or 2,
The polyfunctional (meth) acrylic monomer having a cage silsesquioxane 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 alkyl groups having ¹ to ⁶ carbon atoms, a phenyl group, a (meth) acrylic group, a (meth) acryloyloxyalkyl group, a vinyl group and an oxirane ring, And n is an integer of 6 to 14, m is a number of 0 to 4, 1 is a number of 0 to 4, and n is an integer of 0 to 4, m? 1). A method for molding a resin laminate, characterized in that the resin laminate according to claim 1 is thermoformed to give a predetermined shape. 8. The method of claim 7,
Wherein the resin laminate of the predetermined shape obtained by the molding method of the resin laminate is loaded in the mold and the thermoplastic resin is injection molded and integrated.

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