CN104057680A - Resin laminate and molding method using the same - Google Patents

Abstract

The present invention provides a resin laminate having high surface hardness and high transparency, and a molding method using the same. The above-mentioned resin laminate has at least one hard resin layer and a thermoplastic resin layer; the hard resin layer is a three-dimensional cross-linked type containing a polyfunctional (meth)acryloyl monomer having a cage silsesquioxane structure. A hard resin composition is cured, and the glass transition temperature is above 200°C; a thermoplastic resin layer is on at least one side of the hard resin layer, and the ratio of the elastic modulus at room temperature to the elastic modulus at 150°C is 1-500 The single tensile elastic modulus of the hard resin layer is 2000-4000 MPa, and the total light transmittance is more than 90%; in addition, the pencil hardness of the resin laminate is more than 6H, and the total thickness of the thermoplastic resin layer is the same as that of the hard resin layer. The thickness ratio of the layers is 0.25-10; in addition, the above-mentioned molding method is to fill the resin laminated body in a mold and inject thermoplastic resin.

Description

Resin laminate and molding method using same

technical field

The present invention relates to a moldable resin laminate with a hard coat film and a molding method using the resin laminate, which can be widely used mainly as window glass for automobiles, aircraft, buildings, schools, various shops, etc., automobiles, etc. , lampshades and daylight covers for aircraft, etc., and casings and various parts for personal computers and portable electronic devices. Among them, resin laminates in the state of transparent multilayer sheets are preferably used for display panels and the laminates using the Body forming method.

Background technique

For example, in electronic equipment such as digital cameras and mobile phones, as substrates of liquid crystal displays, etc., or as protective plates for protecting the surface of liquid crystal displays from scratches, contamination, etc., materials made of acrylic, polycarbonate, A laminate made of thermoplastic resin such as polyethylene terephthalate. Since these resins are excellent in optical properties and less likely to be broken than glass, they have come to be widely used in recent years even in fields where glass has been conventionally used. However, thermoplastic resins such as acrylic, polycarbonate, and polyethylene terephthalate have disadvantages in that surface hardness, abrasion resistance, and scratch resistance are inferior to glass, and they are easily scratched.

In order to eliminate this disadvantage, studies on surface modification of resin laminates have been conventionally conducted. For example, a method of applying a thermosetting resin or an ultraviolet curable resin to the surface of a substrate is widely practiced. In these coated resin laminates, a certain degree of improvement in wear resistance and scratch resistance can be seen, but the surface hardness is not sufficient, and the surface hardness such as pencil hardness is lower than that of glass. , there is a big problem in practice.

As a coating technology for further increasing the surface hardness of transparent plastic materials, for example, attempts have been made to increase the surface hardness by mixing a high-hardness filler into the hard coat layer (see Patent Document 1, Patent Document 2, and Patent Document 3). . In addition, as a similar method, in order to increase the film thickness of the hard coat and ease the stress generated, it has been studied to mix inorganic and/or organic cross-linked particles, or to introduce functional groups on the surface of the particles, so that it can be partially integrated with the resin of the hard coat. A so-called organic-inorganic hybrid method of crosslinking (see Patent Document 4 and Patent Document 5). In addition, attempts have been made to obtain higher surface hardness by multilayering the hard coat layer and increasing the overall thickness of the coat layer (see Patent Document 6).

However, in the examples shown as specific examples of these methods, a polyethylene terephthalate film and a cellulose triacetate film, which are inherently higher in pencil hardness than polycarbonate resins, are used as base materials, thereby making Pencil hardness is increased from 4H to 6H. Although this effect was confirmed, pencil hardness cannot be achieved with only a thin hard coating layer, so a hard base layer and auxiliary functions of inorganic materials are required. Therefore, these underlayers and inorganic materials become important factors that hinder transparency, and are not suitable for use in display devices such as liquid crystal displays.

In addition, an attempt has been made to form a two-layer coating film containing a bifunctional aminomethyl group with a specific film thickness on a polycarbonate resin base material using polycarbonate resin, which is a resin with low pencil hardness. ester acrylate, polyfunctional oligomer, polyfunctional monomer, monofunctional monomer, and UV-curable resin having a specific number of functional groups, but the maximum pencil hardness is 4H, which is not sufficient (see Patent Document 7 ).

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2002-107503

Patent Document 2: Japanese Patent Laid-Open No. 2002-060526

Patent Document 3: Pamphlet WO2010/035764

Patent Document 4: Japanese Patent Laid-Open No. 2000-112379

Patent Document 5: Japanese Patent Laid-Open No. 2000-103887

Patent Document 6: Japanese Patent Laid-Open No. 2000-052472

Patent Document 7: Japanese Patent: Publication No. 4626463

Contents of the invention

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

The inventors of the present invention conducted intensive studies to obtain a resin laminate having excellent surface hardness and high transparency, and found that by forming a hard resin layer composed of a predetermined three-dimensional crosslinked hard resin composition and The resin laminate of the predetermined thermoplastic resin layer can achieve these objects at the same time, and the present invention has been accomplished.

That is, the present invention is a resin laminate characterized in that it has at least one hard resin layer and a thermoplastic resin layer; (Meth) acryloyl monomer is cured from a three-dimensional cross-linked hard resin composition, and the glass transition temperature is above 200°C; the above-mentioned thermoplastic resin layer is on at least one side of the hard resin layer, and the elasticity at room temperature The ratio of the modulus E ₁ to the elastic modulus E ₂ at 150°C (E ₁ /E ₂ ) is 1 to 500; the single tensile elastic modulus of the hard resin layer is 2000 to 4000 MPa, and the total light transmittance In addition, the pencil hardness of the resin laminate is 6H or more, and the ratio (t ₁ /t ₂ ) of the total thickness t ₁ of the thermoplastic resin layer to the thickness t ₂ of the hard resin layer is 0.25-10. In addition, "(meth)acryloyl" contains both "methacryloyl" and "acryloyl" here, and it is the same below.

Here, it is preferable that the number of moles of (meth)acryloyl groups per 100 g of resin solid contained in the three-dimensional crosslinked hard resin composition is 0.6-0.9, and the thickness of the obtained hard resin layer is 50 μm-250 μm.

In addition, it is preferable that the above-mentioned hard resin layer and the thermoplastic resin layer are laminated via an adhesive layer, and the adhesive layer is preferably an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, etc. Adhesives or hot melt adhesives. Alternatively, the hard resin layer and the thermoplastic resin layer may be laminated via an easily bonding layer.

In addition, the polyfunctional (meth)acryloyl monomer having a cage silsesquioxane structure is preferably a compound 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)

(where R ¹ to R ⁶ are alkyl groups, phenyl groups, (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, vinyl groups, and oxirane rings with 1 to 6 carbon atoms The groups can be the same group or contain different groups, but there are at least two (meth)acryloyl 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, l is a number from 0 to 4, and m≤1.)

In addition, the present invention is a method for molding a resin laminate characterized by imparting a predetermined shape by thermoforming the above-mentioned resin laminate. Furthermore, the present invention is a molding method characterized in that the resin laminate having a hard resin layer and the thermoplastic resin are formed by filling the thus obtained resin laminate in a predetermined shape into a mold and injecting a thermoplastic resin. integration.

According to the present invention, it is possible to form a resin laminate having high surface hardness while maintaining transparency and sufficient resistance to impact and bending. Therefore, it is excellent in processability such as molding, cutting, and punching, and can be used as a display panel. , Housing with excellent design, etc.

Description of drawings

FIG. 1 is an explanatory diagram schematically showing a resin laminate according to the first aspect of the present invention.

FIG. 2 is an explanatory diagram schematically showing a resin laminate according to a second aspect of the present invention.

FIG. 3 is an explanatory diagram schematically showing a resin laminate according to a third aspect of the present invention.

Fig. 4 is a side view showing an injection molding machine used in an example of the present invention.

Fig. 5 is a cross-sectional view of a molded resin laminate.

Symbol Description

1: hard resin layer

2: adhesive layer

3, 3b: thermoplastic resin layer

4: printing layer

5; Pressure-sensitive adhesive layer

6: Protective sheet

Detailed ways

Below, the present invention is 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)acryloyl monomer having a cage silsesquioxane structure. The glass transition temperature is 200°C or higher.

Among them, the polyfunctional (meth)acryloyl monomer having the above-mentioned curable cage silsesquioxane structure is preferably a compound 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)

(where R ¹ to R ⁶ are alkyl groups, phenyl groups, (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, vinyl groups, and oxirane rings with 1 to 6 carbon atoms The groups can be the same group or contain different groups, but there are at least two (meth)acryloyl 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, l is a number from 0 to 4, and m≤1.)

That is, the polyfunctional (meth)acryloyl monomer having a cage-type silsesquioxane structure is preferably such that all silicon atoms constituting the cage contain organic functional groups having (meth)acryloyl groups or are composed of (meth)acryloyl groups. A monomer whose molecular weight distribution and structure are controlled by reactive functional groups composed of oxyalkyl groups, but part of the functional groups can also be replaced by alkyl groups, phenyl groups, etc. structure. In the case of a partially cleaved structure, the silicone chain to be connected may have a (meth)acryloyl group.

In addition, the three-dimensionally crosslinked hard resin composition of the hard resin layer 1 used in the present invention may use together a (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule. Examples of the polyfunctional (meth)acrylate include difunctional (meth)acrylates and trifunctional or higher (meth)acrylates.

Examples of difunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexanediol (meth)acrylate, long-chain aliphatic Group di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate , Propylene di(meth)acrylate, Glycerin (meth)acrylate, Triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Tetramethylene glycol Di(meth)acrylate, butanediol di(meth)acrylate, dicyclopentyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate base) acrylate, triglycerin di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, methoxy Cyclohexyl di(meth)acrylate, acryloyl isocyanurate, bis(acryloyloxyneopentyl glycol) adipate, bisphenol A di(meth)acrylate, tetrabromo Bisphenol A di(meth)acrylate, Bisphenol S di(meth)acrylate, Butylene glycol di(meth)acrylate, Phthalate di(meth)acrylate, Phosphate di(meth)acrylate ) acrylate, zinc di(meth)acrylate, etc.

In addition, examples of (meth)acrylates having more than trifunctionality include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate. ) acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, phosphoric acid tri(meth)acrylate, tri(acryloxy ethyl) isocyanurate, tris(methacryloxyethyl) isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, bis(trihydroxy Methylpropane) tetraacrylate, Alkyl-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, carboxylic acid modified dipentaerythritol penta(meth)acrylate, urethane tri(meth)acrylate, ester tri(meth)acrylate Acrylates, Urethane Hexa(meth)acrylates, Ester Hexa(meth)acrylates, etc.

In addition, the polyfunctional (meth)acrylate which has a cage silsesquioxane structure may be used individually by 1 type, and may use it in combination of 2 or more types.

In the present invention, the hard resin layer 1 composed of the three-dimensional cross-linked hard resin composition preferably has a mole number of (meth)acryloyl groups per 100 g of solid content of the three-dimensional cross-linked hard resin composition of 0.6 to 0.9. In addition, its thickness is preferably 50 μm to 250 μm. If the number of moles of (meth)acryloyl groups per 100g is less than 0.6, sufficient pencil hardness cannot be obtained, and if it exceeds 0.9, flexibility will be lost, molding will become difficult, and impact resistance will decrease, cutting, punching, etc. Machining becomes difficult. In addition, when the thickness is less than 50 μm, sufficient pencil hardness cannot be obtained, and when the thickness exceeds 250 μm, the total light transmittance decreases, and there is a problem that transparency required for displays and the like cannot be obtained.

The number of moles of (meth)acryloyl groups per 100 g of solid content of the three-dimensionally crosslinked hard resin composition is expressed by the following formula.

(Moles of (meth)acryloyl groups per 100g) = (100/molecular weight) × number of (meth)acryloyl groups in 1 molecule

It should be noted that when using a variety of polyfunctional (meth)acryloyl monomers as the three-dimensional crosslinking type hard resin composition, the average number of (meth)acryloyl groups calculated from the compounding ratio is used, and silica The average value of the number of moles of (meth)acryloyl groups was calculated based on the weight of the filler when the filler was equalized. That is, it corresponds to the molar concentration per unit mass (mol/100 g) of (meth)acryloyl groups present in the solid content of the three-dimensional crosslinked hard resin composition.

The hard resin layer 1 composed of the three-dimensional cross-linked hard resin composition forming the hard resin layer can be expressed in the number of moles of (meth)acryloyl groups per 100 g of solid content of the three-dimensional cross-linked hard resin composition It is combined with monofunctional (meth)acrylate within the range which does not deviate from the range of 0.6-0.9. However, if more than a certain amount of monofunctional (meth)acrylate is added, the surface hardness tends to decrease. Therefore, when blending for the purpose of adjusting viscosity, etc., it is preferable to limit it to a minimum. The resin composition is preferably 30% by weight or less.

Examples of monofunctional (meth)acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, and neopentyl acrylate. , isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, acrylic acid Isodecyl Acrylate, Undecyl Acrylate, Lauryl Acrylate, Tridecyl Acrylate, Myristyl Acrylate, Pentadecyl Acrylate, Isomyristyl Acrylate, Hexadecyl Acrylate Alkyl acrylate, heptadecyl acrylate, stearyl acrylate, nonadecyl acrylate, eicosyl acrylate, n-lauryl acrylate, stearyl acrylate and other alkyl acrylates, acrylic Acylmorpholine, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate -Hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, 1,4-butanediol monoacrylate, 2-hydroxyalkylacryloyl phosphate, 4- Hydroxycyclohexyl ester, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate, compounds obtained by adding cyclic ester compounds such as ε-caprolactone to the above-mentioned hydroxyl-containing acrylate compounds, Compounds obtained by the addition reaction of glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate and acrylic acid, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, acrylic acid Tetrahydrofurfuryl ester, isobornyl acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate, (2-isobutyl-2 -Methyl-1,3-dioxolan-4-yl) methyl ester, etc.

If the resin laminate of the present invention is used as a window glass for automobiles or aircraft, the surface will become hot due to direct sunlight. In addition, when used as a casing of a personal computer, portable electronic device, etc., heat is generated inside the device. Therefore, in order to prevent the hard resin layer from being deformed by heat, heat resistance is required, and the glass transition temperature needs to be 200° C. or higher. In addition, the upper limit of the glass transition temperature of a hard resin layer is 450 degreeC in consideration of containing an organic substance and causing decomposition|disassembly of an organic substance.

In addition, the single tensile elastic modulus of the hard resin layer used in the present invention is 2000 to 4000 MPa. If the tensile elastic modulus is less than 2000 MPa, the pencil hardness of the resin laminate will be less than 6H, and if it exceeds 4000 MPa, there will be a problem that processability such as molding, cutting, and punching will become difficult. Furthermore, since the hard resin layer used in the present invention is suitable for display panels and the like, its total light transmittance needs to be 90% or more.

The (meth)acrylate copolymer can be obtained by radically copolymerizing the three-dimensionally crosslinked hard resin composition used in the present invention. Various additives may be added to the three-dimensional crosslinked hard resin composition of the present invention for the purpose of improving the physical properties of the (meth)acrylic resin copolymer or promoting radical copolymerization. A thermal polymerization initiator, a thermal polymerization accelerator, a photopolymerization initiator, a photoinitiation adjuvant, a sensitizer, etc. are illustrated as an additive for promoting a reaction. When blending a photopolymerization initiator and a thermal polymerization initiator, the amount added 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 three-dimensional crosslinked hard resin composition in total. range. If the added amount is less than 0.1 parts by weight, curing becomes insufficient, resulting in low strength and rigidity of the hard resin layer. On the other hand, if it exceeds 5 parts by weight, problems such as coloring of the hard resin layer may occur. It should be noted that fillers such as silica are not included in a total of 100 parts by weight of the three-dimensional crosslinked hard resin composition.

As the photopolymerization initiator used when making the three-dimensional crosslinked hard resin composition into a photocurable composition, acetophenone series, benzoin series, benzophenone series, thioxanthone (チオキサンスンスンスン) ) series, acyl phosphine oxide series and other compounds. More specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl Base-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-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, methyl phenylglyoxylate, 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyl oxime), 2,4,6-trimethyl phenylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenylketone , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-one, bis-2,6-dimethoxybenzoyl-2,4, 4-trimethylpentylphosphine oxide, benzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4- Propoxythioxanthone, these may be used alone or in combination of two or more.

The three-dimensional crosslinked hard resin composition used in the present invention can be cured by heating or light irradiation by adding a radical polymerization initiator, so that a hard resin layer can be produced in any shape such as a flat surface or a curved surface. When a hard resin layer of an arbitrary shape is produced by heating, the molding temperature can be selected from a wide range from room temperature to about 200°C depending on the selection of thermal polymerization initiators and accelerators. At this time, a hard resin layer having a desired shape can be obtained by polymerizing and solidifying in a mold or on a steel belt.

Moreover, when manufacturing a hard resin layer by light irradiation, it can obtain by irradiating the ultraviolet-ray of wavelength 10-400nm, and the visible ray of wavelength 400-700nm. The wavelength of light to be used is not particularly limited, but it is particularly preferable to use near ultraviolet light with a wavelength of 200 to 400 nm. Examples of lamps used as sources of ultraviolet rays include low-pressure mercury lamps (output: 0.4 to 4W/cm), high-pressure mercury lamps (40 to 160W/cm), ultra-high pressure mercury lamps (173 to 435W/cm), and metal halide lamps. object lamp (80~160W/cm), pulse xenon lamp (80~120W/cm), electrodeless discharge lamp (80~120W/cm), etc. Since each of these ultraviolet lamps has its own characteristics in terms of its spectral distribution, it is selected according to the type of photoinitiator used.

As a method of obtaining a hard resin layer of an arbitrary shape used in the present invention by light irradiation, for example, a method of injecting a three-dimensional cross-section into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass The hard resin composition is polymerized and cured by irradiating ultraviolet light with the above-mentioned ultraviolet lamp, and released from the mold to manufacture a molded body (hard resin layer) of a desired shape. In the case of not using a mold, for example, the following method can be exemplified: on a moving steel strip, use a doctor blade or a roll-shaped coater to coat the three-dimensional crosslinked hard resin composition of the present invention, and use the above-mentioned ultraviolet ray A lamp is used to polymerize and solidify, thereby producing a sheet-like molded body.

It should be noted that when the three-dimensional crosslinked hard resin composition is cured by the ultraviolet irradiation method in this way, since the ultraviolet curing reaction is a radical reaction, the reaction is inhibited by oxygen. Therefore, from the viewpoint of inhibiting the reaction hindrance caused by oxygen in the curing reaction of the three-dimensional crosslinking type hard resin composition, it is preferable to use a transparent plastic film after coating the three-dimensional crosslinking type hard resin composition. The formed protective layer covers its surface. In addition, the oxygen concentration on the surface of the three-dimensional crosslinked hard resin composition is preferably 1% or less, more preferably 0.1% or less, by covering the surface of the three-dimensional crosslinked dendritic hard resin composition with the protective layer in this way. In order to reduce the oxygen concentration in this way, it is preferable to use a transparent plastic film that has no voids on the surface and has a low oxygen transmission rate. Examples of such film materials include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, vinyl fluoride resin, polyamide, polyarylate, cellophane, polyethersulfone, norbornene resin and other plastics. These plastics can be used individually by 1 type or in combination of 2 or more types.

Since the above-mentioned plastic film must be peelable from the hard resin layer and thermoplastic resin layer composed of a three-dimensional crosslinked hard resin composition, it is preferable to use a plastic film that has been subjected to an easy-release treatment such as silicon coating or fluorine coating on the surface of the plastic film. plastic film.

In addition, the above-mentioned 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 viewpoint of heat resistance, transparency, weather resistance, solvent resistance, rigidity, and cost.

<Thermoplastic resin layer>

As the thermoplastic resin layer 3 (3b) used in the present invention, it is preferably excellent in transparency, and polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate, etc. can be preferably used. Ester (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), poly Vinyl chloride (PVC), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, aromatic polyamide and other resin films, from heat resistance, transparency, weather resistance, solvent resistance , hardness, moldability, stiffness, and cost, it is preferable to use polyethylene terephthalate, polymethyl methacrylate, or polycarbonate. As these films, unstretched films may be used, or stretched films may be used.

The ratio (E ₁ /E ₂ ) of the elastic modulus E ₁ at room temperature to the elastic modulus E ₂ at 150° C. of the thermoplastic resin layer used in the present invention is in the range of 1 to 500. Assuming that the standard temperature of the mold or injection molding resin at the time of molding described later is 150°C, if the elastic modulus at room temperature is higher than the elastic modulus at this temperature, it will change due to the elastic deformation recovery caused by the hard resin layer. It is impossible to maintain the shape when molded. Therefore, the larger the ratio of the elastic modulus at room temperature to the elastic modulus at 150°C, the easier it is to mold at the molding temperature, and the easier it is to maintain the shape at room temperature. Therefore, when the elastic modulus ratio exceeds 500, the pencil hardness of the resin laminate becomes lower than 6H, and there is a problem that shape control during thermoforming becomes difficult. It should be noted that in the measurement of the elastic modulus ratio, the thermoplastic resin layer was heated from room temperature to 230°C at a temperature increase rate of 5°C/min for dynamic viscoelasticity measurement, and the storage elastic modulus at room temperature and 150°C (E ')Ratio. It should be noted that the room temperature referred to in the present invention refers to a temperature of about 23 to 27°C, and 25°C is used as a reference in the measurement of the elastic modulus.

The ratio of the total thickness of the thermoplastic resin layers used in the present invention to the thickness of the hard resin layer (thermoplastic resin layer/hard resin layer) is 0.25-10. If the thickness ratio is less than 0.25, there is a problem that the processability such as molding, cutting, and piercing becomes difficult, and if it exceeds 10, there is a problem that the pencil hardness is lower than 6H. It should be noted that the thickness of the thermoplastic resin layer (in the case of multiple layers, the total) is preferably 30 μm to 1000 μm. If it is less than 30 μm, there is a problem that cracks and cracks are generated in the hard resin layer during injection molding. On the other hand, if it exceeds 1000 μm, there is a problem that the pencil hardness is lower 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 the pressure-sensitive adhesive layer 2 in either a film shape or a sheet shape. The pressure-sensitive adhesive layer 2 preferably has a thickness of 0.01 to 30 μm, more preferably 0.1 to 10 μm. If it is less than 0.01 μm, it will be difficult to obtain a sufficient adhesive effect, and if it is more than 30 μm, it will not be possible to sufficiently obtain the pencil hardness of the resin laminated body. It should be noted that the adhesive layer 2 here may be any one of the following adhesive layer or easy-adhesion layer.

<Adhesive layer>

Examples of the layer constituting the adhesive layer 2 include adhesive layers using adhesive adhesives, pressure-sensitive adhesives, photocurable adhesives, thermosetting adhesives, and hot-melt adhesives. , As such adhesives, acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified Non-toxic polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl chloride-vinyl acetate adhesives, styrene-butadiene-styrene copolymer (SBS copolymer) adhesives agent, its hydrogenated product (SEBS copolymer) adhesive, ethylene-vinyl acetate copolymer, ethylene-styrene copolymer and other ethylene adhesives, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer It is not particularly limited as long as adhesiveness, transparency, and processability are good, such as ethylene-ethyl methacrylate copolymer and acrylate adhesives such as ethylene-ethyl acrylate copolymer.

〈Easily Adhesive Layer〉

Moreover, an easily bonding layer is mentioned as another layer which comprises the pressure-sensitive adhesive layer 2. The easily-adhesive layer is a layer in which the surface of the poorly-adhesive resin layer is treated to provide chemical or physical adhesive properties. Chemical easy adhesion performance refers to the performance of obtaining adhesion by forming a thin film layer of resin with functional groups on the substrate layer and forming a chemical bond with the hard resin layer. Physical easy adhesion performance refers to the performance of forming on the substrate layer. A resin film layer or an inorganic film layer with concavo-convexity, thereby utilizing the anchoring effect to obtain the performance of the adhesive force with the hard resin layer. Examples of materials with chemical adhesion properties include polyfunctional (meth)acrylates, epoxies, and mercapto-containing compounds, and materials with physical adhesion properties include SiO ₂ , SiN, etc. , SiC and other vapor-deposited films.

In FIG. 1, 1st Embodiment is shown as an example of embodiment of the resin laminated body which concerns on this invention. As shown in FIG. 1 , the resin laminate is as follows: on both sides of the thermoplastic resin layer 3, a hard resin layer 1 is formed on the upper and lower sides through an adhesive layer 2, and on one side of the hard resin layer 1 The lower surface has a structure including a printed layer 4 , and a protective sheet 6 is formed on the outermost surface on the back of these surfaces. Among them, each adhesive layer 2 functions as an adhesive layer for integrating the hard resin layer 1 and the thermoplastic resin layer 3 .

As shown in FIG. 1 , by forming the printing layer 4 on the lower surface of the resin laminate according to the present invention, graphics, text, and the like can be formed. The printing pattern of the printing layer 4 includes patterns such as wood grain, stone grain, cloth grain, sand grain, geometric figure, text, solid surface (full surface), metal, etc., and can be set arbitrarily.

It is preferable to mix a resin component having good affinity with the hard resin layer and the thermoplastic resin layer in the printing layer 4, for example, polyvinyl-based resins such as vinyl chloride/vinyl acetate copolymers, polyamide-based resins, Polyester-based resins, acrylic resins, polyurethane-based resins, polyvinyl acetal-based resins, polyester-urethane-based resins, cellulose ester-based resins, alkyd resins, chlorinated polyolefin resins, and the like. By blending such a resin component, peeling and peeling of printing can be suppressed. In addition, when forming the printed layer 4, a colorant containing a pigment or dye of an appropriate color can be used.

Examples of the method for forming the printing layer 4 include printing methods such as offset printing, gravure printing, and screen printing; coating methods such as roll coating and spray coating; and flexographic printing. In addition, the thickness of the printing layer 4 may be appropriately selected so as to obtain a desired surface appearance in the laminated sheet, the laminated product of the film, or the laminated product of the laminated sheet, and is usually preferably 0.5 to 30 μm. about.

About the resin laminated body of this invention, the structure shown to FIG. 2, FIG. 3 can be illustrated as 2nd, 3rd embodiment.

Among them, in the second embodiment shown in FIG. 2 , a printing layer 4 is formed on the upper surface of the thermoplastic resin layer 3 , and pressure-sensitive adhesives are respectively sandwiched between the upper part of the printing layer 4 side and the side where the printing layer 4 is not formed. The hard resin layer 1 is formed on the printed layer 4 side, the thermoplastic resin layer 3b is formed on the side where the printed layer 4 is not formed, and the protective sheets 6 are formed on both sides of the adhesive layer 5 .

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

On the other hand, in the 3rd embodiment shown in FIG. 4. A thermoplastic resin 3 b is formed on the lower surface of the thermoplastic resin layer 3 on which the printing layer 4 is formed via the adhesive layer 2 or the pressure-sensitive adhesive layer 5 , and protective sheets 6 are formed on both surfaces thereof. Such a resin laminated body in the third embodiment is suitable for, for example, processing of a shape having a smaller curvature radius r.

A well-known pressure-sensitive adhesive can be used for the pressure-sensitive adhesive layer 5 used in the embodiment of FIG. 2 and FIG. 3 . Specifically, for example, binders such as natural rubber-based resins, synthetic rubber-based resins, silicone-based resins, acrylic resins, vinyl acetate-based resins, and urethane-based resins can be used. These adhesives are not limited as long as the desired light transmission properties, adhesive properties, and weather resistance can be obtained. In addition, depending on the layer structure, in order to prevent deterioration of the pigment, it is preferable to contain a UV absorber (benzotriazole, etc.) having an effect of absorbing ultraviolet rays in the binder.

The pressure-sensitive adhesive layer 5 has an average thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm. If it is less than 0.01 μm, sufficient adhesive strength cannot be obtained, and the effect of absorbing and flattening unevenness of the printed layer also decreases. Moreover, when it is 30 micrometers or more, the pencil hardness of a laminated body cannot fully be obtained.

In FIGS. 2 and 3 as embodiments of the present invention, a three-dimensional shape can be imparted by thermoforming in the state of the resin laminate. The thermoplastic resin layers 3 and 3b in FIGS. 2 and 3 can be molded by heat. Since the hard resin layer 1 has sufficient flexibility, it can follow the shape of the thermoplastic resin layer and form an integral molded product through the adhesive layer 2. . Examples of thermoforming include vacuum forming, pressure forming, and press forming.

In addition, in the case of a layered structure such as the resin laminate shown in FIG. 2 according to the embodiment of the present invention, it is possible to use the A part and the B part respectively molded into predetermined shapes in advance, and bond them via the pressure-sensitive adhesive layer 5. . That is, it is possible to combine the A portion comprising the protective sheet 6, the hard resin layer 1, the pressure-sensitive adhesive layer 5, the printing layer 4, and the thermoplastic resin layer 3 with the B portion composed of the thermoplastic resin layer 3b and the protective sheet 6. A part is bonded via the pressure-sensitive adhesive layer 5 .

In addition, for the resin laminate shown in FIG. 3 of the embodiment of the present invention, part C (protective sheet 6, hard resin layer 1, adhesive layer 2, thermoplastic resin layer 3. Printing layer 4, and adhesive layer 2 (or pressure-sensitive adhesive layer 5)), and injection molding is used to inject thermoplastic resin layer 3b, and then set protective sheet 6 to form part B (thermoplastic resin layer 3b and protective sheet 6).

It should be noted that the printed layers 4 are respectively formed in Figs. 1 to 3 of the embodiment, but the printed layers 4 may be omitted, and may be formed between any layers by any printing method in accordance with the laminate manufacturing process.

As shown in FIG. 3 , in the present invention, a resin laminate that is thermoformed as necessary to form a predetermined shape is charged in a mold, and the thermoplastic resin is injection-molded, thereby enabling integration with the thermoplastic resin. The thermoplastic resin for injection molding in this way is preferably transparent, and polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl Methyl acrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin Various resin films such as copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aramid, from the viewpoint of heat resistance, transparency, weather resistance, solvent resistance, stiffness, and cost, Polyethylene terephthalate, polymethyl methacrylate, or carbonate is preferably used, and polycarbonate is particularly preferable from the viewpoint of impact resistance.

Example

Hereinafter, the present invention will be described in more detail using examples. In addition, the evaluation method and symbol used in this invention are as follows.

1) Pencil hardness Hardness: Measured based on JIS K5600.

2) Total light transmittance: measured based on JIS K7361-1.

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

4) Tensile modulus of elasticity: measured based on JIS K7127.

5) Machinability: A router (manufactured by Uchizawa, blade diameter 2 mm, straight edge) was installed in a router (ルーター) processing machine (manufactured by MEGAROTECHNICA Co., Ltd.), and processed under the processing conditions of 20,000 rpm and 900 mm/min of feed rate. The resin laminates obtained in Examples were machined, and the cut surfaces were observed under a microscope. When a chip (chip) was observed on the cut surface, it was rated as ×, and when it was not observed, it was rated as ◯.

6) Moldability: Observe the molded body obtained after performing the following vacuum compression molding or injection molding, and evaluate the case where any of cracks, cracks, cracks, and whitening is observed as ×, and it will be evaluated as a good state is ○.

[Synthesis Example 1]

Into a reaction container equipped with a stirrer, a dropping funnel, and a thermometer, 400 ml of 2-propanol (IPA) as a solvent and 5% aqueous tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were charged. 150 ml of IPA and 126.9 g of 3-methacryloxypropyltrimethoxysilane (MTMS: Dow Corning Toray Silicone Co., Ltd. SZ-6030) were added to the dropping funnel, and the reaction vessel was stirred at room temperature for 30 minutes. A solution of MTMS in IPA was added dropwise. After the dropwise addition of MTMS was completed, 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 then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 86 g of a cage-type silsesquioxane compound having methacryloyl groups on all silicon atoms. The silsesquioxane is a colorless viscous liquid soluble in various organic solvents.

[Example 1]

(Preparation of hard resin layer)

The cage-type silsesquioxane compound having methacryloyl groups on all silicon atoms obtained in the above synthesis example was mixed: 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, dicyclopentyl diacrylate: 32 parts by weight, Parts by weight, urethane acrylate oligomer 1: 6 parts by weight, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight, and a transparent three-dimensional crosslinked hard resin composition was obtained. For the obtained three-dimensional cross-linked hard resin composition, the number of moles of (meth)acryloyl groups per 100 g of resin solid content contained in the three-dimensional cross-linked hard resin composition was calculated using the formula described above, and the result was 0.76. Table 1 shows the composition of the three-dimensionally crosslinked hard resin composition.

In addition, the abbreviations in Table 1 are as follows.

A: The compound obtained in Synthesis Example 1

B: Dipentaerythritol hexaacrylate (KAYARADDPHA manufactured by Nippon Kayaku Co., Ltd.)

C: Trimethylolpropane trimethacrylate (LightEster TMP manufactured by Kyoeisha Chemical Co., Ltd.)

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

H: Dicyclopentyl dimethacrylate (NK EsterDCP manufactured by Shin-Nakamura Chemical Co., Ltd.)

I: Polymethyl methacrylate (PMMA) (Parapet LW manufactured by KURARAY Co., Ltd.: weight average molecular weight about 34000)

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

K: Urethane acrylate oligomer 2 (NK OligoUA-122P manufactured by Shin-Nakamura Chemical Co., Ltd.: number average molecular weight about 1100)

L: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator, IRGACURE 184 manufactured by BASF Japan Co., Ltd.)

Next, using a roll coater, the three-dimensional crosslinked hard resin composition was cast (cast) on the peeled PET so that the thickness became 0.15 mm, and the other peeled PET was laminated on the After casting the three-dimensional cross-linked hard resin composition, use a 30W/cm high-pressure mercury lamp to cure it with a cumulative exposure dose of 4000mJ/ ^cm2 , and remove all the PET that has been peeled off, thus obtaining It becomes a sheet-shaped hard resin layer with a predetermined thickness (150 μm). As a result of measuring the glass transition temperature of the obtained hard resin layer, no glass transition temperature was observed in the measurement up to 300°C. In addition, the tensile elastic modulus and total light transmittance of the hard resin layer were measured. The results are shown in Table 1.

(Manufacturing of resin laminates)

Polycarbonate (PC-1151, manufactured by Teijin Corporation, 200mm×200mm×thickness: 0.5mm) was coated and cast with a cationic photocurable adhesive (manufactured by Kyoritsu Chemical Industry Co., Ltd.) to a thickness of 5 μm , the hard resin layer obtained above is attached to the entire surface of one side of polycarbonate, and after crimping, a metal halide lamp is used to irradiate ultraviolet light from both sides at a ratio of 500mJ/cm ² to treat the hard resin layer. A protective sheet was provided to obtain a resin laminate (part A). It should be noted that the polycarbonate used as a thermoplastic resin layer is heated from room temperature (25°C) to 230°C at a temperature increase rate of 5°C/min, and the dynamic viscoelasticity (DMA) is measured, based on the storage elastic modulus at room temperature The elastic modulus ratio (E ₁ /E ₂ ) was calculated from the quantity E ₁ and the storage elastic modulus E ₂ at 150°C, and the result was 1.35.

(Example of vacuum compression molding)

The resin laminated body (A part) obtained above is sandwiched from the top and bottom by silicone rubber (thickness 0.8mm), and the resin laminated body (A part) is molded at a pressure of 5 atmospheres and a mold temperature of 150°C to 250°C above and below. The delay until depressurization was 10 seconds, and the pressure holding time was 30 seconds, whereby the resin laminate (part A) was molded into a curved surface with four sides (curvature radius a: 8mm) and a cross-sectional shape as shown in Fig. 5 shape (height b: 7mm). When the pencil hardness of the surface of the hard resin layer was measured about the molded body of the obtained resin laminate, it was 8H. In addition, the processability and moldability of the above-mentioned resin laminate were evaluated. The results are collectively shown in Table 2.

[Example 2]

(Preparation of hard resin layer)

The cage-type silsesquioxane compound having methacryloyl groups on all silicon atoms obtained in the above synthesis example was mixed: 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, dicyclopentyl diacrylate: 32 parts by weight, Parts by weight, urethane acrylate oligomer 1:6 parts by weight, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight, and a transparent three-dimensional Cross-linked hard resin composition.

Next, using a roll coater, the three-dimensional cross-linked hard resin composition was cast (cast) on 200 mm x 200 mm x 100 μm thick PET that was subjected to an easy-adhesive treatment so that the thickness became 0.1 mm. After laminating other peeled PET of the same size as a protective sheet on the cast three-dimensional cross-linked hard resin composition, a high-pressure mercury lamp of 30W/cm was used with a cumulative exposure of 4000mJ/ ^cm2 This was cured to obtain a sheet having PET as a thermoplastic resin layer on both the front and back sides of the hard resin layer (100 μm). A printing layer and an adhesive layer were provided on the surface opposite to the easy-adhesion surface of the obtained thermoplastic resin layer subjected to the easy-adhesion treatment to obtain a resin laminate (part C). The glass transition temperature of the hard resin layer in the part C was not observed in the measurement up to 300°C, and the individual tensile modulus and total light transmittance are shown in Table 1. In addition, the elastic modulus ratio (E ₁ /E ₂ ) of PET used as the thermoplastic resin layer is collectively shown in Table 1 as well.

(Example of vacuum compression molding)

The obtained resin laminated body (C part) is clamped from top to bottom by silicone rubber (thickness 0.8mm), and the resin laminated body (C part) is compressed at a pressure of 5 atmospheres at a mold temperature of 150°C to 250°C at the top and bottom. The delay is 10 seconds, and the pressure holding time is 30 seconds, thereby forming the same curved surface shape as in Example 1. When the pencil hardness of the hard resin layer was measured about the molded body of the obtained resin laminate, it was 7H. In addition, the processability and moldability of the above-mentioned resin laminate were evaluated. The results are collectively shown in Table 2.

(Injection molding example)

Next, after filling the curved-surface-molded resin laminate (part C) in the first injection mold shown in FIG. 4 , the second injection mold was superimposed on the first injection mold. Under the conditions of temperature 320°C, mold temperature 90°C-120°C, mold internal pressure 300-500kg/cm ² , and injection time 5 seconds, inject the mold that has been dried at 120°C for 24 hours from the injection gate to the cavity in the mold. Polycarbonate resin (manufactured by SABIC, trade name "HFD1810"), thereby obtaining a resin laminate (part C) having a hard resin layer and a thermoplastic resin (part B) 500 μm integrated as shown in Figure 3 injection molded body.

[Comparative example 1]

Dipentaerythritol hexaacrylate: 85 parts by weight, PMMA: 15 parts by weight were heated and kneaded to 110°C, and then 1-hydroxycyclohexyl phenyl ketone: 2.5 parts by weight as a photopolymerization initiator was mixed to obtain three-dimensional crosslinking Type hard resin composition.

Next, in the same manner as in Example 2, after obtaining the hard resin layer, a resin laminate was produced and evaluated. The results are shown in Table 2.

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

Make the compounding composition into the weight ratio shown in Table 1, in addition, in embodiment 3, embodiment 7, comparative example 2 and comparative example 4 in the same manner as embodiment 1, in embodiment 4, embodiment 5, In Example 6, Example 8, 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. Table 2 shows the evaluation results of the obtained molded body together.

[Synthesis Example 2]

4.0 moles (825g) of dicyclopentyl acrylate, 3.0 moles (390g) of 2-hydroxyethyl methacrylate, 3.0 moles (595g) of 1,4-butanediol diacrylate, 2,4-diphenyl - 4.0 moles (889 g) of 4-methyl-1-pentene and 2,400 ml of toluene were put into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90° C., 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 15 g of copolymer A (yield: 34%)

Mw of the obtained copolymer A was 15200, Mn was 3900, and Mw/Mn was 3.9. Copolymer A contains a total of 37.8 mol% of structural units derived from dicyclopentyl acrylate, a total of 29.3 mol% of structural units derived from 2-hydroxyethyl methacrylate, and a total of 29.3 mol% of structural units derived from 1,4-butanediol diacrylate. Structural unit 32.9 mol%. In addition, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is compared to dicyclopentyl acrylate, 2-hydroxyethyl methacrylate, 1,4-butylene The total amount of alcohol diacrylate, and 2,4-diphenyl-4-methyl-1-pentene was present at 9.8 mol%. In addition, the ratio of side chain acrylate (pendent acrylate) was 16.5 mol%. Mb is 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 moles (49.5g) of dicyclopentyl acrylate, 2.6 moles (729.4g) of dimethyloltricyclodecane diacrylate, 0.96 moles (190.1g) of 1,4-butanediol diacrylate, acrylic acid 0.96 moles (124.9g) of 2-hydroxypropyl ester, 0.48 moles (113.4g) of 2,4-diphenyl-4-methyl-1-pentene, 3.12 moles (631.5g) of tertiary dodecyl mercaptan, 700 ml of toluene was put into a 3.0 L reactor, and 72 mmol of benzoyl peroxide was added at 90° C. to react 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 696.9 g of copolymer B (yield: 63.7 mol %).

Mw of the obtained copolymer B was 39500, Mn was 7240, and Mw/Mn was 5.5. As a result of ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer A contained 4.9 mol% of structural units derived from dicyclopentyl acrylate, and contained 4.9 mol% of structural units derived from dimethyloltricyclodecane diacrylate and The structural units of 1,4-butanediol diacrylate totaled 75.5 mol%, and contained 19.6 mol% of structural units derived from 2-hydroxypropyl acrylate. In addition, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene was compared to that derived from dicyclopentyl acrylate, dimethyloltricyclodecane diacrylate, The total amount of end groups in the structure of -hydroxypropyl ester, 2,4-diphenyl-4-methyl-1-pentene, and t-dodecylmercaptan (hereinafter referred to as the total amount of the total constituent units ) present at 3.7 mol%. On the other hand, the terminal group derived from the structure of t-dodecylmercaptan was present in 18.6 mol % with respect to the total amount of the total constitutional units. And the ratio of the side chain acrylate was 43.5 mol%.

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

[Embodiments 9-12]

Except having made the compounding composition into the weight ratio shown in Table 3, it carried out similarly to Example 1, and obtained the hard resin layer and the resin laminated body. Table 3 shows the evaluation results of the obtained molded body together.

[table 3]

Example 9 Example 10 Example 11 Example 12 m 10 10 N 20 B 35 35 30 20 o 35 35 30 25 P 20 20 Q 20 G 30 R 20 J 5 L 2.5 2.5 2.5 2.5 Acryloyl moles 0.79 0.73 0.72 0.81 film thickness 150 150 150 150 Tensile modulus of elasticity 2620 2250 2150 3050 Transmittance 90.6 90.5 90.3 90.1 Part A PC(500um) PC(500um) PC(500um) PC(500um) Part B Part C Elastic modulus ratio 1.35 1.35 1.35 1.35 Thickness ratio 3.33 3.33 3.33 3.33 pencil hardness 8H 6H 6H 8H Processability ○ ○ ○ ○ Formability ○ ○ ○ ○

In addition, the abbreviations other than the above 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 Co., Ltd.)

O: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

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

P: 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

Q: Dicyclopentyl acrylate (manufactured by Hitachi Chemical Industries, Ltd.)

R: Tripentaerythritol octaacrylate

Claims (8)

1. A resin laminate, characterized in that it has at least one hard resin layer and a thermoplastic resin layer; based) a three-dimensional cross-linked hard resin composition of acryloyl monomer cured, and the glass transition temperature is above 200 ° C; the thermoplastic resin layer is on at least one side of the hard resin layer, and the elasticity at room temperature The ratio E ₁ /E ₂ of the modulus E ₁ to the elastic modulus E ₂ at 150°C is 1-500; the single tensile elastic modulus of the hard resin layer is 2000-4000 MPa, and the total light transmittance is 90 % or more; in addition, the pencil hardness of the resin laminate is 6H or more, and the ratio t ₁ /t ₂ of the total thickness t ₁ of the thermoplastic resin layer to the thickness t ₂ of the hard resin layer is 0.25-10. 2. The resin laminate according to claim 1, wherein the number of moles of (meth)acryloyl groups per 100 g of resin solid content contained in the three-dimensionally crosslinked hard resin composition is 0.6 to 0.9, and, The thickness of the hard resin layer is 50 μm to 250 μm. 3. The resin laminate according to claim 1 or 2, wherein the hard resin layer and the thermoplastic resin layer are laminated via an adhesive layer. 4. The resin laminate according to claim 1 or 2, wherein the adhesive layer is an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, or Any of the hot melt adhesives. 5. The resin laminate according to claim 1 or 2, wherein the hard resin layer and the thermoplastic resin layer are laminated via an easily bonding layer. 6. The resin laminate according to claim 1 or 2, wherein the polyfunctional (meth)acryloyl 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) In the formula, R ¹ to R ⁶ are groups having alkyl, phenyl, (meth)acryloyl, (meth)acryloyloxyalkyl, vinyl, or oxirane rings with 1 to 6 carbon atoms groups, which can be the same group or contain different groups, but there are at least two (meth)acryloyl groups in the formula, n, m, and l are average values, n is a number from 6 to 14, and m is A number of 0 to 4, l is a number of 0 to 4, and m≤1. 7. A method for molding a resin laminate, wherein a predetermined shape is imparted by thermoforming the resin laminate according to claim 1. 8. The molding method of a resin laminated body according to claim 7, wherein the resin laminated body of a predetermined shape obtained by the method according to claim 7 is filled in a mold, and a thermoplastic resin is injected and molded to form an integral body. change.