TW201438909A - Resin laminate and a forming method using the resin laminate - Google Patents

Abstract

This invention provides a resin laminate having a high surface hardness and high transparency, and a forming method using the resin laminate. The resin laminate has a at least one layer of hard resin layer constituted by hardening a three dimensionally cross-linked hard resin composition containing a multifunctional (meth) acyclic monomer having a cage type silsesquioxane construction which has a glass transition temperature of 200 DEG C or higher, and a thermoplastic resin layer on at least one surface of the hard resin layer, the thermoplastic resin layer having a ratio of an elasticity at room temperature to an elasticity at 150 DEG C of 1 to 500. The hard resin layer has tensile elasticity as a single substance of 2, 000 to 4, 000 MPa and full light permeability of 90% or higher. The resin laminate has a pencil hardness of 6H or higher, and a ratio of the sum of the thickness of the thermoplastic resin layers to the thickness of the hard resin layer of 0.25 or more to 10 or less. This invention also provides a forming method for injection molding a thermoplastic resin by placing the resin laminate in a mold.

Description

Resin laminate and forming method using the same

The present invention relates to a formable resin laminate with a hard coat film, and a method for forming the resin laminate, that is, for example, in addition to windows, automobiles, buildings, schools, window panes of various shops, etc., or In addition to the lamp cover and the lighting cover of automobiles, airplanes, etc., it is widely used as a frame or various parts such as a personal computer or a portable electronic device, and is also suitable for a display panel and has a transparent multilayer sheet. A resin laminate in a state, and a molding method using the resin laminate.

For example, in an electronic device such as a digital camera or a mobile phone, a laminate made of a thermoplastic resin such as acrylic or polycarbonate or polyethylene terephthalate is used as a substrate for a liquid crystal display or the like. A protective plate or the like for preventing damage or contamination of the surface of a liquid crystal display or the like. These resins have been widely used in the field of using glass because they have excellent optical characteristics and are less likely to be broken than glass. However, thermoplastic resins such as acrylic acid, polycarbonate, and polyethylene terephthalate have poor surface hardness, abrasion resistance, and scratch resistance as compared with glass, and are disadvantageous in that they are easily scratched.

In order to eliminate this disadvantage, the laminate with the resin has been gradually carried out in the past. Research on surface modification. For example, it is widely applied to apply a thermosetting resin or an ultraviolet curable resin to the surface of a substrate. In the resin laminated body to which the coating is applied, although the abrasion resistance and the scratch resistance are somewhat improved, the surface hardness is still insufficient, and the surface of the pencil hardness or the like is compared with the glass. Low hardness and practical problems.

A coating technique for further improving the surface hardness of a transparent plastic material, for example, an attempt has been made to mix a high-hardness filler into a hard coat layer to increase the surface hardness (refer to Patent Document 1, Patent Document 2, and Patent Document 3). In addition, in a similar method, it has been studied to set a film thickness of a hard coat layer to a large extent, and to mix inorganic and/or organic crosslinked particles for mitigating the generated stress, or to introduce a functional group to the surface of the particle. The so-called organic-inorganic hybrid method in which the resin of the hard coat layer is partially crosslinked (refer to Patent Document 4 and Patent Document 5). Further, attempts have been made to multilayer the hard coat layer to increase the thickness of the entire coating layer, thereby obtaining a higher surface hardness (refer to Patent Document 6).

However, as a specific example of such methods, a polyethylene terephthalate film or a cellulose triacetate film having a higher pencil hardness than polycarbonate is used as a substrate to achieve a pencil hardness of 4H. 6H, although this effect can be demonstrated, since it is not possible to achieve pencil hardness with only a thin hard coat layer, it is necessary to have an auxiliary function of a hard underlayer or an inorganic material. Therefore, such underlying or inorganic materials are factors that hinder transparency, and are not suitable as display devices for liquid crystal displays.

In addition, some people have tried to use a polycarbonate resin with a lower pencil hardness and, with a specific film thickness, will contain a difunctional urethane urethane, a polyfunctional oligomer, a polyfunctional monomer, a monofunctional monomer, and a coating film composed of a specific functional group of an ultraviolet curable resin to form a double layer on a polycarbonate resin substrate However, the pencil hardness is at most 4H, which is not sufficient (refer to Patent Document 7).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-107503

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-060526

[Patent Document 3] WO2010/035764 manual

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-112379

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-103887

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-052472

[Patent Document 7] Japanese Patent No. 4246643

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

The present inventors have intensively studied to obtain a resin laminate having excellent surface hardness and high transparency, and as a result, it has been found that a hard resin layer composed of a predetermined three-dimensional crosslinked type hard resin composition and a predetermined one are formed. The resin laminate of the thermoplastic resin layer can simultaneously achieve such characteristics, and thus the present invention has been completed.

In other words, the resin laminate of the present invention has a glass transition obtained by hardening a three-dimensional crosslinked type hard resin composition containing a polyfunctional (meth)acrylic monomer having a cage type sesquisesquioxane structure. temperature of at least one layer of the hard resin layer above the 200 ℃, and in the hard resin layer of at least one surface having a room temperature elastic modulus E ₁ E and elastic modulus 150 ℃ ratio ₂ of (E ₁ / E ₂₎ is A resin laminate having a thermoplastic resin layer of 1 to 500, characterized in that the hard resin layer-based monomer has a tensile modulus of 2,000 to 4,000 MPa and a total light transmittance of 90% or more, and further, a resin layer a pencil hardness of 6H or more thereof, the total thickness of the thermoplastic resin layer is t ₁ and the thickness t of the hard resin layer ₂ ratio (t ₁ / t ₂₎ is 0.25 or more 10 or less. Here, "(meth)acrylic acid" has the meaning of both "methacrylic acid" and "acrylic acid", and the same applies hereinafter.

Here, it is preferable that the resin solid content contained in the three-dimensional crosslinked type hard resin composition may be from 0.6 to 0.9 per 100 g of the (meth)acrylic mole, and the thickness of the obtained hard resin layer may be 50 μm or more and 250 μm or less.

Further, preferably, the hard resin layer and the thermoplastic resin layer may be laminated via an adhesive layer, and the adhesive layer may preferably be an adhesive adhesive, a pressure sensitive adhesive, a photocurable adhesive, or a thermosetting adhesive. Any one of a agent or a hot melt adhesive. Alternatively, the hard resin layer and the thermoplastic resin layer may be laminated via an easy-adhesion layer.

Further, the above polyfunctional (meth)acrylic monomer having a caged sesquisesquioxane 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 an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group, a group having an oxirane ring; And respectively may be the same group or may contain different groups, but have at least 2 (meth)acrylic groups in the formula, n, m, l are average values, n is a number from 6 to 14, m is 0 A number of 4, l is a number from 0 to 4, and satisfies m≦1).

Moreover, the method for molding a resin laminate according to the present invention is characterized in that a predetermined shape is imparted by thermoforming the resin laminate. Further, the molding method of the present invention is characterized in that a resin laminated body having a predetermined shape obtained therein is loaded into a mold, and a thermoplastic resin is injection-molded to thereby form a resin laminated body having a hard resin layer and a thermoplastic resin. Form one.

According to the present invention, since a resin laminate having high surface hardness and high surface hardness and sufficient resistance against impact or bending can be formed, the workability such as molding, cutting, and chiseling is excellent, and it can be used as Display frame or frame with excellent design.

1‧‧‧hard resin layer

2‧‧‧Binder layer

3, 3b‧‧‧ thermoplastic resin layer

4‧‧‧Printing layer

5‧‧‧pressure-sensitive adhesive layer

6‧‧‧Protective sheet

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

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

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

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

Fig. 5 is a cross-sectional view showing the formed resin laminate after molding.

The invention is described in detail below.

<hard resin layer>

The hard resin layer of the resin laminate of the present invention is obtained by curing a three-dimensional crosslinked type hard resin composition containing a polyfunctional (meth)acrylic monomer having a cage type sesquisesquioxane structure. The temperature is above 200 °C.

Among them, the above-mentioned polyfunctional (meth)acrylic monomer having a cage-type mercaptopropane 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 an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group, a group having an oxirane ring; And respectively may be the same group or may contain different groups, but have at least 2 (meth)acrylic groups in the formula, n, m, l are average values, n is a number from 6 to 14, m is 0 a number up to 4, l is a number from 0 to 4, and satisfies m≦1)

That is, the above-mentioned polyfunctional (meth)acrylic monomer having a cage-type mercaptopropane structure preferably has an organic functional group having a (meth)acrylic group, or a reactive functional group composed of a (meth) acryloxyalkyl group, and having a molecular weight distribution and a molecular structure controlled, a part of the functional group may be substituted by an alkyl group, a phenyl group or the like, or may be incompletely blocked. The polyhedral structure may also be a partially split structure. In the case of a partially split structure, the linked polyoxygen chain may have a (meth)acryl group.

Further, the three-dimensional crosslinked type hard resin composition of the hard resin layer 1 used in the present invention can be used in combination with a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. The polyfunctional (meth) acrylate may, for example, be a difunctional (meth) acrylate or a trifunctional or higher (meth) acrylate.

Examples of the difunctional (meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and hexanediol (meth)acrylate. Ester, long-chain aliphatic di(meth) acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxytrimethylacetate di(meth)acrylate, hard di(meth)acrylate Fatty acid modified neopentyl glycol ester, propylene di(meth)acrylate, glyceryl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate Ester, butylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, di( Poly(meth)acrylate, triglyceride di(meth)acrylate, neopentyl glycol di(methyl)acrylate modified trimethylolpropane, dicyclohexyl (meth)acrylate, Di(hexa)cyclohexyl (meth)acrylate, acrylated isocyanate, bis(propyleneoxy neopentyl glycol) adipate, bisphenol A di(meth)acrylate, di(meth)acrylic acid Tetrabromobisphenol A ester, bis(meth)acrylic acid bisphenol S ester, di(meth)acrylic acid butylene glycol ester, di(meth)acrylic acid phthalate, di(meth)acrylic acid phosphate Two (methyl) Acid zinc.

Further, examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tris(meth)acrylate, trimethylolethane tri(meth)acrylate, and tri(meth)acrylic acid. Glyceryl ester, neopentyl glycol di(meth)acrylate, neopentyl glycol tri(meth)acrylate, alkyl modified dipentaerythritol tris(meth)acrylate, tris(meth)acrylic acid Phosphate ester, tris(methacryloxyethyl) isocyanate, neopentyl tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, di(tetramethylene) Hydroxymethyl)propane ester, tetra(meth)acrylic acid alkyl modified dipentaerythritol ester, pentaerythritol pentaerythritol monohydroxy ester, hexa(meth)acrylic acid dipivalol Ester, di-n-pentaerythritol penta(meth)acrylate, alkyl-modified pentaerythritol penta(meth)acrylate, modified pentaerythritol penta(meth)acrylate, three (meth)acrylic acid ethyl urethane, tri (meth) acrylate, hexa (meth) acrylate urethane, hexa (meth) acrylate, and the like.

The polyfunctional (meth) acrylate having a cage-type sesquiterpene structure can be used singly or in combination of two or more.

In the hard resin layer 1 composed of the three-dimensional crosslinked type hard resin composition of the present invention, the solid content of the three-dimensional crosslinked type hard resin composition is preferably from 0.6 to 0.9 per 100 g of the (meth)acrylic mole number. In addition, the thickness is preferably 50 μm or more and 250 μm or less. When the number of (meth)acrylic moles per 100 g is less than 0.6, sufficient pencil hardness cannot be obtained, and when it is more than 0.9, it is difficult to form without flexibility, and the impact resistance is lowered to make it difficult to cut and cut. Wait for machining. Further, 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 is lowered, and there is a problem that transparency required for the display cannot be obtained.

The number of (meth)acrylic moles per 100 g of the solid content of the three-dimensional crosslinked type hard resin composition was calculated by the following formula.

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

When a plurality of polyfunctional (meth)acrylic monomers are used as the three-dimensional crosslinked type hard resin composition, the average number of (meth)acrylic groups calculated based on the blending ratio is used, and when a filler such as cerium oxide is blended At this time, the average value of the number of (meth)acrylic moles was calculated under the weight. That is, it corresponds to the molar concentration per unit mass (mole/100 g) of the (meth)acrylic group present in the solid content of the three-dimensional crosslinked type hard resin composition.

The hard resin layer 1 composed of the three-dimensional crosslinked type hard resin composition forming the hard resin layer does not deviate from the (meth)acrylic mole number per 100 g of the solid content of the three-dimensional crosslinked type hard resin composition. Within the range of 0.9 Combined with a monofunctional (meth) acrylate. However, when a certain amount or more of monofunctional (meth) acrylate is blended, the surface hardness tends to decrease, and even when it is formulated for the purpose of viscosity adjustment or the like, it is preferably only at a minimum, relative to three dimensions. The crosslinked type hard resin composition is preferably 30% by weight or less.

Examples of the monofunctional (meth) acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, amyl acrylate, and neopentyl acrylate. Ester, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, decyl acrylate, Isodecyl acrylate, eleven acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, isodecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate , alkyl acrylates, decyl acrylate, n-lauryl acrylate, stearyl acrylate, etc.; acryloyl morpholine, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentene acrylate Oxyethyl ester, dicyclopentyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenyl acrylate Propyl ester, 1,4-butanediol monoacrylate, 2-hydroxyalkyl propylene decyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate The ester or a cyclic esterified product such as ε-caprolactone is added to the hydroxyl group-containing acrylate compound, and the shrinkage of the alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate or the like is contained. a compound obtained by the addition reaction of a glyceryl compound with acrylic acid, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, tetrahydrofuran acrylate, isodecyl acrylate, acrylic acid (2-ethyl-2-methyl-1) , 3-dioxolan-4-yl)methyl ester, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)-acrylic acid Ester and the like.

When the resin laminate of the present invention is used as a window glass for an automobile or an aircraft, the surface is subjected to direct sunlight to become a high temperature. In addition, when used as a frame for a personal computer or a portable electronic device, heat is generated inside the machine. Therefore, in order to prevent heat deformation, the hard resin layer must have heat resistance, and the glass transition temperature must be 200 ° C or higher. When the organic matter is contained and the organic matter is decomposed or the like, the upper limit of the glass transition temperature of the hard resin layer is 450 °C.

The hard resin layer used in the present invention has a tensile modulus of from 2,000 to 4,000 MPa per monomer. When the tensile modulus is less than 2,000 MPa, the pencil hardness of the resin laminate is less than 6H, and if it exceeds 4,000 MPa, the workability such as forming, cutting, and cutting is difficult to proceed. Further, since the hard resin layer used in the present invention is suitable for a display panel or the like, its total light transmittance must be 90% or more.

The three-dimensional crosslinked type hard resin composition used in the present invention can obtain a (meth)acrylic resin copolymer by radical copolymerization of the composition. In order to improve the physical properties of the (meth)acrylic resin copolymer or to promote radical copolymerization, various additives may be formulated in the three-dimensional crosslinked type hard resin composition of the present invention. The additive for promoting the reaction may, for example, be a thermal polymerization initiator, a thermal polymerization promoter, a photopolymerization initiator, a photoinitiator, a sensitizer or the like. When the photopolymerization initiator or the thermal polymerization initiator is blended, the amount of addition may be in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.1 to 5 parts by weight based on 100 parts by total of the three-dimensional crosslinked type hard resin composition. A range of 0.1 to 3 parts by weight. When the amount is less than 0.1 part by weight, the hardening is insufficient, and the strength and rigidity of the obtained hard resin layer are lowered. On the other hand, when the amount is more than 5 parts by weight, problems such as coloring of the hard resin layer may occur. Here, the total amount of the three-dimensional crosslinked type hard resin composition is 100 parts by weight, and does not include two. A filler such as ruthenium oxide.

When the photopolymerization initiator used in the photocurable composition is used as the photocurable composition, a acetophenone-based, benzoin-based, diphenylketone-based, thioxanthone-based or anthracene can be suitably used. A compound such as a phosphine oxide system. Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- can be exemplified Phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[ 4-[4-(2-hydroxy-2-methyl-propenyl)benzyl]phenyl]-2-methyl-1-propan-1-one, methyl phenylglyoxylate, 2,4 ,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 1,2-octanedione, 1- [4-(phenylsulfanyl)-,2-(benzonitrile)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]-,1-(O-benzidine)], 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-methyl-1-[4-(methyl Thio)phenyl]-2-morpholinpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) -butanone-1-one, bis-2,6-dimethoxybenzhydryl-2,4,4-trimethylpentylphosphine oxide, diphenyl ketone, thioxanthone, 2-chloro Thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, these may be used alone or in combination of two Used on.

The three-dimensional crosslinked type hard resin composition used in the present invention may be formulated with a radical polymerization initiator and hardened by heating or light irradiation to produce a hard resin layer in an arbitrary 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 in a wide range from room temperature to 200 ° C depending on the selection of the thermal polymerization initiator and the accelerator. At this time, a hard resin layer of a desired shape can be obtained by polymerization hardening in a mold or a steel strip.

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

A method of obtaining a hard resin layer of any shape used in the present invention by light irradiation, for example, a three-dimensional crosslinked type hard resin composition is injected into a transparent material having a shape of an arbitrary groove and made of quartz glass or the like. In the mold which is formed, a method of performing polymerization hardening by irradiating ultraviolet rays with the ultraviolet lamp, and then releasing the mold from the mold to produce a molded body (hard resin layer) having a desired shape. When the mold is not used, for example, a three-dimensional crosslinked type hard resin composition of the present invention is applied onto a moving steel strip using a doctor blade or a roll coater, and is cured by polymerization by the above ultraviolet lamp. A method of producing a sheet-shaped formed body or the like.

As described above, when the three-dimensional crosslinked type hard resin composition is cured by the ultraviolet irradiation method, the ultraviolet curing reaction is a radical reaction, and thus the reaction by oxygen is inhibited. Therefore, from the viewpoint of suppressing the reaction inhibition by oxygen in the hardening reaction of the three-dimensional crosslinked type hard resin composition, after coating the three-dimensional crosslinked type hard resin composition, it is preferably composed of a transparent plastic film. A cover layer covers the surface. In addition, it is preferable that the surface of the three-dimensional crosslinked type hard resin composition covers the surface of the three-dimensional crosslinked type hard resin composition with an oxygen concentration of 1% or less, and more preferably 0.1% or less. In order to reduce the oxygen concentration, it is preferred to use a surface. Transparent plastic film with no holes and low oxygen permeability. Examples of the material of such a film include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), and PC (polycarbonate). ), plastics such as polypropylene, polyethylene, acetate resin, acrylic resin, vinyl fluoride resin, polyamide, polyarylate, celecoxib, polyether oxime, and decene-based resin. These plastics may be used alone or in combination of two or more.

In the plastic film, since it is necessary to be able to peel off the hard resin layer and the thermoplastic resin layer composed of the three-dimensional crosslinked type hard resin composition, it is preferable to apply a polyfluorene coating, a fluorine coating, or the like to the surface of the plastic film. Easy to peel off the processor.

Further, the above plastic film can also be used as the protective sheet 6. When used as the protective sheet 6, a polyethylene terephthalate film or a polycarbonate film is preferably used from the viewpoint of heat resistance, transparency, weather resistance, solvent resistance, rigidity, and cost.

<Thermoplastic resin layer>

The thermoplastic resin layer 3 (3b) used in the present invention is preferably one having excellent transparency, and polyethylene terephthalate (PET), cellulose triacetate (TAC), and polyethylene naphthalate B can be suitably used. Diester (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), Various resin films of polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene resin, polyether oxime, celecoxib, aromatic polyamine, etc., from heat resistance, transparency, weather resistance, From the viewpoints of solvent resistance, hardness, formability, rigidity, and cost, polyethylene terephthalate, polymethyl methacrylate or polycarbonate is preferably used. These films may be used without stretching or by a stretcher.

At room temperature elastic modulus of the thermoplastic resin layer used in the present invention, the ratio of E ₁ and E ₂ of the elastic modulus at _{150 ℃ (E 1 / E 2} ) is in the range 1 to 500. The 150 ° C system assumes that the standard temperature of the mold or the injection molding resin at the time of molding described later is higher than the elastic modulus at the temperature when the modulus at room temperature is higher than that at the temperature, and the molding cannot be maintained due to the rebound caused by the hard resin layer. shape. Therefore, the elastic modulus at room temperature E ₁ E and elastic modulus at 150 deg.] C of greater than _2, more easily molded at a molding temperature, and easy to maintain the shape at room temperature. However, when the modulus ratio exceeds 500, the pencil hardness of the resin laminate is less than 6H, or it is difficult to control the shape at the time of thermoforming. The elastic modulus ratio was measured by measuring the dynamic viscoelasticity of the thermoplastic resin layer at a temperature elevation rate of 5 ° C/min from room temperature to 230 ° C, and calculating the ratio of room temperature to storage elastic modulus (E') at 150 ° C. The room temperature referred to in the present invention means a temperature of approximately 23 to 27 ° C, and is based on 25 ° C in the measurement of the modulus of elasticity.

The ratio (thickness of the thermoplastic resin layer/hard resin layer) of the thickness of the hard resin layer of the total thickness of the thermoplastic resin layer used in the present invention is 0.25 or more and 10 or less. When the thickness ratio is less than 0.25, there is a problem that it is difficult to perform processing such as forming, cutting, and cutting. When the thickness ratio exceeds 10, there is a problem that the pencil hardness is less than 6H. The thickness of the thermoplastic resin layer (total of the plurality of layers) may be from 30 μm to 1000 μm. When it is less than 30 μm, there is a problem that cracks or cracks occur in the hard resin layer at the time of injection molding. Conversely, when it exceeds 1000 μm, there is a problem that the pencil hardness is less than 6H or it is difficult to process.

The hard resin layer 1 and the thermoplastic resin layer 3 of the resin laminate of the present invention can be laminated by the adhesive layer 2 of any one of a film shape and a sheet shape. The adhesive layer 2 has a thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm. When it is less than 0.01 μm, it is difficult to obtain a sufficient adhesive effect, and when it is 30 μm or more, the pencil hardness of the resin laminate cannot be sufficiently obtained. The adhesive layer 2 here may be the following adhesive layer Or easy to adhere to the layer.

<adhesive layer>

Examples of the adhesive layer 2 include an adhesive layer using an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. Examples of such adhesives include acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, and polyvinyl alkane ethers. Adhesive, rubber adhesive, vinyl chloride-vinyl acetate adhesive, styrene-butadiene-styrene copolymer (SBS copolymer) adhesive, hydride (SEBS copolymer) adhesive, ethylene-vinyl acetate Ethylene adhesive such as ester copolymer, ethylene-styrene copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-ethyl acrylate copolymer The acrylate adhesive such as the material is not particularly limited as long as it is excellent in adhesion, transparency, and workability.

<easy adhesion layer>

Moreover, the other which comprises the adhesive layer 2 is an easy adhesion layer. The easy-adhesive layer applies a layer which is treated by chemical adhesion or physical adhesion to the surface of the resin layer which is difficult to adhere. The chemical adhesion can form a film layer of a resin having a functional group on a substrate layer, and form a chemical bond with the hard resin layer to obtain a close contact force. The so-called physical adhesion can form a resin film layer having irregularities on the substrate. Or the inorganic thin film layer is obtained by the anchoring effect to obtain a close contact with the hard resin layer. Examples of the chemically-adhesive material include polyfunctional (meth)acrylates, epoxy resins, and thiol-containing compounds, and materials having physical adhesion properties include SiO ₂ , SiN, and SiC. Such as vapor deposition film.

Fig. 1 shows a first embodiment as a resin laminate of the present invention. The embodiment of the body. As shown in Fig. 1, the resin laminate has the following structure, that is, a hard resin layer 1 is formed on both sides of the thermoplastic resin layer 3 via the adhesive layer 2, and further, one of the layers. The lower surface of the hard resin layer 1 is provided with a structure of the printed layer 4, and the protective sheet 6 is formed on the outermost surface of the front and back. Each of the adhesive layers 2 has a function of forming an adhesive layer in which the hard resin layer 1 and the thermoplastic resin layer 3 are integrally formed.

As shown in Fig. 1, by forming the printed layer 4 on the lower surface of the resin laminate of the present invention, a pattern, a character, or the like can be formed. The printed pattern of the printed layer 4 may be a pattern of wood grain, stone grain, cloth grain, sand grain, geometric pattern, text, full blank, metal, etc., and can be arbitrarily set.

In the printing layer 4, a resin component having a good compatibility with a hard resin layer or a thermoplastic resin layer is preferably blended, and examples thereof include a polyvinyl resin such as a vinyl chloride-vinyl acetate copolymer, and a polyamide resin. Polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, chlorinated polyolefin resin, etc. . By blending such a resin component, peeling or peeling off of printing can be suppressed. Further, at the time of formation of the printed layer 4, a coloring agent containing a pigment or a dye of an appropriate color may be used.

Examples of the method of forming the printing layer 4 include a printing method such as a lithography method, a gravure wheel rotary printing method, or a screen printing method, a coating method such as a roll coating method or a spray coating method, and a flexographic printing method. Further, the thickness of the printed layer 4 is selected to have an appropriate thickness so as to obtain a desired surface appearance in the laminated sheet, the laminated layer molded article or the laminated laminate-formed article, and is generally 0.5 to 30 μm.

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

In the second embodiment shown in Fig. 2, the printed layer 4 is formed on the upper surface of the thermoplastic resin layer 3, and the pressure is sandwiched between the upper portion of the printed layer 4 side and the side where the printed layer 4 is not formed. The adhesive layer 5 has a hard resin layer 1 formed on the side of the printing layer 4, a thermoplastic resin layer 3b formed on one side where the printing layer 4 is not formed, and a protective sheet 6 formed on both sides.

In the second embodiment, the thermoplastic resin layer 3 to be used is not particularly limited as long as it has transparency, but polymethyl methacrylate (PMMA) is preferred. When the thermoplastic resin layer 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, a high pencil hardness can be formed.

On the other hand, in the third embodiment shown in Fig. 3, the adhesive layer 2 is sandwiched between the thermoplastic resin layer 3 to form the hard resin layer 1, and the printed layer 4 is formed on the lower surface of the thermoplastic resin layer 3. On the lower surface of the thermoplastic resin layer 3 on which the printing layer 4 is formed, the thermoplastic resin layer 3b is formed via the adhesive layer 2 or the pressure-sensitive adhesive layer 5, and the protective sheet 6 is formed on both sides. The resin laminate of the third embodiment is suitable for processing such as a shape having a smaller radius of curvature r.

A well-known pressure-sensitive adhesive can be used for the pressure-sensitive adhesive layer 5 used in the second and third embodiments. Specifically, for example, an adhesive such as a natural rubber-based resin, a synthetic rubber-based resin, a polyoxymethylene-based resin, an acrylic resin, a vinyl acetate-based resin, or an urethane-based resin can be used. These adhesives are not particularly limited as long as they have desired light penetration, adhesion, and weather resistance. Further, in order to prevent deterioration of the dye due to the difference in layer constitution, it is preferred to contain a UV absorber (benzotriazole or the like) having an ultraviolet absorbing effect in the adhesive.

The pressure-sensitive adhesive layer 5 has an average thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm. When it is less than 0.01 μm, it is difficult to obtain sufficient adhesion strength. Further, the effect of absorbing the unevenness of the printed layer to achieve flatness is also lowered, and when the thickness is 30 μm or more, the pencil hardness of the laminated body cannot be sufficiently obtained.

In the second embodiment and the third embodiment of the present invention, in the state of the resin laminate, the three-dimensional shape can be imparted by thermoforming. The thermoplastic resin layers 3 and 3b in Figs. 2 and 3 can be formed by heat, and since the hard resin layer 1 has sufficient flexibility, it can be formed by the adhesive layer 2 following the shape of the thermoplastic resin layer. One-piece molded product. Examples of the thermoforming include vacuum forming, compression molding, and press molding.

Further, in the layer structure of the resin laminate shown in Fig. 2 of the embodiment of the present invention, the A member and the B member which have been formed into a predetermined shape in advance, and the pressure-sensitive adhesive layer 5 can be used. fit. That is, the A-part having 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 may be bonded via the pressure-sensitive adhesive layer 5, and may be made of thermoplastic The B member composed of the resin layer 3b and the protective sheet 6.

Further, in the resin laminated body shown in Fig. 3 of the embodiment of the present invention, the C member (protective sheet 6, hard resin layer 1, adhesive layer 2, thermoplastic resin layer 3, printed layer 4, and adhesive) can be used. After the layer 2 (or the pressure-sensitive adhesive layer 5) is filled in a mold of a desired shape, the thermoplastic resin layer 3b is injected by injection molding, and then the protective sheet 6 is provided to form a B member (the thermoplastic resin layer 3b and the protective sheet). 6).

In the first to third embodiments, the printed layer 4 is formed, but the printed layer 4 may be omitted, or may be formed between arbitrary layers by any printing method in accordance with a laminate manufacturing process.

As shown in FIG. 3, in the present invention, it can be performed as needed The resin layered body which is formed into a predetermined shape by thermoforming is loaded into a mold, and the thermoplastic resin is injection-molded to be integrated with the thermoplastic resin layer. The molded thermoplastic resin is preferably transparent, and polyethylene terephthalate (PET), cellulose triacetate (TAC), polyethylene naphthalate (PEN), and poly are suitably used. Methyl methacrylate (PMMA), polycarbonate (PC), polyimine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), Various resin films of cycloolefin copolymer (COC), decene-containing resin, polyether oxime, celecoxib, aromatic polyamine, etc., from heat resistance, transparency, weather resistance, solvent resistance, rigidity, cost From the viewpoint of the use, polyethylene terephthalate, polymethyl methacrylate or polycarbonate is preferably used. From the viewpoint of impact resistance, polycarbonate is preferably used.

[Examples]

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

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

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

3) Film thickness: It was measured using ID-SX manufactured by Mitutoyo Co., Ltd.

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

5) Machinability: The engraving knives (manufactured by Neiyama Blade Co., Ltd., 2 mm, straight edge) were attached to an engraving machine (manufactured by Megaro Technica Co., Ltd.), and the processing conditions were 20,000 rpm and 900 mm/min. The resin laminate obtained in the examples was subjected to a cutting process, and a microscopic observation of the cut surface was carried out so that the notch (crash angle) was observed as × on the cut surface, and ○ was not observed.

6) Formability: The molded body obtained by the following vacuum compression molding or injection molding was observed to observe that any of cracking, cracking, and whitening was ×, and a good state was obtained. It is ○.

[Synthesis Example 1]

400 ml of 2-propanol (IPA) as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 150 mL of IPA and 126.9 g of 3-methacryloxypropyltrimethoxy decane (MTMS: SZ-6030, manufactured by Toray Dow Corning Silicone Co., Ltd.) were placed in a dropping funnel, and the reaction vessel was stirred while being at room temperature. The IPMS solution of MTMS was added dropwise over 30 minutes. After the completion of the dropwise addition of MTMS, stirring was continued 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 a saturated saline solution until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 86 g of a cage-type mercaptosulfanyl compound having a methacryl oxime group on all of the ruthenium atoms. The sesquisesquioxane is a colorless viscous liquid which is soluble in various organic solvents.

[Example 1]

(Production of hard resin layer)

The cage-type sesquioxalic acid compound having a methacryl fluorenyl group on all the ruthenium atoms prepared in the above Synthesis Example 1 : 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, diacrylic acid Cyclopentyl ester: 32 parts by weight, hexamide acrylate oligomer 1:6 parts by weight, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight, to obtain a transparent three-dimensional cross A joint type hard resin composition. The obtained three-dimensional crosslinked type hard resin composition was obtained by using the formula described above to obtain a (meth)acrylic mole number per 100 g of the resin solid content contained in the three-dimensional crosslinked type hard resin composition. It is 0.76. The first table shows the composition of the three-dimensional crosslinked type hard resin composition.

The abbreviations in Table 1 are as follows.

A: Compound obtained in Synthesis Example 1

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

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

D: neopentyl glycol 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: Dimethylol tricyclodecyl acrylate (dicyclopentenyl diacrylate) (Light Acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.)

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

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

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

K: urethane urethane oligomer 2 (NK Oligo UA-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, a three-dimensional crosslinked type hard resin composition was cast (hang) on the peeled PET using a roll coater so as to have a thickness of 0.15 mm, and the PET which was additionally subjected to the release treatment was laminated on the PET. After the three-dimensional crosslinked type hard resin composition to be cast, a high-pressure mercury lamp of 30 W/cm is used, and hardening is performed at an accumulated exposure amount of 4000 mJ/cm ² , and all of the peeled PET is peeled off to obtain a predetermined thickness. A sheet-like hard resin layer of (150 μm). The glass transition temperature of the obtained hard resin layer was not observed until 300 °C. Further, the tensile modulus and the total light transmittance of the hard resin layer were measured. The results are shown in Table 1.

(Production of resin laminate)

A cationic photocurable adhesive (manufactured by Kyoritsu Chemical Co., Ltd.) was applied to a polycarbonate (manufactured by Teijin Co., Ltd., PC-1151, 200 mm × 200 mm × thickness: 0.5 mm) so as to have a thickness of 5 μm. The hard resin layer obtained above was bonded to the single-sided side of the polycarbonate and pressed, and then irradiated with ultraviolet rays from both sides at a ratio of 500 mJ/cm ² by a metal halide lamp to obtain a hard resin layer. A resin laminate (Part A) that forms a protective sheet. For the polycarbonate used herein as the thermoplastic resin layer, dynamic viscoelasticity (DMA) was measured at a temperature elevation rate of 5 ° C/min from room temperature (25 ° C) to 230 ° C, and the storage modulus from room temperature was measured. The storage elastic modulus E _{2 of} E ₁ and 150 ° C was determined as the elastic modulus ratio (E ₁ /E ₂ ), and as a result, it was 1.35.

(Vacuum compression molding example)

The resin laminated body (A part) obtained above was sandwiched from the upper and lower sides by a ruthenium rubber (thickness: 0.8 mm), and the compression delay was set to 10 at a pressure of atmospheric pressure of 5 atmospheres and a mold temperature of 150 ° C to 250 ° C. In the second step, the pressure holding time was set to 30 seconds to form a resin laminated body (A member), and the resin laminated body (A member) was formed into a curved surface (curvature radius a: 8 mm) on four sides and had the same as shown in FIG. Curved shape of profile shape (height b: 7mm). The pencil hardness of the surface of the hard resin layer was measured for the molded body of the obtained resin laminate, and it was 8H. Further, the processability and moldability of the above-mentioned resin laminate were evaluated. The results are summarized in Table 2.

[Embodiment 2]

(Production of hard resin layer)

The above-mentioned synthesis example obtained a cage type sesquioxalic acid compound having a methacryl fluorenyl group on all of the ruthenium atoms: 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, dicyclopentanyl diacrylate 32 parts by weight, hexyl acrylate methacrylate oligomer: 6 parts by weight, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight, and obtained as shown in Table 1 A transparent three-dimensional crosslinked type hard resin composition composed of a transparent resin composition.

Next, a three-dimensional crosslinked type hard resin composition was cast (collapsed) on a PET of 200 mm × 200 mm × thickness 100 μm which was easily adhered by a roll coater so as to have a thickness of 0.10 mm, and another The PET of the same size as the release film was used as a protective sheet, and after being laminated on the three-dimensional crosslinked type hard resin composition to be cast, it was hardened by using a 30 W/cm high-pressure mercury lamp at an accumulated exposure amount of 4000 mJ/cm ² . On the both sides of the front and back sides of the hard resin layer (100 μm), there was a sheet of PET as a thermoplastic resin layer. A printed layer or a pressure-sensitive adhesive layer is provided on one surface of the obtained sheet opposite to the easy-adhesion surface of the thermoplastic resin layer which is easily adhered to obtain a resin laminate (C member). The glass transition temperature of the hard resin layer of the C member was not observed in the measurement at 300 ° C, and the tensile modulus and total light transmittance of the monomer were as shown in Table 1. Further, the elastic modulus ratio (E ₁ /E ₂ ) of PET used as the thermoplastic resin layer is also collectively shown in the first table.

(Vacuum compression molding example)

The resin laminated body (C member) obtained above was sandwiched from the upper and lower sides with a ruthenium rubber (thickness: 0.8 mm), and the compression time was set to 10 seconds at a pressure of atmospheric pressure of 5 atm, and a mold temperature of 150 ° C to 250 ° C. The holding time is set to 30 seconds to form a resin product. The layer body (C member) was formed into the same curved shape as in the first embodiment. The pencil hardness of the surface of the hard resin layer was measured for the molded body of the obtained resin laminate, and it was 7H. Further, the processability and moldability of the above-mentioned resin laminate were evaluated. The results are summarized in Table 2.

(Injection molding example)

Then, the resin laminated body (C member) formed by the curved surface is placed in the first injection molding die of FIG. 4, and then the second injection molding die is superposed on the first injection molding die, and in this state, in advance. Polycarbonate resin (product name "HFD1810", manufactured by Sabic Co., Ltd.) which was dried at 120 ° C for 24 hours, at a resin temperature of 320 ° C, a mold temperature of 90 to 120 ° C, an in-mold pressure of 300-500 kg/cm ² , and an ejection time of 5 seconds. Under the condition, the injection runner is ejected into the cavity in the mold, thereby obtaining a resin laminated body (C member) having a hard resin layer and a thermoplastic resin layer (B member) of 500 μm as shown in FIG. The molded body is injected.

[Comparative Example 1]

Dimethyl pentaerythritol hexaacrylate: 85 parts by weight and PMMA: 15 parts by weight at 110 ° C, and then kneaded by heating, and then mixed with 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by weight to obtain three-dimensional intersection A joint type hard resin composition.

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

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

The third embodiment, the seventh embodiment, the second comparative example, and the comparative example 4 are the same as the first embodiment except that the blending composition is the weight ratio shown in the first table, and the fourth embodiment and the fifth embodiment are used. 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 were obtained in the same manner as in Example 2. Laminated body. The evaluation results of the obtained molded body are shown together in the second table.

[Synthesis Example 2]

Dicyclopentyl acrylate 4.0 mol (825 g), 2-hydroxyethyl methacrylate 3.0 mol (390 g), 1,4-butanediol diacrylate 3.0 mol (595 g), 2,4-di Phenyl-4-methyl-1-pentene 4.0 mol (889 g) and 2400 ml of toluene were placed in a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C 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 a copolymer A615 g (yield: 34%).

The obtained copolymer A had a Mw of 15,200, an Mn of 3,900 and a Mw/Mn of 3.9. Copolymer A contained: a total of 37.8 mol% of structural units derived from dicyclopentyl acrylate, and a total of 29.3 mol% of structural unit derived from 2-hydroxyethyl methacrylate derived from 1,4-butanediol diacrylate The structural unit of the ester totaled 32.9 mol%. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is compared with dicyclopentanyl acrylate, 2-hydroxyethyl methacrylate, and 1,4-butyl diacrylate. The total amount of the diol ester and 2,4-diphenyl-4-methyl-1-pentene was 9.8 mol%. Further, the ratio of the pendant acrylate was 16.5 mol%. Mb is 0.29. Copolymer A was soluble in ethanol, 2-propanol, butanol, toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed.

[Synthesis Example 3]

Dicyclopentyl acrylate 0.24 mol (49.5 g), dihydroxymethyl tricyclodecane diacrylate 2.6 mol (729.4 g), 1,4-butylene glycol diacrylate 0.96 mol (190.1 g), 2-hydroxypropyl acrylate 0.96 mol (124.9 g), 2,4-diphenyl-4-methyl-1-pentene 0.48 mol (113.4 g), tert-dodecyl mercaptan 3.12 mol ( 631.5g), toluene 700ml cast Into a 3.0 L reactor, 72 mmol of benzamidine 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 obtained polymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer B696.9 g (yield: 63.7 mol%).

The obtained copolymer B had Mw of 39,500, Mn of 7,240, and Mw/Mn of 5.5. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, it was found that the copolymer B contained: 4.9 mol% of the structural unit derived from dicyclopentyl acrylate, derived from dimethylol tricyclodecane diacrylate. The structural unit of 1,4-butylene glycol diacrylate was 75.5 mol% in total, and the structural unit derived from 2-hydroxypropyl acrylate was 19.6 mol%. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is relative to dicyclopentanyl acrylate, dimethylol tricyclodecane diacrylate, 2-hydroxy acrylate The total amount of the terminal groups of the structures of propyl ester, 2,4-diphenyl-4-methyl-1-pentene and tertiary tridecyl mercaptan (hereinafter referred to as the total amount of the total constituent units) exists 3.7% of the mole. On the other hand, the terminal group derived from the structure of the tertiary dodecylmercaptan has 18.6 mol% with respect to the total amount of the total constituent units. Further, the ratio of the pendant acrylate was 43.5 mol%.

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

[Examples 9 to 12]

A hard resin layer and a resin laminate were obtained in the same manner as in Example 1 except that the blending composition was constituted by the weight ratio shown in Table 3. The evaluation results of the obtained molded body are shown together in Table 3.

Abbreviations other than those already appearing 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 (Daicel Cytec Co., Ltd.)

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

G: Dimethylol tricyclodecyl acrylate (dicyclopentenyl 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 Co., Ltd.)

R: triconyl octadecyl acrylate

1‧‧‧hard resin layer

2‧‧‧Binder layer

3‧‧‧ thermoplastic resin layer

4‧‧‧Printing layer

6‧‧‧Protective sheet

Claims (8)

A resin laminate comprising a glass transition temperature of 200 ° C or higher obtained by curing a three-dimensional crosslinked type hard resin composition containing a polyfunctional (meth)acrylic monomer having a cage type sesquisesquioxane structure elastic modulus at least one side of at least one layer of the hard resin layer, and in the hard resin layers having a room temperature E _{1 2} ratio of E and the elastic modulus at _{150 ℃ (E 1 / E 2} ) 1 to 500 of A resin laminate having a thermoplastic resin layer, characterized in that the tensile modulus of the hard resin layer monomer is 2,000 to 4,000 MPa, and the total light transmittance is 90% or more, and further, the pencil hardness of the resin laminate 6H is more, the total thickness of the thermoplastic resin layer to the thickness t ₁ t ratio of the rigid resin layer ₂ of (t ₁ / t ₂₎ is 0.25 or more 10 or less. The resin laminate according to the first aspect of the invention, wherein the resin solid content of the three-dimensional crosslinked type hard resin composition is from 0.6 to 0.9 per 100 g of the (meth)acrylic mole, and the hard resin The thickness of the layer is 50 μm or more and 250 μm or less. 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. 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 a hot melt adhesive. Any of them. The resin laminate according to claim 1 or 2, wherein the hard resin layer and the thermoplastic resin layer are laminated via the easy-adhesion layer. The resin laminate according to claim 1 or 2, wherein the polyfunctional (meth)acrylic monomer having a cage-type sesquisesquioxane 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 alkane having 1 to 6 carbon atoms a base, a phenyl group, a (meth)acrylic group, a (meth) acryloxyalkyl group, a vinyl group, a group having an oxirane ring, and each may be the same group or may contain a different group, but There are at least two (meth)acrylic groups in the formula, n, m, and l are average values, n is a number from 6 to 14, m is a number from 0 to 4, and l is a number from 0 to 4, and satisfies m≦ 1). A method for forming a resin laminate, which is characterized in that a resin laminate according to claim 1 is thermoformed to give a predetermined shape. The method for forming a resin laminate according to claim 7, wherein the resin laminate having a predetermined shape obtained by the method of claim 7 is filled in a mold, and the thermoplastic resin is used. Injection molding forms an integral body.