TW201500203A - Resin laminate - Google Patents

Abstract

The object of the present invention is to provide a resin laminate with high surface hardness and high transparency. The present resin laminate, which comprises a hard resin layer formed by a curable resin composition having a multifunctional (meth)acrylate monomer as main component and having a three dimension crosslink structure and a thickness equal to or higher than 25 μm and equal to or less than 250 μm, and a substrate layer constructed by monolayer or a plurality of layers of two or more layers of a thermoplastic resin, is characterized by that the hard resin layer has a single tension elasticity of 2,000 to 4,000 Mpa and a full-spectrum transparency of 90% or more, also, the ratio of total thickness of the substrate layer t1 to the thickness of the hard resin layer t2 (t1 / t2) is equal to or higher than 0.25 and equal to or less than 10, the scratch hardness of the resin laminate is equal to or higher than 40 g.

Description

Resin laminate

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

In an electronic device such as a digital camera or a mobile phone, a laminate made of a thermoplastic resin such as acrylate, polycarbonate or polyethylene terephthalate is used as a substrate for a liquid crystal display or the like, or to avoid liquid crystal. A protective plate or the like that is scratched, soiled, or the like on the surface of the display or the like. The resin which forms such a laminated body is widely used in the field of glass in the past because it has excellent optical characteristics and is not easily broken by glass. However, thermoplastic resins such as acrylate, polycarbonate, and polyethylene terephthalate have disadvantages such as surface hardness, abrasion resistance, and scratch resistance which are inferior to glass and are easily scratched.

In order to solve such a drawback, there has been a review on the surface modification of a resin laminate. For example, a thermosetting resin or an ultraviolet curable resin is applied to the surface of the substrate. Although the resin laminate to which these coatings are applied can be improved to some extent in terms of abrasion resistance and scratch resistance, the surface hardness is insufficient, and the surface hardness is insufficient. It is lower than glass and has a big problem in practical use.

In order to further improve the coating of the surface hardness of a transparent plastic material, attempts have been made, for example, to mix a high-hardness filler in a hard coat layer to improve surface hardness (refer to Patent Document 1, Patent Document 2, and Patent Literature). 3). Further, as a similar method, there is a method of reviewing the so-called organic-inorganic mixing, in which the film thickness of the hard coat layer is increased, and inorganic and/or organic crosslinked particles are mixed in order to alleviate the generated stress, or A method of introducing a functional group on the surface of the particle and partially crosslinking the resin with the hard coat layer (see Patent Document 4 and Patent Document 5). In addition, attempts have been made to increase the thickness of the entire coating film by multilayering the hard coat layer, thereby obtaining a higher surface hardness (refer to Patent Document 6).

However, a specific example of such methods is to use a polyethylene terephthalate film or a cellulose triacetate film having a pencil hardness higher than that of a polycarbonate resin to achieve a pencil hardness of 4H to 6H. Although the effect is proved by empirically, the pencil hardness cannot be achieved only by a thin hard coating layer, so a supplementary function of a hard underlayer or an inorganic material is required. Therefore, such underlayer or inorganic materials are a factor that hinders transparency, and are not suitable for use as a display device such as a liquid crystal display.

In addition, there has been attempted to use a polycarbonate resin having a resin having a low pencil hardness to contain a bifunctional amine ester acrylate, a polyfunctional oligomer, a polyfunctional monomer, a monofunctional monomer, and ultraviolet curing with a specific functional group number. In the coating film formed of the resin, two layers are formed on the polycarbonate resin substrate in a specific film thickness. However, in this technique, the pencil hardness is at most 4H and is insufficient (see Patent Document 7).

Further, the above Patent Document 7 evaluates the scratch hardness by a pencil method in accordance with JIS K 5600-5-4, but the thermal plasticity is observed when a hard coat layer or a hard resin layer is laminated on the thermoplastic resin layer. The properties and thickness of the resin and the hard resin layer are affected by the thermoplastic resin of the lower layer, resulting in plastic deformation or elastic deformation due to the concave, and it is not easy to discriminate at the first sight only the surface surface or the scratch caused by the scratch. . Further, depending on the material of the hard resin layer, cracking may occur due to deformation due to the concave which is not originally thought, and it is difficult to accurately measure the surface hardness by only the measurement of the pencil hardness. Further, when it is used for a protective plate or the like of the liquid crystal display or the like as described above, it is necessary to take into consideration the protection against scratches caused by hard metal or minerals in daily life, and thus it is softer than metal or mineral. The determination by the pencil method is contrary to the actual wear resistance and scratch resistance of the daily life.

[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

[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 in view of the above problems of the prior art, and it is an object of the invention to provide a resin laminate having high surface hardness and high transparency.

In order to obtain a resin laminate having excellent surface hardness and high transparency, the inventors of the present invention have found that a resin laminate including a hard resin layer having a predetermined curable resin composition and a base layer containing a thermoplastic resin is obtained. The above problems can be achieved at the same time, and the present invention has been completed.

In other words, the present invention provides a resin laminate comprising a three-dimensional crosslinked structure formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer as an essential component, and having a thickness of 25 μm or more and 250 μm or less. a hard resin layer having a thickness; and a base layer formed of a single layer of thermoplastic resin or a plurality of layers of two or more layers, wherein the hard resin layer alone has a tensile elastic modulus of 2,000 to 4,000 MPa, and a total light the total thickness of more than 90% transmittance, and the base layer ₁ and the thickness t of the hard resin layer is t ₂ ratio (t ₁ / t ₂₎ in 10 or less than 0.25, scratch hardness laminate resin 40g the above.

Among them, the hardness evaluation of the resin laminate of the present invention is the scratch hardness according to the evaluation method of ISO 1518-2. This method is a method of evaluation by the load variation method, so that the properties of the upper hard resin layer and the lower thermoplastic resin are not affected by the thickness, and the evaluation of the laminate is not biased, and the hardness can be evaluated.

In the present invention, it is desirable to use a curable resin per 100 g. The solid content of the composition is preferably a resin having a functional group having 4 or more functional groups of a (meth)acrylic acid monomer in a curable resin composition forming a hard resin layer of 40 g or more.

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

Further, in the present invention, the polyfunctional (meth)acrylic monomer contained in the curable resin composition forming the hard resin layer is a cage-type silsesquioxane structure. ideal. More preferably, the polyfunctional (meth)acrylic acid monoacid having a cage sesquiterpene 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 a carbon number of 1 to 6, a phenyl group, a (meth)acrylic group a (meth)acryloxyalkylene group, a vinyl group or an oxirane ring group, which may respectively contain the same group or a different group, but has at least two (meth)acrylic groups in the formula Further, n, m, and l represent average values, n represents a number from 6 to 14, m represents a number from 0 to 4, and l represents a number from 0 to 4, and satisfies m≦l).

The resin laminate of the present invention can maintain the original transparency Sexual and has a high surface hardness. In addition, since it is a resin laminated body which is sufficiently resistant to punching and bending, it is excellent in workability such as molding, cutting, punching, and the like, and can be used as a display panel and an outer casing having excellent design properties.

1‧‧‧hard resin layer

2‧‧‧ adhesive layer

3‧‧‧Substrate layer

3b‧‧‧ substrate layer

4‧‧‧Printing layer

5‧‧‧ Pressure-sensitive adhesive layer

Fig. 1 is an explanatory view showing a laminated body of the invention according to a first aspect of the present invention.

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

Fig. 3 is an explanatory view schematically showing a laminated body of the third aspect of the invention.

Hereinafter, the present invention will be described in detail.

<hard resin layer>

The curable resin composition in which the hard resin layer is formed in the resin laminate of the present invention is not particularly limited as long as it contains a polyfunctional (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule. limits. That is, the above polyfunctional (meth) acrylate may, for example, be a difunctional (meth) acrylate or a trifunctional or higher (meth) acrylate.

Among them, examples of the difunctional (meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and hexanediol (meth)acrylate. Long-chain aliphatic di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di Methacrylate Ester, propylene glycol di(meth)acrylate, glycerol (meth) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, butylene glycol di(a) Acrylate, butanediol di(meth)acrylate, dicyclopentanyl (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, three Dimethyl (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di Methyl) acrylate, acrylated isocyanate, bis(acryloxy neopentyl glycol) adipate, bisphenol A di(meth)acrylate, tetrabromobisphenol A di(meth)acrylic acid Ester, bisphenol S di(meth) acrylate, butanediol di(meth) acrylate, di(meth) acrylate, di(meth) acrylate, zinc di(meth) acrylate (zinc dimethacrylate) and so on.

Further, examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and glycerol tri(methyl). Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, tris(meth)acrylate, propylene (propylene oxy) Ethyl)trimeric isocyanate, ginseng (methacryloxyethyl)trimeric isocyanate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, bis(trimethylolpropane)tetra Acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkane Base modified dipentaerythritol penta (meth) acrylate, carboxylic acid modified dipentaerythritol penta (meth) acrylate, amine ester tri(meth) propylene An acid ester, an ester tri(meth)acrylate, an amine ester hexa(meth)acrylate, an ester hexa(meth)acrylate, or the like.

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

Further, the curable resin composition is preferably a compound having a curable cage type sesquiterpene oxide as a polyfunctional (meth)acrylic monomer.

In addition, the compound having the above-described curable cage type sesquiterpene oxide structure is preferably a cage type sesquiterpene oxide resin 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 have a carbon number of 1 to The alkyl group, the phenyl group, the (meth)acrylic group, the (meth)acryloxyalkyl group, the vinyl group or the oxirane ring group may have the same group or a different group, respectively. (1) at least two (meth)acrylic groups, n, m, 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 Meet m≦l)

In the case of the above-mentioned cage sesquioxane resin, a reaction having a (meth)acrylic group-containing organic functional group or a (meth)acryloxyalkyl group in all of the ruthenium atoms constituting the cage is used. a functionally functional group having a molecular weight distribution and a molecular structure controlled by a caged sesquiterpene alkane resin, but a part of which may be substituted by an alkyl group, a phenyl group or the like may or may not be a completely closed polyhedral structure, but There is a part of the broken structure. For a part of the fractured structure, it may also have (meth)acrylic acid in the linked oxime chain. base.

The hard resin layer containing the curable resin composition used in the present invention has a thickness of 25 μm or more and 250 μm or less. When the thickness is less than 25 μm, sufficient scratch 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 a display or the like cannot be obtained.

Further, the monomer body of the hard resin layer used in the present invention has a tensile modulus of elasticity of 2,000 to 4,000 MPa. When the tensile modulus is less than 2,000 MPa, the scratch hardness of the resin laminate is less than 40 g. When it exceeds 4,000 MPa, there is a problem that workability such as molding, cutting, punching, and the like is difficult. Further, the hard resin layer used in the present invention is suitable for a display panel or the like, so that the total light transmittance is required to be 90% or more.

In addition, the content ratio of the functional group of the (meth)acrylic acid monomer having a hardening resin composition of the hard resin layer of 4 or more is preferably 40 g or more per 100 g of the curable resin composition per solid content. When the number of functional groups of the (meth)acrylic acid monomer is 4 or more, if it is less than 40 g, the thickness may not be sufficiently scratched even if it is 25 μm or more.

In addition, the curable resin composition is preferably composed of a curable resin having a solid layer of 100 g per solid point, from the viewpoint of obtaining a sufficient scratch hardness as a resin laminate and good machinability such as cutting and punching. The molar number of the (meth)acrylic group of the substance is preferably in the range of 0.6 to 0.9. Here, the number of moles of the (meth)acrylic group of the curable resin composition per 100 g of the solid content was calculated by the following formula.

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

When a plurality of polyfunctional (meth)acrylic monomers are used as the curable resin composition, the average number of moles of the (meth)acrylic group calculated using the blending ratio is used, and when a filler such as cerium oxide is formulated, The average value of the number of moles of the (meth)acryl group containing the weight of the filler was calculated.

Further, the hard resin layer containing the hardening type resin composition may be a monofunctional group in a range in which the number of moles of the (meth)acrylic group per 100 g of the curable resin composition is not more than 0.6 to 0.9. Base) Acrylate. However, when a certain amount or more of a monofunctional (meth) acrylate is blended, the surface hardness tends to be lowered. Therefore, when blending for the purpose of adjusting the viscosity or the like, it is preferable to keep it at a minimum. The curable resin composition is preferably 30% by weight or less.

Among them, examples of the monofunctional (meth) acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, and butyl acrylate. Ester, neopentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate , decyl acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, isomyristyl acrylate, hexadecyl acrylate, heptadecyl acrylate , octadecyl acrylate, octadecyl acrylate, icosyl acrylate, n-lauryl acrylate, stearyl acrylate and other alkyl acrylates; acryloyl morpholine, cyclohexyl acrylate, acrylic acid Dicyclopentenyl ester, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy butyl acrylate Ester, 2-hydroxy-3-phenyloxypropyl acrylate, 1,4-butanediol monoacrylate, 2-hydroxyalkyl propylene decyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6- Hexanediol monoacrylate, neopentyl glycol monoacrylate; a cyclic ester compound such as ε-caprolactone added to the above hydroxyl group-containing acrylate compound; alkyl glycidyl ether, allyl glycidol a compound obtained by an addition reaction of a glycidyl compound and acrylic acid, such as an ether or a glycidyl acrylate; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, tetrahydrofurfuryl acrylate, isodecyl acrylate, acrylic acid ( 2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl ester, acrylic acid (2-isobutyl-2-methyl-1,3 dioxacyclopentane) 4-yl)methyl ester and the like.

In the curable resin composition used in the present invention, a (meth)acrylic resin copolymer can be obtained by these radical copolymerization reactions. In order to improve the physical properties of the (meth)acrylic resin copolymer or to promote the radical copolymerization reaction, various additives may be formulated in the curable resin composition of the present invention. Examples of the additive for promoting the reaction include a thermal polymerization initiator, a thermal polymerization promoter, a photopolymerization initiator, a photoinitiator, a sensitizer, and the like. When the photopolymerization initiator or the thermal polymerization initiator is blended, the amount thereof is preferably in the range of 0.1 to 5 parts by weight, and in the range of 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the curing resin composition. For the better. If the amount is less than 0.1 part by weight, the curing is insufficient, and the strength and rigidity of the obtained hard resin layer are lowered. In the case of parts by weight, there are problems such as coloring of the hard resin layer.

The photopolymerization initiator used in the case of using the curable resin composition as a photocurable composition can be suitably used as an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based or mercaptophosphine-based compound. A compound such as an acylphosphine oxide. More specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl can be exemplified 1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2- Hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl]-2-methyl-propan-1-one, methyl phenylglyoxylate (phenylglyoxylic acid methyl ester), 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 1, 2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindolyl)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) Mercapto)-9H-carbazol-3-yl]-,1-(0-acetamidofluorene), 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1 -(4-morpholinylphenyl)-butanone-1-one, bis-2,6-dimethoxybenzylidene-2,4,4-trimethylpentylphosphine oxide, benzophenone , thioxanthone, 2-chlorothiazinone, 2,4-diethylthiaxanone, isopropyl thioxanthone, 1-chloro-4-propoxythiazinone, In addition it may be used alone or outside, or two or more may be used.

The curable resin composition used in the present invention can be produced into a hard resin layer having an arbitrary shape such as a flat surface or a curved surface by blending a radical polymerization initiator with heating or light irradiation. When a hard resin layer of any shape is produced by heating, the forming temperature can be regarded as a thermal polymerization initiator and The choice of the agent is selected from a wide range from room temperature to 200 ° C. At this time, a hard resin layer having a desired shape can be obtained by polymerization hardening in a mold or a steel strip.

Further, when the hard resin layer is produced by light irradiation, it can be obtained by irradiating ultraviolet rays having a wavelength of 10 to 400 nm or irradiating visible light having a wavelength of 400 to 700 nm. The wavelength of the light to be used is not particularly limited, and in particular, near ultraviolet rays having a wavelength of 200 to 400 nm can be suitably used. As the lamp used as the ultraviolet light generating source, a low pressure mercury lamp (output: 0.4 to 4 W/cm), a high pressure mercury lamp (40 to 160 W/cm), an ultrahigh pressure mercury lamp (173 to 435 W/cm), a halogenated metal lamp (for example) can be exemplified ( 80 to 160 W/cm), pulsed xenon lamp (80 to 120 W/cm), electrodeless discharge lamp (80 to 120 W/cm), and the like. These ultraviolet lamps have their characteristics in terms of their spectral distribution, and are selected depending on the type of photoinitiator used.

In the method of obtaining a hard resin layer of any shape used in the present invention by light irradiation, for example, injecting curability into a mold having an arbitrary cavity shape and a transparent material such as quartz glass can be exemplified. a resin composition which is subjected to polymerization curing by irradiation with ultraviolet rays by the above-mentioned ultraviolet lamp, and is released from a mold to produce a hard resin layer of a desired shape; or when a mold is not used, for example, a moving steel strip A method of producing a sheet-like hard resin layer by applying a curing resin composition of the present invention with a doctor blade or a roll coater and polymerizing and curing the above-mentioned ultraviolet lamp.

<Substrate layer>

The substrate layer of the present invention desirably has excellent transparency. Suitable for use: polyethylene terephthalate (PET), cellulose triacetate (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC ), polyamine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cyclic olefin copolymer (COC), resin containing norbornene Various resin films such as polyether oxime, cellophane, and aromatic polyamine. These films may be used without extension or by those who have been subjected to elongation processing, but from the viewpoints of heat resistance, transparency, weather resistance, solvent resistance, impact resistance, workability, and cost. It is particularly preferable to use polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), or polycarbonate (PC).

The base material layer imparts rigidity to the resin laminate of the present invention, and is sufficiently resistant to punching and bending. For example, the hard resin layer of the present invention is formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer having a cage type sesquiterpene oxide structure, and suitably has a scratch hardness of 40 g or more. When the thickness of the hard resin layer is 250 μm or less in order to ensure transparency, the punching resistance is insufficient. Therefore, in the present invention, it is sufficiently resistant to punching, bending, and the like by the base material layer. With respect to the substrate layer, the total thickness thereof is from 0.5 to 2000 μm, preferably from 10 to 1000 μm. If it is less than 0.5 μm, sufficient rigidity cannot be obtained, and if it exceeds 2000 μm, processing such as molding, cutting, and punching becomes difficult. Further, the total thickness of the substrate layer of the present invention a thickness t ₁ and a hard resin layer is t ₂ ratio (t ₁ / t ₂₎ is 0.25 or more and 10 or less. If the ratio of the thickness is less than 0.25, there are problems in processing such as forming, cutting, punching, and the like, and if it exceeds 10, the scratch hardness is less than 40 g.

<Next layer>

In the resin laminate of the present invention, the hard resin layer and the base layer can be laminated through a film or a sheet-like adhesive layer (adhesive layer).

In the case of the adhesive layer, the thickness thereof is from 0.01 to 30 μm, preferably from 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 exceeds 30 μm or more, the laminated body cannot obtain sufficient scratch hardness.

Moreover, as an adhesive agent which comprises an adhesive layer as an adhesive layer, an adhesive bond, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive can also be used. Examples of such an adhesive include an acrylic adhesive, an amine ester adhesive, an epoxy adhesive, a polyester adhesive, a polyvinyl alcohol adhesive, a polyolefin adhesive, a modified polyolefin adhesive, and a polyvinyl alkyl ether adhesive. , rubber adhesive, vinyl chloride/vinyl acetate adhesive, styrene/butadiene/styrene copolymer (SBS copolymer) adhesive, hydride (SEBS copolymer) adhesive, ethylene/vinyl acetate copolymer, Acrylates such as ethylene-styrene copolymer, ethylene/methyl methacrylate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/ethyl acrylate copolymer, etc. The agent or the like is not particularly limited as long as it has good adhesion, transparency, and processability.

<easy layer>

Moreover, it is mentioned that it is an adhesive layer, and an easy adhesion layer is mentioned. The easy-adhesion layer is a layer to which a chemically easy-to-attach ability or a physical easy-to-attach ability is applied to the surface of the hard-to-adhere resin. Among them, the chemical easy adhesion ability, in detail, is to form a film layer of a resin having a functional group on the substrate layer, and form a chemical bond with the hard resin layer to obtain a close contact; on the other hand, physical easy The next step is to obtain a adhesion force to the hard resin layer by an anchoring effect by forming a resin film layer or an inorganic film layer having irregularities on the base material layer. Examples of the material having a chemically easy adhesion ability include polyfunctional (meth) acrylates, epoxy resins, and thiol group-containing compounds, and materials having physical adhesion ability include SiO ₂ and SiN. A vapor deposition film such as SiC.

Fig. 1 is a view showing a first aspect of the resin laminate of the present invention. In the resin laminate shown in Fig. 1, the adhesive layer 2 is formed on both surfaces of the base material layer 3 containing the thermoplastic resin, and the hard resin layer 1 is layered on the upper and lower sides. Moreover, the resin laminated body of the first aspect has a structure in which the printed layer 4 is formed on one side of the hard resin layer 1. Among them, the adhesive layer 2 functions as an adhesive layer that integrates the hard resin layer 1 and the base material layer 3 . Further, a pattern, a character, or the like can be formed by forming the printed layer 4 on the lower surface of the resin laminate of the present invention. The printing pattern of the printing layer 4 can be arbitrarily selected, and examples thereof include wood grain, stone grain, cloth grain, sand grain, geometric pattern, letter, full-page printing, and rnetallic pattern. Further, the adhesive layer 2 may be any of the aforementioned adhesive layer or easy-adhesion layer.

In the printing layer 4, a resin component having a good compatibility with a hard resin layer or a base material layer is preferably used, and examples thereof include a polyethylene resin such as a vinyl chloride/vinyl acetate copolymer, and a polyamide compound. A resin, a polyester resin, an acrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyesteramine resin, a cellulose ester resin, an alkyd resin, and a chlorinated polyolefin resin. Hydrogenation of this resin component can inhibit The peeling and peeling off of the printing.

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

The method of forming the printing layer 4 may, for example, be a printing method such as a lithography method, a gravure rotary printing method or a screen printing method, a coating method such as a roll coating method or a spray coating method, or a flexographic printing method.

The thickness of the printed layer 4 is preferably a thickness of 0.5 to 30 μm as long as the resin laminate can obtain a desired surface appearance.

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

In the second embodiment shown in Fig. 2, the printed layer 4 is formed on the upper surface of the base material layer 3b, and the pressure-sensitive adhesive layer is bonded to the upper portion of the printed layer 4 side and the side where the printed layer 4 is not formed. 5. The hard resin layer 1 is formed on the side of the printed layer 4, and the base material layer 3 is formed on the side where the printed layer 4 is not formed.

In the second drawing, the base material layer 3b to be used is not particularly limited as long as it is transparent, but polymethyl methacrylate (PMMA) is preferred.

Further, in the third embodiment shown in Fig. 3, the hard resin layer 1 is formed on the upper surface of the base material layer 3 via the adhesive layer 2, and the printed layer 4 is formed on the lower surface of the base material layer 3, and The second base material layer 3 is formed on the lower portion via the pressure-sensitive adhesive layer 5.

In the embodiment of FIGS. 2 and 3, a known pressure-sensitive adhesive can be used as the pressure-sensitive adhesive layer 5 to be used. Specifically For example, an adhesive such as a natural rubber-based resin, a synthetic rubber-based resin, a polyoxymethylene-based resin, a propylene-based resin, a vinyl acetate-based resin, or an amine-ester resin can be used.

The above-mentioned adhesive is not limited to a specific adhesive as long as it can obtain desired light transmittance, adhesiveness, and weather resistance. Further, in order to prevent deterioration of the dye in the layer constitution, it is preferred to include a UV absorber (such as benzotriazole) 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 the thickness is less than 0.01 μm, sufficient adhesion strength cannot be obtained, and the effect of absorbing the unevenness of the printed layer and flattening is also lowered. Moreover, when it exceeds 30 micrometers, it is the main cause of the fall of the scratch hardness of a laminated body.

In the first and third embodiments of the present invention, the state of the resin laminate can be imparted to a three-dimensional shape by thermoforming. The base material layer 3 of FIGS. 1 and 3 can be thermoformed, and the hard resin layer 1 can be formed into an integrally molded product via the adhesive layer 2 in accordance with the shape of the base material layer 3 because of its sufficient flexibility. Examples of the heat formation include vacuum forming, pressure forming, press forming, and the like.

Further, in the layer constitution of the resin laminate as shown in Fig. 2 of the embodiment of the present invention, it is possible to form the A portion (hard resin layer 1 and pressure-sensitive adhesive layer 5) which are previously formed into a predetermined shape. The printed layer 4, the base material layer 3b) and the B portion (the pressure-sensitive adhesive layer 5, the base material layer 3) are bonded via the pressure-sensitive adhesive layer 5, and the base material layer 3 constituting the B portion is also However, those who form the pressure-sensitive adhesive layer 5 in part A in advance are loaded in the desired shape. After the inside of the mold, the injection molding resin is injected by injection molding.

Further, in the first embodiment to the third embodiment, the printed layer 4 is formed separately, but the printed layer 4 may be omitted, and any one of the layers may be formed by any printing method in accordance with the manufacturing process of the laminated body. can.

When the base material layer 3 is injection molded, it is preferable that the thermoplastic resin for injection molding is transparent, and it can be suitably used: polyethylene terephthalate (PET), cellulose triacetate (TAC), and poly Ethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamine (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol Various resin films (PVA), polyvinyl chloride (PVC), cyclic olefin copolymer (COC), decene-containing resin, polyether oxime, celorophan, aromatic polyamine, etc., but heat-resistant and transparent From the viewpoints of properties, weather resistance, solvent resistance, rigidity, and cost, it is desirable to use polyethylene terephthalate or polycarbonate, and polycarbonate is special from the viewpoint of impact resistance. ideal.

The hardness evaluation method of the present invention is explained here. In ISO 1518-2, a method for determining the hardness of a scratch by using a variable load method of an indenter having an acute tip shape is disclosed. This method is a method of applying a load, and moving the sample in a state where the surface of the sample is pressed against the indenter, and using the formula shown below to evaluate the hardness Fc (g) from the load when the flaw caused by the indenter is observed.

Fc={(100-d)/100}×(Ff-Fi)

d: the distance (mm) from the start to the end of the scratch when the distance from the start point to the end point is 100 mm

Ff: load at the end point (g)

Fi: measuring the load of the starting point (g)

The inventors of the present invention conducted hardness evaluation on various materials by this method, and as a result, found that the degree of difficulty in scratching which was not determined by the pencil hardness can be accurately determined to examine the characteristics of the material at this time. That is, the scratch hardness of the variable load method is preferably in a range of 40 g or more. If the evaluation value is smaller than this range, it will be easily scratched by a small amount of load, which is not preferable. Further, it is not preferable to make a supplementary explanation for the case where the value of the scratch hardness is extremely large, that is, it is synonymous with the difficulty of processing which is not scratched by adding a large load. Further, when the hard resin layer has a property of being bent by the load, the value of the scratch hardness may be large. However, even if no scratch is caused, dents are formed and the texture is lowered, which is not preferable. Further, the load weight at the time of measuring the scratch hardness by the variable load method is not particularly limited, but is preferably measured in the range of from about 0 to several hundreds g at the measurement starting point and from several tens to several hundreds g at the end point.

[Examples]

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

1) Scratch hardness: in accordance with ISO 1518-2 (paint and varnish - determination of scratch resistance - part 2: variable load method), using a sapphire needle with a tip R of 0.03 ± 0.005 mm, the needle moving speed of 10 mm / s, the load was increased from 0 to 200 g, and was evaluated by microscopic observation from the load when visually scratched.

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

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

4) Tensile elastic modulus: Measured in accordance with JIS7127.

5) Machinability: A die-cutting tool (manufactured by MEGARO TECHNICA Co., Ltd.) was used to assemble a die-cutting knife (2 mm, a straight edge), and the resin laminate obtained in the example was conveyed at a number of revolutions of 20,000 rpm. The processing conditions at a speed of 900 mm/min were subjected to cutting processing, and microscopic observation of the cut surface was carried out, and it was observed that the chipping was × on the cut surface, and ○ was not observed.

[Example 1] (Production of hard resin layer)

Dipentaerythritol hexaacrylate: 85 parts by weight and PMMA: 15 parts by weight, heat-kneaded at 110 ° C, and then mixed with 1-hydroxycyclohexyl benzophenone as a photopolymerization initiator: 2.5 parts by weight to obtain a curable resin Composition.

Next, the curable resin composition was cast on the peel-treated PET to a thickness of 0.15 _m using a roll coater, and another peel-treated PET laminate was applied to the cast curable resin composition. Thereafter, a high-pressure mercury lamp of 30 W/cm was used, and the exposure amount was hardened at a cumulative amount of 4000 mJ/cm ² , and all of the peeled-treated PET was peeled off, thereby obtaining a sheet-like hard resin layer having a predetermined thickness. The tensile modulus of elasticity and the total light transmittance were measured for the obtained hard resin layer. The results are shown in Table 1.

(Production of resin laminate)

A cast cationic photocurable adhesive (manufactured by Kyoritsu Chemical Co., Ltd.) was applied as a base material layer of polycarbonate (PC-1151, manufactured by Teijin Co., Ltd., 200 mm × 200 mm × thickness: 0.5 mm (t ₁ )) to a thickness of 5 μm. Thereafter, the hard resin layer obtained above was bonded to one surface of the polycarbonate in its entirety, and after pressing, a metal halide lamp was irradiated from both surfaces at a ratio of ultraviolet rays of 500 mJ/cm ² to obtain a resin laminate. The obtained resin laminate was evaluated for scratch hardness and workability. The results of the hard resin layer thickness (t ₂ ), the thickness ratio (t ₁ /t ₂ ), and the scratch hardness at this time are shown in Table 1.

[Embodiment 2]

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

[Synthesis Example 1]

In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 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 charged. 126.9 g of IPA 150 ml and 3-methyl propylene methoxy propyl trimethoxy decane (MTMS: SZ-6030, manufactured by TORAY-DOW CORNING SILICONE Co., Ltd.) were placed in a dropping funnel, and the reaction vessel was stirred at room temperature. The IPMS solution of MTMS was dripped in 30 minutes. After the completion of the dropping of the MTMS, the mixture was stirred without heating for 2 hours. 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 dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off, and 86 g of a cage sesquiterpoxide compound having a methacryl oxime group on all ruthenium atoms was obtained by concentration. This sesquiterpene is a colorless viscous liquid which is soluble in various organic solvents.

[Example 3]

The above-mentioned Synthesis Example 1 has methyl propyl groups on all of the ruthenium atoms. An ethylenic group cage sesquiterpoxide compound: 25 parts by weight, dipentaerythritol hexaacrylate: 40 parts by weight, dicyclopentanyl acrylate: 30 parts by weight, amine ester acrylate oligomer 1: 5 parts by weight, and The 1-hydroxycyclohexyl benzophenone as a photopolymerization initiator was mixed in an amount of 2.5 parts by weight to obtain a transparent curable resin composition.

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

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

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

The code numbers in the table are as follows.

A: Compound obtained in Synthesis Example 1

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

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

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

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

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

G: Dicyclopentyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.; LIGHT ACRYLATE DCP-A)

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

I: PMMA (PARAPET LW manufactured by KURARAY Co., Ltd.: weight average molecular weight of about 34,000)

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

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

L: 1-hydroxycyclohexyl benzophenone (polymerization initiator, IR G ACURE 184 manufactured by BASF JAPAN Co., Ltd.)

1‧‧‧hard resin layer

2‧‧‧ adhesive layer

3‧‧‧Substrate layer

4‧‧‧Printing layer

Claims (8)

A resin laminate comprising a hard resin layer having a three-dimensional crosslinked structure and having a thickness of 25 μm or more and 250 μm or less, which is formed of a curable resin composition containing a polyfunctional (meth)acrylic monomer as an essential component; And a base layer formed of a single layer of thermoplastic resin or a plurality of layers of two or more layers, wherein the hard resin layer alone has a tensile elastic modulus of 2,000 to 4,000 MPa, and the total light transmittance is 90%. In addition, the ratio (t ₁ /t ₂ ) of the total thickness t _{1 of the} base material layer and the thickness t ₂ of the hard resin layer is 0.25 or more and 10 or less, and the scratch hardness of the resin laminated body is 40 g or more. The resin laminate according to the first aspect of the invention, wherein the content of the functional group of the (meth)acrylic monomer in the curable resin composition forming the hard resin layer is 4 or more, per solid fraction. 100 g of the curable resin composition contains 40 g or more. The resin laminate according to the first or second aspect of the invention, wherein the hard resin layer and the base layer are laminated via an adhesive layer. The resin laminate according to claim 3, wherein the adhesive layer comprises an adhesive adhesive, a pressure-sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt adhesive. One or two or more selected from the group. The resin laminate according to the first or second aspect of the invention, wherein the hard resin layer and the thermoplastic resin layer are laminated via an easy adhesion layer. For example, the resin laminate described in claim 1 or 2, Among them, the polyfunctional (meth)acrylic single system contained in the curable resin composition forming the hard resin layer has a cage sesquiterpene structure. The resin laminate according to claim 6, wherein the polyfunctional (meth)acrylic monomer having a cage sesquiterpene structure is 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) wherein R ¹ to R ⁶ are an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth)acrylic group, a (meth)acryloxyalkyl group, a vinyl group, or a group having an oxirane ring, which may be the same group or may contain a different group, but 1) at least 2 (meth)acrylic groups, and n, m, l are average values, n represents a number from 6 to 14, m represents a number from 0 to 4, and l represents a number from 0 to 4, and Meet m≦l. The resin laminate according to the first or second aspect of the invention, wherein the base layer has a hard resin layer on both sides of the front and back sides.