TW201615416A - Synthetic resin laminate - Google Patents

Abstract

The purpose of the present invention is to provide a synthetic resin laminate having excellent surface hardness, for use as a transparent substrate material and protective material. When the water vapor permeability on the base material layer side is low, the laminate exhibits low curling after being left in a high-temperature, high-humidity environment. A synthetic resin laminate having excellent surface hardness is obtained, wherein (i) the pencil hardness of a high-hardness layer is at least F, and (ii) by making the synthetic resin laminate have, after the laminate is left in a high-temperature, high-humidity environment, a laminate-only curl shape in which the convexity of the high-hardness layer side has a curvature radius of R ≥ 2.0 m, a laminate in which the water vapor permeability on a base material side has been reduced, has, after the laminate is left in a high-temperature, high-humidity environment, a curl shape in which the convexity of both the high-hardness layer side and the base material layer side has a curvature radius that is kept to R ≥ 3.2 m.

Description

Synthetic resin laminate

The present invention relates to a synthetic resin laminate. Specifically, the present invention relates to a substrate material or a protective material used for transparency, a synthetic resin laminate having a base layer and a surface resin layer (high hardness layer), and a bonding of OCA and ITO to PET, In a state where the water vapor transmission rate on the side of the base material layer is small, the synthetic resin laminate having excellent surface hardness is suppressed from being curled after being placed in a high temperature and high humidity environment.

The polycarbonate resin sheet is excellent in transparency, impact resistance, and heat resistance, and is used for a sound insulating wall or a carport, a kanban, an glazing material, a lighting fixture, an OA, an electronic device display, or a touch panel front panel, and the like. However, since the surface hardness is low and there is a disadvantage that it is easily injured, the use is limited.

Patent Document 1 proposes a method of coating a surface with an ultraviolet curable resin or the like, and a method of performing a hard coat treatment (HARD COAT) on a substrate in which a polycarbonate resin and an acrylic resin are coextensive in order to improve the disadvantage.

However, since the surface of the polycarbonate resin is subjected to a hard film treatment and cannot satisfy the required pencil hardness, it is sometimes impossible to use a high surface. The use of hardness.

In addition, the laminate of the acrylic resin and the polycarbonate resin has a certain surface hardness, and is widely used in displays for electronic devices, front panels of touch panels, etc., but the plate placed in a high temperature and high humidity environment has a large surface. The problem of the stability of the shape such as curling has become a major drawback in the use of electronic devices such as a liquid crystal display sheath or a touch panel front panel.

The method of suppressing the curl after being placed in a high temperature and high humidity environment has a method of laminating an acrylic resin layer on both sides of a polycarbonate resin layer, but when the one side of the laminate is subjected to surface impingement, the opposite side of the acrylic layer The resin layer is prone to cracking, which may cause problems due to the method of use.

Patent Document 2 discloses that a method of suppressing curl after being placed in a high temperature and high humidity environment is a method of laminating a methyl methacrylate-styrene copolymer of a resin having a low water absorption ratio lower than that of an acrylic resin to a polycarbonate resin. The laminate, but under the conditions of 40 ° C / 90% of the environmental test used here, is still not sufficient as a high temperature and high humidity condition.

Patent Document 3 discloses a laminate in which a high-hardness-denatured polycarbonate resin is laminated on a polycarbonate resin, but the shape stability in the case of environmental change is not mentioned. The directionality of the curl of the sheet placed in a high-temperature, high-humidity environment is used in the front panel of the display or the like to form a convex curl on the surface of the surface resin layer, which is allowed to some extent, but the substrate layer side is formed. The convex curl is not ideal in appearance.

Patent Document 4 discloses a laminate in which a resin having a (meth) acrylate and an aliphatic vinyl ester as a constituent unit is laminated on a polycarbonate resin, and the size of the curl after being placed in a high temperature and high humidity environment is inhibition. But did not say the direction of the curl. Moreover, in the patent document 5, the method of specifying the difference of the Tg of the laminated resin, etc., and the magnitude|size of the crimp after the high temperature and high-humidity environment is suppressed, and the surface resin side is formed, and the base material layer side is formed. The convex, all curled.

As described above, the shape after being placed in a high-temperature, high-humidity environment is a resin laminate which is convexly curled only on the surface resin side, determines the directivity, and does not suppress the curl.

In addition to the above facts, in general, when a transparent resin laminate is used as a front panel of a touch panel, the surface of the base layer side of the transparent resin laminate (the surface of the surface resin side) is passed through an optical adhesive sheet (OCA) or the like. The layer is bonded to PET formed by ITO or the like. In the case of bonding, the water vapor transmission rates of the unattached surface side and the bonding surface side are different. For example, as a sensor for a touch panel, when two OCAs of 50 μm and PET of 25 μm of ITO are laminated, water vapor is transmitted through a Lyssy water vapor transmission rate meter L80-5000 (manufactured by PBI Dansenor). The rate becomes 0.6g/m ² . Day, the water vapor transmission rate when only the laminate was measured was 18.4 g/m ² . Day. Therefore, the curl after being placed in a high temperature and high humidity environment is greatly affected by the conformity of the touch panel, and the influence is smaller. However, there has been no resin laminate which has a shape which is placed in a high-temperature and high-humidity environment and which suppresses the curl of a state in which the water vapor transmission rate on only one surface side is small.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-103169

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-167659

[Patent Document 3] Japanese Patent Publication No. 2009-500195

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-145630

[Patent Document 5] International Publication No. 2014/061817

An object of the present invention is to provide a substrate material or a protective material which is used for transparency, and in a state where the water vapor transmission rate on the side of the substrate layer is small, the curl can be suppressed after being placed in a high-temperature and high-humidity environment, and the surface hardness is excellent. A synthetic resin laminate.

In order to solve the above problems, the inventors of the present invention have found a laminate having a curl shape having a curvature radius R of 2.0 m or more after being placed in a high-temperature and high-humidity environment and having a convexity on the side of the high-hardness layer. In the state where the water vapor transmission rate on the side of the base material layer is small, the curl after being placed in a high-temperature and high-humidity environment can be suppressed, and the present invention is achieved. Specifically, the present invention is as follows.

<1> A synthetic resin laminate comprising: a base layer containing a thermoplastic resin (A); and a thermoplastic resin (B) different from the thermoplastic resin (A) laminated on at least one surface thereof a synthetic resin laminate of a high hardness layer, (i) the thickness of the high hardness layer is 10 to 250 μm, the total thickness of the base material layer and the high hardness layer is 0.1 to 2.0 mm, and the ratio of the thickness of the high hardness layer/the base material layer is 0.01 to 0.8. (ii) the pencil hardness of the high-hardness layer is F or more, and (iii) the crimped shape of the synthetic resin laminate after being placed in a high-temperature and high-humidity environment is such that the high-hardness layer side is convex and becomes a radius of curvature R. ≧2.0m.

<2> The synthetic resin laminate according to <1>, wherein the third layer is further laminated, and the water vapor transmission rate in the surface of the base material layer opposite to the high hardness layer is 0.2 to 0.6 g. /m ² . The curling shape of the synthetic resin laminate after being placed in a high-temperature, high-humidity environment is such that the high-hardness layer side is convex, or the base material layer side is convex, and the laminate has a radius of curvature R≧3.2 m. .

<3> The synthetic resin laminate according to the item <1>, wherein the thermoplastic resin (A) contained in the base material layer is a resin containing polycarbonate (a1), and the high hardness layer is contained. The thermoplastic resin (B) is a resin containing an aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) and a resin (b2) having a vinyl monomer as a constituent unit. The above (b1) is 45 to 80% by mass of the aromatic vinyl monomer unit, 5 to 45% by mass of the (meth) acrylate monomer unit, and 10 to 30% by mass of the unsaturated dicarboxylic anhydride monomer unit. % of an aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer, wherein the resin (B) is 50 to 100 parts by mass of the above (b1) and 50 to 0 parts by mass of the above (b2) Mixed resin.

<4> The synthetic resin laminate according to <3>, wherein the (meth) acrylate monomer unit of the above (b1) is methyl methacrylate.

<5> A synthetic resin laminate according to <3> or <4>, wherein the aforementioned resin (B) is the aforementioned aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid having a weight average molecular weight of 50,000 to 300,000 Copolymer (b1) 50 to 100 parts by mass of a mixed resin of 50 to 0 parts by mass of a methyl methacrylate resin (b2) having a weight average molecular weight of 50,000 to 500,000.

The synthetic resin laminate according to any one of <1> to <5> wherein the polycarbonate (a1) has a weight average molecular weight of 25,000 to 75,000.

The synthetic resin laminate according to any one of <1> to <6> wherein the high hardness layer and/or the base material layer contains an ultraviolet absorber.

<8> The synthetic resin laminate according to any one of <1> to <7> wherein the surface of the high hardness layer is subjected to a hard coat treatment.

<9> The synthetic resin laminate according to any one of <1> to <8> wherein the anti-reflection treatment, antifouling treatment, fingerprint resistance treatment, antistatic treatment are applied to the single or both sides of the resin laminate. Any one or more of treatment, weather resistance treatment, and anti-glare treatment.

<10> The synthetic resin laminate according to any one of <1> to <9> wherein the high hardness layer and the base material layer each have a tensile modulus of elasticity of 1600 MPa or more.

The synthetic resin laminate according to any one of <1> to <10> wherein the difference between the tensile modulus of elasticity of the high hardness layer and the tensile modulus of the base material layer is 400 MPa or less.

<12> A transparent substrate material characterized by containing A synthetic resin laminate according to any one of <1> to <11>.

<13> A transparent protective material characterized by containing the synthetic resin laminate according to any one of <1> to <11>.

<14> A touch panel front protective sheet, characterized by comprising the synthetic resin laminate according to any one of <1> to <11>.

<15> A laminate of a low water vapor transmission rate plate, characterized in that the synthetic resin laminate according to any one of <1> to <11> is contained.

According to the present invention, in the state where the OVA and the ITO form a PET bond or the like, and the water vapor transmission rate on the side of the base material layer is small, the synthetic resin which is excellent in surface hardness after being placed in a high temperature and high humidity environment is suppressed. As the laminate, the synthetic resin laminate can be used as a transparent substrate material or a transparent protective material. Specifically, the synthetic resin laminate is suitable for a portable display device such as a mobile phone terminal, a portable electronic amusement device, a portable information terminal, a mobile PC, or a notebook PC, a desktop PC LCD monitor, a liquid crystal television, or the like. A display device or the like.

10‧‧‧Previous resin laminates

20‧‧‧Synthetic resin laminate

12,22‧‧‧Substrate layer

14,24‧‧‧Surface (high hardness layer)

16,26‧‧‧ITO layer

18,28‧‧‧hard coating

Fig. 1 is a cross-sectional view schematically showing a state of a synthetic resin laminate of the present invention in a room temperature and a high temperature and high humidity environment.

Fig. 2 is a cross-sectional view schematically showing a state of a synthetic resin laminate of a conventional example in a room temperature and a high temperature and high humidity environment.

[Formation of the Invention]

The present invention will be described in detail below with reference to the preferred embodiments, examples, and the like. The invention is not limited to the exemplified manufacturing examples, examples, and the like, and may be carried out in a more arbitrary manner without significantly departing from the scope of the invention.

<Thermoplastic resin (A)>

The thermoplastic resin (A) is a main component of the base material layer forming the synthetic resin laminate. The thermoplastic resin (A) is mainly a resin containing polycarbonate (a1).

<Polycarbonate (a1)>

The polycarbonate (a1) used in the present invention contains a carbonate bond in a molecular main chain. That is, as long as it contains -[OR-OCO]-unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure), There is no particular limitation, but it is particularly preferred to use a polycarbonate containing a structural unit of the following formula [1]. By using such a polycarbonate, a resin laminate excellent in impact resistance can be obtained.

Specifically, as the polycarbonate (a1), an aromatic polycarbonate resin (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000) or the like can be used.

In the present invention, the weight average molecular weight of the polycarbonate (a1) affects the impact resistance and molding conditions of the synthetic resin laminate. In other words, when the weight average molecular weight is too small, the impact resistance of the synthetic resin laminate is lowered, which is not preferable. When the weight average molecular weight is too high, when the resin layer containing the resin (a1) is laminated, there is a case where an excessive heat source is required, which is not preferable. Further, depending on the molding method, a high temperature is required, and therefore the resin (a1) is exposed to a high temperature, which may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate (a1) is preferably from 15,000 to 75,000, more preferably from 20,000 to 70,000. More preferably, it is 25,000~65,000.

The synthetic resin laminate of the present invention is characterized in that a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) is 50 to 100 parts by mass and a vinyl monomer is used. A resin layer (high hardness layer) in which 50 to 0 parts by mass of the resin (b2) of the constituent unit is blended, and laminated on at least one side of a resin layer (base material layer) containing polycarbonate (a1) Resin laminate.

<Thermoplastic resin (B)>

The thermoplastic resin (B) forms a main component of the high hardness layer of the synthetic resin laminate. The thermoplastic resin (B) mainly contains an aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) and a resin (b2) having a vinyl monomer as a constituent unit.

<Aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1)>

The (b1)-based aromatic vinyl monomer unit used in the laminate of the present invention is 45 to 80% by mass, the (meth) acrylate monomer unit is 5 to 45% by mass, and the unsaturated dicarboxylic anhydride monomer unit 10 is used. ~30% by mass of a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer.

Examples of the aromatic vinyl monomer unit include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 2,4-dimethylbenzene. Ethylene, ethyl styrene, t-butyl styrene, and the like. Among these, from the viewpoint of compatibility, styrene is particularly preferred. These aromatic vinyl monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylate monomer unit include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, and A. Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Among these, methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with a vinyl monomer. (meth)acrylic acid The ester monomer unit may be used alone or in combination of two or more.

The unsaturated dicarboxylic anhydride monomer may, for example, be an acid anhydride such as maleic acid, itaconic acid, citraconic acid or aconitic acid, and is preferably a horse from the viewpoint of compatibility with a vinyl monomer. Anhydride. These unsaturated dicarboxylic anhydride-based monomers may be used alone or in combination of two or more.

The weight average molecular weight of the aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) is preferably from 100,000 to 200,000, more preferably from 120,000 to 180,000. When the weight average molecular weight of the above (b1) is 50,000 to 300,000, compatibility with (b2) a resin having a vinyl monomer as a constituent unit is good. Further, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of (b1) can be measured by gel permeation chromatography using THF or chloroform as a solvent.

<Resin (b2) having a vinyl monomer as a constituent unit>

The resin (b2) having a vinyl monomer as a constituent unit used in the present invention may, for example, be acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate or 2-ethyl acrylate. Vinyl monomers such as hexyl hexyl ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc. are separately polymerized, especially Methyl methacrylate is preferred as the monomer unit. Further, it may be a copolymer containing two or more kinds of the above monomer units.

In the present invention, the weight average molecular weight of the resin (b2) having a vinyl monomer as a constituent unit is related to aromatic vinyl-(methyl)propyl The ease of mixing (dispersion) of the acrylate-unsaturated dicarboxylic acid copolymer (b1) and the ease of manufacture of the blended resin (B) are determined. In other words, when the weight average molecular weight of the resin (b2) having a vinyl monomer as a constituent unit is too large, the difference in melt viscosity between (b1) and (b2) is excessively large, so that the mixing (dispersion) of the two is deteriorated. There may be an unfavorable situation in which the transparency of the resin (B) is deteriorated or the melt-kneading of stability is not continued. On the other hand, when the weight average molecular weight of the resin (b2) having a vinyl monomer as a constituent unit is too small, the strength of the resin (B) is lowered, so that problems such as a decrease in the crush resistance of the synthetic resin laminate may occur. The weight average molecular weight of the resin (b2) having a vinyl monomer as a constituent unit is preferably in the range of 50,000 to 700,000, more preferably in the range of 60,000 to 550,000. More preferably, it is in the range of 70,000 to 500,000.

<Resin (B): a mixture of an aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) and a resin (b2) having a vinyl monomer as a constituent unit>

In the present invention, the mass ratio of the aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) to the resin (b2) having a vinyl monomer as a constituent unit is relative to (b1) The component is 50 to 100 parts by mass, and the component (b2) is 50 to 0 parts by mass. It is preferably 55 to 90 parts by mass with respect to the component (b1) and 45 to 10 parts by mass of the component (b2). More preferably, it is 60 to 85 parts by mass with respect to the component (b1), and 40 to 15 parts by mass of the component (b2). By setting the mass ratio to the inside, it is possible to maintain transparency and excellent surface hardness, and it is suitable for forming a PET bond between OCA and ITO, and water vapor permeation on the substrate layer side. In the state where the rate is small, the resin (B) which is curled after being placed in a high temperature and high humidity environment is suppressed.

The hardness of the high hardness layer is equal to or higher than the pencil hardness F, and preferably the pencil hardness H or more.

<Manufacturing method of various materials>

The method for forming the synthetic resin laminate of the present invention is not particularly limited. For example, a method of laminating an individually formed high hardness layer and a base material layer containing polycarbonate (a1) (resin (A)), hot pressing the two, and separately forming a high hardness layer and a base material layer Lamination, a method of co-extruding a resin (B) forming a high hardness layer and a polycarbonate resin (a1) (resin (A)) by a method of using an adhesive, and using a high hardness formed in advance Although the polycarbonate resin (a1) is subjected to various methods such as a method of in-mold molding integration, it is preferable to carry out co-extrusion molding from the viewpoint of production cost or productivity.

The method for producing the polycarbonate (a1) used in the present invention is a known phosgene method (interfacial polymerization method) or a transesterification method (melting method), and can be appropriately selected depending on the monomer to be used.

In the present invention, the method for producing the resin (B) having a high hardness layer is not particularly limited, and a necessary component can be used, for example, a tumbling mixer, a high-speed mixer (Henschel mixer), a super mixer, or the like. The mixer is pre-mixed, and then a well-known method such as melt-kneading is performed by a machine such as a Banbury mixer, a roll, a Brabender, a uniaxial extruder, a two-axis extruder, or a pressure kneader.

<Synthetic resin laminate>

In the present invention, the thickness of the high hardness layer affects the surface hardness or impact resistance of the synthetic resin laminate. In other words, if the thickness of the high hardness layer is too thin, the surface hardness becomes low, which is not preferable. If the thickness of the high hardness layer is too large, the impact resistance is deteriorated, which is not preferable. The thickness of the high hardness layer is preferably from 10 to 250 μm, more preferably from 30 to 200 μm. More preferably, it is 60 to 150 μm.

In the present invention, the tensile modulus of elasticity of the high hardness layer and the substrate layer at 85 ° C affects the rigidity of the synthetic resin laminate. In other words, when the tensile modulus of elasticity in the environment of 85 ° C is too low, the deformation of the external force becomes large, and the workability such as coating or lamination is poor, which is not preferable. The tensile modulus of elasticity of the high hardness layer and the substrate layer is preferably 1600 MPa or more, and more preferably 1700 MPa or more.

Moreover, the difference between the tensile modulus of the high hardness layer and the substrate layer at 85 ° C is preferably | (the tensile modulus of the high hardness layer) - (the tensile modulus of the substrate layer) | ≦ 400 MPa, more preferably It is | (stretching elastic modulus of high hardness layer) - (stretching elastic modulus of base material layer) | ≦ 300 MPa. Thus, by using a high hardness layer having a small difference in stretch modulus and a base material layer, peeling between the layers of the high hardness layer and the base material layer can be prevented.

In the present invention, the total thickness of the synthetic resin laminate (sheet), the thickness of the high hardness layer, and the composition of the high hardness layer affect the curl of the synthetic resin laminate after being placed in a high temperature and high humidity environment.

In other words, when the overall thickness is too thin, the curl becomes large after being placed in a high temperature and high humidity environment, and when the thickness is thick, it is placed in a high temperature and high humidity environment. The curl afterwards becomes smaller.

Further, when the thickness of the high hardness layer is too thin, the curl after being placed in a high temperature and high humidity environment becomes small, but the hardness is lowered, and when the thickness of the surface layer is thick, the curl after being placed in a high temperature and high humidity environment becomes large, so it is necessary to It is necessary to find the composition of the high hardness layer that matches the thickness of each of the entire thickness and the high hardness layer.

Specifically, the total thickness of the base material layer and the high hardness layer is 0.1 to 2.0 mm, preferably 0.12 to 1.5 mm, more preferably 0.15 to 1.2 mm, and the thickness of the high hardness layer/the base material layer is The ratio is 0.01 to 0.8, preferably 0.02 to 0.7, more preferably 0.04 to 0.6.

Further, the synthetic resin laminate is not further laminated with a layer other than the base layer and the high-hardness layer, and in this state, the crimped shape after being placed in a high-temperature and high-humidity environment as will be described later is formed on the side of the high-hardness layer. Convex, the radius of curvature R ≧ 2.0 m is preferred, and the radius of curvature R ≧ 2.2 m is more preferable. More preferably, the radius of curvature is R ≧ 2.4 m. At this time, it is preferable that the curl on which the base material layer side is convex is not formed. In other words, in a state in which the substrate layer and the layer other than the high hardness layer are not further laminated, the shape of the curl after being placed in a high temperature and high humidity environment is preferably a radius of curvature R=∞.

As described above, in the state where the layer is not further laminated, when the film is formed in a high-temperature and high-humidity environment, only the high-hardness layer side is formed into a convex curl in an appropriate range, and the substrate of the synthetic resin laminate is formed. When the third layer is laminated on the layer side and the water vapor transmission rate on the side of the base material layer is lowered, the curl generated by the synthetic resin laminate can be minimized.

The water vapor transmission rate of the side of the base material layer of the synthetic resin laminate was 3.0 to 20.0 g/m ² . Day. Further, the water vapor transmission rate on the high hardness layer side of the synthetic resin laminate was 2.0 to 20.0 g/m ² . Day.

Further, in the case where the synthetic resin laminate is laminated with the third layer of PET or the like formed of ITO, as described above, the water vapor transmission rate on the surface side in contact with the third layer is lowered. By laminating with the third layer, for example, the water vapor transmission rate on the side of the base material layer of the synthetic resin laminate is, for example, 0.2 to 0.6 g/m ² . Around day. In this way, in the state in which the third layer is laminated, the synthetic resin laminate is placed in a high temperature and high humidity environment, and the shape of the synthetic resin laminate is such that the high hardness layer side is convex or the base material layer is formed. The side is convex and has a radius of curvature R ≧ 3.2 m. More preferably, the radius of curvature is R ≧ 4.2 m, and more preferably the radius of curvature is R ≧ 5.6 m.

In the present invention, the thermoplastic resin (A) forming the base material layer and/or the thermoplastic resin (B) forming the high hardness layer may contain components other than the above-described main components.

For example, a thermoplastic resin (A) and/or a thermoplastic resin (B) may be used in combination with a UV absorber. When the content of the ultraviolet absorber is too small, the light resistance is insufficient, and when the content is too large, the excessive ultraviolet absorber absorbs a high temperature due to the molding method, and the molding environment is contaminated, which may cause an unfavorable situation. The content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, still more preferably 0 to 1% by mass. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2-hydroxyl group. -4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 Dibenzophenone-based ultraviolet absorption of '-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2) -hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenyl Benzotriazole-based ultraviolet absorbers such as ethyl)phenol; phenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate a benzoate-based ultraviolet absorber such as an acid ester; a hindered amine-based ultraviolet absorber such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 2,4- Diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxybenzene 1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl -(2-hydroxy-4-butoxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3 , 5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-( 2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1, 3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, etc. Triazine-based ultraviolet absorber. The mixing method is not particularly limited, and a method of total amount of compounding, a method of dry blending a master batch, a method of full-blown dry blending, and the like can be used.

In the present invention, the thermoplastic resin (A) and/or (B) forming the high hardness layer and/or the substrate layer may be used by mixing various additives. The additive may, for example, be an antioxidant or an anti-staining agent, an antistatic agent, a mold release agent, a slip agent, a dye, a pigment, a plasticizer, a flame retardant, a resin modifier, a compatibilizer, an organic filler or an inorganic filler. Materials, etc. The mixing method is not particularly limited, and a method of total amount of compounding, a method of dry blending a master batch, a method of full-blown dry blending, and the like can be used.

In the present invention, the surface of the high hardness layer or the surface of the polycarbonate substrate layer may be subjected to a hard film treatment. The hardened layer is formed, for example, by hard treatment of the hardened hard coat material using thermal energy and/or light energy. For example, a thermosetting resin composition such as a polyorganosiloxane or a crosslinked acrylic may be used. Further, the hard coat coating which is cured by light energy may, for example, be photohardened by adding a photopolymerization initiator to a resin composition composed of a monofunctional and/or polyfunctional acrylate monomer and/or oligomer. Resin composition and the like.

The hard coat coating applied to the base material layer of the present invention to harden it by using light energy may, for example, be 20 to 60% by weight of 1,9-nonanediol diacrylate, and can be combined with 1,9- a difunctional or higher polyfunctional (meth) acrylate monomer copolymerized with decanediol diacrylate and a polyfunctional urethane (meth) acrylate oligomer having 2 or more functional groups and/or 2 or more functional groups 100 parts by weight of a resin composition comprising 40 to 80% by weight of a compound composed of a polyfunctional polyester (meth) acrylate oligomer and/or a bifunctional or higher polyfunctional epoxy (meth) acrylate A photocurable resin composition of 1 to 10 parts by weight of a photopolymerization initiator is added.

The method of applying the hard coat material in the present invention is not particularly limited, and a known method can be used. For example, a spin coating method, a dipping method, a spray method, a slant plate coating method, a bar coating method, a roll coating method, a gravure coating method, a concave coating method, a letterpress printing method, a screen printing method, a coating method, Brushing method, etc.

In order to improve the adhesion of the hard film, the coating surface is treated before the hard coating. Examples of the treatment examples include sand blasting, solvent treatment, and corona discharge. A well-known method such as a treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and a primer treatment method of a resin composition.

The materials of the high hardness layer, the base material layer and the hard film in the present invention, for example, the resins (A) and (B) and the like are preferably filtered and purified by a filter treatment. By the filter generation or by lamination, a synthetic resin laminate having less appearance defects such as foreign matter or defects can be obtained. The filtration method is not particularly limited, and melt filtration, solution filtration, a combination thereof, or the like can be used.

The filter to be used is not particularly limited, and can be appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material. The filter medium of the filter is not particularly limited, and may be a non-woven fabric or a coarse sand roll of polypropylene, cotton, polyester, mucus or glass fiber, a cellulose impregnated with a phenol resin, a sintered body of a metal fiber nonwoven fabric, a sintered body of a metal powder, Any of a porous plate, or a combination thereof. In particular, in consideration of heat resistance, durability, or pressure resistance, it is preferable to form a sintered metal fiber nonwoven fabric.

The filtration precision is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less, of the polycarbonate layer (a1) of the base material layer. Further, since the filtration precision of the hardener is applied to the outermost layer of the synthetic resin laminate, it is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

Regarding the filtration of the resin (B) of the high hardness layer and the polycarbonate (a1) (resin (A)) of the substrate layer, for example, a polymer filter used for melt filtration of a thermoplastic resin is preferred. Polymer filter, depending on its construction, It can be classified into a disc filter, a candle filter, a disc type filling filter, a cylindrical filter, etc., and a disc filter having a large effective filtration area is particularly preferable.

The synthetic resin laminate of the present invention may be applied to one or both of the antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment, and the antiglare treatment on one or both sides. The method of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and antiglare treatment is not particularly limited, and a known method can be used. For example, a method of applying a coating for reducing a reflective coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited by these examples.

The physical properties of the laminated resin obtained in the production example described later, and the evaluation of the synthetic resin laminates obtained in the examples and the comparative examples were carried out as follows.

<Deposition of Al and SiO ₂ >

Using an electron gun/resistance heating vapor deposition apparatus BMC-800T (manufactured by Kasei Optical Co., Ltd.), after the RF layer treatment was performed on the base material layer (A) using argon, Al was vapor-deposited at 100 μm, and SiO _{2 was} vapor-deposited at 20 μm. The vapor-deposited product was measured using a Lyssy water vapor transmission rate meter L80-5000 (manufactured by PBI Dansenor) to measure the water vapor transmission rate, and the water vapor transmission rate was 0.2 g/m ² . Day, which displays almost the same value as when fitting the sensor for the touch panel.

<Expansion modulus of stretch at 85 ° C environment>

A single-layer extrusion machine with a shaft diameter of 50 mm is formed of a single-layer extrusion device having an auxiliary product and a T-die, and a synthetic resin single-layer body having a thickness of 1 mm is formed from various materials of a high-hardness layer and a base material layer, respectively. A dumbbell-shaped test piece was prepared at the center. The dumbbell-shaped test piece was immersed in water at 23 ° C for 3 days, and then wiped off the water. The autograph AGS-5kNX (manufactured by Shimadzu Corporation) of the attached freezer type high-temperature and high-humidity tank was used, and it was recorded at 85 ° C according to JIS K-7161. The tensile test method measures the tensile modulus of elasticity.

<Evaluation of curl shape (curvature radius R and direction of unevenness)>

The lamination system placed in a high-temperature, high-humidity environment forms a curled shape, so that the convexity of the high-hardness layer (B) is convex or the side of the base material layer (A) is convex for the direction of the radius of curvature and the unevenness. shape. It is defined by the radius of curvature (m) = {arc length [m] (= length of test piece)} ² / (8 x arrow height [m]).

<Evaluation of the curl shape after being placed in a high temperature and high humidity environment>

The test piece was cut into squares of 10 cm x 6 cm. The test piece was placed on a support frame of a 2-point support type, and was placed in an environmental tester set to a temperature of 23 ° C and a relative humidity of 50% for more than 24 hours. After the state adjustment, the support frame was set to a temperature of 85 ° C. Among the environmental test machines having a relative humidity of 85%, this state was maintained for 120 hours. Further, in the environmental testing machine set to a temperature of 23 ° C and a relative humidity of 50%, the support frame was moved as a whole, and after holding for 4 hours in this state, h (= arrow height [m]) was measured. For the measurement of the height, a three-dimensional shape measuring machine equipped with an electric table is used, and the state of the removed test piece is horizontally placed, and is scanned at intervals of 1 mm, and the bulge of the central portion is measured as the height of the arrow, (curvature radius [m ]) = {0.116 (= arc length [m])} ² / (8 × h [m]), the laminate was evaluated only by the laminate and the vapor deposited laminate of Al and SiO ₂ (vapor-deposited). shape.

(in the case of laminate only)

Good (passed): The side of the high hardness layer is convex, and the radius of curvature R ≧ 2.0 m.

Bad (unqualified): Outside the above range.

(in the case of vapor deposition)

Good (passed): The convex side of the high hardness layer is convex, and the radius of curvature R ≧ 3.2 m. Or the side of the substrate layer is convex, and the radius of curvature R ≧ 3.2 m.

Bad (unqualified): Outside the above range.

<pencil hardness test>

According to JIS K 5600-5-4, with an angle of 45 degrees with respect to the surface and a load of 750 g, the surface of the base material layer (the layer of the resin (A)) is gradually increased in hardness, and the pencil is pressed, and the hardest is not caused. The pencil hardness was evaluated as the pencil hardness.

(in the case of tight laminate)

Good (qualified): pencil hardness F or more.

Bad (unqualified): Outside the above range.

(in the case of coated products)

Good (qualified): Pencil hardness is 2H or more.

Bad (unqualified): Outside the above range.

<Examples of various materials>

The thermoplastic resin (A) and the thermoplastic resin (B) are exemplified by the materials described below, but are not limited thereto.

A1: Polycarbonate resin: Mitsubishi Engineering Plastic (share) system, Iupilon S-1000

The stretch modulus of the synthetic resin monolayer having a thickness of 1 mm of S-1000 at 85 ° C was 1977 MPa.

B1: Specific aromatic vinyl-(meth) acrylate-unsaturated dicarboxylic acid copolymer: Electrochemical Industry Co., Ltd. R-200

B2: Specific aromatic vinyl-(meth) acrylate-unsaturated dicarboxylic acid copolymer: Electrochemical Industry Co., Ltd. R-100

B3: Resin containing vinyl monomer: methyl methacrylate resin parapet HR-L manufactured by kuraray

B4: Resin composed of (meth) acrylate and aliphatic vinyl as a constituent unit: synthetic resin (D12)

Production Example 1 [Manufacture of Resin (B11) Particles]

Into the aromatic vinyl-(meth)acrylate-unsaturated dicarboxylate Acid copolymer (b1) fat R-200 (manufactured by the electric chemical industry, weight average molecular weight: 185,000, aromatic vinyl monomer: (meth) acrylate monomer: ratio of unsaturated dicarboxylic anhydride monomer = 55 : 25:20) 50% by mass of paraffin HR-L (manufactured by Kuraray) of a methyl methacrylate resin of a resin (b2) having a vinyl monomer as a constituent unit, 50% by mass of a phosphorus-based additive PEP36 (ADEKA) 500 ppm, and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin) 0.2%, mixed with a mixer for 20 minutes, and then used a 2-axis extruder with a screw diameter of 26 mm (Toshiba Machine, TEM- 26SS, L/D≒40), melt-mixed at a cylinder temperature of 240 ° C, extruded into strands, and pelletized by a granulator. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a fat elongation coefficient of 1716 MPa at 85 ° C.

Production Example 2 [Manufacture of Resin (B12) Particles]

R-200 (60% by mass) as a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1), and a resin having a vinyl monomer as a constituent unit ( B2) A methyl methacrylate resin parapet HR-L (40% by mass), a phosphorus-based additive PEP36 (500 ppm), and stearic acid monoglyceride 0.2% were mixed and mixed in the same manner as in Production Example 1 to carry out granulation. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a fat expansion modulus of 1891 MPa at 85 ° C.

Production Example 3 [Manufacture of Resin (B13) Particles]

R-200 (70% by mass) as a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1), and a resin having a vinyl monomer as a constituent unit ( B2) A methyl methacrylate resin parapet HR-L (30% by mass), a phosphorus-based additive PEP36 (500 ppm), and stearic acid monoglyceride 0.2%, which were then mixed in the same manner as in Production Example 1, and pelletized. The particles can be stably produced.

The above-mentioned elastic resin monolayer having a granular grease thickness of 1 mm was used to have a lipid elongation modulus of 1996 MPa at 85 ° C.

Production Example 4 [Manufacture of Resin (B14) Particles]

R-100 as a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) (manufactured by Electric Chemical Industry, weight average molecular weight: 170,000, aromatic vinyl monomer: (Meth) acrylate monomer: ratio of unsaturated dicarboxylic anhydride monomer = 65:20:15) 65 mass%, methyl methacrylate as resin (b2) having a vinyl monomer as a constituent unit Resin parapet HR-L (35 mass%), a phosphorus-based additive PEP36 (500 ppm), and stearic acid monoglyceride 0.2% were mixed in the same manner as in Production Example 1, and pelletized. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a fat elongation coefficient of 1885 MPa at 85 ° C.

Production Example 5 [Manufacture of Resin (B15) Particles]

Set as a specific aromatic vinyl-(meth) acrylate - not full R-100 (75 mass%) of the dicarboxylic acid copolymer (b1), parapet HR-L (25 mass) of methyl methacrylate resin as a resin (b2) having a vinyl monomer as a constituent unit %), phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride 0.2%, and then mixed in the same manner as in Production Example 1, and granulated. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a fat elongation coefficient of 2089 MPa at 85 ° C.

Production Example 6 [Manufacture of Resin (B16) Particles]

R-100 (85% by mass) as a specific aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1), and a resin having a vinyl monomer as a constituent unit ( B2) A methyl methacrylate resin parapet HR-L (15 mass%), a phosphorus-based additive PEP36 (500 ppm), and stearic acid monoglyceride 0.2% were mixed in the same manner as in Production Example 1, and pelletized. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a fat elongation coefficient of 2152 MPa at 85 ° C.

Production Example 7 [Manufacture of Photocurable Resin Composition (C11) Covered with High Hardness Layer]

Into a mixing tank equipped with a stirring blade, 60 parts by mass of ginseng (2-propenyloxyethyl) isocyanurate (manufactured by Aldrich Co., Ltd.) and neopentyl glycol oligoacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were introduced. , trade name: 215D) 40 parts by mass, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide (Ciba japan Company, trade name: DAROCUR TPO) 1 part by mass, 1-hydroxycyclohexyl phenyl ketone (made by Aldrich) 0.3 parts by mass, and 2-(2H-benzotriazol-2-yl)-4,6- A composition of 1 part by mass of bis(1-methyl-1-phenylethyl)phenol (manufactured by Ciba japan Co., Ltd., trade name: TINUVIN 234) was stirred at 40 ° C for 1 hour to obtain a photocurable resin. Composition (C11: Refer to Table 1 below).

Production Example 8 [Manufacture of Photocurable Resin Composition (C12) Covered on Polycarbonate Substrate Layer]

Into a mixing tank equipped with a stirring blade, 40 parts by mass of a 9-functional urethane acrylate oligomer was introduced from 1,9-nonanediol diacrylate (product name: Viscoat #260, manufactured by Osaka Organic Chemical Industry Co., Ltd.). 40 parts by mass of product (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: U-6HA), condensate of succinic acid/trimethylolethane/acrylic acid molar ratio 1/2/4, 20 parts by mass, 2, 4 6-trimethylbenzimidyl diphenylphosphine oxide (manufactured by Ciba japan Co., Ltd., trade name: DAROCUR TPO) 2.8 parts by mass, benzophenone (manufactured by Aldrich Co., Ltd.), 1 part by mass, and 2-(2H) -benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (manufactured by Ciba japan Co., Ltd., trade name: TINUVIN 234), a composition of 1 part by mass, After stirring for 1 hour while maintaining 40 ° C, a photocurable resin composition (C12) was obtained.

Comparative Production Example 1 [Manufacture of Resin (D11) Particles]

Parapet HR-L (100% by mass), phosphorus additive PEP36 (500 ppm), and stearic acid monoglyceride 0.2% were set, and then the same as in Production Example 1. Mix and granulate. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a tensile modulus of 1015 MPa at 85 ° C.

Comparative Production Example 2 [Manufacture of Resin (D12) Particles]

It is composed of methyl methacrylate methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 77.000 mol%, styrene (manufactured by Wako Pure Chemical Industries, Ltd.), 22.998 mol%, and t-pentyl peroxy-2- as a polymerization initiator. a mixture of ethyl hexanoate (ARKEMA, product name: LUPEROX 575) 0.002 mol%, continuously supplied to a 10 L fully mixed layer with a spiral wing at 1 kg/h, with an average residence time of 2.5 hours, polymerization temperature The polymerization was continuously carried out at 150 ° C, and the liquid was continuously taken out from the bottom to fix the liquid surface of the polymerization tank, and introduced into a desolvation device to obtain a particulate vinyl copolymer resin. This vinyl copolymer resin was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Ltd.) to prepare a 10% by mass methyl isobutyrate solution. 500 parts by mass of 10% by mass of methyl isobutyrate solution and 1 part by mass of 10% by mass of Pd/C (manufactured by NEchemcat) were placed in a 1000 mL autoclave apparatus, and kept at a hydrogen pressure of 9 MPa and 200 ° C for 15 hours to copolymerize vinyl groups. The aromatic double bond portion of the resin is hydrogenated. The catalyst was removed by a filter, introduced into a solvent removal apparatus, and the obtained pellets were mixed with the phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride in the same manner as in Production Example 1, and pelletized. The particles can be stably produced.

The above-mentioned synthetic resin monolayer having a granular grease thickness of 1 mm was used to have a lip extension modulus of 1527 MPa at 85 ° C.

Example 1

The synthetic resin laminate is formed by using a multi-layer extrusion device having a multi-branch die having a plurality of extruders connected to a multi-layer extruder, wherein the multi-layer extruder has a single-axis extruder having a shaft diameter of 32 mm and a single-axis extruder having a shaft diameter of 65 mm. A feed block connected to the all-extruder and a T-die connected to the feed block. The resin (B11) obtained in Production Example 1 was continuously introduced into a uniaxial extruder having a shaft diameter of 32 mm, and was extruded under the conditions of a cylindrical temperature of 240 ° C and a discharge amount of 2.1 kg / h. Further, a polycarbonate resin (A1) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Eupilon S-1000, mass average molecular weight: 27,000) was continuously introduced into a uniaxial extruder having a shaft diameter of 65 mm at a cylindrical temperature of 270 ° C. The discharge amount was 30.0 kg/h. A feed block connected to the all-extracting machine has two types of two-part partition pins, and is introduced at a temperature of 270 ° C (B11) and (A1) for lamination. The T-die, which is connected to the previous temperature of 270 ° C, is extruded into a sheet shape, and three mirror-finishing rollers of 130 ° C, 140 ° C, and 180 ° C are used on the upstream side to cool the mirror surface while transferring, thereby producing ( B11) and (A1) laminate (E11). The total thickness of the obtained laminate (E11) was 1.0 mm, and the thickness of the layer composed of (B11) was 60 μm in the vicinity of the center. The pencil hardness test results are H, qualified, and the evaluation of the curl shape after being placed in a high temperature and high humidity environment is such that when the laminate is only laminated, the high hardness layer side is convex, and the radius of curvature is 42.5 m>R ≧ 11.6 m, After passing the test, the vapor-deposited product was formed to have a convexity on the side of the base material layer, and the radius of curvature was 20.3 m>R ≧ 14.2 m, which was qualified, and was judged to be acceptable by the overall judgment.

Example 2

The discharge amount of the high hardness layer (B11) used in Example 1 was 3.5 kg/h, and the discharge amount of the polycarbonate resin (A1) was set to 28.7 kg/h, and (B11) and (A1 were obtained in the same manner as in Example 1. Laminate (E12). The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B11) was 100 μm in the vicinity of the center. The result of the pencil hardness test is H, qualified, and the evaluation of the curl shape after being placed in a high temperature and high humidity environment is such that when the laminate is only laminated, the high hardness layer side is convex, and the radius of curvature is 5.9 m>R ≧ 2.7 m, When it was passed, the vapor-deposited product was formed to have a convexity on the side of the base material layer, and the radius of curvature was 17.1 m > R ≧ 9.9 m, which was qualified, and was judged to be acceptable by the overall judgment.

Example 3

A laminate (E13) of (B12) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B12) obtained in Production Example 2. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B12) was 60 μm in the vicinity of the center. The results of the pencil hardness test were H and qualified, and the evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 3.7 m>R ≧ 2.4 m, In the case of the vapor-deposited product, the high-hardness layer side was formed to have a convex curvature, and the radius of curvature was 79.1 m>R ≧26.4 m, and it was passed, and it was judged that it was qualified.

Example 4

A laminate (E14) of (B13) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B13) obtained in Production Example 3. The total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B13) was 60 μm in the vicinity of the center. The result of the pencil hardness test is H, and it is qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment is such that when the laminate is laminated, the high-hardness layer side is convex, and the radius of curvature is 4.1 m>R ≧ 2.0 m, In the case of the vapor-deposited product, the high-hardness layer side was formed to have a convex curvature, and the radius of curvature was 16.9 m>R ≧ 9.1 m, which was qualified, and was judged to be acceptable by the overall judgment.

Example 5

A laminate (E15) of (B14) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B14) obtained in Production Example 4. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B14) was 60 μm in the vicinity of the center. The results of the pencil hardness test were F and qualified, and the evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 27.5 m>R≧20.7 m, In the case of the vapor-deposited product, the high-hardness layer side was formed to have a convex curvature, and the radius of curvature was 4.6 m>R ≧ 3.3 m, which was acceptable, and was judged to be acceptable.

Example 6

A laminate (E16) of (B14) and (A1) was obtained in the same manner as in Example 2 except that the high hardness layer was set to the resin (B14) obtained in Production Example 4. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B14) was 100 μm in the vicinity of the center. The result of the pencil hardness test is F, and qualified, the evaluation of the curl shape after being placed in a high-temperature and high-humidity environment, when the laminate is only formed, the high-hardness layer side is convex, and the radius of curvature is 63.0 m>R≧9.5 m, and it is qualified, and when the product is vapor-deposited The substrate side was convex, and the radius of curvature was 5.1 m>R ≧ 3.8 m, which was acceptable, and was judged to be acceptable by comprehensive judgment.

Example 7

A laminate (E17) of (B15) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B15) obtained in Production Example 5. The total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B15) was 60 μm in the vicinity of the center. The results of the pencil hardness test were F and qualified, and the evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 41.5 m>R ≧7.5 m. When it was a vapor-deposited product, the base material side was formed convex, and the curvature radius was 10.8 m>R ≧ 6.1 m, and it passed the test, and it was judged as the pass.

Example 8

A laminate (E18) of (B15) and (A1) was obtained in the same manner as in Example 2 except that the high hardness layer was set to the resin (B15) obtained in Production Example 5. The total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B15) was 100 μm in the vicinity of the center. The result of the pencil hardness test is F, and it is qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment is such that when the laminate is laminated, the high-hardness layer side is convex, and the radius of curvature is 8.5 m>R ≧ 3.4 m. When it is qualified, when the vapor-deposited product is formed, the high-hardness layer side is convex, and the radius of curvature is 77.3 m>R ≧10.4 m, and it is qualified. qualified.

Example 9

A laminate (E19) of (B16) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B16) obtained in Production Example 6. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B16) was 60 μm in the vicinity of the center. The results of the pencil hardness test were F and qualified, and the evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 16.4 m>R ≧4.8 m. When it was a vapor-deposited product, the base material layer side was formed convex, and the curvature radius was 18.5 m>R ≧11.8 m, and it passed the test, and it was judged as the pass.

Example 10

A laminate (E20) of (B16) and (A1) was obtained in the same manner as in Example 2 except that the high hardness layer was set to the resin (B16) obtained in Production Example 6. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B16) was 100 μm in the vicinity of the center. The result of the pencil hardness test is F, and it is qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment is such that when the laminate is laminated, the high-hardness layer side is convex, and the radius of curvature is 7.6 m>R ≧ 3.4 m. In the case of the vapor-deposited product, the high-hardness layer side was formed to have a convex curvature, and the radius of curvature was 26.6 m>R ≧11.3 m, which was acceptable, and was judged to be acceptable as a whole.

Example 11

On the high hardness layer (B12) of the laminate (E13) obtained in Example 3, the photocurable resin composition (C11) obtained in Production Example 7 was applied by a bar coater to form a film after curing. The photocurable resin composition (C12) obtained in Production Example 8 was coated on a base material layer composed of (A1) with a thickness of 3 to 8 μm, covered with a PET film, and coated with a bar coater. The cloth is made to have a thickness of 3 to 8 μm after hardening, and is covered and pressed with a PET film. Next, a conveyor belt equipped with a high-pressure mercury lamp having a light source distance of 12 cm and outputting 80 W/cm was irradiated with ultraviolet rays at a linear velocity of 1.5 m/min, and after curing, the PET film was peeled off to obtain a high hardness layer and a substrate layer. Each of them has a laminate (F11) of a hard coat layer composed of (C11) and (C12). The result of the pencil hardness test was 3H, and it was qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 9.4 m>R≧3.3 m. In the case of the vapor-deposited product, the substrate layer side was formed to have a convexity, and the radius of curvature was 58.6 m>R ≧12.5 m, which was acceptable, and was judged to be acceptable as a whole.

Example 12

(B12) and (A1) were obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B12) obtained in Production Example 2, and the discharge amount of the polycarbonate resin (A1) was set to 20.4 kg/h. The laminate. The total thickness of the obtained laminate was 0.7 mm, and the thickness of the layer composed of (B12) was 60 μm in the vicinity of the center. In the same manner as in Example 11, except for the obtained laminate, each of the high hardness layer and the base material layer was provided with (C11) and (C12) A laminate (F12) of a hard coat layer composed of (C12). The result of the pencil hardness test was 3H, and it was qualified. The curl shape after being placed in a high-temperature and high-humidity environment was evaluated. When the laminate was only laminated, the high-hardness layer side was convex, and the radius of curvature was 30.6 m>R≧4.6 m. In the case of the vapor-deposited product, the high-hardness layer side was formed to have a convex curvature, and the radius of curvature was 18.4 m > R ≧ 5.3 m, which was acceptable, and was judged to be acceptable.

Comparative example 1

A laminate (E21) of (B12) and (A1) was obtained in the same manner as in Example 2 except that the high hardness layer was set to the resin (B12) obtained in Production Example 2. The total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B12) was 100 μm in the vicinity of the center. The result of the pencil hardness test is H, and it is qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment is such that when the laminate is laminated, the high-hardness layer side is convex, and the radius of curvature is 1.8 m>R≧1.3 m. In the case of the vapor deposition product, the base material layer side was convex, and the radius of curvature was 3.0 m > R ≧ 2.4 m, which was unacceptable, and was judged to be unacceptable.

Comparative example 2

A laminate (E22) of (B13) and (A1) was obtained in the same manner as in Example 2 except that the high hardness layer was set to the resin (B13) obtained in Production Example 3. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (B13) was 100 μm in the vicinity of the center. The result of the pencil hardness test is H, and it is qualified. The curl shape after being placed in a high temperature and high humidity environment When the laminate is only laminated, the high hardness layer side is convex, and the radius of curvature is 1.6 m>R ≧ 1.0 m, which is unacceptable. When the product is vapor-deposited, the substrate layer side is convex, and the radius of curvature is 2.4 m>R. ≧ 2.2m, and failed, comprehensive judgment is unqualified.

Comparative example 3

(B12) and (A1) were obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B12) obtained in Production Example 2, and the discharge amount of the polycarbonate resin (A1) was set to 19.1 kg/h. Laminated body (E23). The total thickness of the obtained laminate was 0.7 mm, and the thickness of the layer composed of (B12) was 60 μm in the vicinity of the center. The result of the pencil hardness test is H, and it is qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment is such that when the laminate is laminated, the high-hardness layer side is convex, and the radius of curvature is 1.5 m>R≧1.2 m, In the case of the vapor deposition product, the base material layer side was convex, and the radius of curvature was 1.8 m > R ≧ 1.5 m, which was unacceptable, and was judged to be unacceptable.

Comparative example 4

(B12) and (A1) were obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (B12) obtained in Production Example 2, and the discharge amount of the polycarbonate resin (A1) was set to 19.1 kg/h. Laminate (E24). The total thickness of the obtained laminate was 0.7 mm, and the thickness of the layer composed of (B12) was 100 μm in the vicinity of the center. The result of the pencil hardness test is H, and it is qualified, and the evaluation of the curl shape after being placed in a high temperature and high humidity environment is only In the case of the laminate, the high hardness layer side is convex, and the radius of curvature is 1.3 m>R ≧ 0.9 m, which is unacceptable. When the product is vapor-deposited, the substrate layer side is convex, and the radius of curvature is 1.5 m>R ≧1.3 m. And it is unqualified, and the comprehensive judgment is unqualified.

Comparative Example 5

In the laminate (E21) obtained in Comparative Example 1, a hard coat layer composed of (C11) and (C12) was laminated on each of the high hardness layer and the base layer in the same manner as in Example 11 to obtain a laminate ( F13). The result of the pencil hardness test was 3H, and it was qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature was 1.9 m>R ≧1.7 m. In the case of the vapor deposition product, the convex portion of the high-hardness layer was convex, and the radius of curvature was 3.0 m>R ≧2.7 m, which was unacceptable, and was judged to be unacceptable.

Comparative Example 6

In the laminate (E24) obtained in Comparative Example 4, a hard coat layer composed of (C11) and (C12) was laminated on each of the high hardness layer and the base layer in the same manner as in Example 11 to obtain a laminate ( F14). The result of the pencil hardness test was 3H, and it was qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the high-hardness layer side was convex, and the radius of curvature R was 1.8 m>≧1.3 m. When it was unqualified, when the vapor-deposited product was formed, the high-hardness layer side was convex, and the curvature radius was 2.0 m>R ≧ 1.5 m, and it was unsatisfactory, and it was judged that it was unqualified.

Comparative Example 7

A laminate of (D11) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to compare the resin (D11) obtained in Production Example 1. The total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (D11) was 60 μm in the vicinity of the center. A laminate (F15) each having a hard coat layer composed of (C11) and (C12) on the high hardness layer and the base material layer was obtained in the same manner as in Example 11 except for the obtained laminate. The result of the pencil hardness test was 4H, and it was qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the substrate layer side was convex, and the radius of curvature was 1.5 m>R ≧ 1.2 m. In the case of the vapor deposition product, the base material layer side was convex, and the radius of curvature was 1.1 m>R ≧ 0.9 m, which was unacceptable, and was judged to be unacceptable.

Comparative Example 8

A laminate of (D12) and (A1) was obtained in the same manner as in Example 1 except that the high hardness layer was set to the resin (D12) obtained in Comparative Production Example 2. The thickness of the obtained laminate was 1.0 mm, and the thickness of the layer composed of (D12) was 60 μm in the vicinity of the center. A laminate (F16) each having a hard coat layer composed of (C11) and (C12) on the high hardness layer and the base layer was obtained in the same manner as in Example 11 except for the obtained laminate. The result of the pencil hardness test was 4H, and it was qualified. The evaluation of the curl shape after being placed in a high-temperature and high-humidity environment was such that when the laminate was laminated, the base material layer side was convex, and the radius of curvature was 36.1 m>R ≧ 15.7 m. And it is unqualified, when the vapor-deposited product is formed, the high-hardness layer side is convex, and the radius of curvature is 3.0 m>R≧2.1 m, and it is unqualified. The overall judgment was unqualified.

It is confirmed from the examples, comparative examples, and Table 1 that i) the pencil hardness of the high hardness layer (B) is F or more, and ii) the curl shape after the laminate is placed in a high temperature and high humidity environment is such that the high hardness layer (B) side A synthetic resin laminate having a curvature radius of R ≧ 2.0 m is formed, and a laminated body of the vapor-deposited Al + SiO _{2 having a} reduced water vapor transmission rate is placed in a high-temperature and high-humidity environment to have a high-hardness layer (B). The side is convex, or the base layer (A) side is convex, and converges to a radius of curvature R ≧ 3.2 m.

As described above, the synthetic resin laminate of the present invention has a feature of laminating high hardness and a base material layer, and suppressing curling after being placed in a high-temperature and high-humidity environment in a state where the water vapor transmission rate on the base material layer side is small. For example, as shown in Fig. 1(A), the synthetic resin laminate 20 of the present invention having the laminated base material layer 22 and the surface layer 24 (high hardness layer) and the hard coat layer 28 is placed in a high temperature and high humidity environment in this state. At this time, the surface layer 24 (high hardness layer) is formed into a convex manner, and a number of curls are generated. Further, as shown in Fig. 1(B), the synthetic resin laminate 20 is bonded to the ITO layer 26, and placed in a high-temperature, high-humidity environment, on the side of the base material layer 22 and the surface layer 24 (high hardness layer). As a result of the difference in water vapor transmission rate, the occurrence of curl can be greatly suppressed. In addition, the size of the arrow mark in FIG. 1 schematically shows the value of the water vapor transmission rate, and the member with a large arrow mark means that the water vapor transmission rate is high.

In addition, as shown in FIG. 2(A), in the state where the synthetic resin laminate 10 of the conventional example is placed in a high-temperature and high-humidity environment, the base material layer 12 is formed to be convex, and curling occurs. When the synthetic resin laminate 10 of the conventional example is bonded to the ITO layer 16 and placed in a high-temperature and high-humidity environment, as shown in FIG. 2(B), large curl is generated. This results in the appearance of the surface of the member containing the synthetic resin laminate 10, and the possibility that the synthetic resin laminate 10 is peeled off from the ITO layer 16 is increased in the long term.

Further, each of the embodiments in which the tensile modulus of the base material layer and the surface layer (high hardness layer) is increased, and the difference between the value of the tensile modulus of the base material layer and the value of the tensile modulus of the surface layer (high hardness layer) is lowered, for example, The above confirmed good results, however, the surface layer (high hardness layer) having a low value of the tensile modulus of elasticity, the value of the tensile modulus of the substrate layer and the stretch elasticity of the surface layer (high hardness layer) In Comparative Examples 7 and 8 in which the difference in the values of the coefficients was large, the curl of the laminate after being placed in a high-temperature and high-humidity environment was large.

[Industrial availability]

As described above, the synthetic resin laminate of the present invention which suppresses the curl generated when placed in a high-temperature and high-humidity environment is suitably used as a transparent substrate material, a transparency protective material, etc., and is particularly suitable for use in an OA machine. The front panel of the display unit, the touch panel substrate, and the sheet for thermal bending processing of the electronic device are carried.

20‧‧‧Synthetic resin laminate

22‧‧‧Substrate layer

24‧‧‧Surface (high hardness layer)

26‧‧‧ITO layer

28‧‧‧hard coating

Claims (15)

A synthetic resin laminate comprising: a base material layer containing a thermoplastic resin (A); and a high hardness of a thermoplastic resin (B) different from the thermoplastic resin (A) laminated on at least one surface thereof a synthetic resin laminate of the layer, (i) the high hardness layer has a thickness of 10 to 250 μm, the total thickness of the base material layer and the high hardness layer is 0.1 to 2.0 mm, and the high hardness layer/the base material layer The thickness ratio is 0.01 to 0.8, (ii) the pencil hardness of the high hardness layer is F or more, and (iii) the crimped shape of the synthetic resin laminate after being placed in a high temperature and high humidity environment is such that the high hardness layer side is formed. It is convex and has a radius of curvature R ≧ 2.0 m. The synthetic resin laminate according to claim 1, wherein the third layer is further laminated, and the water vapor transmission rate in the surface of the base material layer opposite to the high hardness layer is 0.2 to 0.6 g/ m ² . The curling shape of the synthetic resin laminate after being placed in a high-temperature, high-humidity environment is such that the high-hardness layer side is convex, or the base material layer side is convex, and the laminate has a radius of curvature R≧3.2 m. . The synthetic resin laminate according to claim 1 or 2, wherein the thermoplastic resin (A) contained in the base material layer is a resin containing polycarbonate (a1), and the heat contained in the high hardness layer The plastic resin (B) is a resin containing an aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer (b1) and a resin (b2) having a vinyl monomer as a constituent unit. The above (b1) is an aromatic vinyl monomer having 45 to 80% by mass of an aromatic vinyl monomer unit, 5 to 45% by mass of a (meth) acrylate monomer unit, and 10 to 30% by mass of an unsaturated dicarboxylic anhydride monomer unit. The (meth) acrylate-unsaturated dicarboxylic acid copolymer, wherein the resin (B) is a mixed resin of 50 to 100 parts by mass of the above (b1) and 50 to 0 parts by mass of the above (b2). The synthetic resin laminate according to claim 3, wherein the (meth) acrylate monomer unit of the above (b1) is methyl methacrylate. The synthetic resin laminate according to claim 3 or 4, wherein the aforementioned resin (B) is the aforementioned aromatic vinyl-(meth)acrylate-unsaturated dicarboxylic acid copolymer having a weight average molecular weight of 50,000 to 300,000. (b1) 50 to 100 parts by mass of a mixed resin of 50 to 0 parts by mass of a methyl methacrylate resin (b2) having a weight average molecular weight of 50,000 to 500,000. The synthetic resin laminate according to any one of claims 1 to 5, wherein the polycarbonate (a1) has a weight average molecular weight of 25,000 to 75,000. The synthetic resin laminate according to any one of claims 1 to 6, wherein the high hardness layer and/or the base material layer contains an ultraviolet absorber. The synthetic resin laminate according to any one of claims 1 to 7, wherein a hard coat treatment is applied to the surface of the high hardness layer. The synthetic resin laminate according to any one of claims 1 to 8, wherein the one or both sides of the resin laminate are subjected to antireflection treatment, antifouling treatment, fingerprint resistance treatment, antistatic treatment, and weather resistance. Sexual treatment And any one or more of anti-glare treatments. The synthetic resin laminate according to any one of claims 1 to 9, wherein each of the high hardness layer and the base material layer has a tensile modulus of elasticity of 1600 MPa or more. The synthetic resin laminate according to any one of claims 1 to 10, wherein a difference between a tensile modulus of elasticity of the high hardness layer and a tensile modulus of the base material layer is 400 MPa or less. A transparent substrate material comprising the synthetic resin laminate according to any one of claims 1 to 11. A transparent protective material comprising the synthetic resin laminate according to any one of claims 1 to 11. A touch panel front protective sheet, which is characterized by comprising a synthetic resin laminate according to any one of claims 1 to 11. A laminate of a low water vapor transmission rate plate, which is characterized by comprising a synthetic resin laminate according to any one of claims 1 to 11.