JP6417936B2 - Laminate and display cover - Google Patents

Description

  The present invention relates to a laminate excellent in scratch resistance, hardness, impact resistance, curl resistance, transparency and the like. Moreover, this invention relates to the display body cover which consists of this laminated body.

  Plastic products such as polycarbonate (PC) resin; polymethyl methacrylate (PMMA) resin; polyethylene terephthalate (PET) resin; polybutylene terephthalate (PBT) resin, acrylonitrile-butadiene-styrene (ABS) resin, styrene-methyl methacrylate (MS) Various resin base materials such as resin, styrene resin such as acrylonitrile-styrene (AS) resin; vinyl chloride resin; cellulose acetate resin such as triacetyl cellulose are excellent in light weight, easy processability, impact resistance, etc. Therefore, they are used in various applications such as containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, substrates of display devices such as liquid crystal displays and plasma displays.

  In industrial electronic devices having display bodies such as mobile phones and PHS (Personal Handy-phone System), the display cover itself has become thinner and lighter as design diversifies, thins and increases in area. There is a growing demand for cost reduction and cost reduction. As this display cover, a glass substrate is generally used. However, due to demands for reducing the thickness, weight, and cost of the display cover itself, it is now a certain thickness that allows the substrate itself to stand on its own. Various uses of PMMA resin sheets, PC resin sheets, and the like have been studied. On the other hand, since these plastic substrates are inferior in scratch resistance and hardness as compared to conventionally used glass substrates, resin sheets coated with various hard coat materials have been studied.

  Conventionally, the following techniques have been disclosed mainly as a laminate for display body covers such as mobile phones and PHS. For example, Patent Document 1 discloses that the scratch resistance of the surface is improved by a laminate in which a PMMA base material is coated with a hard coat material containing urethane acrylate and silicone oil. Patent Document 2 discloses that the scratch resistance of the surface is improved by a laminate in which a hard coat material containing a polyfunctional acrylate is coated on a PMMA base material. Further, in Patent Document 3, the PMMA substrate having a weight average molecular weight of 100,000 or more and a glass transition temperature of 100 ° C. or more is scratched by a laminate in which a hard coat material containing polyfunctional acrylate and silicone oil is coated. It is disclosed to improve the performance. In Patent Document 4, impact resistance, curl resistance and the like are improved by a laminate in which a hard coating material containing bifunctional urethane acrylate and polyfunctional acrylate and / or polyfunctional urethane acrylate is coated on an impact-resistant PMMA base material. Is disclosed. Furthermore, in Patent Document 5, a polycarbonate resin laminate in which a bisphenol C-type polycarbonate (C-PC) layer is laminated on a PC substrate is used as a substrate, and an ultraviolet curable paint is formed on the C-PC layer of the substrate. It is disclosed that a hard coat layer is formed to improve hardness.

JP 2004-299199 A JP 2008-006811 A JP 2008-049797 A JP 2008-1000042 A JP 2010-188719 A

  According to the detailed examinations of the present inventors, impact resistance, scratch resistance, and the like required for touch panels such as smartphones and tablets that have been popular in recent years in the technologies disclosed in Patent Documents 1 to 5, It has been found that the function is insufficient for characteristics such as hardness. That is, a display body cover in a touch panel such as a smartphone or a tablet is not only required to have sufficient impact resistance itself, but also a movement of sliding a finger (flip) is frequently performed in operation. In addition, conventional cellular phones and display covers for PHS have insufficient scratch resistance, hardness, and the like. In addition, in this application, curl resistance is also required in order to install it on the main body without difficulty in the processing process, but the above-mentioned conventional laminate is also insufficient in curl resistance, and in touch panels such as smartphones and tablets. In use as a display cover, the required characteristics cannot be sufficiently satisfied.

  The object of the present invention is to solve various problems as mentioned above. That is, the subject of this invention is providing the laminated body excellent in scratch resistance, hardness, impact resistance, curl resistance, transparency, etc., and the display body cover which consists of this laminated body.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, a laminate having a specific layer structure is formed on a base material layer having a specific type and thickness, resulting in scratch resistance, hardness, impact resistance, and curl resistance. Has been found to be excellent in properties and transparency. That is, the gist of the present invention resides in the following [1] to [ 6 ].

[1] It has at least the following base material layer, the following layer (A) on one surface of the base material layer, and the layer (B) on the other surface, and the thickness of the base material layer is 0.3 to 30 mm. A layered product in which the layer (1) is in contact with the layer (A) and the layer (2) is in contact with the layer (B) .
Base material layer: a layer (1) made of a polycarbonate resin whose main component is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 2,2-bis (4-hydroxyphenyl) ) Polycarbonate resin layer (A) composed of two layers of a polycarbonate resin layer (2) composed mainly of structural units derived from propane : At least one of at least a perfluoropolyether structure and a siloxane structure Layer (B) comprising a curable composition (α) and / or a cured product thereof comprising a compound (A-1) having an acryloyl group and an epoxy (meth) acrylate And modified products thereof, and (meth) acrylates having an alkylene oxide structure and modified products thereof A curable composition comprising a compound (B-1) having at least one acryloyl group and having a content of the compound (B-1) of 20% by weight or more based on the total amount of compounds having an acryloyl group ( β) and / or a layer made of a cured product thereof

[2] The curable composition (α) contains 0.05 to 10% by weight of the compound (A-1) with respect to the total amount of the compound having an acryloyl group in the curable composition (α). The laminate according to [1].

[ 3 ] The laminate according to [1] or [ 2], wherein the layer (A) has a thickness of 1 to 45 μm and the layer (B) has a thickness of 1 to 45 μm.

[ 4 ] The laminate according to any one of [1] to [ 3 ], wherein the thickness ratio of the layer (A) to the layer (B) is 0.5: 2 to 2: 0.5.

[ 5 ] A display cover comprising the laminate according to any one of [1] to [ 4 ].

[ 6 ] The display cover according to [ 5 ], having the layer (A) on the front side and the layer (B) on the back side.

The laminate of the present invention is excellent in scratch resistance, hardness, impact resistance, curl resistance, transparency and the like.
For this reason, the laminated body of the present invention includes optical display parts such as touch panels and liquid crystal televisions; automobile-related parts such as lamp-related articles and window-related articles (rear windows, side windows, skylights, etc.); It can be suitably used for the surface cover of a wide range of articles such as decorative articles and daily life-related articles such as furniture. Among these, it can be particularly suitably used as a surface cover for optical display components such as a touch panel and a liquid crystal television, that is, a display body cover.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression. In the present invention, when the expression “(meth) acryl” is used, it means one or both of “acryl” and “methacryl”. The same applies to “(meth) acrylate” and “(meth) acryloyl”.
In the present specification, “structural unit derived from...” Refers to a repeating unit in which a monomer used as a raw material for producing a polymer constitutes a polymer in a polymer obtained by homopolymerization or copolymerization. It represents one unit that exists as a unit.

[Laminate]
The laminate of the present invention has at least the following base material layer, the following layer (A) on one surface of the base material layer, and the layer (B) on the other surface, and the thickness of the base material layer is 0. .3 to 30 mm.
Base material layer: Polycarbonate resin layer layer (A) having at least a layer (1) composed of a polycarbonate resin whose main component is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane: A curable composition (α) comprising a compound (A-1) having at least one of a perfluoropolyether structure and a siloxane structure and an acryloyl group and / or a layer layer (B) comprising the cured product (B): urethane ( Compound (B-1) having at least one acryloyl group selected from the group consisting of (meth) acrylate and modified products thereof, epoxy (meth) acrylate and modified products thereof, and (meth) acrylate having an alkylene oxide structure and modified products thereof ), And the compound (B-1) content has an acryloyl group A layer consisting of a total of the curable composition is 20 wt% or more based on the amount of (beta) and / or a cured product thereof

  In the present invention, the “acryloyl group” in the curable composition (α) and the curable composition (β) is directly bonded to the C═C carbon atom in the acryloyl group as well as the acryloyl group itself. A hydrogen atom is used in the sense of including other atoms or substituents. For example, a group in which a hydrogen atom directly bonded to C = C of an acryloyl group is substituted with a methyl group or a halogen element, more specifically, a methacryloyl group, a fluoroacryloyl group or the like is also included in the “acryloyl group”. Shall be used.

  The laminate of the present invention has the effect of being excellent in scratch resistance, hardness, impact resistance, curl resistance, transparency and the like. That is, the base material layer of the laminate of the present invention is a layer containing a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane having a high hardness and excellent rigidity as a main component (1 ), It is excellent in scratch resistance and curl resistance. In addition, by forming the high hardness layer (A) on one surface, it becomes higher hardness and excellent scratch resistance, and further, a relatively flexible layer (B) is formed on the other surface. Thereby, it can also be made excellent in the impact resistance with respect to the impact from the surface of a layer (A). Moreover, since the polycarbonate resin layer, the layer (A) and the layer (B) of the base material layer are all highly transparent, the transparency of the laminate of the present invention obtained by laminating these is also good. Since the layers (A) and (B) are laminated on both surfaces of the base material layer of the polycarbonate resin layer, the curl resistance is excellent.

[Base material layer]
The base material layer used for the laminate of the present invention is a layer (1) composed of a polycarbonate resin whose main component is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C). ) At least a polycarbonate resin layer.
Here, the “main component” in the layer (1) and the later-described layer (2) means that the proportion of the structural unit in the structural units derived from all dihydroxy compounds constituting the polycarbonate exceeds 50% by weight. This ratio is preferably 60% by weight or more, more preferably 70 to 100% by weight.

  The polycarbonate resin constituting the layer (1) is not particularly limited as long as it has a structural unit derived from bisphenol C as a main component, and 2,2-bis (4-hydroxyphenyl) propane usually used as a raw material for producing the polycarbonate resin. (Bilphenol A), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxy-3- Bisphenols such as methylphenyl) propane and 2,2′-methyl-4,4′-biphenyldiol It may contain structural units derived from one or more dihydroxy compounds other than.

  The layer (1) has a structural unit derived from bisphenol C as a main component, and thus has high hardness and excellent scratch resistance.

The base material layer according to the present invention may have a single-layer structure of the above layer (1), but the layer (1) mainly composed of a structural unit derived from bisphenol C is excellent in scratch resistance and hardness. On the other hand, it tends to be inferior in impact resistance. For this reason, the base material layer of the laminate of the present invention is composed of the above layer (1) and a polycarbonate mainly composed of a structural unit derived from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The layer (2) is preferably laminated so that the layer (A) compensates for scratch resistance and hardness, and the layer (B) compensates for impact resistance. Furthermore, a combination of these layers (1) and (2) is preferable from the viewpoint of curling resistance.
In this case, it is preferable to form a layer (A) described later on the layer (1) side and a layer (B) described later on the layer (2) side.

  Similar to the layer (1), the polycarbonate constituting the layer (2) may be one having a structural unit derived from bisphenol A as a main component, and 1,1-bis (4) usually used as a polycarbonate raw material. -Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2′-methyl-4,4′-biphenyldioe It may contain structural units derived from one or more dihydroxy compounds other than bisphenol A and the like.

  When the base material layer according to the present invention is composed of only the layer (1), the base material layer is formed by, for example, a melt extrusion method, a solution casting method (casting method) or the like of the polycarbonate resin sheet of the layer (1) according to a conventional method. Can be manufactured by forming a film. Moreover, when the base material layer which concerns on this invention is a 2 layer laminated structure of a layer (1) and a layer (2), a base material layer is a polycarbonate resin sheet and layer of the layer (1) formed into a film in accordance with the conventional method It can be produced by laminating the polycarbonate resin sheet (2) or by two-layer coextrusion molding.

  The layers (1) and (2) are each a layer made of a specific polycarbonate resin, but are not limited to those composed only of the polycarbonate resin. You may contain various additives, such as an absorber, a flame retardant, and antioxidant. Moreover, in the range which does not impair the objective of this invention, resin components other than polycarbonate resin may be included.

  The base material layer according to the present invention may have a laminated structure of three or more layers having layers other than the layer (1) and the layer (2). For example, an adhesive layer may be provided between the layer (1) and the layer (2). Further, in the production process of the base material layer, when the two layers (1) and (2) are coextruded, the layer (1) is formed between the layers (1) and (2). An intermediate layer formed by combining a polycarbonate resin mainly composed of a structural unit derived from bisphenol C and a polycarbonate resin composed mainly of a structural unit derived from bisphenol A constituting the layer (2) You may have.

  In the laminate of the present invention, the total thickness of the base material layer is 0.3 to 30 mm. In order to make the laminate of the present invention self-supporting, the total thickness of the base material layer needs to be 0.3 mm or more. From this viewpoint, the total thickness of the base material layer is preferably 0.4 mm or more. Moreover, the total thickness of a base material layer needs to be 30 mm or less from a viewpoint of thickness reduction and weight reduction for using as a display body etc. From this viewpoint, the total thickness of the base material layer is preferably 3.0 mm or less, and more preferably 1.5 mm or less.

  Moreover, when the base material layer used for this invention is a 2 layer laminated structure of a layer (1) and a layer (2), from a viewpoint of scratch resistance and hardness, the thickness of the layer (1) with respect to the thickness of the whole base material layer The ratio is preferably 0.5% or more, and more preferably 2% or more. On the other hand, from the viewpoint of impact resistance, the ratio of the thickness of the layer (1) is preferably 20% or less, and more preferably 10% or less.

[Layer (A)]
In the laminate of the present invention, the layer (A) comprises at least one of a perfluoropolyether structure and a siloxane structure and a curable composition (α) containing a compound (A-1) having an acryloyl group and / or Or it is the layer which consists of the hardened | cured material.

<Curable composition (α)>
The curable composition (α) contains at least a compound (A-1) having at least one of a perfluoropolyether structure and a siloxane structure and an acryloyl group.
When the curable composition (α) contains the compound (A-1), the laminate of the present invention has high hardness, and scratch resistance is imparted. The curable composition (α) preferably contains the compound (A-1) and an active energy ray-curable compound (A-2) other than the compound (A-1), and the curable composition ( The content of the compound (A-1) in α) is based on the total amount of the compounds having an acryloyl group in the curable composition (α) from the viewpoints of the hardness and scratch resistance of the layer (A). It is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.5% by weight or more. On the other hand, from the viewpoint of improving the curability of the curable composition (α), the content of the compound (A-1) is preferably 10% by weight or less, and preferably 8% by weight or less. More preferably, it is more preferably 6% by weight or less.

  In addition, among what can be understood as the curable composition (α) in the layer (A), what is understood as the curable composition (β) in the layer (B) described later is the curable composition (α). Is regarded as a curable composition (β). Specifically, in order to obtain sufficient scratch resistance and hardness based on the layer (A), the curable composition (α) has a content of a compound (B-1) described later that is curable composition (α). Is less than 20% by weight, preferably not more than 15% by weight, while the lower limit is 0% by weight, based on the total amount of the compounds having an acryloyl group.

(Compound (A-1))
When the curable composition (α) contains the compound (A-1), the layered product of the present invention has good scratch resistance on the layer (A) side.

  Among compounds (A-1), examples of the compound having a perfluoropolyether structure and one or more acryloyl groups include those represented by the following formula (1).

(In said formula (1), X represents a hydrogen atom or a fluorine atom, and m is a number of 0-100.)

  The compound represented by the above formula (1) is preferably m = 1 to 20 and X = F in order to sufficiently exhibit its function. The compound represented by the above formula (1) can be produced by the method described in JP-A-2009-9138.

  A compound having a perfluoropolyether structure and one or more acryloyl groups can also be obtained as a commercially available product. Examples of commercially available products include “Megafac (registered trademark) RS-76-E” manufactured by DIC. “Optool (registered trademark) DAC-HP” manufactured by Daikin Industries, Ltd.

  As the compound having a siloxane structure and one or more acryloyl groups, those having a polydimethylsiloxane structure as the siloxane structure are preferable. Examples of such a compound include polydimethylsiloxane having an acryloyl group at one end (for example, commercially available). As a product, Silaplane (registered trademark) FM0711, FM0721, FM0725, etc. manufactured by JNC), polydimethylsiloxane having an acryloyl group at both ends (for example, X-22-164A manufactured by Shin-Etsu Chemical Co., Ltd.), both Polydimethylsiloxane having an epoxy group at the end and an acryloyl group at the side chain, having polydimethylsiloxane at the main chain and / or side chain, and having 1 to 2 acryloyl groups at the side chain and / or terminal And a copolymer having the same. Among these, polydimethylsiloxane having an acryloyl group at one terminal and / or both terminals is preferable, and in particular, a silicone-containing (meth) acrylate represented by the following formula (2) and a (meth) acrylate having an epoxy group. An acrylic copolymer obtained by reacting a copolymer having a carboxyl group and an acryloyl group with a copolymer obtained by copolymerization (hereinafter sometimes referred to as “acrylic copolymer (a-1)”). .) Is preferred.

(In the above formula (2), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently a methyl group or a phenyl group. , R ⁵ is an alkyl group having 1 to 12 carbon atoms, n is an average value, and is a number of 10 to 100.)

In formula (2), R ¹ represents a hydrogen atom or a methyl group. R ¹ is a methyl group because the glass transition temperature (Tg) of the resulting acrylic copolymer (a-1) is high and the hardness of the surface when the layer (A) is cured is high. Is preferred.

In formula (2), ^{R 2} is an alkylene group having 1 to 12 carbon atoms. The number of carbon atoms is preferably 2 or more, more preferably 3 or more, on the other hand, preferably 10 or less, and preferably 8 or less, in order to easily obtain the raw materials and to produce easily. It is more preferable.

In formula (2), R ³ and R ⁴ are each independently a methyl group or a phenyl group. A methyl group is preferable because the raw material is easily available and is easy to produce.

Wherein (2), ^{R 5} represents an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms in R ⁵ is preferably 2 or more, more preferably 3 or more. On the other hand, the number of carbon atoms in R ⁵ is preferably 10 or less, and more preferably 8 or less. It is preferable for the carbon number of R ⁵ to be in the above range because the raw materials are easily available and are easy to produce.

  In Formula (2), n is an average value and is a number of 10-100. When n is 10 or more, the surface slipperiness of the cured film obtained by curing the curable composition (α) is sufficiently exhibited and the slipperiness is improved. From the viewpoint of making this effect better, n is preferably 25 or more, and more preferably 50 or more. On the other hand, when n is 100 or less, the solubility in a solvent is good. From the viewpoint of making this effect better, n is preferably 90 or less, and more preferably 80 or less. The value of n can be obtained by calculation from the number average molecular weight (Mn).

  The number average molecular weight (Mn) of the silicone-containing (meth) acrylate represented by the formula (2) is sufficient to express the slipperiness of the cured film obtained by curing the curable composition (α). From the viewpoint of improving the quality, it is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. The number average molecular weight (Mn) of the silicone-containing (meth) acrylate represented by the formula (2) is preferably 50,000 or less from the viewpoint of improving the solubility in a solvent. Is more preferably 10,000 or less, and still more preferably 10,000 or less.

  Among the silicone-containing (meth) acrylates represented by the formula (2), those having a polydimethylsiloxane structure are preferable, and polydimethylsiloxane having a methacryloyl group at one end as a particularly preferable one (as a specific example of a commercially available product, And "Silaplane (registered trademark) FM0711", "Silaplane (registered trademark) FM0721", "Silaplane (registered trademark) FM0725", etc.). In addition, the silicone-containing (meth) acrylate represented by the formula (2) may be used alone or in combination of two or more.

  Examples of the (meth) acrylate having an epoxy group used as a raw material for the acrylic copolymer (a-1) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexyl. And methyl (meth) acrylate. Among these, glycidyl (meth) acrylate is preferable. The (meth) acrylate having an epoxy group may be used alone or in combination of two or more.

  When the silicone-containing (meth) acrylate represented by the formula (2) and the (meth) acrylate having an epoxy group are copolymerized, other monomers may be further copolymerized. Other monomers are particularly limited as long as they have a carbon-carbon double bond and can be copolymerized with the silicone-containing (meth) acrylate represented by the formula (2) and the (meth) acrylate having an epoxy group. Although not mentioned, (meth) acrylates other than these, (meth) acrylamide, etc. can be mentioned, for example.

  Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth). Acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n- Tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) ) Acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate (Meth) acrylates such as: N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N- Tylmethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, diacetone (meth) acrylamide, N- Methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis Examples include (meth) acrylamide and (meth) acrylamide such as N, N-ethylenebis (meth) acrylamide. These may be used alone or in combination of two or more. Other monomers are preferably alkyl (meth) acrylates having an alkyl group having 4 to 22 carbon atoms.

  Each of the silicone-containing (meth) acrylate represented by the formula (2), (meth) acrylate having an epoxy group, and other monomers used as necessary are copolymerized to produce an acrylic copolymer. Although there is no restriction | limiting in particular in the usage-amount of a monomer, Preferably the silicone containing (meth) acrylate represented by Formula (2) 5-90 weight%, (meth) acrylate 10-95 weight% which has an epoxy group, and necessity 0 to 80% by weight of other monomers used depending on (however, the silicone-containing (meth) acrylate represented by the formula (2), the (meth) acrylate having an epoxy group, and other monomers used as necessary) The total content is 100% by weight.) Particularly preferably, the silicone-containing (meth) acrylate represented by the formula (2) is 10 to 80 weights. %, Having an epoxy group (meth) acrylate 20 to 90% by weight, and other monomers 5-60 wt% scratch resistance is used in an amount of optionally used, from the viewpoint of antifouling property.

  The reaction of copolymerizing the silicone-containing (meth) acrylate represented by the formula (2), the (meth) acrylate having an epoxy group, and other monomers used as necessary is usually a radical polymerization reaction. Can be carried out in an organic solvent in the presence of a radical polymerization initiator. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvents and radical polymerization initiators that can be used here are as follows.

  Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene and the like. These organic solvents may be used alone or in combination of two or more.

  As the radical polymerization initiator, for example, known initiators generally used for radical polymerization can be used. Organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyl Examples include azo compounds such as nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

  The acrylic copolymer (a-1) used in the present invention includes at least a silicone-containing (meth) acrylate represented by the formula (2), a (meth) acrylate having an epoxy group, and other monomers used as necessary. Is obtained by reacting a copolymer having a carboxyl group and an acryloyl group with a copolymer obtained by copolymerizing the above, and in this reaction, the reaction temperature is preferably 50 to 110 ° C., more preferably 55 ~ 100 ° C. Moreover, reaction time becomes like this. Preferably it is 3 to 50 hours, More preferably, it is 4 to 30 hours. This reaction is usually an addition reaction between the epoxy group in the copolymer and a compound having a carboxyl group and an acryloyl group.

  Examples of the compound having a carboxyl group and an acryloyl group that can be used in this reaction include (meth) acrylic acid, carboxyethyl (meth) acrylate, an adduct of glycerin di (meth) acrylate and succinic anhydride, pentaerythritol tri ( Examples include adducts of meth) acrylate and succinic anhydride, adducts of pentaerythritol tri (meth) acrylate and phthalic anhydride, and the like. Among these, an adduct of (meth) acrylic acid, pentaerythritol tri (meth) acrylate and succinic anhydride is preferable. In addition, the compound which has a carboxyl group and an acryloyl group may be used individually by 1 type, or may be used in combination of 2 or more type.

  The compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110, as the mol% of the carboxyl group with respect to the epoxy group in the copolymer. It is preferable to use it in the proportion of mol% from the viewpoint of allowing the reaction to proceed without excess and deficiency and reducing the amount of raw material residues.

  Moreover, in order to promote the reaction which adds the compound which has a carboxyl group and an acryloyl group to the said copolymer, it can be made to react using a catalyst. Examples of the catalyst include triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the total amount of raw materials. In addition, in this reaction, you may make it react using the organic solvent used for reaction in manufacture of the said copolymer as it is, and you may make it react by adding an organic solvent suitably. The organic solvents that can be used for this reaction are the same as those listed above.

  The number average molecular weight (Mn) of the compound having a siloxane structure and one or more acryloyl groups is preferably 500 or more, more preferably 1,000 or more, while preferably 10,000 or less. Preferably it is 8,000 or less. When the number average molecular weight of this compound is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and slipperiness, and when it is not more than the above upper limit value, it is preferable from the viewpoint of maintaining compatibility with other components. .

  In addition, even if a compound (A-1) has one of a perfluoro polyether structure and a siloxane structure, it may have both of these structures. As the compound (A-1) having both a perfluoropolyether structure and a siloxane structure, for example, at least a compound represented by the formula (1) and a compound represented by the formula (2) are used as raw materials. And compounds obtained by reacting both carbon-carbon double bonds of these compounds.

(Active energy ray-curable compound (A-2))
The active energy ray-curable compound (A-2) contained in the curable composition (α) is a compound other than the compound (A-1) and has a functional group capable of undergoing a curing reaction upon irradiation with active energy rays. If it is a thing, it will not restrict | limit in particular.

  The active energy ray-curable compound (A-2) is preferably a compound containing an acryloyl group, and the hardness and scratch resistance of the cured film is good, and the reactivity at the time of curing is high. The number of acryloyl groups in the energy ray curable compound (A-2) is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. Further, from the viewpoint of suitable viscosity for coating, it is preferably 9 or less, more preferably 7 or less.

  As the active energy ray-curable compound (A-2) having an acryloyl group, specifically, a polyfunctional (meth) acrylate; a polyfunctional (meth) acrylate derivative such as an ester-modified product or a carbonate-modified product; an acryloyl group Examples thereof include silica whose surface is modified with a compound having the same.

  Examples of the polyfunctional (meth) acrylate and polyfunctional (meth) acrylate derivatives include pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane. Multifunctional acrylates such as triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol pentaacrylate adduct to succinic anhydride; side chain or side chain and acryloyl group at the end Polyester (meth) acrylates such as polyester oligomers (specifically, M8030, M7100 manufactured by Toagosei Co., Ltd.) Preparative like; polyesters having a carbonate bond of the reaction products of oligoesters and pentaerythritol triacrylate with polycarbonate diol (meth) acrylate; and the like These polycaprolactone-modified products thereof. These may be used alone or in combination of two or more.

  Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane, due to viscosity, curability, hardness of the resulting cured product surface, etc. Tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; these caprolactone modified products are particularly preferred. In addition to the compounds listed above, the active energy ray-curable compound (A-2) may include those corresponding to the compound (B-1) described later, but the content thereof is as described above. Street.

(Photopolymerization initiator)
The curable composition (α) used in the present invention preferably contains a photopolymerization initiator in order to improve curability. Known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photo radical generator and a photo acid generator.

  Among the photopolymerization initiators that can be used for the curable composition (α), examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone [for example, trade name “Irgacure (registered trademark) 184” Manufactured by BASF], 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1- ON, 2-methyl-1- [4- (meth Acetophenones such as thio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2,4,6-trimethylbenzoyl Phosphine oxides such as diphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; benzophenone and various derivatives thereof; formic acid derivatives such as methyl benzoylformate and ethyl benzoylformate; These may be used alone or in combination of two or more.

  Among these photo radical generators, acetophenones, phosphine oxides and formic acid derivatives are preferable from the viewpoint of light resistance of the cured product, and 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1 are more preferable. -[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Pentylphosphine oxide and methyl benzoylformate are preferable, and 1-hydroxycyclohexyl phenyl ketone and methyl benzoylformate are particularly preferable.

Known photoacid generators can be used. Among them, diaryliodonium salts and triarylsulfonium salts are preferable from the viewpoint of curability and acid generation efficiency. Specific examples include di (alkyl-substituted) phenyliodonium anion salts (specifically, PF ₆ salts, SbF ₅ salts, tetrakis (perfluorophenyl) borate salts, etc.). As a specific example of the anion salt of (alkyl-substituted) phenyliodonium, PF ₆ salt of dialkylphenyliodonium [trade name “Irgacure (registered trademark) 250”, manufactured by BASF] is particularly preferable. These photoacid generators may be used alone or in combination of two or more.

  When the curable composition (α) contains a photopolymerization initiator, the content thereof is a viewpoint of improving curability with respect to a total of 100 parts by weight of the compound having an acryloyl group in the curable composition (α). Therefore, it is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more. On the other hand, from the viewpoint of maintaining the stability of the liquid when the curable composition (α) is used as a solution, the amount is preferably 10 parts by weight or less, more preferably 8 parts by weight or less.

(Organic solvent)
The curable composition (α) preferably contains an organic solvent. The organic solvent is not particularly limited, and can be appropriately selected in consideration of the types of components contained in the curable composition (α). Specific examples of organic solvents that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), and cyclohexanone; diethyl ether and isopropyl ether. , Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, phenetol and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol di Ester solvents such as acetate; dimethylformamide, diethylformamide, N-methylpyrrolide Amide solvents like; methyl cellosolve, ethyl cellosolve, cellosolve solvents butyl cellosolve and the like; methanol, ethanol, propanol, isopropanol, alcohol solvents butanol; dichloromethane, halogenated solvents such as chloroform and the like.

  These organic solvents may be used individually by 1 type, and may use 2 or more types together. Of these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferably used.

  There is no restriction | limiting in particular in the usage-amount of an organic solvent, Considering the applicability | paintability of the prepared curable composition ((alpha)), the viscosity and surface tension of a liquid, compatibility of solid content, etc., it determines suitably. The curable composition (α) is prepared using the above-mentioned solvent, preferably as a coating liquid having a solid content concentration of 20 to 95% by weight, more preferably 30 to 80% by weight. Here, the “solid content” in the curable composition (α) means a component excluding the solvent, and includes not only a solid component but also a semi-solid or viscous liquid material. . The same applies to the curable composition (β) described later.

(Other ingredients)
The curable composition (α) used in the present invention is the above compound (A-1), active energy ray-curable compound (A-2), photopolymerization initiator, and organic solvent as long as the effects of the present invention are not impaired. Other components other than may be included. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropic agents (thickeners). ), Antifoaming agents, antioxidants, leveling agents and the like.

<Thickness of layer (A)>
The thickness of the layer (A) is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 4 μm or more from the viewpoints of hardness and scratch resistance. On the other hand, from the viewpoint of curling resistance, it is preferably 100 μm or less, more preferably 45 μm or less, further preferably 40 μm or less, particularly preferably 35 μm or less, and preferably 30 μm or less. Most preferred.

[Layer (B)]
In the laminate of the present invention, the layer (B) comprises a urethane (meth) acrylate and a modified product thereof, an epoxy (meth) acrylate and a modified product thereof, and a (meth) acrylate having an alkylene oxide structure and a modified product thereof. Of the compound (B-1) having at least one acryloyl group, and the content of the compound (B-1) is relative to the total amount of the compound having an acryloyl group in the curable composition (β) It is a layer which consists of a curable composition ((beta)) and / or its hardened | cured material which are 20 weight% or more.

<Curable composition (β)>
The curable composition (β) of the layer (B) has urethane (meth) acrylate, urethane (meth) acrylate modified product, epoxy (meth) acrylate, epoxy (meth) acrylate modified product, and alkylene oxide structure (meth). A compound (B-1) having at least one acryloyl group selected from the group consisting of a modified (meth) acrylate having an acrylate and alkylene oxide structure, and the content of the compound (B-1) is an acryloyl group. It is 20 weight% or more with respect to the total amount of the compound which has. The curable composition (β) may contain an active energy ray-curable compound (B-2) other than the compound (B-1).

(Compound (B-1))
The laminate of the present invention has good impact resistance when the curable composition (β) contains the compound (B-1). Specific examples of the compound (B-1) include the following compounds.

  Urethane (meth) acrylate and its modified products include isophorone diisocyanate (IPDI) isocyanurate, polytetramethylene glycol (PTMG) and hydroxyethyl acrylate (HEA) reactant, hexamethylene diisocyanate (HDI) isocyanate and Polyfunctional urethane (meth) acrylates such as a reactant of pentaerythritol triacrylate to a PTMG reactant; polyurethane (meth) acrylates having a carbonate bond such as a reactant of IPDI and polycarbonate diol and a reactant of HEA; Triethoxy (meth) acrylates having an isocyanurate ring such as ethoxyisocyanuric acid diacrylate and triethoxyisocyanuric acid triacrylate; Down-modified products, and the like. Examples of such commercially available compounds include UA-160TM, UA-122P, UA-2235PE, UA-4200 manufactured by Shin-Nakamura Chemical Co., Ltd., and Aronix M315, M313 manufactured by Toagosei Co., Ltd.

  Examples of the epoxy (meth) acrylate and modified products thereof include polyfunctional epoxy (meth) acrylates obtained by reacting an epoxy compound as a raw material and polycaprolactone-modified products thereof. More specifically, for example, bisphenol Examples thereof include epoxy acrylate having an A structure. As a commercial item of such a compound, for example, Epoxy Esters 3000A and 3002A (N) manufactured by Seisha Chemical Co., Ltd., EBECRYL600 manufactured by Daicel-Cytec are listed.

  Examples of (meth) acrylate having an alkylene oxide structure and modified products thereof include, for example, ethylene oxide (EO) modified trimethyl (meth) acrylate, propylene oxide (PO) modified trimethyl (meth) acrylate, and ethylene oxide (EO) modified trimethylol. Propane tri (meth) acrylate, propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate, ethylene oxide (EO) modified glycerin tri (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate of bisphenol A and these Examples include polycaprolactone-modified products. Examples of such commercially available compounds include ethoxylated trimethylolpropane triacrylate (A-TMPT-3EO, A-TMPT-9EO, etc.) manufactured by Shin-Nakamura Chemical Co., Ltd .; A-GLY-3E, A-GLY-9E, etc.); Hitachi Chemical's EO-modified bisphenol A diacrylate (FA-321A, FA-324A, etc.); Hitachi Chemical's PO-modified bisphenol A diacrylate FA-P324A, etc. Can be mentioned.

  The number of acryloyl groups in the compound (B-1) is 1 or more, preferably 2 or more. Those having two or more acryloyl groups are preferred from the viewpoint of curability. On the other hand, from the viewpoint of viscosity during coating, the number of acryloyl groups of the compound (B-1) is preferably 7 or less.

  When the curable composition (β) of the layer (B) contains the compound (B-1), impact resistance is imparted to the laminate of the present invention. In order to obtain sufficient impact resistance, the content of the compound (B-1) is 20% by weight or more, preferably 25% by weight based on the total amount of compounds having an acryloyl group in the curable composition (β). % Or more, more preferably 30% by weight or more. On the other hand, the upper limit of the content of the compound (B-1) is not particularly limited and is usually 100% by weight or less, but is preferably 90% by weight or less, more preferably 80% by weight or less from the viewpoint of hardness. is there.

(Active energy ray-curable compound (B-2))
The curable composition (β) may contain an active energy ray-curable compound (B-2) other than the compound (B-1).
The active energy ray-curable compound (B-2) contained in the curable composition (β) is a compound other than the compound (B-1) and has a functional group capable of undergoing a curing reaction upon irradiation with active energy rays. If it is a thing, it will not restrict | limit in particular.

  The active energy ray-curable compound (B-2) is preferably a compound containing an acryloyl group, the hardness and scratch resistance of the cured film is good, and the reactivity during curing is high. The number of acryloyl groups in the energy ray curable compound (B-2) is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. Further, from the viewpoint of suitable viscosity for coating, it is preferably 9 or less, more preferably 7 or less.

  Specifically, as the active energy ray-curable compound (B-2) having an acryloyl group, a polyfunctional (meth) acrylate; a polyfunctional (meth) acrylate derivative such as an ester-modified product or a carbonate-modified product; an acryloyl group Examples thereof include silica whose surface is modified with a compound having the same.

  Examples of the polyfunctional (meth) acrylate and polyfunctional (meth) acrylate derivatives include pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane. Multifunctional acrylates such as triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol pentaacrylate adduct to succinic anhydride; side chain or side chain and acryloyl group at the end Polyester (meth) acrylates such as polyester oligomers (specifically, M8030, M7100 manufactured by Toagosei Co., Ltd.) Preparative like; polyesters having a carbonate bond of the reaction products of oligoesters and pentaerythritol triacrylate with polycarbonate diol (meth) acrylate; and the like These polycaprolactone-modified products thereof. These may be used alone or in combination of two or more.

  Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane, due to viscosity, curability, hardness of the resulting cured product surface, etc. Tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; these caprolactone modified products are particularly preferred.

(Photopolymerization initiator)
The curable composition (β) used in the present invention preferably contains a photopolymerization initiator in order to improve the curability of the layer (B). The photopolymerization initiator that can be used here is the same as that mentioned in the curable composition (α).

  When the curable composition (β) contains a photopolymerization initiator, the content thereof is from the viewpoint of improving curability with respect to a total of 100 parts by weight of the compounds having an acryloyl group in the curable composition (β). The amount is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. On the other hand, from the viewpoint of maintaining the stability of the liquid when the curable composition (β) is used as a solution and the scratch resistance when the curable composition (β) is cured, it is preferably 10 parts by weight or less. More preferably, it is 8 parts by weight or less.

(Organic solvent)
The curable composition (β) used in the present invention preferably contains an organic solvent. The kind and amount of the organic solvent that can be used here, that is, the solid content concentration of the curable composition (β) are the same as those mentioned in the curable composition (α).

(Other ingredients)
The curable resin composition (β) used in the present invention is the above compound (B-1), active energy ray-curable compound (B-2), photopolymerization initiator, and organic as long as the effects of the present invention are not impaired. Other components other than the solvent may be included. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropic agents (thickeners). ), Antifoaming agents, antioxidants, leveling agents and the like.

<Thickness of layer (B)>
From the viewpoint of impact resistance, the thickness of the layer (B) is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and particularly preferably 4 μm or more. On the other hand, from the viewpoint of curling resistance and impact resistance, it is preferably 100 μm or less, more preferably 45 μm or less, further preferably 40 μm or less, particularly preferably 35 μm or less, and 30 μm or less. Most preferably.

The layer (A) and the layer (B) have a thickness ratio in the range of the thickness of the layer (A): the thickness of the layer (B) of 0.5: 2 to 2: 0.5. It is preferably formed to be in the range of 0.5: 1.5 to 1.5: 0.5, more preferably in the range of 0.5: 1 to 1: 0.5. More preferably, it is formed as follows.
When the thickness ratio of the layer (A) and the layer (B) is within the above range, the curled resistance of the laminate of the present invention tends to be better.

[Manufacturing method of laminate]
The laminated body of this invention can be manufactured by forming a layer (A) in one layer of a base material layer, and forming a layer (B) in the other surface. Either the layer (A) or the layer (B) may be formed first, or these may be formed simultaneously.

  Each of the layers (A) and (B) is, for example, coated (coated) with a curable composition (α) and a curable composition (β) on a base material, and optionally 40 to 40- After drying at about 100 ° C., it can be formed by irradiation with active energy rays. In addition, when the base material layer has a two-layer laminated structure of the layer (1) and the layer (2), the curable composition (α) is applied to the layer (1) side, and the curable composition (β) is a layer. (2) It is particularly preferable to apply to the side. Examples of methods for applying (coating) these curable compositions onto a substrate include, for example, reverse coating, gravure coating, rod coating, bar coating, Mayer bar coating, die coating, and spray coating. , Spin coating method, flow coating method, dip coating method, roll coating method, blade coating method, air knife coating method and the like. In addition, the form of the cured product obtained by curing these curable compositions of the present invention is not particularly limited, but usually the cured product obtained by irradiating and curing the active energy ray on the substrate is the substrate. It can be obtained as a state of a cured coating (cured film) on at least a part of one side.

  In addition, in the laminated body of this invention, you may form other layers other than a layer (A) and a layer (B) in the range which does not inhibit the effect of this invention remarkably.

  In addition, the total thickness of the laminate of the present invention is preferably 0.32 mm or more, more preferably 0.40 mm or more from the viewpoint of ensuring the thickness of each layer and fully exhibiting each function. , 0.50 mm or more is particularly preferable. On the other hand, it is preferably 10.02 mm or less, more preferably 3.0 mm or less, and 1.50 mm or less from the viewpoint of thinning and weight reduction of a product to which the laminate of the present invention is applied. Particularly preferred.

  In the laminate of the present invention, active energy rays that can be used when curing the curable compositions (α) and (β) include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and prevention of resin deterioration.

When the curable compositions (α) and (β) are cured by ultraviolet irradiation when the laminate of the present invention is produced, various ultraviolet irradiation devices can be used, and the light source thereof is a xenon lamp, a high pressure Mercury lamps, metal halide lamps, LED-UV lamps, and the like can be used. Irradiation amount of the ultraviolet (in mJ / cm ²⁾ is usually 10~10,000mJ / cm ^2, the flexible curable composition (alpha), curable, the cured product of the (beta) (cured film) preferably in terms of sex, etc. are 15~5,000mJ / cm ^2, more preferably 200~3,000mJ / cm ^2.

  Moreover, when manufacturing the laminated body of this invention, when hardening curable composition ((alpha)) and ((beta)) by electron beam irradiation, a various electron beam irradiation apparatus can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and preferably 1 to 15 Mrad from the viewpoints of curability, flexibility of the cured product, prevention of damage to the substrate, and the like.

[Usage]
The laminate of the present invention is excellent in scratch resistance, hardness, impact resistance, impact resistance, curl resistance, transparency and the like. For this reason, the laminated body of the present invention includes optical display parts such as touch panels and liquid crystal televisions; automobile-related parts such as lamp-related articles and window-related articles (rear windows, side windows, skylights, etc.); It can be suitably used for the surface cover of a wide range of articles such as life-related articles such as decorative panels and furniture. Among these, it can be particularly suitably used as a surface cover for optical display components such as a touch panel and a liquid crystal television, that is, a display body cover. When the laminate of the present invention is used as a display cover, it is preferable that the display has functions of high hardness, scratch resistance and antifouling on the front surface, and impact resistance on the back surface and withstands processing steps. It is preferable to provide a display cover having the layer (A) on the front side and the layer (B) on the back side in the laminate of the present invention because it preferably has a function of obtaining hardness and scratch resistance. preferable.

  EXAMPLES Hereinafter, although the content of this invention is demonstrated more concretely using an Example, this invention is not limited by a following example, unless the summary is exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiment of the present invention, and preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

(Synthesis example)
<Synthesis Example 1>
To a reactor equipped with a stirrer, a reflux condenser, and a thermometer, a one-terminal methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight of 5,000 ("Silaplane (registered trademark) FM0721" manufactured by JNC, formula (2) 20 parts by weight of a compound containing a silicone-containing (meth) acrylate represented by the formula: 60 parts by weight of glycidyl methacrylate (Mitsubishi Rayon “Acryester G”), methyl methacrylate (Mitsubishi Rayon “Acryester M”) 10 Part by weight, 10 parts by weight of stearyl methacrylate (“Acryester S” manufactured by Mitsubishi Rayon Co., Ltd.) and 151 parts by weight of methyl isobutyl ketone (MIBK) were charged, and after the start of stirring, the system was purged with nitrogen, and the temperature was raised to 55 ° C. He2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) “V-65”) 1.2 parts by weight and 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.9 parts by weight were added, and the system was heated to 65 ° C. and stirred for 3 hours. 0.6 part by weight of V-65 was added and stirred at 65 ° C. for 3 hours. The temperature inside the system was raised to 100 ° C. and stirred for 30 minutes, and then 163 parts by weight of MIBK was added, and the temperature inside the system was again raised to 100 ° C. After adding 0.5 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.6 parts by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.), acrylic acid (manufactured by Mitsubishi Chemical Corporation) 31.0 parts by weight was added, the temperature was raised to 110 ° C., and the mixture was stirred for 6 hours. After cooling, 4.8 parts by weight of MIBK was added to obtain a MIBK solution of a copolymer (F1) having a number average molecular weight of 6,500. The composition of the MIBK solution of the copolymer (F1) was [weight of copolymer (F1)] / [weight of MIBK] = 30/70 (solid content 30% by weight).

[Base materials / raw materials]
In the following, used base materials, raw materials and the like and their abbreviations are as follows.

<Base material>
-C-PC / PC sheet: ShinTech PW-10 (thickness: 1.0 mm (thickness of C-PC layer: 0.060 mm, thickness of PC layer: 0.94 mm)) manufactured by Wavelock Japan
-PMMA / PC sheet: ShinTech AW-10 (Thickness: 1.0 mm (PMMA layer thickness: 0.054 mm, PC layer thickness: 0.95 mm), manufactured by Nippon Wavelock Co., Ltd.)
-PMMA sheet: Acrylite manufactured by Mitsubishi Rayon Co., Ltd. (thickness: 1.0 mm)
-Impact resistant PMMA sheet: Mitsubishi Rayon Acrylite (impact resistant grade) (thickness 0.8mm)
・ PC sheet: Iupilon NF-2000 (thickness 1.0 mm) manufactured by Mitsubishi Gas Chemical Company, Inc.
The “C-PC” is a polycarbonate resin having a structural unit derived from bisphenol C as a main component, and the “C-PC layer” corresponds to “layer (1)”. “PC” is a polycarbonate resin whose main component is a structural unit derived from bisphenol A, and “PC layer” corresponds to “layer (2)”. “PMMA” refers to polymethyl methacrylate (polymethyl methacrylate).

<Compound (B-1)>
-UA-160TM: Shin-Nakamura Chemical Co., Ltd. UA160TM (urethane acrylate having a polytetramethylene glycol structure, two acryloyl groups)
M313: manufactured by Toagosei Co., Ltd. Aronix M313 (a mixture of isocyanuric acid ethylene oxide (EO) -modified diacrylate (a kind of urethane acrylate) and isocyanuric acid ethylene oxide (EO) -modified triacrylate (a kind of urethane acrylate)), having 3 acryloyl groups Pieces))
A-TMPT-9EO: Shin-Nakamura Chemical Co., Ltd. A-TMPT-9EO (ethylene oxide (EO) -modified trimethylolpropane triacrylate (a kind of (meth) acrylate having an alkylene oxide structure), three acryloyl groups)

<Compound (A-1)>
RS-76-E: Megafac (registered trademark) RS-76-E (compound having a perfluoropolyether structure and an acryloyl group) manufactured by DIC
DAC-HP: Optool (registered trademark) DAC-HP (compound having a perfluoropolyether structure and an acryloyl group) manufactured by Daikin Industries, Ltd.
Copolymer (F1): Copolymer (F1) obtained in Synthesis Example 1 (compound having a siloxane structure and an acryloyl group)

<Compounds having an acryloyl group other than compound (A-1) and compound (B-1)>
DPHA: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) (active energy ray curable compound (A-2) and active energy ray curable compound (B-2) manufactured by Nippon Kayaku Co., Ltd.) Any of these compounds)

<Compound having a siloxane structure and no acryloyl group>
BYK-306: BYK-306 (polyether-modified polydimethylsiloxane) manufactured by ALTANA

[Preparation of curable composition (α)]
<Curable composition (α-1)>
RS-76-E, DPHA and M313 were blended at a solid content weight ratio of 1.5: 86.5: 12 (total 100 parts by weight), and further 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator. After adding 2.5 parts by weight (“Irgacure (registered trademark) 184” manufactured by BASF), the solid content was reduced with a mixed solvent of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1. It diluted so that it might become 40 weight%, and the curable composition ((alpha) -1) was obtained.

<Curable composition (α-2)>
DAC-HP, DPHA and M313 were blended so that the weight ratio of solids was 1.5: 86.5: 12 (total 100 parts by weight), and 1-hydroxycyclohexyl phenyl ketone (BASF) was used as a photopolymerization initiator. After adding 2.5 parts by weight of “Irgacure (registered trademark) 184” manufactured by the same company, the weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 mixed solvent was 40 wt. % To obtain a curable composition (α-2).

<Curable composition (α-3)>
Copolymer (F1), DPHA, and M313 were blended so that the weight ratio of solids was 1.5: 86.5: 12, and 1-hydroxycyclohexyl phenyl ketone (Irgacure manufactured by BASF Corporation) was used as a photopolymerization initiator. (Registered trademark) 184 ") is added in an amount of 2.5 parts by weight, and the solid content is 40% by weight with a mixed solvent of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1. To obtain a curable composition (α-3).

[Preparation of curable composition (β)]
<Curable composition (β-1)>
DPHA and UA-160TM were blended at a solid content weight ratio of 60:40 (total 100 parts by weight), and 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered trademark) manufactured by BASF AG) as a photopolymerization initiator. 184 ") is added in an amount of 4.5 parts by weight, and the solid content is 40% by weight with a mixed solvent of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio). To obtain a curable composition (β-1).

<Curable composition (β-2)>
DPHA and A-TMPT-9EO were blended at a solids weight ratio of 60:40 (total 100 parts by weight), and 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered by BASF) was registered as a photopolymerization initiator. After adding 4.5 parts by weight of (trademark) 184 "), the solid content was 40% by weight with a mixed solvent of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio). It diluted so that it might become, and the curable composition ((beta) -2) was obtained.

<Curable composition (β-3)>
RS-76-E, DPHA and UA-160TM were blended so that the weight ratio of solids was 1.5: 68.5: 30 (total 100 parts by weight), and further 1-hydroxycyclohexyl as a photopolymerization initiator. After adding 2.5 parts by weight of phenyl ketone (“Irgacure (registered trademark) 184” manufactured by BASF), [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio) It diluted so that solid content might be 40 weight% with a mixed solvent, and the curable composition ((beta) -3) was obtained.

<Curable composition (β-4)>
RS-76-E, DPHA, and A-TMPT-9EO were blended at a solid content weight ratio of 1.5: 68.5: 30 (100 parts by weight in total), and 1- After adding 2.5 parts by weight of hydroxycyclohexyl phenyl ketone (“Irgacure (registered trademark) 184” manufactured by BASF), [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio) ) Was mixed with the mixed solvent so that the solid content was 40% by weight to obtain a curable composition (β-4).

[Preparation of curable composition other than curable composition (α) and curable composition (β)]
<Curable composition (γ-1)>
BYK-306, DPHA, and M313 were blended in a weight ratio of solids of 1.5: 86.5: 12 (total 100 parts by weight), and further 1-hydroxycyclohexyl phenyl ketone (BASF) as a photopolymerization initiator. After adding 2.5 parts by weight of “Irgacure (registered trademark) 184” manufactured by the same company, the weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 mixed solvent was 40 wt. % To obtain a curable composition (γ-1).

[Examples and Comparative Examples]
Hereinafter, examples and comparative examples according to the present invention will be described.

[Method for evaluating laminate]
The laminates obtained in the following examples and comparative examples were evaluated by the following methods.

(1) Scratch resistance Using a # 0000 steel wool, the surface of the layer (A) cured at a load of 160 g / cm ^{2 is} rubbed 300 times, and the degree of damage of the cured film after the test is evaluated as follows. did.
○: No more than 100 scratches ×: More than 100 scratches

(2) Hardness (pencil hardness)
For the surface of the cured layer (A), using a JIS-compliant pencil hardness meter (manufactured by Dazai Equipment Co., Ltd.), perform measurement based on the conditions of JIS K-5400, and check the hardest pencil count without scratches. Evaluation was made according to the following criteria.
○: Pencil hardness 3H or higher Δ: Pencil hardness 2H ×: Pencil hardness H or lower

(3) Impact resistance A 22 g steel ball spontaneously falls from above toward the center of a test piece with a width of 4 cm and a length of 8 cm, with the layer (A) side on the top and the layer (B) side on the bottom. A hard ball drop test was performed, and the impact resistance was evaluated as follows. In addition, the height which drops a steel ball was changed every 5 cm and evaluated.
○: No cracks and scratches even when dropped from above 30 cm x: Cracks or scratches caused by dropping from a position 30 cm or less above

(4) Curling resistance (warping)
A test piece having a width of 8 cm and a length of 15 cm is set in the vertical direction, and is left to stand in an environment of 80 ° C. and 85% humidity for 72 hours using a constant temperature and humidity tester (manufactured by Espec, PL-2ST). The sample was taken out of the machine and left in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 60% for 2 hours to dissipate heat, and the maximum value of the warp at four points was measured with the layer (A) side as the upper surface.
○: The maximum value of warpage is 0.5 mm or less ×: The maximum value of warpage is larger than 0.5 mm

(5) Transparency (haze)
The haze value was measured with a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory) in accordance with JIS K-7136, and 0.3% or less was passed and evaluated as follows.
○: Haze value is 0.3% or less ×: Haze value is greater than 0.3%

[Examples and Comparative Examples]
<Example 1>
The curable composition (β-1) was applied to the PC substrate surface of the C-PC / PC sheet with a bar coater so that the coating film after drying was 10 μm. This coating was heated at 80 ° C. for 1.5 minutes and dried, and then a high-pressure mercury lamp with an output of 120 W / cm was used and irradiated with ultraviolet rays of 450 mW / cm ² and 500 mJ / cm ² to coat the cured film. The layer (B) was formed on the PC substrate surface of the substrate. Next, the curable composition (α-1) was applied to the C-PC substrate surface of the substrate with a bar coater so that the coating film after drying was 10 μm, and heated at 80 ° C. for 1.5 minutes. The coating was dried. Then, using a high-pressure mercury lamp with an output of 80 W / cm, irradiating ultraviolet rays of 100 mW / cm ² and 300 mJ / cm ² to coat the cured film, forming a layer (A) on the C-PC substrate surface A laminate was obtained.

<Examples 2 to 4 and Comparative Examples 1 to 9>
A laminate was obtained in the same manner as in Example 1 except that the type of the curable composition used for each layer of the laminate and the thickness of each layer were changed as shown in Table-1.

  Each evaluation of said (1)-(5) was performed about the obtained laminated body. These results are shown in Table-1.

[Evaluation results]
As can be seen from Table 1, the laminates of Examples 1 to 4 were excellent in scratch resistance, hardness, impact resistance and curl resistance on the layer (A) side, and also had good transparency. On the other hand, in Comparative Example 1, when the layer corresponding to the layer (A) was not formed on the base material layer, the scratch resistance was poor. In Comparative Examples 2, 3, and 5, when the layer corresponding to the layer (A) was not formed on the base material layer, the scratch resistance and hardness were poor. In Comparative Example 4, when the layer corresponding to the layer (B) was not formed on the base material layer, the impact resistance was poor. In Comparative Example 6, since the PMMA / PC base material without the C-PC layer was used, the curl resistance was poor. In Comparative Examples 7 and 8, since the PMMA and impact-resistant PMMA base materials were used instead of the C-PC / PC base materials, the impact resistance and curl resistance were poor. In Comparative Example 9, since the PC single-layer base material was used instead of the C-PC / PC base material, the hardness was poor.

Claims (6)

A laminate having at least the following base material layer, the following layer (A) on one surface of the base material layer, and a layer (B) on the other surface, and the thickness of the base material layer being 0.3 to 30 mm A laminate in which the layer (A) is in contact with the layer (A) and the layer (2) is in contact with the layer (B) .
Base material layer: a layer (1) made of a polycarbonate resin whose main component is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 2,2-bis (4-hydroxyphenyl) ) Polycarbonate resin layer (A) composed of two layers of a polycarbonate resin layer (2) composed mainly of structural units derived from propane : At least one of at least a perfluoropolyether structure and a siloxane structure Layer (B) comprising a curable composition (α) and / or a cured product thereof comprising a compound (A-1) having an acryloyl group and an epoxy (meth) acrylate And modified products thereof, and (meth) acrylates having an alkylene oxide structure and modified products thereof A curable composition comprising a compound (B-1) having at least one acryloyl group and having a content of the compound (B-1) of 20% by weight or more based on the total amount of compounds having an acryloyl group ( β) and / or a layer made of a cured product thereof   The curable composition (α) contains the compound (A-1) in an amount of 0.05 to 10% by weight based on the total amount of the compounds having an acryloyl group in the curable composition (α). The laminated body as described in. The laminate according to claim 1 or 2 , wherein the layer (A) has a thickness of 1 to 45 µm and the layer (B) has a thickness of 1 to 45 µm. The laminate according to any one of claims 1 to 3 , wherein a thickness ratio of the layer (A) to the layer (B) is 0.5: 2 to 2: 0.5. The display body cover which consists of a laminated body of any one of Claims 1 thru | or 4 . The display body cover of Claim 5 which has a layer (A) in the front side, and has a layer (B) in the back side.