JP2014141089A - Resin laminate for molding and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate for molding which has excellent surface hardness and thermal moldability, and to provide a molded product obtained by heat molding the resin laminate for molding.SOLUTION: There is provided a resin laminate for molding which is obtained by laminating at least two layers of a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b. The surface of the resin layer B has a pencil hardness of 5H or more and the elongation rate of the resin laminate for molding at a predetermined temperature is 6% or more and 50% or less. Here, the predetermined temperature is lower by 30°C than the glass transition temperature of the resin layer A.

Description

  The present invention relates to a surface protection panel used by being arranged on the front side (viewing side) of an image display device, in particular, a front cover material such as a mobile phone or a liquid crystal pen tablet having a touch panel function, an in-vehicle display, a guide plate or a display plate. The present invention relates to a molding resin laminate that can be suitably used. Further, the present invention relates to a molded body obtained by thermoforming the molding resin laminate by vacuum molding, pressure molding or the like.

Conventionally, glass has been widely used from the viewpoint of hardness, heat resistance, and transparency in the fields of display covers for electronic devices.
However, since glass is easily broken by impact and the weight of the glass itself is heavy, an alternative to plastic is being studied.

  On the other hand, various electronic devices and devices have become smaller, lighter, and higher in performance and diversified in design, and the requirements for plastics such as display cover materials are becoming more stringent. There is a demand for a molded resin laminate and a molded body that have moldability and punchability.

For these uses, acrylic resins are widely used because of their high transparency and excellent surface hardness.
However, since acrylic resins are very brittle, the processing method is generally performed by cutting, and it cannot be said that the productivity is high.

  In order to eliminate brittleness and low scratch resistance, which are disadvantages of acrylic resins, for example, in Patent Document 1, a total thickness of 50 to 120 μm thick acrylic resin laminated on one side of a polycarbonate resin sheet by coextrusion. A structure in which a hard coat layer is further added to a laminate having a thickness of 0.5 to 1.2 mm has been proposed.

  In Patent Document 2, a layer containing an acrylic resin is formed on the surface of a base material containing a polycarbonate resin by coextrusion, and the surface of the layer containing an acrylic resin is hard-coated, and surface hardness, particularly pencil hardness, A laminate suitable for a liquid crystal display cover with a good balance of impact has been proposed.

  Patent Document 3 proposes a decorative film provided with a hard coat layer by a post-curing method in which a film provided with an ultraviolet curable hard coat layer is cured by UV irradiation after decorative molding.

JP 2006-103169 A International Publication Pamphlet WO2008 / 047940 JP 2012-512247 A

  In the resin laminate disclosed in Patent Documents 1 and 2 above, since acrylic resins are generally difficult to stretch compared to polycarbonate resins, they peel off at the interface between the polycarbonate resin layer and the acrylic resin layer when thermoformed. May occur, causing problems such as whitening, cracking, and foaming. Furthermore, since hard coating agents are generally difficult to extend, it is assumed that they are unsuitable for thermoforming applications.

  In addition, since the resin laminate disclosed in Patent Document 3 is subjected to UV curing treatment after decorative molding, and has unevenness unlike a flat plate, curing by UV irradiation is sufficient particularly on the side of the molded body. It is assumed that the hard coating layer remains uncured and does not occur. As a result, sufficient surface hardness may not be obtained. Further, for the same reason, there is a concern that it is not suitable for the formation of complex molded bodies.

  Accordingly, an object of the present invention is to provide a molding resin laminate having a high surface hardness without causing problems such as whitening, cracking and foaming during thermoforming, and various moldings obtained by thermoforming the resin laminate. To provide a body.

In the resin laminate for molding formed by laminating at least two layers of the resin layer A formed from the thermoplastic resin composition a and the resin layer B formed from the curable resin composition b, An excellent surface can be obtained by adjusting the pencil hardness of the surface of the resin layer B to 5H or more and adjusting the elongation ratio of the molding resin laminate at a predetermined temperature to be in the range of 6% to 50%. It has been found that a new molding resin laminate having hardness and thermoformability can be provided.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.
In addition, at least three layers of the resin layer C formed from the thermoplastic resin composition c, the resin layer A formed from the thermoplastic resin composition a, and the resin layer B formed from the curable resin composition b are formed in this layer. In the molding resin laminate obtained by laminating in order, the pencil hardness of the surface of the resin layer B is 5H or more, and the elongation rate of the molding resin laminate at a predetermined temperature is 6% or more and 50% or less. It has been found that by adjusting to be in the range, a new molding resin laminate having excellent surface hardness and thermoformability can be provided.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.

  Since the resin laminate for molding proposed by the present invention has excellent surface hardness and thermoformability, it is a surface protection panel used on the front side (viewing side) of an image display device, particularly a touch panel function. Can be suitably used as a front cover material for mobile phones, liquid crystal pen tablets, in-vehicle displays, guide boards, display boards, and the like.

1 illustrates a configuration of an embodiment of the present invention.

  Hereinafter, a molding resin laminate (referred to as “the present laminate”) as an example of an embodiment of the present invention will be described. However, the present invention is not limited to this laminate.

The structure of the laminated body according to the first invention is a molding formed by laminating at least two layers of a resin layer A formed from the thermoplastic resin composition a and a resin layer B formed from the curable resin composition b. In the resin laminate, the pencil hardness of the surface of the resin layer B is 5H or more, and the elongation ratio of the molding resin laminate at a predetermined temperature is adjusted to be in the range of 6% to 50%. It is a thing.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.

The configuration of the laminate according to the second invention is formed of a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a curable resin composition b. In the molding resin laminate formed by laminating at least three layers of the resin layer B in this order, the pencil hardness of the surface of the resin layer B is 5H or more, and the elongation rate of the molding resin laminate at a predetermined temperature Is adjusted to be in the range of 6% to 50%.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.

In both the first invention and the second invention, it is important that the lower limit value of the elongation rate of the laminate at a predetermined temperature is 6% or more. When the elongation ratio is 6% or more, when the laminate is thermoformed, no cracks or cracks are generated on the surface of the formed body, and good thermoformability can be obtained. For example, it becomes possible to bend into a U-shape by press molding.
Further, if the elongation rate is 15% or more, for example, it is possible to form a complicated three-dimensional shape such as a box shape by a vacuum / pressure forming method, and it is more preferable because thermoforming is possible in a wide temperature range. .
On the other hand, the upper limit of the elongation rate of the laminate is preferably 50% or less, and more preferably 30% or less. An elongation of 50% or less is preferable because sufficient surface hardness can be maintained in the laminate.

  In any of the above-described configurations, the pencil hardness on the surface of the resin layer B is preferably 5H or more, and more preferably 7H or more. If the pencil hardness is 5H or more, a laminate having excellent surface hardness can be provided.

  Further, when the surface of the resin layer B is rubbed with a load of 500 g using # 0000 steel wool, it is preferable that the number of reciprocations until the scratch occurs is 50 times or more. When the number of reciprocations until the surface is scratched when rubbed with the steel wool is 50 times or more, it is possible to provide a laminate having excellent scratch resistance and being hardly scratched. From this point of view, the number of reciprocations until the surface is scratched is preferably 50 times or more, more preferably 100 times or more, and particularly preferably 500 times or more.

  Below, the resin layer A, the resin layer B, and the resin layer C which comprise this laminated body are demonstrated in order.

(Resin layer A)
This laminate is formed by laminating at least two layers of a resin layer A formed from a thermoplastic resin composition a and a resin layer B formed from a curable resin composition b, or a thermoplastic resin composition c. A resin layer C formed from the above, a resin layer A formed from the thermoplastic resin composition a, and a resin layer B formed from the curable resin composition b are laminated in this order. In any case, the resin layer A is arranged on the back side of the resin layer B, so that the resin layer B has an excellent surface hardness.
Here, when the high-hardness resin layer A is arranged on the back side of the resin layer B, the resin layer A behaves like a hard underlayer, for example, when measuring pencil hardness, a high-hardness needle shape such as a pencil lead. Since the resin layer A itself acts to repel and prevent the object from biting into the resin layer B, the resin layer B is prevented from being scratched or scraped by a needle-like object such as a pencil lead, ie, excellent in the resin layer B. It is preferable because the surface hardness can be expressed. On the other hand, when the flexible resin layer A is disposed on the back side of the resin layer B, for example, a high-hardness needle-like object such as a pencil lead bites into the resin layer B, and the resin layer A itself absorbs in a depressed manner. It cannot be obstructed, and a high-hardness needle-like object such as a pencil lead bites in and the resin layer B is easily scratched or scraped.

For this reason, the hardness of the surface of the resin layer A is preferably a pencil hardness of 3H or more, and more preferably 5H or more. If the pencil hardness on the surface of the resin layer A is 3H or more, it is preferable because excellent hardness is maintained on the surface of the resin layer B even if the thickness of the resin layer B laminated thereon is reduced. When the resin layer A having a surface pencil hardness of 3H or more is disposed on the back side of the resin layer B, the resin layer A behaves like a hard underlayer as described above, for example, when measuring pencil hardness, a pencil lead, etc. Since the resin layer A itself acts to repel and prevent the high hardness needle-like object from biting into the resin layer B, the needle-like object such as a pencil lead bites into the resin layer B even if the resin layer B is thin. It is preferable because scratches and scrapes are prevented from occurring, that is, excellent hardness is maintained on the surface of the resin layer B. On the other hand, if the pencil hardness of the surface of the resin layer A disposed on the back side of the resin layer B is 2H or less, the resin layer A itself can be prevented from biting into the resin layer B by a high hardness needle-like object such as a pencil lead. Since the surface hardness is insufficient, it is necessary to prevent the resin layer B from being scratched or scraped by increasing the thickness of the resin layer B and making it difficult to dent, thereby causing a high-hardness needle-like object such as a pencil lead to bite in. There is.
If the thickness of the resin layer B can be reduced, it is preferable that the resin layer B is easily formed following the deformation of the resin layer A when the laminate is thermoformed.

(Thermoplastic resin composition a)
The resin layer A in this laminate is formed from the thermoplastic resin composition a. The thermoplastic resin that can be used for the thermoplastic resin composition a is not particularly limited as long as it is a thermoplastic resin that can form a film, a sheet, or a plate by melt extrusion. Preferred examples include polyethylene terephthalate, Polyester resins represented by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyesteramide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins, copolymers containing these as main components, or mixtures of these resins.
In particular, in the present invention, polyester resins, polycarbonate resins, and acrylic resins are preferable from the viewpoint that there is almost no absorption in the visible light region. Among these, acrylic resins are particularly preferable in that the resin layer B exhibits excellent surface hardness as described above and has a desired storage elastic modulus difference from the resin layer B.
In addition, when the thermoplastic resin composition a which comprises the resin layer A is a mixture of 2 or more types of resin chosen from the above-mentioned, and they are incompatible with each other, the volume fraction is the highest. The glass transition temperature of the thermoplastic resin is defined as the glass transition temperature of the resin layer A.

(Acrylic resin)
Examples of the monomer constituting the acrylic resin that can be used in the present invention include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) succinic acid ) Acroyloxyethyl, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) Examples include acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.
These may be used by polymerizing alone or in combination of two or more.

The monomer copolymerizable with the monomer constituting the acrylic resin may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule. The polyfunctional monomer may be a compound having at least two polymerizable carbon-carbon double bonds in the molecule.
Here, examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; alkenyl cyan compounds such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimides; and the like. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate; allyl acrylate, allyl methacrylate, cinnamon Alkenyl esters of unsaturated carboxylic acids such as allyl acid; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; aromatic polyalkenyl compounds such as divinylbenzene; etc. Is mentioned. Two or more types of monomers that can be copolymerized with alkyl methacrylate or alkyl acrylate may be used as necessary.

  As a copolymer resin with a monomer constituting the acrylic resin, for example, a methyl methacrylate-styrene copolymer is preferably used from the viewpoint of improving environmental resistance (warpage due to moisture absorption) of the acrylic resin. I can do it. As the methyl methacrylate-styrene copolymer resin, those having 30 to 95% by weight of methyl methacrylate units and 5 to 70% by weight of styrene units are usually used based on all monomer units, preferably methyl methacrylate. Those having 40 to 95% by weight of units and 5 to 60% by weight of styrene units are used, more preferably those having 50 to 90% by weight of methyl methacrylate units and 10 to 50% by weight of styrene units. When the ratio of the methyl methacrylate unit is reduced, the breaking strength of the surface layer itself is lowered, the whole film is easily broken, and the surface hardness is also lowered. Moreover, when the ratio of a methylmethacrylate unit becomes large, environmental resistance will fall.

  The acrylic resin that can be used in the present invention can be prepared by polymerizing the above-described monomer components by a known method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, a chain transfer agent is preferably used at the time of polymerization in order to adjust the glass transition temperature to a desired value or to obtain a viscosity exhibiting suitable moldability when producing a laminate. The amount of the chain transfer agent may be appropriately determined according to the type of monomer component and the composition thereof.

Moreover, in the acrylic resin used for this laminated body, the acrylic resin which has heat resistance (henceforth a heat resistant acrylic resin) can also be preferably used as the thermoplastic resin composition a.
When the resin layer A is formed using a heat-resistant acrylic resin as a main component of the thermoplastic resin composition a, it is preferable in this laminate because it may be easy to impart not only heat resistance but also excellent thermoformability. .
In addition, as will be described later, when the structure of the laminate is formed by laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B in this order, the elongation rate of the laminate at a predetermined temperature. As a means for making the desired range, the absolute value of the difference in the glass transition temperature between the resin layer A and the resin layer C can be within 30 ° C. For this reason, when the main component of the thermoplastic resin composition c forming the resin layer C has a high glass transition temperature, the acrylic resin preferably has a high glass transition temperature as well. From the viewpoint, a heat-resistant acrylic resin can be used advantageously.

(Heat resistant acrylic resin a1)
The heat resistant acrylic resin a1 is a copolymer resin containing a (meth) acrylic acid ester structural unit represented by the following general formula (1) and an aliphatic vinyl structural unit represented by the following general formula (2). The thing characterized by this is mentioned.

  In general formula (1), R1 is hydrogen or a methyl group, and R2 is a C1-C16 alkyl group.

  In general formula (2), R3 is hydrogen or a methyl group, and R4 is a cyclohexyl group having an alkyl substituent having 1 to 4 carbon atoms.

  R2 of the (meth) acrylic acid ester structural unit represented by the general formula (1) is an alkyl group having 1 to 16 carbon atoms, such as methyl group, ethyl group, butyl group, lauryl group, stearyl group, cyclohexyl group, isobornyl. Examples include groups. These can be used alone or in combination of two or more. Of these, a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or an ethyl group is preferable, and a methacrylic acid ester structural unit in which R1 is a methyl group and R2 is a methyl group is more preferable.

  Examples of the aliphatic vinyl structural unit represented by the general formula (2) include those in which R3 is hydrogen or a methyl group, and R4 is a cyclohexyl group or a cyclohexyl group having an alkyl group having 1 to 4 carbon atoms. Can do. These can be used alone or in combination of two or more. Of these, preferred are aliphatic vinyl structural units in which R3 is hydrogen and R4 is a cyclohexyl group.

The molar composition ratio between the (meth) acrylic acid ester structural unit represented by the general formula (1) and the aliphatic vinyl structural unit represented by the general formula (2) is in the range of 15:85 to 85:15. Yes, preferably in the range of 25:75 to 75:25, more preferably in the range of 30:70 to 70:30.
If the molar composition ratio of the (meth) acrylic ester structural unit to the total of the (meth) acrylic ester structural unit and the aliphatic vinyl structural unit is less than 15%, the mechanical strength becomes too low and becomes brittle. Absent. If it exceeds 85%, the heat resistance may be insufficient.

  The heat-resistant acrylic resin a1 is mainly composed of a (meth) acrylic acid ester structural unit represented by the general formula (1) and an aliphatic vinyl structural unit represented by the general formula (2). Although not particularly limited, those obtained by copolymerizing a (meth) acrylate monomer and an aromatic vinyl monomer and then hydrogenating the aromatic ring are preferred. In addition, (meth) acrylic acid shows methacrylic acid and / or acrylic acid. Specific examples of the aromatic vinyl monomer used in this case include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.

  Specific examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. , (Meth) acrylic acid cyclohexyl, (meth) acrylic acid alkyl (meth) acrylates such as isobornyl, etc., but from the balance of physical properties, alkyl methacrylate is used alone, or alkyl methacrylate and It is preferable to use alkyl acrylate together. Of the alkyl methacrylates, methyl methacrylate and ethyl methacrylate are particularly preferable.

  In the heat-resistant acrylic resin a1 mainly composed of the (meth) acrylic acid ester structural unit represented by the general formula (1) and the aliphatic vinyl structural unit represented by the general formula (2), the aromatic vinyl monomer It is preferable that 70% or more of the aromatic ring is obtained by hydrogenation. That is, the proportion of the aromatic vinyl structural unit in the heat resistant acrylic resin a1 is preferably 30% or less in the heat resistant acrylic resin a1. If it is in the range exceeding 30%, the transparency of the heat-resistant acrylic resin a1 may be lowered. More preferably, it is the range of 20% or less, More preferably, it is the range of 10% or less.

  A known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method. In the solution polymerization method, a monomer composition including a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.

  The method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when it is 250 ° C. or lower, the molecular chain is not broken and the ester moiety is not hydrogenated.

  Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, diatomaceous earth. And a solid catalyst supported on a porous carrier.

  The glass transition temperature of the heat-resistant acrylic resin a1 is preferably 110 ° C. or higher. If the glass transition temperature is 110 ° C. or higher, the heat resistance of the laminate will not be insufficient.

(Heat resistant acrylic resin a2)
As heat-resistant acrylic resin a2, on the basis of all monomer units constituting the acrylic resin, methyl methacrylate units 60 to 95% by weight, methacrylic acid units, acrylic acid units, maleic anhydride units, N- Examples thereof include a polymer having 5 to 40% by weight of a unit selected from a substituted or unsubstituted maleimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit, and having a glass transition temperature of 110 ° C. or higher.

Here, the methyl methacrylate unit is a unit [—CH ₂ —C (CH ₃ ) (CO ₂ CH ₃ ) —] formed by polymerization of methyl methacrylate, and the methacrylic acid unit is obtained by polymerization of methacrylic acid. The unit [—CH ₂ —C (CH ₃ ) (CO ₂ H) —] to be formed, and the acrylic acid unit is the unit [—CH ₂ —CH (CO ₂ H) — formed by polymerization of acrylic acid. ]. The maleic anhydride unit is a unit formed by polymerization of maleic anhydride represented by the general formula (3), and the N-substituted or unsubstituted maleimide unit is represented by the general formula (4). Units formed by polymerization of N-substituted or unsubstituted maleimides.

In the general formula (4), R ¹ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, and a phenyl group. Aralkyl groups such as aryl groups and benzyl groups, and the carbon number is usually about 1-20.

  Further, the glutaric anhydride structural unit is a unit having a glutaric anhydride structure, and the glutarimide structural unit is a unit having a glutarimide structure. Typically, each of the following general formula (5) and It is shown by (6).

In general formula (5), R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom or a methyl group. In the general formula (6), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a substituent, and examples of the substituent include a methyl group , An alkyl group such as an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group, and the carbon number is usually about 1 to 20.

  Methyl methacrylate units, methacrylic acid units, acrylic acid units, maleic anhydride units, and N-substituted or unsubstituted maleimide units are used as polymerization raw materials, respectively, as methyl methacrylate, methacrylic acid, acrylic acid, maleic anhydride. , And N-substituted or unsubstituted maleimide.

  The glutaric anhydride structural unit may be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and / or acrylic acid, such as sodium hydroxide, potassium hydroxide, sodium methylate. In the presence of a basic compound, it can be introduced usually by heat treatment at 150 to 350 ° C., preferably 220 to 320 ° C. for modification.

  Moreover, the glutarimide structural unit is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and / or acrylic acid, usually in the presence of ammonia or primary amine, at 150 to 350 ° C., Preferably, it can be introduced by heat treatment in the range of 220 to 320 ° C. for modification.

  As the heat-resistant acrylic resin a2, the monomer unit composition of the acrylic resin is preferably 65 to 95% by weight, more preferably 70 to 92% by weight of methyl methacrylate units, and methacrylic acid units and acrylic acid units. The unit selected from maleic anhydride units, N-substituted or unsubstituted maleimide units, glutaric anhydride structural units, and glutarimide structural units is preferably 5-35 wt%, more preferably 8-30 wt%. It is. The glass transition temperature of the acrylic polymer is preferably 115 ° C. or higher, and usually 150 ° C. or lower.

(Heat resistant acrylic resin a3)
Examples of the heat-resistant acrylic resin a3 include those having a lactone ring structure formed by cyclization condensation reaction of a polymer (α) having a hydroxyl group and an ester group in the molecular chain. The polymer (α) is a copolymer obtained by polymerizing a monomer component containing at least a (meth) acrylate monomer (α1) and a 2- (hydroxyalkyl) acrylate monomer, and the lactone The ring structure is a structure represented by the following general formula (7).

In general formula (7), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.

  In order to form the lactone ring structure represented by the general formula (7), as the polymer (α) having a hydroxyl group and an ester group in the molecular chain, for example, a (meth) acrylate monomer (α1) A polymer obtained by polymerizing a monomer component containing a vinyl monomer (α2) having a structural unit represented by the following general formula (8) is preferred.

In General Formula (8), R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

  The (meth) acrylate monomer (α1) is a so-called (meth) other than a vinyl monomer having a 2- (hydroxymethyl) acrylate structural unit represented by the general formula (8), for example. If it is an acrylic acid alkylester monomer, it will not specifically limit. For example, an aliphatic (meth) acrylate having an alkyl group or the like, an alicyclic (meth) acrylate having a cyclohexyl group or the like, or an aromatic (meth) acrylate having a benzyl group or the like may be used. In addition, a desired substituent or functional group may be introduced into these groups.

  Specific examples of the (meth) acrylate monomer (α1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester and the like. These may be used alone or in combination of two or more. Among these, in terms of the weather resistance, surface gloss, and transparency of the resulting acrylic resin, methyl methacrylate and methyl acrylate are preferable, and in terms of the surface hardness of the resulting acrylic resin, methyl methacrylate is more preferable. Good. Further, (meth) acrylate having a cyclohexyl group is preferable in that it imparts hydrophobicity to the acrylic resin and, as a result, can reduce the water absorption rate of the acrylic resin and can impart weather resistance to the acrylic resin. In addition, (meth) acrylate having an aromatic group is preferable in that the aromatic ring can further improve the heat resistance of the resulting acrylic resin.

  The ratio of the (meth) acrylate monomer (α1) in the monomer component is not particularly limited, but is preferably 95 to 10% by weight, more preferably 90 to 10% by weight. Furthermore, in order to maintain good transparency and weather resistance, it is preferably 90 to 40% by weight, more preferably 90 to 60% by weight, and still more preferably 90 to 70% by weight in the total monomer components. % Should be good.

  In the heat-resistant acrylic resin a3 used in the present invention, an unsaturated monocarboxylic acid (α1 ′) may be used in combination as the (meth) acrylate monomer (α1). By using an unsaturated monocarboxylic acid (α1 ′) in combination, an acrylic resin into which a glutaric anhydride ring structure is introduced together with a lactone ring structure can be obtained, and heat resistance and mechanical strength can be further improved. It is preferable because it is possible. Examples of the unsaturated monocarboxylic acid (α1 ′) include (meth) acrylic acid, crotonic acid, and α-substituted acrylic acid monomers which are derivatives thereof, but are not particularly limited. (Meth) acrylic acid is preferred, and methacrylic acid is preferred from the viewpoint of heat resistance. In addition, the ester group derived from the (meth) acrylate monomer (α1) in the polymer (α) may have a structure equivalent to that of the unsaturated carboxylic acid (α1 ′) depending on conditions such as heating. Further, the carboxyl group possessed by the unsaturated carboxylic acid (α1 ′) may have a structure of a salt such as a metal salt such as a sodium salt, as long as it does not interfere with the cyclization condensation reaction described later. In the monomer component, the ratio of the unsaturated monocarboxylic acid (α1 ′) is not particularly limited, and may be appropriately set within a range not impairing the effects of the present invention.

  Examples of the vinyl monomer (α2) having the structural unit represented by the general formula (8) include 2- (hydroxyalkyl) acrylic acid derivatives. Specifically, 2- (hydroxymethyl) acrylic acid ester monomers are preferred. More specifically, for example, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, normal butyl 2- (hydroxymethyl) acrylate, 2 -(Hydroxymethyl) acrylic acid-t-butyl and the like can be mentioned, among which methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are particularly preferable. Furthermore, 2- (hydroxymethyl) methyl acrylate is most preferred because it has a high effect of improving surface hardness, hot water resistance or solvent resistance. In addition, these may use only 1 type or may use 2 or more types together.

  In the monomer component, the ratio of the vinyl monomer (α2) having the structural unit represented by the general formula (8) is not particularly limited, but is preferably 5 to 50% by weight. . More preferably, it is 10 to 40 weight%, More preferably, it is 15 to 35 weight%. When the proportion of the vinyl monomer (α2) is less than the above range, the amount of the ring structure is reduced, so that the surface hardness of the laminate may be lowered, and the hot water resistance and solvent resistance may be lowered. Moreover, the heat resistance of the laminate may be lowered. On the other hand, when the amount is more than the above range, when a lactone ring structure is formed, a crosslinking reaction occurs and gelation tends to occur, the fluidity is lowered, and melt molding may be difficult. In addition, since unreacted hydroxyl groups are likely to remain, when the resulting acrylic resin is molded, a condensation reaction further proceeds to generate a volatile substance, and bubbles or silver streaks (silver strips on the surface) are generated in the laminate. Pattern or the like) may be easy to enter.

  As the monomer component for obtaining the polymer (α), a polymerizable monomer other than the above (α1) and (α2) can be used as long as the effects of the present invention are not impaired. . Examples thereof include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. In addition, these may use only 1 type or may use 2 or more types together. When the polymerizable monomer is used in combination as a monomer component for obtaining the polymer (α), the content of these monomers is 0 to 30% by weight or less in the monomer component. Preferably, it is 0 to 20% by weight or less, more preferably 0 to 10% by weight or less. When a predetermined amount or more is used in terms of physical properties, physical properties such as weather resistance, surface gloss or transparency, which are good physical properties derived from a (meth) acrylate monomer, may be impaired.

The heat resistant acrylic resin a3 is obtained by forming a ring structure by subjecting the polymer (α) to a cyclization condensation reaction. The cyclocondensation reaction is a reaction in which a hydroxyl group and an ester group (or more carboxyl group) present in the molecular chain of the polymer (α) are cyclized and condensed to form a lactone ring structure by heating, Alcohol and water are by-produced by cyclocondensation. Thus, by forming the ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted and high surface hardness, hot water resistance, and solvent resistance are imparted.
Examples of a method for obtaining an acrylic resin having a lactone ring structure by cyclization condensation of the polymer (α) include 1) cyclization condensation by heating the polymer (α) under reduced pressure in an extruder. Method of reaction (Polym. Prepr., 8, 1,576 (1967), 2) The cyclization condensation reaction of the polymer (α) is carried out in the presence of a solvent, and depolymerization is performed simultaneously with the cyclization condensation reaction. There are a method of volatilization, 3) a method of cyclocondensing the polymer (α) using a specific organophosphorus compound as a catalyst (European Patent No. 1008606), and the like. Of course, it is not limited to these, A plurality of methods may be adopted among the methods 1) to 3). In particular, the reaction rate of the cyclization condensation reaction is high, it is possible to suppress the foam and silver streak from entering the laminate, and the reduction in mechanical strength due to the decrease in molecular weight during devolatilization can be suppressed 2) And 3) are preferred.

  The heat-resistant acrylic resin a3 used in the present invention has a weight average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and most preferably 50,000 to 300,000. Is preferred. When the weight average molecular weight is lower than the above range, not only the surface hardness, hot water resistance or solvent resistance is lowered, but also there is a problem that the mechanical strength is lowered and it is likely to become brittle. This is not preferable because the properties are lowered and the molding becomes difficult.

  The glass transition temperature (Tg) of the heat-resistant acrylic resin a3 is preferably 115 ° C. or higher, more preferably 125 ° C. or higher, and most preferably 130 ° C. or higher.

  As described above, it is preferable to form the resin layer A from the thermoplastic resin composition a mainly composed of any one of the above heat-resistant acrylic resins, because it may be easy to impart excellent thermoformability to the laminate. That is, when this laminate is formed by laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B in this order, for example, the main component of the thermoplastic resin composition c that forms the resin layer C If a polycarbonate resin is used for the resin, the glass transition between the resin layer A and the resin layer C can be achieved by using any one of the above heat-resistant acrylic resins as a main component of the thermoplastic resin composition a forming the resin layer A. It is often preferable that the absolute value of the temperature difference can be within 30 ° C. That is, by setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C to be within 30 ° C., when the laminate is thermoformed, whitening, cracks, and foaming occur in the formed body. This is preferable because it can be avoided.

(Heat resistant acrylic resin a4)
As the heat-resistant acrylic resin a4, not only heat resistance but also an excellent hardness can be used in which a hard dispersed phase is contained in an acrylic resin matrix. More specifically, an acrylic resin containing and dispersing a hard dispersed phase material that has better heat resistance or scratch resistance than the acrylic resin can be used. By using an acrylic resin containing a hard dispersed phase in the matrix, the pencil hardness of the surface of the resin layer A can be 5H or more.

  Examples of the material that forms the hard dispersed phase include thermosetting resins. Specifically, phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, etc. In addition to these polycondensation or addition condensation resins, addition polymerization resins obtained by radical polymerization of unsaturated monomers such as thermosetting acrylic resins, vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, etc. It is done.

  Among these, it is preferable that the unsaturated monomer is a polyfunctional one because the characteristics (insoluble, high glass transition temperature) of a hard material can be obtained by polymerization crosslinking. Examples of unsaturated monomers include polyols and polyesters of acrylic acid and / or methacrylic acid, as well as crosslinkable monomers such as polyaryls and polyvinyl ethers of these polyols. However, it is not limited to these.

  Specific examples of the unsaturated monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate (di-, tri-) acrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, penta Examples include erythritol tetraallyl ether, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate or ethoxylated pentaerythritol tetraacrylate, and mixtures thereof. Among these, considering the affinity with acrylic resins, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA) can be preferably used. However, it is not limited to these.

  You may use a thermosetting resin individually or in combination of 2 or more types. Moreover, you may use combining these thermosetting resins and the thermoplastic resin which has the unsaturated bond which can be bridge | crosslinked.

Examples of the shape of the hard dispersed phase include particles, spheres, lines, fibers, and the like. From the viewpoint of being easily dispersed evenly in the acrylic resin that is a thermoplastic matrix resin, a sphere is preferable. However, it is not limited to this.
The particle diameter of the hard dispersed phase is appropriately set according to the purpose of use, application, etc. of the laminate, but is preferably 0.1 to 1000 μm. The blending amount of the hard dispersed phase in the acrylic resin phase is appropriately set according to the purpose of use, application and the like of the laminate, but is preferably 0.1 to 60% by weight.

Although it does not specifically limit as a method of including a hard dispersion phase in an acrylic resin phase, For example, the following method is mentioned.
a) A thermosetting resin material constituting a hard dispersed phase is added to the acrylic resin material.
b) Next, after being melt-kneaded and molded into a predetermined shape, a hard dispersed phase can be formed by causing phase separation and crosslinking. Alternatively, the thermosetting resin may be previously molded into a particulate form, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not dissolve.

(Other ingredients)
In addition to the resin component, the thermoplastic resin composition a that forms the resin layer A includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, Various additives such as glass fiber and impact modifier may be contained within a range not impairing the effects of the present invention.

  Further, the thermoplastic resin composition a forming the resin layer A can also contain acrylic rubber particles having an elastic polymer portion as long as the effects of the present invention are not impaired. Such acrylic rubber particles have a layer (elastic polymer layer) made of an elastic polymer mainly composed of an acrylate ester, and may be single-layer particles made only of an elastic polymer or elastic. Particles having a multilayer structure composed of a polymer layer and a layer made of a hard polymer (hard polymer layer) may be used, but considering the surface hardness of the resin layer A disposed on the surface of the laminate, A particle having a multilayer structure is preferable. In addition, only 1 type may be sufficient as acrylic rubber particle, and 2 or more types may be sufficient as it.

  As described above, the resin layer A is arranged on the back side of the resin layer B, thereby playing a role of making the resin layer B exhibit excellent surface hardness. For this reason, the thickness of the resin layer A is preferably 40 μm or more, and more preferably 60 μm or more. If the thickness of the resin layer A is 40 μm or more, even if the thickness of the resin layer B is reduced, an excellent surface hardness is expressed on the surface of the resin layer B, which is preferable. On the other hand, the thickness of the resin layer A is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less. A thickness of the resin layer A of 500 μm or less is preferable because the resin layer C can easily compensate for the brittleness of the resin layer A that hinders thermoforming or punching.

(Resin layer B)
The resin layer B in the present invention is a layer that imparts excellent surface hardness to the laminate, and the elongation of the laminate provided with the resin layer B is within a predetermined range at a predetermined temperature. Thus, the laminate can have excellent thermoformability.

  The resin layer B is a layer having excellent scratch resistance, and when it is rubbed with a load of 500 g using # 0000 steel wool, the number of reciprocations until the scratches are preferably 50 times or more. , More preferably 100 times or more, and particularly preferably 500 times or more.

(Curable resin composition b)
The resin layer B of the laminate is formed from the curable resin composition b, and the curable resin composition b that can be used in the present invention is, for example, an energy beam such as an electron beam, radiation, or ultraviolet rays. Although it will not specifically limit if it hardens | cures by irradiation or it hardens | cures by heating, It is preferable to consist of an ultraviolet curable resin from a viewpoint of shaping | molding time and productivity.
Preferred examples of the curable resin constituting the curable resin composition b include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, and alicyclic epoxies. Examples thereof include resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds and the like. These curable resins may be used alone or in combination with a plurality of compounds. Among them, examples of the curable resin imparting excellent surface hardness include radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, polyfunctional epoxy acrylate compounds, alkoxysilanes, and alkylalkoxys. Examples thereof include curable compounds of thermal polymerization type such as silane. Furthermore, the curable resin composition b of the present invention can be an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin.

An example of the curable resin composition b that gives particularly excellent surface hardness to the laminate is an organic / inorganic hybrid curable resin composition. Examples of the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin.
Utilizing an inorganic component having such a reactive functional group, for example, this inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, and thus an organic / inorganic organic component is simply made to contain an inorganic component in an organic binder. Compared to the composite curable resin composition, curing shrinkage is unlikely to occur and high surface hardness can be expressed, which is preferable. Furthermore, from the viewpoint of reducing curing shrinkage, an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.

  As described above, the resin layer B in the present invention has an elongation rate of 6% at a predetermined temperature in any structure of the laminate according to the first invention and the laminate according to the second invention. As mentioned above, the surface hardness and thermoformability which were excellent by adjusting to the range of 30% or less can be provided. Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.

  Here, as a means for adjusting the elongation ratio of the laminate at a predetermined temperature to a range of 6% or more and 50% or less, for example, an inorganic component and / or a reactive functional group contained in the resin layer B is included. The method of adjusting with the density | concentration of an inorganic component is mentioned. That is, the preferred concentration range of the inorganic component and / or the inorganic component having a reactive functional group contained in the resin layer B is preferably 0% by mass or more and 50% by mass or less, and 0% by mass or more and 40% by mass. The following is more preferable. It is preferable that the concentration range is 0 mass% or more and 50 mass% or less because the surface hardness excellent in the resin layer B can be maintained and the elongation of the laminate at a predetermined temperature can be maintained at 6% or more.

As a forming method of the resin layer B, for example, there is a method of forming and laminating on the surface of the resin layer A by coating the surface of the resin layer A as a paint of the curable resin composition b and then forming a cured film. Although there is, it is not limited to this method.
As a lamination method with the resin layer A, a known method is used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned. In addition, for example, a method of laminating the resin layer B on the resin layer A using a transfer sheet in which the resin layer B is formed on the release layer may be employed.

(Surface conditioning component)
The curable resin composition b forming the resin layer B can contain a leveling agent as a surface adjustment component. Examples of the leveling agent include silicone leveling agents and acrylic leveling agents. In particular, those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
Specifically, a polyether-modified polydimethylsiloxane having an acrylic group having a double bond at both ends (for example, “BYK-UV 3500”, “BYK-UV 3530” manufactured by Big Chemie Japan Co., Ltd.), Polyester-modified polydimethylsiloxane having an acrylic group having a total of four double bonds at the end (“BYK-UV 3570” manufactured by Big Chemie Japan Co., Ltd.).
Among these, polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.

  When the curable resin is cured with ultraviolet rays, a photopolymerization initiator is used. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyl dimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, and acylphosphine oxides. The addition amount of the photopolymerization initiator is generally in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin.

  These photopolymerization initiators can be used alone, or many can be used in combination of two or more. Moreover, since these various photoinitiators are marketed, such a commercial item can be used. Examples of commercially available photopolymerization initiators include “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000”, “IRGACURE 2959”, “DAROCUR 1173”, “IRGACURE 907”, “IRGACURE 369”, “IRGACURE 1”, “IRGACURE 1”, “IRGACURE1” "IRGACURE 819", "IRGACURE 784" [The above IRGACURE (Irgacure) series and DAROCUR series are sold by Ciba Specialty Chemicals, Inc.], "KAYACUREITTX", "KAYACUREDETX-S", "KAYACUREB," “KAYACUREBMS”, “KAYACURE2-EA "[More KAYACURE (Kayacure) series, sold by Nippon Kayaku Co., Ltd.], and the like.

(Other ingredients)
In addition to the curable resin component, the curable resin composition b that forms the resin layer B includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, Various additives such as antistatic agents, flame retardants such as silicone compounds, fillers, glass fibers, impact modifiers and the like can be contained within a range not impairing the effects of the present invention.

  The thickness of the resin layer B is preferably in the range of 5 μm to 20 μm. If thickness is 5 micrometers or more, since sufficient hardness can be provided to the resin layer B surface, it is preferable. On the other hand, if the thickness is 20 μm or less, it is preferable because excellent thermoformability can be imparted to the laminate, and further, there is no risk of warping, undulation, peeling, etc. associated with curing / shrinking of the resin layer B. This is also preferable.

(Resin layer C)
Among the laminates, at least three of the resin layer C formed from the thermoplastic resin composition c, the resin layer A formed from the thermoplastic resin composition a, and the resin layer B formed from the curable resin composition b. In the laminate formed by laminating the layers in this order, the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the laminate.

(Thermoplastic resin composition c)
The resin layer C in the present laminate is formed from the thermoplastic resin composition c. The thermoplastic resin that can be used for the thermoplastic resin composition c is not particularly limited as long as it is a thermoplastic resin that can form a film, sheet, or plate by melt extrusion. Preferred examples include polyethylene terephthalate, Polyester resins represented by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyesteramide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins, copolymers containing these as main components, or mixtures of these resins. In particular, in the present invention, a polyester resin, a polycarbonate resin, or an acrylic resin is preferable from the viewpoint that there is almost no absorption in the visible light region.
Of these, polycarbonate resins are particularly preferred in that the laminate can be provided with excellent impact resistance or secondary workability such as punchability.
In addition, when the thermoplastic resin composition c constituting the resin layer C is a mixture of two or more kinds of resins selected from the above, and they are incompatible with each other, the volume fraction is the highest. The glass transition temperature of the thermoplastic resin is defined as the glass transition temperature of the resin layer C.

(Polycarbonate resin)
The polycarbonate-based resin that can be used in the present invention is not particularly limited as long as it can form a film, sheet, or plate by melt extrusion. From the group of aromatic polycarbonate, aliphatic polycarbonate, and alicyclic polycarbonate. At least one selected can be used.

(Aromatic polycarbonate)
Examples of the aromatic polycarbonate include i) those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, and ii) a solid phase transesterification method of a carbonate prepolymer. And iii) those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. Among these, i) a product obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method is preferable in terms of productivity.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy 3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4 , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., and if necessary, use two or more of them You can also.

Among the above-mentioned dihydric phenols, among those described above, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4hydroxyphenyl) -4-methylpentane, 1, A dihydric phenol selected from the group consisting of 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene alone or 2 It is preferable to use more than one species. In particular, bisphenol A alone or 1,1-bis (4hydroxyphenyl) -3,3, -Selected from the group consisting of trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Use in combination with one or more dihydric phenols is preferred.
Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, and two or more of them can be used as necessary.

(Other polycarbonate resins)
Examples of the polycarbonate resin other than the aromatic polycarbonate include aliphatic polycarbonate and alicyclic polycarbonate. What contains at least the structural unit derived from the dihydroxy compound which has a site | part represented by following General formula (9) in a part of structure is preferable.

(However, the case where the site represented by the general formula (9) is a part of —CH ₂ —O—H is excluded.)

  The dihydroxy compound is not particularly limited as long as a part of the molecular structure is represented by the general formula (9). Specifically, 9,9-bis (4- (2 -Hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) 3-isopropylphenyl) fluorene 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9 -Bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-pheny Phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6 -Methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene or the like, an ether having an aromatic group in the side chain and bonded to the aromatic group in the main chain And compounds having a group.

  From the viewpoint of heat resistance, a compound having a cyclic ether structure such as spiroglycol can be preferably used. Specifically, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane (common name: spiroglycol), 3, 9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9-bis (1,1-dipropyl-2-hydroxyethyl) ) -2,4,8,10-tetraoxaspiro (5.5) undecane.

  Other polycarbonate resins may contain structural units derived from dihydroxy compounds other than the above-mentioned dihydroxy compounds (hereinafter sometimes referred to as “other dihydroxy compounds”), and other dihydroxy compounds include ethylene. Glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol Aliphatic dihydroxy compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindi Methanol, 1,5-decalin Alicyclic dihydroxy compounds such as methanol, 2,3-decalin dimethanol, 2,3 norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol, 2,2-bis (4-hydroxy Phenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2 -Bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5 Nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4hydroxyphenyl) Sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4 Aromatic bisphenols such as-(2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene Is mentioned.

(Other ingredients)
In addition to the resin component, the thermoplastic resin composition c forming the resin layer C includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, Various additives such as glass fiber and impact modifier may be contained within a range not impairing the effects of the present invention.

As described above, the laminate is formed from the resin layer C formed from the thermoplastic resin composition c, the resin layer A formed from the thermoplastic resin composition a, and the curable resin composition b. In the molding resin laminate in which at least three layers of the resin layer B are laminated in this order, the elongation rate of the molding resin laminate at a predetermined temperature is adjusted to be in the range of 6% to 50%. Thereby, this laminated body can be equipped with the outstanding surface hardness and thermoformability.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.

Here, as a means for adjusting the elongation ratio of the laminate at a predetermined temperature to a desired range, a resin layer A formed from the thermoplastic resin composition a and a resin formed from the thermoplastic resin composition c For example, the absolute value of the difference in glass transition temperature from the layer C may be within 30 ° C. If the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C is within 30 ° C., the elongation behavior of the resin layer A and the resin layer C will be close to each other. It is preferable because it becomes easy to do. Moreover, since the temperature range which this laminated body shows a desired elongation rate becomes wide, ie, the temperature range suitable for thermoforming becomes wide, it is preferable.
In this way, by setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C to be within 30 ° C., the molded body can be formed by thermoforming, particularly even by deep drawing. It is possible to prevent whitening, cracks, and foaming. From this viewpoint, the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C is more preferably 25 ° C. or less, and further preferably 20 ° C. or less.

Examples of the method for setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C within 30 ° C. include the following methods.
(1) In the thermoplastic resin composition a and / or the thermoplastic resin composition c, by blending thermoplastic resins having different glass transition temperatures, a mixture of at least two kinds of thermoplastic resins is obtained. A method of adjusting the difference in glass transition temperature between A and the resin layer C within 30 ° C. Here, as the two or more types of thermoplastic resins having different glass transition temperatures, the same or different types of thermoplastic resins can be used as long as the glass transition temperatures are different. The thermoplastic resin blended here is compatible with the thermoplastic resin composition a or the thermoplastic resin composition c.
(2) About the thermoplastic resin composition a and / or the thermoplastic resin composition c, a difference in glass transition temperature between the resin layer A and the resin layer C is within 30 ° C. by using a copolymer with other components. How to adjust.
(3) About thermoplastic resin composition a and / or thermoplastic resin composition c, by mixing additives such as plasticizer, the difference in glass transition temperature between resin layer A and resin layer C is within 30 ° C. How to adjust.

  Further, as another method for imparting thermoformability to the laminate by a method other than setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C within 30 ° C., a thermoplastic resin composition In the product a and / or the thermoplastic resin composition c, the elongation behavior of the resin layer A and the resin layer C is close to each other by forming a mixture containing at least two types of mutually incompatible thermoplastic resins. The method of adjusting so that it may become can be mentioned.

  Of the methods in which the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is within 30 ° C., the thermoplastic resin a has the acrylic resin as the main component in the example of (1), and is thermoplastic. The case where the resin composition c consists of a mixture of polycarbonate resin and other thermoplastic resins will be described in detail.

  As described above, the thermoplastic resin composition c in the present invention can be a mixture composed of two or more thermoplastic resins. For example, when the thermoplastic resin composition a has an acrylic resin as a main component and the thermoplastic resin composition c has a polycarbonate resin as a main component, the absolute value of the difference between the glass transition temperatures is 30 ° C. or less. In order to reduce the glass transition temperature of the polycarbonate resin, the other polycarbonate resin is mixed with the latter polycarbonate resin. That is, a method of lowering the glass transition temperature of a polycarbonate resin by melt blending (; mixing and heat-melting) a polycarbonate resin and another thermoplastic resin to form a polymer alloy.

  In general, the glass transition temperature of polycarbonate resin is around 150 ° C, which is higher by 50 ° C than the typical glass transition temperature of acrylic resin, 100 ° C, so other thermoplastic resins are mixed with polycarbonate resin. Thus, the glass transition temperature of the polycarbonate resin is lowered. From this viewpoint, preferred examples of other thermoplastic resins include aromatic polyesters and polyester resins having a cyclic acetal skeleton.

(Aromatic polyester d1)
Examples of the aromatic polyester d1 that can be used as another thermoplastic resin include a resin obtained by condensation polymerization of an aromatic dicarboxylic acid component and a diol component.

  Here, representative examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Further, a part of terephthalic acid may be substituted with another dicarboxylic acid component. Examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid, and the like. These may be one kind or a mixture of two or more kinds, and the amount of other dicarboxylic acids to be substituted can be appropriately selected.

  On the other hand, typical examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexanedimethanol. A part of ethylene glycol may be substituted with another diol component. Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, methoxypolyethylene Examples include alkylene glycol. These may be one kind or a mixture of two or more kinds, and the amount of other diols to be substituted can be appropriately selected.

  Specific examples of the aromatic polyester include polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol, and polybutylene terephthalate obtained by condensation polymerization of terephthalic acid or dimethyl terephthalate and 1,4-butanediol. In addition, a copolyester containing a dicarboxylic acid component other than terephthalic acid and / or a diol component other than ethylene glycol can also be mentioned as a preferred aromatic polyester.

  Among them, as a preferable example, a part of ethylene glycol in polyethylene terephthalate, preferably a copolyester having a structure obtained by substituting 55 to 75 mol% with cyclohexanedimethanol, or a part of terephthalic acid in polybutylene terephthalate, preferably May include a copolymerized polyester having a structure obtained by substituting 10 to 30 mol% with isophthalic acid, or a mixture of these copolymerized polyesters.

  Among the aromatic polyesters described above, it is preferable to select those that can be polymer-alloyed by melt blending with a polycarbonate resin and that can sufficiently reduce the glass transition temperature of the polycarbonate resin.

  From such a viewpoint, a copolymerized polyester having a structure in which 50 to 75 mol% of ethylene glycol, which is a diol component of polyethylene terephthalate, is substituted with 1,4-cyclohexanedimethanol (1,4-CHDM) (so-called “ PCTG "), or a copolyester having a structure obtained by substituting a part of terephthalic acid of polybutylene terephthalate, preferably 10 to 30 mol% with isophthalic acid, or a mixture thereof is the most preferable example. These copolyesters are known to be completely compatible and polymerized by melt blending with a polycarbonate-based resin, and the glass transition temperature can be effectively lowered.

(Polyester resin d2 having a cyclic acetal skeleton)
The polyester resin d2 having a cyclic acetal skeleton that can be used as another thermoplastic resin is a polyester resin that includes a dicarboxylic acid unit and a diol unit, and 1 to 60 mol% of the diol unit is a diol unit having a cyclic acetal skeleton. is there. The diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (10) or (11).

R ¹ , R ² , and R ³ are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.

  Examples of the compounds of the general formulas (10) and (11) include 3,9-bis (1,1-dimethyl-2hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, or 5 -Methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is particularly preferred.

  In the polyester resin d2 having a cyclic acetal skeleton, the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentane. Aliphatic diols such as diol, 1,6-hexanediol, diethylene glycol, propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-de Cycloaliphatic diols such as hydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydro naphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol Bisphenols such as 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonyl bisphenol (bisphenol S), etc. Alkylene oxide adducts of the above bisphenols; hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydipheny Aromatic dihydroxy compounds such as benzophenone; and alkylene oxide adducts of the above aromatic dihydroxy compounds can be exemplified. Ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol are preferable from the viewpoint of mechanical performance and economical efficiency of the polyester resin of the present invention, and ethylene glycol is particularly preferable. The exemplified diol units can be used alone or in combination.

  In addition, the dicarboxylic acid unit of the polyester resin d2 having a cyclic acetal skeleton used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane. Aliphatic dicarboxylic acids such as dicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornane dicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1, Examples include aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid. From the viewpoint of mechanical performance and heat resistance of the film of the present invention, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acids are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferred. Among these, terephthalic acid is most preferable from the viewpoint of economy. The illustrated dicarboxylic acids can be used alone or in combination.

Whether or not the melt-blended mixed resin composition is a polymer alloy, in other words, whether or not it is completely compatible, is determined by, for example, a glass transition temperature measured at a heating rate of 10 ° C./min by differential scanning calorimetry. It can be judged by whether it becomes one. Here, that the glass transition temperature of the mixed resin composition is single means that the glass transition temperature of the mixed resin composition is determined using a differential scanning calorimeter at a heating rate of 10 ° C./min in accordance with JIS K-7121. It means that only one peak indicating the glass transition temperature appears when measured.
Further, when the mixed resin composition was measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement of JIS K-7198A method) at a strain of 0.1% and a frequency of 10 Hz, the maximum loss tangent (tan δ) was obtained. It can also be determined whether there is one value.
If the mixed resin composition is completely compatible (polymer alloying), the blended components are compatible with each other on the nanometer order (molecular level).

  As a means for polymer alloying, a compatibilizer, a secondary block polymerization or a graft polymerization, or a means of dispersing one polymer in a cluster form can be employed.

  The mixing ratio of the polycarbonate resin and the polyester d1 or d2 described above is such that the absolute value of the difference in glass transition temperature between the polycarbonate resin composition obtained by mixing and the acrylic resin is within 30 ° C. Although it does not restrict | limit, it is preferable that it is polycarbonate-type resin: polyester d1 or d2 = 20: 80-90: 10 by a mass ratio from a viewpoint of transparency maintenance, and especially polycarbonate-type resin: polyester d1 or d2 = 30. : 70 to 80:20, in particular, polycarbonate resin: polyester d1 or d2 = 40: 60 to 75:25 is preferable.

  Next, in the method of setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C within 30 ° C., the thermoplastic resin composition a is mainly composed of an acrylic resin in the example of (3). The case where the thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer will be described in detail.

  As described above, in general, the glass transition temperature of polycarbonate resin is around 150 ° C., which is nearly 50 ° C. higher than the typical glass transition temperature of acrylic resin of 100 ° C. In order to make the absolute value of within 30 ° C., there is a method of mixing the latter polycarbonate resin with a plasticizer to lower the glass transition temperature of the polycarbonate resin.

  Examples of the plasticizer that can be used in the laminate include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate. Phosphate compounds such as 2-ethylhexyl diphenyl phosphate; phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate Acid ester compounds; trimellitic acid ester compounds such as tris (2-ethylhexyl) trimellitate; Til adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, Aliphatic dibasic acid ester compounds such as bis (2-ethylhexyl) sebacate and diethyl succinate; Ricinoleic acid ester compounds such as methylacetylricinoleate; Acetic acid ester compounds such as triacetin and octyl acetate; N-butylbenzenesulfone And sulfonamide compounds such as amides. In particular, when the resin component is a polycarbonate resin, among the plasticizers described above, a phosphoric acid ester-based compound is preferable because of its good compatibility with the polycarbonate resin and good transparency of the resin after the compatibility. In particular, cresyl diphenyl phosphate and tricresyl phosphate are more preferable.

  When the thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer, the ratio of both is a mass ratio, preferably polycarbonate resin: plasticizer = 70: 30 to 99: 1. It is more preferable that the system resin: plasticizer = 90: 10 to 98: 2. When the amount of the plasticizer is less than the above-described ratio, the effect of lowering the glass transition temperature due to plasticization becomes insufficient, and the absolute value of the difference in glass transition temperature between the resin layer A and the thermal resin layer C is within 30 ° C. As a result, it may be difficult to improve the thermoformability of the resulting laminate. On the other hand, when the amount of the plasticizer is larger than the above-described ratio, the fluidity of the thermoplastic resin composition c containing the polycarbonate resin is remarkably increased. For example, the laminate can be obtained by coextrusion molding with the thermoplastic resin composition a. When doing so, the appearance may be impaired.

(Other ingredients)
In addition to the resin component, the thermoplastic resin composition c forming the resin layer C includes, for example, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, glass fiber, Various additives such as impact modifiers can be contained within a range not impairing the effects of the present invention.

  As described above, the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the laminate by being laminated with the resin layer A and the resin layer B. From this point of view, it is important that the thickness of the resin layer C is set based on the ratio with the total thickness of the resin layer A and the resin layer B, and the thickness ratio is determined by the resin layer C thickness / (resin layer A (Thickness + resin layer B thickness) is preferably 2 or more, and more preferably 4 or more. A thickness ratio of 2 or more is preferable because secondary laminate properties such as excellent impact resistance or punchability can be imparted to the laminate.

(Configuration of this laminate)
This laminate is configured by laminating at least two layers of a resin layer A and a resin layer B, and more specifically, resin layer A / resin layer B, resin layer B / resin layer A / resin layer B. And the like. Moreover, the multilayer structure of 3 or more layers provided with layers other than the resin layer A and the resin layer B may be sufficient. For example, of the surface of the resin layer A, the resin layer D is laminated on the opposite side of the surface on which the resin layer B is laminated, and more specifically, the resin layer D / resin layer A / resin layer B. And the like.
Further, the present laminate has a configuration in which at least three layers of the resin layer C, the resin layer A, and the resin layer B are laminated in this order, but a multilayer configuration including four or more layers including other layers may be used. Good. For example, of the surface of the resin layer C, the resin layer D is laminated on the opposite side of the surface on which the resin layer A is laminated, and more specifically, the resin layer D / resin layer C / resin layer A. / Structure of resin layer B and the like.

(Thickness)
The thickness of the laminate is not particularly limited, and is preferably, for example, 0.1 mm to 1.5 mm. In particular, in consideration of handling in practical use, it is about 0.2 mm to 1.0 mm. preferable.
For example, the surface protection panel used by being arranged on the front side of the image display device preferably has a thickness of 0.2 mm to 1.2 mm. For example, a front cover such as a mobile phone or a liquid crystal pen tablet having a touch panel function The material preferably has a thickness of 0.3 mm to 1.0 mm.

FIG. 1 illustrates the configuration of an embodiment of the present laminate, and in FIG. 1A, a molding resin formed by laminating a resin layer A (13) and a resin layer B (14) in this order. The laminated body (11) is illustrated.
FIG. 1B illustrates a molding resin laminate (15) formed by laminating three layers in the order of the resin layer C (12), the resin layer A (13), and the resin layer B (14). ing.
Further, in FIG. 1 (c), a molding resin laminate having a structure in which a resin layer B (14) is laminated on both surfaces of a laminate comprising a resin layer C (12) and a resin layer A (13). 16) is illustrated. According to such a configuration, since the resin layer C (12) is also coated with the resin layer B (14), it is possible to suppress the occurrence of process scratches on the surface of the resin layer C (12). Have. The resin layer B (14) on the resin layer C (12) side may be formed of a curable resin different from the resin layer B (14) on the resin layer A (13) side.

<Explanation of terms>
In general, "film" refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) (Industrial standard JIS K-6900), “sheet” generally refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

In the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” and “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It means “smaller”.
Further, in the present invention, when expressed as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and “Y or less” (Y is an arbitrary number). ) Includes the meaning of “preferably smaller than Y” unless otherwise specified.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention.

<Measurement and evaluation method>
The measurement methods and evaluation methods for various physical property values of the resin layers and laminates obtained in Examples and Comparative Examples will be described.

(Glass transition temperature (Tg) of resin layer)
The resin layers obtained in Examples and Comparative Examples were subjected to dynamic viscoelasticity measurement according to JIS K-7198A method using the following apparatus, the peak temperature of loss tangent (tan δ) was read, and the glass transition of the resin layer The temperature (Tg) was used. Moreover, the storage elastic modulus in the glass transition temperature-20 degreeC of the resin layer A was read, and it was set as the storage elastic modulus of the resin layer.
Apparatus: Dynamic viscoelasticity measuring apparatus DVA-200 (made by IT Measurement Control Co., Ltd.)
Distance between chucks: 25mm
Distortion: 0.1%
Temperature range: -50 ° C to 250 ° C
Temperature increase rate: 3 ° C / min
Frequency: 10Hz

(Pencil hardness of resin layer)
About the resin layer obtained by the Example and the comparative example, the measurement of the surface pencil hardness was performed based on JISK-5600-5-4. The load applied during the test was 750 g.

(Scratch resistance on the surface of the resin layer B)
With respect to the surface of the resin layer B of the molding resin laminate obtained in the examples and comparative examples, the number of reciprocations until a scratch was generated was examined using the following apparatus and conditions. The obtained measured values were evaluated for scratch resistance based on the following evaluation criteria. However, the symbol “Δ” is also above the practical level.
Equipment: Friction fastness tester Gakushin type (manufactured by Daiei Scientific Instruments)
Steel wool count: # 0000
Test load: 500gf
Test speed: 30 reciprocations / minute Test stroke: 120 mm
◎: Number of reciprocations until the scratch occurs ≧ 500 times ○: 50 times ≦ Number of reciprocations until the scratch occurs <500 times Δ: Number of reciprocations until the scratch occurs <50 times

(Stretch rate of laminate)
The molding resin laminates obtained in the examples and comparative examples were subjected to a tensile test using the following apparatus in accordance with JIS K-7161, and the distance between chucks when cracks and cracks occurred in the laminates. (Mm) was read and substituted into the following equation to determine the elongation percentage of the laminate.
Apparatus: Intesco Universal Tension Compression Tester INTESCO200X
Distance between chucks: 40mm
Test temperature: 114 ° C. (glass transition temperature of resin layer A—30 ° C.)
Tensile speed: 10 mm / min
Specimen shape: Strips with a width of 40 mm and a length of 100 mm Laminate elongation ratio = (Distance between chucks when cracking occurs−Distance between initial chucks) / Distance between initial chucks × 100 (%)

(Thermoformability of the laminate)
The molding resin laminates obtained in the examples and comparative examples were thermoformed using one of the following molding methods.
・ Forming method A
Molding device: press molding machine laminate preheating condition: 150 ° C for 2 minutes Mold temperature: 130 ° C
Press pressure: 0.2 MPa
Press time: 10 seconds Mold: 180 mm long x 100 mm wide x 10 mm high Tunnel shape
Corner R = 20mm
・ Forming method B
Molding device: Vacuum / pneumatic molding machine laminate preheating temperature: 120 ° C
Mold temperature: 100 ° C
Air pressure: 0.2 MPa
Vacuum pressure: -0.1 MPa
Holding time: 10 seconds Mold: Vertical 140 mm x Horizontal 70 mm x Height 5 mm Three-dimensional box shape
Corner R = 8mm, 20mm
About the obtained molded object, the external appearance was checked visually and the thermoformability was evaluated based on the following evaluation criteria.
○: The molded body has no cracks or cracks ×: The molded body has cracks or cracks <Example 1>
(Preparation of resin composition a-1)
A pellet of an acrylic resin (manufactured by Arkema, trade name “Altglas HT121”, containing a hard dispersed phase) was used as the resin composition a-1.

(Preparation of resin composition c-1)
Polycarbonate-based resin (manufactured by Sumika Styron Co., Ltd .; trade name “CALIBER 301-4”)
) Pellets of polycarbonate resin (manufactured by Sumika Stylon; trade name “SD Polycarbonate SP3030”) and pellets of polyester resin (manufactured by SK Chemical; trade name “SKYGREEN J2003”) 55:25 : After mixing in the mass ratio of 20, it pelletized using the twin-screw extruder heated at 260 degreeC, and produced the resin composition c-1.

(Production of single-layer film constituting each resin layer)
About the single layer sheet for evaluation, about the A-1 layer and the C-1 layer, each of the resin compositions a-1 or c-1 is supplied to an extruder equipped with a single layer T die, After melt-kneading at 240 ° C. and 260 ° C. in an extruder, a sheet-like sample having a single-layer structure having a thickness of 200 μm was obtained.
About the obtained sheet-like sample of each resin layer, glass transition temperature was evaluated. The results are shown in Table 1.

(Preparation of laminate 1)
The resin compositions a-1 and c-1 are respectively supplied to the extruders A and B. In each extruder, after melt-kneading at 240 ° C. and 260 ° C., the two types and two layers heated to 250 ° C. And then extruded into a sheet shape so as to have a two-layer structure of resin layer A-1 / resin layer C-1, cooled and solidified, and a thickness of 600 μm (resin layer A-1: 80 μm, resin layer C -1: A 520 μm laminate 1 was obtained, and the pencil hardness was evaluated on the surface of the resin layer A-1 of the obtained laminate 1. The results are shown in Table 1.

(Preparation of molded resin laminate 1)
The organic / inorganic hybrid ultraviolet curable resin composition b-1 (manufactured by MOMENTIVE, trade name “UVHC7800FS”) was applied to the surface of the laminate 1 on the resin layer A-1 side using a bar coater, and 90 ° C. After drying for 1 minute, exposure was performed at an exposure amount of 500 mJ / cm ² to obtain a molding resin laminate 1 provided with a curable resin layer B-1 having a thickness of 10 μm. Here, the concentration of the reactive functional group-containing silica in the resin layer B-1 was 46% by mass. About the obtained resin laminate 1 for molding, pencil hardness and abrasion resistance were evaluated about the elongation rate of the laminate and the surface of the resin layer B-1. The results are shown in Table 1.

(Preparation of molded body 1)
Using the obtained molding resin laminate 1, thermoforming was performed by the molding method A to obtain a molded body 1.
The obtained molded body 1 was evaluated for thermoformability. The results are shown in Table 1.

<Example 2>
(Preparation of molded resin laminate 2)
Organic / inorganic hybrid ultraviolet curable resin composition b-1 (manufactured by MOMENTIVE, trade name “UVHC7800FS”) and urethane acrylate ultraviolet curable resin composition b-2 (trade name “8BR- 500 ”)) at a mass ratio of 85:15 to obtain a curable resin composition b-3. The resin composition b-3 was applied to the surface of the laminate 1 obtained in Example 1 on the resin layer A-1 side using a bar coater, dried at 90 ° C. for 1 minute, and then 500 mJ / cm ² . It exposed with the exposure amount and obtained the resin laminated body 2 for shaping | molding provided with curable resin layer B-3 of thickness 10 micrometers. Here, the concentration of the reactive functional group-containing silica in the resin layer B-3 was 41% by mass. The surfaces of the obtained molding resin laminate 2 and resin layer B-3 were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Preparation of molded body 2)
Using the obtained resin laminate 2 for molding, thermoforming was performed by the molding method A to obtain a molded body 2.
The obtained molded body 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
(Preparation of molded resin laminate 3)
Organic / inorganic hybrid ultraviolet curable resin composition b-1 (manufactured by MOMENTIVE,
(Trade name “UVHC7800FS”) and urethane acrylate ultraviolet curable resin composition b-2 (manufactured by Taisei Fine Chemical Co., Ltd., (trade name “8BR-500”)) are mixed at a mass ratio of 60:40 to be cured. Resin composition b-4 was obtained. The resin composition b-4 was applied to the surface of the laminate 1 obtained in Example 1 on the resin layer A-1 side using a bar coater, dried at 90 ° C. for 1 minute, and then 500 mJ / cm ² . It exposed with the exposure amount and obtained the resin laminated body 3 for shaping | molding provided with curable resin layer B-4 of thickness 10 micrometers. Here, the concentration of the reactive functional group-containing silica in the resin layer B-4 was 31% by mass. The surfaces of the obtained molding resin laminate 3 and resin layer B-4 were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Preparation of molded body 3)
Using the obtained resin laminate 3 for molding, thermoforming was performed by the molding method A to obtain a molded body 3.
The obtained molded body 3 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
(Preparation of molded body 4)
Using the molding resin laminate 3 obtained in Example 3, thermoforming was performed by molding method B to obtain a molded body 4. The obtained molded body 4 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
(Preparation of molding resin laminate 5)
An organic / inorganic hybrid ultraviolet curable resin composition b-5 (manufactured by MOMENTIVE, trade name “UVHC7800G”) is applied to the surface of the laminate 1 obtained in Example 1 on the resin layer A-1 side, and a bar coater is used. And then dried at 90 ° C. for 1 minute, and then exposed at an exposure amount of 500 mJ / cm ² to obtain a molding resin laminate 5 having a curable resin layer B-5 having a thickness of 10 μm. The surface of the obtained molded resin laminate 5 and the resin layer B-5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Preparation of molded body 5)
Using the molding resin laminate 5, thermoforming was performed by molding method A to obtain a molded body 5. The obtained molded body 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As apparent from Table 1, the molding resin laminates of the present invention in Examples 1 to 4 have excellent surface hardness with a pencil hardness of 5H or more on the surface of the resin layer B, and the laminates at a predetermined temperature. Since the elongation rate was adjusted to a range of 6% or more and 50% or less, it was found that the film had excellent thermoformability. Among them, in the molding resin laminates of Example 3 and Example 4 in which the elongation ratio of the laminate is 15% or more, not only can a U-shaped bending process be performed by a press molding method, It was found that the box-shaped complex three-dimensional shape can be formed by vacuum / pressure forming.

  On the other hand, the molding resin laminate of Comparative Example 1 has an excellent surface hardness with a pencil hardness of 5H or more on the surface of the resin layer B, but the elongation percentage of the laminate at a predetermined temperature is less than 6%. It was found that the thermoformability was inferior.

From the above, it was found that the molding resin laminates of Examples 1 to 4 of the present invention have good surface hardness and thermoformability.
In addition, when thermoforming was performed using the resin laminate for molding of the present invention of Examples 1 to 4, a molded body having good transparency was obtained.

  Since the resin laminate for molding proposed by the present invention has excellent surface hardness and thermoformability, it is a surface protection panel used on the front side (viewing side) of an image display device, particularly a touch panel function. It is suitably used for front cover materials such as mobile phones, liquid crystal pen tablets, in-vehicle displays, guide plates and display plates.

11, 15, 16: This laminate 12: Resin layer C
13: Resin layer A
14: Resin layer B

Claims (11)

In a resin laminate for molding formed by laminating at least two layers of a resin layer A formed from the thermoplastic resin composition a and a resin layer B formed from the curable resin composition b,
A molding resin laminate, wherein a pencil hardness of the surface of the resin layer B is 5H or more, and an elongation ratio of the molding resin laminate at a predetermined temperature is 6% or more and 50% or less.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C. At least three layers of a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a resin layer B formed from the curable resin composition b are laminated in this order. In the molded resin laminate,
A molding resin laminate, wherein a pencil hardness of the surface of the resin layer B is 5H or more, and an elongation ratio of the molding resin laminate at a predetermined temperature is 6% or more and 50% or less.
Here, the predetermined temperature refers to a temperature at which the resin layer A has a glass transition temperature of −30 ° C.   The molding resin laminate according to claim 2, wherein an absolute value of a difference in glass transition temperature between the resin layer A and the resin layer C is within 30 ° C.   The resin laminate for molding according to any one of claims 1 to 3, wherein a pencil hardness of the surface of the resin layer A is 3H or more.   The molding resin laminate according to any one of claims 1 to 4, wherein the thermoplastic resin composition a contains an acrylic resin as a main component.   The molding resin laminate according to claim 5, wherein the acrylic resin has a glass transition temperature of 110 ° C. or higher.   The molding resin laminate according to claim 5 or 6, wherein the acrylic resin contains or disperses a hard dispersed phase material.   The molding resin laminate according to any one of claims 2 to 7, wherein the thermoplastic resin composition c contains a polycarbonate-based resin as a main component.   9. The molding resin laminate according to claim 1, wherein the resin layer B has a thickness of 5 μm to 20 μm.   10. The curable resin composition b mainly comprises a curable resin composition that is cured by an energy beam selected from an electron beam, radiation, and ultraviolet rays. Molded resin laminate.   The molded object obtained by thermoforming the resin laminated body for shaping | molding of any one of Claim 1 to 10.

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