JP7413071B2 - Transparent resin laminate, transparent substrate material and transparent protective material using the same - Google Patents

Description

The present invention relates to a resin laminate used for transparent substrate materials and protective materials. More specifically, the present invention relates to a resin laminate having excellent thermoformability at low temperatures.

Acrylic resin has excellent surface hardness, transparency, scratch resistance, and weather resistance. On the other hand, polycarbonate resin has excellent impact resistance. Therefore, a laminate having an acrylic resin layer and a polycarbonate resin layer has excellent surface hardness, transparency, scratch resistance, weather resistance, and impact resistance, and is used in automobile parts, home appliances, electronic devices, and portable information terminals. Used in display windows.

In recent years, with the diversification of design needs, there has been a demand for products with enhanced design features such as the front panels of display devices through thermoforming such as vacuum forming and pressure forming. Attempts have been made to apply a laminate having an acrylic resin layer and a polycarbonate resin layer to a front panel due to its excellent performance as described above. However, when thermoforming a laminate having an acrylic resin layer and a polycarbonate resin layer, it is necessary to heat the sheet to a temperature at which the polycarbonate resin sufficiently stretches, which results in applying excessive heat to the acrylic resin. Peeling may occur at the interface between the acrylic resin layer and the polycarbonate resin layer, resulting in whitening of the surface or cracking.

Patent Document 1 discloses a molding resin sheet of polycarbonate resin and acrylic resin having specific terminal groups as a molding resin sheet suitable for thermoforming such as vacuum forming or pressure forming. Such a resin sheet is suppressed from whitening and cracking during bending during thermoforming. However, when the surface of the acrylic resin layer of such a resin sheet is hard coated, there is a problem in that cracks occur during bending during thermoforming.

International Publication No. 2016/060100

An object of the present invention is to provide a resin laminate having excellent thermoformability at low temperatures.

The present inventors have completed the present invention as a result of extensive studies to solve the above problems. Specifically, the present invention is as follows.

[1] A layer containing a thermoplastic resin (B) is provided on at least one surface of the layer containing the polycarbonate resin (A), and a hard coat layer is provided on at least one surface of the layer containing the thermoplastic resin (B). A resin laminate having:
The thermoplastic resin (B) contains a methacrylic resin (C),
A copolymer in which the methacrylic resin (C) contains a methacrylic acid ester monomer unit (c1), an N-alkylmaleimide monomer unit (c2), and an N-arylmaleimide monomer unit (c3). and
The total of (c1), (c2) and (c3) is 80 to 100% by mass based on the total of all monomer units in the methacrylic resin (C),
The proportion of (c1) is 50 to 96% by mass with respect to the total of (c1), (c2) and (c3),
The proportion of the above (c2) is 2 to 25% by mass with respect to the total of the above (c1), (c2) and (c3),
The resin laminate, wherein the proportion of (c3) is 2 to 25% by mass based on the total of (c1), (c2) and (c3).
[2] The resin laminate according to [1] above, which does not generate cracks after being thermoformed to a radius of 50 mm using a heat press machine.
[3] The method according to [1] or [2] above, wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 30°C. resin laminate.
[4] The resin laminate according to any one of [1] to [3] above, wherein the thermoplastic resin (B) is a polymer alloy of a resin that is compatible with the methacrylic resin (C).
[5] The resin laminate according to any one of [1] to [4] above, wherein the N-alkylmaleimide monomer unit (c2) contained in the methacrylic resin (C) is N-cyclohexylmaleimide.
[6] The resin laminate according to any one of [1] to [5] above, wherein the N-arylmaleimide monomer unit (c3) contained in the methacrylic resin (C) is N-phenylmaleimide.
[7] The above [1] to [6], wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.1 to 4.0 mm. ] The resin laminate according to any one of the above.
[8] At least one of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber, [1] to [7] above. The resin laminate according to any one of the above.
[9] The resin laminate according to any one of [1] to [8] above, wherein the hard coat layer is an acrylic hard coat.
[10] The resin laminate is subjected to at least one of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment and antifouling treatment on one or both sides of the resin laminate, [1] to The resin laminate according to any one of [9].
[11] A thermoformed article obtained by heat bending the resin laminate according to any one of [1] to [10] above.
[12] A transparent substrate material comprising the resin laminate according to any one of [1] to [10] above or the thermoformed article according to [11] above.
[13] A transparent protective material comprising the resin laminate according to any one of [1] to [10] above or the thermoformed article according to [11] above.
[14] A touch panel front protection plate comprising the resin laminate according to any one of [1] to [10] above, or the thermoformed body according to [11] above.
[15] A front plate for car navigation systems, office automation equipment, or portable electronic devices, comprising the resin laminate according to any one of [1] to [10] above, or the thermoformed body according to [11] above.

According to the present invention, there is provided a resin laminate that can be molded into a thermoformed article that is excellent in thermoforming at low temperatures. That is, in the resin laminate of the present invention, whitening and cracking during thermoforming are suppressed, and a molded product having a good appearance can be obtained.
The resin laminate can be used as a transparent substrate material or a transparent protective material. Specifically, portable display devices such as mobile phone terminals, portable electronic play equipment, personal digital assistants, and mobile PCs, as well as installed display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs, etc. For example, it can be suitably used as a front plate to protect these devices.

Hereinafter, the present invention will be explained in detail by illustrating manufacturing examples, examples, etc., but the present invention is not limited to the illustrated manufacturing examples, examples, etc., and within a range that does not significantly deviate from the content of the present invention. If so, you can change it to any method you like.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a polycarbonate resin (A) containing polycarbonate resin as a main component. Here, "containing polycarbonate resin as a main component" means that the content of polycarbonate resin exceeds 50% by mass. The polycarbonate resin (A) preferably contains 75% by mass or more of polycarbonate resin, more preferably contains 90% by mass or more of polycarbonate resin, and even more preferably consists essentially of polycarbonate resin. . The polycarbonate resin (A) contains carbonate ester bonds in its molecular main chain. That is, -[O-R-OCO]- units (wherein R is an aliphatic group, an aromatic group, or contains both an aliphatic group and an aromatic group, and also has a linear structure or a branched structure) Although there are no particular limitations as long as the polycarbonate contains a structural unit represented by the following formula (2), it is particularly preferable to use a polycarbonate containing a structural unit represented by the following formula (2). By using such a polycarbonate, a resin laminate with excellent impact resistance can be obtained.
Specifically, as the polycarbonate resin (A), aromatic polycarbonate resins (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, commercially available from Mitsubishi Engineering Plastics Corporation), etc. are used. It is possible.
The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 115°C or more and 170°C or less, more preferably 120°C or more and 165°C or less, particularly preferably 120°C or more and 160°C or less.
In recent years, there has been an increasing demand for bending the front panel, so polycarbonate resin (A) is synthesized using monohydric phenol represented by the following general formula (3) as a terminal capping agent. is preferred.
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms,
R ₂ to R ₅ each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have a substituent; It is an alkyl group having 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. )

The monohydric phenol of general formula (3) is more preferably a monohydric phenol represented by the following general formula (4).
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)

It is more preferable that the number of carbon atoms in R ₁ in general formula (3) or general formula (4) is within a specific numerical range. Specifically, the upper limit of the number of carbon atoms in R ₁ is preferably 36, more preferably 22, and particularly preferably 18. Furthermore, the lower limit of the number of carbon atoms in R ₁ is preferably 8, and more preferably 12.

Among monohydric phenols (terminal capping agents) represented by general formula (3) or general formula (4), either or both of para-hydroxybenzoic acid hexadecyl ester and para-hydroxybenzoic acid 2-hexyldecyl ester is terminal-terminated. Particular preference is given to using it as an agent.

For example, when a monohydric phenol (terminal stopper) having an alkyl group having 16 carbon atoms is used as R ₁ in the general formula (3) or the general formula (4), the glass transition temperature, melt fluidity, moldability, It has excellent drawdown resistance and solubility of monohydric phenol in solvents during the production of polycarbonate resin, and is particularly preferred as a terminal capping agent for use in the polycarbonate resin used in the present invention.

On the other hand, if the number of carbon atoms in R ₁ in general formula (3) or general formula (4) increases too much, the solubility of monohydric phenol (terminal stopper) in organic solvents tends to decrease, and Productivity may decrease.
For example, if the number of carbon atoms in R ₁ is 36 or less, productivity is high and economical efficiency is also good in producing polycarbonate resin. When the number of carbon atoms in R ₁ is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity can be extremely high in producing polycarbonate resin, and the economic efficiency can also be improved.
If the number of carbon atoms in R ₁ in general formula (3) or general formula (4) is too small, the glass transition temperature of the polycarbonate resin will not be a sufficiently low value, and thermoformability may deteriorate.

Other resins included in the polycarbonate resin (A) include polyester resins. The polyester resin only needs to contain terephthalic acid as a main component as a dicarboxylic acid component, and may contain dicarboxylic acid components other than terephthalic acid. For example, it is formed by polycondensation of a glycol component containing 20 to 40 (mole ratio, total 100) of 1,4-cyclohexanedimethanol to 80 to 60 (mole ratio) of ethylene glycol as the main component and a dicarboxylic acid component. Polyester resin, so-called "PETG" is preferred. Further, the polycarbonate resin (A) may include a polyester carbonate resin having an ester bond and a carbonate bond in the polymer skeleton.

In the present invention, the weight average molecular weight of the polycarbonate resin (A) influences the impact resistance and molding conditions of the resin laminate. That is, if the weight average molecular weight is too small, the impact resistance of the resin laminate will decrease, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating layers containing the polycarbonate resin (A), which is not preferable. Moreover, since high temperatures are required depending on the molding method, the polycarbonate resin (A) is exposed to high temperatures, which may have an adverse effect on its thermal stability. The weight average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.

<Method for measuring weight average molecular weight of polycarbonate resin (A)>
The weight average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP-A No. 2007-179018. Details of the measurement method are shown below.

After performing measurements using polystyrene (PS) as a standard polymer, the relationship between the elution time and the molecular weight of polycarbonate (PC) is determined by a universal calibration method and used as a calibration curve. Then, the PC elution curve (chromatogram) is measured under the same conditions as the calibration curve, and each average molecular weight is determined from the elution time (molecular weight) and the peak area (number of molecules) at that elution time. When the number of molecules of molecular weight Mi is set to Ni, the weight average molecular weight is expressed as follows. The following conversion formula was used.
(Weight average molecular weight)
Mw=Σ(NiMi ² )/Σ(NiMi)
(conversion formula)
MPC=0.47822MPS ^1.01470
Note that MPC indicates the molecular weight of PC, and MPS indicates the molecular weight of PS.

The glass transition temperature of the polycarbonate resin (A) used in the present invention was measured using a differential scanning calorimeter at a heating rate of 10°C/min, and was calculated from the intersection of the baseline and the tangent at the inflection point. This is the temperature at that time.

The melt flow rate of the polycarbonate resin (A) is preferably in the range of 1 to 30 g/10 minutes, more preferably in the range of 4 to 10 g/10 minutes, and more preferably in the range of 5 to 8 g/10 minutes. It is even more preferable. When the melt flow rate is in the range of 1 to 30 g/10 minutes, the stability of hot melt molding is good. Note that the melt flow rate of the polycarbonate resin (A) in this specification is measured using a melt indexer at a temperature of 300° C. and under a load of 1.2 kg.

The method for producing the polycarbonate resin (A) used in the present invention can be appropriately selected depending on the monomers used, such as the known phosgene method (interfacial polymerization method) or transesterification method (melt method).

<Thermoplastic resin (B)>
The thermoplastic resin (B) used in the present invention contains a methacrylic resin (C), but may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Preferred examples of other thermoplastic resins include polymethyl methacrylate, a copolymer of methyl methacrylate and methyl acrylate, and a copolymer of methyl methacrylate and styrene. The proportion of the methacrylic resin (C) in the entire thermoplastic resin (B) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 98 to 100% by mass, Particularly preferred is 100% by mass.
Each component contained in the methacrylic resin (C) will be explained below.

<Methacrylic resin (C)>
The methacrylic resin (C) contained in the thermoplastic resin (B) according to the present invention contains a methacrylic acid ester monomer unit (c1), an N-alkylmaleimide monomer unit (c2), and an N-arylmaleimide monomer unit. (c3), and the total proportion of the methacrylic acid ester monomer unit (c1), the N-alkylmaleimide monomer unit (c2), and the N-arylmaleimide monomer unit (c3) is The amount is 80 to 100% by mass, preferably 90 to 100% by mass, and more preferably 98 to 100% by mass based on the total of all monomer units in the methacrylic resin (C).
That is, the methacrylic resin (C) contains methacrylic acid ester monomer units (c1) and N-alkylmaleimide monomer units (c2) within a range of 20% by mass or less based on the total of all monomer units. , and a monomer unit other than the N-arylmaleimide monomer unit (c3). Examples of monomer units other than the above (c1), (c2) and (c3) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. Preferable examples include aromatic vinyl monomers such as , and cyclic acid anhydride monomer units such as acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
On the other hand, it is also preferable that the methacrylic resin (C) used in the present invention is a copolymer consisting only of the above (c1), (c2) and (c3).

The methacrylic acid ester monomer (c1) of the methacrylic resin (C) includes methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert methacrylate. - Methacrylic acid alkyl esters such as butyl, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, Cycloalkyl methacrylates such as cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate; aryl methacrylates such as phenyl methacrylate; benzyl methacrylate From the viewpoint of availability, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-methacrylate are listed. Butyl is preferred, and methyl methacrylate is most preferred. Two or more types of copolymerizable methacrylic acid ester monomer units may be used in combination.

Examples of the N-alkylmaleimide monomer (c2) of the methacrylic resin (C) include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of availability, N-cyclohexylmaleimide is preferred. Two or more types of copolymerizable N-alkylmaleimide monomer units may be used in combination.

The N-arylmaleimide monomer (c3) of the methacrylic resin (C) includes N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2, Examples include 6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide, and N-chlorophenylmaleimide, and from the viewpoint of availability. , N-phenylmaleimide are preferred. Two or more types of copolymerizable N-arylmaleimide monomer units may be used in combination.

The proportion of the methacrylic acid ester monomer unit (c1) is 50 to 96% by mass based on the total of (c1), (c2) and (c3) in the methacrylic resin (C), preferably It is 70 to 93% by mass, more preferably 80 to 90% by mass. The proportion of the N-alkylmaleimide monomer unit (c2) is 2 to 25% by mass, preferably 5 to 15% by mass, based on the total of (c1), (c2) and (c3). , more preferably 5 to 10% by mass. The proportion of the N-arylmaleimide monomer unit (c3) is 2 to 25% by mass, preferably 5 to 15% by mass, based on the total of (c1), (c2) and (c3). , more preferably 5 to 10% by mass.
If the ratio of the methacrylic acid ester monomer unit (c1) to the total of (c1), (c2) and (c3) is other than 50 to 96% by mass, the hardness such as pencil hardness will be insufficient. . Furthermore, if the ratio of the N-alkylmaleimide monomer unit (c2) to the total of (c1), (c2) and (c3) is less than 2% by mass, the heat resistance will be insufficient, and the N-alkylmaleimide monomer unit (c2) will have insufficient heat resistance. - If the proportion of the alkylmaleimide monomer unit (c2) is greater than 25% by mass, moldability is poor. Furthermore, if the ratio of the N-arylmaleimide monomer (c3) to the total of (c1), (c2) and (c3) is less than 2% by mass, the heat resistance will be insufficient and the N- When the proportion of the arylmaleimide monomer (c3) is greater than 25% by mass, moldability is poor.

The weight average molecular weight of the methacrylic resin (C) is determined by the ease of manufacturing the thermoplastic resin (B). That is, if the weight average molecular weight of the methacrylic resin (C) is too large, a problem may occur that stable melt-kneading cannot be continued. On the other hand, if the weight average molecular weight of the methacrylic resin (C) is too small, the strength of the thermoplastic resin (B) will decrease, which may cause problems such as a decrease in the impact resistance of the resin laminate. The weight average molecular weight of the methacrylic resin (C) is preferably in the range of 5,000 to 700,000, more preferably in the range of 50,000 to 500,000. More preferably, it is in the range of 70,000 to 200,000. The above weight average molecular weight is a standard polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The glass transition temperature of the methacrylic resin (C) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Since the glass transition temperature is 110° C. or higher, the laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment. In addition, the glass transition temperature of the methacrylic resin (C) in this specification is measured using a differential scanning calorimeter at a heating rate of 10 ° C./min, and calculated from the intersection of the baseline and the tangent at the inflection point. This is the temperature at that time.

The melt flow rate of the methacrylic resin (C) is preferably in the range of 1 to 10 g/10 minutes. The lower limit of the melt flow rate is more preferably 1.2 g/10 minutes or more, and even more preferably 1.5 g/10 minutes or more. Further, the upper limit value of the melt flow rate is more preferably 7.0 g/10 minutes or less, and even more preferably 4.0 g/10 minutes or less. When the melt flow rate is in the range of 1 to 10 g/10 minutes, the stability of hot melt molding is good.

The method for producing the methacrylic resin (C) is not particularly limited, but can be appropriately selected from known solution polymerization methods, bulk polymerization methods, suspension polymerization methods, and the like.

The glass transition temperature of the thermoplastic resin (B) used in the present invention is relatively high and there is little difference from the glass transition temperature of the polycarbonate resin (A). Even if it approaches the glass transition temperature of (A), there is an advantage that there is less problem of poor appearance in the layer containing the thermoplastic resin (B). The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 30°C, more preferably in the range of 0 to 20°C. .

<Hard coat layer>
Further layers may be present between the hard coat layer according to the invention and the layer containing thermoplastic resin (B), but preferably the hard coat layer is on the surface or both sides of the layer containing thermoplastic resin (B). Laminated on. The hard coat layer is preferably an acrylic hard coat. As used herein, the term "acrylic hard coat" refers to a coating film in which a crosslinked structure is formed by polymerizing monomers, oligomers, or prepolymers containing (meth)acryloyl groups as polymerizable groups. The composition of the acrylic hard coat preferably contains 2 to 98% by mass of a (meth)acrylic monomer, 2 to 98% by mass of a (meth)acrylic oligomer, and 0 to 15% by mass of a surface modifier, and further, It is preferable that 0.001 to 7 parts by mass of a photopolymerization initiator be contained per 100 parts by mass of the total of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier.

The hard coat layer more preferably contains 5 to 50% by mass of a (meth)acrylic monomer, 50 to 95% by mass of a (meth)acrylic oligomer, and 1 to 10% by mass of a surface modifier, particularly preferably , 20 to 40% by mass of a (meth)acrylic monomer, 60 to 80% by mass of a (meth)acrylic oligomer, and 2 to 5% by mass of a surface modifier.
The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier, Particularly preferred is 0.1 to 3 parts by mass.

As the (meth)acrylic monomer, any one having a (meth)acryloyl group as a functional group in the molecule can be used, and may be a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher functional monomer.
Examples of monofunctional monomers include (meth)acrylic acid and (meth)acrylic acid esters, and specific examples of difunctional and/or trifunctional or higher (meth)acrylic monomers include diethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate. Propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxy Neopentyl glycol pivalate diacrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene glycol Diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane propoxy Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerylpropoxytri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, etc. can be exemplified.
The hard coat layer may contain one or more types of (meth)acrylic monomers.

Examples of (meth)acrylic oligomers include polyfunctional urethane (meth)acrylate oligomers with two or more functionalities [hereinafter also referred to as polyfunctional urethane (meth)acrylate oligomers], and polyfunctional polyester (meth)acrylate oligomers with two or more functionalities [hereinafter also referred to as polyfunctional urethane (meth)acrylate oligomers]. , polyfunctional polyester (meth)acrylate oligomer], polyfunctional epoxy (meth)acrylate oligomer having two or more functionalities (hereinafter also referred to as polyfunctional epoxy (meth)acrylate oligomer), and the like. The hard coat layer may contain one or more types of (meth)acrylic oligomers.
Polyfunctional urethane (meth)acrylate oligomers include urethanization reaction products of polyisocyanates and (meth)acrylate monomers having at least one (meth)acryloyloxy group and hydroxyl group in one molecule; Examples include urethane reaction products of isocyanate compounds obtained by reacting with (meth)acrylate monomers having at least one (meth)acryloyloxy group and hydroxyl group in one molecule.

Examples of (meth)acrylate monomers having at least one (meth)acryloyloxy group and hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta (Meth)acrylates are mentioned.

Polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates. (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, or polyisocyanates obtained by polymerizing diisocyanates. can be mentioned.

As polyols used in the urethanization reaction, aromatic, aliphatic, and alicyclic polyols, as well as polyester polyols, polyether polyols, and the like are generally used. Aliphatic and cycloaliphatic polyols typically include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, Examples include methylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, and the like.

Examples of polyester polyols include those obtained by a dehydration condensation reaction between the above-mentioned polyols and polycarboxylic acids. Specific examples of polycarboxylic acids include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. In addition to polyalkylene glycols, examples of polyether polyols include polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxide.

Moreover, a polyfunctional polyester (meth)acrylate oligomer is obtained by a dehydration condensation reaction using (meth)acrylic acid, polycarboxylic acid, and polyol. Examples of the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. Polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylol Examples include butyrionic acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

A polyfunctional epoxy (meth)acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth)acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

The surface modifier used in the present invention is one that changes the surface performance of the hard coat layer, such as a leveling agent, an antistatic agent, a surfactant, a water and oil repellent, inorganic particles, and organic particles.
Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, and silicone-modified acrylic.

Examples of the antistatic agent include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactants, anionic surfactants, and the like.
Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.
Examples of the organic particles include acrylic particles and silicon particles.
Examples of surfactants and water/oil repellents include fluorine-containing surfactants such as oligomers containing fluorine-containing groups and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups. and water and oil repellents.

The hard coat layer may contain a photopolymerization initiator. In this specification, a photopolymerization initiator refers to a photoradical generator.

Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocur 2959: manufactured by Merck & Co., Ltd.]; α-hydroxy -α,α'-dimethylacetophenone [Darocur 1173: manufactured by Merck & Co., Ltd.]; Acetophenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], and 1-hydroxy-cyclohexylphenyl ketone benzoin ether initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, acyl phosphonates, and the like.

Although the method for forming the hard coat layer is not particularly limited, it can be formed, for example, by applying a hard coat liquid onto a layer located below the hard coat layer and then photopolymerizing it.

The method of applying the hard coat liquid (polymerizable composition) is not particularly limited, and any known method can be used. Examples include spin coat method, dip method, spray method, slide coat method, bar coat method, roll coat method, gravure coat method, meniscus coat method, flexographic printing method, screen printing method, beat coat method, and separation method. .

Lamps used for light irradiation in photopolymerization are those that have an emission distribution at a light wavelength of 420 nm or less, examples of which include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, and black light lamps. , microwave-excited mercury lamps, metal halide lamps, etc. Among these, high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator, and emit short wavelength light that reduces the viscoelastic properties of the resulting polymer through crosslinking, or heats the reaction composition. This is preferable because it does not emit a large amount of long-wavelength light that would cause evaporation.

The irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled depending on the performance of the target product. When a common cleavage type initiator having an acetophenone group is blended, the illumination intensity is preferably in the range of 0.1 to 300 mW/cm ² . In particular, it is preferable to use a metal halide lamp and set the illumination intensity to 10 to 40 mW/cm ² .

The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable that the light irradiation be performed using a method that can eliminate the reaction inhibition caused by oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen, and then irradiate the reactive composition with light through the film. Alternatively, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is always introduced in order to maintain the atmospheric oxygen concentration at a low level. The introduction of this inert gas generates an air current on the surface of the reactive composition, causing monomer evaporation. In order to suppress the level of monomer evaporation, the air flow velocity of the inert gas is preferably 1 m/sec or less relative to the laminate coated with the hard coat liquid moving in the inert gas atmosphere, More preferably, it is 0.1 m/sec or less. By setting the airflow velocity within the above range, monomer evaporation due to the airflow can be substantially suppressed.

In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated. Examples of treatments include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.

The hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet light (254 nm) using a metal halide lamp with an irradiation output of 20 mW/cm ² .

The thickness of the hard coat layer is preferably 1 μm or more and 40 μm or less, more preferably 2 μm or more and 10 μm or less. Sufficient hardness can be obtained by having a film thickness of 1 μm or more. Furthermore, by having a film thickness of 40 μm or less, it is possible to suppress the occurrence of cracks during bending. The thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.

<Resin laminate>
In the present invention, the thickness of the layer containing the thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. That is, if the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness will be low, which is not preferable. If the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance will deteriorate, which is not preferable. The thickness of the layer containing the thermoplastic resin (B) is preferably 10 to 250 μm, more preferably 20 to 200 μm. More preferably, it is 30 to 150 μm.

In the present invention, molding is difficult if the total thickness of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer is too thin or too thick. The total thickness of the resin laminate is preferably 0.1 to 4.0 mm, more preferably 0.5 to 3.5 mm, and still more preferably 0.5 to 3.0 mm.

The resin laminate of the present invention can be subjected to one or more of anti-fingerprint treatment, antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and antiglare treatment on one or both sides thereof. Methods for antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and antiglare treatment are not particularly limited, and known methods can be used. Examples include a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like.

<Optional additives>
In the present invention, the polycarbonate resin (A) forming the base layer and/or the thermoplastic resin (B) forming the surface layer may contain components other than the above-mentioned main components.

For example, an ultraviolet absorber can be mixed with the polycarbonate resin (A) and/or the thermoplastic resin (B). In the present invention, the hard coat layer may contain an ultraviolet absorber. If the content of the ultraviolet absorber is too large, depending on the molding method, the excess ultraviolet absorber may scatter due to high temperatures and contaminate the molding environment, causing problems. From this, the content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2-hydroxybenzophenone. -4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc. Benzophenone UV absorber, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3 Benzotriazole UV absorbers such as -t-butyl-5-methylphenyl)benzotriazole, (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, salicylic acid Benzoate UV absorbers such as phenyl, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis(2,2,6,6-tetramethylpiperidine-4 Hindered amine UV absorbers such as -yl) sebacate, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2- Hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2- hydroxy-4-butoxyphenyl)1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2, 4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3, Triazine UV absorbers such as 5-triazine, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2- (6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl) -2H-benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]propyl acrylate, 4-[ 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl) yl)-2H-benzotriazol-5-yl]butyl acrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl methacrylate, 2 -[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3] ]Dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H -benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propa Noyloxy]butyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]butyl acrylate, 2-[ 3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxy Benzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 2-(methacryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxole- 5-yl)-2H-benzotriazole-5-carboxylate, 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(acryloyloxy)butyl 2-(6-hydroxybenzo Examples include sesamol type benzotriazole ultraviolet absorbers such as [1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate. The mixing method is not particularly limited, and methods such as total compounding, dry blending of a masterbatch, and total dry blending can be used.

In the present invention, the polycarbonate resin (A) forming the base layer and/or the thermoplastic resin (B) forming the surface layer may contain various additives in addition to the above-mentioned ultraviolet absorbers. I can do it. Examples of such additives include antioxidants, anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, and Examples include reinforcing materials such as inorganic fillers. The method of mixing is not particularly limited, and methods such as a method of total compounding, a method of dry blending a masterbatch, a method of total dry blending, etc. can be used.

In the present invention, each material of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer, such as the polycarbonate resin (A) and the thermoplastic resin (B), is subjected to filter treatment. It is preferable to purify by filtration. By passing the resin through a filter or laminating it, it is possible to obtain a resin laminate with less appearance defects such as foreign matter and defects. There are no particular restrictions on the filtration method, and melt filtration, solution filtration, or a combination thereof can be used.

There are no particular restrictions on the filter to be used, and any known filter can be used, and is appropriately selected depending on the operating temperature, viscosity, and filtration accuracy of each material. Filter media include, but are not limited to, polypropylene, cotton, polyester, viscose rayon, glass fiber nonwoven fabrics or roving yarn rolls, phenolic resin-impregnated cellulose, metal fiber nonwoven sintered bodies, metal powder sintered bodies, breaker plates, Alternatively, any combination of these can be used. In particular, in consideration of heat resistance, durability, and pressure resistance, a type made of sintered metal fiber nonwoven fabric is preferable.

The filtration accuracy is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less for the polycarbonate resin (A) and thermoplastic resin (B). Furthermore, since the hard coating agent is applied to the outermost layer of the resin laminate, the filtration accuracy of the hard coating agent is 20 μm or less, preferably 10 μm or less, and more preferably 2 μm or less.

Regarding the filtration of the polycarbonate resin (A) and the thermoplastic resin (B), it is preferable to use, for example, a polymer filter used for thermoplastic resin melt filtration. Polymer filters are classified into leaf disc filters, candle filters, pack disc filters, cylindrical filters, etc. depending on their structure, and leaf disc filters with a large effective filtration area are particularly suitable.

<Heat bending process>
The heat bending process of the resin laminate of the present invention is not particularly limited. For example, "hot press molding" involves attaching a convex (male) and a concave (female) mold to a press machine and sandwiching a heat-softened laminated sheet between the two molds; "Vacuum forming" is a process in which the laminated sheet is brought into close contact with the mold by applying a vacuum to the (male) mold, and finished into the desired shape. There is ``pressure forming,'' which applies a large amount of pressure to make the laminated sheet adhere to the mold and form it into the desired shape.

<Thermoformed body>
A resin laminate having a layer containing a thermoplastic resin on a layer containing a polycarbonate resin and a hard coat layer on the surface of the layer containing the thermoplastic resin is hot press molded at a low temperature of 120 ° C. to 130 ° C. If this is done, cracks may occur in the bent portion of the resin laminate.

On the other hand, since the resin laminate of the embodiment of the present invention uses a specific thermoplastic resin (B), when heat bending is performed at a low temperature (for example, 120 to 130°C), the resin laminate cannot be bent. It is possible to obtain a thermoformed article with excellent design properties at low temperatures without cracks occurring in the parts.

<Application>
The molded product (for example, thermoformed product) of the embodiment is a molded product that includes the resin laminate of the present invention including the various preferred forms and configurations described above. There are no restrictions on the shape, pattern, color, size, etc. of the molded product, and they may be arbitrarily set depending on the intended use.
The resin laminate and thermoformed product of the embodiments have excellent thermoformability at low temperatures (for example, 120 to 130° C.). Therefore, it is suitably used as a transparent substrate material, a transparent protective material, etc. Specifically, these include portable display devices such as mobile phone terminals, portable electronic play equipment, personal digital assistants, and mobile PCs, as well as stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD televisions. It can be used as a transparent substrate material and a transparent protective material (e.g., front plate), such as touch panel front protective plates that require high design quality, front panels for car navigation systems, OA equipment, or portable electronic devices. Suitable for use as a face plate.

Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited to these Examples.

<Glass transition temperature>
A differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Co., Ltd. was used. Under nitrogen flow of 30ml/min., 10°C/min. The temperature was raised from 30°C to 200°C at 50°C/min. The temperature was lowered from 200°C to 30°C, and then again at 10°C/min. The temperature was raised from 30°C to 200°C. The intersection of the baseline and the tangent at the inflection point in the second heating was used as the glass transition temperature.

<Total light transmittance>
The total light transmittance of the resin laminate was measured according to JIS K7361-1 using a reflection/transmittance meter model HR-100 (manufactured by Murakami Color Research Institute Co., Ltd.).

<Haze>
The haze of the resin laminate was measured according to JIS K7136 using a reflection/transmittance meter model HR-100 (manufactured by Murakami Color Research Institute Co., Ltd.).

<Pencil hardness>
In accordance with JIS K 5600-5-4, the hardness is gradually increased to the surface under a load of 750 g at an angle of 45 degrees to the surface of the hard coat layer on the layer containing thermoplastic resin (B) near the center of the resin laminate. The hardness of the hardest pencil that did not cause any scars was evaluated as the pencil hardness.

<Hot press moldability>
A convex (male) mold and a concave (female) mold in which a 1 mm thick resin laminate is bent to a radius of 50 mm were prepared. Before molding, the resin laminate is preheated at 90°C for 1 minute, placed in a mold so that the hard coat surface is convex, pressed for 3 minutes at a mold temperature of 120°C, and allowed to cool naturally. A press molded body was produced.

<Crack on bent part>
Cracks in the bent portions of the hot press molded bodies were visually evaluated. Pass/fail judgment was made for cracks in the bent portion according to the following criteria, and 〇 was considered to be a pass.
○: No cracks are visible in the bent part of the hot press molded product ×: Cracks are visible in the bent part of the hot press molded product

For the examples, the materials shown below were used as polycarbonate resin (A-1), thermoplastic resin (B-1), methacrylic resin (C-1), and hard coat (D-1). It is not limited to these. On the other hand, for comparative examples, thermoplastic resins (E-1) to (E-2) and methacrylic resins (F-1) to (F-2) shown below were used, respectively.

<Polycarbonate resin (A-1), methacrylic resin (C-1), methacrylic resin (F-1) to (F-2)>
Polycarbonate resin (A-1): Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (glass transition temperature: 147°C)
Methacrylic resin (C-1): Delpet SK540N manufactured by Asahi Kasei Corporation (glass transition temperature: 125°C, methyl methacrylate/N-cyclohexylmaleimide/N-phenylmaleimide = 85.2% by mass/6.6% by mass/8 .2% by mass)
Methacrylic resin (F-1): Delpet SK420N manufactured by Asahi Kasei Corporation (glass transition temperature: 118°C, methyl methacrylate/N-cyclohexylmaleimide = 94.9% by mass/5.1% by mass)
Methacrylic resin (F-2): Delpet SK430N manufactured by Asahi Kasei Corporation (glass transition temperature: 118°C, methyl methacrylate/N-cyclohexylmaleimide = 92.9% by mass/7.1% by mass)

Production Example 1A [Preparation of pellets of thermoplastic resin (B-1)]
For 100 parts by mass of methacrylic resin (C-1), 500 ppm of phosphorus additive PEP-36 (manufactured by ADEKA Co., Ltd.) and 0.0 ppm of stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.). 2 parts by mass were added and melt-mixed at a cylinder temperature of 240°C using a twin-screw extruder with a screw diameter of 26mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L/D≒40) equipped with a polymer filter with an opening of 10μm. It was milled, extruded into strands, and pelletized using a pelletizer. Pellets of thermoplastic resin (B-1) could be stably produced.

Comparative Production Example 1A [Preparation of pellets of thermoplastic resin (E-1)]
To 100 parts by mass of methacrylic resin (F-1), 500 ppm of phosphorus additive PEP-36 and 0.2 parts by mass of stearic acid monoglyceride were added, and mixed and pelletized in the same manner as in Production Example 1A. Pellets of thermoplastic resin (E-1) could be stably produced.

Comparative Production Example 2A [Preparation of pellets of thermoplastic resin (E-2)]
To 100 parts by mass of methacrylic resin (F-2), 500 ppm of phosphorus additive PEP-36 and 0.2 parts by mass of stearic acid monoglyceride were added, and mixed and pelletized in the same manner as in Production Example 1A. Pellets of thermoplastic resin (E-2) could be stably produced.

Example 1 [Manufacture of resin laminate (G-1)]
A multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die with a width of 650 mm connected to the feed block. A resin laminate was molded using a multilayer extrusion device having a multi-manifold die connected to an extruder. The thermoplastic resin (B-1) obtained in Production Example 1A was continuously introduced into a single-screw extruder with a shaft diameter of 32 mm, and extruded at a cylinder temperature of 240° C. and a discharge rate of 2.0 kg/h. Further, polycarbonate resin (A-1) was continuously introduced into a single-screw extruder with a shaft diameter of 65 mm, and extruded at a cylinder temperature of 280° C. and a discharge rate of 31.8 kg/h. A feed block connected to the entire extruder was equipped with distribution pins of two types and two layers, and the thermoplastic resin (B-1) and polycarbonate resin (A-1) were introduced and laminated at a temperature of 270°C.
It is extruded into a sheet using a T-die connected to the end at a temperature of 270°C, and then cooled while transferring the mirror surface using three mirror-finishing rolls at temperatures of 130°C, 140°C, and 180°C from the upstream side. A resin laminate of (B-1) and polycarbonate resin (A-1) was obtained. The overall thickness of the central portion of the resulting resin laminate (G-1) was 1000 μm, and the thickness of the surface layer (layer containing thermoplastic resin (B-1)) was 60 μm. Thereafter, 60 parts by mass of hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) and PEG200# diacrylate (product name: : 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 35 parts by mass, and oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, and a UV-reactive group (product name: RS-90, manufactured by DIC Corporation) 5 parts by mass Using a bar coater, add 1 part by mass of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-cyclohexylphenyl ketone] manufactured by BASF Corporation) to a total of 100 parts by mass. The hard coat was cured by applying a metal halide lamp (20 mW/cm ² ) for 5 seconds to produce a resin laminate (G-1). The thickness of the hard coat layer (D-1) was 6 μm.
This resin laminate (G-1) had a total light transmittance of 91.3%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: 0.

Example 2 [Manufacture of resin laminate (G-2)]
The resin laminate of Example 1 (G A resin laminate (G-2) of a hard coat layer (D-1), a thermoplastic resin (B-1) and a polycarbonate resin (A-1) was obtained in the same manner as in -1). The overall thickness of the central part of the obtained resin laminate (G-2) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (B-1)) was 100 μm, and the thickness of the hard coat layer (D-1). was 6 μm.
This resin laminate (G-2) had a total light transmittance of 91.4%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: 0.

Example 3 [Manufacture of resin laminate (G-3)]
The output rate of a single screw extruder with a shaft diameter of 32 mm was changed to 3.9 kg/h, and the output rate of a single screw extruder with a shaft diameter of 65 mm was changed to 28.1 kg/h. The resin laminate of Example 1 (G In the same manner as in -1), a resin laminate (G-3) of a hard coat layer (D-1), a thermoplastic resin (B-1) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (G-3) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (B-1)) was 60 μm and 60 μm, and the thickness of the hard coat layer (D-1) was 1006 μm. The film thickness was 6 μm. This resin laminate (G-3) had a total light transmittance of 91.4%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: 0.

Comparative Example 1 [Manufacture of resin laminate (H-1)]
A hard coat layer (D-1), A resin laminate (H-1) of a thermoplastic resin (E-1) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-1) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-1)) was 60 μm, and the thickness of the hard coat layer (D-1). was 6 μm. This resin laminate (H-1) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: x.

Comparative Example 2 [Manufacture of resin laminate (H-2)]
A hard coat layer (D-1), A resin laminate (H-2) of a thermoplastic resin (E-1) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-2) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-1)) was 100 μm, and the thickness of the hard coat layer (D-1). was 6 μm. This resin laminate (H-2) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 5H, and a crack in the bent portion during hot press molding: x.

Comparative Example 3 [Manufacture of resin laminate (H-3)]
A hard coat layer (D-1), A resin laminate (H-3) of a thermoplastic resin (E-1) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-3) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-1)) was 60 μm and 60 μm, and the thickness of the hard coat layer (D-1) was 1006 μm. The film thickness was 6 μm. This resin laminate (H-3) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: x.

Comparative Example 4 [Manufacture of resin laminate (H-4)]
A hard coat layer (D-1), A resin laminate (H-4) of a thermoplastic resin (E-2) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-4) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-2)) was 60 μm, and the thickness of the hard coat layer (D-1). was 6 μm. This resin laminate (H-4) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: x.

Comparative Example 5 [Manufacture of resin laminate (H-5)]
A hard coat layer (D-1), A resin laminate (H-5) of a thermoplastic resin (E-2) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-5) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-2)) was 100 μm, and the thickness of the hard coat layer (D-1). was 6 μm. This resin laminate (H-5) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: x.

Comparative Example 6 [Manufacture of resin laminate (H-6)]
A hard coat layer (D-1), A resin laminate (H-6) of a thermoplastic resin (E-2) and a polycarbonate resin (A-1) was obtained. The overall thickness of the central part of the obtained resin laminate (H-6) was 1006 μm, the thickness of the surface layer (layer containing thermoplastic resin (E-2)) was 60 μm and 60 μm, and the thickness of the hard coat layer (D-1) was 1006 μm. The film thickness was 6 μm. This resin laminate (H-6) had a total light transmittance of 91.5%, a haze of 0.2%, a pencil hardness of 4H, and a crack in the bent portion during hot press molding: x.

As described above, by satisfying the conditions of the present invention, it is possible to obtain a resin laminate having excellent thermoformability at low temperatures.

That is, Examples 1 to 3 in which a thermoplastic resin (B) obtained by pelletizing a specific methacrylic resin (C) and a polycarbonate resin (A) are laminated, and a hard coat is provided on one surface of the thermoplastic resin (B). A thermoplastic resin (E) made by pelletizing a methacrylic resin (F) other than the specific methacrylic resin (C) and a polycarbonate resin (A) are laminated, and a hard coat is applied to one surface of the thermoplastic resin (E). When compared with Comparative Examples 1 to 6 having the following properties, the resin laminates of Examples 1 to 3 suppressed cracking at the bent portion during hot press molding.

Claims (12)

A resin having a layer containing a thermoplastic resin (B) on at least one surface of the layer containing the polycarbonate resin (A), and a hard coat layer on at least one surface of the layer containing the thermoplastic resin (B). A laminate,
The thermoplastic resin (B) contains a methacrylic resin (C),
A copolymer in which the methacrylic resin (C) contains a methacrylic acid ester monomer unit (c1), an N-alkylmaleimide monomer unit (c2), and an N-arylmaleimide monomer unit (c3). and
The total of (c1), (c2) and (c3) is 80 to 100% by mass based on the total of all monomer units in the methacrylic resin (C),
The proportion of the above (c1) is 80 to 90 % by mass with respect to the total of the above (c1), (c2) and (c3),
The proportion of the above (c2) is 5 to 10 % by mass with respect to the total of the above (c1), (c2) and (c3),
The proportion of the above (c3) is 5 to 10 % by mass with respect to the total of the above (c1), (c2) and (c3) ,
The N-alkylmaleimide monomer unit (c2) contained in the methacrylic resin (C) is N-cyclohexylmaleimide,
The N-arylmaleimide monomer unit (c3) contained in the methacrylic resin (C) is N-phenylmaleimide,
The resin laminate, wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 30°C . The resin laminate according to claim 1, wherein no cracks occur after thermoforming to a radius of 50 mm with a heat press machine. The resin laminate according to claim 1 or 2 , wherein the thermoplastic resin (B) is a polymer alloy of a resin that is compatible with the methacrylic resin (C). According to any one of claims 1 to 3 , wherein the layer containing the thermoplastic resin (B) has a thickness of 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.1 to 4.0 mm. resin laminate. According to any one of claims 1 to 4 , at least one of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber. Resin laminate. The resin laminate according to any one of claims 1 to 5 , wherein the hard coat layer is an acrylic hard coat. Any one of claims 1 to 6 , wherein one or both sides of the resin laminate is subjected to at least one of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, and antifouling treatment. The resin laminate described in . A thermoformed article obtained by heat bending the resin laminate according to any one of claims 1 to 7 . A transparent protective material comprising the resin laminate according to any one of claims 1 to 7 or the thermoformed article according to claim 8 . A transparent substrate material comprising the resin laminate according to any one of claims 1 to 7 or the thermoformed article according to claim 8 . A touch panel front protection plate comprising the resin laminate according to any one of claims 1 to 7 or the thermoformed body according to claim 8 . A front plate for a car navigation system, an OA device, or a portable electronic device, comprising the resin laminate according to any one of claims 1 to 7 or the thermoformed body according to claim 8 .