HK1200774B - Synthetic resin laminate - Google Patents

Description

Synthetic resin laminate

Technical Field

The present invention relates to a synthetic resin laminate, and more particularly, to a synthetic resin laminate which is used for a transparent substrate material or protective material, has a layer containing a polycarbonate resin and a resin layer containing a specific (meth) acrylate copolymer and a polycarbonate resin, and is excellent in shape stability, surface hardness, impact resistance, weather resistance and heat resistance under a high-temperature and high-humidity environment.

Background

Polycarbonate resin sheets are excellent in transparency, impact resistance and heat resistance, and are used for soundproof partitions, carports, signboards, glazing materials, lighting fixtures and the like, but have a drawback of being easily damaged due to low surface hardness, and thus their use is limited.

Patent document 1 proposes a method of coating the surface with an ultraviolet curable resin or the like to improve the above-mentioned drawbacks, and a method of applying a hard coat layer to a substrate obtained by co-extruding a polycarbonate resin and an acrylic resin.

However, if a hard coat layer is applied to the surface of the polycarbonate resin, the required pencil hardness cannot be satisfied, and the hard coat layer cannot be used in applications requiring surface hardness.

Further, in a method of applying an acrylic resin to the surface layer, since the surface hardness is improved to some extent, the use in a front panel of an information display device or the like is widened, and this method is constituted by two layers of different materials, and a large warpage is generated depending on the difference in water absorption characteristics between the acrylic resin and the polycarbonate resin or the heat resistance represented by the glass transition temperature, and thus a problem may occur in the use in which an environmental change occurs.

Patent document 2 discloses a laminate in which a resin having a low water absorption is laminated on a polycarbonate resin as a method for suppressing warpage, but the condition of high temperature and high humidity at 40 ℃/90% in an environmental test is insufficient, and it cannot be said that the required performance of low warpage is sufficiently evaluated. Further, the MS resin used in this document is considered to have low heat resistance and may cause a problem in post-processing.

Further, as a method for suppressing the warpage, there is a laminate in which acrylic resin layers are laminated on both sides of a polycarbonate resin layer, but when a surface impact is applied to one side of the laminate, cracks are likely to occur in the acrylic resin layer on the opposite side, and there are cases where problems are caused depending on the method of use.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2006-103169

Patent document 2: japanese patent laid-open publication No. 2010-167659

Disclosure of Invention

Problems to be solved by the invention

In view of the above-described circumstances, an object of the present invention is to provide a synthetic resin laminate which is used for a transparent substrate material or protective material and is excellent in shape stability, surface hardness, impact resistance, weather resistance and heat resistance under high-temperature and high-humidity environments.

Means for solving the problems

The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that a synthetic resin laminate having the above-mentioned properties can be obtained by laminating a resin layer containing a specific (meth) acrylate copolymer and a polycarbonate resin on one surface of a layer containing a polycarbonate resin to obtain a synthetic resin laminate, and have completed the present invention.

That is, the present invention provides the following synthetic resin laminate and a transparent material using the same.

< 1 > A synthetic resin laminate characterized in that it comprises a substrate layer (B) containing polycarbonate and, laminated on one or both surfaces thereof, a resin layer (A) containing 5 to 55 mass% of a (meth) acrylate copolymer (C) and 95 to 45 mass% of a polycarbonate (D),

the (meth) acrylate copolymer (C) contains an aromatic (meth) acrylate unit (C1) and a methyl methacrylate unit (C2) in a mass ratio (C1/C2) of 5 to 80/20 to 95, and the mass average molecular weight of the (meth) acrylate copolymer (C) is 5,000 to 30,000,

the mass average molecular weight of the polycarbonate (D) is 21,000 to 40,000.

< 2 > the synthetic resin laminate according to the above < 1 >, wherein the glass transition temperature of the resin layer (A) is 110 to 130 ℃.

< 3 > the synthetic resin laminate according to the above < 1 > or < 2 >, wherein the resin layer (A) has a water absorption of 0.03 to 0.28%.

< 4 > the synthetic resin laminate according to any one of the above < 1 > -to < 3 >, wherein the thickness of the resin layer (A) is 10 to 250 μm, the total thickness (X) of the synthetic resin laminate is 0.1 to 2.0mm, and the thickness ratio of (A)/(X) is 0.01 to 0.5.

< 5 > the synthetic resin laminate according to any one of the above < 1 > -4 >, wherein the base layer (B) has a mass average molecular weight of 18,000-40,000.

< 6 > the synthetic resin laminate according to any one of the above < 1 > to < 5 >, wherein the resin layer (A) and/or the substrate layer (B) contains an ultraviolet absorber.

< 7 > the synthetic resin laminate according to any one of the above < 1 > to < 6 >, wherein the resin layer (A) is subjected to a hard coat treatment.

< 8 > the synthetic resin laminate according to any one of the above < 1 > -to < 6 >, wherein a hard coat treatment is applied to the resin layer (A) and the base layer (B).

< 9 > the synthetic resin laminate according to any one of the above < 1 > to < 8 >, wherein one or both surfaces of the synthetic resin laminate are subjected to at least one of an antireflection treatment, an antifouling treatment, a fingerprint resistance treatment, an antistatic treatment, a weather resistance treatment and an antiglare treatment.

< 10 > a transparent substrate material comprising the synthetic resin laminate as defined in any one of the above < 1 > to < 9 >.

< 11 > a transparent protective material comprising the synthetic resin laminate as defined in any one of the above < 1 > to < 9 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is provided a synthetic resin laminate excellent in shape stability, surface hardness, impact resistance, weather resistance and heat resistance under high-temperature and high-humidity environments, which is useful as a transparent substrate material or a transparent protective material. Specifically, the present invention is suitably used for portable display devices such as mobile phone terminals, portable electronic entertainment devices, portable information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PCs, liquid crystal monitors, and liquid crystal televisions.

Detailed Description

The present invention will be described in detail below by way of examples of production examples and examples, but the present invention is not limited to the examples of production and examples, and can be carried out by changing to any method without largely departing from the scope of the present invention.

The synthetic resin laminate is characterized in that a resin layer (A) containing 5-55 mass% of a (meth) acrylate copolymer (C) and 95-45 mass% of a polycarbonate (D) is laminated on one or both surfaces of a substrate layer (B) containing a polycarbonate,

the (meth) acrylate copolymer (C) contains an aromatic (meth) acrylate unit (C1) and a methyl methacrylate unit (C2) in a mass ratio (C1/C2) of 5 to 80/20 to 95, and the (meth) acrylate copolymer (C) has a mass average molecular weight of 5,000 to 30,000 and the polycarbonate (D) has a mass average molecular weight of 21,000 to 40,000.

In the synthetic resin laminate of the present invention, a resin layer (a) containing a specific (meth) acrylate copolymer and polycarbonate is laminated on one or both surfaces of a substrate layer (B) containing polycarbonate, in order to increase the surface hardness of the polycarbonate resin. When a surface impact is applied to the resin layer (a) side as a hard structure by laminating the resin layer (a) only on one side, the opposite side is a base layer (B) having a soft structure, whereby the impact is relaxed and breakage due to the impact is less likely to occur. Further, by laminating the resin layer (a) having a water absorption close to that of polycarbonate, the problem of warpage occurring when resins having different water absorption are laminated can be alleviated.

Further, in the laminate in which the resin layer (a) is laminated on both surfaces of the base layer (B), since the resin layer (a) contains polycarbonate, the laminate is excellent in impact resistance, and therefore, even if a surface impact is applied to one surface of the laminate, the opposite surface is less likely to be broken by the impact. Further, since the same resin is laminated on both sides, the structure is symmetrical, and the occurrence of warpage is further suppressed, which is preferable.

The method for forming the synthetic resin laminate of the present invention is not particularly limited. Examples include: a method of laminating a resin layer (a) and a base material layer (B) which are formed separately, and heating and pressure bonding the both; a method of laminating a resin layer (a) and a base material layer (B) formed separately and bonding them with an adhesive; various methods such as a method of coextrusion molding of the resin layer (a) and the base material layer (B), and a method of in-mold molding and integrating a polycarbonate resin which is a main component of the base material layer (B) using a resin layer (a) formed in advance are used.

The polycarbonate used for the substrate layer (B) and the polycarbonate (D) used for the resin layer (a) in the present invention are not particularly limited as long as they contain a unit of- [ O-R-OCO ] -containing a carbonate bond in the main molecular chain (R is a group containing an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure).

The method for producing the polycarbonate used for the substrate layer (B) and the polycarbonate (D) used for the resin layer (a) in the present invention is known as a phosgene method (interfacial polymerization method), a transesterification method (melt method), or the like, and can be appropriately selected depending on the monomer used.

The (meth) acrylate copolymer (C) used in the present invention comprises aromatic (meth) acrylate units (C1) and methyl methacrylate units (C2). In the present invention, the term (meth) acrylate means acrylate or methacrylate.

The aromatic (meth) acrylate constituting the aromatic (meth) acrylate unit (c1) is a (meth) acrylate having an aromatic group in the ester portion. Examples of the aromatic (meth) acrylate include: phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These substances may be used in combination of 1 or 2 or more. Among them, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable. By having the aromatic (meth) acrylate unit (c1), the transparency of a molded article mixed with the aromatic polycarbonate resin can be improved.

The monomer constituting the methyl methacrylate unit (c2) is methyl methacrylate. The methyl methacrylate unit (c2) has an effect of dispersing well with the polycarbonate-based resin, and is transferred to the surface of the molded article, so that the surface hardness of the molded article can be improved.

The (meth) acrylate copolymer (C) contains 5 to 80 mass% of aromatic (meth) acrylate units (C1) and 20 to 95 mass% of methyl methacrylate units (C2) (wherein the total of (C1) and (C2) is 100 mass%). If the content of the aromatic (meth) acrylate unit (C1) in the (meth) acrylate copolymer (C) is 5% by mass or more, the transparency can be maintained in the high addition region of the (meth) acrylate copolymer (C), and if it is 80% by mass or less, the compatibility with the aromatic polycarbonate is not excessively high, and the transferability to the surface of a molded article is not lowered, so that the surface hardness is not lowered.

The mass average molecular weight of the (meth) acrylate copolymer (C) is 5,000 to 30,000, preferably 10,000 to 25,000. When the mass average molecular weight is 5,000 to 30,000, the compatibility with the aromatic polycarbonate is good, and the effect of improving the surface hardness is excellent. The mass average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the (meth) acrylate copolymer (C) can be measured by gel permeation chromatography using THF or chloroform as a solvent.

In the present invention, the method for producing the resin layer (a) is not particularly limited, and the following can be applied: a known method is, for example, a method in which the required components are mixed in advance using a mixer such as a tumbler, a henschel mixer, or a super mixer, and then melt-kneaded by a machine such as a banbury mixer, a roll, a Brabender mixer, a single-screw extruder, a twin-screw extruder, or a pressure kneader.

In the present invention, the composition ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) is: the amount of the component (D) is 95 to 45% by mass based on 5 to 55% by mass of the component (C). Preferably, the amount of the component (D) is 80 to 50% by mass based on 20 to 50% by mass of the component (C). More preferably, the amount of the component (D) is 70 to 50% by mass based on 30 to 50% by mass of the component (C). By setting the composition ratio within this range, the resin layer (a) is obtained which maintains transparency and has a balanced surface hardness and various physical properties such as impact resistance and water absorption.

In the present invention, the mass average molecular weight of the polycarbonate (D) is determined by the ease of mixing (dispersion) with the (meth) acrylate copolymer (C) and the ease of production of the resin layer (a). That is, if the mass average molecular weight of the polycarbonate (D) is too large, the difference in melt viscosity between the component (D) and the component (C) is too large, and therefore, the mixing (dispersion) of the two components is deteriorated, which may cause a problem that the transparency of the resin layer (a) is deteriorated or stable melt kneading cannot be continued. On the other hand, if the mass average molecular weight of the polycarbonate (D) is too small, the strength of the resin layer (A) is lowered, and therefore, there is a problem that the impact resistance of the synthetic resin laminate is lowered. The mass average molecular weight of the polycarbonate (D) is preferably in the range of 21,000 to 40,000. More preferably 24,000 to 38,000. More preferably, the content is in the range of 27,000 to 36,000.

In the present invention, the glass transition temperature of the resin layer (a) has an influence on the heat resistance of the synthetic resin laminate. That is, when the glass transition temperature is too low, the heat resistance of the synthetic resin laminate is undesirably lowered. When the glass transition temperature is too high, an excessive heat source may be required for laminating the resin layer (a), which is not preferable. The glass transition temperature of the resin layer (A) is preferably 110 to 130 ℃. More preferably 115 to 130 ℃. More preferably 118 to 125 ℃.

In the present invention, the water absorption of the resin layer (a) affects the amount of deformation (warpage) of the synthetic resin laminate when exposed to high temperature and high humidity. That is, when the water absorption is too high, the deformation (g) becomes large, which is not preferable. When the water absorption rate is too low, the magnitude relationship of the water absorption rate of the base material layer (B) is reversed, and therefore, the deformation amount (h) in the opposite direction to the deformation may occur, which is not preferable. The resin layer (A) preferably has a water absorption of 0.03 to 0.28%. More preferably 0.05 to 0.2%. More preferably 0.1 to 0.17%.

In the present invention, the thickness of the resin layer (a) has an influence on the surface hardness and impact resistance of the synthetic resin laminate. That is, when the thickness of the resin layer (a) is too thin, the surface hardness becomes low, which is not preferable. When the thickness of the resin layer (a) is too large, impact resistance is not preferable. The thickness of the resin layer (A) is preferably 10 to 250 μm. More preferably 30 to 200 μm. More preferably 60 to 100 μm.

In the present invention, the total (total) thickness of the synthetic resin laminate has an influence on the amount of deformation (amount of warpage) and impact resistance of the synthetic resin laminate when exposed to high temperature and high humidity. That is, when the total thickness is too thin, the deformation amount (warpage amount) at the time of high-temperature and high-humidity exposure becomes large, and the impact resistance is lowered. When the total thickness is large, the amount of deformation (amount of warpage) upon exposure to high temperature and high humidity becomes small, and impact resistance is secured, but when the thickness is as large as necessary, the raw materials are used excessively in the polycarbonate (D) and it is uneconomical. The total thickness of the synthetic resin laminate is preferably 0.1 to 2.0 mm. More preferably 0.3 to 2.0 mm. More preferably 0.5 to 1.5 mm.

The ratio ((a)/(X)) of the thickness of the resin layer (a) to the total thickness (X) of the synthetic resin laminate has an influence on the surface hardness and impact resistance of the synthetic resin laminate. That is, when the thickness ratio is too small, the surface hardness becomes low, which is not preferable. When the thickness ratio is too high, impact resistance is deteriorated, which is not preferable. The thickness ratio is preferably 0.01 to 0.5. More preferably 0.015 to 0.4. More preferably 0.02 to 0.3.

In the present invention, the mass average molecular weight of the base layer (B) has an influence on the impact resistance and molding conditions of the synthetic resin laminate. That is, when the mass average molecular weight is too small, the impact resistance of the synthetic resin laminate is lowered, which is not preferable. When the mass average molecular weight is too high, an excessive heat source may be required when the resin layer (a) is laminated, which is not preferable. In addition, since a high temperature is required in accordance with the molding method, the resin layer (a) is exposed to a high temperature, and the thermal stability thereof may be adversely affected. The substrate layer (B) preferably has a mass average molecular weight of 18,000 to 40,000. More preferably 23,000 to 38,000. More preferably 27,000 to 36,000.

In the present invention, an ultraviolet absorber may be mixed with the resin layer (a) and/or the base layer (B). When the content is too small, the light resistance is insufficient, and when the content is too large, the ultraviolet absorber excessively scatters due to application of high temperature according to the molding method, and the molding environment is contaminated, which may cause troubles. The content ratio thereof is 0 to 5% by mass, preferably 0 to 3% by mass, and more preferably 0 to 1% by mass. Examples of the ultraviolet absorber include: benzophenone-based ultraviolet absorbers such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone and the like, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) benzotriazole Benzotriazole-based ultraviolet absorbers such as (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, benzoate-based ultraviolet absorbers such as phenyl salicylate and 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate, hindered amine-based ultraviolet absorbers such as bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, 2, 4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-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-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) -one-substituted Triazine ultraviolet absorbers such as 1,3, 5-triazine and 2, 4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3, 5-triazine. The method of mixing is not particularly limited, and a method of mixing the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

In the present invention, various additives may be mixed with the resin layer (a) and/or the base layer (B). Examples of additives include: antioxidants, stainblocker, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizing agents, reinforcing materials such as organic fillers and inorganic fillers, and the like. The method of mixing is not particularly limited, and a method of mixing the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

In the present invention, the hard coating treatment forms a hard coating layer by using a hard coating paint which is cured by thermal energy and/or light energy. Examples of the hard coat coating material to be cured by heat energy include: a thermosetting resin composition such as polyorganosiloxane and crosslinking acrylic. Examples of the hard coat coating material to be cured by the application of light energy include a photocurable resin composition obtained by adding a photopolymerization initiator to a resin composition comprising a 1-functional and/or polyfunctional acrylate monomer and/or oligomer.

In the present invention, as the hard coat paint to be cured by the heat energy applied to the resin layer (a), for example, a thermosetting resin composition in which 1 to 5 parts by weight of an amine carboxylate and/or a quaternary ammonium carboxylate (a13) is added to 100 parts by weight of a resin composition comprising 100 parts by weight of organotrialkoxysilane (a11) and 50 to 200 parts by weight of a colloidal silica solution (a12) containing 10 to 50% by weight of colloidal silica having a particle diameter of 4 to 20nm, and the like can be cited.

In the present invention, as the hard coat paint to be cured by light energy applied to the resin layer (a), for example, a photocurable resin composition comprising 100 parts by weight of a resin composition comprising 40 to 80% by weight of tris (acryloxyethyl) isocyanurate (a21) and 20 to 40% by weight of a 2-functional and/or 3-functional (meth) acrylate compound (a22) copolymerizable with (a21), and 1 to 10 parts by weight of a photopolymerization initiator (a23) may be used.

Examples of the hard coat coating material to be cured by light energy applied to the base layer (B) in the present invention include a photocurable resin composition in which 1 to 10 parts by weight of a photopolymerization initiator (B3) is added to 100 parts by weight of a resin composition comprising 20 to 60 parts by weight of 1, 9-nonanediol diacrylate (B1), 2 or more functional (meth) acrylate monomer copolymerizable with (B1), and 40 to 80 parts by weight of a compound (B2) comprising 2 or more functional urethane (meth) acrylate oligomer and/or 2 or more functional polyfunctional polyester (meth) acrylate oligomer and/or 2 or more functional epoxy (meth) acrylate oligomer.

The method for applying the hard coat paint of the present invention is not particularly limited, and a known method can be used. Examples thereof include: spin coating, dipping, spraying, slide coating (slide coat), bar coating, roll coating, gravure coating, meniscus coating (meniscuscoat), flexographic printing, screen printing, kiss coating (ビートコート), flow coating (eight け), and the like.

The pretreatment of the coated surface may be performed before the hard coat coating in order to improve the adhesion of the hard coat layer. Examples of the treatment include: known methods such as sand blasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and undercoating treatment using a resin composition.

In the present invention, each material of the resin layer (a), the base layer (B), and the hard coat layer is preferably purified by filtration through a filter treatment. By forming or laminating the filter, a synthetic resin laminate with less appearance defects such as foreign matters and defects can be obtained. The filtration method is not particularly limited, and melt filtration, solution filtration, a combination thereof, or the like can be used.

The filter to be used is not particularly limited, and a known filter can be used, and is appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material. The filter medium of the filter is not particularly limited, and polypropylene, cotton, polyester, a nonwoven fabric or roving roll of viscose or glass fiber, a phenol resin-impregnated cellulose, a metal fiber nonwoven fabric sintered body, a metal powder sintered body, a rubber filter plate, or a combination thereof may be used. In particular, in consideration of heat resistance, durability, and pressure resistance, a type obtained by sintering a 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 with respect to the resin layer (a) and the base material layer (B). The hard coating agent has a filtration accuracy of 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less, from the viewpoint of application to the outermost layer of the synthetic resin laminate.

For filtration of the resin layer (a) and the base material layer (B), for example, a polymer filter for melt filtration of a thermoplastic resin is preferably used. The polymer filter is classified into a vane disc filter, a candle filter, a packed disc filter, a cylinder filter, and the like according to its structure, and particularly, a vane disc filter having a large effective filtration area is preferable.

The synthetic resin laminate of the present invention may be subjected to one or both of antireflection treatment, stain-proofing treatment, antistatic treatment, weather resistance treatment and antiglare treatment. The methods of the antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment and the antiglare treatment are not particularly limited, and known methods can be used. Examples thereof include: a method of applying a reflection reducing coating material, a method of depositing a dielectric thin film, a method of applying an antistatic coating material, and the like.

Examples

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples in any way.

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

< mass average molecular weight >

The (meth) acrylate copolymer and the polycarbonate resin were measured by Gel Permeation Chromatography (GPC) in the same manner with reference to a calibration curve obtained by dissolving standard polystyrene in chloroform in advance and measuring the standard polystyrene by GPC. By comparing the two, the respective mass average molecular weights were calculated. The GPC apparatus is configured as follows.

The device comprises the following steps: wates2690

Column: shodex GPCKF-805L8 phi x 300mm2 link

Developing solvent: chloroform

Flow rate: 1ml/min

Temperature: 30 deg.C

A detector: UV 486nm polycarbonate

RI-special acrylate

< Water absorption >

Pellets of each material were placed in a dish in such a manner that the thickness thereof did not exceed 5mm, thinly and widely, and dried in an oven at a temperature of 80 ℃ overnight in accordance with JIS-K7209. Then, the sample was put into an environmental tester set at 23 ℃ and 50% relative humidity for 24 hours. The state-adjusted pellets were subjected to water absorption [% ] measurement under nitrogen flow using a trace moisture measuring device CA-200 manufactured by Mitsubishi chemical corporation.

< glass transition temperature >

An appropriate amount of each material pellet was set in accordance with JIS-K7121 in a thermal analyzer TG-DTA2000SA manufactured by BRUKER, and then the temperature was raised at a rate of 20 ℃ per minute in a nitrogen atmosphere to measure the glass transition temperature Tg [ ° C ].

< high temperature and high humidity Exposure test >

The test piece was cut into a 10X 6cm square. The test piece was set on a 2-point support type holder (holder), and after conditioning for 24 hours or longer in an environmental tester set at a temperature of 23 ℃ and a relative humidity of 50%, the warpage was measured. Next, (before treatment), the test piece was set on a holder, and the test piece was put into an environmental tester set at a temperature of 85 ℃ and a relative humidity of 85%, and held in this state for 120 hours. Further, the test piece was moved together with the holder in an environmental tester set at a temperature of 23 ℃ and a relative humidity of 50%, and held in this state for 4 hours, and then the warpage was measured again. For the measurement of warpage (after processing), the test piece taken out was horizontally left standing in a convex state by using a 3-dimensional shape measuring machine equipped with an electric stage, and scanned at 1mm intervals, and the bulge at the center was measured as warpage. The (amount of warpage after treatment) - (amount of warpage before treatment) was evaluated as shape stability. The test piece having a thickness of 1mm was qualified as a non-coated product and a double-coated product, when the variation was 300 μ or less, and was qualified as a one-coated product, when the variation was less than 1000 μ. The test piece having a thickness of 0.5mm was qualified as having a variation of 600 μ or less for the uncoated article and the two-coated article, and as having a variation of 1900 μ or less for the one-coated article. The limit of measurement by this measuring instrument was 2000. mu. and a test piece warped above this limit was considered as impossible to measure.

< Pencil scratch hardness test >

According to JISK5600-5-4, the pencil was pressed with an angle of 45 degrees with respect to the surface and a load of 750g while gradually increasing the hardness on the surface of the base material layer (B), and the hardness of the hardest pencil with no scratch was evaluated as the pencil hardness. The test piece not treated with the hard coat layer was qualified in terms of pencil hardness HB or more, and the test piece treated with the hard coat layer was qualified in terms of pencil hardness H or more.

< impact resistance test >

The test piece was cut into 80mm squares. After the state was adjusted by leaving the substrate layer (B) at a temperature of 23 ℃ and a relative humidity of 50% for 24 hours or more, the substrate layer (B) was fixed to a circular flange having a diameter of 50mm at the top, and a metal hammer having a tip radius of 2.5mm was dropped on the substrate layer (B) so that the tip of the hammer collided. The weight of the hammer is gradually increased from 40g to 160g, or the falling height of the hammer is increased, so that the applied falling energy is increased. The impact resistance was evaluated by using the highest drop energy [ J ] at which no fracture occurred. The test pieces of the 1mm thick test piece which were not subjected to the hard coat layer treatment, and the one side of the hard coat layer treatment and the both side of the hard coat layer treatment were qualified as those having a drop energy of less than 0.9J and not causing breakage, and the test pieces of the 0.5mm thick test piece which were not subjected to the hard coat layer treatment, the one side of the hard coat layer treatment and the both side of the hard coat layer treatment were qualified as those having a drop energy of less than 0.3J and not causing breakage.

< light resistance test >

This test was carried out on a test piece coated with a hard coat layer (a 2). The test piece was cut into 8X 5cm pieces. After the conditioning was performed by leaving the sheet in an environment at a temperature of 23 ℃ and a relative humidity of 50% for 24 hours or more, the sheet was adhered to an iron plate with the resin layer (a) side being the upper side and the aluminum adhesive tape so that the central portion was exposed. The plate was placed in a black box equipped with a UVB lamp (280-360 nm) outputting 19mW and irradiated for 72 hours. YI before and after UVB irradiation was measured, and it was judged that Δ YI was 1 or less as a pass.

< Heat resistance test >

This test was carried out on a test piece having a hard coat layer on the surface layer side. The test piece was cut into 10X 20cm pieces, and the entire circumference of the outer periphery was 1cm inside and scored linearly with a cutter. The drying machine is suspended from a dryer which is heated to a predetermined temperature with a corner therebetween. After leaving for 30 minutes, the sample was taken out from the dryer, and it was judged as acceptable that the temperature was 120 ℃ or higher when no crack was present in the frame having the score mark applied thereto.

Production example 1[ production of pellet for laminated resin (A11) ]

30% by mass of MetablenH-880 (manufactured by Mitsubishi RAYON, Mass. average molecular weight: 14,000, C1/C2 ═ 33/66) as the (meth) acrylate copolymer (C) and 70% by mass of IlpilonE-2000 (manufactured by Mitsubishi engineering plastics, Ltd., Mass. average molecular weight: 36,000) as the polycarbonate (D) were mixed with a feed mixer for 30 minutes, and then the mixture was extruded using a twin-screw extruder (manufactured by Toshiba machine, TEM-26SS, S.sub.D.),) The resulting mixture was melt-kneaded at a cylinder temperature of 240 ℃ and extruded in a strand form, followed by pelletizing in a pelletizer. The pellet is stable and can be produced.

Production example 2[ production of pellet for laminated resin (A12) ]

Except that the feed ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) was set to 40: except for 60, pelletization was performed in the same manner as in production example 1. The pellet is stable and can be produced.

Production example 3[ production of pellet for laminated resin (A13) ]

Except that the feed ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) was set to 50: 50, pelletization was carried out in the same manner as in production example 1. The pelletized material is somewhat unstable but can be produced.

Production example 4[ production of pellet for laminated resin (A14) ]

Except that the feed ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) was set to 60: except for 40, pelletization was performed in the same manner as in production example 1. The granulation was unstable and could not be carried out.

Production example 5[ production of pellet for laminated resin (A15) ]

Except that the feed ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) was set to 20: except for 80, pelletization was performed in the same manner as in production example 1. The pellet is stable and can be produced.

Production example 6[ production of pellet for laminated resin (A21) ]

A mixture of 30 mass% of MetablenH-880 (manufactured by Mitsubishi RAYON corporation, mass average molecular weight: 14,000) as a (meth) acrylate copolymer (C) and 70 mass% of IlpilonS-3000 (manufactured by Mitsubishi engineering plastics corporation, mass average molecular weight: 27,000) as a polycarbonate (D) was mixed with a feed mixer for 30 minutes, and then a twin-screw extruder (manufactured by Toshiba machine, TEM-26SS, Japan) having a screw diameter of 26mm was used,) The resulting mixture was melt-kneaded at a cylinder temperature of 240 ℃ and extruded in a strand form, followed by pelletizing in a pelletizer. The pelletization is stably performed.

Production example 7[ production of pellet for laminated resin (A22) ]

Except that the feed ratio of the (meth) acrylate copolymer (C) and the polycarbonate (D) was set to 40: except for 60, pelletization was performed in the same manner as in production example 6. The pelletization is stably performed.

Production example 8[ production of thermosetting resin composition (a1) coated on resin layer (A) ]

100 parts by mass of methyltrimethoxysilane and 1 part by mass of acetic acid were added to a mixing tank equipped with a stirring blade and a dropping device, and mixed, cooled in an ice-water bath, and stirred while being maintained at 0 to 10 ℃. Then, 84 parts by mass of a 30% by weight solution of colloidal silica (trade name: SNOWTEX30, manufactured by Nissan chemical Co., Ltd.) having an average particle diameter of 10 to 20nm was added dropwise thereto, and the mixture was stirred for 4 hours while being maintained at 10 ℃. 84 parts by mass of a 25 to 26 wt% solution (trade name: SNOWTEXIBA-ST, manufactured by Nissan chemical industries, Ltd.) of colloidal silica having an average particle diameter of 10 to 20nm was further added dropwise thereto, and the mixture was stirred for 50 hours while maintaining the temperature at 20 ℃. A mixture comprising 45 parts by mass of cellosolve acetate, 50 parts by mass of isobutanol, and 0.02 part by mass of a polyoxyalkylene glycol dimethylsiloxane copolymer (product of shin-Etsu chemical Co., Ltd.; trade name: KP-341) was added dropwise over 1 hour while maintaining the temperature at 25 ℃ to obtain a thermosetting resin composition (a1) by adding 10 parts by mass of 2, 4-dihydroxybenzophenone to 100 parts by mass of the resin component.

Production example 9[ production of photocurable resin composition (a2) coated on resin layer (A) ]

A composition comprising 60 parts by mass of tris (2-acryloyloxyethyl) isocyanurate (manufactured by Aldrich Co.), 40 parts by mass of neopentyl glycol oligoacrylate (manufactured by Osaka organic chemical industries, Ltd., trade name: 215D), 1 part by mass of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: DAROCURTPO), 0.3 part by mass of 1-hydroxycyclohexylphenylketone (manufactured by Aldrich Co.), and 1 part by mass of 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Japan, trade name: TINUVIN234) was introduced into a mixing vessel equipped with a stirring blade, the mixture was stirred for 1 hour while being maintained at 40 ℃ to obtain a photocurable resin composition (a 2).

Production example 10[ production of photocurable resin composition (B) coated on substrate layer (B) ]

A mixing vessel equipped with a stirring blade was charged with 40 parts by mass of 1, 9-nonanediol diacrylate (product of Osaka chemical industry Co., Ltd., trade name: Viscoat #260), 40 parts by mass of 6-functional urethane acrylate oligomer (product of Ninghamu chemical industry Co., Ltd., trade name: U-6HA), 20 parts by mass of a 1/2/4 condensate having a molar ratio of succinic acid/trimethylolethane/acrylic acid, 2.8 parts by mass of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (product of Ciba Japan Co., Ltd., trade name: DAROCURTPO), 1 part by mass of benzophenone (product of Aldrich Co.), 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (product of Ciba Japan Co., Ltd.),), Trade name: TINUVIN234)1 part by mass, and stirred at 40 ℃ for 1 hour to obtain a photocurable resin composition (b).

Example 1

The synthetic resin laminate was molded using a multilayer extrusion apparatus having a single screw extruder with an axial diameter of 32mm, a single screw extruder with an axial diameter of 65mm, a feed block (feedblock) connected to all the extruders, and a T-die connected to the feed block. The laminated resin (A11) obtained in production example 1 was continuously introduced into a single-screw extruder having an axial diameter of 32mm, and extruded under conditions of a cylinder temperature of 240 ℃ and a discharge rate of 2.1 kg/h. Further, a polycarbonate resin (B1) (product name: IipolonS-3000, mass average molecular weight: 27,000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 270 ℃ and a discharge rate of 30.0 kg/h. The feedblock connected to all extruders was equipped with 2 kinds of 2-layer distribution rods (pin), set at 270 ℃, and introduced (a11) and (B1) for lamination. The resulting laminate was extruded into a sheet form through a T die connected to the tip thereof and having a temperature of 270 ℃ and cooled while mirror-transferring the sheet through 3 mirror-finishing rolls having temperatures of 130 ℃, 140 ℃ and 180 ℃ from the upstream side, to obtain a laminate (E1) of (A11) and (B1). The thickness of the laminate obtained was 1.0mm, and the thickness of the (A11) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 2.5 μm, F, and the impact resistance was 2.3J or more, and the test was judged as acceptable.

Example 2

A laminate (E2) of (a11) and (B1) was obtained in the same manner as in example 1, except that the discharge rate of the laminate resin (a11) used in example 1 was set to 3.0kg/h and the discharge rate of the polycarbonate resin (B1) was set to 20 kg/h. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A11) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was acceptable at 9.8. mu.m, the test result of the pencil scratch hardness was acceptable at F, the test result of the impact resistance was acceptable at 2.3J or more, and the test result was comprehensively judged to be acceptable.

Example 3

The thermosetting resin composition (a1) obtained in production example 8 was coated on the (a11) layer of the laminate (E1) obtained in example 1 using a bar coater so that the thickness of the coating film after curing was 3 to 8 μm, and after drying at 25 ℃ for 15 minutes, it was cured in a hot air circulation dryer set to 130 ℃ for 1 hour to obtain a laminate (F1) having a hard coat layer (a1) in the (a11) layer. The test result of the high-temperature and high-humidity exposure was 13 μm, the test result of the pencil scratch hardness was 4H, the test result of the impact resistance was 2.3J, the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 4

The photocurable resin composition (a2) obtained in production example 9 was coated on the (a11) layer of the laminate (E1) obtained in example 1 using a bar coater so that the thickness of the cured coating film was 3 to 8 μm, and the coating film was covered with a PET film and pressure-bonded, and the PET film was peeled off by irradiating with ultraviolet light under the condition that the linear speed of a conveyor equipped with a high-pressure mercury lamp having a light source distance of 12cm and an output of 80W/cm was 1.5 m/min, to obtain a laminate (F2) having a hard coat layer (a2) on the (a11) layer. The test result of the high-temperature and high-humidity exposure was satisfactory at 10 μm, the test result of the pencil scratch hardness was satisfactory at 3H, the test result of the impact resistance was satisfactory at 2.3J, the light resistance was satisfactory at 0.4, the heat resistance was satisfactory at 130 ℃, and the test result was comprehensively judged as satisfactory.

Example 5

The photocurable resin composition (a2) obtained in production example 9 was coated with a PET film and pressure-bonded to the (a11) layer of the laminate (E1) obtained in example 1 using a bar coater so that the cured coating film thickness was 3 to 8 μm, and the photocurable resin composition (B) obtained in production example 10 was coated with a bar coater so that the cured coating film thickness was 3 to 8 μm, and pressure-bonded to the (B1) layer, and the PET film was peeled off by irradiating with ultraviolet light under the condition that the distance from the light source was 12cm and the belt speed of a high-pressure mercury lamp, which outputs 80W/cm, was 1.5 m/min, to obtain a laminate (F3) having a hardcoat layer (a2) and a hardcoat layer (B) in the (a11) layer and the (B1) layer, respectively. The test result of the high-temperature and high-humidity exposure was 3 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 1.88J, the light resistance was 0.4, the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 6

A laminate (F4) having a hard coat layer (a1) in the (a11) layer was obtained in the same manner as in example 3, except that the laminate (E2) obtained in example 2 was used in place of the laminate (E1) used in example 3 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was judged to be acceptable at 49 μm, the test result of the pencil scratch hardness was judged to be acceptable at 4H, the test result of the impact resistance was judged to be acceptable at 2J, and the test result of the heat resistance was judged to be acceptable at 130 ℃.

Example 7

A laminate (F5) having a hard coat layer (a2) in the (a11) layer was obtained in the same manner as in example 4, except that the laminate (E2) obtained in example 2 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure test was 39 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 2J, the light resistance was 0.4, the heat resistance was 130 ℃, and the test result was comprehensively judged as pass.

Example 8

A laminate (F6) having hard coat layers (a2) and (B) in the (a11) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E2) obtained in example 2 was used instead of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 12 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 1.8J, the light resistance was 0.4, the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 9

A laminate (E3) of (a12) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a12) obtained in production example 2 was used in place of the laminated resin (a11) used in example 1. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A12) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 17 μm, the test result of the pencil scratch hardness was H, the test result of the impact resistance was 1.7J, and the test result was comprehensively judged as passed.

Example 10

A laminate (E4) of (a12) and (B1) was obtained in the same manner as in example 2, except that the laminated resin (a12) obtained in production example 2 was used in place of the laminated resin (a11) used in example 2. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A12) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was found to be satisfactory at 50 μm, the test result of the pencil scratch hardness was found to be satisfactory at H, and the test result of the impact resistance was found to be satisfactory at 0.47J, and the test result was found to be satisfactory in all cases.

Example 11

A laminate (F7) having a hard coat layer (a1) in the (a12) layer was obtained in the same manner as in example 3, except that the laminate (E3) obtained in example 9 was used in place of the laminate (E1) used in example 3 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 85 μm, 4H, 1.3J, and 130 ℃ respectively, and the test result was judged to be satisfactory.

Example 12

A laminate (F8) having a hard coat layer (a2) in the (a12) layer was obtained in the same manner as in example 4, except that the laminate (E3) obtained in example 9 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 70 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 1.3J, the light resistance was 0.4, the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 13

A laminate (F9) having hard coat layers (a2) and (B) in the (a12) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E3) obtained in example 9 was used instead of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 20 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 1J, the light resistance was 0.4, the heat resistance was 130 ℃, and the test result was comprehensively judged as pass.

Example 14

A laminate (F10) having a hard coat layer (a1) in the (a12) layer was obtained in the same manner as in example 3, except that the laminate (E4) obtained in example 10 was used in place of the laminate (E1) used in example 3 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 250 μm, 4H, 0.38J, and 130 ℃ respectively, and the test result was judged to be satisfactory.

Example 15

A laminate (F11) having a hard coat layer (a2) in the (a12) layer was obtained in the same manner as in example 4, except that the laminate (E4) obtained in example 10 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure test was 200 μm and 3H, respectively, and the test result of the impact resistance test was 0.38J and 0.4, respectively, and the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 16

A laminate (F12) having hard coat layers (a2) and (B) in the (a12) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E4) obtained in example 10 was used instead of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 55 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 0.33J, the light resistance was 0.4, the heat resistance was 130 ℃ and the test result was comprehensively judged as pass.

Example 17

A laminate (E5) of (a13) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a13) obtained in production example 3 was used in place of the laminated resin (a11) used in example 1. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A13) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure test was 95 μm, the test result of the pencil scratch hardness test was H, the test result of the impact resistance test was 1.2J, and the test result was comprehensive judgment as pass.

Example 18

A laminate (E6) of (a13) and (B1) was obtained in the same manner as in example 2, except that the laminated resin (a13) obtained in production example 3 was used in place of the laminated resin (a11) used in example 2. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A13) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was found to be satisfactory at 300 μm, the test result of the pencil scratch hardness was found to be satisfactory at H, and the test result of the impact resistance was found to be satisfactory at 0.46J, and the test result was comprehensively judged to be satisfactory.

Example 19

A laminate (F13) having a hard coat layer (a1) in the (a13) layer was obtained in the same manner as in example 3, except that the laminate (E5) obtained in example 17 was used in place of the laminate (E1) used in example 3 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 450 μm, the test result of the pencil scratch hardness was 4H, the test result of the impact resistance was 0.9J, the heat resistance was 125 ℃ and the test result was comprehensively judged as pass.

Example 20

A laminate (F14) having a hard coat layer (a2) in the (a13) layer was obtained in the same manner as in example 4, except that the laminate (E5) obtained in example 17 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was satisfactory at 400 μm, the test result of the pencil scratch hardness was satisfactory at 3H, the test result of the impact resistance was satisfactory at 0.9J, the light resistance was satisfactory at 0.4, the heat resistance was satisfactory at 125 ℃, and the test result was comprehensively judged as satisfactory.

Example 21

A laminate (F15) having hard coat layers (a2) and (B) in the (a13) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E5) obtained in example 17 was used instead of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 105 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 0.8J, the light resistance was 0.4, the heat resistance was 125 ℃, and the test results were comprehensively judged as pass.

Example 22

A laminate (F16) having a hard coat layer (a1) in the (a13) layer was obtained in the same manner as in example 3, except that the laminate (E6) obtained in example 18 was used in place of the laminate (E1) used in example 3 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 1500 μm, the test result of the pencil scratch hardness was 4H, the test result of the impact resistance was 0.37J, the heat resistance was 125 ℃ and the test result was comprehensively judged as pass.

Example 23

A laminate (F17) having a hard coat layer (a2) in the (a13) layer was obtained in the same manner as in example 4, except that the laminate (E6) obtained in example 18 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 1200 μm, the test result of the pencil scratch hardness was 3H, the test result of the impact resistance was 0.37J, the light resistance was 0.4, the heat resistance was 125 ℃, and the test results were comprehensively judged as pass.

Example 24

A laminate (F18) having hard coat layers (a2) and (B) in the (a13) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E6) obtained in example 18 was used in place of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 350 μm and 3H, respectively, and the test result of the impact resistance was 0.32J, light resistance was 0.4, heat resistance was 125 ℃, and the test result was comprehensively judged as pass.

Example 25

A laminate (E7) of (a13) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a13) obtained in production example 3 was used in place of the laminated resin (a11) used in example 1, and the discharge rate was set to 1.1kg/h and the discharge rate of the polycarbonate resin (B1) was set to 31 kg/h. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A13) layer was 30 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 80 μm, F and 1.5J, respectively, and the test result was judged to be satisfactory.

Example 26

A laminate (E8) of (a13) and (B1) was obtained in the same manner as in example 1, except that in example 25, the discharge rate of the laminate resin (a13) was set to 1.5kg/h and the discharge rate of the polycarbonate resin (B1) was set to 21 kg/h. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A13) layer was 30 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 270 μm, F and 0.5J, respectively, and the test result was judged to be acceptable.

Example 27

A laminate (F19) having a hard coat layer (a2) in the (a13) layer was obtained in the same manner as in example 4, except that the laminate (E7) obtained in example 25 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 320 μm, 2H, 1.2J, 0.4 light resistance, 125 ℃ and comprehensive judgment of acceptability, the pencil scratch hardness test, the impact resistance test, and the heat resistance test.

Example 28

A laminate (F20) having a hard coat layer (a2) in the (a13) layer was obtained in the same manner as in example 4, except that the laminate (E8) obtained in example 26 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 1100 μm, the test result of the pencil scratch hardness was 2H, the test result of the impact resistance was 0.4J, the light resistance was 0.4, the heat resistance was 125 ℃, and the test results were comprehensively judged as pass.

Example 29

A laminate (F21) having hard coat layers (a2) and (B) in the (a13) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E8) obtained in example 26 was used instead of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was found to be satisfactory at 300 μm, the test result of the pencil scratch hardness was found to be satisfactory at 2H, the test result of the impact resistance was found to be satisfactory at 0.35J, the light resistance was found to be satisfactory at 0.4, the heat resistance was found to be satisfactory at 125 ℃, and the test results were comprehensively judged to be satisfactory.

Example 30

A laminate (E9) of (a15) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a15) obtained in production example 5 was used in place of the laminated resin (a11) used in example 1, and the discharge rate was set to 7.0kg/h and the discharge rate of the polycarbonate resin (B1) was set to 25 kg/h. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A15) layer was 200 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure test was found to be acceptable at 130 μm, the test result of the pencil scratch hardness test was found to be acceptable at HB, the test result of the impact resistance test was found to be acceptable at 1.3J, and the test result was found to be acceptable comprehensively.

Example 31

A laminate (E10) of (a15) and (B1) was obtained in the same manner as in example 1, except that in example 30, the discharge rate of the laminated resin (a15) was changed to 10kg/h and the discharge rate of the polycarbonate resin (B1) was changed to 13 kg/h. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A15) layer was 200 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure test was found to be satisfactory at 400 μm, the test result of the pencil scratch hardness test was found to be satisfactory at HB, the test result of the impact resistance test was found to be satisfactory at 1J, and the test results were comprehensively judged to be satisfactory.

Example 32

A laminate (F22) having a hard coat layer (a2) in the (a15) layer was obtained in the same manner as in example 4, except that the laminate (E9) obtained in example 30 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 520 μm, the test result of the pencil scratch hardness was 2H, the test result of the impact resistance was 1J, the light resistance was 0.4, the heat resistance was 135 ℃, and the test results were comprehensively judged as pass.

Example 33

A laminate (F23) having a hard coat layer (a2) in the (a15) layer was obtained in the same manner as in example 4, except that the laminate (E10) obtained in example 31 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was 1600 μm, 2H, 0.8J, 0.4 light resistance, 135 ℃ and comprehensive judgment of acceptability, the pencil scratch hardness test, the impact resistance test, and the heat resistance test.

Example 34

A laminate (F24) having hard coat layers (a2) and (B) in the (a15) layer and the (B1) layer was obtained in the same manner as in example 5, except that the laminate (E10) obtained in example 31 was used in place of the laminate (E1) used in example 5 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was acceptable at 500 μm, the test result of the pencil scratch hardness was acceptable at 2H, the test result of the impact resistance was acceptable at 0.7J, the light resistance was acceptable at 0.4, the heat resistance was acceptable at 135 ℃, and the test result was comprehensively judged to be acceptable.

Example 35

A laminate (E11) of (A13) and (B2) was obtained in the same manner as in example 2, except that the laminate resin (A13) obtained in production example 3 was used in place of the laminate resin (A11) used in example 2, and a polycarbonate resin (B2) (product name: IipilonH-3000, mass average molecular weight: 19,000, manufactured by Mitsubishi engineering plastics corporation) was used in place of the polycarbonate resin (B1). The thickness of the laminate obtained was 0.5mm, and the thickness of the (A13) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 100 μm, the test result of the pencil scratch hardness was H, the test result of the impact resistance was 0.43J, and the test result was comprehensively judged as pass.

Example 36

A laminate (F25) having a hard coat layer (a2) in the (a13) layer was obtained in the same manner as in example 4, except that the laminate (E11) obtained in example 35 was used in place of the laminate (E1) used in example 4 (the laminate obtained in example 1). The test result of the high-temperature and high-humidity exposure was acceptable at 500 μm, the test result of the pencil scratch hardness was acceptable at 3H, the test result of the impact resistance was acceptable at 0.34J, the light resistance was acceptable at 0.4, the heat resistance was acceptable at 125 ℃, and the test result was comprehensively judged to be acceptable.

Example 37

A laminate (F26) having hard coat layers (a2) and (B) in the (a13) layer and the (B2) layer was obtained in the same manner as in example 5, except that the laminate (E11) obtained in example 35 was used in place of the laminate (E1) used in example 5 (the laminate obtained in example 1). 120 μm in the high-temperature and high-humidity exposure test was acceptable, 3H in the pencil scratch hardness test was acceptable, 0.3J in the impact resistance test was acceptable, 0.4 in the light resistance, 125 ℃ in the heat resistance, and comprehensively judged as acceptable.

Example 38

A laminate (E12) of (a21) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a21) obtained in production example 6 was used in place of the laminated resin (a11) used in example 1. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A21) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 2.5 μm, F, and the impact resistance was 2.3J or more, and the test was judged as acceptable.

Example 39

A laminate (E13) of (a21) and (B1) was obtained in the same manner as in example 2, except that the laminated resin (a21) obtained in production example 6 was used in place of the laminated resin (a11) used in example 2. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A21) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was satisfactory at 10 μm, the test result of the pencil scratch hardness was satisfactory at F, the test result of the impact resistance was satisfactory at 2.3J or more, and the test result was comprehensively judged as satisfactory.

Example 40

A laminate (E14) of (a21) and (B2) was obtained in the same manner as in example 2, except that the laminate resin (a21) obtained in production example 6 was used in place of the laminate resin (a11) used in example 2, and the polycarbonate resin (B2) was used in place of the polycarbonate resin (B1). The thickness of the laminate obtained was 0.5mm, and the thickness of the (A21) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 10 μm, F and 2J, respectively.

EXAMPLE 41

A laminate (E15) of (a22) and (B1) was obtained in the same manner as in example 1, except that the laminated resin (a22) obtained in production example 7 was used in place of the laminated resin (a11) used in example 1. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A22) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was 17 μm, the test result of the pencil scratch hardness was H, the test result of the impact resistance was 1.7J, and the test result was comprehensively judged as passed.

Example 42

A laminate (E16) of (a22) and (B1) was obtained in the same manner as in example 2, except that the laminated resin (a22) obtained in production example 7 was used in place of the laminated resin (a11) used in example 2. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A22) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was found to be satisfactory at 50 μm, the test result of the pencil scratch hardness was found to be satisfactory at H, and the test result of the impact resistance was found to be satisfactory at 0.47J, and the test result was found to be satisfactory in all cases.

Example 43

A laminate (E17) of (a22) and (B2) was obtained in the same manner as in example 2, except that the laminate resin (a22) obtained in production example 7 was used in place of the laminate resin (a11) used in example 2, and the polycarbonate resin (B2) was used in place of the polycarbonate resin (B1). The thickness of the laminate obtained was 0.5mm, and the thickness of the (A22) layer was 60 μm in the vicinity of the center. The test result of the high-temperature and high-humidity exposure was found to be satisfactory at 50 μm, the test result of the pencil scratch hardness was found to be satisfactory at H, and the test result of the impact resistance was found to be satisfactory at 0.43J, and the test result was found to be satisfactory in all cases.

Comparative example 1

A laminate (E18) of (A3) and (B1) was obtained in the same manner as in example 1, except that MS resin (A3) (trade name: MS600, manufactured by Nippon iron chemical Co., Ltd.) was used in place of the laminating resin (A11) used in example 1, and the barrel temperature of a single-screw extruder having an axial diameter of 32mm was set to 220 ℃. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A3) layer was 60 μm in the vicinity of the center. Further, a laminate (F27) including the hard coat layers (a2) and (B) in the (A3) layer and the (B1) layer of the laminate (E18) was obtained in the same manner as in example 5. As a result of the high temperature and high humidity exposure test, 400 μm was judged as a fail, 0.7J was judged as an impact resistance test, and 95 ℃ was judged as a fail, and the heat resistance test was judged as a fail.

Comparative example 2

A laminate (E19) of (A3) and (B1) was obtained in the same manner as in example 2, except that MS resin (A3) (trade name: MS600, manufactured by Nippon iron chemical Co., Ltd.) was used in place of the laminating resin (A11) used in example 2, and the barrel temperature of a single-screw extruder having an axial diameter of 32mm was set to 220 ℃. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A3) layer was 60 μm in the vicinity of the center. As a result of the high-temperature high-humidity exposure test, 1000 μm was judged as a failure, and the impact resistance was 0.19J as a failure, and the test was comprehensively judged as a failure.

Comparative example 3

A laminate (E20) of (A4) and (B1) was obtained in the same manner as in example 1, except that a polymethyl methacrylate resin (A4) (product name: ALTUGLSV 020, manufactured by ARKEMA) was used in place of the laminate resin (A11) used in example 1. The thickness of the laminate obtained was 1.0mm, and the thickness of the (A4) layer was 60 μm in the vicinity of the center. Further, a laminate (F28) including hard coat layers (a2) and (B) in the layers (a4) and (B1) of the laminate (E20) was obtained in the same manner as in example 5. The test result of the high-temperature and high-humidity exposure was found to be a failure of 1200 μm, a failure of 0.4J in the impact resistance test, and a failure of 110 ℃ in the heat resistance test, which were judged to be a failure comprehensively.

Comparative example 4

A laminate (E21) of (A4) and (B1) was obtained in the same manner as in example 2, except that a polymethyl methacrylate resin (A4) (product name: ALTUGLSV 020, manufactured by ARKEMA) was used in place of the laminate resin (A11) used in example 2. The thickness of the laminate obtained was 0.5mm, and the thickness of the (A4) layer was 60 μm in the vicinity of the center. As a result of the high-temperature and high-humidity exposure test, the test was impossible to measure and was judged as being unsatisfactory, and further, the impact resistance was 0.15J and was judged as being unsatisfactory in total.

Comparative example 5

A laminate (E22) of (A5) and (B1) was obtained in the same manner as in example 2, except that a polycarbonate resin (A5) (product name: Iumylon H-3000, mass average molecular weight: 19,000, manufactured by Mitsubishi engineering plastics corporation) was used in place of the laminate resin (A11) used in example 2. The thickness of the obtained laminate was 0.5mm, and the thickness of the (A5) layer was difficult to be distinguished from that of the (B1) layer, and the thickness of the (A5) layer was not clear. Further, a laminate (F29) having a hard coat layer (a1) on the (a5) layer of the laminate (E22) was obtained in the same manner as in example 3. The 20 μm in the high-temperature and high-humidity exposure test was acceptable, but the HB in the pencil scratch hardness test was unacceptable, and the test was judged comprehensively to be unacceptable.

[ Table 1]

Table 1

[ Table 2-1]

Table 2

O is passed, X is not passed, and the item is not measured

[ tables 2-2]

Watch 2 (continuation)

O is passed, X is not passed, and the item is not measured

MS: MS resin

PMMA: polymethyl methacrylate resin

As can be seen from tables 1 and 2: the synthetic resin laminate of the present invention is excellent in shape stability, surface hardness, impact resistance, weather resistance and heat resistance under high-temperature and high-humidity environments.

Industrial applicability of the invention

The synthetic resin laminate of the present invention has excellent shape stability under high-temperature and high-humidity environments, surface hardness, impact resistance, weather resistance and heat resistance, and is suitable for use as a transparent substrate material, a transparent protective material and the like, and particularly suitable for use as a display front panel or a touch panel substrate of OA equipment or portable electronic equipment, and a sheet for thermal bending.

Claims (11)

1. A synthetic resin laminate characterized by comprising:

the resin layer (A) is laminated on one or both surfaces of a substrate layer (B) containing polycarbonate, wherein the resin layer (A) contains 5-55 mass% of a (meth) acrylate copolymer (C) and 95-45 mass% of polycarbonate (D),

the (meth) acrylate copolymer (C) contains an aromatic (meth) acrylate unit (C1) and a methyl methacrylate unit (C2) in a mass ratio (C1/C2) of 5 to 80/20 to 95, and the (meth) acrylate copolymer (C) has a mass average molecular weight of 5,000 to 30,000, and the aromatic (meth) acrylate constituting the aromatic (meth) acrylate unit (C1) is selected from 1 or 2 kinds of phenyl (meth) acrylate and benzyl (meth) acrylate,

the mass average molecular weight of the polycarbonate (D) in the resin layer (A) is 21,000-40,000.

2. The synthetic resin laminate according to claim 1, wherein:

the glass transition temperature of the resin layer (A) is 110-130 ℃.

3. The synthetic resin laminate according to claim 1 or 2, wherein:

the resin layer (A) has a water absorption of 0.03 to 0.28%.

4. The synthetic resin laminate according to claim 1 or 2, wherein: the thickness of the resin layer (A) is 10 to 250 [ mu ] m, the total thickness (X) of the synthetic resin laminate is 0.1 to 2.0mm, and the ratio of the thickness of the resin layer (A)/the total thickness (X) of the synthetic resin laminate is 0.01 to 0.5.

5. The synthetic resin laminate according to claim 1 or 2, wherein: the substrate layer (B) has a mass average molecular weight of 18,000-40,000.

6. The synthetic resin laminate according to claim 1 or 2, wherein: the resin layer (A) and/or the base material layer (B) contain an ultraviolet absorber.

7. The synthetic resin laminate according to claim 1 or 2, wherein: a hard coat treatment is applied on the resin layer (a).

8. The synthetic resin laminate according to claim 1 or 2, wherein: a hard coat layer treatment is applied to the resin layer (A) and the base material layer (B).

9. The synthetic resin laminate according to claim 1 or 2, wherein: one or both surfaces of the synthetic resin laminate are subjected to at least one of antireflection treatment, stain-proofing treatment, fingerprint resistance treatment, antistatic treatment, weather resistance treatment and antiglare treatment.

10. A transparent substrate material, characterized in that:

which comprises the synthetic resin laminate according to any one of claims 1 to 9.

11. A transparent protective material characterized by:

which comprises the synthetic resin laminate according to any one of claims 1 to 9.