阅读说明：本技术 红外线遮蔽性层叠片及其制造方法 (Infrared shielding laminate and method for producing same ) 是由 大泽侑史 太田大介 于 2019-07-25 设计创作，主要内容包括：本发明提供色调良好、具有良好的红外线遮蔽性、耐候性优良的层叠片。本发明涉及层叠片(10X),其在含有聚碳酸酯树脂的基材层(11)的至少单面层叠有含有甲基丙烯酸类树脂的表面层(12A、12B)。基材层(11)包含着色剂。总厚度为3.0～10.0mm,在将基材层(11)的厚度设为T1、将表面层(12A、12B)的总厚度设为T2时,满足T1＞T2。总光线透射率为3～60％,波长1500nm下的透射率为60％以下。在JIS Z8781-4所定义的L~*a~*b~*颜色空间中,a~*值的绝对值为10.0以下且b~*的绝对值为10.0以下。(The present invention provides a laminate sheet having good color tone, good infrared shielding properties, and excellent weather resistance. The invention relates to a laminateAnd a sheet (10X) in which surface layers (12A, 12B) comprising a methacrylic resin are laminated on at least one surface of a substrate layer (11) comprising a polycarbonate resin. The substrate layer (11) contains a colorant. The total thickness is 3.0 to 10.0mm, and T1 > T2 is satisfied when the thickness of the base material layer (11) is T1 and the total thickness of the surface layers (12A, 12B) is T2. The total light transmittance is 3-60%, and the transmittance at a wavelength of 1500nm is 60% or less. L defined in JIS Z8781-4 * a * b * In color space, a * Absolute value of 10.0 or less and b * The absolute value of (A) is 10.0 or less.)

1. A laminated sheet comprising a substrate layer comprising a polycarbonate resin and a surface layer comprising a methacrylic resin laminated on at least one surface of the substrate layer,

the substrate layer comprises a colorant,

the total thickness of the laminated sheet is 3.0-10.0 mm,

t1 > T2 is satisfied when the thickness of the base material layer is T1 and the total thickness of the surface layer is T2,

the total light transmittance is 3-60%,

a transmittance at a wavelength of 1500nm of 60% or less,

l defined in JIS Z8781-4^*a^*b^*In color space, a^*Absolute value of 10.0 or less and b^*The absolute value of (A) is 10.0 or less.

2. The laminate of claim 1, wherein the colorant is carbon black and/or an organic dye.

3. The laminate of claim 1 or 2, wherein the surface layer comprises an infrared absorber.

4. The laminate sheet of claim 3, wherein the infrared absorber is at least 1 type of particle selected from the group consisting of:

general formula W_yO_z(wherein W is tungsten, O is oxygen, and z/y is 2.2. ltoreq. 2.999),

General formula M_xW_yO_z(wherein M is at least 1 element selected from the group consisting of H, He, alkali metal, alkaline earth metal and rare earth element, W is tungsten, O is oxygen, x/y is 0.001. ltoreq. x/y.ltoreq.1, z/y is 2.2. ltoreq. z/y.ltoreq.3), and a composite tungsten oxide fine particle,

General formula LaXO₃(wherein X is at least 1 metal element selected from the group consisting of Ni, Co, Fe and Mn),

General formula XB_m(wherein X is at least 1 metal element selected from the group consisting of Y, Sr, Ca and lanthanides, and 4.0. ltoreq. m.ltoreq.6.2) and boride fine particles,

Indium tin oxide fine particles,

And antimony tin oxide fine particles.

5. The laminate sheet according to any one of claims 1 to 4, wherein the surface layer contains 5 to 90 mass% of a methacrylic resin and 95 to 10 mass% of a copolymer comprising an aromatic vinyl compound unit and a maleic anhydride unit.

6. The laminate sheet according to claim 5, wherein the copolymer comprises 50 to 84 mass% of the aromatic vinyl compound unit, 15 to 49 mass% of the maleic anhydride unit, and 1 to 35 mass% of the methacrylate unit.

7. The laminate sheet according to any one of claims 1 to 4, wherein the surface layer comprises a methacrylic resin and multilayer-structured rubber particles.

8. The laminate sheet according to any one of claims 1 to 7, further comprising a scratch-resistant layer, an antiglare layer or an antireflection layer on the surface layer.

9. The laminate sheet according to any one of claims 1 to 8, which is used for plexiglas.

10. The method for producing a laminate sheet according to any one of claims 1 to 9, wherein a laminated structure of the substrate layer and the surface layer is formed by coextrusion molding.

Technical Field

The present invention relates to an infrared shielding laminate sheet and a method for producing the same.

Background

Glass windows used in transportation machines such as automobiles are being replaced with materials from glass to thermoplastic resins for the purpose of weight reduction of members and improvement of safety. As an alternative material, a polycarbonate resin excellent in impact resistance has been studied. Generally, polycarbonate resins tend to have poor scratch resistance and weather resistance, but these properties can be improved by forming a hard coating layer on the surface of the polycarbonate resin.

For example, patent document 1 discloses a laminate in which a hard coat layer having excellent weather resistance and comprising a first layer obtained by thermally curing an acrylic resin composition comprising an acrylic copolymer (a) having a cycloalkyl group-containing unit and a polyisocyanate compound (B) and a second layer obtained by thermally curing an organosiloxane resin composition is formed on a polycarbonate resin sheet (claims 1 and 12).

When the infrared shielding material is used for window members of automobiles, buildings, and the like, temperature rise in the interior of the automobile, the interior of a room, and the like can be suppressed, and the sensible temperature of a human can be reduced. In particular, from the viewpoint of weight reduction of materials and thermal management, the material has infrared shielding propertiesCO reduction of transparent resins₂The effect of reducing the environmental load such as the discharge amount is large, and therefore, this is preferable.

Patent documents 2 to 4 relate to infrared shielding materials.

Patent document 2 discloses a laminated glass including a heat ray reflection film having a sandwich structure, the heat ray reflection film being formed of a ZnO film or a TiO film₂Film, ITO film or SnO₂A pair of transparent metal oxide films made of a film or the like sandwiching an Ag film (claim 2).

Patent document 3 discloses a multilayered polymer film which reflects infrared energy and transmits visible light, and which has a plurality of mutually alternating layers of a crystalline naphthalenedicarboxylic acid polyester and a polymer selected from other polymers (claims 1, 29).

Patent document 4 discloses a composition in which an inorganic infrared shielding additive and carbon black are added to a polycarbonate resin (claim 1).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2007/105741

Patent document 2: japanese laid-open patent publication No. 7-187727

Patent document 3: international publication No. 1995/17303 (Japanese Kohyo publication No. 9-506837)

Patent document 4: international publication No. 2007/008476 (Japanese patent publication No. 2009-501266)

Disclosure of Invention

Problems to be solved by the invention

In patent document 2, the heat ray reflection film is formed by vapor phase deposition by sputtering (example), which is not preferable because of high production cost.

The multilayer film described in patent document 3 is not preferable because it is expensive to produce. In addition, there is a fear that the performance is deteriorated by heat processing at the time of bonding with the polycarbonate resin sheet.

Although the composition described in patent document 4 can be produced at low cost, it is not preferable because the color tone of the composition is black with red peculiar to carbon black. In the application of resin glass or the like, a black color close to a jet black is preferable. In addition, the temperature of the resin may increase by absorbing infrared rays, which may accelerate deterioration of the polycarbonate resin, which is originally inferior in weather resistance, and accelerate discoloration (coloration) in a weather resistance test.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminate sheet having good color tone, good infrared shielding properties, and excellent weather resistance, and a method for producing the same.

Means for solving the problems

The present invention provides the following laminated sheets [1] to [10] and a method for producing the same.

[1] A laminated sheet comprising a substrate layer comprising a polycarbonate resin and a surface layer comprising a methacrylic resin laminated on at least one surface of the substrate layer,

the above-mentioned base material layer contains a coloring agent,

the total thickness of the laminated sheet is 3.0-10.0 mm,

t1 > T2 is satisfied when the thickness of the base material layer is T1 and the total thickness of the surface layer is T2,

the total light transmittance is 3-60%,

a transmittance at a wavelength of 1500nm of 60% or less,

l defined in JIS Z8781-4^*a^*b^*In color space, a^*Absolute value of 10.0 or less and b^*The absolute value of (A) is 10.0 or less.

[2] The laminate sheet according to [1], wherein the colorant is carbon black and/or an organic dye.

[3] The laminate sheet according to [1] or [2], wherein the surface layer contains an infrared absorber.

[4] The laminate sheet according to [3], wherein,

the infrared absorber is at least 1 kind of fine particles selected from the group consisting of:

general formula W_yO_z(wherein W is tungsten, O is oxygen, and z/y is 2.2. ltoreq. 2.999),

General formula M_xW_yO_z(formula (II)Wherein M is at least 1 element selected from the group consisting of H, He, alkali metal, alkaline earth metal and rare earth element, W is tungsten, O is oxygen, x/y is 0.001. ltoreq. x/y.ltoreq.1, z/y is 2.2. ltoreq. z/y.ltoreq.3), fine particles of a composite tungsten oxide, a binder for,

General formula LaXO₃(wherein X is at least 1 metal element selected from the group consisting of Ni, Co, Fe and Mn),

General formula XB_m(wherein X is at least 1 metal element selected from the group consisting of Y, Sr, Ca and lanthanides, and 4.0. ltoreq. m.ltoreq.6.2) and boride fine particles,

Indium tin oxide fine particles,

And antimony tin oxide fine particles.

[5] The laminate sheet according to any one of [1] to [4], wherein the surface layer contains 5 to 90 mass% of a methacrylic resin and 95 to 10 mass% of a copolymer comprising an aromatic vinyl compound unit and a maleic anhydride unit.

[6] The laminate sheet according to [5], wherein the copolymer contains 50 to 84 mass% of the aromatic vinyl compound unit, 15 to 49 mass% of the maleic anhydride unit, and 1 to 35 mass% of the methacrylate unit.

[7] The laminate sheet according to any one of [1] to [4], wherein the surface layer contains a methacrylic resin and multilayered rubber particles.

[8] The laminate sheet according to any one of [1] to [7], further comprising a scratch-resistant layer, an antiglare layer or an antireflection layer on the surface layer.

[9] The laminate sheet according to any one of [1] to [8], which is used for plexiglass.

[10] [1] A method for producing a laminate sheet according to any one of [1] to [9], wherein a laminate structure of the base material layer and the surface layer is formed by coextrusion molding.

Effects of the invention

The present invention can provide a laminate sheet having good color tone, good infrared shielding properties, and excellent weather resistance, and a method for producing the same.

Drawings

Fig. 1 is a schematic cross-sectional view of a laminate sheet according to a first embodiment of the present invention.

Figure 2 is a schematic cross-sectional view of a laminate according to a second embodiment of the present invention.

Fig. 3 is a schematic view of an apparatus for manufacturing a laminated sheet according to an embodiment of the present invention.

Fig. 4 is an explanatory view (schematic sectional view) of the ball drop test.

Detailed Description

[ laminated sheet ]

The laminate sheet of the present invention has a structure in which a surface layer containing a methacrylic resin (PM) is laminated on at least one surface of a substrate layer containing a polycarbonate resin (PC).

Fig. 1 and 2 are schematic cross-sectional views of laminates according to first and second embodiments of the present invention. In these drawings, the same components are denoted by the same reference numerals.

The laminate sheet 10X of the first embodiment shown in fig. 1 has a structure in which surface layers 12A and 12B containing a methacrylic resin (PM) are laminated on both surfaces of a base material layer 11 containing a polycarbonate resin (PC), respectively. The composition and thickness of the surface layer 12A and the surface layer 12B may be the same or different.

The laminate sheet 10Y of the second embodiment shown in fig. 2 has a structure in which a surface layer 12 containing a methacrylic resin (PM) is laminated on one surface of a substrate layer 11 containing a polycarbonate resin (PC).

In the laminated sheets 10X and 10Y, the thickness of each layer can be appropriately designed. The laminated sheets 10X and 10Y may have any layer other than the above.

The laminate sheet of the present invention is suitable as an infrared shielding laminate sheet for resin glass and the like.

The total light transmittance (Tt) of the laminate sheet of the present invention is 3 to 60% from the viewpoint of a good balance between light-shielding properties and light transmittance when used as a resin glass or the like.

The laminate sheet of the present invention has a transmittance of 60% or less at a wavelength of 1500nm from the viewpoint of having infrared shielding properties suitable as resin glass or the like.

The laminate sheet of the present invention has L defined in JIS Z8781-4 from the viewpoint of exhibiting a color tone close to jet black suitable for plexiglas and the like^*a^*b^*A in color space^*Absolute value of 10.0 or less and b^*The absolute value of (A) is 10.0 or less.

In the laminate sheet of the present invention, the substrate layer containing a polycarbonate resin (PC) contains one or more kinds of colorants. In addition, the surface layer containing the methacrylic resin (PM) may preferably contain one or two or more kinds of infrared absorbers.

Total light transmittance (Tt), transmittance at wavelength of 1500nm, and color tone (a)^*Sum of absolute values of values b^*Absolute value of value) can be adjusted by the kind and addition concentration of the one or more coloring agents added to the base material layer, the thickness of the base material layer, the kind and addition concentration of the one or more infrared absorbers added to the surface layer as needed, and the thickness of the surface layer.

(substrate layer)

< polycarbonate resin (PC) >)

The substrate layer contains one or more polycarbonate resins (PC). In the present specification, unless otherwise specified, the polycarbonate resin is a usual non-modified polycarbonate resin such as a bisphenol a type polycarbonate resin.

The polycarbonate resin (PC) is preferably obtained by copolymerizing one or more dihydric phenols with one or more carbonate precursors. Examples of the dihydric phenol include 2, 2-bis (4-hydroxyphenyl) propane (generally called bisphenol a), 1-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl) sulfone, and bisphenol a is preferable. Examples of the carbonate precursor include acid halides such as phosgene, carbonate esters such as diphenyl carbonate, and haloformates such as dihaloformates of dihydric phenols.

Examples of the method for producing a polycarbonate resin (PC) include: an interfacial polymerization method in which an aqueous solution of a dihydric phenol and an organic solvent solution of a carbonate precursor are reacted at an interface; and an ester exchange method in which a dihydric phenol is reacted with a carbonate precursor under high-temperature, reduced-pressure, solvent-free conditions.

The weight average Molecular Weight (MW) of the polycarbonate resin (PC) is preferably 10000 to 100000, more preferably 20000 to 70000. When Mw is 10000 or more, the laminate sheet of the present invention has excellent impact resistance and heat resistance. When Mw is 100000 or less, the moldability of the polycarbonate resin (PC) is excellent, and the productivity of the laminate sheet of the present invention can be improved.

From the viewpoint of stability of the hot melt molding, the Melt Flow Rate (MFR) of the resin constituting the base layer comprising one or more polycarbonate resins (PC) is preferably 1 to 30g/10 min, more preferably 3 to 20g/10 min, and particularly preferably 5 to 10g/10 min. In the present specification, unless otherwise specified, the MFR of the resin constituting the base layer is a value measured by using a melt index meter under conditions of a temperature of 300 ℃ and a load of 1.2 kg.

Commercially available polycarbonate resins (PC) can be used. Examples thereof include "カリバー (registered trademark)" and "SD ポリカ (registered trademark)" manufactured by Katsubishi polycarbonate Co., Ltd, "ユーピロン/ノバレックス (registered trademark)" manufactured by Mitsubishi engineering plastics Co., Ltd, "タフロン (registered trademark)" manufactured by Kashin Kaisha and "パンライト (registered trademark)" manufactured by Kaisha, Ltd.

< coloring agent >

The base material layer contains one or more than two coloring agents. As the colorant, pigments and organic dyes can be cited. In general, a pigment is excellent in weather resistance, but tends to be more likely to cause dispersion failure than an organic dye, and an organic dye is inferior in weather resistance than a pigment, but is less likely to cause dispersion failure, and tends to be excellent in productivity.

As the colorant, carbon black and/or an organic dye as an inorganic pigment is preferable. The color of the base material layer colored with the colorant is not particularly limited, and may be black or another color. In the application to plexiglass and the like, black is preferable, and black close to jet black is particularly preferable. When the color of the base material layer is black, one or two or more kinds of colorants which are black alone may be used, or a plurality of kinds of colorants which are black in combination may be used.

Although the organic dye tends to have poor weather resistance as compared with an inorganic pigment such as carbon black, in the laminate sheet of the present invention, the organic dye that can be contained in the base material layer can be protected from external light by the surface layer (for example, an ultraviolet absorber or the like contained in the surface layer), and therefore deterioration of the organic dye and deterioration of color tone caused by the deterioration can be suppressed in a weather resistance test.

The substrate layer preferably does not contain an infrared absorber. In general, a layer to which an infrared absorber is added tends to absorb infrared rays and increase in temperature in a weather resistance test, thereby promoting a deterioration reaction of a resin or the like. When an infrared absorber is added to a substrate layer containing a polycarbonate resin (PC) having poor weather resistance, discoloration (coloration) may be promoted in a weather resistance test.

The carbon black may be any known carbon black, and the type of raw material and the production method thereof are not particularly limited. Examples thereof include oil furnace black, channel black, acetylene black, and ketjen black.

The average particle diameter of the carbon black is not particularly limited, but is preferably 5 to 60nm, more preferably 7 to 55nm, and particularly preferably 10 to 50nm, from the viewpoints of suppressing the haze of the laminate and suppressing the occurrence of aggregation defects of the carbon black.

As the organic dye, known organic dyes can be used, and examples thereof include anthraquinones, azo dyes, anthrapyridones, perylenes, anthracenes, violanthrones, indanthrones, quinacridones, xanthenes, thioxanthenes, xanthenes,azines, their derivatives,Azolines, indigoids, thioindigoids, quinophthalones, naphthalimides, cyanines, methines, quinolines, pyrazolones, lactones, coumarins, bis-benzophenonesAzolyl thiophenes, naphthalene tetracarboxylic acids, phthalocyanines, triarylmethanes, aminoketones, bis (styryl) biphenyls, azines, rhodamines, and derivatives thereof. From the viewpoints of high heat resistance, a property of having a wide light absorption band in a long wavelength band, and weather resistance, anthraquinones, perylenes, perinones, azos, methines, quinolines, and the like are preferable.

One or more organic dyes of any color may be used. As described above, in the use of resin glass or the like, it is preferable to use one or two or more organic dyes which are black alone or a plurality of organic dyes which are black in combination.

Hereinafter, preferred specific examples of the organic dye are shown by common names of color indexes.

Examples of the anthraquinones include solvent red 52, solvent red 111, solvent red 149, solvent red 150, solvent red 151, solvent red 168, solvent red 191, solvent red 207, dispersion red 22, dispersion red 60, dispersion violet 31, solvent blue 35, solvent blue 36, solvent blue 63, solvent blue 78, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent green 3, solvent green 20, solvent green 28, dispersion violet 28, solvent violet 13, solvent violet 14, and solvent violet 36.

Examples of the perinone include solvent orange 60, solvent orange 78, solvent orange 90, solvent violet 29, solvent red 135, solvent red 162, and solvent red 179.

Examples of perylenes include solvent green 3, solvent green 5, solvent orange 55, reduced red 15, reduced orange 7, F orange 240, F red 305, F red 339, and F yellow 83.

Examples of azo-based compounds include solvent yellow 14, solvent yellow 16, solvent yellow 21, solvent yellow 61, solvent yellow 81, solvent red 23, solvent red 24, solvent red 27, solvent red 8, solvent red 83, solvent red 84, solvent red 121, solvent red 132, solvent violet 21, solvent black 23, solvent black 27, solvent black 28, solvent black 31, solvent orange 37, solvent orange 40, and solvent orange 45.

Examples of the methine group include solvent orange 80 and solvent yellow 93.

The quinolines include solvent yellow 33, solvent yellow 98, solvent yellow 157, disperse yellow 54, and disperse yellow 160.

Preferably, two or more organic dyes are used in combination, whereby a laminate sheet having high depth of color and clarity and excellent color tone can be obtained. Preferably, two or more selected from the group consisting of anthraquinones, perylenes, perinones, azos, methines, and quinolines are combined. For the same reason, it is also preferable to use one or two or more organic dyes in combination with carbon black as the colorant.

The concentration and mass per unit area of the colorant (preferably carbon black and/or organic dye) contained in the base material layer can be designed so that the total light transmittance (Tt) of the laminate sheet is 3 to 60% depending on the thickness of the base material layer and the thickness of the entire laminate sheet. The concentration of the colorant contained in the base material layer is preferably 0.0005 to 0.03 mass%, more preferably 0.000625 to 0.0257 mass%, and particularly preferably 0.000714 to 0.0225 mass%, although it depends on the thickness of the base material layer. The mass of the colorant contained in each unit area of the substrate layer is preferably 60-1080 mg/m²More preferably 75 to 925mg/m²Particularly preferably 85 to 810mg/m²。

The timing of adding the colorant is not particularly limited, and may be after the polymerization of the polycarbonate resin (PC).

< optional ingredients >

The substrate layer may contain one or more other polymers as needed. The other polymers are not particularly limited, and include: polyolefins such as polyethylene and polypropylene, other thermoplastic resins such as polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide and polyacetal; thermosetting resins such as phenol resins, melamine resins, silicone resins, and epoxy resins. The content of the other polymer in the base material layer is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The base material layer may contain various additives other than the colorant as needed. Examples of the other additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, light diffusers, delustering agents, impact modifiers such as core-shell particles and block copolymers, and phosphors. The content of the additive may be appropriately set within a range not impairing the effects of the present invention. For example, the content of the antioxidant is preferably 0.01 to 1 part by mass, the content of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, the content of the light stabilizer is preferably 0.01 to 3 parts by mass, and the content of the lubricant is preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the constituent resin of the base layer.

When another polymer and/or another additive is added to the base layer, the timing of addition may be at the time of polymerization of the polycarbonate resin (PC) or after polymerization.

(surface layer)

The surface layer is a methacrylic resin-containing layer containing one or more methacrylic resins (PM). The methacrylic resin (PM) is excellent in gloss, transparency, surface hardness, and the like. The content of the methacrylic resin (PM) in the surface layer is preferably 20 to 100 mass%.

From the viewpoint of stability of the hot melt molding, the Melt Flow Rate (MFR) of the constituent resin of the methacrylic resin-containing layer containing one or more methacrylic resins (PM) is preferably 1 to 10g/10 min, more preferably 1.5 to 7g/10 min, and particularly preferably 2 to 4g/10 min. In the present specification, unless otherwise specified, the MFR of the constituent resin of the methacrylic resin-containing layer is a value measured at a temperature of 230 ℃ and under a load of 3.8kg using a melt index meter.

As the methacrylic resin-containing layer preferable as the surface layer, there can be mentioned: a methacrylic resin-containing layer (MLA) composed of a methacrylic resin (composition) which may contain one or more methacrylic resins (PM) and, if necessary, one or more other polymers; a methacrylic resin-containing layer (MLB) composed of a methacrylic resin composition (MR1) containing a methacrylic resin (PM) and an SMA resin (S) (details are described later) and further optionally containing one or more other polymers; a methacrylic resin-containing layer (MLC) comprising a methacrylic resin composition (MR2) containing a methacrylic resin (PM) and multi-layer Rubber Particles (RP) (details are described later) and further optionally containing one or more other polymers.

< methacrylic resin (PM) >)

The methacrylic resin (PM) contained in the methacrylic resin-containing layers (MLA) to (MLC) is preferably a homopolymer or a copolymer containing a structural unit derived from one or more kinds of hydrocarbon methacrylate (hereinafter also simply referred to as methacrylate) containing Methyl Methacrylate (MMA). The hydrocarbon group in the methacrylate may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group, or a propyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group such as a phenyl group. From the viewpoint of transparency, the content of the methacrylate ester monomer unit in the methacrylic resin (PM) is preferably 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.

The methacrylic resin (PM) may contain a structural unit derived from one or more other monomers than methacrylate. Examples of the other monomers include Methyl Acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, acrylic esters such as 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, methylphenyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. Among them, from the viewpoint of availability, MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate are preferable, MA and ethyl acrylate are more preferable, and MA is particularly preferable. The content of the structural unit derived from another monomer in the methacrylic resin (PM) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The methacrylic resin (PM) is preferably obtained by polymerizing one or more methacrylic acid esters containing MMA and other monomers as necessary. In the case of using a plurality of monomers, polymerization is generally carried out after preparing a monomer mixture by mixing the plurality of monomers. The polymerization method is not particularly limited, and radical polymerization methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization are preferred from the viewpoint of productivity.

The methacrylic resin (PM) preferably has a weight average molecular weight (Mw) of 40000 to 500000. When Mw is 40000 or more, the methacrylic resin-containing layer has excellent scratch resistance and heat resistance, and when Mw is 500000 or less, the methacrylic resin-containing layer has excellent moldability. In the present specification, unless otherwise specified, "Mw" is a standard polystyrene conversion value measured by a Gel Permeation Chromatograph (GPC).

< methacrylic resin composition (MR1) >)

The methacrylic resin composition (MR1) contains the above-mentioned methacrylic resin (PM) and SMA resin (S), and may further contain one or more other polymers as required. The content of the methacrylic resin (PM) in the resin composition (MR1) is preferably 5 to 80 mass%, more preferably 5 to 55 mass%, and particularly preferably 10 to 50 mass%. The content of the SMA resin (S) in the resin composition (MR1) is preferably 95 to 20 mass%, more preferably 95 to 45 mass%, and particularly preferably 90 to 50 mass%. When the content of these resins is within the above range, the heat resistance of the surface layer is improved, and the surface condition of the laminate can be suppressed from being roughened when the laminate is heated in the step of forming a cured coating film. Further, the difference in glass transition temperature between the substrate layer and the polycarbonate resin (PC) used for the substrate layer can be reduced, and the warpage of the laminated sheet in sheet molding can be reduced.

In the present specification, the SMA resin (S) means a copolymer containing structural units derived from one or more aromatic vinyl compounds and one or more anhydrides containing Maleic Anhydride (MAH). As the aromatic vinyl compound, there may be mentioned: styrene (St); nuclear alkyl-substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-ethylstyrene and 4-tert-butylstyrene; alpha-alkyl substituted styrenes such as alpha-methylstyrene and 4-methyl-alpha-methylstyrene. Among them, styrene (St) is preferable from the viewpoint of availability. The content of the aromatic vinyl compound monomer unit in the SMA resin (S) is preferably 50 to 85 mass%, more preferably 55 to 82 mass%, and particularly preferably 60 to 80 mass%, from the viewpoint of transparency and moisture resistance of the resin composition (MR 1). As the acid anhydride, at least Maleic Anhydride (MAH) is used from the viewpoint of availability, and other acid anhydrides such as citraconic anhydride and dimethylmaleic anhydride may be used as necessary. From the viewpoint of transparency and heat resistance of the resin composition (MR1), the content of the acid anhydride monomer unit in the SMA resin (S) is preferably 15 to 50 mass%, more preferably 18 to 45 mass%, and particularly preferably 20 to 40 mass%.

The SMA resin (S) may contain one or more structural units derived from a methacrylate monomer in addition to the structural units derived from the aromatic vinyl compound and the acid anhydride. Examples of the methacrylic acid esters include MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate and 1-phenylethyl methacrylate. Among them, alkyl methacrylate in which the alkyl group has 1 to 7 carbon atoms is preferable. MMA is particularly preferable from the viewpoint of heat resistance and transparency of the SMA resin (S). The content of the methacrylate monomer unit in the SMA resin (S) is preferably 1 to 35 mass%, more preferably 3 to 30 mass%, and particularly preferably 5 to 26 mass%, from the viewpoint of the bending workability and transparency of the laminate sheet. In this case, the content of the aromatic vinyl compound monomer unit is preferably 50 to 84% by mass, and the content of the acid anhydride monomer unit is preferably 15 to 49% by mass.

The SMA resin (S) may have a structural unit derived from a monomer other than the aromatic vinyl compound, the acid anhydride, and the methacrylate ester. As the other monomer, other monomers described in the description of the methacrylic resin (PM) can be used. The content of the other monomer unit in the SMA resin (S) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The SMA resin (S) is obtained by polymerizing an aromatic vinyl compound, an acid anhydride, if necessary, a methacrylate, and if necessary, other monomers. In this polymerization, a monomer mixture is usually prepared by mixing a plurality of monomers, and then the polymerization is carried out. The polymerization method is not particularly limited, and radical polymerization methods such as bulk polymerization and solution polymerization are preferred from the viewpoint of productivity.

The Mw of the SMA resin (S) is preferably 40000 to 300000. When Mw is 40000 or more, the methacrylic resin-containing layer has excellent scratch resistance and impact resistance, and when Mw is 300000 or less, the methacrylic resin-containing layer has excellent moldability.

The resin composition (MR1) is obtained by mixing a methacrylic resin (PM), an SMA resin (S), and other polymers as needed. The mixing method includes a melt mixing method and a solution mixing method. In the melt-mixing method, melt-mixing can be carried out in an inert gas atmosphere such as nitrogen, argon, or helium, if necessary, using a single-screw or multi-screw mixer, a melt-mixer such as an open roll, a banbury mixer, or a kneader, or the like. In the solution mixing method, the methacrylic resin (PM) and the SMA resin (S) may be dissolved in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone and mixed.

< methacrylic resin composition (MR2) >)

The methacrylic resin composition (MR2) contains the above-mentioned methacrylic resin (PM) and the multilayer-structure Rubber Particles (RP), and may further contain one or more other polymers as required. The content of the methacrylic resin (PM) in the resin composition (MR2) is preferably 80 to 99% by mass, more preferably 85 to 95% by mass. The content of the multilayered Rubber Particles (RP) in the resin composition (MR2) is preferably 20 to 1% by mass, more preferably 15 to 5% by mass. By containing the multilayered Rubber Particles (RP) in the surface layer, the fracture resistance and the like of the laminate sheet can be improved. When the content of the multilayered Rubber Particles (RP) is too small, the end portion may be cracked depending on the conditions during punching. On the other hand, if the content of the multilayered rubber particles is too large, the laminate sheet may be whitened during molding, bending, or the like, the surface hardness of the surface layer may be reduced, damage may be easily caused, and the appearance of the product after shape transfer may be deteriorated.

In the present specification, the multilayer Rubber Particle (RP) is an acrylic multilayer rubber particle. As the multilayered Rubber Particle (RP), there can be mentioned an acrylic multilayered rubber particle having one or more graft copolymer layers containing one or more kinds of alkyl acrylate copolymers. As the acrylic multilayer rubber particles, those disclosed in japanese unexamined patent publication No. 2004-352837 and the like can be used. The acrylic multi-layer rubber particle preferably has a crosslinked polymer layer containing an alkyl acrylate unit having 6 to 12 carbon atoms.

The number of layers of the multilayered Rubber Particles (RP) is not particularly limited, and may be two or three or more. The multilayered Rubber Particles (RP) are preferably core-shell multilayered particles having three or more layers including an innermost layer (RP-a), one or more intermediate layers (RP-b), and an outermost layer (RP-c).

The constituent polymer of the innermost layer (RP-a) contains MMA units and a grafting or crosslinking monomer unit, and may further contain one or more other monomer units as required. The content of MMA units in the polymer constituting the innermost layer (RP-a) is preferably 80 to 99.99% by mass, more preferably 85 to 99% by mass, and particularly preferably 90 to 98% by mass. The proportion of the innermost layer (RP-a) in the multilayer-structured particle (RP) having three or more layers is preferably 0 to 15% by mass, more preferably 7 to 13% by mass. By setting the proportion of the innermost layer (RP-a) within this range, the heat resistance of the surface layer can be improved.

The polymer constituting the intermediate layer (RP-b) contains an alkyl acrylate unit having 6 to 12 carbon atoms and a grafting or crosslinking monomer unit, and may further contain one or more other monomer units as required. The content of the alkyl acrylate unit in the polymer constituting the intermediate layer (RP-b) is preferably 70 to 99.8% by mass, more preferably 75 to 90% by mass, and particularly preferably 78 to 86% by mass. The proportion of the intermediate layer (RP-b) in the three or more layers of the multilayered Rubber Particle (RP) is preferably 40 to 60% by mass, and more preferably 45 to 55% by mass. When the proportion of the intermediate layer (RP-b) is within this range, the surface hardness of the surface layer can be increased, and the surface layer can be made less likely to crack.

The constituent polymer of the outermost layer (RP-c) contains MMA units, and may further contain one or more other monomer units as required. The MMA unit content in the polymer constituting the outermost layer (RP-c) is preferably 80 to 100 mass%, more preferably 85 to 100 mass%, and particularly preferably 90 to 100 mass%. The proportion of the outermost layer (RP-c) in the multilayer-structured particle (RP) having three or more layers is preferably 35 to 50% by mass, and more preferably 37 to 45% by mass. When the ratio of the outermost layer (RP-c) is within this range, the surface hardness of the surface layer can be increased, and the surface layer can be made less likely to crack.

The particle diameter of the multilayered Rubber Particles (RP) is preferably 0.05 to 0.3 μm. The particle size can be measured by a known method such as electron microscope observation and dynamic light scattering measurement. The measurement by electron microscope observation can be performed, for example, by the following method: specific layers of the multilayer-structured Rubber Particles (RP) were selectively dyed by an electron dyeing method, and the particle diameters of a plurality of particles were actually measured by a Transmission Electron Microscope (TEM) or a Scanning Electron Microscope (SEM), and the average value thereof was determined. The dynamic light scattering method is a measurement method using the principle that the larger the particle size, the stronger the brownian motion of the particles.

In order to suppress the decrease in handling properties due to the adhesion of the multilayered Rubber Particles (RP) to each other and the decrease in impact resistance due to poor dispersion during melt kneading, the multilayered Rubber Particles (RP) may be used in the form of a latex or powder containing the multilayered Rubber Particles (RP) and the particles (D) for dispersion. The particles (D) for dispersion are composed of, for example, a (co) polymer of one or more monomers mainly composed of MMA, and particles having a relatively small particle diameter compared with the multilayered Rubber Particles (RP) can be used.

The particle diameter of the dispersing particles (D) is preferably as small as possible from the viewpoint of improving dispersibility, and is preferably 40 to 120nm, more preferably 50 to 100nm from the viewpoint of production reproducibility by emulsion polymerization. The amount of the dispersion particles (D) to be added is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total amount of the multilayered Rubber Particles (RP) and the dispersion particles (D), from the viewpoint of the effect of improving dispersibility.

< Infrared absorber >

The surface layer may preferably contain one or two or more infrared absorbers.

As the infrared ray absorber, a known infrared ray absorber can be used, and at least 1 kind of fine particles selected from the group consisting of:

general formula W_yO_z(wherein W is tungsten, O is oxygen, and z/y is 2.2. ltoreq. 2.999),

General formula M_xW_yO_z(wherein M is at least 1 element selected from the group consisting of H, He, alkali metal, alkaline earth metal and rare earth element, W is tungsten, O is oxygen, x/y is 0.001. ltoreq. x/y.ltoreq.1, z/y is 2.2. ltoreq. z/y.ltoreq.3), and a composite tungsten oxide fine particle,

General formula LaXO₃(wherein X is at least 1 metal element selected from the group consisting of Ni, Co, Fe and Mn),

General formula XB_m(wherein X is at least 1 metal element selected from the group consisting of Y, Sr, Ca and lanthanides, and 4.0. ltoreq. m.ltoreq.6.2) and boride fine particles,

Indium Tin Oxide (ITO) microparticles,

And Antimony Tin Oxide (ATO) fine particles.

The concentration of the infrared absorber contained in the surface layer may be designed so that the transmittance at a wavelength of 1500nm of the laminate sheet becomes 60% or less depending on the thickness of the surface layer. Although it depends on the thickness of the surface layer, it is preferably 0.01 to 1.00 mass%, more preferably 0.05 to 0.50 mass%, particularly preferably 0.10 to 0.30 mass%.

Generally, the layer to which the infrared absorber is added has a downward orientation: in the weather resistance test, the temperature rises due to the absorption of infrared rays, and the deterioration reaction of the resin or the like is promoted. In the present invention, the infrared absorber is added not to the base layer comprising the polycarbonate resin (PC) having poor weather resistance but to the surface layer comprising the methacrylic resin (PM) having excellent weather resistance, whereby discoloration (coloration) in the weather resistance test can be suppressed. Specifically, the Δ E value as a parameter of discoloration (coloring) in the weather resistance test can be suppressed to preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 2.5 or less.

The timing of adding the infrared absorber may be at the time of or after polymerization of the methacrylic resin (PM), SMA resin (S), multilayer-structure Rubber Particles (RP), or at the time of or after mixing of a plurality of resins including the methacrylic resin (PM).

< optional ingredients >

The other polymer that can be contained in the surface layer is not particularly limited, and the same other polymer as described in the description of the base material layer can be used. The content of the other polymer in the surface layer is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The surface layer may contain various other additives other than the infrared absorber as needed. As the other additive, the same other additives as those described in the description of the base layer can be used. The content of the additive may be appropriately set within a range not impairing the effects of the present invention. The amount of the antioxidant is preferably 0.01 to 1 part by mass, the amount of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, the amount of the light stabilizer is preferably 0.01 to 3 parts by mass, and the amount of the lubricant is preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the resin constituting the surface layer.

From the viewpoint of preventing deterioration of the polycarbonate resin (PC) contained in the base material layer and the organic dye that the base material layer may contain, the surface layer preferably contains an ultraviolet absorber.

When the surface layer contains other polymer and/or other additive other than the infrared absorber, the timing of addition may be at the time of or after polymerization of the methacrylic resin (PM), SMA resin (S), and resin such as the multilayer-structure Rubber Particles (RP), or at the time of or after mixing of a plurality of resins including the methacrylic resin (PM).

(Total thickness of laminate sheet)

The total thickness of the laminate sheet of the present invention is 3.0 to 10.0mm, preferably 3.5 to 8.0mm, and more preferably 4.0 to 7.0 mm. If the total thickness is 3.0mm or more, the rigidity of the laminated sheet can be secured, and the deflection of the laminated sheet can be suppressed even when a large area is formed. When the total thickness is 3.0mm or more, the toughness of the laminate sheet can be ensured, and the occurrence of cracks or fissures in the laminate sheet in the ball drop test can be suppressed. From the viewpoint of material cost and weight reduction, the total thickness is not preferably more than 10.0 mm.

(relationship between the thickness of the base material layer (T1) and the total thickness of the surface layer (T2))

The laminate sheet of the present invention satisfies T1 > T2 when the thickness of the base material layer is T1 and the total thickness of the surface layer is T2.

The total thickness of the surface layer (T2) is the sum of the thicknesses of the surface layers 12A and 12B formed on both surfaces of the base material layer 11 in the case of the laminate sheet 10X of the first embodiment shown in fig. 1, and is the thickness of the surface layer 12 alone formed on one surface of the base material layer 11 in the case of the laminate sheet 10Y of the second embodiment shown in fig. 2.

The total thickness (T2) of the surface layer is preferably 0.05 to 0.60mm, more preferably 0.10 to 0.50mm, particularly preferably 0.10 to 0.40mm, and most preferably 0.10 to 0.30 mm. If the total thickness (T2) of the surface layer is less than 0.05mm, the rigidity of the laminate sheet decreases, and there is a possibility that the surface hardness becomes insufficient after laminating a cured coating film functioning as a hard coat layer or the like. If the total thickness (T2) of the surface layer exceeds 0.60mm, the toughness of the laminate sheet may be reduced, and cracking or chipping may occur during the ball drop test.

(Total light transmittance (Tt) of laminate sheet)

The total light transmittance (Tt) of the laminate sheet of the present invention is 3 to 60%, preferably 5 to 50%, more preferably 10 to 40%. When the total light transmittance (Tt) is within the above range, the balance between light-shielding property and light-transmitting property becomes good when the glass is used as a resin glass or the like.

(transmittance at wavelength of 1500nm of laminate sheet)

The transmittance of the laminate of the present invention at a wavelength of 1500nm is 60% or less, preferably 50% or less, and more preferably 40% or less. When the transmittance at a wavelength of 1500nm is within the above range, infrared rays can be effectively blocked when used as resin glass or the like. For example, when used for window members of automobiles, buildings, and the like, it is possible to suppress temperature increases in the interior of the automobile, the room, and the like, and to reduce the temperature felt by a person.

When the base material layer contains carbon black, good infrared shielding properties can be achieved without adding an infrared absorber to the surface layer. Therefore, when the base material layer contains carbon black, the infrared absorber may not be added to the surface layer.

When the base material layer does not contain carbon black, a desired infrared shielding property can be achieved by adding an infrared absorber to the surface layer.

(color tone of laminate sheet)

The color tone of the laminate can be measured using a spectrophotometer in the transmission mode. The laminate sheet of the present invention is L defined in JIS Z8781-4^*a^*b^*A in color space^*Has an absolute value of 10.0 or less and b^*The absolute value of (A) is 10.0 or less. Preferably a^*Has an absolute value of 9.0 or less and b^*The absolute value of (A) is 9.0 or less. More preferably a^*Has an absolute value of 8.0 or less and b^*The absolute value of (A) is 8.0 or less. Particularly preferred is a^*Has an absolute value of 7.0 or less and b^*The absolute value of (A) is 7.0 or less. If the absolute value of a^*And b^*When the absolute value of (b) is within the above range, the laminate of the present invention can exhibit a black color close to jet black, and is preferable.

When only carbon black is used as the colorant added to the base layer, the color tone of the laminate sheet tends to become black with a red color peculiar to carbon black (see comparative example 2 in the [ example ] section described later). When carbon black is used as the colorant added to the base layer, the reddening can be reduced by using an organic dye in combination, and a color tone close to jet black can be obtained.

A color tone close to jet black can be obtained also by using one or two or more organic dyes which are black alone or in combination as a colorant added to the base layer, without using carbon black.

(other layer)

The laminate sheet of the present invention may have another layer as long as it is a laminate sheet in which a surface layer is laminated on at least one surface of a base material layer.

The laminate of the present invention may have a cured coating film on the outermost surface as required. The cured coating film can function as a scratch-resistant layer (hard coat layer) or a low-reflective layer for improving visibility. The cured coating film can be formed by a known method.

Examples of the material of the cured coating include inorganic, organic-inorganic, and silicone materials, and from the viewpoint of productivity, organic and organic-inorganic materials are preferable.

The inorganic cured coating film can be formed by vapor deposition of SiO by vacuum deposition, sputtering or the like₂、Al₂O₃、TiO₂And ZrO₂And an inorganic material such as a metal oxide.

The organic curable coating film can be formed by, for example, applying a coating material containing a resin such as a melamine resin, an alkyd resin, a urethane resin, or an acrylic resin and curing the coating material by heating, or applying a coating material containing a polyfunctional acrylic resin and curing the coating material by ultraviolet rays.

The organic-inorganic cured film can be formed, for example, by applying an ultraviolet-curable hard coat paint containing inorganic ultrafine particles such as silica ultrafine particles having a photopolymerizable functional group introduced into the surface thereof and a curable organic component, and polymerizing the photopolymerizable functional group of the curable organic component and the inorganic ultrafine particles by ultraviolet irradiation. This method can obtain a network-like crosslinked coating film in which inorganic ultrafine particles are dispersed in an organic matrix in a state of being chemically bonded to the organic matrix.

The silicone-based cured coating film can be formed by, for example, polycondensing a partial hydrolysate of a carbon-functional alkoxysilane, an alkyltrialkoxysilane, a tetraalkoxysilane, or the like, or a material obtained by adding colloidal silica to these.

Among the above methods, various roll coating methods such as dip coating and gravure roll coating, flow coating, bar coating, blade coating, spray coating, die coating, and bar coating can be cited as coating methods of the material.

The thickness of the scratch-resistant (hard coat) cured coating (scratch-resistant layer, hard coat) is preferably 2 to 30 μm, more preferably 5 to 20 μm. If the thickness is too thin, the surface hardness becomes insufficient, and if the thickness is too thick, cracking may occur due to bending in the manufacturing process. The thickness of the low-reflective cured coating (low-reflective layer) is preferably 80 to 200nm, more preferably 100 to 150 nm. Too thin or too thick may cause insufficient low reflection performance.

The laminate sheet of the present invention may have a known surface treatment layer such as an anti-glare (anti-reflection) layer, an anti-reflection (anti-reflection) layer, and an anti-fingerprint layer on the surface thereof as needed.

[ method for producing laminated sheet ]

Preferred embodiments of the method for producing a laminate sheet of the present invention will be described below. The laminate of the present invention can be produced by a known method, preferably by a production method including coextrusion molding.

The structure of a manufacturing apparatus for a laminated sheet according to an embodiment of the present invention will be described with reference to the drawings.

The manufacturing apparatus 30 shown in fig. 3 includes a substrate layer extruder 31, a substrate layer metering pump 33, and a substrate layer filter unit 34, which are connected via a substrate layer single pipe 32. The resin material for the base layer is melt-plasticized using the extruder 31 for the base layer and extruded into the single pipe 32 for the base layer. The molten resin material for a base layer extruded into the single pipe 32 for a base layer is sent downstream by a metering pump 33 such as a gear pump. A filtration unit 34 for a base material layer such as a polymer filter is disposed at the rear stage of the metering pump 33, and resin degradation products and other foreign matters are removed before lamination.

The manufacturing apparatus 30 includes a surface layer extruder 41, a surface layer metering pump 43, and a surface layer filter unit 44, which are connected to each other via a surface layer single pipe 42. The resin material for the surface layer is melt-plasticized using the extruder 41 for the surface layer and extruded into the single tube 42 for the surface layer. The resin material for a surface layer in a molten state extruded into the single pipe 42 for a surface layer is sent downstream by a metering pump 43 such as a gear pump. A surface layer filter unit 44 such as a polymer filter is disposed at the rear stage of the metering pump 43, and resin degradation products and other foreign matters are removed before lamination.

The manufacturing apparatus 30 includes a T-die 51, a plurality of cooling rollers (first to third cooling rollers 52 to 54 in the example of the figure), and a pair of take-off rollers 55.

The molten resin material for the base layer that has passed through the filter unit 34 for the base layer and the molten resin material for the surface layer that has passed through the filter unit 44 for the surface layer are coextruded in a molten state from a T-die 51 having a wide discharge opening in a form of a thermoplastic resin laminate in which the surface layer is laminated on at least one surface of the base layer. Examples of the lamination method include a dispenser (フィードブロック) method in which lamination is performed before the T-die flows in, and a multi-manifold method in which lamination is performed inside the T-die. From the viewpoint of improving the interface smoothness between layers of the laminate sheet, the multi-manifold system is preferable.

The thermoplastic resin laminate in a molten state after being coextruded from the T-die 51 is pressed and cooled by a plurality of cooling rollers (first to third cooling rollers 52 to 54 in the example shown in the figure). The number of the cooling rolls can be designed appropriately.

Examples of the cooling roll include a metal roll and an elastic roll having a metal outer cylinder on the outer circumferential portion thereof (hereinafter also referred to as a metal elastic roll). Examples of the metal roll include a drill roll and a spiral roll. The surface of the metal roller may be a mirror surface, or may have a pattern, unevenness, or the like. The metal elastic roller is composed of, for example, a roller made of stainless steel or the like, a metal outer cylinder made of stainless steel or the like covering the outer peripheral surface of the roller, and a fluid sealed between the roller and the metal outer cylinder, and can exhibit elasticity in the presence of the fluid. The thickness of the metal outer cylinder is preferably about 2mm to about 5 mm. The metal outer cylinder preferably has buckling property, flexibility, and the like, and preferably has a seamless structure without a welded joint portion. The metal elastic roller having such a metal outer cylinder is excellent in durability, and can be easily used because it can be treated in the same manner as a normal mirror roller when the metal outer cylinder is mirror-finished, and because it can be transferred in shape when a pattern, an irregularity, or the like is provided to the metal outer cylinder.

The laminate 56 obtained after cooling is pulled off by a pair of pull-off rollers 55. The above steps of co-extrusion, cooling and drawing are carried out continuously. In the present specification, a substance in a heated and molten state is mainly referred to as a "thermoplastic resin laminate", and a substance after curing is referred to as a "laminate sheet", but there is no clear boundary between the two.

The structure of the manufacturing apparatus may be changed as appropriate without departing from the scope of the present invention.

In the laminate sheet of the present invention, the substrate layer containing a polycarbonate resin (PC) contains one or more kinds of colorants. As the colorant, carbon black and/or an organic dye is preferable.

In the laminate sheet of the present invention, the surface layer containing a methacrylic resin (PM) may preferably contain one or two or more kinds of infrared absorbers.

According to the present invention, a laminate sheet having light-shielding properties, light-transmitting properties, infrared-shielding properties, and color tone suitable for use as resin glass or the like can be provided by adjusting the kind and addition concentration of one or more colorants added to the base layer, the thickness of the base layer, the kind and addition concentration of one or more infrared absorbers added to the surface layer as needed, and the thickness of the surface layer.

In the laminate sheet of the present invention, the polycarbonate resin (PC) contained in the base material layer and the organic dye contained in the base material layer can be protected from external light by the surface layer (for example, an ultraviolet absorber or the like contained in the surface layer), and therefore deterioration of the polycarbonate resin (PC) and the organic dye and deterioration of color tone thereof can be suppressed in a weather resistance test.

In addition, in general, a layer to which an infrared absorber is added tends to absorb infrared rays and increase in temperature during a weather resistance test, thereby promoting a deterioration reaction of a resin or the like. When the infrared absorber is used, the infrared absorber is added not to the substrate layer containing the polycarbonate resin (PC) having poor weather resistance and the organic dye as needed but to the surface layer containing the methacrylic resin (PM) having excellent weather resistance, whereby discoloration (coloration) in the weather resistance test can be suppressed.

By the above effects, the laminate sheet of the present invention is excellent in weather resistance.

The laminate sheet of the present invention has a total thickness of 3.0 to 10.0mm, and has excellent toughness because T1 > T2 is satisfied when the thickness of the base material layer is T1 and the total thickness of the surface layer is T2. Therefore, the occurrence of cracking and crazing at the time of the ball drop test is suppressed.

As described above, according to the present invention, a laminate sheet having good color tone, good infrared shielding properties, and excellent weather resistance, and a method for producing the same can be provided.

[ use ]

The laminate sheet of the present invention is suitable as resin glass and the like used for transportation machines such as automobiles, window members of buildings and the like.

Examples

Examples of the present invention and comparative examples will be described.

[ evaluation items and evaluation methods ]

The evaluation items and evaluation methods are as follows.

(copolymerization composition of SMA resin (S))

The copolymerization composition of the SMA resin (S) was prepared by using a nuclear magnetic resonance apparatus ("GX-270" manufactured by Nippon electronics Co., Ltd.) according to the following procedure¹³Determined by C-NMR method.

Dissolving 1.5g of SMA resin (S) in 1.5ml of deuterated chloroform to prepare a sample solution, and measuring the sample solution at room temperature under the condition that the cumulative number of times is 4000-5000 times¹³The following values were obtained from the C-NMR spectrum.

[ Integrated intensity of carbon peaks (around 127ppm, 134ppm, 143 ppm) of benzene ring (carbon number 6) in styrene unit ]/6

[ Integrated intensity of carbon Peak (around 170 ppm) of carbonyl site (carbon number 2) in maleic anhydride Unit ]/2

[ Integrated intensity of carbon Peak (around 175 ppm) of carbonyl site (carbon number 1) in MMA Unit ]/1

The molar ratios of styrene unit, maleic anhydride unit and MMA unit in the sample were determined from the area ratios of the above values. The mass composition of each monomer unit in the SMA resin (S) was determined from the obtained molar ratio and the mass ratio of each monomer unit (styrene unit: maleic anhydride unit: MMA unit: 104: 98: 100).

(weight average molecular weight (Mw))

The Mw of the resin was determined by GPC method according to the following procedure. Tetrahydrofuran was used as an eluent, and 2 columns of "TSKgel SuperMultipore HZM-M" and "SuperHZ 4000" manufactured by Tosoh corporation were used as columns connected in series. As the GPC apparatus, HLC-8320 (product number) manufactured by Tosoh corporation and equipped with a differential refractive index detector (RI detector) was used. A sample solution was prepared by dissolving 4mg of the resin in 5ml of tetrahydrofuran. The temperature of the column oven was set to 40 ℃ and 20. mu.l of the sample solution was injected at an eluent flow rate of 0.35 ml/min to determine the chromatogram. A standard curve showing the relationship between retention time and molecular weight was prepared by measuring 10 points of standard polystyrene having a molecular weight in the range of 400 to 5000000 by GPC. The Mw is determined based on the standard curve.

(glass transition temperature of resin (composition))

Regarding the glass transition temperature of the resin (composition), 10mg of the resin (composition) was charged into an aluminum pan and measured using a differential scanning calorimeter ("DSC-50", manufactured by Kabushiki Kaisha). After the nitrogen substitution was performed for 30 minutes or more, the temperature was raised from 25 ℃ to 200 ℃ at a rate of 20 ℃/min in a nitrogen gas flow of 10 ml/min, the mixture was held for 10 minutes, and the mixture was cooled to 25 ℃ (one scan). Subsequently, the temperature was raised to 200 ℃ at a rate of 10 ℃/min (secondary scanning), and the glass transition temperature was calculated by the midpoint method from the results obtained in the secondary scanning. When a plurality of Tg data are obtained in a resin composition containing two or more resins, the value of the resin derived from the main component is used as the Tg data.

(Total light transmittance (Tt))

From the resulting laminated sheet, a test piece of 50 mm. times.50 mm was cut out. Total light transmittance (Tt) of the test piece was measured using "HM-150" manufactured by village color technology research.

(transmittance at wavelength 1500nm, initial color tone of laminate sheet)

From the resulting laminated sheet, a test piece of 50 mm. times.50 mm was cut out. The absorption spectrum of the laminate in the wavelength region of 300 to 3000nm was measured using an "Shimadzu ultraviolet, visible and near infrared spectrophotometer UV-3600" manufactured by Shimadzu corporation to determine the transmittance at a wavelength of 1500 nm. The lower the transmittance at a wavelength of 1500nm, the higher the infrared shielding property of the laminate sheet. Next, L defined in JIS Z8781-4 was measured^*a^*b^*Color coordinates (L) of a color space^*Value a^*Value b^*Value) as the initial tone.

(Infrared shielding property)

A heat-insulating container made of expanded styrene having an outer dimension of about 40cm in length, width and height, and an upper surface opened, was prepared. In this heat insulating container, a black plate was provided in parallel with the bottom surface at a position 5cm below the upper surface having the opening portion, so that the temperature of the black plate could be measured by a thermocouple.

From the resulting laminate, a test piece of 450 mm. times.450 mm was cut out. On the upper surface of the heat-insulating container with an openingThe test piece was placed so that there was no gap between the heat-insulating container and the eye. At this time, the test piece was set so that the surface layer of the laminated sheet was outside the container. The heat-insulating container thus provided with the test piece was set outside the room at an air temperature of 30 ℃ and irradiated with direct sunlight. 30 minutes after the start of outdoor installation, the black panel temperature almost reached saturation, and the temperature (T) of the black panel was recorded_BP). The temperature T_BPThe lower the thickness, the more excellent the infrared shielding property and the heat insulating property of the laminate sheet.

(weather resistance)

From the resulting laminated sheet, a test piece of 50 mm. times.50 mm was cut out. In "SUPER XENON WEATHER METER SX-75" manufactured by SUGA TESTER, Inc., a test piece was placed so that the surface layer was the light source side. In UV irradiation intensity: 180W/m²Black panel temperature: the weather resistance test was carried out for 2000 hours under conditions of 63 ℃ and rainfall for 18 minutes within 120 minutes. After the test, the surface of the test piece was gently wiped and cleaned with a polyurethane sponge containing a neutral detergent. Next, an absorption spectrum in the wavelength region of 300 to 3000nm of the laminate sheet was measured by using an "Shimadzu ultraviolet, visible, and near infrared spectrophotometer UV-3600" manufactured by Shimadzu corporation. Next, L defined in JIS Z8781-4 was measured in the same manner as in the initial measurement (before the weather resistance test)^*a^*b^*Color coordinates (L) of a color space^*Value a^*Value b^*Value) as a color tone after the weather resistance test. The color difference (Δ E value) before and after the weather resistance test was obtained. The smaller the Δ E value, the less discoloration of the laminate after the weather resistance test, and the more preferable.

(falling ball test)

From the resulting laminated sheet, a test piece of 400 mm. times.400 mm was cut. As shown in fig. 4, a box-shaped sample holder 62 having a gripping portion 62H for gripping a peripheral edge portion (a region 10mm from the end of each side) of the test piece 61 at the upper portion and having an open upper surface is prepared. A test piece 61 is mounted on the sample holder 62. The height from the inner bottom surface of the sample holder 62 to the lower surface of the test piece 61 was 100 mm.

The 250g iron ball 63 was allowed to naturally fall vertically from the center of the iron ball 63 to the position where the height of the surface of the test piece 61 was 7m with respect to the upper surface of the test piece 61 attached to the sample holder 62 as described above. The appearance of the test piece 61 was visually observed after the ball was dropped, and the presence or absence of cracks or fissures was confirmed. This test was carried out on 5 test pieces, and the evaluation was carried out according to the following criteria.

A (good): no cracking or crazing was observed after ball dropping for all test pieces.

B (passing): cracking and/or crazing was observed after ball drop for 1 test piece.

C (poor): in the case of more than 2 test pieces, cracks and/or crazes were observed after dropping the ball.

[ Material ]

The materials used are as follows.

< polycarbonate resin (PC) >)

(PC1)

"SD ポリカ (registered trademark)" manufactured by Suxistalong polycarbonate Co., Ltd. (MFR of 6.7g/10 min under a load of 1.2kg at 300 ℃ C.).

< polycarbonate resin (PC) + additive >

One or two of an organic dye (Macrolex Green 5B, Macrolex violet 3R, diapesin orange HS), carbon black ("# 1000" manufactured by mitsubishi metal mine), and an infrared absorber (YMDS-874 "manufactured by sumitomo metal mine) were added to a polycarbonate resin (PC1), and melt-kneaded by a twin-screw extruder, thereby obtaining a plurality of polycarbonate resin-containing compositions (either composition had a temperature of 300 ℃ and an MFR of 7.0g/10 min under a load of 1.2 kg).

The amounts of the organic dye and carbon black added were adjusted, depending on the examples, so that the total light transmittance (Tt) of the laminate sheet became values shown in tables 1-2 and 2-2.

The amount of the infrared absorber added was adjusted, according to the examples, so that the transmittance at a wavelength of 1500nm of the laminate sheet became the values shown in tables 1-2 and 2-2.

< methacrylic resin (PM) >)

(PM1)

Polymethyl methacrylate (PMMA), manufactured by jel, "パラペット (registered trademark) HR" (MFR 2.0g/10 min under 3.8kg load at 230 ℃ c. and Tg 115 ℃).

< methacrylic resin (PM) + additive >

To a methacrylic resin (PM1), 1.00 mass% of an ultraviolet absorber (LA-31 RG manufactured by ADEKA) and/or 0.75 mass% of an infrared absorber (YMDS-874 manufactured by sumitomo metal mine) were added and melt-kneaded by a twin-screw extruder to obtain various methacrylic resin-containing compositions (the temperature of each composition was 230 ℃, MFR under 3.8kg load was 2.0g/10 min, Tg was 115 ℃).

< SMA resin (S) >

(S1)

SMA resins were obtained according to the method described in international publication No. 2010/013557 (styrene-maleic anhydride-MMA copolymer, styrene unit/maleic anhydride unit/MMA unit (mass ratio): 56/18/26, Mw 150000, Tg 138 ℃).

< methacrylic resin-containing resin composition (MR1) >)

(MR1-1)

Mixing a methacrylic resin (PM1) and an SMA resin (S1) in a mass ratio of 30: 70 to obtain a methacrylic resin-containing resin composition (MR 1-1).

< methacrylic resin-containing resin composition (MR1) + additive >

A methacrylic resin-containing resin composition (MR1-1) was melt-kneaded by adding 1.00 mass% of an ultraviolet absorber ("LA-31 RG" manufactured by ADEKA) and/or 0.75 mass% or 1.50 mass% of an infrared absorber ("YMDS-874" manufactured by Sumitomo Metal mining) to a methacrylic resin-containing resin composition (MR1-1) using a twin-screw extruder.

< multilayer Rubber Particle (RP) >)

(RP1)

An innermost layer (RP-a1), an intermediate layer (RP-b1) and an outermost layer (RP-c1) were formed in this order from a copolymer having the following composition, thereby producing acrylic multi-layer structured rubber particles (RP1) having a 3-layer structure. The particle size was 0.23. mu.m.

Innermost layer (RP-a 1): methyl Methacrylate (MMA) units/Methyl Acrylate (MA) units/allyl methacrylate units as a crosslinkable monomer (mass ratio) 32.91/2.09/0.07,

Intermediate layer (RP-b 1): butyl acrylate unit/styrene unit/allyl methacrylate unit as crosslinkable monomer (mass ratio) 37.00/8.00/0.90,

Outermost layer (RP-c 1): methyl Methacrylate (MMA) units/Methyl Acrylate (MA) units (mass ratio) was 18.80/1.20.

< particles for dispersion (D) >)

(D1) Methacrylic copolymer particles, Methyl Methacrylate (MMA) units/methyl acrylate units (mass ratio) 90/10, particle diameter: 0.11 μm.

Powder (RD1) containing rubber particles having a multilayer structure

The latex containing the multilayered rubber particles (RP1) and the latex containing the particles for dispersion (D1) were mixed in a ratio of 67 to 33 in terms of the mass ratio of solid content. The resulting mixed latex was frozen at-30 ℃ for 4 hours. The frozen latex was put into 90 ℃ warm water 2 times the amount of the frozen latex, dissolved to prepare a slurry, and then the slurry was kept at 90 ℃ for 20 minutes to dehydrate the slurry and dried at 80 ℃ to obtain a powder containing multilayered rubber particles (RD 1).

< methacrylic resin-containing resin composition (MR2) >)

(MR2-1)

A methacrylic resin (PM1) and a multilayer-structure rubber particle-containing powder (RD1) were melt-kneaded at a mass ratio of 88: 12 to obtain a methacrylic resin-containing resin composition (MR 2-1).

< methacrylic resin-containing resin composition (MR2) + additive >

To a methacrylic resin-containing resin composition (MR2-1), one or two of 1.00 mass% of an ultraviolet absorber (LA-31 RG manufactured by ADEKA), 0.75 mass% or 1.50 mass% of an infrared absorber (YMDS-874 manufactured by Sumitomo Metal mining), an organic dye (Macrolex Green 5B, Macrolex violet 3R, Diarsesin orange HS) and Indium Tin Oxide (ITO) fine particles (PI-6T manufactured by Mitsubishi Materials Electronic Chemicals) functioning as an infrared absorber were added, and the mixture was melt-kneaded by a twin-screw extruder to obtain a methacrylic resin-containing resin composition.

The amount of the organic dye added was adjusted, according to the examples, so that the total light transmittance of the laminate sheet became the values shown in tables 1-2 and 2-2.

The amounts of the infrared absorber and the ITO fine particles functioning as the infrared absorber were adjusted, according to the examples, so that the transmittance at a wavelength of 1500nm of the laminate sheet became values shown in tables 1-2 and 2-2.

The ITO fine particles are also one kind of infrared absorbers, but the "infrared absorber" in the table is "YMDS-874" manufactured by Sumitomo Metal mining.

[ examples 1 and 2]

The laminate sheet was formed using the manufacturing apparatus shown in fig. 3.

As the extruder 31 for the base layer, a resin material for the base layer, which is obtained by adding an organic dye and carbon black to a polycarbonate resin (PC1), was melt-extruded using a 150 mm-diameter single screw extruder (manufactured by toshiba mechanical corporation). As the surface layer extruder 41, a 65mm diameter single screw extruder (manufactured by toshiba mechanical corporation) was used, and a resin material for a surface layer, in which 1.00 mass% of an ultraviolet absorber was added to a methacrylic resin (PM1), was melt-extruded. In example 1, two surface layer extruders 41 were prepared.

These resins in a molten state are laminated by a multi-manifold type die, and a 3-layer structure (surface layer 1/base material layer/surface layer 2) (example 1) or a 2-layer structure (thermoplastic resin laminate of surface layer 1/base material layer (example 2)) in a molten state is given in total from a T-shaped die 51, and this molten thermoplastic resin laminate is sandwiched between a first cooling roller 52 and a second cooling roller 53 adjacent to each other and wound around the second cooling roller 53, and sandwiched between the second cooling roller 53 and a 3 rd cooling roller 54 and wound around a 3 rd cooling roller 54, whereby cooling is performed, and after cooling, the obtained laminate sheet 56 is separated by a pair of separation rollers 55.

The laminated structure (composition and thickness of each layer), the relationship of the thicknesses of the layers, the total thickness, and the evaluation results are shown in tables 1-1 and 1-2.

Examples 3 to 15, comparative examples 1 to 6, and reference example 1

Laminates having a 2-layer structure or a 3-layer structure were produced in the same manner as in example 1 or example 2, except that the composition and thickness of each layer were changed as shown in table 1-1 or table 2-1. In these examples, the conditions not shown in the table are general conditions. The evaluation results of the examples are shown in tables 1-2 and 2-2.

[ tables 1-2]

[ tables 2-2]

[ conclusion of the results ]

In examples 1 to 6, carbon black and an organic dye were added as colorants to a substrate layer containing a polycarbonate resin. In examples 7 to 15, an organic dye alone or a combination of carbon black and an organic dye was added as a colorant to a substrate layer containing a polycarbonate resin, and an infrared absorber was further added to a surface layer containing a methacrylic resin. In each of examples 1 to 15, a laminate sheet having a total light transmittance (Tt) of 3 to 60% and a transmittance at 1500nm of 60% or less was obtained. The laminate of any of the examples satisfies a^*Has an absolute value of 10.0 or less and b^*Has an absolute value of 10.0 or less, exhibits a black color close to a jet black color, and has a good color tone and excellent appearance quality. The black panel temperature T (in the infrared shielding test) of the laminate sheet of any of the examples_BP) Both of them are at most 80 ℃ and have good infrared shielding properties and heat shielding properties. The color difference Δ E before and after the weather resistance test of the laminate of any of the examples was small, and the weather resistance was good. The laminates of any of the examples showed good results in ball drop tests and good toughness.

The transmittance at 1500nm of the laminate sheet of comparative example 1, in which only the organic dye as the colorant was added to the base layer and the infrared absorber was not added to the surface layer, was as high as 85%, and the black plate temperature (T) in the test of infrared shielding property_BP) The infrared shielding property is poor at 85 ℃. When an organic dye is used as the colorant added to the base material layer, it is preferable to use carbon black in combination or to add an infrared absorber to the surface layer.

The transmittance at 1500nm of the laminate sheet of comparative example 2, in which only carbon black as a colorant was added to the base material layer and no infrared absorber was added to the surface layer, was as low as 45%, and the black plate temperature (T) in the test of infrared shielding property_BP) The temperature is as low as 75 ℃, and the infrared shielding property is good. However, b^*The value of (A) is as high as 14.4, the hue is reddish black, and the appearance quality is poor. When carbon black is used as the colorant added to the base layer, it is preferable to use an organic dye in combination.

The laminates of comparative examples 3 to 5 having a total thickness of less than 3.0mm were cracked and/or cracked in a ball drop test, and had poor toughness.

The laminate of comparative example 6, in which the colorant was not added to the base material layer but the organic dye was added to the surface layer, had a large color difference Δ E before and after the weather resistance test, and was poor in weather resistance. It is considered that when the organic dye is added to the base material layer, the organic dye is protected by the ultraviolet absorber contained in the surface layer, and when the organic dye is added to the surface layer, the same effect cannot be obtained. The surface layer preferably does not contain an organic dye.

The laminate sheet of reference example 1, in which the organic dye and the infrared absorber were added to the base layer and the infrared absorber was not added to the surface layer, had a large color difference Δ before and after the weather resistance test, and was poor in weather resistance. It is considered that the temperature of the layer containing the infrared absorber increases during the weather resistance test, and the deterioration reaction of the resin or the like is accelerated. Therefore, it is preferable not to add an infrared absorber to the layer containing a polycarbonate resin or an organic dye having poor weather resistance.

The present invention is not limited to the above-described embodiments and examples, and the design can be appropriately changed without departing from the gist of the present invention.

This application is based on the priority claim of japanese application No. 2018-141338 filed on 7/27 of 2018, the entire disclosure of which is incorporated into the present application.

Description of the reference symbols

10X, 10Y laminate

11 base material layer

12. 12A, 12B surface layer