Multilayer body and dustproof cover for head-up display

Abstract

Provided are a multilayered body and a dust-proof cover for a head-up display, said dust-proof cover using said multilayered body. The multilayered body has a substrate layer and an infrared ray absorption layer, wherein the infrared ray absorption layer includes an ultraviolet ray-curable resin and a tungsten oxide, the ultraviolet ray-curable resin includes a component derived from a multifunctional (meth)acrylate with a weight average molecular weight of 1000 or greater, and the percentage of the tungsten oxide in the infrared ray absorption layer is 25-50 mass%.

Description

[Technical Field]

[0001] The present invention relates to a multilayer body and a dustproof cover for a head-up display, and more particularly to a multilayer body having a polycarbonate resin layer and an acrylic resin layer. [Background technology]

[0002] Polycarbonate resin is widely used in a variety of fields, not only because of its excellent transparency, but also because it is easier to process and has better impact resistance than glass, and because it does not emit toxic gases compared to other plastic materials. It is also used as a thermoforming material for vacuum forming, pressure forming, and other processes.

[0003] On the other hand, polycarbonate resin generally has low surface hardness, so that the surface of molded products made of polycarbonate resin tends to be easily scratched. Therefore, when polycarbonate resin is made into a film, it has been studied to form a layer containing an acrylic resin or an infrared absorbing layer (protective layer) on the surface to prevent scratches on the product surface. Such multilayer bodies are described in Patent Document 1 and Patent Document 2. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 060100 [Patent Document 2] International Publication No. 2021 / 215435 Summary of the Invention [Problem to be solved by the invention]

[0005] Here, in order to suppress the transmission of near-infrared rays, tungsten oxide is generally blended into the infrared absorbing layer as described above. In order to further improve weather resistance, it is considered to increase the content of tungsten oxide. However, the inventors have found that the adhesion between layers (particularly, the adhesion of the infrared absorbing layer to the substrate) deteriorates depending on the content of tungsten oxide. The present invention aims to solve such problems and to provide a multilayer body that has excellent weather resistance and excellent adhesion between layers, and a dustproof cover for a head-up display that uses the same. [Means for solving the problem]

[0006] In view of the above problems, the present inventors have conducted research and found that the above problems can be solved by using a specific ultraviolet-curable resin together with tungsten oxide in the infrared absorbing layer. Specifically, the above problems were solved by the following means. <1> It has a base layer and an infrared absorbing layer, the infrared absorbing layer contains an ultraviolet curable resin and tungsten oxide; the ultraviolet curable resin contains a component derived from a polyfunctional (meth)acrylate having a weight average molecular weight of 1000 or more, A multilayer body, wherein the proportion of the tungsten oxide in the infrared absorbing layer is 25 to 50 mass %. <2> The ultraviolet curable resin contains a component derived from a polyfunctional urethane (meth)acrylate. <1> The multilayer body according to claim 1. <3> the substrate layer includes an acrylic resin layer and a polycarbonate resin layer, the infrared absorbing layer is located on the surface of the polycarbonate resin layer opposite to the acrylic resin layer; <1> or <2> The multilayer body according to claim 1. <4> The haze measured according to JIS K7136 is 2.0% or less. <1> ~ <3> 10. The multilayer body according to any one of the preceding items. <5> The infrared absorbing layer contains the tungsten oxide in an amount of 30 to 50 mass %. <1> ~ <4> 10. The multilayer body according to any one of the preceding items. <6> Further, the film has a hard coat layer, The hard coat is formed by laminating an infrared absorbing layer, a polycarbonate resin layer, an acrylic resin layer, and a hard coat layer in this order. <1> ~ <5> 10. The multilayer body according to any one of the preceding items. <7> The hard coat layer contains inorganic particles. <6> The multilayer body according to claim 1. <8> Further, the optical element has an anti-reflection layer. <1> ~ <7> 10. The multilayer body according to any one of the preceding items. <9> Further, the polarizing layer is provided. <1> ~ <8> 10. The multilayer body according to any one of the preceding items. <10> <1> ~ <9> A dustproof cover for a head-up display, comprising the multilayer body according to any one of claims 1 to 11. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a multilayer body having excellent weather resistance and excellent interlayer adhesion, and a dustproof cover for a head-up display using the same. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the multilayer body of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. In this specification, unless otherwise specified, the weight average molecular weight and number average molecular weight are values ​​measured by GPC (gel permeation chromatography) in terms of polystyrene. In this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate. The term "multilayer body" as used herein includes those in the form of a film or sheet. The terms "film" and "sheet" refer to generally flat molded articles that are thin relative to their length and width, respectively. The terms "film" and "sheet" as used herein may be either single-layer or multi-layer. If the measurement methods, etc. described in the standards shown in this specification differ from year to year, they will be based on the standards in effect as of January 1, 2022, unless otherwise stated. The drawings attached to the specification are schematic diagrams, and may not be drawn to scale. In this specification, near-infrared light refers to light having a wavelength of 700 nm to 2500 nm.

[0010] The multilayer body of the present embodiment has a base layer and an infrared absorbing layer, the infrared absorbing layer contains an ultraviolet curable resin and tungsten oxide, the ultraviolet curable resin contains a component derived from a polyfunctional (meth)acrylate having a weight average molecular weight of 1000 or more, and the proportion of the tungsten oxide in the infrared absorbing layer is 25 to 50 mass%. By adopting such a constitution, a multilayer body having excellent weather resistance and excellent adhesion between layers can be obtained. By adjusting the content of tungsten oxide in the infrared absorbing layer to 25 to 50 mass %, weather resistance can be improved. However, whether the content of tungsten oxide is high or low results in insufficient curing and poor adhesion. The resin composition of this embodiment was able to maintain high adhesion by using a polyfunctional (meth)acrylate with a weight-average molecular weight of 1000 or more. The reason for this is presumed to be that the large molecular weight allows the shrinkage stress between crosslinking points to be alleviated, thereby reducing cure shrinkage. The present invention will be described in detail below.

[0011] <Infrared absorbing layer> The infrared absorbing layer in this embodiment contains an ultraviolet curable resin and tungsten oxide, and the ultraviolet curable resin contains a component derived from a polyfunctional (meth)acrylate having a weight average molecular weight of 1000 or more. Typically, the infrared absorbing layer is formed in a cured state of the polyfunctional (meth)acrylate having a weight average molecular weight of 1000 or more.

[0012] <<UV curable resin>> The ultraviolet curable resin used in this embodiment is not particularly limited in type, and any known resin can be used as long as it is a polyfunctional (meth)acrylate with a weight average molecular weight of 1000 or more.

[0013] Examples of ultraviolet-curable resins include polyfunctional (meth)acryloyl group-containing polymers having a weight-average molecular weight of 1000 or more, and polyfunctional urethane (meth)acrylate oligomers having a weight-average molecular weight of 1000 or more, with polyfunctional urethane (meth)acrylate oligomers having a weight-average molecular weight of 1000 or more being preferred.

[0014] A polyfunctional (meth)acryloyl group-containing polymer having a weight-average molecular weight of 1000 or more can be obtained, for example, by copolymerizing (meth)acrylic acid and (meth)acrylic acid glycidyl ether to synthesize an epoxy compound having a (meth)acrylate skeleton, and then adding acrylic acid, methacrylic acid, etc. to this. A synthesis example is shown below. [ka]

[0015] Epoxy (meth)acrylates used in polyfunctional (meth)acryloyl group-containing polymers having a weight average molecular weight of 1000 or more include those having a repeating unit represented by the following formula (I). [ka] In formula (I), m is an alkylene group having 1 to 4 carbon atoms or a single bond, n is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, p is a single bond or an alkylene group having 1 or 2 carbon atoms, and q is an alkyl group having a total of 1 to 12 carbon atoms which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group, or a hydrogen atom.

[0016] The polyfunctional epoxy (meth)acrylate polymer having a weight average molecular weight of 1000 or more more preferably contains the following repeating unit, that is, a repeating unit in which, in the above formula (I), m is an alkylene group having 1 or 2 carbon atoms, n is an alkyl group having 1 or 2 carbon atoms, p is a single bond or a methylene group, and q is an alkyl group having a total of 1 to 6 carbon atoms which may contain at least one substituent selected from the group consisting of a glycidyl group, a hydroxyl group, and an acryloyl group, or a hydrogen atom. For example, in the above formula (I), m is a methylene group, n is a methyl group, p is a single bond, and q is a methyl group, an alkyl group having 5 or less carbon atoms and containing a glycidyl group (epoxy group), an alkyl group having 8 or less carbon atoms and containing a hydroxyl group and an acryloyl group, or the like.

[0017] Specific examples of repeating units contained in a polyfunctional epoxy (meth)acrylate polymer having a weight average molecular weight of 1000 or more include those represented by the following formulae (II-a), (II-b), and (II-c). [ka]

[0018] In a polyfunctional (meth)acrylate polymer having a weight-average molecular weight of 1000 or more, the repeating unit of the formula (II-a) preferably accounts for 30 to 85 mol %, more preferably 40 to 80 mol %, based on the total number of moles of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b), and the repeating unit of the formula (II-c). The repeating unit of the formula (II-b) preferably accounts for 5 to 30 mol %, more preferably 10 to 25 mol %, based on the total number of moles. The repeating unit of the formula (II-c) preferably accounts for 10 to 40 mol %, more preferably 10 to 35 mol %, based on the total number of moles. The molar ratio of the repeating units of the above formula (II-a), the repeating units of the above formula (II-b), and the repeating units of the above formula (II-c) is preferably 4.5-5.5:1.5-2.5:2.5-3.5, for example, 5:2:3.

[0019] Such polyfunctional (meth)acryloyl group-containing polymers having a weight-average molecular weight of 1,000 or more are commercially available and readily available. Examples include SMP-220A (Kyoeisha Chemical Co., Ltd.), SMP-250A (Kyoeisha Chemical Co., Ltd.), SMP-360A (Kyoeisha Chemical Co., Ltd.), SMP-550A (Kyoeisha Chemical Co., Ltd.), HA7975 (Showa Denko Materials Co., Ltd.), HA7975D (Showa Denko Materials Co., Ltd.), RA-4101 (Negami Chemical Industrial Co., Ltd.), 8KX-078 (Taisei Fine Chemical Co., Ltd.), and 8KX-212 (Taisei Fine Chemical Co., Ltd.).

[0020] Examples of polyfunctional urethane (meth)acrylate oligomers having a weight average molecular weight of 1,000 or more include urethane reaction products of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; and urethane reaction products of an isocyanate compound obtained by reacting a polyol with a polyisocyanate and a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule.

[0021] Examples of the (meth)acrylate monomer having at least one (meth)acryloyloxy group and one hydroxyl group per molecule used in the urethanization reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0022] Examples of polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

[0023] Polyols used in the urethanization reaction generally include aromatic, aliphatic, and alicyclic polyols, as well as polyester polyols, polyether polyols, etc. Typical aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, and hydrogenated bisphenol A.

[0024] Examples of polyester polyols include those obtained by the dehydration condensation reaction of the above-mentioned polyols with polycarboxylic acids. Specific examples of polycarboxylic acid compounds include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. Examples of polyether polyols include polyalkylene glycols and polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or phenols with alkylene oxides.

[0025] Multifunctional polyester (meth)acrylate oligomers can be obtained by a dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyol. Examples of polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may also be anhydrides. Examples of polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0026] Multifunctional epoxy (meth)acrylate oligomers with a weight-average molecular weight of 1,000 or more can be obtained by the addition reaction of polyglycidyl ethers with (meth)acrylic acid. Examples of polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

[0027] Commercially available polyfunctional urethane (meth)acrylates can also be used, such as UN-3320HA, UN-3320HC, UN-906S, UN-901T, UN-952, UN-904, UN-905, UN-3320HS, and H-575 (all manufactured by Negami Chemical Industrial Co., Ltd.), U-6LPA and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL5129, EBECRYL4738, EBECRYL4740, EBECRYL4513, EBECRYL8254, EBECRYL220, and EBECRYL8701 (all manufactured by Daicel Allnex Corporation).

[0028] The double bond equivalent of the ultraviolet curable resin is 400 g / mol or less, preferably 360 g / mol or less, and more preferably 250 g / mol or less. By making it equal to or greater than the lower limit, the hardness of the obtained infrared absorbing layer tends to be improved. The lower limit is preferably 100 g / mol or more.

[0029] The weight-average molecular weight of the ultraviolet-curable resin is 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more. By making it equal to or greater than the lower limit, cure shrinkage can be more effectively suppressed. Furthermore, the weight-average molecular weight of the ultraviolet-curable resin is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. By making it equal to or less than the upper limit, coating can be made easier. The weight average molecular weight of the ultraviolet curable resin in this embodiment is a value measured according to the following method. The weight-average molecular weight of the ultraviolet-curable resin can be measured based on the description in paragraphs 0061 to 0064 of JP-A No. 2007-179018. Details of the measurement method are given below. First, a calibration curve showing the relationship between elution time and the molecular weight of the UV-curable resin is created using the universal calibration method with polystyrene as the standard polymer. The elution curve (chromatogram) of the UV-curable resin is then measured under the same conditions as for the calibration curve described above. Furthermore, the weight-average molecular weight (Mw) is calculated from the elution time (molecular weight) of the UV-curable resin and the peak area (number of molecules) at that elution time. The weight-average molecular weight is expressed by the following formula (A), where Ni represents the number of molecules having a molecular weight Mi. Mw=Σ(NiMi 2 ) / Σ(NiMi)····(A) Equipment: Waster, Alliance Column: Showa Denko Shodex K-805L (2 columns) Detector: UV detector, wavelength 254 nm Eluent: chloroform

[0030] In addition to the above, the ultraviolet-curable resin may contain a monofunctional alkyl (meth)acrylate monomer and / or a polyfunctional alkyl (meth)acrylate monomer, a styrene monomer, a styrene oligomer, a cyclic acid anhydride, an N-substituted maleimide compound, a lactone ring compound, and the like.

[0031] The content of the component derived from the polyfunctional (meth)acrylate having a weight-average molecular weight of 1000 or more contained in the infrared absorbing layer of this embodiment is preferably 45% by mass or more, more preferably 50% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, in the infrared absorbing layer (cured product). By setting the content at or above the lower limit, a multilayer body with higher toughness and hardness tends to be obtained. On the other hand, by setting the content at or below the upper limit, a coating film with a good balance between transmittance and infrared absorption can be obtained. The infrared absorbing layer of the present embodiment may contain only one kind or two or more kinds of components derived from an ultraviolet curable resin or a polyfunctional (meth)acrylate having a weight average molecular weight of 1000 or more. When two or more kinds are contained, the total amount is preferably in the above range.

[0032] <<Tungsten oxide>> The infrared absorbing layer in this embodiment contains tungsten oxide.

[0033] The colorant used in this embodiment contains tungsten oxide. By containing tungsten oxide, the multilayer body can block near-infrared rays, and can be more preferably used as a dustproof cover for a head-up display. As the tungsten oxide, cesium tungsten oxide (CWO) is preferred.

[0034] The content of tungsten oxide in the infrared absorbing layer of this embodiment is 25% by mass or more, preferably 28% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, or may be 40% by mass or more, and is 50% by mass or less, preferably 47% by mass or less, more preferably 45% by mass or less, or may be 44% by mass or less. By setting the content at or above the lower limit, the infrared absorbing effect tends to be further improved. Furthermore, by setting the content at or below the upper limit, excellent transparency can be maintained. The infrared absorbing layer of the present embodiment may contain only one type of tungsten oxide, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0035] The infrared absorbing layer in this embodiment may or may not contain a colorant other than tungsten oxide. The infrared absorbing layer in this embodiment preferably does not substantially contain any pigments (or colorants) other than tungsten oxide. "Substantially free" means that the content of pigments (or colorants) other than tungsten oxide contained in the infrared absorbing layer is preferably less than 10% by mass, more preferably less than 5% by mass, and even more preferably less than 1% by mass of the content of tungsten oxide.

[0036] <<Photopolymerization initiator>> In this embodiment, the infrared absorbing layer may contain a photopolymerization initiator. Any known photopolymerization initiator can be used as long as it can cure the ultraviolet curable resin. The photopolymerization initiator is preferably a photoradical generator that is cleaved by visible light or ultraviolet light having a wavelength shorter than 450 nm to generate radicals, and examples of such a photopolymerization initiator include photopolymerization initiators having an acylphosphine oxide skeleton, an α-hydroxyketone skeleton, a benzyl dimethyl ketal skeleton, an aminoketone skeleton, a benzophenone skeleton, or a trichloromethyl group-containing triazine skeleton, and it is preferable to include a photopolymerization initiator having an acylphosphine oxide skeleton and / or an α-hydroxyketone skeleton. Specific examples of the photopolymerization initiator include benzophenone, thioxanthone, benzil dimethyl ketal, α-hydroxyketone, α-hydroxyalkylphenone, α-aminoketone, α-aminoalkylphenone, monoacylphosphine oxide, bisacylphosphine oxide, hydroxybenzophenone, aminobenzophenone, titanocene, oxime ester, and oxyphenylacetic acid ester. In addition to the above, as the polymerization initiator, the description in paragraph 0039 of WO 2023 / 095664, the description in paragraphs 0234 to 0238 of WO 2022 / 102736, the description in paragraph 0135 of JP-A-2010-106268, the description in paragraphs 0018 to 0025 of JP-A-2009-13115, and the description in paragraphs 0018 to 0025 of JP-A-2005-154312 can be referred to, the contents of which are incorporated herein by reference.

[0037] The content of the photopolymerization initiator contained in the infrared absorbing layer of this embodiment is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, and is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less. By setting the content to be equal to or greater than the lower limit, sufficient curability can be achieved. Furthermore, by setting the content to be equal to or less than the upper limit, storage stability and deterioration over time tend to be further improved. The infrared absorbing layer of the present embodiment may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0038] <<Other Ingredients>> In addition to the above components, the infrared absorbing layer may contain a leveling agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, a flame retardant assistant, a colorant, an antistatic agent, a fluorescent brightening agent, an antifogging agent, a flowability improver, a plasticizer, a dispersant, an antibacterial agent, an antiblocking agent, an impact improver, a sliding improver, a hue improver, an acid trapping agent, etc. These components may be used alone or in combination of two or more. The total amount of these other components in the infrared absorbing layer is preferably 0% by mass or more and less than 10% by mass, more preferably 0% by mass or more and less than 5% by mass, and may be 0% by mass or more and less than 1% by mass.

[0039] <<Light stabilizers>> Examples of light stabilizers that can be used include hindered amine light stabilizers such as bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1-undecanoxyl-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-13 pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate, and bis[1,2,2,6,6-pentamethyl-4-piperidinyl] 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate. The content of the light stabilizer in the infrared absorbing layer is preferably 0 to 5 mass %, more preferably 0 to 3 mass %, and even more preferably 0 to 1 mass %. By keeping it at or below the upper limit, the ultraviolet curable resin tends to be cured more effectively.

[0040] Examples of flame retardants include halogen-based flame retardants and phosphorus-based flame retardants. Phosphorus-based flame retardants include aromatic phosphate ester compounds, phosphaphenanthrene compounds, metal phosphinate salts, ammonium polyphosphate, melamine polyphosphate, phosphoric acid ester amide, and red phosphorus. For flame retardants, see paragraphs 0054 to 0082 of Japanese Patent Publication No. 2022-104214 and paragraphs 0052 to 0077 of Japanese Patent No. 7021724, the contents of which are incorporated herein by reference.

[0041] In the infrared absorbing layer, the total of the ultraviolet curable resin, the photopolymerization initiator, the colorant, and the light stabilizer preferably accounts for 90% by mass or more of the infrared absorbing layer, more preferably 95% by mass or more, and even more preferably 97% by mass or more. In addition, in the infrared absorbing layer, the total amount of the ultraviolet curable resin, the photopolymerization initiator, the colorant, and the light stabilizer does not exceed 100% by mass.

[0042] The thickness of the infrared absorbing layer is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 1.5 μm or more, and is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less. By setting the thickness to the upper limit or less, curing defects do not occur when curing with UV. Furthermore, by setting the thickness to the lower limit or more, the infrared absorbing layer exhibits better effects.

[0043] <Layer structure of multilayer body> Next, the layer structure of the multilayer body of this embodiment will be described. The multilayer body of this embodiment has a base layer and an infrared absorbing layer. The base layer preferably contains an acrylic resin layer and a polycarbonate resin layer, and more preferably contains an acrylic resin layer and a polycarbonate resin layer, with the infrared absorbing layer being located on the side of the polycarbonate resin layer opposite the acrylic resin layer. This configuration allows for a multilayer body with even better weather resistance to be obtained. A preferred example of the multilayer body of this embodiment will be described below with reference to Fig. 1. It goes without saying that the multilayer body of this embodiment is not limited to that shown in Fig. 1. FIG. 1 is a cross-sectional schematic diagram showing an example of a multilayer body of this embodiment, in which 1 indicates the multilayer body, 2 indicates an acrylic resin layer, 3 indicates a polycarbonate resin layer, and 4 indicates an infrared absorbing layer. In the multilayer body 1 of this embodiment, it is preferable that the infrared absorbing layer 4 is located on the surface of the polycarbonate resin layer 3 opposite to the acrylic resin layer 2. This configuration can improve the weather resistance of the multilayer body. In this specification, the acrylic resin layer 2 and the polycarbonate resin layer 3 may be collectively referred to as the substrate. Needless to say, the substrate may include other layers within the scope of the present invention. Details of the other layers will be described later.

[0044] The infrared absorbing layer 4 may be the outermost layer of the multilayer body 1. Providing the infrared absorbing layer 4 tends to further improve the surface hardness of the multilayer body. In the multilayer body 1 of this embodiment, the acrylic resin layer 2, the polycarbonate resin layer 3, and the infrared absorbing layer 4 are laminated in this order, and the infrared absorbing layer 4 is preferably located on the surface of the polycarbonate resin layer 3. By being located on the surface of the polycarbonate resin layer 3, the formability of the infrared absorbing layer 2 (applicability of the infrared absorbing layer-forming composition) can be further improved. The multilayer body of this embodiment may have other layers within the scope of this embodiment, as long as the acrylic resin layer 2, the polycarbonate resin layer 3, and the infrared absorbing layer 4 are laminated in the above order; however, it is preferable that the multilayer body does not have other layers, i.e., that the layers are adjacent to each other. Furthermore, the multilayer body of this embodiment may be a flame-retardant substrate in which the content of the metal sulfonate in at least one of the acrylic resin layer and the polycarbonate resin layer is 0.01 to 0.80% by mass. By using such a flame-retardant substrate, it can be preferably used in applications requiring flame retardancy. Details of these will be described later.

[0045] The thickness (total thickness) of the multilayer body is not particularly limited, but is preferably 30 μm or more, more preferably 100 μm or more. The thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, and even more preferably 2,000 μm or less, and may be 1,000 μm or less, or 500 μm or less.

[0046] The multilayer body of this embodiment preferably has excellent infrared shielding properties. Specifically, the light transmittance of the multilayer body of this embodiment at a wavelength of 1000 μm is preferably 60% or less, more preferably 40% or less, even more preferably 25% or less, even more preferably 20% or less, and even more preferably 10% or less. There is no particular lower limit, but a value of more than 0% is practical.

[0047] The multilayer body of this embodiment also preferably has excellent transparency. Specifically, the haze of the multilayer body measured in accordance with JIS K7136 is more preferably 3.0% or less, even more preferably 2.0% or less, even more preferably 1.5% or less, and even more preferably 1.0% or less. The lower limit is preferably 0% or more, but more practically, a value greater than 0%. Specifically, the total light transmittance of the multilayer body of this embodiment is preferably 60% or more, more preferably 65% ​​or more, and even more preferably 70% or more. Ideally, 100% is preferred, but even if it is 90% or less, the required performance is fully satisfied.

[0048] The multilayer body of this embodiment also preferably has excellent weather resistance. Specifically, the haze of the multilayer body measured according to JIS K7136 after a weather resistance test is more preferably 10.0% or less, even more preferably 8.0% or less, even more preferably 5.0% or less, and even more preferably 4.5% or less. The lower limit is preferably 0% or more, but more preferably more than 0% is practical.

[0049] The multilayer body of the present embodiment may also have flame retardancy. Specifically, the multilayer body preferably satisfies a C rating in the FMVSS test (burns up to the B standard line but has a burning rate of 102 mm / min or less), and more preferably satisfies a B rating in the FMVSS test (burns within 51 mm (and self-extinguishes within 60 seconds) from the A standard line). The light transmittance at a wavelength of 1000 nm, the total light transmittance, the haze after the heat resistance test, and the FMVSS test are measured according to the descriptions in the examples below.

[0050] The multilayer body of this embodiment preferably further includes a hard coat layer. The hard coat layer is preferably provided on at least one surface of the multilayer body, and more preferably on the side of the acrylic resin layer of the multilayer body opposite the polycarbonate resin layer. The hard coat layer may be the outermost layer of the multilayer body. By providing a hard coat layer, the surface hardness of the multilayer body tends to be further improved. In the multilayer body of this embodiment, the hard coat layer is preferably formed by laminating an infrared absorbing layer, a polycarbonate resin layer, an acrylic resin layer, and a hard coat layer in this order. In the multilayer body of this embodiment, the hard coat layer is preferably provided on the surface of the acrylic resin layer. By providing a hard coat layer on the surface of the acrylic resin layer, the coatability of the hard coat layer can be further improved.

[0051] The hard coat layer that may be included in the multilayer body of the present embodiment is a layer having a surface hardness higher than that of the polycarbonate resin layer. By including such a hard coat layer, the surface hardness of the multilayer body or molded article can be increased. The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, even more preferably 2.5 μm or more, and even more preferably 3 μm or more. By making the thickness equal to or greater than the lower limit, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be further improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 12 μm or less, even more preferably 10 μm or less, even more preferably 8 μm or less, and may be 5 μm or less. By making the thickness equal to or less than the upper limit, the flame retardancy tends to be further improved.

[0052] The hard coat layer is preferably obtained by applying a hard coat material that can be cured by heat or active energy rays, and then curing the applied material. Examples of coating materials that can be cured using active energy rays include resin compositions composed of one or more monofunctional or polyfunctional (preferably di- to deca-functional) (meth)acrylate monomers or oligomers, and preferably resin compositions containing monofunctional or polyfunctional (preferably di- to deca-functional) urethane (meth)acrylate oligomers. These resin compositions preferably contain a photopolymerization initiator as a curing catalyst. Examples of thermosetting resin coatings include polyorganosiloxane-based and crosslinked acrylic-based coatings. Some of these resin compositions are commercially available as hard coating agents for acrylic or polycarbonate resin films or sheets, and an appropriate coating material may be selected taking into consideration suitability for the coating line. For the hard coat layer, the descriptions in paragraphs 0045 to 0055 of JP 2013-020130 A, paragraphs 0073 to 0076 of JP 2018-103518 A, and paragraphs 0062 to 0082 of JP 2017-213771 A can be referred to, the contents of which are incorporated herein by reference.

[0053] In addition to the above components, the hard coat layer preferably contains inorganic particles, organic pigments, ultraviolet absorbers, light stabilizers, heat stabilizers, flame retardants, flame retardant assistants, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc., and more preferably contains inorganic particles. These components may be used alone or in combination of two or more.

[0054] Preferred examples of inorganic particles include nanoparticles made of metals or metal compounds. Examples include gold, silver, copper, platinum, palladium, nickel, cobalt, iron, manganese, silicon, titanium, zirconium, tungsten, molybdenum, chromium, zinc, aluminum, and composite metals made of two or more of these. Preferred metal compounds include metal oxides such as iron oxide, silicon oxide, zirconium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, cobalt oxide, nickel oxide, cerium oxide, cupric oxide, zinc oxide, tin oxide, antimony oxide, titanium dioxide, aluminum oxide, indium tin oxide (ITO), cesium tungsten oxide (CWO), and mixtures thereof; metal carbides, metal borides, metal carbonates, zeolites, clay, and composites thereof. Silicon oxide is more preferred.

[0055] The inorganic particles may be surface-treated or may not be surface-treated. Preferably, the inorganic particles are surface-treated. The surface treatment agent is preferably a silane coupling agent.

[0056] The average particle size (D50) of the inorganic particles is preferably 5 nm or more, more preferably 7 nm or more, and is preferably 30 nm or less, more preferably 20 nm or less. By making the particle size equal to or greater than the lower limit, flame retardancy tends to be further improved. On the other hand, by making the particle size equal to or less than the upper limit, transparency tends to be further improved.

[0057] The content of inorganic particles in the hard coat layer of this embodiment is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the hard coat layer. By making the content equal to or greater than the lower limit, flame retardancy tends to be further improved. On the other hand, by making the content equal to or less than the upper limit, the effect of suppressing cracking during heat resistance testing tends to be further improved. The hard coat layer may contain only one type of inorganic particles or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0058] Examples of flame retardants include halogen-based flame retardants and phosphorus-based flame retardants. Phosphorus-based flame retardants include aromatic phosphate ester compounds, phosphaphenanthrene compounds, metal phosphinate salts, ammonium polyphosphate, melamine polyphosphate, phosphoric acid ester amide, and red phosphorus. For flame retardants, see paragraphs 0054 to 0082 of Japanese Patent Publication No. 2022-104214 and paragraphs 0052 to 0077 of Japanese Patent No. 7021724, the contents of which are incorporated herein by reference.

[0059] The multilayer body of the present embodiment may have other layers in addition to the above. Specific examples include an adhesive layer, a pressure-sensitive adhesive layer, an antifouling layer, an antireflection layer, and a polarizing layer, with an antireflection layer being preferred. The antireflection layer is usually preferably provided on the underside 4 (for example, in FIG. 1) of the infrared absorbing layer, on the side opposite to the polycarbonate resin layer. For details of the antireflection layer, please refer to paragraphs 0062 to 0083 of JP 2023-114940 A, paragraphs 0013 to 0041 of JP 2022-174051 A, and paragraphs 0043 to 0046 of JP 2021-081596 A, the contents of which are incorporated herein by reference. The polarizing layer is usually preferably provided below the infrared absorbing layer 4 (for example, in FIG. 1) on the side opposite to the polycarbonate resin layer. For details of the polarizing layer, please refer to paragraphs 0022 to 0029 of JP 2008-105225 A, paragraphs 0011 to 0021 of JP 2020-52406 A, and paragraphs 0014 to 0037 of JP 2023-13533 A, the contents of which are incorporated herein by reference.

[0060] The multilayer body may be subjected to one or more of the following treatments on at least one surface: anti-fingerprint treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, anti-fouling treatment, and anti-blocking treatment. The anti-blocking treatment refers to a treatment that enables films to be easily peeled even when they are in close contact with each other, and examples of such treatment include adding an anti-blocking agent and providing unevenness on the surface of the multilayer body.

[0061] <<Polycarbonate resin layer>> The polycarbonate resin layer in this embodiment contains a polycarbonate resin. The polycarbonate resin is not particularly limited as long as it contains a -[OR-OCO]- structural unit (R is a hydrocarbon group (for example, an aliphatic group, an aromatic group, or one containing both an aliphatic group and an aromatic group, and further one having a linear or branched structure)) that contains a carbonate bond in the molecular main chain, and various polycarbonate resins can be used, with aromatic polycarbonate resins being preferred.

[0062] In this embodiment, the polycarbonate resin preferably contains a bisphenol-type polycarbonate resin. A bisphenol-type polycarbonate resin refers to a polycarbonate resin in which 80 mol % or more, preferably 90 mol % or more, and more preferably 95 mol % or more of the structural units constituting the polycarbonate resin are carbonate structural units derived from bisphenol and / or a derivative thereof. The bisphenol and / or a derivative thereof is preferably bisphenol A, bisphenol AP, bisphenol C, bisphenol BP, or a derivative thereof, more preferably bisphenol A, bisphenol AP, or a derivative thereof, and even more preferably bisphenol A or a derivative thereof. The bisphenol polycarbonate resin is preferably a bisphenol A polycarbonate resin.

[0063] The molecular weight of the polycarbonate resin is not particularly limited, but is preferably 20,000 or more, more preferably 22,000 or more, in terms of viscosity average molecular weight calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent. The viscosity average molecular weight is preferably 35,000 or less, more preferably 32,000 or less, and even more preferably 30,000 or less. By setting the viscosity average molecular weight at or above the lower limit, the strength of the resulting flat-plate molded article can be increased. By setting the viscosity average molecular weight at or below the upper limit, moldability tends to be improved. Here, the viscosity average molecular weight [Mv] is determined by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity [η] (unit: dL / g) at a temperature of 25°C, and then calculating it using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dL). sp ] was measured and the value was calculated according to the following formula.

number

[0064] The onset glass transition temperature (Tg) of the polycarbonate resin used in this embodiment is preferably 160° C. or lower, more preferably 155° C. or lower, even more preferably 154° C. or lower, even more preferably 153° C. or lower, even more preferably 152° C. or lower, and even more preferably 151° C. or lower. The onset glass transition temperature (Tg) of the polycarbonate resin used in this embodiment is, for example, 140° C. or higher, and may further be 143° C. or higher, 145° C. or higher, 147° C. or higher, or 148° C. or higher. The glass transition temperature is measured according to the description in paragraph 0056 of JP 2022-080270 A.

[0065] For details of the polycarbonate resin, reference can be made to paragraphs 0011 to 0020 of JP-A-2012-144604 and paragraphs 0014 to 0035 of JP-A-2019-002023, the contents of which are incorporated herein by reference, as long as they do not deviate from the spirit of this embodiment.

[0066] In this embodiment, the content of polycarbonate resin in the polycarbonate resin layer is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 94% by mass or more, still more preferably 96% by mass or more, and even more preferably 97% by mass or more, and may be 98% by mass or more, based on 100% by mass of the polycarbonate resin layer. The upper limit may be 100% by mass. When the polycarbonate resin layer in this embodiment contains two or more types of polycarbonate resins, the total amount thereof preferably falls within the above range.

[0067] The polycarbonate resin layer in this embodiment may contain a metal sulfonate, which is a component generally used as a flame retardant for polycarbonate resins.

[0068] The metal sulfonate is preferably an alkali metal salt. The alkali metal constituting the alkali metal salt is preferably lithium, sodium, potassium, or rubidium, and more preferably sodium or potassium. The metal sulfonate may also contain a fluorine atom. The molecular weight of the sulfonic acid metal salt used in this embodiment is preferably 100-900, and more preferably 100-500.

[0069] Specific examples of the metal sulfonate salt used in this embodiment are shown below. It goes without saying that the metal sulfonate salt used in this embodiment is not limited to these. [ka]

[0070] The content of the metal sulfonate in the polycarbonate resin layer is preferably 0.01 to 0.80% by mass, more preferably 0.7% by mass or less, even more preferably 0.6% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less, and may be less than 0.1% by mass or 0.05% by mass or less depending on the application, etc. The polycarbonate resin layer in the present embodiment may contain only one type of sulfonic acid metal salt, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0071] The polycarbonate resin layer of this embodiment may contain flame retardants other than metal sulfonates, such as phosphorus-based flame retardants such as condensed phosphate esters and phosphazenes, silicone-based flame retardants such as polyorganosiloxanes, and halogen-based flame retardants such as Br-polycarbonate oligomers. Specific examples of phosphorus-based flame retardants include condensed phosphate esters such as resorcinol bis-diphenylphosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenylphosphate (BDP), and biphenyl bis-diphenylphosphate, as well as linear phenoxyphosphazenes and cyclic phenoxyphosphazenes. The content of the flame retardant in the polycarbonate resin layer is preferably 0.3 to 20% by mass, and more preferably 0.5 to 10% by mass.

[0072] The polycarbonate resin layer in this embodiment may contain an ultraviolet absorber such as a triazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber. The content of the ultraviolet absorber in the polycarbonate resin layer is preferably 0.1 to 5.0% by mass, and more preferably 0.5 to 2.0% by mass.

[0073] In addition to the above components, the polycarbonate resin layer in this embodiment may contain antioxidants, release agents, flame retardant aids, heat stabilizers, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc. These components may be used alone or in combination of two or more. The total content of the above components is preferably 0 to 5% by mass of the polycarbonate resin layer, more preferably 0 to 3% by mass, even more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, even more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.

[0074] Examples of antioxidants include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, etc. Among these, in the present embodiment, phosphorus-based antioxidants and phenol-based antioxidants (more preferably hindered phenol-based antioxidants) are preferred, and phosphorus-based antioxidants are more preferred.

[0075] The phosphorus-based antioxidant is preferably a phosphite-based antioxidant, and a phosphite compound represented by the following formula (1) or (2) is preferred. [ka] (In formula (1), R 11 and R 12 each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. [ka] (In formula (2), R 13 ~R 17 each independently represents a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

[0076] In the above formula (1), R 11 , R 12Each of the alkyl groups represented by R is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 11 , R 12 When is an aryl group, it is preferably an aryl group represented by any one of the following formulae (1-a), (1-b), and (1-c): In the formula, * represents the bonding position.

[0077] [ka] (In formula (1-a), R A each independently represents an alkyl group having 1 to 10 carbon atoms. B each independently represents an alkyl group having 1 to 10 carbon atoms.

[0078] For the hindered phenol-based antioxidant, reference can be made to the descriptions in paragraph 0063 of JP-A-2018-090677 and paragraph 0076 of JP-A-2018-188496, the contents of which are incorporated herein by reference.

[0079] In addition to the above, the antioxidants can be found in paragraphs 0057 to 0061 of JP 2017-031313 A, the contents of which are incorporated herein by reference.

[0080] The content of the antioxidant is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, even more preferably 0.010 part by mass or more, and even more preferably 0.050 part by mass or more, relative to 100 parts by mass of the polycarbonate resin layer. The upper limit of the content of the antioxidant is preferably 0.500 part by mass or less, more preferably 0.300 part by mass or less, even more preferably 0.200 part by mass or less, even more preferably 0.150 part by mass or less, even more preferably 0.100 part by mass or less, and particularly more preferably 0.080 part by mass or less, relative to 100 parts by mass of the polycarbonate resin layer. The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total amount is preferably within the above range.

[0081] Next, the release agent that can be contained in the polycarbonate resin layer will be described. The type of release agent is not particularly limited, but examples thereof include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polyethers having a number average molecular weight of 100 to 5,000, and polysiloxane-based silicone oils.

[0082] For details about the release agent, please refer to paragraphs 0035 to 0039 of WO 2015 / 190162, the contents of which are incorporated herein by reference.

[0083] The content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, even more preferably 0.010 part by mass or more, and even more preferably 0.050 part by mass or more, relative to 100 parts by mass of the polycarbonate resin layer, and the upper limit is preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less, and even more preferably 0.1 part by mass or less. The release agent may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0084] The thickness of the polycarbonate resin layer is preferably 50 μm or more, more preferably 100 μm or more, and even more preferably 150 μm or more. By making the thickness equal to or greater than the lower limit, molding becomes easier and flame retardancy tends to be improved. Furthermore, the upper limit of the thickness of the polycarbonate resin layer is preferably 1000 μm or less, more preferably 750 μm or less, and even more preferably 500 μm or less.

[0085] <<Acrylic resin layer>> The acrylic resin layer in this embodiment contains an acrylic resin. The acrylic resin layer may be a single layer or may be a multilayer, but is preferably a single layer.

[0086] As described above, the acrylic resin layer in this embodiment contains an acrylic resin. An example of the acrylic resin is preferably a polymer containing alkyl (meth)acrylate units (preferably alkyl methacrylate units) in an amount of 50% by mass or more (preferably 90% by mass or more) of all structural units, and more preferably a polymer containing methyl (meth)acrylate units (preferably methyl methacrylate units) in an amount of 50% by mass or more (preferably 90% by mass or more) of all structural units. Examples of structural units other than alkyl (meth)acrylate units include other (meth)acrylate units, styrene units, cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units.

[0087] The acrylic resin layer may be made of only acrylic resin, or may contain other thermoplastic resins in addition to acrylic resin. The other thermoplastic resin preferably includes at least one thermoplastic resin selected from a styrene-based resin, a fluorine-based resin such as polyvinylidene fluoride, and an aromatic polyether resin such as polyphenylene ether, and more preferably includes a styrene-based resin.

[0088] An example of the acrylic resin layer is a layer composed of 90% by mass or more (preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more) of acrylic resin. Another example of an acrylic resin is a layer composed of 90% by mass or more (preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more) of the above acrylic resin and other thermoplastic resins (preferably styrene-based resins).

[0089] The weight-average molecular weight of the acrylic resin is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, even more preferably 50,000 or more, even more preferably 60,000 or more, and even more preferably 70,000 or more. The weight-average molecular weight of the acrylic resin is preferably 250,000 or less, more preferably 200,000 or less, even more preferably 150,000 or less, even more preferably 100,000 or less, and even more preferably 90,000 or less.

[0090] The glass transition temperature of the acrylic resin layer used in this embodiment is preferably 80° C. or higher, more preferably 90° C. or higher, even more preferably 95° C. or higher, even more preferably 100° C. or higher, and even more preferably 105° C. or higher. There is no particular upper limit, but a practical value is, for example, 200° C. or lower. The glass transition temperature is measured according to the description in paragraph 0056 of JP 2022-080270 A.

[0091] In addition to the above components, the acrylic resin layer may contain inorganic particles, antioxidants, release agents, UV absorbers, heat stabilizers, flame retardants, flame retardant aids, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc. These components may be used alone or in combination of two or more. The total content of the above components is preferably 0 to 5% by mass of the acrylic resin layer, more preferably 0 to 3% by mass, even more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, even more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.

[0092] <<Ultraviolet absorber>> In order to prevent ultraviolet degradation of the polycarbonate resin layer, the acrylic resin layer, and the infrared absorbing layer in this embodiment, the acrylic resin layer in this embodiment may contain an ultraviolet absorber, as described above.

[0093] Usable ultraviolet absorbers include benzotriazoles, benzophenones, salicylic acid phenyl esters, benzoxazines, malonic acid esters, triazines, and polymeric ultraviolet absorbers having these compounds added as pendants. Benzotriazole-based UV absorbers include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylenebutyl)-6-(2H-benzotriazol-2-yl)phenol], and 2-(2H-benzotriazole-2 Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, and 2,2-dihydroxy-4,4'-dimethoxybenzophenone. Examples of salicylic acid phenyl ester-based ultraviolet absorbers include pt-butylphenyl salicylic acid ester, etc. Examples of benzoxazine-based ultraviolet absorbers include 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one], etc. Examples of malonic acid ester-based ultraviolet absorbers include dimethyl [(4-methoxyphenyl)-methylene]malonate. Examples of triazine-based ultraviolet absorbers include 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, and 2,6-di(4-biphenyl)-4-(2-hydroxy-4-(2-ethylhexyl)oxyphenyl)-1,3,5-triazine. azine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyethoxy)-1,3,5-triazine, and the like, but are not limited to these, and commonly available ultraviolet absorbers and the like can be used. Examples of polymeric UV absorbers include those with a hydroxybenzophenone or hydroxybenzotriazole structure in the molecule, some of which have alkyl groups substituted for the hydrogen atoms. One example of a polymeric UV absorber is UVA-633L (2-hydroxy-4-(methacryloyloxyethoxy)benzophenone) methyl methacrylate copolymer, which is commercially available from BASF.

[0094] As described above, the acrylic resin layer in this embodiment may contain an antioxidant. Examples of antioxidants include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. Among these, phosphorus-based antioxidants are preferred in this embodiment.

[0095] The phosphorus-based antioxidant is preferably a phosphite-based antioxidant, and more preferably a phosphite compound represented by the following formula (1) or (2). [ka] (In formula (1), R 11 and R 12 each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. [ka] (In formula (2), R 13 ~R 17 each independently represents a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

[0096] In the above formula (1), R 11 , R 12 Each of the alkyl groups represented by R is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 11 , R 12 When is an aryl group, it is preferably an aryl group represented by any one of the following formulae (1-a), (1-b), and (1-c): In the formula, * represents the bonding position.

[0097] [ka]

[0098] The content of the antioxidant is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and even more preferably 0.010 part by mass or more, relative to 100 parts by mass of the acrylic resin layer. The upper limit of the content of the antioxidant is preferably 0.500 part by mass or less, more preferably 0.300 part by mass or less, even more preferably 0.200 part by mass or less, even more preferably 0.150 part by mass or less, still more preferably 0.100 part by mass or less, and even more preferably 0.080 part by mass or less, relative to 100 parts by mass of the acrylic resin layer. The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total amount is preferably within the above range.

[0099] <<Release Agent>> As described above, the acrylic resin layer in this embodiment may contain a release agent. The type of release agent is not particularly limited, but examples thereof include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number-average molecular weight of 200 to 15,000, polyethers having a number-average molecular weight of 100 to 5,000, and polysiloxane-based silicone oils.

[0100] For details about the release agent, please refer to paragraphs 0035 to 0039 of WO 2015 / 190162, the contents of which are incorporated herein by reference.

[0101] The content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, even more preferably 0.010 part by mass or more, and even more preferably 0.050 part by mass or more, relative to 100 parts by mass of the acrylic resin layer. The upper limit is preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less, and even more preferably 0.2 part by mass or less. The release agent may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0102] As described above, the acrylic resin layer in this embodiment may contain inorganic particles, such as silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.

[0103] As described above, the acrylic resin layer in this embodiment may contain a flame retardant. Examples of the flame retardant that may be contained in the acrylic resin layer include phosphorus-based flame retardants and metal sulfonates, and phosphorus-based flame retardants are preferred.

[0104] Examples of phosphorus-based flame retardants include aromatic phosphate ester compounds, phosphazene compounds, phosphaphenanthrene compounds, metal phosphinates, ammonium polyphosphate, melamine polyphosphate, phosphate ester amides, and red phosphorus, with aromatic phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds being preferred.

[0105] Examples of aromatic phosphate ester compounds include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, biphenyl diphenyl phosphate, etc. Commercially available products thereof include PX-202, CR-741, PX-200, and PX-201 manufactured by Daihachi Chemical Industry Co., Ltd., and FP-500, FP-600, FP-700, and PFR manufactured by ADEKA Corporation.

[0106] Examples of aromatic phosphate ester compounds include cyclic phenoxyphosphazene and its derivatives, etc. Commercially available products include Lavitol FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd.

[0107] Phosphaphenanthrene compounds are phosphorus-based flame retardants having at least one phosphaphenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA, SANKO-220, and M-Ester manufactured by Sankosha.

[0108] The metal phosphinate salt is a phosphinate salt and / or a diphosphinate salt and / or a polymer thereof. Examples of the salt include calcium, aluminum, and zinc salts. Commercially available metal phosphinate salts include "Exolit" (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan.

[0109] Phosphate ester amide is an aromatic amide flame retardant containing a phosphorus atom and a nitrogen atom. Commercially available phosphorus ester amide products such as SP-703 manufactured by Shikoku Chemicals Co., Ltd. are preferably used.

[0110] Examples of ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl ammonium polyphosphate. Examples of the melamine polyphosphate include melamine phosphate, melamine pyrophosphate, and melamine polyphosphates such as melamine, melam, and melem phosphates. Preferred examples include MPP-A manufactured by Sanwa Chemical Co., Ltd. and PMP-100 and PMP-200 manufactured by Nissan Chemical Co., Ltd.

[0111] When the acrylic resin layer contains a flame retardant (phosphorus-based flame retardant, sulfonic acid metal salt, or other flame retardant), the content thereof is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, and still more preferably 7 parts by mass or more, per 100 parts by mass of the acrylic resin layer. The upper limit of the content of the flame retardant is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the acrylic resin layer. The acrylic resin layer may contain only one type of flame retardant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0112] The thickness of the acrylic resin layer is preferably 50 μm or more, more preferably 100 μm or more, and even more preferably 150 μm or more. By making the thickness equal to or greater than the lower limit, molding becomes easier and hardness tends to improve. Furthermore, the upper limit of the thickness of the acrylic resin layer is preferably 1000 μm or less, more preferably 750 μm or less, and even more preferably 500 μm or less.

[0113] <Method of manufacturing a multilayer body> The multilayer body of this embodiment can be produced according to a known method. The multilayer body of this embodiment can be produced by, for example, using a main extruder that extrudes a polycarbonate resin layer-forming composition and a sub-extruder that extrudes an acrylic resin layer-forming composition, melting the resins under the conditions of the resins used, introducing them into an extrusion die, laminating them inside the die and forming them into a sheet, or laminating them after forming them into a sheet, thereby forming a substrate.Furthermore, the multilayer body can be produced by applying a composition for forming an infrared absorbing layer to the polycarbonate resin layer side of the substrate and curing it.

[0114] The multilayer body of this embodiment may be used as is, but can also be processed, particularly by heat processing, to form a molded article.

[0115] <Application> The multilayer body of this embodiment can be suitably used for optical parts, decorative products, anti-reflection molded articles, and the like. The multilayer body of this embodiment is suitable for use in components for display devices, electrical and electronic devices, office automation equipment, portable information terminals, machine parts, home appliances, vehicle parts, various containers, lighting equipment, etc. Among these, it is particularly suitable for use in housings for various displays, electrical and electronic devices, office automation equipment, portable information terminals, and home appliances, lighting equipment, and vehicle parts (particularly vehicle interior parts), surface films for smartphones, touch panels, etc., optical materials, and optical discs. In particular, the multilayer body of this embodiment is preferably used as a dustproof cover for head-up displays. [Example]

[0116] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0117] 1.Raw materials SMP-220A: Acryloyl group-containing polymer, solid content 50% by mass, weight average molecular weight 20,000, acrylic equivalent 220 g / mol, manufactured by Kyoeisha Chemical Co., Ltd. UN-901T: Urethane acrylate, solid content 80% by mass, weight average molecular weight 4,000, number of functional groups 9, manufactured by Negami Chemical Industrial Co., Ltd. PE3A: Multifunctional acrylate, solid content 100% by mass, molecular weight 298, number of functional groups 3, manufactured by Kyoeisha Chemical Co., Ltd. PE4A: Multifunctional acrylate, solid content 100% by mass, molecular weight 352, number of functional groups 4, manufactured by Kyoeisha Chemical Co., Ltd. YMF-02A: CWO (cesium tungsten oxide) dispersion, CWO content 18.5% by mass, manufactured by Sumitomo Metal Mining Co., Ltd. BYK-UV3575: Silicone leveling agent, manufactured by BYK PGM: Propylene glycol monomethyl ether Omnirad 819: Acylphosphine oxide photoinitiator, 100% solids, manufactured by IGM Resins BV

[0118] DF02U: Two-layer film consisting of a polycarbonate resin layer and an acrylic resin layer, manufactured by Mitsubishi Gas Chemical Company, thickness 0.375 mm

[0119] E-2000F: Polycarbonate resin obtained by interfacial polymerization using bisphenol A as the starting material (Mitsubishi Gas Chemical Company, Inc., E-2000F, viscosity average molecular weight: 27,000, Tg: 150°C) KSS-FR: Arichem, KSS-FR, potassium diphenylsulfone-3-sulfonate NATS: NATS, sodium p-toluenesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd. F-114P: F-114P, potassium perfluorobutanesulfonate, manufactured by DIC Corporation 2112: Tris(2,4-di-tert-butylphenyl)phosphite (phosphorus antioxidant, manufactured by ADEKA Corporation, Adekastab 2112) S-100A: Glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.) 80HD: Asahi Kasei Corporation, polymethyl methacrylate

[0120] 2. Examples 1 to 9 and Comparative Examples 1 to 4 <Preparation of multilayer body (coating of infrared absorbing layer)> The compositions for forming an infrared absorbing layer were prepared by blending the components shown in Tables 1 and 2. In Tables 1 and 2, the proportion of each component indicates the solid content (parts by mass). The infrared absorbing layer-forming composition obtained above was applied with a bar coater to the coated surface of the substrate shown in Tables 1 and 2. The applied infrared absorbing layer-forming composition was dried in an oven at 80°C for 3 minutes, and then irradiated with an ultraviolet ray irradiator manufactured by Heraeus K.K. under a nitrogen atmosphere with an integrated light dose of 500 mJ / cm. 2 (UV illuminance meter manufactured by Oak Corporation, measurement wavelength 360 nm) and curing was carried out.

[0121] <Total light transmittance (%)> The total light transmittance of the multilayer body was measured using "HM-150" manufactured by Murakami Color Co., Ltd.

[0122] <Transmittance (%) at wavelength 1000 nm> The light transmittance of the multilayer body was measured at a wavelength of 1000 nm. The light transmittance was measured using a spectrophotometer U-4000 manufactured by Hitachi High-Technologies Corporation.

[0123] <Haze (%) of multilayer body after weather resistance test> The acrylic resin layer side of the multilayer structure was used as the irradiated surface, and light irradiation was carried out under the following conditions. Device: SUV-W161 manufactured by Iwasaki Electric Co., Ltd. Light source: Metal halide lamp Test environment: 85°C (black panel temperature), 50% RH Illuminance: 100mW / cm2 (365nm) Irradiation cycle: 24 hours (continuous irradiation) Irradiation time: 200 hours The haze of the multilayer body was evaluated based on JIS K 7136:2000. Haze was measured using "HM-150" manufactured by Murakami Shikisai Co., Ltd. The unit is shown as %.

[0124] <Adhesion> The adhesion of the infrared absorption layer to the substrate was evaluated according to the evaluation method of JIS K5600-5-6:1999. For the examples and comparative examples with the evaluation result being classification 0, the adhesion was evaluated as "A", and those with the evaluation result being classifications 1 to 5 were evaluated as "C" for adhesion.

[0125] <Heat resistance test> The fabricated laminate was heated in an oven at 120 °C for 5 minutes, and the degree of crack generation was evaluated as follows. The evaluation was performed visually, confirmed by 5 experts, and judged by a majority vote. A: No cracks were observed. B: Slight cracks were observed. C: Obvious cracks were observed.

[0126] <FMVSS test> For the multilayer body obtained above, using the FMVSS No. 302 flammability test apparatus, a burner flame 38 mm from the right end of the test piece (350 mm × 100 mm × 0.375 mm) was applied indirectly for 15 seconds, and the combustion rate at a combustion distance of 254 mm between the marked lines was measured. The test fixture was measured without a wire and evaluated as follows. A: The test piece did not ignite or self-extinguished before the A standard line. B: Self-extinguished within 51 mm (and within 60 seconds) from the A standard line for the combustion distance. C: Burned up to the B standard line, but the combustion rate was 102 mm / min or less. D: Burned up to the B standard line, and the combustion rate was faster than 102 mm / min.

[0127]

Table 1

[0128]

Table 2

[0129] 3. Examples 10 to 12 <Production of flame-retardant substrate> A resin composition (pellet) for forming a polycarbonate resin layer (PC layer) and a resin composition (pellet) for forming an acrylic resin layer were produced according to the following method. Each of the components described above was weighed out so as to obtain the amount of addition shown in Table 3 (each component in Table 3 is expressed as % by mass). After mixing for 15 minutes in a tumbler, the mixture was melt-kneaded in a vented twin-screw extruder with a screw diameter of 32 mm ("TEX30α" manufactured by The Japan Steel Works, Ltd.) and pellets were obtained by strand cutting. The resin composition (pellets) for forming the polycarbonate resin layer was melt-kneaded at 260 to 300°C, with the temperature being changed as needed depending on the resin viscosity, and the resin composition (pellets) for forming the acrylic resin layer was melt-kneaded at 260°C.

[0130] Flame-retardant substrates were molded using a multilayer extrusion device equipped with a single-screw extruder with a 32 mm shaft diameter, a single-screw extruder with a 65 mm shaft diameter, a feedblock connected to all extruders, and a 650 mm-wide T-die connected to the feedblock. The resin composition (pellets) for the acrylic resin layer of each flame-retardant substrate listed in the table was introduced into the single-screw extruder with a 32 mm shaft diameter and extruded at a cylinder temperature of 240°C and a throughput of 0.3 to 6.4 kg / h. The resin composition (pellets) for the polycarbonate resin layer of each flame-retardant substrate listed in Table 1 was continuously introduced into the single-screw extruder with a 65 mm shaft diameter and extruded at a throughput of 17.4 to 23.5 kg / h while the cylinder temperature was changed from 250°C to 290°C depending on the resin viscosity. The feedblock connected to all extruders was equipped with a two-type, two-layer distributor pin, and the extruded layers were laminated. The material was extruded into a sheet using a T-die connected to the end of the die, and cooled while transferring the mirror surface using three mirror-finishing rolls set at temperatures of 120°C, 120°C, and 140°C from the upstream side, to obtain each flame-retardant substrate.

[0131] <Preparation of multilayer body (coating of infrared absorbing layer)> The same composition for forming an infrared absorbing layer as in Example 9 was applied to the polycarbonate resin layer surface of the substrate layer obtained above, dried in an oven at 80°C for 3 minutes, and then irradiated with a UV irradiator manufactured by Heraeus K.K. under a nitrogen atmosphere with an integrated light dose of 500 mJ / cm.2 (UV illuminance meter manufactured by Oak Corporation, measurement wavelength 360 nm) and curing was carried out.

[0132] <Evaluation> As in Example 1, the total light transmittance, the transmittance at a wavelength of 1000 nm, the haze after the weather resistance test, Adhesion, heat resistance and FMVSS were evaluated.

[0133] [Table 3]

[0134] 4. Examples 13 to 16 <Preparation of a multilayer body having an infrared absorbing layer> A multilayer body having an infrared absorbing layer was produced by the same method as in Example 9 or Example 10.

[0135] <Coating a hard coat layer on the opposite side> A hard coat layer was formed on the surface of the multilayer body prepared above opposite to the surface on which the infrared absorbing layer was formed. In Table 4, a and b indicate the resin compositions used in the hard coat layer, and the following resin compositions were used. a: Fujikura Kasei HO3313U-10 b: A resin composition for a hard coat layer, which is a mixture of 67.5% by mass of UN-3320HC manufactured by Negami Chemical Industries, 29.0% by mass of silica particles surface-treated with 3-acryloxypropyltrimethoxysilane, 2.5% by mass of a photoinitiator, and 1% by mass of a leveling agent. The resin composition for the hard coat layer was applied with a bar coater to the outermost surface (the surface of the acrylic resin layer) of the multilayer body opposite to the side where the infrared absorbing layer was provided. The applied resin composition for the hard coat layer was dried in an oven at 80°C for 3 minutes, and then irradiated with an ultraviolet irradiator manufactured by Heraeus GmbH under a nitrogen atmosphere with an integrated light dose of 500 mJ / cm. 2 (UV illuminance meter manufactured by Oak Corporation, measurement wavelength 360 nm) to form a hard coat layer with a thickness of 4.5 μm.

[0136] <Evaluation> As in Example 1, the total light transmittance, the transmittance at a wavelength of 1000 nm, the haze after the weather resistance test, the adhesion, the heat resistance test, and the FMVSS were evaluated.

[0137] [Table 4]

[0138] In the above table, the HC layer paint indicates the composition of the hard coat layer formed on the surface of the acrylic resin layer, and a and b indicate the composition of the resin composition for the hard coat layer. As is clear from the results in Tables 1 to 4 above, the multilayer bodies of the present invention had low haze after the weather resistance test and excellent interlayer adhesion (Examples 1 to 16). Furthermore, the multilayer bodies of the present invention had high total light transmittance, low near-infrared transmittance, and excellent heat resistance. Furthermore, when a flame-retardant substrate was used (Examples 10 to 12, 15, and 16), the multilayer bodies also had excellent flame retardancy. [Explanation of symbols]

[0139] 1 Multilayer body 2 Acrylic resin layer 3 Polycarbonate resin layer 4. Infrared absorbing layer

Claims

1. It has a base layer and an infrared absorbing layer, the infrared absorbing layer contains an ultraviolet curable resin and tungsten oxide; the ultraviolet curable resin contains a component derived from a polyfunctional (meth)acrylate having a weight average molecular weight of 1,000 to 30,000, the proportion of the tungsten oxide in the infrared absorbing layer is 25 to 50 mass %, the substrate layer includes a polycarbonate resin layer and / or an acrylic resin layer, and the polycarbonate resin layer or the acrylic resin layer is in contact with the infrared absorbing layer; multilayer body.

2. The multilayer body according to claim 1 , wherein the ultraviolet curable resin contains a component derived from a polyfunctional urethane (meth)acrylate.

3. the substrate layer includes an acrylic resin layer and a polycarbonate resin layer, the infrared absorbing layer is located on the surface of the polycarbonate resin layer opposite to the acrylic resin layer; The multilayer body according to claim 1 or 2.

4. 3. The multilayer body according to claim 1, which has a haze of 2.0% or less as measured in accordance with JIS K7136.

5. 3. The multilayer body according to claim 1, wherein the infrared absorbing layer contains 30 to 50 mass % of the tungsten oxide.

6. Further, it has a hard coat layer, 3. The multilayer body according to claim 1, wherein the hard coat is formed by laminating an infrared absorbing layer, a polycarbonate resin layer, an acrylic resin layer, and a hard coat layer in this order.

7. The multilayer body according to claim 6 , wherein the hard coat layer contains inorganic particles.

8. The multilayer body according to claim 1 or 2, further comprising an anti-reflection layer.

9. The multilayer body according to claim 1 or 2, further comprising a polarizing layer.

10. A dustproof cover for a head-up display, comprising the multilayer body according to claim 1 or 2.

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