Laminated bodies, their manufacturing methods and applications

Abstract

This invention prepares a laminate comprising an integral layer formed by a first resin composition comprising a first resin and a second resin composition comprising a second resin, wherein the first resin comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more, and the second resin comprises an acid-modified (meth)acrylate resin. Alternatively, the second resin may have a carboxyl group of 100 mmol / kg or more. Alternatively, the acid-modified (meth)acrylate resin may be an acid-modified polymethyl methacrylate resin. Alternatively, the average thickness of the first layer may be 0.15 times or more relative to the average thickness of the second layer. Alternatively, the average thickness of the first layer may be 200 μm or more. The laminate may also have a DuPont impact strength of 500 N / inch or more when dropped to the second layer side. The laminate exhibits excellent transparency, lightweight, lightfastness, and impact resistance.

Description

Technical Field

[0001] This disclosure relates to a laminate that can be used as a transparent molded body such as a sunroof for automobiles, as well as its manufacturing method and uses. Background Technology

[0002] For transparent molded structures used outdoors, such as skylights, lightweight, lightfastness, impact resistance, and rigidity are required. Common materials used in such transparent molded structures include general-purpose glass, polycarbonate, and polymethyl methacrylate (PMMA). However, these materials have the following drawbacks: glass has low lightweight and low impact resistance, polycarbonate has low lightfastness, and PMMA has low impact resistance. Therefore, it has been explored to improve these properties by laminating sheets formed from plastic materials.

[0003] Japanese Patent Application Publication No. 2008-213436 (Patent Document 1) discloses a plastic polarizing lens body, characterized by comprising at least a sheet-like polarizer having polarizers, wherein a (meth)acrylate resin layer is formed on at least one side of the sheet-like polarizer, and a thermoforming resin such as a polyamide resin is formed by hot-melt lamination of at least the (meth)acrylate resin layer by injection molding. As the (meth)acrylate resin layer, an ultraviolet-curable composition is described.

[0004] Japanese Patent Application Publication No. 2010-501380 (Patent Document 2) discloses a multilayer sheet comprising a layer of polyamide molding material, an inner layer containing a fixative, and a support containing a poly(meth)acrylate molding material. The inner layer contains 5-100% by mass of a copolymer having: 70-99.9% by mass of acrylic acid derivatives, methacrylic acid derivatives, monomer units derived from α-olefins and vinyl compounds selected from vinyl aromatics; and 0.1-30% by mass of monomer units having functional groups selected from carboxylic anhydride groups, epoxy groups, and oxazoline groups. In an embodiment, a sheet with a total thickness of 3 mm, having a 240 μm fixative layer and an 180 μm polyamide layer laminated on a PMMA support, is manufactured by insert molding lamination.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2008-213436

[0008] Patent Document 2: Japanese Patent Application Publication No. 2010-501380 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, in the plastic polarizing lens body of Patent Document 1, in addition to the complex layer structure, the adhesion between the (meth)acrylate resin layer and the lens body formed by thermoforming resin is low. Furthermore, in the multilayer sheet of Patent Document 2, in addition to low impact resistance, the adhesion between the layer containing polyamide molding material and the inner layer is insufficient.

[0011] Therefore, the object of the present invention is to provide a laminate with excellent transparency, lightweight, lightfastness, and impact resistance, as well as a method for manufacturing the same and its uses.

[0012] Technical solution

[0013] In order to achieve the aforementioned objective, the inventors conducted in-depth research and discovered the following facts, thereby completing the present invention: by integrating a first layer formed from a first resin composition with a second layer formed from a second resin composition through mutual contact, transparency, lightness, lightfastness, and impact resistance can be improved. The first resin composition comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more, and the second resin composition comprises an acid-modified (meth)acrylic resin.

[0014] That is, the laminate of this disclosure is integrally formed by a first layer formed of a first resin composition comprising a first resin and a second layer formed of a second resin composition comprising a second resin in contact with each other, wherein the first resin comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more, and the second resin comprises an acid-modified (meth)acrylate resin. Alternatively, the second resin may have a carboxyl group of 100 mmol / kg or more. Alternatively, the acid-modified (meth)acrylate resin may be an acid-modified polymethyl methacrylate resin. Alternatively, the average thickness of the first layer may be 0.15 times or more relative to the average thickness of the second layer. Alternatively, the average thickness of the first layer may be 200 μm or more. Regarding the laminate, the DuPont impact strength at the second layer side may also be 500 N / in or more.

[0015] This disclosure also includes a manufacturing method for the laminate, wherein the laminate is obtained by solidification through contact in a molten state of at least one of a first precursor for forming a first layer and a second precursor for forming a second layer.

[0016] This disclosure also includes a molded body formed from the laminated body. Alternatively, the molded body may be a second layer of a sunroof for a vehicle disposed on the exterior side.

[0017] This disclosure also includes a method of using the laminate as a partition wall separating indoor and outdoor spaces, wherein the second layer is disposed on the outdoor side.

[0018] Invention Effects

[0019] In this disclosure, a first layer formed from a first resin composition and a second layer formed from a second resin composition are integrated in contact with each other, thereby improving transparency, lightweight, lightfastness, and impact resistance. The first resin composition comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more, and the second resin composition comprises an acid-modified (meth)acrylic resin. In particular, the mechanical properties are improved compared to a single layer due to lamination, and the integration without an adhesive layer also suppresses discoloration originating from the adhesive layer. Furthermore, the mechanical properties are stronger against impacts from the second layer side, and by positioning the second layer side on the side requiring strength, the mechanical properties can be further improved. In addition, the second layer comprises an acid-modified (meth)acrylic resin, thus exhibiting high compatibility (wetting) with general-purpose (meth)acrylic hard coatings. By laminating the hard coating onto the second layer according to the application, the surface strength can be further improved. Due to its high rigidity, it is also suitable for applications such as automotive sunroofs (transparent sunroofs). Detailed Implementation

[0020] [Layered Body]

[0021] The laminate of this disclosure is formed of a first layer and a second layer, the first layer being formed of a first resin composition comprising a first resin and the second layer being formed of a second resin composition comprising a second resin.

[0022] (First layer)

[0023] The first resin comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more.

[0024] The alicyclic polyamide resin has an amino group concentration of 20 mmol / kg or higher, thus improving the adhesion between the first and second layers. The reason for this improved adhesion is that the alicyclic polyamide resin has an amino group concentration sufficient to fully react with the carboxyl groups of the acid-modified (meth)acrylic resin in the second layer. Therefore, the alicyclic polyamide resin and the acid-modified (meth)acrylic resin react fully at the interface between the first and second layers, resulting in a strong, integrated bond between the two layers. This suggests that the laminate of this disclosure is lightweight while also improving mechanical properties such as impact resistance and rigidity.

[0025] Amino concentration C of alicyclic polyamide resins NH2(Unit: mmol / kg) A concentration of 20 or higher is acceptable, for example, 20–80, preferably 25–80, further preferably 30–70, more preferably 30–60, and most preferably 30–50. If the amino concentration is too low, the adhesion to the second layer will decrease. The amino concentration can also be the terminal amino concentration, which is usually the terminal amino concentration.

[0026] The concentration (unit: mmol / kg) of the carboxyl group (terminal carboxyl group) of the alicyclic polyamide resin is not particularly limited, and can be less than 200, for example, 10 to 200, preferably 30 to 160, more preferably 40 to 130, more preferably 50 to 120, and most preferably 70 to 110.

[0027] In alicyclic polyamide resins, there is no particular limitation on the ratio of amino to carboxyl groups. For example, the ratio (molar ratio) of amino to carboxyl groups in alicyclic polyamide resins is amino / carboxyl = 15 / 85 to 100 / 0, preferably 20 / 80 to 100 / 0, more preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 80 / 20, and most preferably 35 / 65 to 70 / 30.

[0028] It should be noted that, in this specification and claims, the amino and carboxyl concentrations can be determined by conventional methods such as titration. Specifically, the amino concentration can be determined by preparing a 1% by mass solution of the alicyclic polyamide resin (sample) in a mixed solvent of phenol and ethanol at a volume ratio of 10:1, followed by neutralization titration with a 1 / 100 equivalent of an aqueous HCl solution. Similarly, the carboxyl concentration can be determined by preparing a 1% by mass benzyl alcohol solution of the alicyclic polyamide resin (sample) in benzyl alcohol, followed by neutralization titration with a 1 / 100 equivalent of an ethanol KOH solution.

[0029] The number average molecular weight of the alicyclic polyamide resin is, for example, 8,000 to 200,000, preferably 9,000 to 150,000, and more preferably 10,000 to 100,000. If the molecular weight is too small, the mechanical properties may be reduced; conversely, if the molecular weight is too large, the productivity of the laminate may be reduced.

[0030] It should be noted that, in this specification and claims, the number-average molecular weight of alicyclic polyamide resins can be determined by conventional methods. For example, from the perspective of more conveniently determining the correct molecular weight, when the terminal groups of the alicyclic polyamide resin are capped or have functional groups other than the terminal groups (including the case of additives with functional groups, etc.), it can be determined by gel permeation chromatography using polystyrene or the like as a standard substance. When the terminal groups of the alicyclic polyamide resin are not capped and do not have functional groups other than the terminal groups, it can be calculated based on the amount of terminal groups obtained by titration. When the amount of terminal groups is x mmol / kg, it can be calculated based on the formula: 1 ÷ (x / 2) × 1000000.

[0031] The melting point of the alicyclic polyamide resin is, for example, 150–350°C, preferably 180–300°C, more preferably 200–280°C, more preferably 220–270°C, and most preferably 230–260°C. If the melting point is too low, the heat resistance may decrease; conversely, if the melting point is too high, the productivity of the laminate may decrease.

[0032] The glass transition temperature (Tg) of the alicyclic polyamide resin is, for example, 30–250°C, preferably 50–200°C, more preferably 100–180°C, more preferably 120–160°C, and most preferably 130–150°C. If the glass transition temperature is too low, the rigidity may decrease; conversely, if the glass transition temperature is too high, the productivity of the laminate may decrease.

[0033] It should be noted that, in this specification and claims, the melting point and glass transition temperature of alicyclic polyamide resins can be determined by differential scanning calorimetry (DSC). In the case of multiple peaks generated by DSC, the temperature refers to the peak corresponding to the highest temperature among the multiple peaks.

[0034] Examples of alicyclic polyamide resins include homopolymers or copolymers comprising at least one alicyclic diamine and an alicyclic dicarboxylic acid as constituent components. For instance, alicyclic polyamides obtained by using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a portion of the diamine and dicarboxylic acid components can be used. In particular, it is preferable to use an alicyclic diamine and / or an alicyclic dicarboxylic acid in combination with the alicyclic diamine and / or alicyclic dicarboxylic acid components, and a combination of alicyclic diamine and alicyclic dicarboxylic acid is especially preferred. Such alicyclic polyamide resins have high transparency and are known as so-called transparent polyamides.

[0035] Examples of alicyclic diamine components include: diaminocyclohexane and other diaminocycloalkanes (diaminoC...5-10 Cycloalkanes, etc.; bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2,2-bis(4'-aminocyclohexyl)propane, and other bis(aminocycloalkyl)alkanes; hydrogenated phenylenediamine, etc. Alicyclic diamines optionally contain alkyl groups (methyl, ethyl, etc. C... 1-6 Alkyl group, preferably C 1-4 Alkyl, more preferably C 1-2 Alkyl groups and other substituents. These alicyclic diamine components can be used alone or in combination of two or more.

[0036] Examples of aliphatic diamines include: tetramethylenediamine, hexamethylenediamine, and dodecanediamine. 4-16 Alkylene diamines, etc.

[0037] Among these diamine components, alicyclic diamine components such as bis(aminocycloalkyl)alkanes are preferred, and bis(4-aminocyclohexyl)methane and other bis(aminoC) diamine components are particularly preferred. 5-8 cycloalkyl)C 1-3 Alkanes.

[0038] Examples of alicyclic dicarboxylic acids include cycloalkane dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid (C...). 5-10 Cycloalkanes-dicarboxylic acids, etc.

[0039] Examples of aliphatic dicarboxylic acids include: adipic acid, sebacic acid, and dodecanoic acid. 4-20 Alkane-dicarboxylic acid, etc.

[0040] Of these dicarboxylic acid components, C is preferred. 6-18 Alkane-dicarboxylic acid and other aliphatic dicarboxylic acid components, especially dodecanoic acid and other C-carboxylic acids are preferred. 8-12 Alkane-dicarboxylic acid.

[0041] Representative alicyclic polyamide resins include, for example, alicyclic diamine components [such as bis(aminocyclohexyl)alkanes, etc.] and aliphatic dicarboxylic acid components [such as alkane dicarboxylic acids (e.g., C14-C ... 4-20 Condensates of alkane-dicarboxylic acid components, etc.

[0042] The alicyclic polyamide resin in the first resin can be 50% by mass or more, preferably 80% by mass or more, further preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass. If the proportion of alicyclic polyamide resin is too low, the impact resistance may decrease.

[0043] In addition to alicyclic polyamide resins, the first resin may also contain other resins. These other resins can be selected from general thermoplastic resins, and aliphatic polyamide resins and aromatic polyamide resins are preferred considering compatibility. The proportion of other resins in the first resin can be 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0044] The first resin may be 70% by mass or more in the first resin composition, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, most preferably 99% by mass or more, and may also be 100% by mass. If the proportion of the first resin is too small, the impact resistance may be reduced.

[0045] The amino concentration C of the first resin NH2 (Unit: mmol / kg) A concentration of 20 or higher is acceptable, for example, 20–80, preferably 25–80, further preferably 30–70, more preferably 30–60, and most preferably 30–50. If the amino concentration is too low, the adhesion to the second layer will decrease. The amino concentration can also be the terminal amino concentration, which is usually the terminal amino concentration.

[0046] In addition to the first resin, the first resin composition may also contain conventional additives. Examples of conventional additives include, for instance, stabilizers (heat stabilizers, weather stabilizers, antioxidants, UV absorbers, etc.), colorants, fillers, plasticizers, lubricants, flame retardants, antistatic agents, silane coupling agents, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives in the first resin composition may be less than 30% by mass (e.g., 0.01 to 10% by mass).

[0047] From the perspective of improving lightweight and impact resistance, the average thickness of the first layer is preferably 200 μm or more. In particular, the average thickness of the first layer can be appropriately selected according to the application, for example, 0.2 to 50 mm, preferably 0.3 to 30 mm, more preferably 0.5 to 20 mm, more preferably 1 to 10 mm, and most preferably 2 to 5 mm.

[0048] (Second layer)

[0049] The second resin comprises an acid-modified (meth)acrylic resin.

[0050] The (meth)acrylic resin constituting the acid-modified (meth)acrylic resin can be any polymer containing (meth)acrylic acid, (meth)acrylate, or other (meth)acrylic monomers. From the perspective of improving transparency, lightfastness, and rigidity, polymethyl methacrylate resin containing methyl methacrylate units as the main component is preferred.

[0051] In addition to methyl methacrylate units, polymethyl methacrylate resins (unmodified polymethyl methacrylate resins) may also contain other copolymer units.

[0052] Monomers that constitute other copolymer units include, for example, methyl acrylate; ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (meth)acrylate C 2-12 Alkyl esters; 2-hydroxyethyl (meth)acrylate, etc. (meth)acrylate hydroxy C 2-4 Alkyl esters; cyclohexyl (meth)acrylate and other cycloalkyl (meth)acrylates; phenyl (meth)acrylate; aryl (meth)acrylates; benzyl (meth)acrylate and other aralkyl (meth)acrylates; cyanide derivatives such as (meth)acrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; conjugated dienes such as butadiene and isoprene; aromatic ethylene derivatives such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and bromostyrene; olefins such as ethylene and propylene; dimethyl maleate and other dimethyl maleate. 1-6 Alkyl esters; maleimides such as phenylmaleimide and cyclohexylmaleimide. These monomers can be used alone or in combination of two or more. Among them, (meth)acrylic acid C is preferred. 2-6 Alkyl esters, styrene, and other aromatic vinyl monomers.

[0053] In polymethyl methacrylate (PMMA) resins, the proportion of methyl methacrylate units in all monomers (monomers of unmodified PMMA resins) can be 50 mol% or more, preferably 70 mol% or more, further preferably 80 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. If the proportion of methyl methacrylate units is too low, transparency, lightfastness, and rigidity may decrease.

[0054] Acid-modified (meth)acrylic resins (especially acid-modified polymethyl methacrylate resins) can be any (meth)acrylic resin modified with carboxylic acid, preferably (meth)acrylic resins having carboxyl groups and / or anhydride groups, and particularly preferably (meth)acrylic resins having carboxyl groups. As for the acid modification method, it is not particularly limited as long as carboxyl groups and / or anhydride groups are introduced into the backbone of the (meth)acrylic resin. However, considering mechanical properties, it is preferable to introduce monomers having carboxyl groups and / or anhydride groups through copolymerization. As for the copolymerization method, block copolymerization, graft copolymerization, etc., are possible, but random copolymerization is preferred from the perspective of improving adhesion to the first layer and the mechanical strength of the laminate.

[0055] Examples of monomers having carboxyl and / or anhydride groups (monomers for acid modification) include: unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and unsaturated dicarboxylic acids or their anhydrides such as maleic acid (anhydride), fumaric acid, citraconic acid (anhydride), and itaconic acid (anhydride). These monomers can be used alone or in combination of two or more. Among these monomers, unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred, and methacrylic acid is particularly preferred.

[0056] The concentration of carboxyl groups (unit: mmol / kg) in the acid-modified poly(meth)acrylic resin is not particularly limited and can be 100 or more, for example, 100 to 1000, preferably 200 to 900, further preferably 300 to 800, more preferably 400 to 800, and most preferably 500 to 700.

[0057] It should be noted that, in this specification and claims, the concentration of carboxyl groups in the acid-modified poly(meth)acrylic resin can be determined by conventional methods, such as based on... 1 The concentration of carboxyl groups can be determined by methods such as ¹H-NMR and titration. In a preferred method, the concentration of carboxyl groups can be determined by preparing a 1% by mass solution by dissolving an acid-modified (meth)acrylic resin (sample) in benzyl alcohol and then neutralizing and titrating it with a 1 / 100 equivalent KOH ethanol solution.

[0058] Among acid-modified poly(meth)acrylate resins, acid-modified polymethyl methacrylate resins are particularly preferred, especially those having only carboxyl groups as polar or reactive groups other than methyl ester groups. Acid-modified polymethyl methacrylate resins without carboxylic anhydride groups or without imide rings are also acceptable. From the perspective of high transparency and minimal discoloration, acid-modified polymethyl methacrylate resins containing carboxyl groups and without anhydride groups are preferred. From the perspective of minimal discoloration and good adhesion to other materials, acid-modified polymethyl methacrylate resins containing carboxyl groups and without imide rings are also preferred.

[0059] The number average molecular weight of acid-modified poly(meth)acrylic resins (especially acid-modified polymethyl methacrylate resins) is, for example, 60,000 to 900,000, preferably 70,000 to 800,000, and more preferably 90,000 to 750,000. If the molecular weight is too small, the mechanical properties may be reduced; conversely, if the molecular weight is too large, the productivity of the laminate may be reduced.

[0060] It should be noted that, in this specification and claims, the number-average molecular weight of acid-modified poly(meth)acrylic resin can be determined by using polymethyl methacrylate as a standard substance, through methods such as gel permeation chromatography.

[0061] The melting point of acid-modified poly(meth)acrylic resins (especially acid-modified polymethyl methacrylate resins) is, for example, 150–350°C, preferably 180–300°C, more preferably 180–280°C, more preferably 200–270°C, and most preferably 220–250°C. If the melting point is too low, the heat resistance may decrease; conversely, if the melting point is too high, the productivity of the laminate may decrease.

[0062] It should be noted that, in this specification and claims, the melting point of the acid-modified poly(meth)acrylic resin can be determined by differential scanning calorimetry (DSC). In the case of multiple peaks generated by DSC, the temperature refers to the peak corresponding to the highest temperature among the multiple peaks.

[0063] The Vicat softening point of acid-modified poly(meth)acrylic resins (especially acid-modified polymethyl methacrylate resins) is, for example, 50–250°C, preferably 80–200°C, more preferably 90–150°C, more preferably 100–130°C, and most preferably 110–120°C. If the softening point is too low, the rigidity may decrease; conversely, if the softening point is too high, the productivity of the laminate may decrease.

[0064] It should be noted that, in this specification and claims, the Vicat softening point of the acid-modified poly(meth)acrylic resin can be determined according to ISO 306 (B50 method).

[0065] The glass transition temperature (Tg) of acid-modified poly(meth)acrylic resins (especially acid-modified polymethyl methacrylate resins) is, for example, 50–170°C, preferably 80–160°C, more preferably 100–150°C, more preferably 110–140°C, and most preferably 120–130°C. If the glass transition temperature is too low, the rigidity may decrease; conversely, if the glass transition temperature is too high, the productivity of the laminate may decrease.

[0066] It should be noted that, in this specification and claims, the glass transition temperature of the acid-modified poly(meth)acrylic resin can be determined according to ISO 11357.

[0067] The acid-modified (meth)acrylic resin in the second resin can be 10% by mass or more, preferably 30% by mass or more, further preferably 50% by mass or more, more preferably 80% by mass or more, most preferably 90% by mass or more, and may also be 100% by mass. If the proportion of acid-modified (meth)acrylic resin is too small, the adhesion of the laminate may be reduced.

[0068] In addition to the acid-modified (meth)acrylic resin, the second resin may also contain other resins. These other resins can be selected from general thermoplastic resins; considering compatibility, (meth)acrylic resins (unmodified (meth)acrylic resins) are preferred, and polymethyl methacrylate resins (unmodified polymethyl methacrylate resins) are particularly preferred. The proportion of other resins in the second resin can be 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, more preferably 30% by mass or less, and most preferably 10% by mass or less.

[0069] Unmodified polymethyl methacrylate resins and other unmodified (meth)acrylate resins can be combined to adjust the concentration of carboxyl groups in the second resin. When combined with other resins, a combination of acid-modified polymethyl methacrylate resin and unmodified polymethyl methacrylate resin is particularly preferred.

[0070] As an unmodified polymethyl methacrylate (PMMA) resin, the resin exemplified as a PMMA resin constituting the acid-modified PMMA resin can be used. Furthermore, the ratio of other copolymeric units to PMMA units, including preferred embodiments, is the same as that of the PMMA resin constituting the acid-modified PMMA resin.

[0071] The number average molecular weight of the unmodified polymethyl methacrylate resin is, for example, 60,000 to 900,000, preferably 70,000 to 800,000, and more preferably 90,000 to 750,000. If the molecular weight is too small, the mechanical properties may be reduced; conversely, if the molecular weight is too large, the productivity of the laminate may be reduced.

[0072] The melting point of the unmodified polymethyl methacrylate resin is, for example, 150–350°C, preferably 180–300°C, more preferably 180–280°C, more preferably 200–270°C, and most preferably 220–260°C. If the melting point is too low, the heat resistance may be reduced; conversely, if the melting point is too high, the productivity of the laminate may be reduced.

[0073] The Vicat softening point of the unmodified polymethyl methacrylate resin is, for example, 50–250°C, preferably 80–200°C, more preferably 90–150°C, more preferably 100–120°C, and most preferably 105–110°C. If the softening point is too low, the rigidity may decrease; conversely, if the softening point is too high, the productivity of the laminate may decrease.

[0074] The glass transition temperature (Tg) of the unmodified polymethyl methacrylate resin is, for example, 50–170°C, preferably 80–160°C, more preferably 90–150°C, more preferably 95–130°C, and most preferably 100–120°C. If the glass transition temperature is too low, the rigidity may decrease; conversely, if the glass transition temperature is too high, the productivity of the laminate may decrease.

[0075] It should be noted that, in this specification and claims, the number-average molecular weight, melting point, glass transition temperature, and Vicat softening point of the unmodified polymethyl methacrylate resin can be determined using the same methods as those used for the acid-modified polymethyl methacrylate resin.

[0076] The concentration of carboxyl groups in the second resin (unit: mmol / kg) is not particularly limited and can be 100 or more, for example, 100 to 1000, preferably 200 to 900, further preferably 300 to 800, more preferably 400 to 800, and most preferably 500 to 700.

[0077] It should be noted that, in this specification and claims, the concentration of carboxyl groups in the second resin can be determined by conventional methods such as titration. Specifically, the carboxyl group concentration can be determined by dissolving the second resin (in the case of a combination of acid-modified polymethyl methacrylate and unmodified polymethyl methacrylate resin, using a mixed resin as the sample) in benzyl alcohol to prepare a 1% by mass solution, and then performing a neutralization titration with a 1 / 100 equivalent KOH ethanol solution.

[0078] The second resin may comprise 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, most preferably 99% by mass or more, and may also comprise 100% by mass. If the proportion of the second resin is too low, the rigidity may decrease.

[0079] In addition to the second resin, the second resin composition may also contain conventional additives. Examples of conventional additives include, for instance, stabilizers (heat stabilizers, weather stabilizers, antioxidants, UV absorbers, etc.), colorants, fillers, plasticizers, lubricants, flame retardants, antistatic agents, silane coupling agents, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives in the second resin composition may be less than 30% by mass (e.g., 0.01 to 10% by mass).

[0080] From the perspective of improving rigidity, the average thickness of the second layer is preferably 250 μm or more. In particular, the average thickness of the second layer can be appropriately selected according to the application, for example, 0.25 to 50 mm, preferably 0.3 to 30 mm, more preferably 0.5 to 10 mm, more preferably 0.6 to 5 mm, and most preferably 0.8 to 3 mm.

[0081] (Properties of laminates)

[0082] In the laminated body disclosed herein, the average thickness of the first layer relative to the average thickness of the second layer can be 0.15 times or more (e.g., 0.2 to 30 times), for example 0.3 to 25 times, preferably 0.5 to 20 times, more preferably 1 to 10 times, more preferably 1.5 to 5 times, and most preferably 2 to 4 times. If the thickness of the first layer is too thin relative to the thickness of the second layer, the impact resistance may decrease; conversely, if the thickness of the first layer is too thick relative to the thickness of the second layer, the rigidity may decrease.

[0083] The laminate of this disclosure exhibits anisotropic impact resistance on both the first and second layer sides. Specifically, the second layer side of the laminate of this disclosure has higher impact resistance than the first layer side, making it suitable for applications where impacts are easily received from the second layer side. Therefore, for example, in the case of using the laminate of this disclosure as a partition between indoor and outdoor spaces (particularly as a sunroof in a car), it is preferable to place the second layer on the outdoor side. It should be noted that, compared to the alicyclic polyamide resin constituting the first layer, the poly(meth)acrylic acid resin represented by PMMA constituting the second layer is brittle and prone to cracking, exhibiting low impact resistance; this is common knowledge in the art. Therefore, the characteristic of the second layer side having higher impact resistance than the first layer side in the laminate of this disclosure is a distinct characteristic in the art.

[0084] In the laminated body disclosed herein, the DuPont impact strength of the drop hammer to the second layer side can be 300 N / inch or more, for example, 500 N / inch or more, preferably 700 N / inch or more, further preferably 800 N / inch or more, more preferably 1000 N / inch or more, and most preferably 1200 N / inch or more (e.g., 1200 to 2000 N / inch).

[0085] It should be noted that, in this specification and claims, the DuPont impact strength of the laminate can be determined by the method described in the embodiments described later.

[0086] Furthermore, in the laminates of this disclosure, the peel test used to represent the adhesion strength between the first and second layers is difficult to measure because the second layer is brittle and prone to cracking when bent. Therefore, in the laminates of this disclosure, the adhesion between the first and second layers is evaluated based on the DuPont impact strength of the drop hammer on the second layer side.

[0087] The laminate disclosed herein has high rigidity and therefore low deflection, making it ideal for applications such as sunroofs in automobiles. The flexural modulus of the laminate (4 mm thickness) disclosed herein can be 2000 MPa or more, preferably 2400 MPa or more, and even more preferably 2700 MPa or more (e.g., around 2700 to 3600 MPa).

[0088] It should be noted that, in this specification and claims, the flexural modulus can be determined by the method described in the embodiments described later.

[0089] The laminate disclosed herein can also laminate a hard coating formed from a cured product of a curable composition comprising a curable (meth)acrylic resin onto a second layer. The second layer comprises an acid-modified (meth)acrylic resin, and therefore has high affinity (wetting properties) for the hard coating, enabling the hard coating to be firmly adhered to the second layer.

[0090] As a curable (meth)acrylic resin for hard coating, for example, a general (meth)acrylic ester having two or more (meth)acryloyl groups in the molecule (e.g., about 2 to 8), and from the perspective of strength, a trifunctional or higher (meth)acrylic ester (e.g., pentaerythritol tri- to tetra(meth)acrylic ester, dipentaerythritol penta- to hexa(meth)acrylic ester, etc.) is preferred.

[0091] The average thickness of the hard coating is, for example, 0.5 to 30 μm, preferably 0.8 to 20 μm, and more preferably 1 to 10 μm.

[0092] The laminate disclosed herein can also be laminated with other functional layers instead of the hard coating layer. These other functional layers can be laminated between the hard coating layer and the second layer, or they can be laminated on top of the first layer. Examples of these other functional layers include: optical layers such as anti-reflective layers and anti-glare layers; and printed layers, etc.

[0093] [Manufacturing method of laminated bodies]

[0094] The laminate of this disclosure can be manufactured by contacting and curing at least one of a first precursor (first resin composition) used to form a first layer and a second precursor (second resin composition) used to form a second layer in a molten state. Specifically, it can be manufactured by heating and melting at least one of the first precursor and the second precursor, and then contacting and bonding them in a molten state.

[0095] As a specific joining method, it can be a method of joining the first precursor and the second precursor during the molding process by means of the following conventional molding methods, such as: thermoforming (hot pressing, injection pressing, etc.), injection molding (insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, etc.), extrusion molding (co-extrusion molding, T-die lamination, etc.), blow molding, etc.

[0096] For example, in molding methods such as insert injection molding and compression molding, a first precursor can be heated and melted, and molding can be performed while the molten first precursor is in contact with a second precursor to bond them together; alternatively, the second precursor can be heated and melted, and molding can be performed while the molten second precursor is in contact with the first precursor to bond them together. Furthermore, in molding methods such as two-color injection molding and co-extrusion molding, the first and second precursors can be heated and melted separately, and molding can be performed while the molten first precursor is in contact with the molten second precursor to bond them together. After melting at least one of the precursors, and bringing the first and second precursors into contact and bonding, cooling is typically performed to obtain a laminate with a strong bond between the first and second layers.

[0097] More specifically, in the hot pressing process, at least one of the first precursor and the second precursor can be melted in the pressing mold, so that the two precursors come into contact, are pressurized and joined to produce a molded body.

[0098] In insert injection molding, laminates can be manufactured by molding either a first precursor or a second precursor using methods such as injection molding, extrusion molding, sheet molding, or film molding. After the sheet-like precursor to be shaped is housed in a mold, the other precursor is injection molded into the gap between the precursor and the mold. In insert injection molding, it is preferable to preheat the sheet-like precursor housed in the mold.

[0099] In two-color injection molding, laminates can be manufactured in the following way: using two or more injection molding machines, either the first precursor or the second precursor is injection molded in a mold, and the mold cavity is changed by rotating or moving the mold, and the other precursor is injection molded in the gap formed between the resulting sheet-like precursor and the mold.

[0100] In the core-pulling injection molding method, a laminate can be manufactured by injection molding either the first precursor or the second precursor in a mold, expanding the cavity volume of the mold, and then injection molding the other precursor in the gap formed between the resulting sheet-like precursor and the mold.

[0101] Among these molding methods, considering factors such as productivity, thermoforming methods such as injection molding and injection molding methods (insert injection molding, two-color injection molding, core-pulling injection molding, sandwich injection molding, etc.) are preferred.

[0102] It should be noted that the precursor can be melted by heating to a temperature above the melting point of alicyclic polyamide resins and / or acid-modified (meth)acrylic resins (especially resins with higher melting points). In the case of resins that are not substantially crystallizing, they can be melted by heating to a temperature above the glass transition temperature (Tg) of the resin.

[0103] In hot melt welding, the heating temperature (e.g., barrel temperature) can be selected according to the type of resin forming the precursor, for example, 200-350°C, preferably 250-320°C, and more preferably 260-300°C.

[0104] Furthermore, the various schemes disclosed in this specification can be combined with any other features disclosed in this specification.

[0105] Example

[0106] The present invention will now be described in further detail based on embodiments, but the present invention is not limited to these embodiments. The following materials were used in the following embodiments and comparative examples.

[0107] [Alicyclic polyamide resins]

[0108] Alicyclic polyamide A: a condensation of dodecanoic acid and bis(4-aminocyclohexyl)methane, with an amino group concentration of 80 mmol / kg, a carboxyl group concentration of 50 mmol / kg, and a number-average molecular weight of 15384 (calculated by titration using the formula: 1 ÷ ((50 + 80) / 2) × 1000000. The same applies below).

[0109] Alicyclic polyamide B: a condensation of dodecanoic acid and bis(4-aminocyclohexyl)methane, with an amino concentration of 50 mmol / kg, a carboxyl concentration of 90 mmol / kg, and a number-average molecular weight of 14286.

[0110] Alicyclic polyamide C: a condensation of dodecanoic acid and bis(4-aminocyclohexyl)methane, with an amino concentration of 30 mmol / kg, a carboxyl concentration of 100 mmol / kg, and a number-average molecular weight of 15385.

[0111] Alicyclic polyamide D: a condensation of dodecanoic acid and bis(4-aminocyclohexyl)methane, with an amino concentration of 10 mmol / kg, a carboxyl concentration of 110 mmol / kg, and a number-average molecular weight of 16667.

[0112] [Polymethyl methacrylate resin]

[0113] Acid-modified polymethyl methacrylate (acid-modified PMMA): manufactured by DAICL EVONIK Co., Ltd., “PLEXIGLAS (registered trademark) FT15 clear”, carboxyl concentration 600 mmol / kg.

[0114] Polymethyl methacrylate (unmodified PMMA): manufactured by DAICL EVONIK Co., Ltd., "PLEXIGLAS (registered trademark) 8N clear", carboxyl concentration 5 mmol / kg.

[0115] Example 1

[0116] A flat plate of alicyclic polyamide A (20mm thick × 100mm × 100mm) was placed in an injection mold, and acid-modified PMMA was melted at 280℃ and injected into the mold to obtain a laminate with a thickness of 25mm.

[0117] Example 2

[0118] A flat plate of alicyclic polyamide A (20mm thickness × 100mm × 100mm) was placed in an injection mold. Acid-modified PMMA and unmodified PMMA were dry-mixed at 280℃ with a mass ratio of acid-modified PMMA:unmodified PMMA = 1:2 as polymethyl methacrylate resin. The mixture was then injected into the mold to obtain a laminate with a thickness of 30mm.

[0119] Example 3

[0120] A flat plate of alicyclic polyamide B (30 mm thick × 100 mm × 100 mm) was placed in an injection mold. Acid-modified PMMA was melted at 280 °C and injected into the mold to obtain a laminate with a thickness of 31.5 mm.

[0121] Example 4

[0122] Two extruders, a and b, were used. Cyclomeric polyamide C was added to extruder a and heated to 280°C, while acid-modified PMMA was added to extruder b and heated to 280°C. The two materials were then combined in the T-die, resulting in a laminate with a thickness ratio of 1:1 (total thickness 8 mm) of cyclomeric polyamide C to acid-modified PMMA.

[0123] Example 5

[0124] A plate of acid-modified PMMA (20mm thick × 100mm × 100mm) was placed in an injection mold, and alicyclic polyamide B was melted at 280℃ and injected into the mold to obtain a laminate with a thickness of 24mm.

[0125] Comparative Example 1

[0126] A flat plate of alicyclic polyamide D (20 mm thick × 100 mm × 100 mm) was placed in an injection molding mold, and otherwise, a laminate with a thickness of 25 mm was obtained in the same manner as in Example 1.

[0127] Comparative Example 2

[0128] A flat sheet of unmodified PMMA (20 mm thick × 100 mm × 100 mm) was placed in an injection molding mold, and otherwise, a laminate with a thickness of 24 mm was obtained in the same manner as in Example 5.

[0129] The laminates obtained in Examples 1-5 and Comparative Examples 1-2 were evaluated by measuring the DuPont impact strength using the following method.

[0130] (DuPont impact strength)

[0131] Regarding the obtained laminate, according to the DuPont impact strength test method of ASTM D 2794, under the following conditions, a weighted hammer was dropped from a varying height, and the 50% breaking energy of the obtained film was calculated based on whether or not it was damaged. The results were evaluated according to the following criteria. It should be noted that, regarding the hammer, it was dropped onto the surface of the second layer formed from acid-modified PMMA, etc.

[0132] (condition)

[0133] The hammer tip diameter is 15.9mm, the support platform is 16.3mm, and the hammer weight is 0.5kg.

[0134] (Evaluation Criteria)

[0135] 〇: 500N / inch or more.

[0136] ×: Less than 500 N / inch.

[0137] The results are shown in Table 1.

[0138] [Table 1]

[0139]

[0140] As can be clearly seen from the results in Table 1, the laminate of the embodiment has high impact resistance, while the laminate of the comparative example has low impact resistance compared to the laminate in which the first and second layers are firmly bonded together.

[0141] Example 6

[0142] Using alicyclic polyamide B and acid-modified PMMA, laminates with total thicknesses of 4 mm, 3 mm, and 2 mm (laminates of a first layer formed of alicyclic polyamide B and a second layer formed of acid-modified PMMA) were manufactured by varying the thickness as shown in Table 2, using the same method as in Example 3. The following three-point bending tests were evaluated, and the DuPont impact strength was evaluated in the same manner as in Example 3. Furthermore, a single layer of alicyclic polyamide B and a single layer of acid-modified PMMA are also described for comparison. In Table 2, "upper" and "lower" in each laminate indicate that either the first or second layer was evaluated as the upper or lower layer in the evaluation test. That is, regarding the DuPont impact strength, the hammer was dropped onto the upper layer; therefore, unlike Examples 1-5 and Comparative Examples 1-2, the hammer was dropped not only onto the surface of the second layer but also onto the surface of the first layer.

[0143] (Three-point bending test)

[0144] According to JIS K7171, using a sample with a width of 25 mm, under the conditions of a span distance of 64 mm and a compression speed of 2 mm / min, the elastic modulus, maximum point, maximum point displacement strain, and maximum displacement strain were measured.

[0145] The results are shown in Table 2.

[0146] [Table 2]

[0147]

[0148] As can be clearly seen from the results in Table 2, for any total thickness, the displacement until failure is significantly increased when the second layer is on top (in terms of DuPont impact strength, the hammer falls onto the surface of the second layer) compared to when the first layer is on top.

[0149] Industrial availability

[0150] The laminated body disclosed herein can be used in molded bodies in various fields requiring transparency, such as daily necessities, containers, electrical / electronic equipment parts, optical sheets, lenses, structural components of vehicles (transportation equipment or means of transportation), building materials, etc. In particular, due to its excellent light resistance, it is preferred as a partition wall separating indoor and outdoor spaces in vehicles, buildings, etc., and is especially preferred as a window or partition (particularly a sunroof of a car) in vehicles (cars, etc.), trains, airplanes or aircraft, ships, etc.

Claims

1. A method of use, wherein the laminated body is used as a partition wall separating indoor and outdoor spaces. The laminate is a laminate in which a first layer formed by a first resin composition containing a first resin and a second layer formed by a second resin composition containing a second resin are in contact with each other and integrated. The first resin comprises an alicyclic polyamide resin having an amino group of 20 mmol / kg or more, and the second resin comprises an acid-modified (meth)acrylic resin having a carboxyl group of 100 mmol / kg or more. in, The second layer is located on the outdoor side.

2. The method of use according to claim 1, wherein, Acid-modified (meth)acrylic resin is an acid-modified polymethyl methacrylate resin.

3. The method of use according to claim 1, wherein, The average thickness of the first layer is more than 0.15 times that of the average thickness of the second layer.

4. The method of use according to claim 1, wherein, The average thickness of the first layer is over 200 μm.

5. The method of use according to claim 1, wherein, The DuPont impact strength of the drop hammer to the second layer side is over 500 N / inch.

6. The method of use according to claim 1, wherein, The molded body is a second layer of a car sunroof located on the outdoor side.

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