Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
  • B29C45/14811—Multilayered articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
  • B60J7/00—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs
  • B60J7/02—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs of sliding type, e.g. comprising guide shoes
  • B60J7/04—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs of sliding type, e.g. comprising guide shoes with rigid plate-like element or elements, e.g. open roofs with harmonica-type folding rigid panels
  • B60J7/043—Sunroofs e.g. sliding above the roof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
  • B29K2033/04—Polymers of esters
  • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0058—Liquid or visquous
  • B29K2105/0067—Melt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/10—Building elements, e.g. bricks, blocks, tiles, panels, posts, beams
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3005—Body finishings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/402—Coloured
  • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/54—Yield strength; Tensile strength
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
  • B32B2309/08—Dimensions, e.g. volume
  • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Definitions

• This disclosure relates to a laminated body that can be used as a transparent molded body such as a sunroof of an automobile, and a manufacturing method and application thereof.
• a transparent molded body used outdoors such as a sunroof is required to have light weight, light resistance, impact resistance, rigidity, and the like.
• a material used for such a transparent molded product glass, polycarbonate, polymethylmethacrylate (PMMA) and the like are widely used.
• glass has the disadvantages of low lightness and impact resistance
• polycarbonate has low light resistance
• polymethylmethacrylate has low impact resistance. Therefore, attempts have been made to improve the physical properties by laminating sheets made of a plastic material.
• Patent Document 1 describes a plastics polarizing lens body including a sheet-shaped polarizing body having at least a polarizing sheet, and a (meth) acrylate-based resin on at least one surface of the sheet-shaped polarizing body.
• a plastics polarized lens characterized in that a layer is formed, and at least on the (meth) acrylate-based resin layer, a thermoforming resin such as a polyamide resin is thermoformed and laminated by an injection molding method.
• the body is disclosed.
• As the (meth) acrylate-based resin layer an ultraviolet curable composition is described.
• Patent Document 2 Japanese Patent Application Laid-Open No. 2010-501380 (Patent Document 2) describes a multilayer sheet consisting of a layer made of a polyamide molding material, an inner layer made of a fixing agent, and a support made of a polyalkyl (meth) acrylate molding material.
• the inner layer contains 5-100% by mass of the copolymer, and the copolymer is derived from a vinyl compound selected from acrylic acid derivatives, methacrylic acid derivatives, ⁇ -olefins and vinyl aromatics, with the monomer units 70 to 70.
• a multilayer sheet having 99.9% by mass and 0.1 to 30% by mass of a monomer unit having a functional group selected from a carboxylic acid anhydride group, an epoxy group and an oxazoline group is disclosed.
• a sheet having a total thickness of 3 mm in which a fixing agent layer 240 ⁇ m and a polyamide layer 180 ⁇ m are laminated on a PMMA support is manufactured by insert mold lamination.
• the layer structure is complicated, and the adhesion between the (meth) acrylate-based resin layer and the lens body formed of the thermoforming resin is low. Further, in the multilayer sheet of Patent Document 2, the impact resistance is low, and the adhesion between the layer made of the polyamide molding material and the inner layer is not sufficient.
• an object of the present invention is to provide a laminate having excellent transparency, light weight, light resistance and impact resistance, and a method and application thereof.
• the present inventors have conducted a diligent study to obtain a first layer formed of a first resin composition containing an alicyclic polyamide-based resin having an amino group of 20 mmol / kg or more, and an acid.
• a first resin composition containing an alicyclic polyamide-based resin having an amino group of 20 mmol / kg or more By contacting and integrating the second layer formed of the second resin composition containing the modified (meth) acrylic resin with each other, transparency, lightness, light resistance and impact resistance can be improved. And completed the present invention.
• the first layer formed of the first resin composition containing the first resin and the second layer formed of the second resin composition containing the second resin are in contact with each other.
• the first resin contains an alicyclic polyamide-based resin having an amino group of 20 mmol / kg or more
• the second resin contains an acid-modified (meth) acrylic resin. ..
• the second resin may have a carboxyl group of 100 mmol / kg or more.
• the acid-modified (meth) acrylic resin may be an acid-modified polymethyl methacrylate resin.
• the average thickness of the first layer may be 0.15 times or more the average thickness of the second layer.
• the average thickness of the first layer may be 200 ⁇ m or more.
• the laminated body may have a DuPont impact strength of 500 N / inch or more dropped on the second layer side.
• the laminate obtained by contacting and solidifying at least one of a first precursor for forming the first layer and a second precursor for forming the second layer in a molten state to obtain a laminate It also includes how to make the body.
• the present disclosure also includes a molded body formed of the laminated body.
• the molded body may be a sunroof of an automobile in which the second layer is arranged on the outdoor side.
• the present disclosure includes a method of using the laminated body as a partition wall separating indoors and outdoors, and also includes a method of arranging the second layer on the outdoor side.
• the second layer contains an acid-modified (meth) acrylic resin, it has a high degree of familiarity (wetting property) with a general-purpose (meth) acrylic hard coat layer, and the hard layer is placed on the second layer depending on the application.
• the surface strength can be further improved by laminating the coat layer. Since it has high rigidity, it is also suitable for automobile sunroofs (transparent skylights).
• the laminate of the present disclosure is formed of a first layer formed of a first resin composition containing a first resin and a second layer formed of a second resin composition containing a second resin.
• the first resin contains an alicyclic polyamide-based resin having an amino group of 20 mmol / kg or more.
• the adhesion between the first layer and the second layer can be improved.
• the reason why the adhesion can be improved is that the alicyclic polyamide-based resin has an amino group concentration capable of sufficiently reacting with the carboxyl group of the acid-modified (meth) acrylic resin of the second layer, so that the first layer and the first layer can be improved.
• the alicyclic polyamide resin and the acid-modified (meth) acrylic resin sufficiently react at the interface with the two layers, and the first layer and the second layer are firmly integrated. Thereby, it can be presumed that the laminated body of the present disclosure can improve mechanical properties such as impact resistance and rigidity while being lightweight.
• the amino group concentration C NH2 (unit: mmol / kg) of the alicyclic polyamide resin may be 20 or more, for example, 20 to 80, preferably 25 to 80, more preferably 30 to 70, and more preferably 30 to 30. 60, most preferably 30-50. If the amino group concentration is too low, the adhesion to the second layer is lowered.
• the amino group concentration may be a terminal amino group concentration, and is usually a terminal amino group concentration.
• the concentration (unit: mmol / kg) of the carboxyl group (terminal carboxyl group) of the alicyclic polyamide resin is not particularly limited and may be 200 or less, for example, 10 to 200, preferably 30 to 160, and further. It is preferably 40 to 130, more preferably 50 to 120, and most preferably 70 to 110.
• the amino group concentration and the carboxyl group concentration can be measured by a conventional method, for example, a titration method.
• the amino group concentration is determined by dissolving an alicyclic polyamide resin (sample) in a mixed solvent having a volume ratio of phenol and ethanol of 10: 1 to prepare a 1% by mass solution, and preparing a 1% by mass aqueous solution of HCl. It can be measured by neutralization titration with.
• the carboxyl group concentration can be measured by dissolving an alicyclic polyamide resin (sample) in benzyl alcohol to prepare a 1% by mass benzyl alcohol solution, and then neutralizing and titrating with a 1/100 standard KOH ethanol solution.
• the number average molecular weight of the alicyclic polyamide resin is, for example, 8000 to 200,000, preferably 9000 to 150,000, and more preferably 10,000 to 100,000. If the molecular weight is too small, the mechanical properties may deteriorate, and if it is too large, the productivity of the laminate may decrease.
• the number average molecular weight of the alicyclic polyamide-based resin can be measured by a conventional method, and for example, the alicyclic polyamide-based resin can be measured more easily and accurately.
• the terminal group of is sealed or has a functional group other than the terminal group (such as when an additive having a functional group is contained), it can be measured by a method by gel permeation chromatography using polystyrene or the like as a standard substance.
• the terminal group of the alicyclic polyamide resin is not sealed and has no functional group other than the terminal group, it can be calculated from the amount of the terminal group by the titration method, and the amount of the terminal group is x mmol / kg. If, it can be obtained based on the formula: 1 ⁇ (x / 2) ⁇ 1000000.
• the melting point of the alicyclic polyamide resin is, for example, 150 to 350 ° C., preferably 180 to 300 ° C., more preferably 200 to 280 ° C., more preferably 220 to 270 ° C., and most preferably 230 to 260 ° C. If the melting point is too low, the heat resistance may decrease, and if it is too high, the productivity of the laminate may decrease.
• the glass transition temperature (Tg) of the alicyclic polyamide resin is, for example, 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 100 to 180 ° C., more preferably 120 to 160 ° C., and most preferably 130 to 150 ° C. °C. If the glass transition temperature is too low, the rigidity may decrease, and conversely, if it is too high, the productivity of the laminate may decrease.
• the melting point and the glass transition temperature of the alicyclic polyamide resin can be measured by a differential scanning calorimeter (DSC), and when a plurality of peaks occur in the DSC, among the plurality of peaks. It means the temperature corresponding to the peak on the hottest side.
• DSC differential scanning calorimeter
• Examples of the alicyclic polyamide-based resin include homopolyamides and copolyamides containing at least one selected from the alicyclic diamine component and the alicyclic dicarboxylic acid component as constituent components, and examples thereof include a diamine component and a dicarboxylic acid component.
• alicyclic polyamide obtained by using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a part of the components can be used.
• the diamine component and the dicarboxylic acid component it is preferable to use the aliphatic diamine component and / or the aliphatic dicarboxylic acid component in combination with the alicyclic diamine component and / or the alicyclic dicarboxylic acid component, and the alicyclic diamine component is preferable.
• an aliphatic dicarboxylic acid component are particularly preferable.
• Such an alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide.
• Examples of the alicyclic diamine component include diaminocycloalkanes such as diaminocyclohexane (diaminoC 5-10cycloalkanes and the like); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, and the like.
• Examples include bis (aminocycloalkyl) alkanes such as 2,2-bis (4'-aminocyclohexyl) propane; hydrogenated xylylene diamines and the like.
• the alicyclic diamine component has a substituent such as an alkyl group (C 1-6 alkyl group such as methyl group or ethyl group, preferably C 1-4 alkyl group, more preferably C 1-2 alkyl group). May be.
• alkyl group C 1-6 alkyl group such as methyl group or ethyl group, preferably C 1-4 alkyl group, more preferably C 1-2 alkyl group. May be.
• These alicyclic diamine components can be used alone or in combination of two or more.
• aliphatic diamine component examples include C 4-16 alkylene diamines such as tetramethylenediamine, hexamethylenediamine and dodecanediamine.
• alicyclic diamine components such as bis (aminocycloalkyl) alkanes are preferable, and bis (amino C 5-8 cycloalkyl) C 1-3 alkanes such as bis (4-aminocyclohexyl) methane are preferable. Especially preferable.
• alicyclic dicarboxylic acid component examples include cycloalkanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid (C 5-10 cycloalkane-dicarboxylic acid and the like).
• aliphatic dicarboxylic acid component examples include C 4-20 alkane-dicarboxylic acids such as adipic acid, sebacic acid, and dodecanedioic acid.
• dicarboxylic acid components an aliphatic dicarboxylic acid component such as C 6-18 alkane-dicarboxylic acid is preferable, and C 8-12 alkane-dicarboxylic acid such as dodecanedioic acid is particularly preferable.
• Typical alicyclic polyamide-based resins include, for example, an alicyclic diamine component [eg, bis (aminocyclohexyl) alkane, etc.] and an aliphatic dicarboxylic acid component [eg, an alkanedicarboxylic acid (eg, C 4-20 alkane). -A condensate with [dicarboxylic acid component, etc.)], etc. can be mentioned.
• the alicyclic polyamide resin may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass in the first resin. %. If the proportion of the alicyclic polyamide resin is too small, the impact resistance may decrease.
• the first resin may further contain other resins in addition to the alicyclic polyamide-based resin.
• a general-purpose thermoplastic resin can be selected, but an aliphatic polyamide-based resin and an aromatic polyamide-based resin are preferable from the viewpoint of compatibility and the like.
• the ratio of the other resin may be 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less in the first resin.
• the first resin may be 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, and most preferably 99% by mass in the first resin composition. As mentioned above, it may be 100% by mass. If the proportion of the first resin is too small, the impact resistance may decrease.
• the amino group concentration CNH2 (unit: mmol / kg) of the first resin may be 20 or more, for example, 20 to 80, preferably 25 to 80, more preferably 30 to 70, more preferably 30 to 60, and most. It is preferably 30 to 50. If the amino group concentration is too low, the adhesion to the second layer is lowered.
• the amino group concentration may be a terminal amino group concentration, and is usually a terminal amino group concentration.
• the first resin composition may further contain a conventional additive in addition to the first resin.
• Conventional additives include, for example, stabilizers (heat-resistant stabilizers, weather-resistant stabilizers, antioxidants, UV absorbers, etc.), colorants, fillers, plasticizers, lubricants, flame retardants, antistatic agents, silane cups, etc. Ring agents and the like can be mentioned. These additives can be used alone or in combination of two or more. The total ratio of these additives may be 30% by mass or less (for example, 0.01 to 10% by mass) in the first resin composition.
• the average thickness of the first layer is preferably 200 ⁇ m or more from the viewpoint of improving lightness and impact resistance.
• the average thickness of the first layer can be appropriately selected depending on the intended use, 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. It is preferably 2 to 5 mm.
• the second resin contains an acid-modified (meth) acrylic resin.
• the (meth) acrylic resin constituting the acid-modified (meth) acrylic resin may be a polymer containing a (meth) acrylic monomer such as (meth) acrylic acid or (meth) acrylic acid ester.
• a polymethyl methacrylate-based resin containing a methyl methacrylate unit as a main component is preferable from the viewpoint of improving transparency, light resistance and rigidity.
• the polymethyl methacrylate-based resin may further contain other copolymerizable units in addition to the methyl methacrylate unit.
• Examples of the monomer constituting another copolymerizable unit include methyl acrylate; (meth) acrylic acid such as ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• Conjugate dienes such as butadiene and isoprene; Aromatic vinyls such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene and bromostyrene; Olefins such as ethylene and propylene; DiC 1 maleate such as dimethyl maleate -6 Alkyl ester; Maleimides such as phenylmaleimide and cyclohexylmaleimide can be mentioned. These monomers can be used alone or in combination of two or more. Of these, aromatic vinyl-based monomers such as (meth) acrylic acid C 2-6 alkyl ester and styrene are preferable.
• the ratio of the methyl methacrylate-based resin may be, for example, 50 mol% or more in all the monomers (monomers of the polymethyl methacrylate-based resin not modified with acid). It is preferably 70 mol% or more, more 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 small, transparency, light resistance and rigidity may decrease.
• the acid-modified (meth) acrylic resin may be any carboxylic acid-modified (meth) acrylic resin and has a carboxyl group and / or an acid anhydride group.
• a (meth) acrylic resin is preferable, and a (meth) acrylic resin having a carboxyl group is particularly preferable.
• the acid modification method may be such that a carboxyl group and / or an acid anhydride group is introduced into the skeleton of the (meth) acrylic resin, and is not particularly limited, but from the viewpoint of mechanical properties and the like, the carboxyl group and / or the acid anhydride group may be introduced.
• a method of introducing a monomer having an acid anhydride group by copolymerization is preferable.
• the form of copolymerization may be block copolymerization, graft copolymerization, or the like, but random copolymerization is preferable from the viewpoint of improving the adhesion to the first layer and the mechanical strength of the laminate.
• Examples of the monomer having a carboxyl group and / or an acid anhydride group include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; (anhydrous) maleic acid and fumal. Examples thereof include unsaturated dicarboxylic acids such as acid, (anhydrous) citraconic acid, and (anhydrous) itaconic acid, or acid anhydrides thereof. These monomers can be used alone or in combination of two or more. Of these monomers, unsaturated monocarboxylic acids such as (meth) acrylic acid are preferred, and methacrylic acid is particularly preferred.
• the concentration (unit: mmol / kg) of the carboxyl group of the acid-modified poly (meth) acrylic resin is not particularly limited and may be 100 or more, for example, 100 to 1000, preferably 200 to 900, and more preferably 100. It is 300 to 800, more preferably 400 to 800, and most preferably 500 to 700.
• the concentration of the carboxyl group of the acid-modified poly (meth) acrylic resin can be measured by a conventional method, for example, a method by 1 H-NMR or a titration method.
• the carboxyl group concentration is determined by dissolving an acid-modified (meth) acrylic resin (sample) in benzyl alcohol to prepare a 1% by mass solution, and then neutralizing and titrating with a 1/100 standard KOH ethanol solution. Can be measured.
• the acid-modified polymethylmethacrylate resin is an acid-modified polymethylmethacrylate resin having only a carboxyl group as a polar group other than the methyl ester group or a reactive group. Is particularly preferable, and an acid-modified polymethyl methacrylate-based resin containing no carboxylic acid anhydride group may be used, or an acid-modified polymethyl methacrylate-based resin containing no imide ring may be used.
• the acid-modified polymethylmethacrylate resin containing a carboxyl group and not containing an acid anhydride group is preferable in terms of optical properties such as high transparency and little discoloration, and contains a carboxyl group and does not contain an imide ring.
• the acid-modified polymethyl methacrylate resin is preferable in terms of less discoloration and adhesion to other materials.
• the number average molecular weight of the acid-modified poly (meth) acrylic resin is, for example, 60,000 to 900,000, preferably 70,000 to 800,000, and more preferably 90. It is 000 to 750,000. If the molecular weight is too small, the mechanical properties may deteriorate, and if it is too large, the productivity of the laminate may decrease.
• the number average molecular weight of the acid-modified poly (meth) acrylic resin can be measured by gel permeation chromatography or the like using methyl polymethacrylate as a standard substance.
• the melting point of the acid-modified poly (meth) acrylic resin is, for example, 150 to 350 ° C, preferably 180 to 300 ° C, more preferably 180 to 280 ° C, and more preferably 200 ° C. It is 270 ° C, most preferably 220 to 250 ° C. If the melting point is too low, the heat resistance may decrease, and if it is too high, the productivity of the laminate may decrease.
• the melting point of the acid-modified poly (meth) acrylic resin can be measured by a differential scanning calorimeter (DSC), and when a plurality of peaks occur in the DSC, the melting point of the plurality of peaks is the most. It means the temperature corresponding to the peak on the high temperature side.
• DSC differential scanning calorimeter
• the Vicat softening point of the acid-modified poly (meth) acrylic resin is, for example, 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 90 to 150 ° C, more preferably. Is 100 to 130 ° C, most preferably 110 to 120 ° C. If the softening point is too low, the rigidity may decrease, and conversely, if it is too high, the productivity of the laminated body may decrease.
• the bicut softening point of the acid-modified poly (meth) acrylic resin can be measured in accordance with ISO306 (B50 method).
• the glass transition temperature (Tg) of the acid-modified poly (meth) acrylic resin is, for example, 50 to 170 ° C, preferably 80 to 160 ° C, and more preferably 100 to 150 ° C. , More preferably 110 to 140 ° C, most preferably 120 to 130 ° C. If the glass transition temperature is too low, the rigidity may decrease, and conversely, if it is too high, the productivity of the laminate may decrease.
• the glass transition temperature of the acid-modified poly (meth) acrylic resin can be measured in accordance with ISO11357.
• the acid-modified (meth) acrylic resin may be 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 80% by mass or more in the second resin. It is 90% by mass or more, and may be 100% by mass. If the proportion of the acid-modified (meth) acrylic resin is too small, the adhesion of the laminate may decrease.
• the second resin may further contain other resins in addition to the acid-modified (meth) acrylic resin.
• a general-purpose thermoplastic resin can be selected, but a (meth) acrylic resin (non-modified (meth) acrylic resin) is preferable from the viewpoint of compatibility and the like, and a polymethyl methacrylate-based resin (non-methyl methacrylate) is preferable. Modified polymethyl methacrylate resin) is particularly preferable.
• the ratio of the other resin may be 90% by mass or less in the second resin, preferably 70% by mass or less, further preferably 50% by mass or less, more preferably 30% by mass or less, and most preferably 10% by mass. It is as follows.
• a non-modified (meth) acrylic resin such as a non-modified polymethyl methacrylate resin may be blended to adjust the concentration of the carboxyl group in the second resin, and when another resin is blended, it is acid-modified.
• a combination of a polymethyl methacrylate-based resin and a non-modified polymethyl methacrylate-based resin is particularly preferable.
• the resin exemplified as the polymethylmethacrylate resin constituting the acid-modified polymethylmethacrylate resin can be used. Further, the ratio of the other copolymerizable unit and the methyl methacrylate unit is the same as that of the polymethyl methacrylate-based resin constituting the acid-modified polymethyl methacrylate-based resin, including preferred embodiments.
• the number average molecular weight of the non-modified 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 deteriorate, and if it is too large, the productivity of the laminate may decrease.
• the melting point of the non-modified polymethyl methacrylate resin is, for example, 150 to 350 ° C., preferably 180 to 300 ° C., more preferably 180 to 280 ° C., more preferably 200 to 270 ° C., and most preferably 220 to 260 ° C. .. If the melting point is too low, the heat resistance may decrease, and if it is too high, the productivity of the laminate may decrease.
• the Vicat softening point of the non-modified polymethyl methacrylate resin is, for example, 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 90 to 150 ° C, more preferably 100 to 120 ° C, and most preferably 105 to 110 ° C. Is. If the softening point is too low, the rigidity may decrease, and conversely, if it is too high, the productivity of the laminated body may decrease.
• the glass transition temperature (Tg) of the non-modified polymethyl methacrylate resin is, for example, 50 to 170 ° C, preferably 80 to 160 ° C, more preferably 90 to 150 ° C, more preferably 95 to 130 ° C, and most preferably 100. It is about 120 ° C. If the glass transition temperature is too low, the rigidity may decrease, and conversely, if it is too high, the productivity of the laminate may decrease.
• the number average molecular weight, melting point, glass transition temperature and Vicat softening point of the non-modified polymethyl methacrylate resin are measured by the same method as that of the acid-modified polymethyl methacrylate resin. can.
• the concentration of the carboxyl group (unit: mmol / kg) of the second resin is not particularly limited and may be 100 or more, for example, 100 to 1000, preferably 200 to 900, more preferably 300 to 800, and more preferably. Is 400 to 800, most preferably 500 to 700.
• the concentration of the carboxyl group of the second resin can be measured by a conventional method, for example, a titration method.
• the second resin (when the second resin is a combination of an acid-modified polymethylmethacrylate resin and a non-modified polymethylmethacrylate resin, a mixed resin as a sample) is used as a benzyl alcohol. It can be measured by dissolving to prepare a 1% by mass solution and neutralizing and titrating with a 1/100 standard KOH ethanol solution.
• the second resin may be 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, and most preferably 99% by mass in the second resin composition. As mentioned above, it may be 100% by mass. If the proportion of the second resin is too small, the rigidity may decrease.
• the second resin composition may further contain a conventional additive in addition to the second resin.
• Conventional additives include, for example, stabilizers (heat-resistant stabilizers, weather-resistant stabilizers, antioxidants, UV absorbers, etc.), colorants, fillers, plasticizers, lubricants, flame retardants, antistatic agents, silane cups, etc. Ring agents and the like can be mentioned. These additives can be used alone or in combination of two or more. The total ratio of these additives may be 30% by mass or less (for example, 0.01 to 10% by mass) in the second resin composition.
• the average thickness of the second layer is preferably 250 ⁇ m or more from the viewpoint of improving the rigidity.
• the average thickness of the second layer can be appropriately selected depending on the intended use, for example, 0.25 to 50 mm, preferably 0.3 to 30 mm, more preferably 0.5 to 10 mm, and more preferably 0.6 to 5 mm. Most preferably, it is 0.8 to 3 mm.
• the average thickness of the first layer may be 0.15 times or more (for example, 0.2 to 30 times) the average thickness of the second layer, for example, 0.3 to 25 times. It is double, 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 with respect to the second layer, the impact resistance may decrease, and conversely, if it is too thick, the rigidity may decrease.
• the laminate of the present disclosure has anisotropy in impact resistance between the first layer side and the second layer side. Specifically, the laminate of the present disclosure has higher impact resistance on the second layer side than on the first layer side, and is therefore suitable for applications that are susceptible to impact from the second layer side. Therefore, for example, when the laminate of the present disclosure is used as a partition wall separating indoors and outdoors (particularly when it is used as a sunroof of an automobile), it is preferable to arrange the second layer on the outdoor side for use. ..
• the poly (meth) acrylic resin represented by PMMA that constitutes the second layer is brittle, easily cracked, and has low impact resistance.
• the characteristic that the second layer side has higher impact resistance than the first layer side is a characteristic different in the art.
• the impact strength of the dupon dropped on the second layer side may be 300 N / inch or more, for example, 500 N / inch or more, preferably 700 N / inch or more, and more preferably 800 N / inch or more. It is more preferably 1000 N / inch or more, and most preferably 1200 N / inch or more (for example, 1200 to 2000 N / inch).
• the DuPont impact strength of the laminated body can be measured by the method described in Examples described later.
• the peeling test for showing the adhesion strength between the first layer and the second layer is difficult to measure because the second layer is fragile to bending and easily cracked. Therefore, in the laminated body of the present disclosure, the adhesion between the first layer and the second layer is evaluated by the DuPont impact strength dropped on the second layer side.
• the flexural modulus of the laminated body (thickness of 4 mm) of the present disclosure may be 2000 MPa or more, preferably 2400 MPa or more, more preferably 2700 MPa or more (for example, about 2700 to 3600 MPa).
• the flexural modulus can be measured by the method described in Examples described later.
• a hard coat layer formed of a cured product of a curable composition containing a curable (meth) acrylic resin may be laminated on the second layer. Since the second layer contains an acid-modified (meth) acrylic resin, it has a high affinity (wetting property) for the hard coat layer, and the hard coat layer is firmly adhered to the second layer. can.
• the curable (meth) acrylic resin of the hard coat layer for example, a (meth) acrylate having two or more (for example, about 2 to 8) (meth) acryloyl groups in the molecule is widely used, and from the viewpoint of strength.
• a trifunctional or higher functional (meth) acrylate eg, pentaerythritol tri or tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate, etc.
• pentaerythritol tri or tetra (meth) acrylate dipentaerythritol penta or hexa (meth) acrylate, etc.
• the average thickness of the hard coat layer is, for example, 0.5 to 30 ⁇ m, preferably 0.8 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
• another functional layer may be laminated instead of the hard coat layer, another functional layer may be laminated between the hard coat layer and the second layer, and the first layer may be laminated. Another functional layer may be laminated on top of it. Examples of other functional layers include optical layers such as antireflection layers and antiglare layers, and printing layers.
• the laminate of the present disclosure comprises at least one of a first precursor (first resin composition) for forming the first layer and a second precursor (second resin composition) for forming the second layer. It may be manufactured by contacting and solidifying in a molten state. Specifically, at least one of the first precursor and the second precursor is heated and melted, and at least one of them is brought into contact with each other in a molten state to be bonded. It may be manufactured by the above.
• Specific joining methods include, for example, thermal molding (heat press molding, injection press molding, etc.), injection molding (insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, etc.), extrusion molding (co-molding). It may be a method of joining the first precursor and the second precursor in the molding process by a conventional molding method such as extrusion molding, T-die laminating molding, etc.) or blow molding.
• the first precursor is heated and melted, the first precursor in this molten state is molded while being in contact with the second precursor, and both are joined.
• the second precursor may be heated and melted, and the second precursor in this molten state may be molded while being in contact with the first precursor, and both may be bonded.
• molding methods such as two-color injection molding and co-extrusion molding
• the first precursor and the second precursor are heated and melted, respectively, and the first precursor in the molten state and the second precursor in the molten state are brought into contact with each other. While molding, both may be joined. At least one of the precursors is melted, the first precursor and the second precursor are brought into contact with each other and bonded, and then usually cooled to firmly bond the first layer and the second layer. Can be obtained as a laminated body.
• At least one of the first precursor and the second precursor is melted in a press molding die, and both are contacted, pressed, and joined to form a molded body. Can be manufactured.
• one of the first precursor and the second precursor is molded by a molding method such as injection molding, extrusion molding, sheet molding, film molding, and a shaped sheet-like precursor is obtained.
• the laminate After being stored in the mold, the laminate can be manufactured by injection molding the other in the gap between the precursor and the mold. In insert injection molding, it is preferable to preheat the sheet-like precursor to be stored in the mold.
• one of the components of the first precursor and the second precursor is injection-molded into a mold using two or more injection molding machines, and the mold is rotated or moved to mold the mold.
• a laminated body can be manufactured by exchanging the cavity of the mold and injection molding the other precursor into the void formed between the obtained sheet-shaped precursor and the mold.
• one of the components of the first precursor and the second precursor is injection molded into a mold to expand the cavity volume of the mold, and the obtained sheet-like precursor and gold are obtained.
• a laminate can be manufactured by injection molding the other precursor into the voids formed between the mold and the mold.
• a hot press molding method such as an injection press molding method, an injection molding method (insert injection molding method, two-color injection molding method, core back injection molding method, sandwich injection molding method, sandwich injection molding method) Etc.) is preferable.
• the precursor can be melted by heating to a temperature higher than the melting point of the alicyclic polyamide resin and / or the acid-modified (meth) acrylic resin (particularly, the melting point of the resin having a higher melting point).
• a resin that does not substantially crystallize it can be melted by heating to a temperature equal to or higher than the glass transition point (Tg) of the resin.
• the heating temperature (eg, cylinder temperature) can be selected depending on the type of resin forming the precursor, for example, 200 to 350 ° C, preferably 250 to 320 ° C, more preferably 260 to 300 ° C. be.
• Alicyclic polyamide resin Alicyclic polyamide A: Condensate of dodecanedioic acid and bis (4-aminocyclohexyl) methane, amino group concentration 80 mmol / kg, carboxyl group concentration 50 mmol / kg, number average molecular weight 15384 (the terminal group determined by the titration method). From the quantity, the formula was calculated as 1 ⁇ ((50 + 80) / 2) ⁇ 1000000. The same shall apply hereinafter).
• Alicyclic polyamide B Condensate of dodecane diic acid and bis (4-aminocyclohexyl) methane, amino group concentration 50 mmol / kg, carboxyl group concentration 90 mmol / kg, number average molecular weight 14286
• Alicyclic polyamide C condensate of dodecane diic acid and bis (4-aminocyclohexyl) methane, amino group concentration 30 mmol / kg, carboxyl group concentration 100 mmol / kg, number average molecular weight 15385
• Alicyclic polyamide D a condensate of dodecane diic acid and bis (4-aminocyclohexyl) methane, amino group concentration 10 mmol / kg, carboxyl group concentration 110 mmol / kg, number average molecular weight 16667.
• Example 1 A flat plate (20 mm thickness ⁇ 100 mm ⁇ 100 mm) of alicyclic polyamide A was set in an injection molding die, acid-modified PMMA was melted at 280 ° C., and injected into the die to obtain a laminate having a thickness of 25 mm. ..
• Example 2 A flat plate (20 mm thickness x 100 mm x 100 mm) of alicyclic polyamide A is set in an injection molding mold, and acid-modified PMMA and non-modified PMMA are used as polymethyl methacrylate-based resins.
• Acid-modified PMMA: non-modified PMMA A dry-blended resin having a blend ratio of 1: 2 (mass ratio) was melted at 280 ° C. and injected into a mold to obtain a laminate having a thickness of 30 mm.
• Example 3 A flat plate (30 mm thickness x 100 mm x 100 mm) of alicyclic polyamide B is set in an injection molding die, acid-modified PMMA is melted at 280 ° C., and injected into the die to form a 31.5 mm thick laminate. Obtained.
• Example 4 Using two extruders a and b, the alicyclic polyamide C was charged into the extruder a and heated to 280 ° C., and the acid-modified PMMA was charged into the extruder b and heated to 280 ° C. By merging in the T-die, a laminate having a thickness ratio of 1: 1 (total thickness 8 mm) between the alicyclic polyamide C and the acid-modified PMMA was obtained.
• Example 5 A flat plate (20 mm thickness ⁇ 100 mm ⁇ 100 mm) of the acid-modified PMMA was set in an injection molding die, and the alicyclic polyamide B was melted at 280 ° C. and injected into the die to obtain a laminated body having a thickness of 24 mm.
• Comparative Example 1 A laminated body having a thickness of 25 mm was obtained in the same manner as in Example 1 except that a flat plate (20 mm thickness ⁇ 100 mm ⁇ 100 mm) of the alicyclic polyamide D was set in the injection molding die.
• Comparative Example 2 A laminated body having a thickness of 24 mm was obtained in the same manner as in Example 5 except that a flat plate (20 mm thickness ⁇ 100 mm ⁇ 100 mm) of the non-modified PMMA was set in the injection molding die.
• the DuPont impact strength of the laminates obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured and evaluated by the following method.
• the obtained laminated film was dropped by changing the height of a weight having a constant weight under the following conditions in accordance with the DuPont impact strength measurement method of ASTM D 2794, and the film obtained depending on the presence or absence of fracture. 50% of the destructive energy was calculated and evaluated according to the following criteria.
• the weight was dropped on the surface on the second layer side formed by acid-modified PMMA or the like.
• the laminate of the example has high impact resistance, and the first layer and the second layer are firmly adhered to each other to obtain an integrated laminate.
• the laminated body of the comparative example had low impact resistance.
• Example 6 Using the alicyclic polyamide B and the acid-modified PMMA, the thickness was changed as shown in Table 2 in the same manner as in Example 3, and the total thickness of the laminate was 4 mm, 3 mm, and 2 mm (in the alicyclic polyamide B). A laminate of the formed first layer and the second layer formed by the acid-modified PMMA) was produced, and the following three-point bending test was evaluated, and the DuPont impact strength was evaluated in the same manner as in Example 3. .. In addition, a single layer of alicyclic polyamide B and a single layer of acid-modified PMMA are also described for comparison.
• the second layer was positioned on the upper side (DuPont impact strength on the second layer side) as compared with the case where the first layer was positioned on the upper side in any total thickness. The amount of displacement until fracture was greatly improved when the weight was dropped on the surface).
• the laminated body of the present disclosure is a molded body in various fields requiring transparency, for example, daily necessities, containers, electrical / electronic equipment parts, optical sheets, lenses, structural members of vehicles (transportation equipment or means), building materials. Since it has excellent light resistance, it is preferable to use it as a partition partition between indoors and outdoors in vehicles and buildings, such as vehicles (automobiles, etc.), trains, airplanes or aircraft, ships, etc. It is particularly preferable to use it as a window or a partition plate (particularly, a sunroof of an automobile) of a vehicle.

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• 2021
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