WO2020075619A1 - ポリカーボネートシートのプレス成形体の製造方法 - Google Patents
ポリカーボネートシートのプレス成形体の製造方法 Download PDFInfo
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- WO2020075619A1 WO2020075619A1 PCT/JP2019/039082 JP2019039082W WO2020075619A1 WO 2020075619 A1 WO2020075619 A1 WO 2020075619A1 JP 2019039082 W JP2019039082 W JP 2019039082W WO 2020075619 A1 WO2020075619 A1 WO 2020075619A1
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- resin
- mold
- resin layer
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- sheet
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- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
- B29C2043/3602—Moulds for making articles of definite length, i.e. discrete articles with means for positioning, fastening or clamping the material to be formed or preforms inside the mould
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- 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
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
- B29K2025/08—Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene
-
- 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
- B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
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- 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
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
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- 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
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
Definitions
- the present invention relates to a method for producing a press-formed body of a polycarbonate sheet.
- Resin moldings are often used for interior and exterior parts of automobiles and aircraft, electrical and electronic equipment, and home appliances.
- glass plates, transparent resin plates, etc. are used for the components of the display surface of automobile interior parts such as instrument covers, home appliances, office automation equipment, personal computers, small portable devices, etc.
- a resin molded body (resin molded body) is used.
- a transparent sheet, especially a glass plate is attached to a frame part made of injection-molded resin (resin molded body) with double-sided adhesive tape, etc.
- a stack of bodies is used.
- a resin material having a high elastic modulus is selected from the viewpoints of thinness, strength, scratch resistance and fingerprint wipeability.
- the resin molded product used for the above-mentioned applications can be manufactured by molding a resin sheet, but various measures have been taken to impart characteristics according to the application.
- a resin sheet is modified with a hard coat layer, a decorative sheet, or the like, a resin sheet is formed by laminating resin layers having different compositions, or the composition of the resin used is devised. .
- an acrylic resin is used, one having a hard coat layer on the upper surface or the lower surface of the acrylic resin layer, or provided with a design such as printing on the acrylic resin layer, Films that are laminated together are also used.
- Patent Document 1 discloses a decorative sheet in which a transparent acrylic resin sheet layer, a pattern printing ink layer, an ABS resin sheet layer and an ABS resin backer layer are laminated in this order from the surface side.
- Patent Document 2 discloses a multilayer film in which a layer composed of a methacrylic resin and acrylic rubber particles is laminated on the surface of a polycarbonate resin layer, and one side of the multilayer film is decorated and the addition thereof is performed.
- a decorative sheet in which a thermoplastic resin sheet is laminated on the decorative surface is disclosed.
- a decorative molded product manufactured by injection molding a thermoplastic resin on the decorative surface is also disclosed.
- Patent Document 3 discloses a resin molded article molded using a sheet in which a thermosetting or ultraviolet curing type hard coat layer is provided on a resin base material.
- Patent Document 4 discloses a decorative hard coat film having a layer formed by using a hard coat paint having a specific composition on one surface of a base film, and a print layer is provided on the base film. Good points are also described. This decorative film can be thermoformed. The decorative film described in Patent Document 4 is integrated with a molding resin to form a decorative molded product.
- Patent Document 5 discloses a laminated sheet in which a coating layer containing an acrylic resin as a main component is provided on one surface of a base material layer containing a polycarbonate resin composition as a main component.
- Patent Document 6 discloses a method for manufacturing a two-dimensionally bent hard coat sheet. The method of the document discloses that two-dimensional bending is performed by adjusting the Tg difference between the laminated resin layers and the processing temperature of the two-dimensional bending.
- a resin layer (B) containing a high hardness resin (B) as a main component and a hard coat layer (C) were sequentially laminated on at least one surface of a resin layer (A) containing a polycarbonate resin as a main component.
- a method for producing a press-formed body of a polycarbonate sheet comprising the following steps: Step (I): a step of preheating the polycarbonate sheet to a temperature in the range of the glass transition point of the resin layer (A) from ⁇ 45 ° C.
- the time from the completion of the step (I) to placing the polycarbonate sheet between the upper mold and the lower mold of the mold is 60 seconds or less, [1] Method.
- the temperature of the molding die is in the range of the glass transition point of the resin layer (A) from ⁇ 10 ° C. or higher to the glass transition point or lower, [1] or [2]. the method of. [4] The method according to any one of [1] to [3], wherein in the step (III), the mold clamping force is 2000 kgf or less.
- the polycarbonate sheet has a pencil hardness of 2H or more.
- the high hardness resin (B) is the following resins (B1) to (B5): Resin (B1) The following general formula (1): (In the formula (1), R1 represents a hydrogen atom or a methyl group; R2 represents a C1-18 alkyl group or a C1-4 hydrocarbon group which may be substituted with a C1-4 hydrocarbon group.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms.
- a resin containing Resin (B3) The following general formula (6):
- the polycarbonate resin has the general formula (7):
- the compound represented by the general formula (5): (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)
- the glass transition point of the resin layer (A) and the glass transition point of the resin layer (B) have the following relationship: ⁇ 10 ° C. ⁇ (glass transition point of resin layer (B)) ⁇ (glass transition point of resin layer (A)) ⁇ 40 ° C.
- a new method for producing a press-formed body of a polycarbonate sheet is provided.
- a resin molded product that has high hardness and is unlikely to cause hard coat cracks or sheet breakage during molding.
- FIG. 2A is a cross-sectional photograph of the molded body of Example 13
- FIG. 2B is a cross-sectional photograph of the molded body of Example 5.
- the present invention will be described in detail by exemplifying production examples and examples, but the present invention is not limited to the exemplified production examples and examples and the like, and does not largely deviate from the contents of the present invention. If so, the method can be changed to an arbitrary method.
- One mode of the present invention is to provide a resin layer (B) containing a high hardness resin (B) as a main component and a hard coat layer (C) on at least one surface of a resin layer (A) containing a polycarbonate resin as a main component.
- the present invention relates to a method for manufacturing a press-formed product of polycarbonate sheets laminated in order.
- the manufacturing method includes the following steps (I) to (III). Step (I): Preheating the polycarbonate sheet to a temperature in the range of the glass transition point of the resin layer (A) from ⁇ 45 ° C.
- the inventors of the present invention have earnestly studied a method for producing a press-molded body of a high-hardness polycarbonate sheet (molding resin sheet) that includes a polycarbonate resin as a base material and has a hard coat layer on the surface.
- the polycarbonate sheet used for molding has a predetermined laminate structure (resin layer (A), resin layer (B), and hard coat layer (C)), and is molded by a predetermined press molding method. It has been found that it is possible to provide a molded product that is hard to break even in a sheet having high hardness, suppresses the occurrence of cracks during molding, and is less likely to cause abnormal appearance.
- thermoforming of the resin laminated body having the hard coat layer by the conventional method, which has various curved surface shapes (for example, two-dimensional shape (for example, a thickness of 2 mm).
- a sheet can use a tunnel type having a radius of curvature of 70 mm or less, further a radius of curvature of 50 mm or less), a hemispherical mold, and a three-dimensional mold having a radius of curvature of about 100 mmR or more). It has been found that a hot press molded product having a three-dimensional shape, for example, can be obtained.
- a polycarbonate sheet for molding (hereinafter, also simply referred to as “resin sheet”) used for molding of the present invention includes at least a resin layer (A) containing a polycarbonate resin (a1) as a main component and a resin layer (A). It has a resin layer (B) containing a high hardness resin (B) as a main component and a hard coat layer (C) located on one surface. The resin layer (B) is located between the resin layer (A) and the hard coat layer (C).
- the resin sheet includes a resin layer (A) containing a polycarbonate resin (a1) as a main component, and a resin layer (B) laminated directly on at least one surface of the resin layer (A), And a hard coat layer (C) laminated directly on the resin layer (B).
- the resin layer (B) and the hard coat layer (C) may be provided on at least one side of the resin layer (A), and there is no particular limitation on the configuration of the other side. Further, the resin layer (B) may be provided on both sides of the resin layer (A), in which case the hard coat layer (C) can be provided on one or both of the resin layers (B).
- the resin layer (B) is provided on both sides of the resin layer (A)
- the resin layer (A) is a layer serving as a base material of the polycarbonate sheet, and is a resin layer containing the polycarbonate resin (a1) as a main component.
- the polycarbonate resin (a1) contained in the resin layer (A) may be one type or two or more types.
- the phrase "predominantly comprises the polycarbonate resin (a1)” means that the content of the polycarbonate resin (a1) in the resin layer (A) is 50% by mass with respect to the total mass of the resin layer (A). It means to occupy the above.
- the content of the polycarbonate resin (a1) in the resin layer (A) is preferably 75% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. Impact resistance is improved by increasing the content of the polycarbonate resin.
- the polycarbonate resin (a1) is a unit containing a carbonic acid ester bond in the molecular main chain, that is, a-[O-R-OCO]-unit (where R is an aliphatic group, an aromatic group, or an aliphatic group). It may contain both a group and an aromatic group, and may have a linear structure or a branched structure), and is not particularly limited. Among them, an aromatic polycarbonate resin is preferable, an aromatic polycarbonate resin obtained by using an aromatic dihydroxy compound is more preferable, and a polycarbonate resin containing a structural unit represented by the following formula (7) is particularly preferable. By using such a polycarbonate resin, it is possible to obtain a resin sheet having more excellent impact resistance.
- the polycarbonate resin (a1) is preferably an aromatic polycarbonate resin (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the like. These polycarbonate resins can be used alone or in combination of two or more.
- aromatic polycarbonate resin for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.
- a polycarbonate resin to which a monohydric phenol represented by the following general formula (4) is added as a terminal stopper is also used.
- a polycarbonate resin containing a structural unit represented by the above formula (7) and manufactured using a monohydric phenol represented by the general formula (4) as a terminal terminating agent is also used.
- R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
- R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent.
- the “alkyl group” and “alkenyl group” may be linear or branched and may have a substituent. More preferably, the monohydric phenol represented by the general formula (4) is represented by the following general formula (5). (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)
- the carbon number of R 1 in the general formula (4) or the general formula (5) is more preferably within a specific numerical range.
- the upper limit of the carbon number of R 1 is preferably 30, more preferably 22 and particularly preferably 18.
- the lower limit of the carbon number of R 1 is preferably 10 and more preferably 12.
- one or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester are used as a terminal terminating agent. Is particularly preferable.
- a monohydric phenol in which R 1 is an alkyl group having 16 carbon atoms in the general formula (5) is used as a terminal stopper, it is excellent in glass transition temperature, melt fluidity, moldability, drawdown resistance and the like. It is particularly preferable because a polycarbonate resin can be obtained.
- Examples of the polycarbonate resin using such a monohydric phenol as a terminal stopper include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Inc.) and the like.
- the weight average molecular weight (Mw) of the polycarbonate resin (a1) can affect the impact resistance and thermal stability of the resin sheet.
- the weight average molecular weight (Mw) of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 20,000 to 65,000.
- the weight average molecular weight (Mw) in this specification is a standard polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC).
- the glass transition point of the resin layer (A) preferably satisfies the following relationship with the glass transition point of the resin layer (B). ⁇ 10 ° C. ⁇ (glass transition point of resin layer (B)) ⁇ (glass transition point of resin layer (A)) ⁇ 40 ° C.
- a resin sheet for molding which has high hardness and is less likely to cause abnormal appearance such as cracks and flow marks during molding.
- abnormal appearance is unlikely to occur during thermoforming, and such a resin sheet can be said to be a resin sheet suitable for thermoforming because the conditions (temperature, heating time, etc.) during thermoforming can be set widely.
- the glass transition point of the resin layer (A) and the resin layer (B) is ⁇ 10 ° C. ⁇ (glass transition point of the resin layer (B)) ⁇ (glass transition point of the resin layer (A)) ⁇ 30 ° C. Is preferable, and ⁇ 7 ° C. ⁇ (glass transition point of resin layer (B)) ⁇ (glass transition point of resin layer (A)) ⁇ 30 ° C. is more preferable.
- the Tg of the resin layer (B) is extremely lower than the Tg of the resin layer (A)
- the high hardness resin forming the resin layer (B) becomes a rubber state or a molten state at the time of thermoforming, which facilitates movement.
- the hard coat layer (C) which has a highly cross-linked structure and remains hard even when heat is applied, cannot easily follow the movement of the high hardness resin that has become easy to move, and easily cracks.
- the Tg of the resin layer (B) is too high as compared with the Tg of the resin layer (A)
- the viscosity of the high hardness resin forming the resin layer (B) and the polycarbonate resin forming the resin layer (A) Difference becomes large, the interface becomes rough when these are stacked, and flow marks may occur.
- the Tg of the polycarbonate resin (a1) is preferably 90 to 190 ° C., more preferably 100 to 170 ° C., and particularly preferably 110 to 150 ° C.
- the “glass transition point of the resin layer (A)” means the glass transition temperature of the polycarbonate resin (a1) which is the main component of the resin layer (A).
- the glass transition point when the resin layer (A) contains two or more kinds of polycarbonate resins (a1) is the glass transition temperature of the polycarbonate resin mixture.
- the "glass transition point of the resin layer (B)” means the glass transition temperature of the high hardness resin which is the main component of the resin layer (B).
- the glass transition point when the resin layer (B) contains two or more kinds of high hardness resins is the glass transition temperature of the high hardness resin mixture.
- the glass transition point is a temperature measured by a midpoint method measured by a differential scanning calorimeter at a sample of 10 mg and a heating rate of 10 ° C./min.
- the resin layer (A) may contain other resin in addition to the polycarbonate resin (a1).
- resins include polyester resins.
- the polyester resin preferably mainly contains terephthalic acid as a dicarboxylic acid component, but may contain a dicarboxylic acid component other than terephthalic acid.
- polyester obtained by polycondensing a glycol component containing 20 to 40 mol% of 1,4-cyclohexanedimethanol (total 100 mol%) with respect to 80 to 60 mol% of ethylene glycol as a main component, and a dicarboxylic acid component. Resins (so-called "PETG”) are preferred.
- the resin in the resin layer (A) is preferably only the polycarbonate resin (a1), but when other resin is included, the amount thereof is 0 to 50% by mass relative to the total mass of the resin layer (A). Is preferable, 0 to 30% by mass is more preferable, and 0 to 20% by mass is particularly preferable.
- the resin layer (A) may further contain additives and the like.
- additives those usually used in the resin sheet can be used, and as such an additive, for example, an antioxidant, an anti-coloring agent, an antistatic agent, a release agent, a lubricant, a dye, Examples include pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.
- the method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry blending the masterbatch, a method of dry blending the entire amount, and the like can be used.
- the amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, based on the total mass of the resin layer (A). preferable.
- the thickness of the resin layer (A) is preferably 0.3 to 10 mm, more preferably 0.3 to 5 mm, and particularly preferably 0.3 to 3.5 mm.
- the resin layer (B) is a resin layer containing a high hardness resin as a main component.
- “having a high hardness resin as a main component” means, for example, that the content of the high hardness resin in the resin layer (B) occupies 50% by mass or more based on the total mass of the resin layer (B). Shall be said.
- the content of the high-hardness resin in the resin layer (B) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 100% by mass.
- the high hardness resin means a resin having a pencil hardness of HB or higher.
- the pencil hardness of the high-hardness resin is preferably HB or more and 3H or less, and more preferably H or more and 3H or less.
- the pencil hardness of the high-hardness resin referred to here is the hardness of the hardest pencil that did not cause a scar when the pencil was pressed against the surface of the resin layer formed of the high-hardness resin at an angle of 45 degrees and a load of 750 g to gradually increase the hardness. (Pencil scratch hardness test according to JIS K 5600-5-4: 1999).
- the high hardness resin contained in the resin layer (B) may be one type or two or more types.
- the high hardness resin preferably contains, for example, at least one of the following resins (B1) to (B5).
- the resin (B1) contains a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2). It is a resin containing the copolymer (b1).
- the resin (B1) may be an alloy of the copolymer (b1) and another polymer.
- the content of the copolymer (b1) in the resin (B1) is preferably 80 to 100% by mass, more preferably 95 to 100% by mass, based on the total mass (100% by mass) of the resin (B1). .
- R1 is a hydrogen atom or a methyl group
- R2 is a C5-18 alkyl group which may be substituted with a C1-18 alkyl group or a C1-4 hydrocarbon group. It is a cycloalkyl group.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms.
- the “hydrocarbon group” may be linear, branched or cyclic, and may have a substituent.
- cycloalkyl may be either monocyclic or bicyclic.
- R2 is an alkyl group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 4 carbon atoms (preferably having 1 to 4 carbon atoms). Is a cycloalkyl group having 5 to 18 carbon atoms which may be substituted with, and is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. preferable.
- (meth) acrylic acid ester structural units (a) preferred are (meth) acrylic acid ester structural units in which R2 is a methyl group or an ethyl group, and more preferred are R1 is a methyl group and R2 is It is a methyl methacrylate structural unit that is a methyl group.
- R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
- R4 is a cyclohexyl group or a cyclohexyl group substituted with a hydrocarbon group having 1 to 4 carbon atoms (eg, methyl group, butyl group), and is preferably a cyclohexyl group having no substituent.
- aliphatic vinyl structural units (b) more preferred are aliphatic vinyl structural units in which R3 is a hydrogen atom and R4 is a cyclohexyl group.
- the copolymer (b1) may contain one or more kinds of (meth) acrylic acid ester constitutional unit (a), and may contain one or more kinds of aliphatic vinyl constitutional unit (b). May be.
- the total content of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is preferably 90 to 100 mol% with respect to all the structural units of the copolymer (b1), It is more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol%.
- the copolymer (b1) may contain a structural unit other than the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b).
- the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on all the constituent units of the resin (B1).
- the (meth) acrylic acid ester monomer and the aromatic vinyl monomer are polymerized and then the aromatic vinyl is used.
- the aromatic vinyl examples thereof include a structural unit derived from an aromatic vinyl monomer containing an unhydrogenated aromatic double bond, which is generated in the process of hydrogenating the aromatic double bond derived from the monomer to produce the copolymer (b1).
- an aromatic vinyl structural unit represented by the following general formula (3) may be mentioned.
- R5 is a hydrogen atom or a methyl group
- R6 is a phenyl group or a cyclohexadiene group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms (eg, methyl group, butyl group). , A cyclohexene group.)
- the content of the (meth) acrylic acid ester constitutional unit (a) represented by the general formula (1) is preferably 65 to 80 mol% with respect to all the constitutional units in the resin (B1), and more preferably It is 70 to 80 mol%.
- the ratio of the (meth) acrylic acid ester structural unit (a) to all the structural units in the resin (B1) is 65 mol% or more, a resin layer excellent in adhesiveness to the resin layer (A) and surface hardness is obtained. Obtainable. If it is 80 mol% or less, the resin sheet is less likely to warp due to water absorption.
- the content of the aliphatic vinyl constitutional unit (b) represented by the general formula (2) is preferably 20 to 35 mol%, more preferably 20 to 30 mol% based on all the constitutional units in the resin (B1). Mol%.
- the content of the aliphatic vinyl structural unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, and when it is 35 mol% or less, the interface with the base material can be improved. Peeling can be prevented.
- the “copolymer” may have any structure of random, block and alternating copolymers.
- the method for producing the copolymer (b1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the aromatic vinyl monomer-derived aromatic Those obtained by hydrogenating the group double bond are preferable.
- (meth) acrylic acid refers to methacrylic acid and / or acrylic acid.
- Specific examples of the aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method.
- the copolymer (b1) is preferably one in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the unhydrogenated rate of the aromatic double bond contained in the constitutional unit derived from the aromatic vinyl monomer is preferably less than 30%. When the unhydrogenated ratio is less than 30%, a resin having excellent transparency can be obtained. The unhydrogenated ratio is more preferably less than 10%, further preferably less than 5%.
- the weight average molecular weight (Mw) of the resin (B1) is not particularly limited, but from the viewpoint of strength and moldability, it is preferably 50,000 to 400,000, and 70,000 to 300,000. Is more preferable.
- the glass transition point (Tg) of the resin (B1) is preferably in the range of 110 to 140 ° C, more preferably 110 to 135 ° C, and particularly preferably 110 to 130 ° C.
- the glass transition point (Tg) is 110 ° C. or higher, the resin sheet provided by the present invention is less likely to be deformed or cracked in a heat environment or a wet heat environment.
- the temperature is 140 ° C. or lower, workability is excellent when molding is performed by continuous heat shaping using a mirror surface roll or shaping roller, or batch heat shaping using a mirror surface die or shaping die.
- resin (B1) examples include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical).
- the polycarbonate resin (a1) contains the structural unit represented by the general formula (7), and the terminal stopper is represented by the general formula (5). It is preferable to use a polycarbonate resin manufactured using a monohydric phenol (for example, Upizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Inc.)).
- a monohydric phenol for example, Upizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Inc.)
- the structural unit represented by the general formula (1) R1 and R2 are both methyl groups; methyl methacrylate
- the structural unit represented by the general formula (2) (R3 is hydrogen).
- a copolymer containing 25 mol% of atoms and R4 is a cyclohexyl group is used, the polycarbonate resin (a1) contains the constitutional unit of the general formula (7), and the endcapping agent is represented by the general formula (5).
- An embodiment in which a polycarbonate resin produced by using a hydric phenol (R1 has 8 to 22 carbon atoms) is particularly preferable.
- the resin (B2) is a copolymer (D containing 6 to 77% by mass of (meth) acrylic acid ester constitutional unit, 15 to 71% by mass of styrene constitutional unit, and 5 to 25% by mass of unsaturated dicarboxylic acid constitutional unit. ) Containing a resin.
- the resin (B) may be a resin that is an alloy of the copolymers (D), or a resin that is an alloy of the copolymer (D) and a polymer having a high hardness other than the copolymer (D). .
- high hardness polymers other than the copolymer (D) include methyl methacrylate-styrene copolymer, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer and the like.
- alloying in order to avoid a decrease in Tg of the high hardness resin, it is preferable to alloy the polymers having higher Tg.
- Examples of the (meth) acrylic acid ester monomer constituting the (meth) acrylic acid ester constitutional unit include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned, with methyl methacrylate being particularly preferred. You may use these (meth) acrylic acid ester monomers in mixture of 2 or more types.
- the content of the (meth) acrylic acid ester structural unit is 6 to 77% by mass, preferably 6 to 70% by mass, and more preferably 20 to 70% by mass, based on the total mass of the copolymer (D). More preferable.
- the styrene structural unit is not particularly limited, and any known styrene-based monomer can be used. From the viewpoint of easy availability, styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like are preferable. Among these, styrene is particularly preferable from the viewpoint of compatibility. These styrene-based monomers may be used as a mixture of two or more kinds. The content of the styrene structural unit is 15 to 71% by mass, more preferably 20 to 71% by mass, based on the total mass of the copolymer (D).
- Examples of the unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid structural unit include maleic acid, itaconic acid, citraconic acid, acid anhydrides such as aconitic acid, and a phase with a styrene-based monomer.
- Maleic anhydride is preferred from the viewpoint of solubility.
- Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed and used.
- the content of the unsaturated dicarboxylic acid constituent unit is 5 to 25% by mass, preferably 6 to 24% by mass, and more preferably 8 to 23% by mass, based on the total mass of the copolymer (D). .
- the total content of the (meth) acrylic acid ester constitutional unit, the styrene constitutional unit and the unsaturated dicarboxylic acid constitutional unit is preferably 90 to 100 mol% with respect to all the constitutional units of the copolymer (D), and It is preferably 95 to 100 mol%, particularly preferably 98 to 100 mol%. That is, the copolymer (D) may contain a structural unit other than the (meth) acrylic acid ester structural unit, the styrene structural unit, and the unsaturated dicarboxylic acid structural unit. The amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on all the constituent units of the copolymer (D).
- Examples of other constituent units include N-phenylmaleimide.
- the method for producing the copolymer (D) is not particularly limited, and examples thereof include a bulk polymerization method and a solution polymerization method.
- resin (B2) examples include Resphi R100, R200, R310 (manufactured by Denka), Delpet 980N (manufactured by Asahi Kasei Chemical), hw55 (manufactured by Daicel Evonik) and the like.
- the weight average molecular weight (Mw) of the resin (B2) is not particularly limited, but is preferably 50,000 to 300,000, more preferably 80,000 to 200,000.
- the glass transition point (Tg) of the resin (B2) is preferably 90 to 150 ° C., more preferably 100 to 150 ° C., and particularly preferably 115 to 150 ° C.
- the resin (B2) is used as the high hardness resin, it is preferable to use the polycarbonate resin containing the structural unit of the general formula (7) as the polycarbonate resin (a1). Furthermore, an embodiment in which a polycarbonate resin produced by using a monohydric phenol (R1 has 8 to 22 carbon atoms) represented by the general formula (5) as a terminal stopper is particularly preferable.
- a copolymer R100, R200, or R310; 6 to 26 mass% of methyl methacrylate structural unit, 55 to 71 mass% of styrene structural unit, and 15 to 23 mass% of maleic anhydride structural unit).
- the resin (B2) a copolymer (R100; made by Denka) composed of 21% by mass of methyl methacrylate structural unit, 64% by mass of styrene, and 15% by mass of maleic anhydride is used, and as a polycarbonate resin (a1).
- a polycarbonate resin for example, Iupizeta T-1380
- a constitutional unit represented by the general formula (7) and produced by using the monohydric phenol represented by the general formula (5) as a terminal stopper is used. Is particularly preferable.
- the resin (B3) is a resin containing a copolymer containing a structural unit (c) represented by the following general formula (6) and optionally a structural unit (d) represented by the following general formula (7). is there.
- the resin (B3) may or may not contain the structural unit (d), but preferably contains it.
- the proportion of the structural unit (c) in all the structural units of the resin (B3) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. Particularly preferred.
- the proportion of the structural unit (d) in all the structural units of the resin (B3) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and 0 to 30 mol%. Particularly preferred.
- the total content of the structural unit (c) and the structural unit (d) is preferably 90 to 100 mol% with respect to the resin (B3), more preferably 95 to 100 mol%, and particularly preferably 98 to It is 100 mol%.
- the resin (B3) may contain a structural unit other than the structural unit (c) and the structural unit (d). When it contains other structural units, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the structural units of the resin (B3). Is particularly preferred. Examples of the other structural unit include a structural unit represented by the general formula (8) described below.
- the production method of the resin (B3) is not particularly limited, but it can be produced by the same method as the production method of the polycarbonate resin (a1) described above except that bisphenol C is used as a monomer.
- resin (B3) examples include Iupilon KH3410UR, KH3520UR, KS3410UR (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the like.
- the weight average molecular weight (Mw) of the resin (B3) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.
- the glass transition point (Tg) of the resin (B3) is preferably 105 to 150 ° C, more preferably 110 to 140 ° C, and particularly preferably 110 to 135 ° C.
- the resin (B3) is used as the high hardness resin
- the polycarbonate resin containing the structural unit of the general formula (7) was prepared by using a monohydric phenol (R1 having 8 to 22 carbon atoms) represented by the general formula (5) as a terminal terminating agent containing the structural unit represented by the general formula (7).
- An embodiment using a polycarbonate resin is particularly preferable.
- An example of such a polycarbonate resin is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Inc.).
- the other resin contained in the resin layer (B) is preferably a resin containing the structural unit (d) but not the structural unit (c), and the structural unit ( A resin consisting only of d) is more preferable.
- an aromatic polycarbonate resin for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering Plastics
- the resin (B3) is contained in a proportion of preferably 45% by mass or more, more preferably 55% by mass or more, based on all the resins contained in the resin layer (B).
- the resin (B4) is a copolymer containing 5 to 20% by mass of a styrene structural unit, 60 to 90% by mass of a (meth) acrylic acid ester structural unit, and 5 to 20% by mass of an N-substituted maleimide structural unit. It is a resin containing G).
- the resin (B4) may be an alloy of the copolymer (G) and the above copolymer (D) or another polymer. In the case of an alloy, in order to avoid a decrease in Tg of the resin layer (B), an alloy of resins having a higher Tg is preferable.
- the styrene structural unit is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene. Preference is given to styrene, p-methylstyrene, t-butylstyrene and the like. Among these, styrene is particularly preferable from the viewpoint of compatibility.
- the copolymer (G) may contain two or more of these styrene structural units.
- the content of the styrene structural unit is 5 to 20% by mass, preferably 5 to 15% by mass, more preferably 5 to 10% by mass, based on the total mass of the copolymer (G). .
- Examples of the (meth) acrylic acid ester structural unit include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate. , Structural units derived from 2-ethylhexyl methacrylate, and the like, and structural units derived from methyl methacrylate are particularly preferable. Further, the copolymer (G) may contain two or more kinds of these (meth) acrylic acid ester constitutional units. The content of the (meth) acrylic acid ester structural unit is 60 to 90% by mass, preferably 70 to 90% by mass, and preferably 80 to 90% by mass, based on the total mass of the copolymer (G). More preferably.
- N-substituted maleimide structural unit in the copolymer (G) examples include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Structural units derived from N-arylmaleimides such as N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide and the like are mentioned, and derived from N-phenylmaleimide from the viewpoint of compatibility with acrylic resins. Structural units are preferred.
- the copolymer (G) may contain two or more of these N-substituted maleimide structural units.
- the content of the N-substituted maleimide structural unit is 5 to 20% by mass, preferably 5 to 15% by mass, and preferably 5 to 10% by mass, based on the total mass of the copolymer (G). Is more preferable.
- the total content of the styrene structural unit, the (meth) acrylic acid ester structural unit, and the N-substituted maleimide structural unit is preferably 90 to 100 mol%, more preferably 95, based on the copolymer (G). To 100 mol%, and particularly preferably 98 to 100 mol%.
- the copolymer (G) may contain a structural unit other than the above structural units. When other structural units are included, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the structural units of the copolymer (G). Is particularly preferable.
- Examples of the other structural unit include a structural unit derived from the following general formula (1) and a structural unit derived from the general formula (2).
- R1 is a hydrogen atom or a methyl group
- R2 is an alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, etc.) or carbon atom having 1 to 4 carbon atoms)
- a cycloalkyl group having 5 to 18 carbon atoms which may be substituted with a hydrogen group (preferably an alkyl group having 1 to 4 carbon atoms) (eg cyclohexyl group, isobornyl group, etc.).
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms (eg, methyl group, butyl group).)
- the method for producing the copolymer (G) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.
- resin (B4) examples include Delpet PM120N (manufactured by Asahi Kasei Chemical Co., Ltd.).
- the weight average molecular weight (Mw) of the resin (B4) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.
- the glass transition point (Tg) of the resin (B4) is preferably 110 to 150 ° C, more preferably 115 to 140 ° C, and particularly preferably 115 to 135 ° C.
- the resin (B4) is used as the high hardness resin, it is preferable to use the polycarbonate resin containing the structural unit of the general formula (7) as the polycarbonate resin (a1). Furthermore, it was prepared by using a monohydric phenol (R1 having 8 to 22 carbon atoms) represented by the general formula (5) as a terminal terminating agent containing the structural unit represented by the general formula (7).
- a polycarbonate resin is particularly preferable.
- An example of such a polycarbonate resin is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Inc.).
- Delpet PM-120N consisting of 7% styrene structural unit, 86% (meth) acrylic acid ester structural unit, and 7% N-substituted maleimide structural unit was used, and the polycarbonate resin (a1) was used. It is preferable to use Iupizeta T-1380 as.
- the resin (B5) is a resin containing the polymer (E) containing the structural unit (e) represented by the following general formula (8).
- the proportion of the structural unit (e) in all the structural units of the polymer (E) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and 95 to 100 mol%. Is particularly preferable.
- the polymer (E) may contain a structural unit other than the structural unit (e), but it is preferably a polycarbonate resin composed of the structural unit (e). When other structural units are contained, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the structural units of the polymer (E). It is particularly preferable that
- the other structural unit examples include a structural unit (c) represented by the following general formula (6) and a structural unit (d) represented by the general formula (7). That is, the resin (B5) includes the structural unit (e) represented by the general formula (8), the structural unit (c) optionally represented by the general formula (6), and optionally the general formula (7). ) Is a resin containing a polymer containing the structural unit (d).
- the method for producing the polymer (E) is not particularly limited, but it can be produced by the same method as the above-described method for producing the polycarbonate resin (a1) except that bisphenol AP is used as a monomer.
- Specific examples of the resin (B5) include Upizeta FPC0220 (manufactured by Mitsubishi Gas Chemical Co., Inc.).
- the weight average molecular weight (Mw) of the resin (B5) is preferably 10,000 to 1,000,000, more preferably 15,000 to 50,000.
- the glass transition point of the resin (B5) is preferably 120 to 200 ° C., more preferably 130 to 190 ° C., and particularly preferably 140 to 190 ° C.
- the resin (B5) is used as the high hardness resin
- the polycarbonate resin containing the structural unit of the general formula (7) is used as the polycarbonate resin (a1).
- examples of such a polycarbonate resin include Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics).
- Iupizeta FPC0220 manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics
- the other polymer contained in the resin layer (B) does not include the structural unit (e) but the structural unit (d) described in the resin (B3).
- the polymer containing is preferable, and the polymer consisting only of the structural unit (d) is more preferable.
- an aromatic polycarbonate resin for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering Plastics
- the amount of the polymer (E) is preferably 45% by mass or more, more preferably 55% by mass or more, based on all the polymers contained in the resin layer (B). Included as a percentage.
- the high hardness resin contained in the resin layer (B) may be one kind or two or more kinds. When two or more kinds are selected from the resins (B1) to (B5), the same or different category. It may be selected from the above, and may further contain a high hardness resin other than the resins (B1) to (B5). In a preferred embodiment, the high hardness resin contains the resin (B2).
- the resin layer (B) may contain other resin in addition to the high hardness resin as described above.
- resins include methyl methacrylate-styrene copolymer, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and various types. Examples thereof include elastomers.
- the resin in the resin layer (B) is preferably only a high hardness resin, but when other resins are included, the amount thereof is preferably 35% by mass or less with respect to the resin layer (B), and 25% by mass. % Or less, and more preferably 10% by mass or less.
- the resin layer (B) may further contain additives and the like.
- additive the same additives as those described in the above “2. Resin layer (A)” can be used, and the amounts thereof are also the same.
- the thickness of the resin layer (B) affects the surface hardness and impact resistance of the molding resin sheet. That is, if the resin layer (B) is too thin, the surface hardness will be low, and if it is too thick, the impact resistance will be low.
- the thickness of the resin layer (B) is preferably 10 to 250 ⁇ m, more preferably 30 to 200 ⁇ m, and particularly preferably 60 to 150 ⁇ m.
- Laminate of resin layer (A) and resin layer (B) As described above, a further layer may be present between the resin layer (A) and the resin layer (B), but here, the resin layer A case where the resin layer (B) is laminated directly on (A) will be described.
- the stacking method is not particularly limited, and the same stacking can be performed when other layers are present. For example, a method in which the resin layer (A) and the resin layer (B) that are individually formed are overlapped with each other, and the two are thermocompression-bonded; the resin layer (A) and the resin layer (B) that are formed separately are overlapped with each other.
- a method of adhering both with an adhesive a method of co-extrusion molding the resin layer (A) and the resin layer (B); an in-mold of the resin layer (A) on the resin layer (B) previously formed
- various methods such as molding and integration.
- the method of coextrusion molding is preferable from the viewpoint of manufacturing cost and productivity.
- the method of coextrusion is not particularly limited.
- the resin layer (B) is arranged on one side of the resin layer (A) by the feed block, and the sheet is extruded by a T die, then cooled while passing through a molding roll to obtain a desired lamination. Form the body.
- the resin layer (B) is arranged on one surface of the resin layer (A) in the multi-manifold die, extruded in a sheet shape, and then cooled while passing through a molding roll to obtain a desired laminate. To form.
- the total thickness of the resin layer (A) and the resin layer (B) is preferably 0.5 to 3.5 mm, more preferably 0.5 to 3.0 mm, and particularly preferably 1.2 to 3.0 mm. .
- the ratio of the thickness of the resin layer (A) to the total thickness of the resin layer (A) and the resin layer (B) is preferably 75% to 99%, more preferably 80 to 99%, and particularly preferably It is 85 to 99%.
- Hard coat layer (C) The resin sheet of the present invention has a hard coat layer (C) on the resin layer (B). Although a further layer may be present between the hard coat layer (C) and the resin layer (B), the hard coat layer (C) is preferably laminated directly on the resin layer (B).
- a resin sheet having a hard coat layer (C) of high hardness on the surface is superior in impact resistance and safe as compared with a normal glass plate. Highly flexible and lightweight. Further, it is easier to bend than a normal glass plate, and is less likely to break with a slight bend. It is considered that this is because the hard coat layer (C) in the resin sheet has some flexibility.
- the resin layer (B) is arranged between the resin layer (A) and the hard coat layer (C), which can further increase the hardness of the resin sheet.
- the hard coat layer (C) is not particularly limited, and known acrylic, silicone, melamine, urethane, and epoxy hard coats can be used. Above all, the hard coat layer (C) is preferably an acrylic hard coat.
- the “acrylic hard coat” means a coating film obtained by polymerizing a monomer, an oligomer or a prepolymer having a (meth) acryloyl group as a polymerizing group to form a crosslinked structure.
- the composition of the acrylic hard coat preferably contains 2 to 98% by mass of a (meth) acrylic monomer, 2 to 98% by mass of a (meth) acrylic oligomer, and 0 to 15% by mass of a surface modifier. It is preferable to include 0.001 to 7 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier.
- the hard coat layer (C) more preferably contains 5 to 50 mass% of (meth) acrylic monomer, 50 to 95 mass% of (meth) acrylic oligomer, and 1 to 10 mass% of surface modifier. Particularly preferably, it contains 20 to 40 mass% of (meth) acrylic monomer, 60 to 80 mass% of (meth) acrylic oligomer, and 2 to 5 mass% of surface modifier.
- the amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier. Particularly preferably, it is 0.1 to 3 parts by mass.
- (Meth) acrylic monomer As the (meth) acrylic monomer, any one having a (meth) acryloyl group as a functional group in the molecule can be used, and a monofunctional monomer, a bifunctional monomer, or a trifunctional monomer can be used. The above monomers may be used.
- Examples of the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester.
- Specific examples of the bifunctional and / or trifunctional or higher functional (meth) acrylic monomers include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, polyethylene glycol diacrylate, 1,4-butanediol Goacrylate, neopen
- (Meth) acrylic oligomer As the (meth) acrylic oligomer, a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer [hereinafter also referred to as a polyfunctional urethane (meth) acrylate oligomer] or a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer A functional polyester (meth) acrylate oligomer [hereinafter also referred to as a polyfunctional polyester (meth) acrylate oligomer], a bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer [hereinafter also referred to as a polyfunctional epoxy (meth) acrylate oligomer], and the like. Can be mentioned.
- the hard coat layer (C) may include one type or two or more types of (meth) acrylic oligomer.
- polyfunctional urethane (meth) acrylate oligomer a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and polyisocyanate; polyols to polyisocyanate Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
- Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate may be mentioned.
- polyisocyanate used in the urethanization reaction examples include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates.
- diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate
- diphenyl or tripolyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate
- polyisocyanates obtained by dimerizing diisocyanates Is mentioned.
- polyols used in the urethanization reaction in general, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are used.
- aliphatic and alicyclic polyols 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, diene
- examples thereof include methylolpropionic acid, dimethylolbutyronic acid, glycerin and hydrogenated bisphenol A.
- polyester polyols include those obtained by the dehydration condensation reaction of the above-mentioned polyols and polycarboxylic acid.
- specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid and terephthalic acid. These polycarboxylic acids may be anhydrides.
- examples of the polyether polyol include polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxide.
- the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, polycarboxylic acid and polyol.
- the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.
- Examples of the polyol used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylol heptane, dimethylol propionic acid, and dimethylol.
- Butyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned.
- a polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction of polyglycidyl ether and (meth) acrylic acid.
- the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.
- the surface modifier used in the present invention is a leveling agent, an antistatic agent, a surfactant, a water / oil repellent agent, inorganic particles, organic particles, or other hard coat layer (C). It changes the surface performance.
- the leveling agent include polyether modified polyalkyl siloxane, polyether modified siloxane, polyester modified hydroxyl group-containing polyalkyl siloxane, alkyl group-containing polyether modified polydimethyl siloxane, modified polyether, and silicone modified acrylic.
- antistatic agent examples include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, and anionic surfactant.
- examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, glass particles and the like.
- organic particles include acrylic particles and silicon particles.
- surfactant and the water / oil repellent examples include fluorine-containing surfactants such as fluorine-containing group / lipophilic group-containing oligomers and fluorine-containing group / hydrophilic group / lipophilic group / UV reactive group-containing oligomers. And water and oil repellents.
- the hard coat layer (C) may contain a photopolymerization initiator.
- the photopolymerization initiator refers to a photo radical generator.
- Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocur 2959: manufactured by Merck]; ⁇ -hydroxy - ⁇ , ⁇ '-Dimethylacetophenone [Darocur 1173: manufactured by Merck]; acetophenone initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], 1-hydroxy-cyclohexylphenylketone Examples thereof include benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and halogenated ketones, acyl phosphinoxides, acyl phosphonates, and the like.
- the method for forming the hard coat layer (C) is not particularly limited, but for example, on a layer (eg, resin layer (B)) located below the hard coat layer (C). Can be formed by applying a hard coat solution to the above and then photopolymerizing.
- the method of applying the hard coat liquid is not particularly limited, and a known method can be used. Examples thereof include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexo printing, screen printing, beat coating, and sorting. .
- a lamp used for light irradiation in photopolymerization a lamp having an emission distribution at a light wavelength of 420 nm or less is used, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and a black light lamp. , Microwave-excited mercury lamps, metal halide lamps and the like.
- the irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled depending on the performance of the target product.
- the illuminance is preferably in the range of 0.1 to 300 mW / cm 2 .
- the photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out the light irradiation by using a method capable of eliminating the reaction inhibition by oxygen.
- a method capable of eliminating the reaction inhibition by oxygen there is a method of covering the reactive composition with a film made of polyethylene terephthalate or Teflon (registered trademark) to cut off contact with oxygen, and irradiating the reactive composition with light through the film.
- the composition may be irradiated with light through a light transmissive window under an inert atmosphere in which oxygen is replaced by an inert gas such as nitrogen gas or carbon dioxide gas.
- the coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer (C).
- the treatment include known methods such as a sandblast method, a solvent treatment method, a corona discharge treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and a primer treatment method with a resin composition. Can be mentioned.
- the hard coat layer (C) preferably has a pencil hardness of 2H or more when irradiated with ultraviolet rays using a metal halide lamp having an irradiation output of UV light (254 nm) of 20 mW / cm 2 .
- the thickness of the hard coat layer (C) is preferably 1 ⁇ m or more and 40 ⁇ m or less, more preferably 2 ⁇ m or more and 10 ⁇ m or less. When the film thickness is 1 ⁇ m or more, sufficient hardness can be obtained. Further, when the film thickness is 40 ⁇ m or less, generation of cracks during bending can be suppressed.
- the film thickness of the hard coat layer (C) can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.
- the hard coat layer (C) may be further modified.
- any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment can be applied.
- These treatment methods are not particularly limited, and known methods can be used.
- a method of applying a reflection reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint and the like can be mentioned.
- the pencil hardness of the resin sheet is preferably 2H or more, for example, 2H or more and 4H or less, and particularly preferably 3H or more and 4H or less.
- the pencil hardness of the resin sheet as used herein means the hardness of the hardest pencil that did not cause a scar when the pencil was pressed against the surface of the hard coat layer (C) at an angle of 45 degrees and a load of 750 g to gradually increase the hardness. (Pencil scratch hardness test based on JIS K 5600-5-4: 1999).
- the press molding method includes a step of preheating a polycarbonate sheet before hot pressing (step (I)); a step of placing the preheated sheet in a hot pressing mold (step (II)), And a step of clamping and molding (step (III)).
- step (I) a step of preheating a polycarbonate sheet before hot pressing
- step (II) a step of placing the preheated sheet in a hot pressing mold
- step (III) a step of clamping and molding
- the polycarbonate sheet (resin sheet) is preheated to a temperature in the range of not lower than the glass transition point of the resin layer (A) -45 ° C. and not higher than the glass transition point of the resin layer (A).
- the temperature of preheating refers to the temperature of the preheated polycarbonate sheet before the step (step (II)) of arranging in the hot pressing mold.
- the preheating method is not particularly limited, and examples thereof include a method of drying in a dryer; and a method of heating by radiation.
- Process (II) In this step, the preheated polycarbonate sheet (resin sheet) is placed between the upper die and the lower die of the metal mold. At this time, the time from the completion of step (I) until the polycarbonate sheet is placed between the upper mold and the lower mold (arrangement time) is 90 seconds or less. By setting the placement time to 90 seconds or less, the temperature drop of the preheated sheet can be suppressed, and cracking of the sheet during pressing can be prevented.
- the arrangement time is preferably as short as possible in terms of suppressing springback, preferably 60 seconds or less, and more preferably 50 seconds or less.
- one mold of the upper mold and the lower mold is pressed against the other mold by clamping the molding mold to obtain a press-molded body of the polycarbonate sheet (resin sheet).
- the temperature of the mold is set to a temperature not higher than the glass transition point (Tg) of the resin layer (A).
- Tg glass transition point
- the temperature of the mold is preferably in the range of the glass transition point of the resin layer (A) which is -20 ° C or higher and the glass transition point or lower.
- the temperature of the mold is more preferably a glass transition point of the resin layer (A) in the range of ⁇ 10 ° C.
- the temperature is in the range of ⁇ 5 ° C. to the glass transition point.
- the temperature of the molding die means the temperature of at least one of the upper die and the lower die, which is in contact with the polycarbonate sheet. Therefore, the portion of the molding die in contact with at least one polycarbonate sheet of the upper die or the lower die may satisfy the above temperature conditions, but preferably, the portion of the upper die and the lower die contacting the polycarbonate sheet have the above temperature. It is preferable to satisfy the condition.
- the material of the molding die is not particularly limited as long as it can control the temperature to the predetermined temperature.
- a metal material such as aluminum, stainless steel, or steel can be used.
- a mold having various curved surfaces for example, a two-dimensional shape (for example, a sheet having a thickness of 2 mm has a radius of curvature of 70 mm or less, and further a radius of curvature of 50 mm).
- the following tunnel type mold, hemispherical mold, and three-dimensional mold for example, a radius of curvature of about 100 mmR or more can be used.
- the driving method for clamping the mold is not particularly limited, and a servo motor, a hydraulic jack, an air cylinder, or a weighted load can be used.
- the mold clamping force of the molding die is preferably 3000 kgf or less.
- the mold clamping force of the molding die is more preferably 2000 kgf or less from the viewpoint of preventing the occurrence of satin-like irregularities. Further, 100 kgf or more and 1500 kgf or less is more preferable, and 100 kgf or more and 1000 kgf or less is particularly preferable.
- the press-molded body obtained by the above-mentioned manufacturing method has various curved surface shapes (for example, a two-dimensional shape (for example, a sheet having a thickness of 2 mm, a radius of curvature of 70 mm or less, further a radius of curvature of 50 mm or less). Tunnel type), and a molded product having a three-dimensional shape (for example, radius of curvature of about 100 mmR or more)).
- a component having a flat portion and a continuous bent portion can be successfully manufactured, and thus a product having a novel design or function can be provided.
- the press-molded article obtained by the production method of the present invention has a hard hard coat layer on the surface layer, and therefore is not easily scratched and has high chemical resistance.
- the press-molded product of the present invention can be used in display surface components such as personal computers and mobile phones, automobile exterior and interior members, mobile phone terminals, personal computers, tablet PCs, car navigation systems and the like. It can be used for a case having a curved surface or a front plate.
- the press-molded body is a component / member used for an automobile, an electric / electronic device, a home electric appliance, or an aircraft.
- the heat press machines used in the examples and comparative examples have a mechanism of driving the mold clamping by a servo motor, and the maximum value of the mold clamping force is 3000 kgf.
- Example 1 Using a multi-layer extruder having a single-screw extruder having a shaft diameter of 35 mm, a single-screw extruder having a shaft diameter of 65 mm, a feed block connected to each extruder, and a T-die connected to the feed block, a resin is prepared. A laminate comprising the layer (A) and the resin layer (B) was molded. Specifically, a copolymer of a high hardness resin (B2) (21% by mass of a methyl methacrylate structural unit, 64% by mass of a styrene structural unit, and 15% by mass of a maleic anhydride structural unit) is added to a single screw extruder having a shaft diameter of 35 mm.
- B2 a high hardness resin
- the extruded high hardness resin and polycarbonate resin were introduced into a feed block equipped with a distribution pin of two types and two layers, and the high hardness resin and the polycarbonate resin were laminated at a temperature of 240 ° C. Furthermore, it was introduced into a T-die at a temperature of 240 ° C. and extruded into a sheet, and cooled while transferring the mirror surface from the upstream side by three mirror finishing rolls at a temperature of 120 ° C., 130 ° C. and 190 ° C., and a resin layer ( A laminate of B) and the polycarbonate resin layer (resin layer (A)) was obtained.
- the obtained laminate had a thickness of 2 mm, and the resin layer (B) had a thickness of 60 ⁇ m near the center.
- a hard coat layer (C) was formed on the resin layer (B) side of the laminate obtained above.
- the materials of the hard coat layer (C) are as follows.
- -(Meth) acrylic oligomer U6HA 6-functional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd.) 60% by mass
- -(Meth) acrylic monomer 4EG-A PEG200 # diacrylate (tetraethylene glycol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 35% by mass
- the above materials are applied to the laminated body with a bar coater, and a metal halide lamp (20 mW / cm 2 ) is applied for 5 seconds to cure the hard coat layer, and a resin layer (A), a resin layer (B), and a hard coat layer ( A resin sheet was manufactured by stacking C) in order.
- the film thickness of the hard coat layer (C) was 6 ⁇ m.
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 3 minutes. The temperature of the sheet taken out from the tray dryer was 80 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Example 2 Using the same multi-layer extrusion device as in Example 1, a laminate composed of the resin layer (A) and the resin layer (B) was molded. Specifically, a copolymer of a high hardness resin (B2) (methyl methacrylate structural unit 6% by mass, styrene structural unit 71% by mass, and maleic anhydride structural unit 23% by mass) in a single screw extruder having a shaft diameter of 35 mm.
- Regisphi R310 manufactured by Denka
- Tg 141 ° C.
- pencil hardness: 2H were continuously introduced, under the conditions of a cylinder temperature of 240 ° C.
- Polycarbonate resin (Iupilon S-1000; manufactured by Mitsubishi Engineering Plastics, Tg: 147 ° C., weight average molecular weight (Mw): 49,500) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm. Then, it was extruded under conditions of a cylinder temperature of 280 ° C. and a discharge rate of 83.0 kg / h.
- the extruded high-hardness resin and polycarbonate resin were introduced into a feed block equipped with a two-kind two-layer distribution pin, and the high-hardness resin and the polycarbonate resin were laminated at a temperature of 280 ° C. Furthermore, it was introduced into a T-die at a temperature of 280 ° C. and extruded into a sheet, and cooled while transferring the mirror surface from the upstream side by three mirror-finishing rolls at temperatures of 120 ° C., 130 ° C. and 190 ° C. A laminate of B) and the polycarbonate resin layer (resin layer (A)) was obtained. The obtained laminate had a thickness of 2 mm, and the resin layer (B) had a thickness of 60 ⁇ m near the center.
- the hard coat layer (C) was formed in the same manner as in Example 1 to obtain a resin sheet in which the resin layer (A), the resin layer (B), and the hard coat layer (C) were sequentially laminated.
- Hot pressing process (process I) The obtained resin sheet was put in a tray dryer set at 150 ° C. and preheated for 3 minutes. The temperature of the sheet taken out from the tray dryer was 110 ° C. (Step II) After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds. (Step III) The resin sheet was hot-press molded with an aluminum hot-pressing die (FIG. 1) having a clearance (a gap between the upper and lower sides of the forming sheet sandwiching the forming sheet) of 2 mm and a lower die having a radius of curvature R of 50 mm. The temperature of the upper and lower molds was 144 ° C., the clamping force was 200 kgf, and the pressing time was 3 minutes.
- Example 3 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 10 minutes. The temperature of the sheet taken out from the tray dryer was 90 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Example 4 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Hot pressing process (process I) The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 3 minutes. The temperature of the sheet taken out from the tray dryer was 80 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 1000 kgf
- the pressing time was 3 minutes.
- Example 5 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 1000 kgf
- the pressing time was 3 minutes.
- Example 6 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the clamping force was 1900 kgf
- the pressing time was 3 minutes.
- Example 7 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 122 ° C., the clamping force was 100 kgf, and the pressing time was 3 minutes.
- Example 8 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 122 ° C., the mold clamping force was 200 kgf, and the pressing time was 3 minutes.
- Example 9 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 115 ° C., the clamping force was 200 kgf, and the pressing time was 3 minutes.
- Example 10 In the same manner as in Example 2, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 150 ° C. and preheated for 3 minutes. The temperature of the sheet taken out from the tray dryer was 110 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 135 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Example 11 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 80 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 122 ° C., the mold clamping force was 200 kgf, and the pressing time was 3 minutes.
- Example 12 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 105 ° C., the clamping force was 200 kgf, and the pressing time was 3 minutes.
- Example 13 In the same manner as in Example 1, a resin sheet was obtained by sequentially laminating the resin layer (A), the resin layer (B), and the hard coat layer (C).
- Process I The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm. The temperature of the upper and lower molds was 122 ° C., the clamping force was 3000 kgf, and the pressing time was 3 minutes.
- Hot pressing process (process I) The obtained resin sheet was put in a tray dryer set at 80 ° C. and preheated for 1 minute. The temperature of the sheet taken out from the tray dryer was 60 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Process I The obtained resin sheet was put in a tray dryer set at 150 ° C. and preheated for 10 minutes. The temperature of the sheet taken out from the tray dryer was 130 ° C.
- Step II After taking out the hard-coated polycarbonate from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Process I The obtained resin sheet was put in a tray dryer set at 150 ° C. and preheated for 1 minute. The temperature of the sheet taken out from the tray dryer was 80 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 50 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 144 ° C., the clamping force was 200 kgf, and the pressing time was 3 minutes.
- Hot pressing process (process I) The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 10 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 130 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- Hot pressing process (process I) The obtained resin sheet was put in a tray dryer set at 120 ° C. and preheated for 6 minutes. The temperature of the sheet taken out from the tray dryer was 85 ° C.
- Step II After taking out the resin sheet from the tray dryer, it was placed in the lower mold of the aluminum hot press mold (FIG. 1) in 100 seconds.
- Step III The resin sheet was hot press molded with an aluminum hot press mold (FIG. 1) having a clearance (a gap between the upper and lower parts of the mold for sandwiching the molding sheet) of 2 mm and a radius of curvature R of the lower mold of 50 mm.
- the temperature of the upper and lower molds was 122 ° C.
- the mold clamping force was 200 kgf
- the pressing time was 3 minutes.
- the press-molded product of the resin sheet of the example which was preheated, placed in a molding die, and clamped under the predetermined conditions of the present invention, had high hardness and had abnormal appearance of hard coat cracks and cracks after thermoforming. I know that not.
- the press-molded product of the resin sheet obtained in the example did not have abnormal appearance of flow marks.
- FIG. 2B is a cross-sectional photograph of the molded body of Example 5. On the other hand, satin finish was observed in Example 13 in which the mold clamping force of the mold exceeded 2000 kgf (Fig. 2 (a)).
- Example 8 In comparison with Example 12 in which the temperature of the molding die during molding is less than the glass transition point of the resin layer (A) -10 ° C, the temperature of the molding die during molding is the glass transition point of the resin layer (A)- In Examples 8 and 9 in which the temperature was not lower than 10 ° C. and not higher than the glass transition point, and the conditions other than the temperature of the molding die were the same, the radius of curvature R of the molded body was close to the radius of curvature (50 mm) of the lower die, and spring back was used. It is confirmed that the occurrence of is reduced.
- Example 8 compared to Example 11 in which the time from the completion of step (I) until the resin sheet is placed in the molding die is more than 60 seconds and 90 seconds or less, the placement time is 60 seconds or less and other than the placement time. It is confirmed that in Example 8 in which the conditions are the same, the radius of curvature R of the molded body is close to the radius of curvature (50 mm) of the lower mold, and the springback is further suppressed.
- the press-molded body of the resin sheet of Comparative Example has hard coat cracks and / or cracks formed by thermoforming. Specifically, in Comparative Examples 1 and 3 in which the preheating temperature was lower than the glass transition point of the resin layer (A) ⁇ 45 ° C., cracks were observed in the sheet due to thermoforming. In Comparative Example 2 in which the preheating temperature exceeded the glass transition point of the resin layer (A), hard coat cracks occurred. In Comparative Example 4 in which the temperature of the molding die during molding exceeds the glass transition point of the resin layer (A), hard coat cracking occurred due to thermoforming. In Comparative Example 5 in which the time from the completion of step (I) until the resin sheet was placed in the molding die was more than 90 seconds, cracks were found in the sheet.
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Abstract
Description
また、特許文献4には、基材フィルムの片面に特定組成のハードコート塗料を用いて形成した層を有する加飾用ハードコートフィルムが開示されており、基材フィルム上に印刷層を設けてよいことも記載されている。この加飾フィルムは、熱成形が可能である。特許文献4に記載の加飾フィルムは、成形用樹脂と一体化され、加飾成形品となる。
従来、異なる種類の樹脂層を積層し、その上にハードコート層を設ける場合には、各層に含まれる樹脂のガラス転移点(Tg)や溶融粘度が異なり、クラック等の不具合が生じないように熱成形することが難しいという問題があった。
[1] ポリカーボネート樹脂を主成分とする樹脂層(A)の少なくとも一方の面上に高硬度樹脂(B)を主成分とする樹脂層(B)およびハードコート層(C)を順に積層させたポリカーボネートシートのプレス成形体の製造方法であって、以下の工程:
工程(I):前記ポリカーボネートシートを前記樹脂層(A)のガラス転移点-45℃以上ガラス転移点以下の範囲の温度に予備加熱する工程、
工程(II):予備加熱された前記ポリカーボネートシートを金属製の成形型の上型および下型の間に配置する工程であって、前記工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間が90秒以内である、工程、および
工程(III):成形型を型締めすることにより上型および下型の一方の型を他方の型に対して押圧して、ポリカーボネートシートのプレス成形体を得る工程であって、前記成形型の温度が前記樹脂層(A)のガラス転移点以下の温度である、工程
を含む、製造方法。
[2] 前記工程(II)において、工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間が60秒以内である、[1]に記載の方法。
[3] 前記工程(III)において、前記成形型の温度が前記樹脂層(A)のガラス転移点-10℃以上ガラス転移点以下の範囲の温度である、[1]または[2]に記載の方法。
[4] 前記工程(III)において、成形型の型締め力が2000kgf以下である、[1]~[3]のいずれかに記載の方法。
[5] 前記ポリカーボネートシートの鉛筆硬度が2H以上である、[1]~[4]のいずれかに記載の方法。
[6] 高硬度樹脂(B)は、下記樹脂(B1)~(B5):
樹脂(B1) 下記一般式(1):
で表される(メタ)アクリル酸エステル構成単位(a)、および、下記一般式(2):
で表される脂肪族ビニル構成単位(b)を含む共重合体を含む樹脂;
樹脂(B2) (メタ)アクリル酸エステル構成単位を6~77質量%、スチレン構成単位を15~71質量%、および、不飽和ジカルボン酸構成単位を5~25質量%含む共重合体(D)を含む樹脂;
樹脂(B3) 下記一般式(6):
樹脂(B4) スチレン構成単位を5~20質量%、(メタ)アクリル酸エステル構成単位を60~90質量%、および、N-置換型マレイミド構成単位を5~20質量%含む共重合体(G)を含む樹脂;ならびに
樹脂(B5) 下記一般式(8):
任意に前記一般式(7)で表される構成単位(d)を含む重合体を含む樹脂;
から選択される少なくとも1つを含む、[1]~[5]のいずれかに記載の方法。
[7] 前記ポリカーボネート樹脂が、一般式(7):
で表される1価フェノールを使用して製造されたポリカーボネート樹脂である、[1]~[6]のいずれかに記載の方法。
[8] 樹脂層(A)のガラス転移点と、樹脂層(B)のガラス転移点とが、以下の関係:
-10℃≦(樹脂層(B)のガラス転移点)-(樹脂層(A)のガラス転移点)≦40℃
を満たす、[1]~[7]のいずれかに記載の方法。
[9] 前記プレス成形体は、自動車、電機・電子機器、家電製品、または航空機の用途に用いられる部品・部材である、[1]~[8]のいずれかに記載の方法。
本発明の一つの態様によれば、硬度が高く、成形時にハードコートクラックやシートの割れが生じにくい樹脂成形体を提供することができる。
本発明の好ましい態様によれば、成形時にスプリングバックが小さい樹脂成形体を提供することができる。
本発明の好ましい態様によれば、成形時に梨地状の凹凸の発生が抑制された樹脂成形体を提供することができる。
本発明の好ましい態様によれば、二次元曲げ用成形型だけでなく多様な曲面形状の成形型を用いて製造された熱プレス成形体を提供することができる。
工程(I):前記ポリカーボネートシートを前記樹脂層(A)のガラス転移点-45℃以上ガラス転移点以下の範囲の温度に予備加熱する工程
工程(II):予備加熱された前記ポリカーボネートシートを金属製の成形型の上型および下型の間に配置する工程であって、前記工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間が90秒以内である、工程
工程(III):成形型を型締めすることにより上型および下型の一方の型を他方の型に対して押圧して、ポリカーボネートシートのプレス成形体を得る工程であって、前記成形型の温度が前記樹脂層(A)のガラス転移点以下の温度である、工程
1.ポリカーボネートシート
本発明の成形に用いる成形用のポリカーボネートシート(以下、単に「樹脂シート」とも称する)は、ポリカーボネート樹脂(a1)を主成分とする樹脂層(A)と、樹脂層(A)の少なくとも一方の面上に位置する、高硬度樹脂(B)を主成分とする樹脂層(B)と、ハードコート層(C)とを有する。樹脂層(B)は、樹脂層(A)とハードコート層(C)との間に位置する。樹脂層(A)と樹脂層(B)の間、樹脂層(B)とハードコート層(C)の間には、それぞれさらなる層が存在していてもよい。さらなる層としては、接着剤層、プライマー層等が挙げられるが、これらに限定されるものではない。さらなる層は存在していなくてもよい。1つの実施形態として、樹脂シートは、ポリカーボネート樹脂(a1)を主成分とする樹脂層(A)と、樹脂層(A)の少なくとも一方の面の直上に積層された樹脂層(B)と、樹脂層(B)の直上に積層されたハードコート層(C)とを有する。
2.樹脂層(A)
樹脂層(A)は、は、ポリカーボネートシートの基材となる層であり、ポリカーボネート樹脂(a1)を主成分として含む樹脂層である。樹脂層(A)に含まれるポリカーボネート樹脂(a1)は、1種類であっても2種類以上であってもよい。ここで「ポリカーボネート樹脂(a1)を主成分とする」とは、例えば、樹脂層(A)中のポリカーボネート樹脂(a1)の含有量が、樹脂層(A)の全質量に対して50質量%以上を占めることをいうものとする。樹脂層(A)中のポリカーボネート樹脂(a1)の含有量は、75質量%以上であることが好ましく、90質量%以上であることがより好ましく、100質量%であることが特に好ましい。ポリカーボネート樹脂の含有量を増やすことで、耐衝撃性が向上する。
本明細書中において、「アルキル基」および「アルケニル基」は、直鎖状であっても分岐鎖状であってもよく、置換基を有していてもよい。
より好ましくは、一般式(4)で表される1価フェノールは、下記一般式(5)で表される。
一般式(4)または一般式(5)におけるR1の炭素数が上記範囲であると、生産性(経済性)に優れ、しかもポリカーボネート樹脂のガラス転移点の上昇が抑制され、熱成形性に優れる。
-10℃≦(樹脂層(B)のガラス転移点)-(樹脂層(A)のガラス転移点)≦40℃
このような関係を満たすことにより、硬度が高く、成形する際にクラック、フローマーク等の外観異常が生じにくい成形用樹脂シートを得ることができる。特に熱成形時に外観異常が生じにくく、このような樹脂シートは、熱成形時の条件(温度、加熱時間等)を広く設定することができるため、熱成形に適した樹脂シートであると言える。
なお、本明細書において、「樹脂層(A)のガラス転移点」とは、樹脂層(A)の主成分であるポリカーボネート樹脂(a1)のガラス転移温度を意味する。樹脂層(A)が2種以上のポリカーボネート樹脂(a1)を含んでいる場合のガラス転移点は、ポリカーボネート樹脂混合物のガラス転移温度である。また、「樹脂層(B)のガラス転移点」とは、樹脂層(B)の主成分である高硬度樹脂のガラス転移温度を意味する。樹脂層(B)が2種以上の高硬度樹脂を含んでいる場合のガラス転移点は、高硬度樹脂混合物のガラス転移温度である。本明細書において、ガラス転移点とは、示差走査熱量測定装置を用いて、試料10mg、昇温速度10℃/分で測定し、中点法で算出した温度である。
例えば、主成分であるエチレングリコール80~60モル%に対して1,4-シクロヘキサンジメタノールを20~40モル%(合計100モル%)含むグリコール成分とジカルボン酸成分とが重縮合してなるポリエステル樹脂(所謂「PETG」)が好ましい。樹脂層(A)における樹脂は、ポリカーボネート樹脂(a1)のみであることが好ましいが、その他の樹脂を含む場合には、その量は樹脂層(A)の全質量に対して0~50質量%であることが好ましく、0~30質量%であることがより好ましく、0~20質量%であることが特に好ましい。
樹脂層(B)は、高硬度樹脂を主成分として含む樹脂層である。ここで「高硬度樹脂を主成分とする」とは、例えば、樹脂層(B)中の高硬度樹脂の含有量が、樹脂層(B)の全質量に対して50質量%以上を占めることをいうものとする。樹脂層(B)中の高硬度樹脂の含有量は、70~100質量%以上であることが好ましく、80~100質量%以上であることがより好ましく、100質量%であることが特に好ましい。
本明細書において、高硬度樹脂とは、鉛筆硬度がHB以上の樹脂を意味する。高硬度樹脂の鉛筆硬度は、HB以上3H以下であることが好ましく、H以上3H以下であることがより好ましい。ここでいう高硬度樹脂の鉛筆硬度は、高硬度樹脂で構成した樹脂層の表面に対して角度45度、荷重750gで次第に硬度を増して鉛筆を押し付け、傷跡を生じなかった最も硬い鉛筆の硬度を意味する(JIS K 5600-5-4:1999に準拠した鉛筆ひっかき硬度試験)。
樹脂層(B)に含まれる高硬度樹脂は、1種類であっても2種類以上であってもよい。高硬度樹脂は、例えば、以下に示す樹脂(B1)~(B5)の少なくとも1つを含むことが好ましい。
樹脂(B1)は、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含む共重合体(b1)を含む樹脂である。樹脂(B1)は、該共重合体(b1)と他の重合体とのアロイでもよく、例えば、該共重合体(b1)と以下<樹脂(B2)>で説明する共重合体(b2)とのアロイであってよい。好ましくは、樹脂(B1)は、樹脂(B1)の総質量(100質量%)に対して共重合体(b1)の含有量が80~100質量%が好ましく、95~100質量%がより好ましい。
本明細書中において、「炭化水素基」は、直鎖状、分岐鎖状、環状のいずれであってもよく、置換基を有していてもよい。
本明細書中において、「シクロアルキル」は、単環式または二環式のいずれであってもい。
(メタ)アクリル酸エステル構成単位(a)のうち、好ましいのはR2がメチル基またはエチル基である(メタ)アクリル酸エステル構成単位であり、更に好ましいのはR1がメチル基であり、R2がメチル基であるメタクリル酸メチル構成単位である。
脂肪族ビニル構成単位(b)のうち、より好ましいのはR3が水素原子であり、R4がシクロヘキシル基である脂肪族ビニル構成単位である。
(メタ)アクリル酸エステル構成単位(a)と脂肪族ビニル構成単位(b)との合計含有量は、共重合体(b1)の全構成単位に対して好ましくは90~100モル%であり、より好ましくは95~100モル%であり、特に好ましくは98~100モル%である。
なお、本明細書において、「共重合体」は、ランダム、ブロックおよび交互共重合体のいずれの構造であってもよい。
この際に使用される芳香族ビニルモノマーとしては、具体的にはスチレン、α-メチルスチレン、p-ヒドロキシスチレン、アルコキシスチレン、クロロスチレン、およびそれらの誘導体などが挙げられる。これらの中で好ましいのはスチレンである。
樹脂(B2)は、(メタ)アクリル酸エステル構成単位を6~77質量%、スチレン構成単位を15~71質量%、および不飽和ジカルボン酸構成単位を5~25質量%含む共重合体(D)を含む樹脂である。樹脂(B)は共重合体(D)同士のアロイである樹脂、更には、共重合体(D)と共重合体(D)以外の高硬度の重合体のアロイである樹脂であってよい。共重合体(D)以外の高硬度の重合体としては、メタクリル酸メチル-スチレン共重合体、ポリメタクリル酸メチル、アクリロニトリル-ブタジエン-スチレン共重合体などが挙げられる。アロイにする場合には、高硬度樹脂のTg低下を避けるため、より高Tgである重合体同士のアロイが良い。
(メタ)アクリル酸エステル構成単位の含有量は、共重合体(D)の全質量に対して6~77質量%であり、6~70質量%が好ましく、20~70質量%であることがより好ましい。
スチレン構成単位の含有量は、共重合体(D)の全質量に対して15~71質量%であり、20~71質量%であることがより好ましい。
不飽和ジカルボン酸構成単位の含有量は、共重合体(D)の全質量に対して5~25質量%であり、6~24質量%が好ましく、8~23質量%であることがより好ましい。
すなわち、共重合体(D)は、上記(メタ)アクリル酸エステル構成単位、スチレン構成単位および不飽和ジカルボン酸構成単位以外の構成単位を含有していてもよい。その量は、共重合体(D)の全構成単位に対して10モル%以下であることが好ましく、5モル%以下であることがより好ましく、2モル%以下であることが特に好ましい。
共重合体(D)の製造方法は、特に限定されないが、塊状重合法や溶液重合法が挙げられる。
樹脂(B3)は、下記一般式(6)で表される構成単位(c)と、任意に下記一般式(7)で表される構成単位(d)とを含む共重合体を含む樹脂である。樹脂(B3)は、構成単位(d)を含んでいても含んでいなくてもよいが、含んでいることが好ましい。
その他の構成単位としては、例えば、後述する一般式(8)で表される構成単位などが挙げられる。
樹脂(B4)は、スチレン構成単位を5~20質量%、(メタ)アクリル酸エステル構成単位を60~90質量%、およびN-置換型マレイミド構成単位を5~20質量%含む共重合体(G)を含む樹脂である。樹脂(B4)は、共重合体(G)と上記共重合体(D)またはその他の重合体とのアロイであってもよい。アロイの場合には、樹脂層(B)のTg低下を避けるため、より高Tg同士の樹脂のアロイが良い。
共重合体(G)は、上記構成単位以外の構成単位を含んでいてもよい。その他の構成単位を含む場合、その量は、共重合体(G)の全構成単位に対して10モル%以下であることが好ましく、5モル%以下であることがより好ましく、2モル%以下であることが特に好ましい。
重合体(E)は、構成単位(e)以外の構成単位を含んでいてもよいが、構成単位(e)からなるポリカーボネート樹脂であることが好ましい。その他の構成単位を含む場合、その量は、重合体(E)の全構成単位に対して10モル%以下であることが好ましく、5モル%以下であることがより好ましく、2モル%以下であることが特に好ましい。
樹脂(B5)として、具体的には、ユピゼータ FPC0220(三菱ガス化学社製)が挙げられる。
好ましい一態様では、高硬度樹脂は、樹脂(B2)を含む。
上述したとおり、樹脂層(A)と樹脂層(B)の間にはさらなる層が存在していてもよいが、ここでは、樹脂層(A)直上に樹脂層(B)を積層する場合について説明する。その積層方法は特に限定されず、他の層が存在する場合にも同様に積層することができる。例えば、個別に形成した樹脂層(A)と樹脂層(B)とを重ね合わせて、両者を加熱圧着する方法;個別に形成した樹脂層(A)と樹脂層(B)とを重ね合わせて、両者を接着剤によって接着する方法;樹脂層(A)と樹脂層(B)とを共押出成形する方法;予め形成しておいた樹脂層(B)に、樹脂層(A)をインモールド成形して一体化する方法、などの各種方法がある。これらのうち、製造コストや生産性の観点から、共押出成形する方法が好ましい。
本発明の樹脂シートは、樹脂層(B)上にハードコート層(C)を有する。ハードコート層(C)と樹脂層(B)の間にさらなる層が存在していてもよいが、好ましくは、ハードコート層(C)は樹脂層(B)の直上に積層される。
本発明の樹脂シートは、樹脂層(A)とハードコート層(C)との間に樹脂層(B)が配置されており、これにより、樹脂シートの硬度をさらに高めることができる。ポリカーボネートの樹脂層(A)上に直接ハードコート層(C)を設けた場合には、弾性率が低く座屈しやすいという問題が生じ得るが、樹脂層(B)を設けることによりこのような問題も解決することができる。また、本発明によると、所定の積層体(樹脂層(A)、樹脂層(B)、およびハードコート層(C))の構成とし、さらに、所定の熱プレス条件を用いることにより、クラック等の不具合を抑制しつつ熱成形することができる。
光重合開始剤の量は、(メタ)アクリル系モノマーと(メタ)アクリル系オリゴマーと表面改質剤との総和100質量部に対して、0.01~5質量部であることがより好ましく、0.1~3質量部であることが特に好ましい。
(メタ)アクリル系モノマーとしては、分子内に(メタ)アクリロイル基が官能基として存在するものであれば使用でき、1官能モノマー、2官能モノマー、または3官能以上のモノマーであって良い。
ハードコート層(C)は、(メタ)アクリル系モノマーを1種類または2種類以上含んでいてよい。
(メタ)アクリル系オリゴマーとしては、2官能以上の多官能ウレタン(メタ)アクリレートオリゴマー〔以下、多官能ウレタン(メタ)アクリレートオリゴマーともいう〕、2官能以上の多官能ポリエステル(メタ)アクリレートオリゴマー〔以下、多官能ポリエステル(メタ)アクリレートオリゴマーともいう〕、2官能以上の多官能エポキシ(メタ)アクリレートオリゴマー〔以下、多官能エポキシ(メタ)アクリレートオリゴマーともいう〕などが挙げられる。ハードコート層(C)は、(メタ)アクリル系オリゴマーを1種類または2種類以上含んでいてよい。
本発明で使用される表面改質剤とは、レベリング剤、帯電防止剤、界面活性剤、撥水撥油剤、無機粒子、有機粒子などのハードコート層(C)の表面性能を変化させるものである。
レベリング剤としては、例えば、ポリエーテル変性ポリアルキルシロキサン、ポリエーテル変性シロキサン、ポリエステル変性水酸基含有ポリアルキルシロキサン、アルキル基を有するポリエーテル変性ポリジメチルシロキサン、変性ポリエーテル、シリコン変性アクリルなどが挙げられる。
無機粒子としては、例えば、シリカ粒子、アルミナ粒子、ジルコニア粒子、シリコン粒子銀粒子、ガラス粒子などが挙げられる。
有機粒子としては、例えば、アクリル粒子、シリコン粒子などが挙げられる。
界面活性剤および撥水撥油剤としては、例えば、含フッ素基・親油性基含有オリゴマー、含フッ素基・親水性基・親油性基・UV反応性基含有オリゴマーなどのフッ素を含有した界面活性剤および撥水撥油剤が挙げられる。
ハードコート層(C)は、光重合開始剤を含んでいてよい。本明細書において、光重合開始剤とは光ラジカル発生剤を指す。
ハードコート層(C)の形成方法は特に限定されないが、例えば、ハードコート層(C)の下に位置する層(例えば樹脂層(B))上に、ハードコート液を塗布した後、光重合させることにより形成することができる。
プレス成形方法は、ポリカーボネートシートを熱プレス成形する前に予備加熱する工程(工程(I));予備加熱されたシートを熱プレス用成形型に配置する工程(工程(II))、および型締めを行い成形する工程(工程(III))を含む。以下、実施形態に係るプレス成形方法の各工程について説明する。
本工程では、上記ポリカーボネートシート(樹脂シート)を前記樹脂層(A)のガラス転移点-45℃以上樹脂層(A)のガラス転移点以下の範囲の温度に予備加熱する。予備加熱の温度を樹脂層(A)のガラス転移点-45℃以上の温度とすることにより、プレス時のシートの割れが防止できる。予備加熱の温度を樹脂層(A)のガラス転移点以下の温度とすることにより、プレス時のハードコート層へのクラックの発生を抑制できる。ここで、予備加熱の温度は、熱プレス用成形型に配置する工程(工程(II))前の予備加熱されたポリカーボネートシートの温度を指す。
予備加熱の方法は特に制限されず、乾燥機中で乾燥する方法;輻射により加熱する方法などが挙げられる。
本工程では、予備加熱された上記ポリカーボネートシート(樹脂シート)を金属製の成形型の上型および下型の間に配置する。この際、工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間(配置時間)が90秒以内である。配置時間を90秒以内とすることにより、予備加熱したシートの温度の低下が抑制され、プレス時のシートの割れが防止され得る。
配置時間は、スプリングバックの抑制の点で短いほど好ましく、60秒以内が好ましく、50秒以内がより好ましい。
本工程では、成形型を型締めすることにより上型および下型の一方の型を他方の型に対して押圧して、上記ポリカーボネートシート(樹脂シート)のプレス成形体を得る。この際、成形型の温度を樹脂層(A)のガラス転移点(Tg)以下の温度とする。成形型の温度を樹脂層(A)のTg以下とすることにより、ハードコートへのクラックの発生を抑制し得る。
成形型の温度は、好ましくは、樹脂層(A)のガラス転移点-20℃以上ガラス転移点以下の範囲の温度である。成形型の温度は、スプリングバックの抑制の点で、より好ましくは樹脂層(A)のガラス転移点-10℃以上ガラス転移点以下の範囲の温度、さらに好ましくは樹脂層(A)のガラス転移点-5℃~ガラス転移点の範囲の温度である。
ここで、成形型の温度とは、上型または下型の少なくとも一つの、ポリカーボネートシートと接する部分の温度をいう。したがって、成形型のうち上型または下型の少なくとも一つのポリカーボネートシートと接する部分が、上記温度条件を満たせばよいが、好ましくは、上型および下型の両方のポリカーボネートシートと接する部分が上記温度条件を満たすことが好ましい。
成形型の材質は、上記所定温度への温度制御が可能な材質であれば特に制限されない。例えば、アルミニウム、ステンレス、鋼材等の金属製のものが使用できる。また、本工程のプレス成形では、二次元曲げ用成形型だけでなく多様な曲面形状の成形型(例えば、二次元形状(例えば厚さ2mmのシートにて曲率半径70mm以下、さらには曲率半径50mm以下のトンネル型)の金型、半球状の金型、三次元形状の金型(例えば曲率半径約100mmR以上))を用いることができる。
なお、特許文献6の方法であると、厚さ2mmのシートでは二次元形状の成形では曲率半径100mmでもクラックが生じてしまうため、曲率半径の大きい(緩い形状)の成形品しか得られない。さらには三次元形状には成形することは不可能であった。
型締めの駆動方法は特に制限されず、サーボモーター、油圧ジャッキ、エアシリンダー、重量物による加重を用いることができる。
成形型の型締め力は、好ましくは3000kgf以下である。成形型の型締め力は、梨地状の凹凸の発生を防止する点で、2000kgf以下であることがより好ましい。また、100kgf以上1500kgf以下がさらに好ましく、100kgf以上1000kgf以下が特に好ましい。
上記製造方法で得られたプレス成形体は、硬度が要求される多様な曲面形状(例えば、二次元形状(例えば厚さ2mmのシートにて曲率半径70mm以下、さらには曲率半径50mm以下のトンネル型)、三次元形状(例えば曲率半径約100mmR以上))を有する成形品として好適に使用することができる。例えば、平面部と連続した曲げ部を有する構成部品を首尾よく製造することができるため、新規なデザインや機能を有する製品を提供することもできる。
従来の樹脂シートでは、上記のような形状を有する成形品を製造しようとした場合、熱プレス成形、真空成形、圧空成形、TOM成形などの熱成形時にクラックが生じるなどの不具合が多く発生していた。そこで、熱成形時のクラック発生を抑制するために、ハードコートの硬さを低下させるなどの工夫をする必要があった。しかしながら、ハードコートの硬さを低下させた場合、熱成形性は向上するものの、ハードコートが軟らかいため傷が付きやすい、耐薬品性が低下するという新たな問題が生じていた。
<ガラス転移点(Tg)の測定>
日立ハイテクサイエンス製示差走査熱量計DSC7020を使用し、昇温速度10℃/分、窒素雰囲気下で、実施例および比較例で使用したポリカーボネート樹脂および高硬度樹脂のガラス転移点を測定した。測定に使用した樹脂の重量は10~20mgである。
実施例および比較例で製造したハードコート層(C)を形成する前の樹脂層(B)と樹脂層(A)との積層体(樹脂シート)について、樹脂層(B)側の鉛筆硬度をJIS K 5600-5-4:1999に準拠した鉛筆ひっかき硬度試験にて評価した。樹脂層(B)の表面に対して角度45度、荷重750gで次第に硬度を増して鉛筆を押し付け、傷跡を生じなかった最も硬い鉛筆の硬度を樹脂層(B)を構成する高硬度樹脂の鉛筆硬度として評価した。
実施例および比較例で製造した熱プレス工程前の樹脂シートを、JIS K 5600-5-4:1999に準拠した鉛筆ひっかき硬度試験にて評価した。ハードコート層(C)の表面に対して角度45度、荷重750gで次第に硬度を増して鉛筆を押し付け、傷跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として評価した。
硬度が2H以上を合格とした。
触針式輪郭形状測定機(東京精密製 コンターレコード2700SD3にて6mm/秒の速度で成形体の曲率半径Rを測定し、スプリングバックを評価した。金型(下型)の曲率半径Rに近いほど良好な結果である。
実施例および比較例で用いた熱プレス機はサーボモーターにより型締め駆動する仕組みであり、型締め力の最大値は3000kgfである。
軸径35mmの単軸押出機と、軸径65mmの単軸押出機と、各押出機に連結されたフィードブロックと、フィードブロックに連結されたTダイとを有する多層押出装置を用いて、樹脂層(A)と樹脂層(B)とからなる積層体を成形した。具体的には、軸径35mmの単軸押出機に高硬度樹脂(B2)(メタクリル酸メチル構成単位21質量%、スチレン構成単位64質量%、および無水マレイン酸構成単位15質量%の共重合体;レジスファイ R100(デンカ製)、Tg:124℃、重量平均分子量(Mw):171,000、鉛筆硬度:H)を連続的に導入し、シリンダ温度230℃、吐出速度2.6kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(ユピゼータT-1380;三菱ガス化学製、Tg:125℃、重量平均分子量(Mw):44,500)を連続的に導入し、シリンダ温度240℃、吐出速度83.0kg/hの条件で押し出した。
・(メタ)アクリル系オリゴマー:U6HA 6官能ウレタンアクリレートオリゴマー(新中村化学工業(株)製)60質量%、
・(メタ)アクリル系モノマー:4EG-A PEG200#ジアクリレート(テトラエチレングリコールジアクリレート、共栄社化学(株)製)35質量%、
および
・表面改質剤:RS-90 含フッ素基・親水性基・親油性基・UV反応性基含有オリゴマー(DIC(株)製)5質量%の混合物100質量部に対して、
・光重合開始剤:I-184(BASF(株)製〔化合物名:1-ヒドロキシ-シクロヘキシルフェニルケトン〕)を1質量部。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を3分間行った。棚段乾燥機から取り出したシートの温度は80℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同じ多層押出装置を用いて、樹脂層(A)と樹脂層(B)からなる積層体を成形した。具体的には、軸径35mmの単軸押出機に高硬度樹脂(B2)(メタクリル酸メチル構成単位6質量%、スチレン構成単位71質量%、および無水マレイン酸構成単位23質量%の共重合体;レジスファイ R310(デンカ製)、Tg:141℃、重量平均分子量(Mw):132,000、鉛筆硬度:2Hを連続的に導入し、シリンダ温度240℃、吐出速度2.6kg/hの条件で押し出した。また、軸径65mmの単軸押出機にポリカーボネート樹脂(ユーピロンS-1000;三菱エンジニアリングプラスチックス社製、Tg:147℃、重量平均分子量(Mw):49,500)を連続的に導入し、シリンダ温度280℃、吐出速度83.0kg/hの条件で押し出した。
ハードコート層(C)は実施例1と同様に形成し、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを150℃に設定した棚段乾燥機に入れ、予備加熱を3分間行った。棚段乾燥機から取り出したシートの温度は110℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに144℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を10分間行った。棚段乾燥機から取り出したシートの温度は90℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を3分間行った。棚段乾燥機から取り出したシートの温度は80℃であった。
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は1000kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は1000kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は1900kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は100kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに115℃、型締め力は200kgf、プレス時間は3分で行った。
実施例2と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを150℃に設定した棚段乾燥機に入れ、予備加熱を3分間行った。棚段乾燥機から取り出したシートの温度は110℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに135℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、80秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに105℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
(工程III)
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は3000kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを80℃に設定した棚段乾燥機に入れ、予備加熱を1分間行った。棚段乾燥機から取り出したシートの温度は60℃であった。
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを150℃に設定した棚段乾燥機に入れ、予備加熱を10分間行った。棚段乾燥機から取り出したシートの温度は130℃であった。
(工程II)
棚段乾燥機からハードコート付きポリカーボネートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った。
実施例2と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを150℃に設定した棚段乾燥機に入れ、予備加熱を1分間行った。棚段乾燥機から取り出したシートの温度は80℃であった。
(工程II)
棚段乾燥機から樹脂シートを取り出し後、50秒でアルミ製熱プレス金型(図1)の下型に設置した。
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに144℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
棚段乾燥機から樹脂シートを取り出し後、10秒でアルミ製熱プレス金型(図1)の下型に設置した。
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに130℃、型締め力は200kgf、プレス時間は3分で行った。
実施例1と同様にして、樹脂層(A)、樹脂層(B)、およびハードコート層(C)を順に積層した樹脂シートを得た。
(工程I)
得られた樹脂シートを120℃に設定した棚段乾燥機に入れ、予備加熱を6分間行った。棚段乾燥機から取り出したシートの温度は85℃であった。
棚段乾燥機から樹脂シートを取り出し後、100秒でアルミ製熱プレス金型(図1)の下型に設置した。
樹脂シートをクリアランス(金型上下で成形用シートを挟み込む隙間)が2mmで下型の曲率半径Rが50mmのアルミ製熱プレス用金型(図1)で熱プレス成形した。上下の金型の温度はともに122℃、型締め力は200kgf、プレス時間は3分で行った
実施例および比較例で製造した樹脂シートのプレス成形体について、スプリングバック評価のために曲率半径Rを測定した。また、目視にてハードコートのクラックの有無、成形体のシートの割れおよび成形体表面の梨地の有無を観察した。その結果を以下の表1に示す。
また、成形型の型締め力が2000kgf以下である実施例1~12は梨地の発生がなかった。図2(b)は、実施例5の成形体の断面写真である。一方、成形型の型締め力が2000kgfを超える実施例13は梨地が観察された(図2(a))。
成形時の成形型の温度が、樹脂層(A)のガラス転移点-10℃未満である実施例12と比較して、成形時の成形型の温度が樹脂層(A)のガラス転移点-10℃以上ガラス転移点以下の温度であり、成形型の温度以外の条件が同一である実施例8,9は、成形体の曲率半径Rが下型の曲率半径(50mm)に近く、スプリングバックの発生が低減されたことが確認される。
さらに、工程(I)完了後から樹脂シートを成形型に配置するまでの時間が60秒を超え90秒以下である実施例11と比較して、配置時間が60秒以下であり、配置時間以外の条件が同一である実施例8は、成形体の曲率半径Rが下型の曲率半径(50mm)に近く、スプリングバックがより抑制されたことが確認される。
具体的には、予備加熱の温度が樹脂層(A)のガラス転移点-45℃未満である比較例1,3は、熱成形によりシートに割れが見られた。
予備加熱の温度が樹脂層(A)のガラス転移点を超える比較例2はハードコートクラックが発生した。成形時の成形型の温度が樹脂層(A)のガラス転移点を超える比較例4は、熱成形によりハードコートクラックが発生した。
工程(I)完了後から樹脂シートを成形型に配置するまでの時間が90秒を超える比較例5は、シートに割れが見られた。
Claims (9)
- ポリカーボネート樹脂を主成分とする樹脂層(A)の少なくとも一方の面上に高硬度樹脂(B)を主成分とする樹脂層(B)およびハードコート層(C)を順に積層させたポリカーボネートシートのプレス成形体の製造方法であって、以下の工程:
工程(I):前記ポリカーボネートシートを前記樹脂層(A)のガラス転移点-45℃以上ガラス転移点以下の範囲の温度に予備加熱する工程、
工程(II):予備加熱された前記ポリカーボネートシートを金属製の成形型の上型および下型の間に配置する工程であって、前記工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間が90秒以内である、工程、および
工程(III):成形型を型締めすることにより上型および下型の一方の型を他方の型に対して押圧して、ポリカーボネートシートのプレス成形体を得る工程であって、前記成形型の温度が前記樹脂層(A)のガラス転移点以下の温度である、工程
を含む、製造方法。 - 前記工程(II)において、工程(I)の完了後からポリカーボネートシートを成形型の上型および下型の間に配置するまでの時間が60秒以内である、請求項1に記載の製造方法。
- 前記工程(III)において、前記成形型の温度が前記樹脂層(A)のガラス転移点-10℃以上ガラス転移点以下の範囲の温度である、請求項1または2に記載の方法。
- 前記工程(III)において、成形型の型締め力が2000kgf以下である、請求項1~3のいずれか一項に記載の方法。
- 前記ポリカーボネートシートの鉛筆硬度が2H以上である、請求項1~4のいずれか一項に記載の方法。
- 高硬度樹脂(B)は、下記樹脂(B1)~(B5):
樹脂(B1) 下記一般式(1):
で表される(メタ)アクリル酸エステル構成単位(a)、および、下記一般式(2):
で表される脂肪族ビニル構成単位(b)を含む共重合体を含む樹脂;
樹脂(B2) (メタ)アクリル酸エステル構成単位を6~77質量%、スチレン構成単位を15~71質量%、および、不飽和ジカルボン酸構成単位を5~25質量%含む共重合体(D)を含む樹脂;
樹脂(B3) 下記一般式(6):
樹脂(B4) スチレン構成単位を5~20質量%、(メタ)アクリル酸エステル構成単位を60~90質量%、および、N-置換型マレイミド構成単位を5~20質量%含む共重合体(G)を含む樹脂;ならびに
樹脂(B5) 下記一般式(8):
任意に前記一般式(7)で表される構成単位(d)を含む重合体を含む樹脂;
から選択される少なくとも1つを含む、請求項1~5のいずれか一項に記載の方法。 - 樹脂層(A)のガラス転移点と、樹脂層(B)のガラス転移点とが、以下の関係:
-10℃≦(樹脂層(B)のガラス転移点)-(樹脂層(A)のガラス転移点)≦40℃
を満たす、請求項1~7のいずれか一項に記載の方法。 - 前記プレス成形体は、自動車、電機・電子機器、家電製品、または航空機の用途に用いられる部品・部材である、請求項1~8のいずれか一項に記載の方法。
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WO2023048054A1 (ja) * | 2021-09-21 | 2023-03-30 | 三菱瓦斯化学株式会社 | 樹脂積層体 |
CN116622112A (zh) * | 2023-06-08 | 2023-08-22 | 兰州理工大学 | 一种聚碳酸酯表面多功能复合强化层的制备方法 |
JP7470597B2 (ja) | 2020-08-05 | 2024-04-18 | 三菱瓦斯化学株式会社 | 透明樹脂積層体並びにそれを用いた透明基板材料及び透明保護材料 |
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