WO2013018835A1 - ポリカーボネート樹脂積層体 - Google Patents
ポリカーボネート樹脂積層体 Download PDFInfo
- Publication number
- WO2013018835A1 WO2013018835A1 PCT/JP2012/069604 JP2012069604W WO2013018835A1 WO 2013018835 A1 WO2013018835 A1 WO 2013018835A1 JP 2012069604 W JP2012069604 W JP 2012069604W WO 2013018835 A1 WO2013018835 A1 WO 2013018835A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polycarbonate resin
- structural unit
- resin laminate
- formula
- ppm
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Definitions
- the present invention relates to a polycarbonate resin laminate having excellent surface hardness, excellent color tone, and excellent impact resistance.
- Polycarbonate resin is excellent in mechanical properties such as impact resistance, electrical properties, heat resistance, moldability, transparency, etc., so it can be used for various display devices, automotive interior parts, or protective equipment. Widely used as a member. Among these, when a lightweight and transparent structural element is required, a sheet using a polycarbonate resin is often used, and at that time, a multilayer sheet or a hard coat process is applied. It is often done.
- Patent Document 1 reports a single-layer sheet of polycarbonate resin having a 2,2-bis (4-hydroxy-3-methylphenyl) propane skeleton. Although this polycarbonate resin sheet has a surface hardness of 2H as pencil hardness and a high surface hardness, the color tone of the sheet is poor and yellowish, so it cannot be used for applications where color tone is important. Moreover, impact resistance is also inferior.
- Patent Document 2 discloses a polycarbonate resin layer having a 2,2-bis (4-hydroxy-3-methylphenyl) propane skeleton on the surface layer and 2,2-bis (4-hydroxyphenyl) propane (core layer on the core layer). That is, a laminated sheet using a polycarbonate resin layer having a bisphenol A) skeleton has been reported.
- the polycarbonate resin having a bisphenol A skeleton has a pencil hardness of 2B, and the surface is easily scratched. Therefore, the surface hardness is improved by forming a laminate having a surface layer having a high surface hardness with respect to the core layer. Although this has a high surface hardness, it has a very poor impact resistance.
- Patent Document 3 reports a polycarbonate resin laminate in which a polycarbonate resin layer having a pencil hardness of HB or higher is used for the surface layer, a polycarbonate resin layer having a bisphenol A skeleton is used for the core layer, and the surface layer is hard-coated. Further, the impact resistance is insufficient, and a hard coat is essential for this laminate.
- Patent Document 4 reports a polycarbonate resin sheet obtained by copolymerizing cyclododecane biscresol and bisphenol A as a polycarbonate resin sheet having a high surface hardness. Was insufficient.
- Japanese Unexamined Patent Publication No. 64-69625 Japanese Unexamined Patent Publication No. 2010-188719 Japanese Unexamined Patent Publication No. 2011-88402 Japanese Unexamined Patent Publication No. 2010-126594
- polycarbonate resin In applications such as display device members, display device covers, protective device members, and automotive parts, surface hardness is high, color tone is good, and impact resistance is excellent. Required. However, until now, a polycarbonate resin sheet or a polycarbonate resin laminate having a high surface hardness and excellent color tone and impact resistance is not known regardless of the thickness of the sheet. It is an object of the present invention to provide a polycarbonate resin laminate having a high surface hardness and excellent color tone and impact resistance regardless of the thickness of the sheet.
- the present inventor has a resin layer on the surface made of a plurality of specific polycarbonate resins and a resin layer of one or more polycarbonate resins, and has a specific layer thickness.
- the present inventors have found that a laminate satisfying a specific surface hardness is useful for solving the above-described problems, and completed the present invention.
- the surface layer (A) includes at least a polycarbonate resin (a) having at least a structural unit represented by the following formula (1) and a polycarbonate resin (b) having a structural unit different from the polycarbonate resin (a). It is a layer made of a polycarbonate resin composition.
- the mass ratio of the polycarbonate resin (a) to the polycarbonate resin (b) in the surface layer (A) is in the range of 45:55 to 99: 1.
- the pencil hardness defined by ISO 15184 measured from the surface layer (A) side of the polycarbonate resin laminate is H or more.
- the resin layer (B) further comprises a polycarbonate resin composition containing a polycarbonate resin (a), and the proportion of the polycarbonate resin (a) in the resin layer (B) is 30 to 1% by mass, and the polycarbonate resin (b ) Is a polycarbonate resin laminate according to the above [3].
- the polycarbonate resin (a) includes a structural unit derived from a compound represented by the following formula (8), and the content of the structural unit is 20 ppm or more and 1,000 ppm or less.
- R 1 represents a hydrogen atom or a methyl group.
- R 1 represents a hydrogen atom or a methyl group.
- the polycarbonate resin (a) includes a structural unit derived from a compound represented by the following formula (9), and the content of the structural unit is 10 ppm or more and 3,500 ppm or less.
- the polycarbonate resin composition constituting the surface layer (A) and / or the resin layer (B) comprises at least one stabilizer selected from the group consisting of a phosphorus stabilizer, a phenol stabilizer and a sulfur stabilizer.
- a protective window, a display device member, a display device cover, a protective device member, or an in-vehicle component for a portable display body comprising the polycarbonate resin laminate according to any one of [1] to [15].
- the polycarbonate resin laminate of the present invention has excellent surface hardness, good color tone, and excellent impact resistance. Therefore, a display device member, a display device cover, a protective member, an in-vehicle component, etc. It can be particularly preferably used. Thereby, it is useful for applications such as a protective window for a portable display, for example, where surface hardness is particularly required.
- the surface layer (A) in the polycarbonate resin laminate of the present invention has a large portion in contact with the outside, and the hardness and color tone are highly likely to determine the superiority of product quality.
- the surface layer (A) is a polycarbonate resin composition containing at least a polycarbonate resin (a) having at least a structural unit represented by the formula (1) and a polycarbonate resin (b) having a structural unit different from the polycarbonate resin (a). It is a layer consisting of things.
- the surface layer (A) has high surface hardness, excellent color tone, and excellent impact resistance.
- the polycarbonate resin (a) only one kind may be used, or two or more kinds of raw material dihydroxy compounds, production methods, and different viscosity average molecular weights may be mixed and used.
- the constituent part of the polycarbonate resin (a) having at least the structural unit represented by the formula (1), and the constituent part of the polycarbonate resin (b) having a structural unit different from the polycarbonate resin (a) Is in the range of 45:55 to 99: 1, preferably 50:50 to 95: 5, more preferably 55:45 to 90:10, and even more preferably 60:40 to 85. : 15.
- the structural unit contained in the polycarbonate resin (b) of the surface layer (A) is preferably represented by the following formula (2).
- X is the following group.
- R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon which may have a substituent having 6 to 12 carbon atoms. Indicates a group.
- Z is preferably bonded to carbon C bonded to the two phenyl groups in the above formula (2) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms.
- the divalent alicyclic carbon hydrogen group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. It is done.
- the substituted ones include those having these methyl substituents and ethyl substituents.
- a cyclohexylidene group a methyl-substituted cyclohexylidene group (preferably 3,3,5-trimethyl-substituted), and a cyclododecylidene group are preferable.
- polycarbonate structural unit represented by the above formula (2) examples include 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “bisphenol A”), that is, the following formula It is a structural unit derived from bisphenol A represented by (2a).
- bisphenol A 2,2-bis (4-hydroxyphenyl) propane
- the polycarbonate resin having the structural unit of the formula (2a) can be obtained by using 2,2-bis (4-hydroxyphenyl) propane as a monomer.
- the surface layer (A) constituting the polycarbonate resin laminate of the present invention is a mixture of the polycarbonate resin (a) having the structural unit of the formula (1) and the polycarbonate resin (b) having the structural unit of the formula (2). It may be a composition resin, or may be a copolymer resin containing at least each structural unit. More preferred is a mixed composition in which the composition ratio can be easily changed. The mixed composition and copolymer resin may further contain other structural units other than the structural units of the formulas (1) and (2). In addition, content of the said structural unit in polycarbonate resin can be calculated
- each structural unit depends on the dihydroxy compound used when synthesizing the polycarbonate resin, which is observed when 1 H-NMR measurement of a deuterated chloroform solution of the polycarbonate resin is performed using a nuclear magnetic resonance apparatus (NMR apparatus).
- NMR apparatus nuclear magnetic resonance apparatus
- the molar composition of each structural unit can be determined from the characteristic signal area intensity ratio.
- the mass ratio of each structural unit is determined from the obtained molar composition and the formula amount of each structural unit.
- the resin layer (B) of the polycarbonate resin laminate of the present invention contains at least the polycarbonate resin (b), 100 to 70% by mass of the polycarbonate resin (b), and 0 to 30% by mass of the polycarbonate resin (a). It is preferable to consist of a polycarbonate resin composition. More preferably, the polycarbonate resin (b) is 99 to 70% by mass, and the polycarbonate resin (a) is 1 to 30% by mass. More preferably, the polycarbonate resin (b) is 99 to 80% by mass and the polycarbonate resin (a) is 1 to 20% by mass.
- the polycarbonate resin of the resin layer (B) does not necessarily need to be a resin having high hardness like the polycarbonate resin of the surface layer (A), and the cost of the polycarbonate resin laminate can be reduced by using a less expensive resin. It becomes possible to reduce.
- the polycarbonate resin (a) contained in the resin layer (B) is the same as the polycarbonate resin (a) contained in the surface layer (A), that is, 2,2-bis (3-methyl-4- Hydroxyphenyl) propane structural unit.
- Polycarbonate resin (a) can also have structural units other than the structural unit of said Formula (1). For example, you may have the structural unit derived from the structural unit of the said Formula (2), or another dihydroxy compound.
- the content ratio of structural units other than the structural unit of the formula (1) is usually 60 mol% or less, preferably 55 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, especially It is preferably 30 mol% or less, particularly preferably 20 mol% or less, particularly preferably 10 mol% or less, and most preferably 5 mol% or less.
- the polycarbonate resin (b) contained in the resin layer (B) is the same as the polycarbonate resin (b) contained in the surface layer (A) and has at least a structural unit represented by the formula (2).
- the description of the polycarbonate resin (b) which is a polycarbonate resin and contained in the surface layer (A) described above is similarly applied.
- the polycarbonate resin laminate of the present invention has at least the surface layer (A) and the resin layer (B), so that the surface hardness is high, the impact is high, and the color tone is excellent. it can.
- the polycarbonate resin laminate of the present invention preferably has a yellow index of 7 or less, more preferably 9 or less, more preferably 9 or less, when a 7% by mass methylene chloride solution dissolved in methylene chloride is measured at an optical path length of 50 mm. 8 or less.
- the yellow index is large, the color tone is deteriorated and the design as a laminate is poor, and particularly in a laminate requiring coloring, the brightness is not sufficient, and there is a possibility that the color becomes dull.
- the thickness of the surface layer (A) is preferably smaller than the thickness of the resin layer (B), and the surface hardness (measured in accordance with ISO 15184) measured from the surface layer (A) side is preferably H or more in pencil hardness. .
- the pencil hardness is less than H, the polycarbonate resin laminate tends to be damaged when it is made into a product.
- the pencil hardness is 2B, B, HB, F, H, 2H, 3H, 4H from the lowest rank.
- the pencil hardness of the polycarbonate resin laminate is measured by the method described in Examples described later.
- the polycarbonate resin (a) preferably has a higher pencil hardness as defined by ISO 15184 than the polycarbonate resin (b).
- the pencil hardness defined by ISO 15184 of the polycarbonate resin (a) is preferably H or higher, more preferably 2H or higher. If the pencil hardness of the polycarbonate resin (a) is not H or higher, it is difficult to obtain a polycarbonate resin laminate having a high surface hardness.
- the pencil hardness defined by ISO 15184 of the polycarbonate resin (b) is 3B or more, particularly 2B or more in a range lower than the pencil hardness of the polycarbonate resin (a), for example, one step or more lower as the pencil hardness. It is preferable that However, since the surface hardness of the polycarbonate resin laminated body obtained when the pencil hardness of polycarbonate resin (b) is too low falls, it is preferable that it is more than said hardness.
- regulated by ISO 15184 of a polycarbonate resin (a) and a polycarbonate resin (b) is measured by the method described in the term of the below-mentioned Example.
- the polycarbonate resin laminate of the present invention has a high surface hardness, excellent color tone, and excellent impact resistance when the surface layer (A) is a layer mainly composed of the polycarbonate resin (a). Further, on such a surface layer (A), a resin layer (B) containing at least a polycarbonate resin (b) different from the polycarbonate resin (a) is laminated to form a multilayer, and the surface layer (A) is changed to a resin layer (B ), The laminate is free of brittleness and has a better balance of surface hardness, color tone, and impact resistance.
- the polycarbonate resin laminate is too thick, for example, during the production of a laminate by coextrusion, even if the laminate surface is cooled on a cooling roll, the inside of the laminate is cooled later, and the inside shrinks and laminates. The body surface may become rough. If the polycarbonate resin laminate is too thin, it may be easily broken.
- the thickness of the polycarbonate resin laminate is preferably 100 to 6,000 ⁇ m, more preferably 100 to 5,000 ⁇ m, still more preferably 300 to 4,000 ⁇ m, and particularly preferably 300 to 1,500 ⁇ m.
- the thickness of the surface layer (A) is preferably thinner than the thickness of the resin layer (B). If the surface layer (A) is excessively thick and the resin layer (B) is thin, the laminate becomes brittle and it may be difficult to balance the surface hardness, color tone, and impact resistance. Conversely, if the surface layer (A) is excessively thin and the resin layer (B) is excessively thick, there is a possibility that a high surface hardness due to the surface layer (A) cannot be obtained sufficiently.
- the thickness of the surface layer (A) is preferably 5 to 1,000 ⁇ m, more preferably 20 to 1,000 ⁇ m, and still more preferably 20 to 200 ⁇ m.
- the thickness of the resin layer (B) is preferably 10 to 5,000 ⁇ m, more preferably 300 to 4,000 ⁇ m, and still more preferably 1,000 to 3,000 ⁇ m.
- the polycarbonate resin laminate of the present invention has a two-layer laminate structure of a surface layer (A) and a resin layer (B), but if necessary, between the surface layer (A) and the resin layer (B). May be provided with an adhesive layer, other functional layers, and the like. Moreover, an adhesive layer, other functional layers, etc. may be provided on the surface layer (A) side.
- the viscosity average molecular weights (Mv) of the polycarbonate resins (a) and (b) in the surface layer (A) and the resin layer (B) constituting the polycarbonate resin laminate of the present invention are all 18,000 to 33,000. Preferably there is.
- Mv is too high, the melt viscosity of the composition containing the polycarbonate resins (a) and (b) becomes high, which may make it difficult to mold the polycarbonate resin laminate.
- Mv is too low, molding of the polycarbonate resin laminate may be difficult, and cracking may occur in the polycarbonate resin laminate.
- the Mv of the polycarbonate resins (a) and (b) is more preferably 30,000 or less, still more preferably 28,000 or less, and the lower limit is more preferably 20,000.
- the polycarbonate resins (a) and (b) may be adjusted to the above Mv by mixing two or more kinds of polycarbonate resins having different Mv. Moreover, you may mix and use the polycarbonate resin which Mv is outside said suitable range as needed.
- the polycarbonate resin laminate of the present invention contains a specific amount of a structural unit derived from a compound by-produced when producing a polycarbonate resin at a high temperature such as a melt polymerization reaction or when producing a polycarbonate resin laminate. It is preferable.
- the structural unit derived from the following formula (8), formula (9), and formula (10) is included in a specific amount, the thickness unevenness of the polycarbonate resin laminate is reduced, or the appearance defect such as foreign matter is reduced. It becomes possible to suppress, and it becomes possible to obtain the polycarbonate resin laminated body provided with the outstanding performance.
- R 1 represents a hydrogen atom or a methyl group.
- the content of each structural unit in the polycarbonate resin laminate is preferably as follows. That is, the content of the structural unit derived from the compound represented by the formula (8) in the polycarbonate resin laminate is preferably 0.05 to 1,000 ppm, more preferably 0.5 to 500 ppm, and still more preferably. 1.0 to 250 ppm, particularly preferably 1.5 to 100 ppm, most preferably 2 to 30 ppm.
- the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large.
- the content of the structural unit derived from the compound represented by the formula (9) is preferably 0.02 to 3,500 ppm, more preferably 1.0 to 2,500 ppm, still more preferably 10 to 1, It is 300 ppm, particularly preferably 30 to 800 ppm, most preferably 100 to 400 ppm.
- the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large.
- the content of the structural unit derived from the compound represented by the formula (10) is preferably 0.1 to 600 ppm, more preferably 0.5 to 300 ppm, still more preferably 1.0 to 200 ppm, particularly preferably. Is from 1.5 to 150 ppm, most preferably from 2.0 to 100 ppm.
- the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large.
- the polycarbonate resin laminate of the present invention is produced using a specific amount of the polycarbonate resin (a). Therefore, it is preferable that the polycarbonate resin (a) contains a specific amount of structural units derived from the formula (8), formula (9), and formula (10). That is, the content of the structural unit derived from the compound represented by the formula (8) in the polycarbonate resin (a) is preferably 20 ppm or more and 1,000 ppm or less, more preferably 30 to 800 ppm, and further preferably 40 to 600 ppm. preferable. When there is too little content of the structural unit derived from the compound represented by said Formula (8), the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large. Moreover, when there is too much, there exists a possibility that a foreign material may generate
- the content of the structural unit derived from the compound represented by the formula (9) is preferably 10 ppm or more and 3,500 ppm or less, more preferably 30 to 3,000 ppm, and further preferably 40 to 2,000 ppm.
- the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large.
- the content of the structural unit derived from the compound represented by the formula (10) is preferably 40 ppm or more and 600 ppm or less, more preferably 50 to 400 ppm, and still more preferably 60 to 300 ppm.
- the melt viscosity change with respect to temperature will be large, and the thickness spot of a laminated body may become large.
- the amount of the structural unit derived from the above formula (8), formula (9), and formula (10) is quantified by the following alkaline hydrolysis method. That is, it is measured by liquid chromatography after alkali hydrolysis of the polycarbonate resin or polycarbonate resin laminate. Specifically, 0.5 g of polycarbonate resin or polycarbonate resin laminate is dissolved in 5 ml of methylene chloride. A solution obtained by adding 45 ml of methanol and 5 ml of a 25% by weight aqueous sodium hydroxide solution to the solution and stirring for 30 minutes at 70 ° C. was analyzed by liquid chromatography, and the compound represented by the formula (8), It is calculated by quantifying the amount of the compound represented by the formula (9) and the compound represented by the formula (10).
- each content of the compound represented by said Formula (8), Formula (9), and Formula (10) means content of the structural unit derived from each compound.
- the manufacturing method of polycarbonate resin (a) and (b) used by this invention is demonstrated below.
- the polycarbonate resin (a) and the polycarbonate resin (b) may be collectively referred to as a polycarbonate resin.
- the polycarbonate resin is obtained by polymerization using a dihydroxy compound and a carbonyl compound.
- an interfacial polycondensation method for producing a polycarbonate resin by reacting a dihydroxy compound and carbonyl chloride (sometimes referred to as “phosgene”) at an interface between an organic phase and an aqueous phase that are not mixed arbitrarily.
- interface method a melt polycondensation method in which a polycarbonate resin is produced by transesterifying a dihydroxy compound and a carbonyl compound in the presence of a transesterification catalyst in a molten state, for example.
- a melting method a melt polycondensation method in which a polycarbonate resin is produced by transesterifying a dihydroxy compound and a carbonyl compound in the presence of a transesterification catalyst in a molten state, for example.
- polycarbonate resin produced by the melting method is suitable for extrusion molding because of its viscosity characteristics at the time of melting. That is, in the case of extrusion molding, it is preferable to use a polycarbonate resin produced by a melting method.
- ⁇ Interface method> In the method for producing a polycarbonate resin by the interfacial method, an alkaline aqueous solution of a dihydroxy compound is usually prepared, and as a condensation catalyst, for example, an interfacial polycondensation reaction between the dihydroxy compound and phosgene is performed in the presence of an amine compound, followed by neutralization, A polycarbonate resin is obtained through a washing and drying process.
- a condensation catalyst for example, an interfacial polycondensation reaction between the dihydroxy compound and phosgene is performed in the presence of an amine compound, followed by neutralization, A polycarbonate resin is obtained through a washing and drying process.
- the polycarbonate resin production process by the interfacial method is a raw material process for preparing raw materials such as monomer components, an oligomerization process in which an oligomerization reaction is performed, a polycondensation process in which a polycondensation reaction using an oligomer is performed, A washing step for washing the reaction solution after the polycondensation reaction by alkali washing, acid washing and water washing, a polycarbonate resin isolation step for concentrating the washed reaction solution and isolating the polycarbonate resin after granulation It has at least a drying step of drying the polycarbonate resin particles.
- each step will be described.
- dihydroxy compound examples of the dihydroxy compound that is a raw material of the polycarbonate resin include one or more of the above-described dihydroxy compounds.
- alkali metal compound and / or alkaline earth metal compound As the alkali metal compound and / or alkaline earth metal compound, a hydroxide is usually preferable. For example, one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like are used. Is mentioned. Among these, sodium hydroxide is particularly preferable.
- the ratio of the alkali metal compound and / or alkaline earth metal compound to the dihydroxy compound is usually 1.0 to 1.5 (equivalent ratio), preferably 1.02 to 1.04 (equivalent ratio).
- the alkaline earth metal is a Group 2 element in the periodic table.
- a phosgenation reaction of a dihydroxy compound is carried out in a predetermined reactor using an alkaline aqueous solution of the dihydroxy compound prepared in the original preparation step and phosgene in the presence of an organic solvent such as methylene chloride. Is called.
- a condensation catalyst such as triethylamine and a chain terminator such as pt-butylphenol are added to the mixed solution in which the phosgenation reaction of the dihydroxy compound has been performed, and an oligomerization reaction of the dihydroxy compound is performed.
- the oligomerization reaction liquid of the dihydroxy compound was introduced into a predetermined stationary separation tank after further oligomerization reaction, and the organic phase containing the carbonate oligomer and the aqueous phase were separated and separated.
- the organic phase is fed to the polycondensation step.
- the residence time in the oligomerization step from when the alkaline aqueous solution of the dihydroxy compound is supplied to the reactor in which the phosgenation reaction of the dihydroxy compound is performed until entering the stationary separation tank is usually 120 minutes or less, preferably 30 to 60 minutes.
- the phosgene used in the oligomerization step is usually used in liquid or gaseous form.
- the preferred amount of phosgene used in the oligomerization step is appropriately selected depending on the reaction conditions, particularly the reaction temperature and the concentration of the dihydroxy compound in the aqueous phase, and is not particularly limited. Usually, it is 1 to 2 moles, preferably 1.05 to 1.5 moles of phosgene with respect to 1 mole of the dihydroxy compound.
- the amount of phosgene used is excessively large, unreacted phosgene increases and the basic unit tends to be extremely deteriorated.
- the amount of phosgene used is too small, the amount of chloroformate group is insufficient, and there is a tendency that proper molecular weight extension is not performed.
- organic solvent In the oligomerization step, an organic solvent is usually used.
- organic solvent reaction products such as phosgene and carbonate oligomers and polycarbonate resins are dissolved at the reaction temperature and reaction pressure in the oligomerization step, and are not compatible with water (or do not form a solution with water).
- An active organic solvent is mentioned.
- inert organic solvents examples include chlorinated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene; benzene, toluene, xylene, and the like.
- chlorinated hydrocarbons such as dichloromethane and chlorobenzene are preferably used.
- These inert organic solvents can be used alone or as a mixture with other solvents.
- the oligomerization reaction can be performed in the presence of a condensation catalyst.
- the addition timing of the condensation catalyst is preferably after phosgene is consumed.
- the condensation catalyst can be arbitrarily selected from many condensation catalysts used in the two-phase interfacial condensation method. Examples thereof include one or more of trialkylamine, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine, N-isopropylmorpholine and the like. Of these, triethylamine and N-ethylpiperidine are preferable.
- monophenol is usually used as a chain terminator.
- monophenols include phenols; alkylphenols such as pt-butylphenol and p-cresol (the alkyl group has 1 to 20 carbon atoms); halogens such as p-chlorophenol and 2,4,6-tribromophenol. 1 type (s) or 2 or more types of modified phenol are mentioned.
- the amount of monophenol used is appropriately selected according to the molecular weight of the carbonate oligomer obtained, and is usually 0.5 to 10 mol%, preferably 6 to 8 mol%, based on the dihydroxy compound.
- the molecular weight of the polycarbonate resin is determined by the addition amount of a chain terminator such as monophenol.
- the chain stopper is preferably added immediately after the consumption of the carbonate-forming compound is completed and before the molecular weight extension starts.
- a chain terminator such as monophenol.
- the chain stopper is preferably added immediately after the consumption of the carbonate-forming compound is completed and before the molecular weight extension starts.
- monophenol is added in the presence of a carbonate-forming compound, a large amount of condensates (diphenyl carbonates) of monophenols are produced, and it is difficult to obtain a polycarbonate resin having a target molecular weight.
- the addition time of monophenol is extremely delayed, it becomes difficult to control the molecular weight, resulting in a resin having a specific shoulder on the low molecular weight side in the molecular weight distribution, which tends to cause problems such as sagging during molding.
- Branching agent Any branching agent can be used in the oligomerization step.
- Such branching agents include, for example, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4- Examples thereof include one or more of hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, 1,4-bis (4,4′-dihydroxytriphenylmethyl) benzene and the like.
- 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and the like can also be used.
- a branching agent having at least three phenolic hydroxyl groups is preferable.
- the amount of branching agent used is appropriately selected according to the degree of branching of the carbonate oligomer obtained, and is usually preferably 0.05 to 2 mol%, more preferably 0.1 to 1 mol%, based on the dihydroxy compound.
- the organic phase containing the dihydroxy compound, the alkali metal compound, and the alkali metal compound aqueous solution and / or the alkaline earth metal compound aqueous solution of the dihydroxy compound and the phosgene are contacted. It is particularly preferred that an aqueous phase containing an alkaline earth metal compound is brought into contact with an organic phase not arbitrarily mixed with water to form an emulsion.
- Examples of means for forming such an emulsion include a stirrer having a predetermined stirring blade, a homogenizer, a homomixer, a colloid mill, a flow jet mixer, a dynamic mixer such as an ultrasonic emulsifier, a static mixer, and the like. It is preferable to use a mixer.
- the emulsion usually has a droplet diameter of 0.01 to 10 ⁇ m and has emulsion stability.
- the emulsion state of the emulsion is usually represented by the Weber number or P / q (load power value per unit volume).
- the Weber number is preferably 10,000 or more, more preferably 20,000 or more, and most preferably 35,000 or more. Also, about 1,000,000 is sufficient as the upper limit.
- P / q is preferably 200 kg ⁇ m / L or more, more preferably 500 kg ⁇ m / L or more, and most preferably 1,000 kg ⁇ m / L or more.
- the contact between the emulsion and phosgene (CDC) is preferably carried out under mixing conditions that are weaker than the emulsification conditions described above in terms of suppressing the dissolution of CDC in the organic phase.
- the Weber number is less than 10,000, preferably less than 5,000, and more preferably less than 2,000. Further, P / q is less than 200 kg ⁇ m / L, preferably less than 100 kg ⁇ m / L, and more preferably less than 50 kg ⁇ m / L.
- the contact of phosgene can be achieved by introducing CDC into a tubular reactor or tank reactor.
- the reaction temperature in the oligomerization step is usually 80 ° C. or lower, preferably 60 ° C. or lower, more preferably 10 to 50 ° C.
- the reaction time is appropriately selected depending on the reaction temperature, and is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. If the reaction temperature is excessively high, side reactions cannot be controlled and the phosgene basic unit tends to deteriorate. If the reaction temperature is excessively low, this is a favorable situation in terms of reaction control, but the refrigeration load increases and the cost tends to increase.
- the carbonate oligomer concentration in the organic phase may be in a range in which the obtained carbonate oligomer is soluble, and is specifically preferably about 10 to 40% by mass, more preferably 12 to 25% by mass.
- the proportion of the organic phase is preferably a volume ratio of 0.2 to 1.0 with respect to the aqueous phase containing the aqueous alkali metal salt solution or alkaline earth metal salt solution of the dihydroxy compound.
- the organic phase containing the carbonate oligomer separated from the aqueous phase in the stationary separation tank is transferred to an oligomer storage tank having a stirrer.
- a condensation catalyst such as triethylamine is further added to the oligomer storage tank.
- the organic phase stirred in the oligomer storage tank is introduced into a predetermined polycondensation reaction tank.
- an organic solvent such as demineralized water and methylene chloride, an aqueous sodium hydroxide solution, and the like are supplied into the polycondensation reaction tank, and the mixture is stirred and mixed to carry out a polycondensation reaction of the carbonate oligomer.
- the polycondensation reaction liquid in the polycondensation reaction tank is successively and sequentially introduced into a plurality of polycondensation reaction tanks. Thereby, the polycondensation reaction of the carbonate oligomer is completed.
- the residence time in the polycondensation reaction tank in which the polycondensation reaction of the carbonate oligomer is continuously carried out is usually 12 hours or less, preferably 0.5 to 5 hours.
- an organic phase containing a carbonate oligomer and an aqueous phase are separated, and an inert organic solvent is added to the separated organic phase as necessary to adjust the concentration of the carbonate oligomer.
- the amount of the inert organic solvent is adjusted so that the concentration of the polycarbonate resin in the organic phase obtained by the polycondensation reaction is 5 to 30% by mass, preferably 8 to 14% by mass.
- a condensation catalyst is preferably added, and a polycondensation reaction is performed according to the interfacial polycondensation method. I do.
- alkali metal compound and / or alkaline earth metal compound examples include compounds similar to those used in the oligomerization step described above. Of these, sodium hydroxide is preferred industrially.
- the amount of the alkali metal compound and / or alkaline earth metal compound used may be at least the amount by which the reaction system is always kept alkaline during the polycondensation reaction. These compounds may be added all at once at the start of the polycondensation reaction, or may be added in appropriate divided portions during the polycondensation reaction.
- the concentration of the alkali metal compound and / or alkaline earth metal compound contained in the aqueous phase after completion of the polycondensation reaction is preferably 0.05 N (normality) or more, more preferably about 0.05 to 0.3 N. It is good to be.
- the temperature of the polycondensation reaction in the polycondensation step is usually around room temperature.
- the reaction time is about 0.5 to 5 hours, preferably about 1 to 3 hours.
- the polycondensation reaction solution is subjected to alkali washing with an alkali washing solution, acid washing with an acid washing solution, and water washing with washing water by a known method.
- the total residence time in the washing step is usually 12 hours or less, preferably 0.5 to 6 hours.
- the polycondensation reaction solution containing the polycarbonate resin washed in the washing step is prepared as a concentrated solution concentrated to a predetermined solid content concentration.
- the solid content concentration of the polycarbonate resin in the concentrated liquid is usually 5 to 35% by mass, preferably 10 to 30% by mass.
- the concentrate is continuously supplied to a predetermined granulation tank, and stirred and mixed with demineralized water at a predetermined temperature.
- a granulation treatment for evaporating the organic solvent while maintaining a suspended state in water is performed, and a water slurry containing polycarbonate resin granules is formed.
- the temperature of the demineralized water is usually 37 to 67 ° C, preferably 40 to 50 ° C.
- the solidification temperature of the polycarbonate resin by the granulation treatment performed in the granulation tank is usually 37 to 67 ° C., preferably 40 to 50 ° C.
- the water slurry containing the polycarbonate resin powder continuously discharged from the granulation tank is then continuously introduced into a predetermined separator, and water is separated from the water slurry.
- the drying process in the separator, the polycarbonate resin powder from which water has been separated from the water slurry is continuously supplied to a predetermined dryer, retained for a predetermined residence time, and then continuously extracted.
- the dryer include a fluidized bed dryer.
- a plurality of fluidized bed dryers may be connected in series to continuously perform the drying process.
- the dryer usually has a heating means such as a heat medium jacket, and is usually maintained at 0.1 to 1.0 MPa-G, preferably 0.2 to 0.6 MPa-G with water vapor, for example.
- the temperature of nitrogen (N 2 ) flowing through the dryer is usually kept at 100 to 200 ° C., preferably 120 to 180 ° C.
- a polycarbonate resin is produced by subjecting a dihydroxy compound and a carbonyl compound to a transesterification reaction in a molten state in the presence of a transesterification reaction catalyst.
- dihydroxy compound Specific examples of the dihydroxy compound that is a raw material of the polycarbonate resin include one or more of the dihydroxy compounds as described above.
- Carbonated diester Examples of the carbonic acid diester that is a raw material of the polycarbonate resin include compounds represented by the following formula (3).
- A is an optionally substituted linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Two A's may be the same or different from each other.
- the substituent on A includes a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group, Examples include groups.
- the carbonic acid diester examples include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.
- diphenyl carbonate hereinafter sometimes referred to as “DPC”
- substituted diphenyl carbonate are preferable.
- These carbonic acid diesters can be used alone or in admixture of two or more.
- the carbonic acid diester may be substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.
- Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.
- the amount of these carbonic acid diesters is usually 1 carbonic acid diester per 1 mol of the dihydroxy compound. .01 to 1.30 mol, preferably 1.02 to 1.20 mol. If the amount of carbonic acid diester used is excessively small, the transesterification rate will decrease, making it difficult to prepare a polycarbonate resin having the desired molecular weight, or the terminal hydroxyl group concentration of the resulting polycarbonate resin will be high, resulting in thermal stability. It may get worse.
- transesterification catalyst examples include a catalyst used when producing a polycarbonate resin by an ordinary transesterification method, and are not particularly limited.
- examples thereof include basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds.
- basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds.
- an alkali metal compound and an alkaline earth metal compound are preferable for practical use.
- These transesterification catalysts may be used alone or in combination of two or more.
- the amount of the transesterification catalyst used is usually in the range of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 3 mol per 1 mol of all dihydroxy compounds.
- the transesterification catalyst is preferably used in an amount of 1. It is in the range of 0 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 4 mol, more preferably in the range of 1.0 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 5 mol, and particularly preferably in the range of 1.0 ⁇ 10 ⁇ 7 to Within the range of 5.0 ⁇ 10 ⁇ 6 mol.
- the amount of the transesterification catalyst used is less than the above lower limit amount, the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight may not be obtained.
- the amount of branching component is too large, the fluidity is lowered, and a polycarbonate resin having excellent target melting characteristics cannot be produced.
- alkali metal compound examples include inorganic alkali metal compounds such as alkali metal hydroxides, carbonates and hydrogen carbonate compounds; organic alkali metal compounds such as salts with alkali metal alcohols, phenols and organic carboxylic acids; Can be mentioned.
- alkali metal lithium, sodium, potassium, rubidium, cesium etc. are mentioned, for example.
- cesium compounds are preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.
- alkaline earth metal compound examples include inorganic alkaline earth metal compounds such as alkaline earth metal hydroxides and carbonates; salts of alkaline earth metal alcohols, phenols, and organic carboxylic acids; Can be mentioned.
- alkaline earth metal examples include beryllium, magnesium, calcium, strontium, and barium.
- Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, strontium salts, and the like of boron compounds.
- the boron compound for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl Examples include benzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.
- Examples of basic phosphorus compounds include trivalent phosphorus compounds such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, and tributylphosphine, or derivatives thereof. And quaternary phosphonium salts.
- Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydride Kishido, butyl triphenyl ammonium hydroxide, and the like.
- amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
- Catalyst deactivator In the melting method, after the transesterification reaction, a catalyst deactivator for neutralizing and deactivating the transesterification catalyst may be added. Addition of the catalyst deactivator improves the heat resistance and hydrolysis resistance of the obtained polycarbonate resin.
- the catalyst deactivator is preferably an acidic compound having a pKa of 3 or less, such as sulfonic acid or sulfonic acid ester.
- benzenesulfonic acid p-toluenesulfonic acid, methyl benzenesulfonate, ethylbenzenebenzene Propyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, and the like.
- the above may be used.
- p-toluenesulfonic acid and p-toluenesulfonic acid butyl are preferably used.
- a method for producing a polycarbonate resin by a melting method is to prepare a raw material mixed melt of a raw material dihydroxy compound and a carbonic acid diester (original preparation step), and the raw material mixed melt in a molten state in the presence of a transesterification catalyst.
- a polycondensation reaction is performed in multiple stages using a plurality of reaction vessels (polycondensation step).
- the reaction system may be any of a batch system, a continuous system, or a combination of a batch system and a continuous system.
- As the reaction tank for example, a plurality of vertical stirring reaction tanks and, if necessary, at least one horizontal stirring reaction tank are used. Usually, these reaction tanks are installed in series and processed continuously.
- Dihydroxy compounds and carbonic acid diesters used as raw materials for polycarbonate resins are usually mixed and melted using a batch, semi-batch or continuous stirring tank type device in an inert gas atmosphere such as nitrogen or argon. Prepared as a liquid.
- the melt mixing temperature is usually 120 to 180 ° C., preferably 125 to 160 ° C.
- a case where bisphenol A is used as a dihydroxy compound and diphenyl carbonate is used as a raw material as a carbonic acid diester will be described as an example.
- the ratio of the dihydroxy compound to the carbonic acid diester is adjusted so that the carbonic acid diester becomes excessive.
- the carbonic acid diester is usually 1.01 to 1.30 moles per mole of the dihydroxy compound. Preferably, it is adjusted to a ratio of 1.02 to 1.20 mol.
- the polycondensation reaction by the transesterification reaction between the dihydroxy compound and the carbonic acid diester is usually carried out continuously in a multistage system of two or more stages, preferably 3 to 7 stages. Specific reaction conditions at each stage are temperature: 150 to 320 ° C., pressure: normal pressure to 0.01 Torr (1.3 Pa), and average residence time: 5 to 150 minutes.
- the above reaction conditions are carried out in stages and at higher temperatures. Set to high vacuum.
- reaction vessels including a vertical stirring reaction vessel are provided to increase the average molecular weight of the polycarbonate resin.
- 2 to 6 reaction tanks preferably 4 to 5 reactors are installed.
- the reaction tank include a stirring tank type reaction tank, a thin film reaction tank, a centrifugal thin film evaporation reaction tank, a surface renewal type biaxial kneading reaction tank, a biaxial horizontal type stirring reaction tank, a wet wall reaction tank, Examples include a perforated plate type reaction vessel for polycondensation, a perforated plate type reaction vessel with a wire for polycondensation while dropping along a wire.
- the types of stirring blades in the vertical stirring reaction tank include, for example, turbine blades, paddle blades, fiddler blades, anchor blades, full zone blades (manufactured by Shinko Environmental Solution Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max Blend blades ( Sumitomo Heavy Industries, Ltd.), helical ribbon blades, twisted lattice blades (manufactured by Hitachi Plant Technology).
- a horizontal stirring reaction tank means that the rotating shaft of a stirring blade is a horizontal type (horizontal direction).
- a stirring blade of a horizontal stirring reaction tank for example, a single-shaft stirring blade such as a disk type or a paddle type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries), Vivolac (manufactured by Sumitomo Heavy Industries, Ltd.), Alternatively, a biaxial stirring blade such as a spectacle blade or a lattice blade (manufactured by Hitachi Plant Technology) may be used.
- the transesterification catalyst used for the polycondensation reaction of a dihydroxy compound and a carbonic acid diester may usually be prepared as a solution in advance.
- the concentration of the catalyst solution is not particularly limited, and is adjusted to an arbitrary concentration according to the solubility of the catalyst in the solvent.
- the solvent acetone, alcohol, toluene, phenol, water and the like can be appropriately selected.
- water is selected as the solvent, the properties of water are not particularly limited as long as the type and concentration of impurities contained are constant, but usually distilled water, deionized water, and the like are preferably used.
- composition of the polycarbonate resins (a) and (b) is preferably prepared by the following methods (1) to (4).
- each method will be described.
- the pellets or granules of the polycarbonate resin (a) and the pellets or granules of the polycarbonate resin (b) are melt-kneaded using a mixing device such as a kneader, a twin screw extruder, or a single screw extruder, for example.
- the pellets or granules of the polycarbonate resin (a) and the pellets or granules of the polycarbonate resin (b) may be mixed in advance in a solid state and then kneaded, or one of them may be mixed first.
- the other polycarbonate resin may be added thereto and kneaded.
- the kneading temperature is not particularly limited, but is preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and further preferably 260 ° C. or higher. Moreover, 350 degrees C or less is preferable and 320 degrees C or less is especially preferable.
- the kneading temperature is low, the mixing of the polycarbonate resin (a) and the polycarbonate resin (b) is not complete, and when the polycarbonate resin laminate is produced, the pencil hardness and the like may vary. If the kneading temperature is too high, the content of structural units derived from the above formula (8), formula (9), and formula (10) will increase too much, and foreign matter may be generated in the polycarbonate resin laminate. The color tone may deteriorate.
- the molten polycarbonate resin (a) and the molten polycarbonate resin (b) are mixed using a mixing apparatus such as a stirring tank, a static mixer, a kneader, a twin screw extruder, or a single screw extruder.
- a mixing apparatus such as a stirring tank, a static mixer, a kneader, a twin screw extruder, or a single screw extruder.
- a polycarbonate resin obtained by a melt polymerization method may be introduced into the mixing apparatus in a molten state without being cooled and solidified.
- the solvent examples include chlorinated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene; aromatic hydrocarbons such as benzene, toluene, and xylene; And substituted aromatic hydrocarbons such as nitrobenzene and acetophenone.
- chlorinated hydrocarbons such as dichloromethane and chlorobenzene are preferably used.
- These solvents can be used alone or as a mixture with other solvents.
- the mixing apparatus include a stirring tank and a static mixer.
- the mixing temperature is not particularly limited as long as the polycarbonate resin (a) and the polycarbonate resin (b) are dissolved, and the mixing temperature is usually below the boiling point of the solvent used.
- pellets or granules of polycarbonate resin (a) and pellets or granules of polycarbonate resin (b) are dry blended using a tumbler, super mixer, Henschel mixer, Nauter mixer or the like.
- the methods (1) to (4) the methods (1) and (2) in which the polycarbonate resin (a) and the polycarbonate resin (b) are melt-kneaded, or the polycarbonate resin (a) and the polycarbonate resin (b) ) Is preferably dry blended, and the method (1) of melt-kneading the polycarbonate resin (a) and the polycarbonate resin (b) is more preferable.
- additives are added to the polycarbonate resins (a) and (b).
- Such additives include polymer modifiers, heat stabilizers, antioxidants, ultraviolet absorbers, fluorescent brighteners, light stabilizers, colorants such as pigments and dyes, flame retardants, and antistatic agents.
- resin components other than polycarbonate resin for example, polyamide, polyethylene, polypropylene, polyester, polyphenylene ether, polystyrene, polyphenylene sulfide, polysulfone, polyethersulfone, ABS resin, SAN resin, as long as the effects of the present invention are not impaired.
- one or more liquid crystal polymers can be added and mixed.
- the total amount of the polycarbonate resin (a) and the polycarbonate resin (b) is 30% by mass or less, further 10% by mass or less, and particularly 5% by mass or less. preferable.
- polycarbonate resin composition as the polycarbonate resin (b), only one kind may be used, or two or more kinds of raw material dihydroxy compounds, production methods, and different viscosity average molecular weights may be mixed and used. . Similarly, only one type of polycarbonate resin (a) may be used, or two or more types of raw material dihydroxy compounds, production methods, and viscosity average molecular weights may be mixed and used.
- Coextrusion molding method preferably 100 to 200 ° C., more preferably 120 to 180 with respect to the glass transition temperature (hereinafter referred to as Tg) of the resin composition for the surface layer (A) and the resin layer (B).
- Tg glass transition temperature
- the barrel temperature of the extruder when producing a polycarbonate resin laminate is not particularly limited, but is preferably 360 ° C. or lower, more preferably 340 ° C. or lower, and most preferably 320 ° C. or lower.
- 220 degreeC or more is preferable
- 240 degreeC or more is more preferable
- 260 degreeC or more is especially preferable.
- the melt viscosity becomes low and it may be difficult to form a laminate.
- the content of structural units derived from the above formula (8), formula (9), and formula (10) may increase excessively, and foreign matter may be generated in the polycarbonate resin laminate or the color tone may deteriorate. is there.
- the barrel temperature is too low, the melt viscosity increases and the resin pressure increases, so that the T-die may be blocked.
- a die called a T die having a specific thickness is usually attached to the extruder, and the polycarbonate resin laminate is extruded from the T die in a molten state.
- the extruded polycarbonate resin laminate in a molten state is cooled by a roll to become a polycarbonate resin laminate having a uniform thickness.
- the cooling temperature by the roll is 80 to 160 ° C., preferably 90 to 140 ° C. If the roll temperature is too high, the molten polycarbonate resin laminate extruded from the T-die remains attached to the cooling roll, and the laminate cannot be molded. When the roll temperature is too low, the molten polycarbonate resin laminate extruded from the T-die is rapidly cooled on the cooling roll to generate gear marks, resulting in poor surface smoothness of the laminate.
- Injection molding method preferably at a temperature 100 to 200 ° C., more preferably 120 to 180 ° C. higher than the Tg of the resin composition for the surface layer (A) and the resin layer (B). Mold.
- the other is injection molded and integrated. To do.
- thermocompression bonding method Molded sheets of the resin composition for the surface layer (A) and the resin layer (B) previously molded by extrusion molding or injection molding are thermocompression bonded by a laminating machine or a press machine. Or the other sheet
- molded previously is thermocompression-bonded to one sheet
- the thermocompression bonding temperature is 100 to 200 ° C., preferably 90 to 140 ° C. higher than the higher Tg of the resin composition for the resin layer (A) and the resin layer (B).
- the polycarbonate resin laminate of the present invention can also be obtained by adhering preformed sheets of the resin composition for the surface layer (A) and the resin layer (B) using an adhesive or the like.
- waste materials such as cut pieces and burrs are discharged. Is done.
- these waste materials can be appropriately mixed with the resin composition for the surface layer (A) and the resin layer (B) and used for the next molding.
- the amount of these waste materials used is preferably 30% by mass or less, particularly 20% by mass or less, for example, about 0.1 to 10% by mass with respect to the entire raw material.
- additives can be blended in the resin composition for the surface layer (A) and the resin layer (B).
- additives include stabilizers, ultraviolet absorbers, mold release agents, flame retardants, colorants, antistatic agents, thermoplastic resins, thermoplastic elastomers, glass fibers, glass flakes, glass beads, carbon fibers, and wallasts. Examples thereof include knight, calcium silicate, and aluminum borate whisker.
- blend a stabilizer, a mold release agent, a ultraviolet absorber, a flame retardant, etc.
- the mixing method of the resin composition for the surface layer (A) and the resin layer (B) and additives is not particularly limited.
- a method of kneading with an extruder or the like a method of mixing a polycarbonate resin in a molten state and an additive, a melting method or Examples include a method of adding in the middle of the polymerization reaction of the raw material monomer in the interface method or at the end of the polymerization reaction.
- the polycarbonate resin composition preferably contains a stabilizer in order to prevent a decrease in molecular weight, color tone and transparency during molding.
- a stabilizer a phosphorus stabilizer, a phenol stabilizer, and a sulfur stabilizer are preferable.
- the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
- triphenyl phosphite tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, di Decyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4- Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl)
- phenol-based stabilizer examples include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) And hindered phenol stabilizers such as propionate).
- pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.
- These two hindered phenol stabilizers are commercially available from BASF under the names “Irganox 1010” and “Irganox 1076”.
- Sulfur stabilizers include tetrakis [methylene-3- (dodecylthio) propionate] methane, bis [2-methyl-4- ⁇ 3-n-alkyl (C 12 or C 14 ) thiopropionyloxy ⁇ -5-t- Examples include butylphenyl] sulfide, di- (tridecyl-thio) -di-propionate, di- (stearyl-thio) -di-propionate, di- (lauryl-thio) -di-propionate, and the like. These stabilizers can be used individually by 1 type or in combination of 2 or more types.
- the content of the stabilizer is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (a) and the polycarbonate resin (b). 1 mass part or less is preferable, More preferably, it is 0.5 mass part or less, More preferably, it is 0.2 mass part or less. If the content of the stabilizer is below the lower limit value, there may be cases where the effect of improving molecular weight reduction or transparency deterioration cannot be obtained. On the other hand, if the content of the stabilizer exceeds the upper limit value, it may become unstable with respect to heat or moisture.
- the polycarbonate resin composition preferably contains a release agent.
- the release agent include aliphatic carboxylic acids, fatty acid esters obtained by reacting aliphatic carboxylic acids with alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like. It is done. Of these, fatty acid esters obtained by reacting aliphatic carboxylic acids with alcohols are preferred.
- Examples of the aliphatic carboxylic acid constituting the fatty acid ester include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid.
- the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.
- preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and saturated aliphatic monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
- aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, montanic acid, and tetrariacontanic acid. , Adipic acid, azelaic acid and the like.
- Examples of the alcohol constituting the fatty acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and saturated aliphatic monovalent alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable.
- the aliphatic alcohol also includes an alicyclic alcohol.
- these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.
- fatty acid esters obtained by reacting an aliphatic carboxylic acid with an alcohol include beeswax (mixture based on myristyl palmitate), stearic acid stearate, behenic acid behenate, behenic acid stearate, palmitic acid.
- Examples thereof include acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.
- the content of the release agent is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (a) and the polycarbonate resin (b). Is preferably 1 part by mass, more preferably 0.6 parts by mass, and still more preferably 0.4 parts by mass. If the content of the release agent is below the lower limit value, the effect of releasability may not be sufficient. Moreover, when content of a mold release agent exceeds an upper limit, hydrolysis resistance fall, mold contamination at the time of shaping
- the polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber.
- an ultraviolet absorber organic ultraviolet absorbers, such as a benzotriazole compound, a benzophenone compound, a salicylate compound, a cyanoacrylate compound, a triazine compound, an oxanilide compound, a malonic acid ester compound, a hindered amine compound, are mentioned, for example.
- benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and malonic ester ultraviolet absorbers are more preferable.
- the addition of the ultraviolet absorber was particularly good in the polycarbonate resin (a), and it was confirmed that the effect of improving the weather resistance was better than that of the polycarbonate resin (b) and the change in color tone was smaller.
- benzotriazole ultraviolet absorber examples include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -Dimethylbenzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl -5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′- Hydroxy-3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methyle Bis [4- (1,1,3,
- 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N— Benzotriazol-2-yl) phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.
- triazine ultraviolet absorber examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-(2-
- malonic acid ester UV absorber examples include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters.
- PR-25 “ B-CAP ”manufactured by BASF, and the like.
- the content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 5 parts per 100 parts by mass in total of the polycarbonate resins (a) and (b). It is not more than part by mass, more preferably not more than 4 parts by mass, still more preferably not more than 3 parts by mass. If the content of the ultraviolet absorber is lower than the lower limit, the effect of improving weather resistance may be insufficient. Moreover, when content of a ultraviolet absorber exceeds an upper limit, for example, at the time of extrusion molding, a volatile gas etc. will arise and it may cause contamination of a take-up roll.
- the content of the polycarbonate resins (a) and (b) with respect to 100 parts by mass in total is preferably 0.01 to 1 part by mass, more preferably Is 0.05 to 0.7 parts by mass, more preferably 0.1 to 0.5 parts by mass.
- the content of the polycarbonate resins (a) and (b) with respect to 100 parts by mass in total is preferably 1 to 5 parts by mass, more preferably 1 0.5 to 4.5 parts by mass, more preferably 2 to 4 parts by mass.
- the polycarbonate resin laminate of the present invention can also contain a flame retardant.
- the flame retardant to be used include at least one selected from the group consisting of sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, a sulfonic acid metal salt flame retardant is preferable.
- the blending amount of the flame retardant is usually preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass in total of the polycarbonate resins (a) and (b). If the blending amount of the flame retardant is excessively small, the flame retardant effect is lowered. If the blending amount of the flame retardant is excessively large, the mechanical strength and flame retardancy of the resin laminate tend to decrease or the transparency tends to decrease, and the upper limit of the blending amount is preferably 40 parts by mass, more preferably 30. Part by mass.
- the sulfonic acid metal salt flame retardant include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts.
- the metals of these metal salts include sodium, lithium, potassium, rubidium, cesium long-period periodic table group 1 metals; beryllium, magnesium magnesium, and long-period periodic group 2 such as calcium, strontium, and barium. Metal etc. are mentioned.
- a sulfonic acid metal salt can also be used 1 type or in mixture of 2 or more types. Examples of the sulfonic acid metal salts include aromatic sulfonesulfonic acid metal salts and perfluoroalkane-sulfonic acid metal salts.
- the sulfonic acid metal salt-based flame retardant is preferably 0.04 to 0.3 parts by weight, more preferably 0.05 to 0.2 parts by weight based on 100 parts by weight of the total of the polycarbonate resins (a) and (b). Part by mass is added.
- aromatic sulfonesulfonic acid metal salt examples include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4,4′-dibromodiphenyl-sulfone-3-sulfonate, 4 , 4'-dibromodiphenyl-sulfone-3-sulfone potassium, 4-chloro-4'-nitrodiphenylsulfone-3-sulfonate calcium, diphenylsulfone-3,3'-disulphonate disodium, diphenylsulfone-3,3 Examples include dipotassium di-sulfonate.
- perfluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.
- halogen-containing compound flame retardant examples include, for example, tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromo Examples include allyl ether, tetrabromobisphenol A carbonate oligomer, ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane and the like.
- the halogen-containing compound flame retardant is preferably added in an amount of 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the total of the polycarbonate resins (a) and (b).
- Examples of phosphorus-containing compound flame retardants include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphate ester compounds, and phosphazene compounds.
- Specific examples of the phosphate compound include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl.
- Phosphate tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate
- Bis (chloropropyl) monooctyl phosphate bisphenol A bisphosphate, hydroquinone bisphosphate Over DOO, resorcinol bisphosphate, trioxybenzene phosphate.
- the phosphorus-containing compound-based flame retardant is preferably 3 to 15 parts by weight, more preferably 5 to 25 parts by weight, and most preferably 10 to 12 parts by weight based on 100 parts by weight of the total of the polycarbonate resins (a) and (b). Part by mass is added.
- the silicon-containing compound-based flame retardant include silicone varnish, silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain having a branched structure.
- a silicone compound having an aromatic group in the organic functional group contained therein a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of silica powder, and an organopolysiloxane-polycarbonate copolymer Examples include coalescence.
- the polycarbonate resin laminate of the present invention contains a specific amount of the polycarbonate resin (a) having the structural unit represented by the formula (1).
- a flame retardant for example, bisphenol A
- A-PC polycarbonate resin obtained as a raw material monomer
- flame retardancy is improved.
- 2,2-bis (3-methyl-4-hydroxyphenyl) propane, an aromatic dihydroxy compound is added to the polycarbonate resin component.
- C-PC polycarbonate resin obtained as a raw material monomer
- the polycarbonate resin of the present invention has a structural unit derived from the compound represented by the formula (8), a structural unit derived from the compound represented by the formula (9), and the formula (10). Due to the branched structure generated from at least one structural unit selected from the structural units derived from the compound to be produced, the viscosity in the low shear region increases, which suppresses combustion drops (drip) in the combustion test. It is considered that the flame retardancy is improved. Furthermore, C-PC and the like have a methyl group in the benzene ring forming the skeleton, and thus the molecular chain is easily broken and decomposition is faster than A-PC.
- C-PC or the like is rapidly decomposed and graphitized, and easily forms flame retardancy by forming a heat insulating layer (char).
- the thermal decomposition onset temperature of C-PC, etc. is lower than that of A-PC because of the structural difference that “the 3-position of two benzene rings is substituted with a methyl group” of the bisphenol skeleton. It is thought that.
- Pencil hardness (1-1) Pencil hardness of polycarbonate resin
- the polycarbonate resin was thickened with an injection molding machine (manufactured by Nippon Steel Works, J50E2) under the conditions of a barrel temperature of 280 ° C. and a mold temperature of 80 ° C.
- the molded product was 3 mm long, 60 mm long and 60 mm wide.
- pencil hardness was measured by 750g load using the pencil hardness tester (made by Toyo Seiki Seisakusho).
- Viscosity average molecular weight of polycarbonate resin (Mv) The polycarbonate resin was dissolved in methylene chloride (concentration 6.0 g / L (liter)), and the specific viscosity ( ⁇ sp ) at 20 ° C. was measured using an Ubbelohde viscometer, and the viscosity average molecular weight (Mv) was determined by the following formula. Was calculated.
- C concentration
- [ ⁇ ] represents intrinsic viscosity.
- the methylene chloride solution was put in a quartz cell having a width of 50 mm in the container, and the yellow index (solution YI) was measured with a color difference meter (SM color computer, SM-4-2, manufactured by Suga Test Instruments Co., Ltd.). The smaller the value, the better the color tone.
- SM color computer SM-4-2, manufactured by Suga Test Instruments Co., Ltd.
- the impact radius was 1/4 inch, and a cylindrical cradle with an outer diameter of 70 mm and an inner diameter of 50 mm was used as the cradle.
- An appropriate weight according to the impact resistance of each laminate was selected from 100 g, 300 g, 500 g, 1000 g, and 2000 g. The n number of the test was 6 to 10, the 50% fracture height was measured, and the impact energy was calculated from the weight used. In addition, “NB” in Table 22 indicates that no destruction occurred in all tests.
- Number of foreign matter (1) Number of foreign matter of 300 ⁇ m or more in polycarbonate resin single layer sheet For a single layer sheet of polycarbonate resin having a thickness of 200 ⁇ m, count the number of foreign matters with a diameter of 300 ⁇ m or more by visual inspection and using a microscope. It was evaluated as the number per two . (5-2) The number of foreign matters having a diameter of 300 ⁇ m or more in the polycarbonate resin laminate The number of foreign matters having a diameter of 300 ⁇ m or more was counted and evaluated as the number per 1 m 2 for the polycarbonate resin laminate using visual observation and a microscope.
- the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated five times to replace the inside of the first reactor with nitrogen.
- the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. in the heat medium jacket to dissolve the mixture.
- the stirrer was rotated at 55 rpm, the temperature in the heat medium jacket was controlled, and the internal temperature of the 1st reactor was kept at 220 degreeC.
- the pressure in the first reactor is 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off the phenol by-produced by the oligomerization reaction of BPC and DPC performed in the first reactor.
- 13.3 kPa 100 Torr.
- a transesterification reaction was performed for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off the phenol.
- the pressure in the gauge was increased to 0.2 MPa, and the oligomer in the first reactor was passed through a transfer pipe heated to 200 ° C. or higher in advance.
- the second reactor had an internal volume of 200 L, was equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser, and the internal pressure was controlled to atmospheric pressure and the internal temperature was controlled to 240 ° C.
- the oligomer fed into the second reactor was stirred at 16 rpm, the internal temperature was raised with a heat medium jacket, and the inside of the second reactor was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and phenol distilled out was removed out of the system. Further, the temperature was continuously increased, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the polycondensation reaction was performed while maintaining 70 Pa. The final internal temperature in the second reactor was 295 ° C. The polycondensation reaction was completed when the stirrer of the second reactor had a predetermined stirring power determined in advance.
- the MPC of the BPC homopolymer of the obtained polycarbonate resin (hereinafter sometimes abbreviated as “PC (1)”) is 30,000, the pencil hardness is 2H, and the compound represented by the formula (10) is used.
- the content was 420 ppm
- the content of the compound represented by formula (8) was 180 ppm
- the content of the compound represented by formula (9) was 1,850 ppm.
- the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated 5 times, and the inside of the first reactor was replaced with nitrogen.
- the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. in the heat medium jacket to dissolve the mixture.
- the stirrer was rotated at 55 rpm, the temperature in the heat medium jacket was controlled, and the internal temperature of the 1st reactor was kept at 220 degreeC.
- the pressure in the first reactor is 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off the phenol by-produced by the oligomerization reaction of BPC and DPC performed in the first reactor. To 13.3 kPa (100 Torr).
- a transesterification reaction was performed for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off the phenol. Then, after the pressure inside the system was restored to 101.3 kPa with nitrogen, the pressure in the gauge was increased to 0.2 MPa, and the oligomer in the first reactor was passed through a transfer pipe heated to 200 ° C. or higher in advance. Was pumped to the second reactor.
- the second reactor had an internal volume of 200 L, was equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser, and the internal pressure was controlled to atmospheric pressure and the internal temperature was controlled to 240 ° C.
- the oligomer fed into the second reactor was stirred at 16 rpm, the internal temperature was raised with a heat medium jacket, and the inside of the second reactor was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and phenol distilled out was removed from the system. Further, the temperature was continuously increased, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the polycondensation reaction was performed while maintaining 70 Pa. The final internal temperature in the second reactor was 285 ° C.
- the polycondensation reaction was completed when the agitator of the second reactor had a predetermined stirring power determined in advance.
- the pressure was increased to 0.2 MPa with gauge pressure, and the polycarbonate resin was drawn out from the bottom of the second reactor in the form of a strand.
- the mixture was cooled and pelletized using a rotary cutter.
- Mv of the obtained polycarbonate resin (hereinafter sometimes abbreviated as PC (11)) is 31,800, pencil hardness is 2H, content of the compound represented by formula (10) is 420 ppm, formula (8) The content of the compound represented by the formula (180) was 180 ppm, and the content of the compound represented by the formula (9) was 1,850 ppm.
- this reaction liquid / reaction gas was introduced into a second reactor (1.8 L) having the same shape as that of the next first reactor through an overflow pipe attached to the reactor, and reacted.
- 0.21 kg / hour of pt-butylphenol (8 mass% methylene chloride solution) was introduced into the second reactor as a molecular weight regulator.
- the reaction liquid and the reaction gas were introduced into an oligomerization tank (4.5 L) having the same shape as that of the first reactor from an overflow pipe attached to the second reactor.
- 0.020 kg / hour of a 2% by weight trimethylamine aqueous solution was introduced into the oligomerization tank.
- the oligomerized emulsion thus obtained was further introduced into a separation tank (settler) having an internal volume of 5.4 L, and the aqueous phase and the oil tank were separated to obtain an oligomeric methylene chloride solution.
- a separation tank settler
- 2.60 kg of the above oligomer methylene chloride solution was charged into a 6.8 L paddle bladed reactor, 2.44 kg of methylene chloride for dilution was added thereto, and a 25 mass% aqueous sodium hydroxide solution was added in an amount of 0.24 kg.
- the obtained polycarbonate solution was pulverized by feeding into warm water at 60 to 75 ° C. and dried to obtain a powdery polycarbonate resin.
- Mv of the obtained polycarbonate resin (hereinafter sometimes abbreviated as PC (21)) was 30,000, and the pencil hardness was 2H.
- the content of the compound represented by the formula (10) was 0 ppm
- the content of the compound represented by the formula (8) was 0 ppm
- the content of the compound represented by the formula (9) was 0 ppm.
- Mv of the obtained polycarbonate resin (hereinafter sometimes abbreviated as PC (24)) is 21,200, pencil hardness is H, the content of the compound represented by formula (10) is 80 ppm, and formula (8) The content of the compound represented by the formula (70) was 70 ppm, and the content of the compound represented by the formula (9) was 1,200 ppm.
- the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated 10 times to replace the inside of the first reactor with nitrogen.
- the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture.
- This molten mixture was then transferred to the second reactor.
- the second reactor had an internal capacity of 400 L and was equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser. The stirrer was rotated at 60 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the second reactor was kept at 220 ° C.
- the pressure in the first reactor is 101.3 kPa (760 Torr) to 13.3 kPa in terms of absolute pressure while distilling off phenol by-produced by the oligomerization reaction of BPC and DPC performed in the second reactor.
- the pressure was reduced to (100 Torr).
- the second reactor was stirred at 30 rpm, the internal temperature was raised with a heating medium jacket, and the pressure inside the second reactor was reduced from 101.3 kPa to 13.3 kPa in absolute pressure. Thereafter, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure, and the distilled phenol was removed from the system. Further, the temperature was continuously increased, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the polycondensation reaction was performed while maintaining 70 Pa. At that time, the rotation speed of stirring was set to 10 rpm according to the stirring power, and the final internal temperature in the second reactor was set to 306 ° C.
- the polycondensation reaction was completed when the stirrer of the second reactor had a predetermined stirring power determined in advance.
- Mv of the obtained polycarbonate resin (hereinafter sometimes abbreviated as PC (25)) is 34,800, pencil hardness is 2H, content of the compound represented by formula (10) is 861 ppm, formula (8)
- the content of the compound represented by formula (9) was 1,291 ppm, and the content of the compound represented by formula (9) was 7,569 ppm.
- the obtained polycarbonate resin composition pellets were used in an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., set temperature was 270 ° C., mold temperature was 80 ° C., and the table had a length of 100 mm and a width of 100 mm.
- SE100DU injection molding machine
- a sheet-like test piece having the thickness described in 1 was injection molded.
- These sheets were laminated using an epoxy-based adhesive (product name (Araldite) manufactured by Nichiban Co., Ltd.) to obtain a laminate having the layer structure shown in Table 1.
- Each evaluation was performed about the obtained polycarbonate resin laminated body according to the method of the said evaluation item. The results are shown in Table 1.
- Example 11 and 12 and Comparative Example 12 As the polycarbonate resins (a) and (b), BPC homopolymer (PC (11)) and BPA homopolymer (PC (12)), respectively, at a ratio shown in Table 11 have a single vent opening.
- a twin screw extruder (LABOTEX30HSS-32) manufactured by the company, extruded into a strand from the outlet of the twin screw extruder, cooled and solidified with water, pelletized with a rotary cutter, and polycarbonate resin pellets Obtained.
- the barrel temperature of the twin screw extruder was 280 ° C.
- the polycarbonate resin temperature at the outlet of the twin screw extruder was 300 ° C.
- the vent port of the twin screw extruder was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa.
- the obtained polycarbonate resin pellet was subjected to ⁇ 25 mm single screw extrusion for surface layer (A) (manufactured by Soken Co., Ltd.) and BPA homopolymer (PC (12)) was ⁇ 30 mm single screw extrusion for resin layer (B).
- A surface layer
- BPA BPA homopolymer
- PC (12) BPA homopolymer
- Each was melted by a machine (manufactured by Soken Co., Ltd.), extruded from a two-layer T die attached to the tip of both single-screw extruders, and cooled with a roll to obtain a laminate of polycarbonate resin.
- the molding temperature and roll temperature at the time of extrusion molding are as shown in Table 11.
- the obtained polycarbonate resin laminate was evaluated for pencil hardness, solution YI, and DuPont impact strength according to the method described in the above evaluation items. The results are shown in Table 11.
- BPC homopolymer (PC (11)) is ⁇ 25 mm single screw extruder for surface layer (A) (manufactured by Soken Co., Ltd.) and BPA homopolymer (PC (12)) is ⁇ 30 mm single screw extruder for resin layer (B).
- PC (11) BPC homopolymer
- PC (12) BPA homopolymer
- PC (12) BPA homopolymer
- Each was melted by a machine (manufactured by Soken Co., Ltd.), extruded from a two-layer T die attached to the tip of both single-screw extruders, and cooled with a roll to obtain a laminate of polycarbonate resin.
- the molding temperature and roll temperature at the time of extrusion molding are as shown in Table 11. Further, various evaluations were performed in the same manner as in Example 11. The results are shown in Table 11.
- the polycarbonate resin sheet of the present invention has a pencil hardness specified by ISO 15184 of H or higher, a low color solution YI and a suitable color tone, and at the same time has high Dupont impact strength and excellent impact resistance.
- Example 21 to 24 and Comparative Examples 21 and 22 As polycarbonate resins (a) and (b), BPC homopolymer (PC (21), PC (22) or PC (25)), BPC / BPA copolymer (PC (24)), and BPA homopolymer, respectively.
- the polymer (PC (23)) was melt kneaded in a ratio shown in Table 21 in a twin screw extruder (LABOTEX30HSS-32) manufactured by Nippon Steel Works having one vent port. After being extruded in a strand form from the outlet of the resin, cooled and solidified with water, it was pelletized with a rotary cutter to obtain polycarbonate resin pellets.
- the resin temperature during melt kneading was as shown in Table 21. Further, butyl p-toluenesulfonate and Irganox 1076 were added at the ratios shown in Table 21.
- the vent port of the twin screw extruder was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa.
- the obtained polycarbonate resin pellets are extruded at a molding temperature of 280 ° C. into a ⁇ 25 mm single-screw extruder (manufactured by Isuzu Chemical Co., Ltd.) with a single-layer T die attached to the tip, and cooled with a 90 ° C. roll.
- a polycarbonate resin single layer sheet for surface layer having a thickness of 200 ⁇ 10 ⁇ m described in Table 21 was obtained.
- Table 21 shows the result of counting the number of foreign matters of 300 ⁇ m or more in this surface layer polycarbonate resin sheet.
- the obtained polycarbonate resin single layer sheet for the surface layer was attached to the inside of a mold having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm, and a barrel temperature of 280 ° C. using an injection molding machine (J50E2 manufactured by Nippon Steel).
- the polycarbonate resin laminate was injection molded under the condition of a mold temperature of 90 ° C.
- the composition of the core layer at this time is as shown in Table 21.
- the obtained polycarbonate resin laminate was evaluated for pencil hardness, solution YI, DuPont impact strength and the like according to the method described in the above evaluation items. The results are shown in Table 22.
- Example 21 to Example 24 and Comparative Example 21 were compared, Example 21 to Example using BPC homopolymer and BPA homopolymer were compared to Comparative Example 21 using BPC / BPA copolymer (PC (24)). It can be seen that Example 24 has higher pencil hardness and DuPont impact strength and better solution YI. Further, when Examples 21 to 24 and Comparative Example 22 are compared, it can be seen that the amount of foreign matter in the polycarbonate resin molded body using PC (25) is large.
- the present invention it is possible to form a polycarbonate resin laminate having significantly improved surface hardness, good color tone, and excellent impact resistance.
- the polycarbonate resin laminate of the present invention has excellent surface hardness, color tone, and good impact resistance. Therefore, the cellular phone, smartphone, PDA, portable DVD player, portable game machine, portable personal computer display Parts for display devices such as tablet computers, various portable touch panels, cover for display devices, shield covers for motorcycles, protective equipment members such as masks for helmets, decorative parts for car audio, car navigation systems, etc. It can be suitably used for such as, and its utility is high.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
この中でも、軽量で透明な構造要素を要求される場合には、ポリカーボネート樹脂を用いたシートがよく用いられており、その際に多層シートとしたり、ハードコート処理を施したりと付加的な処理を施すことがしばしば行われる。
本発明は、シートの厚さによらず、表面硬度が高く、且つ、色調、耐衝撃性に優れたポリカーボネート樹脂積層体を提供することを課題とする。
[1]表層(A)と樹脂層(B)を少なくとも有するポリカーボネート樹脂積層体であって、以下の条件を満足することを特徴とするポリカーボネート樹脂積層体。
(i)表層(A)が下記式(1)で表される構造単位を少なくとも有するポリカーボネート樹脂(a)と、ポリカーボネート樹脂(a)とは異なる構造単位を有するポリカーボネート樹脂(b)とを少なくとも含むポリカーボネート樹脂組成物からなる層である。
(ii)表層(A)におけるポリカーボネート樹脂(a)とポリカーボネート樹脂(b)との質量比が、45:55~99:1の範囲である。
(iii)ポリカーボネート樹脂積層体の表層(A)側から測定したISO 15184で規定される鉛筆硬度がH以上である。
を示し、R3及びR4は、それぞれ独立して水素原子又はメチル基を示し、ZはCと結合して炭素数6~12の、置換基を有していてもよい脂環式炭化水素を形成する基を示す。)
[4]樹脂層(B)が、さらにポリカーボネート樹脂(a)を含むポリカーボネート樹脂組成物からなり、樹脂層(B)中のポリカーボネート樹脂(a)の割合が30~1質量%、ポリカーボネート樹脂(b)の割合が70~99質量%である前記[3]に記載のポリカーボネート樹脂積層体。
[5]前記ポリカーボネート樹脂(a)が下記式(8)で表される化合物に由来する構造単位を含み、該構造単位の含有量が20ppm以上1,000ppm以下である前記[1]乃至[4]のいずれかに記載のポリカーボネート樹脂積層体。
[6]ポリカーボネート樹脂積層体中の前記式(8)で表される化合物に由来する構造単位の含有量が0.05~1,000ppmである前記[1]乃至[5]のいずれかに記載のポリカーボネート樹脂積層体。
[7]前記ポリカーボネート樹脂(a)が下記式(9)で表される化合物に由来する構造単位を含み、該構造単位の含有量が10ppm以上3,500ppm以下である前記[1]乃至[6]のいずれかに記載のポリカーボネート樹脂積層体。
[8]ポリカーボネート樹脂積層体中の前記式(9)で表される化合物に由来する構造単位の含有量が0.02~3,500ppmである前記[1]乃至[7]のいずれかに記載のポリカーボネート樹脂積層体。
[9]前記ポリカーボネート樹脂(a)が下記式(10)で表される化合物に由来する構造単位を含み、該構造単位の含有量が40ppm以上600ppm以下である前記[1]乃至[8]のいずれかに記載のポリカーボネート樹脂積層体。
[11]ポリカーボネート樹脂積層体の厚みが、200~5,000μmである前記[1]乃至[10]のいずれかに記載のポリカーボネート樹脂積層体。
[12]表層(A)の厚みが20~1,000μmであり、樹脂層(B)の厚みが10~5,000μmである前記[1]乃至[11]のいずれかに記載のポリカーボネート樹脂積層体。
[13]ポリカーボネート樹脂積層体の7質量%塩化メチレン溶液を光路長50mmで測定したイエローインデックスが、10以下である前記[1]乃至[12]のいずれかに記載のポリカーボネート樹脂積層体。
[14]表層(A)及び/又は樹脂層(B)を構成するポリカーボネート樹脂組成物がリン系安定剤、フェノール系安定剤及び硫黄系安定剤からなる群より選ばれる少なくとも1種の安定剤を0.01~1質量部含む前記[1]乃至[13]のいずれかに記載のポリカーボネート樹脂積層体。
[15]安定剤がフェノール系安定剤である前記[14]に記載のポリカーボネート樹脂積層体。
[16]前記[1]乃至[15]のいずれかに記載のポリカーボネート樹脂積層体からなる携帯型表示体の保護窓、表示装置用部材、表示装置用カバー、保護具用部材又は車載用部品。
本発明のポリカーボネート樹脂積層体における表層(A)は、外部と接する部位が大きく、硬度や色調は製品の品質の優位性を決定付ける可能性が高い。
表層(A)は、式(1)で表される構造単位を少なくとも有するポリカーボネート樹脂(a)と、ポリカーボネート樹脂(a)とは異なる構造単位を有するポリカーボネート樹脂(b)とを少なくとも含むポリカーボネート樹脂組成物からなる層である。
表層(A)における、式(1)で表される構造単位を少なくとも有するポリカーボネート樹脂(a)の構成部分と、ポリカーボネート樹脂(a)とは異なる構造単位を有するポリカーボネート樹脂(b)の構成部分との質量比は、45:55~99:1の範囲であり、好ましくは50:50~95:5であり、より好ましくは55:45~90:10であり、さらに好ましくは60:40~85:15である。
式(2)中、Xは、下記の基である。
式(2a)の構造単位を有するポリカーボネート樹脂は、2,2-ビス(4-ヒドロキシフェニル)プロパンをモノマーに使用することにより得ることが可能である。
前記の混合した組成物及び共重合体樹脂は、いずれも、更に式(1)及び式(2)の構造単位以外の他の構造単位を含有してもよい。
なお、ポリカーボネート樹脂中の上記構造単位の含有量は、NMR法により求めることができる。具体的には、核磁気共鳴装置(NMR装置)を使用し、ポリカーボネート樹脂の重クロロホルム溶液を1H-NMR測定した際に観測される、ポリカーボネート樹脂を合成する際に使用したジヒドロキシ化合物に依存した特徴的なシグナルの面積強度比により、各構造単位のモル組成を求めることができる。得られたモル組成と、各構造単位の式量より、各構造単位の質量比が求められる。
本発明のポリカーボネート樹脂積層体の樹脂層(B)は、上記ポリカーボネート樹脂(b)を少なくとも含み、ポリカーボネート樹脂(b)を100~70質量%、上記ポリカーボネート樹脂(a)を0~30質量%含むポリカーボネート樹脂組成物からなることが好ましい。より好ましくは、ポリカーボネート樹脂(b)が99~70質量%であり、上記ポリカーボネート樹脂(a)が1~30質量%である。さらに好ましくは、ポリカーボネート樹脂(b)が99~80質量%であり、上記ポリカーボネート樹脂(a)が1~20質量%である。
樹脂層(B)のポリカーボネート樹脂は、表層(A)のポリカーボネート樹脂のように硬度の高い樹脂であることを必ずしも必要とせず、より安価な樹脂を使用することにより、ポリカーボネート樹脂積層体のコストを低減することが可能となる。
ポリカーボネート樹脂(a)は、前記式(1)の構造単位以外の構造単位を有することもできる。例えば、前記式(2)の構造単位、あるいは他のジヒドロキシ化合物に由来する構造単位を有していてもよい。前記式(1)の構造単位以外の構造単位の含有割合は、通常60モル%以下であり、55モル%以下が好ましく、また50モル%以下がより好ましく、更に好ましくは40モル%以下、とりわけ30モル%以下が好ましく、特には20モル%以下が好ましく、10モル%以下が特段好ましく、なかで5モル%以下が最も好ましい。
本発明のポリカーボネート樹脂積層体は、少なくとも、表層(A)及び樹脂層(B)を有することにより、表面硬度が高く、高衝撃性を有し、また、色調にも優れたものとすることができる。
本発明のポリカーボネート樹脂積層体は、塩化メチレンに溶解した7質量%塩化メチレン溶液を光路長50mmで測定したイエローインデックスが、10以下であることが好ましく、より好ましくは9以下であり、更に好ましくは8以下である。イエローインデックスが大きいと色調が悪くなり、積層体として意匠性が乏しくなり、とりわけ着色が必要な積層体においては明度が十分でなくなり、くすんだ色となる可能性がある。
なお、ポリカーボネート樹脂(a)及びポリカーボネート樹脂(b)のISO 15184で規定される鉛筆硬度は、後述の実施例の項に記載される方法で測定される。
なお、本発明のポリカーボネート樹脂積層体は、表層(A)と樹脂層(B)との2層の積層構造であるが、必要に応じて、表層(A)と樹脂層(B)との間に接着層、その他の機能層等が設けられていてもよい。また、表層(A)側に粘着剤層、その他の機能層等が設けられていてもよい。
ポリカーボネート樹脂(a)及び(b)のMvは、より好ましくは30,000以下であり、更に好ましくは28,000以下であり、その下限は20,000であることがより好ましい。
さらに、ポリカーボネート樹脂(a)及び(b)は、Mvの異なる2種類以上のポリカーボネート樹脂を混合して上記Mvに調整してもよい。また、必要に応じ、Mvが上記の好適範囲外であるポリカーボネート樹脂を混合して用いてもよい。
また、前記式(9)で表される化合物に由来する構造単位の含有量は、0.02~3,500ppmが好ましく、より好ましくは1.0~2,500ppm、更に好ましくは10~1,300ppm、特に好ましくは30~800ppm、最も好ましくは100~400ppmである。前記式(9)で表される化合物に由来する構造単位の含有量が少なすぎると、温度に対する溶融粘度変化が大きく、積層体の厚み斑が大きくなる場合がある。又、多すぎると、異物が発生する虞がある。
また、前記式(10)で表される化合物に由来する構造単位の含有量は、40ppm以上600ppm以下が好ましく、50~400ppmがより好ましく、60~300ppmが更に好ましい。前記式(10)で表される化合物に由来する構造単位の含有量が少なすぎると、温度に対する溶融粘度変化が大きく、積層体の厚み斑が大きくなる場合がある。又、多すぎると、異物が発生する虞がある。
すなわち、ポリカーボネート樹脂又はポリカーボネート樹脂積層体をアルカリ加水分解した後に、液体クロマトグラフィーにより測定される。具体的には、ポリカーボネート樹脂又はポリカーボネート樹脂積層体0.5gを塩化メチレン5mlに溶解する。その溶液にメタノール45ml及び25質量%水酸化ナトリウム水溶液5mlを加え、70℃で30分間攪拌して得られた溶液を、液体クロマトグラフィーにて分析し、前記式(8)で表される化合物、前記式(9)で表される化合物、及び前記式(10)で表される化合物の量を定量して算出される。
(分析条件)
液体クロマトグラフィー装置:島津製作所社製
システムコントローラ:CBM-20A
ポンプ:LC-10AD
カラムオーブン:CTO-10ASvp
検出器:SPD-M20A
分析カラム:YMC-Pack ODS-AM 75mm×Φ4.6mm
オーブン温度:40℃
検出波長:280nm
溶離液:A液:0.1%トリフルオロ酢酸水溶液、B液:アセトニトリル
A/B=60/40(vol%)からA/B=95/5(vol%)まで25分間でグラジエント
流量:1mL/min
試料注入量:20μl
前記式(10)で表される化合物:13.9分
前記式(8)で表される化合物:15.9分
前記式(9)で表される化合物:21分
各化合物の特定は、上記リテンションタイムで観測されたピークに相当する部分を分取し、分取したサンプル中の化合物の1H-NMR、13C-NMR、質量分析法(MS)、赤外線吸収スペクトル(IRスペクトル)等により実施できる。尚、前記式(8)、式(9)、及び式(10)で表される化合物のそれぞれの含有量は、各化合物に由来する構造単位の含有量を意味する。
本発明で使用するポリカーボネート樹脂(a)及び(b)の製造方法について以下に説明する。なお、ポリカーボネート樹脂(a)及びポリカーボネート樹脂(b)を総称してポリカーボネート樹脂という場合がある。
ポリカーボネート樹脂は、ジヒドロキシ化合物とカルボニル化合物とを用いて重合することにより得られる。具体的には、ジヒドロキシ化合物と塩化カルボニル(「ホスゲン」と称することがある。)を、任意に混合しない有機相と水相との界面にて反応させることによりポリカーボネート樹脂を製造する界面重縮合法(以下、「界面法」と称することがある。)と、ジヒドロキシ化合物とカルボニル化合物を、例えばエステル交換反応触媒存在下、溶融状態にてエステル交換反応させることによりポリカーボネート樹脂を製造する溶融重縮合法(以下、溶融法ともいう。)がある。
以下、界面法及び溶融法のそれぞれについて説明する。
界面法によるポリカーボネート樹脂の製造方法では、通常ジヒドロキシ化合物のアルカリ水溶液を調製し、縮合触媒として、例えばアミン化合物の存在下で、ジヒドロキシ化合物とホスゲンとの界面重縮合反応を行い、次いで、中和、水洗、乾燥工程を経てポリカーボネート樹脂が得られる。具体的には、界面法によるポリカーボネート樹脂製造プロセスは、モノマー成分等の原料調製を行う原調工程、オリゴマー化反応が行われるオリゴマー化工程、オリゴマーを用いた重縮合反応が行われる重縮合工程、重縮合反応後の反応液をアルカリ洗浄、酸洗浄、及び水洗浄により洗浄する洗浄工程、洗浄された反応液を濃縮しポリカーボネート樹脂を造粒後に単離するポリカーボネート樹脂単離工程、単離されたポリカーボネート樹脂の粒子を乾燥する乾燥工程を、少なくとも有している。以下、各工程について説明する。
原調工程では、原調タンク中に、ジヒドロキシ化合物と、水酸化ナトリウム等のアルカリ金属化合物の水溶液及び/又は水酸化マグネシウム等のアルカリ土類金属化合物の水溶液と、脱塩水と、さらに必要に応じてハイドロサルファイト等の還元剤とを含む、ジヒドロキシ化合物のアルカリ水溶液等の原料が調製される。
ポリカーボネート樹脂の原料であるジヒドロキシ化合物としては、前記したようなジヒドロキシ化合物の1種又は2種以上が挙げられる。
アルカリ金属化合物及び/又はアルカリ土類金属化合物としては、通常水酸化物が好ましく、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム等の1種又は2種以上が挙げられる。これらの中でも、水酸化ナトリウムが特に好ましい。ジヒドロキシ化合物に対するアルカリ金属化合物及び/又はアルカリ土類金属化合物の割合は、通常1.0~1.5(当量比)、好ましくは1.02~1.04(当量比)である。アルカリ金属化合物及び/又はアルカリ土類金属化合物の割合が過度に多い場合、又は過度に少ない場合は、後述するオリゴマー化工程において得られるカーボネートオリゴマーの末端基に影響し、その結果、重縮合反応が異常となる傾向がある。尚、本発明において、アルカリ土類金属は周期表の第2族元素とする。
オリゴマー化工程では、まず、所定の反応器において、原調工程で調製されたジヒドロキシ化合物のアルカリ水溶液とホスゲンとを用い、塩化メチレン等の有機溶媒の存在下で、ジヒドロキシ化合物のホスゲン化反応が行われる。
続いて、ジヒドロキシ化合物のホスゲン化反応が行われた混合液に、トリエチルアミン等の縮合触媒と、p-t-ブチルフェノール等の連鎖停止剤が添加され、ジヒドロキシ化合物のオリゴマー化反応が行われる。
次に、ジヒドロキシ化合物のオリゴマー化反応液は、さらにオリゴマー化反応が進められた後、所定の静置分離槽に導入され、カーボネートオリゴマーを含有する有機相と水相とが分離され、分離された有機相は、重縮合工程に供給される。
ここで、ジヒドロキシ化合物のホスゲン化反応が行われる反応器にジヒドロキシ化合物のアルカリ水溶液が供給されてから静置分離槽に入るまでのオリゴマー化工程における滞留時間は、通常120分以下、好ましくは30~60分である。
オリゴマー化工程で使用するホスゲンは、通常液状又はガス状で使用される。オリゴマー化工程におけるホスゲンの好ましい使用量は、反応条件、特に、反応温度及び水相中のジヒドロキシ化合物の濃度によって適宜選択され、特に限定されない。通常ジヒドロキシ化合物の1モルに対し、ホスゲン1~2モル、好ましくは1.05~1.5モルである。ホスゲンの使用量が過度に多いと、未反応ホスゲンが多くなり原単位が極端に悪化する傾向がある。また、ホスゲンの使用量が過度に少ないと、クロロフォルメート基量が不足し、適切な分子量伸長が行われなくなる傾向がある。
オリゴマー化工程では、通常有機溶媒を使用する。有機溶媒としては、オリゴマー化工程における反応温度及び反応圧力において、ホスゲン及びカーボネートオリゴマー、ポリカーボネート樹脂等の反応生成物を溶解し、水と相溶しない(又は、水と溶液を形成しない)任意の不活性有機溶媒が挙げられる。
このような不活性有機溶媒として、例えば、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、テトラクロロエタン、ジクロロプロパン、1,2-ジクロロエチレン等の塩素化脂肪族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;クロロベンゼン、o-ジクロロベンゼン、クロロトルエン等の塩素化芳香族炭化水素;ニトロベンゼン、アセトフェノン等の置換芳香族炭化水素等が挙げられる。
なかでも、ジクロロメタン、クロロベンゼン等の塩素化された炭化水素が好適に使用される。
これらの不活性有機溶媒は、単独であるいは他の溶媒との混合物として使用することができる。
オリゴマー化反応は、縮合触媒の存在下で行うことができる。縮合触媒の添加時期は、ホスゲンを消費した後が好ましい。縮合触媒としては、二相界面縮合法に使用されている多くの縮合触媒の中から、任意に選択することができる。例えば、トリアルキルアミン、N-エチルピロリドン、N-エチルピペリジン、N-エチルモルホリン、N-イソプロピルピペリジン、N-イソプロピルモルホリン等の1種又は2種以上が挙げられる。中でも、トリエチルアミン、N-エチルピペリジンが好ましい。
オリゴマー化工程では、通常連鎖停止剤としてモノフェノールを使用する。モノフェノールとしては、例えば、フェノール;p-t-ブチルフェノール、p-クレゾール等のアルキルフェノール(アルキル基の炭素数は1~20);p-クロロフェノール、2,4,6-トリブロモフェノール等のハロゲン化フェノールの1種又は2種以上が挙げられる。モノフェノールの使用量は、得られるカーボネートオリゴマーの分子量に応じ適宜選択され、通常ジヒドロキシ化合物に対して、0.5~10モル%、好ましくは6~8モル%である。
カーボネート形成性化合物の共存下でモノフェノールを添加すると、モノフェノール同士の縮合物(炭酸ジフェニル類)が多く生成し、目標とする分子量のポリカーボネート樹脂が得られにくい傾向がある。モノフェノールの添加時期が極端に遅れると、分子量制御が困難となり、分子量分布において、低分子量側に特異な肩を有する樹脂となり、成形時には垂れを生じる等の弊害が生じる傾向がある。
オリゴマー化工程では、任意の分岐剤を使用することができる。このような分岐剤としては、例えば、2,4-ビス(4-ヒドロキシフェニルイソプロピル)フェノール、2,6-ビス(2-ヒドロキシ-5-メチルベンジル)-4-メチルフェノール、2-(4-ヒドロキシフェニル)-2-(2,4-ジヒドロキシフェニル)プロパン、1,4-ビス(4,4'-ジヒドロキシトリフェニルメチル)ベンゼン等の1種又は2種以上が挙げられる。また、2,4-ジヒドロキシ安息香酸、トリメシン酸、塩化シアヌル等も使用可能である。これらの中でも、少なくとも3個のフェノール性ヒドロキシル基を有する分岐剤が好適である。
分岐剤の使用量は、得られるカーボネートオリゴマーの分岐度に応じ適宜選択され、通常ジヒドロキシ化合物に対し、0.05~2モル%が好ましく、より好ましくは0.1~1モル%である。
このような乳濁液を形成する手段としては、例えば、所定の撹拌翼を有する撹拌機、ホモジナイザー、ホモミキサー、コロイドミル、フロージェットミキサー、超音波乳化機等の動的ミキサー、静的ミキサー等の混合機を使用するのが好ましい。乳濁液は、通常0.01~10μmの液滴径を有し、乳化安定性を有する。
乳濁液とホスゲン(CDC)との接触は、前述した乳化条件よりも弱い混合条件下で行うのがCDCの有機相への溶解を抑制する意味で好ましい。ウェーバー数としては、10,000未満、好ましくは5,000未満、さらに好ましくは2,000未満である。また、P/qとしては、200kg・m/L未満、好ましくは100kg・m/L未満、さらに好ましくは50kg・m/L未満である。ホスゲンの接触は、管型反応器や槽型反応器にCDCを導入することによって達成することができる。
重縮合工程では、静置分離槽で水相と分離されたカーボネートオリゴマーを含有する有機相を、撹拌機を有するオリゴマー貯槽に移送する。オリゴマー貯槽には、トリエチルアミン等の縮合触媒が、さらに添加される。
続いて、オリゴマー貯槽内で撹拌された有機相は、所定の重縮合反応槽に導入される。次いで、重縮合反応槽中に、脱塩水、塩化メチレン等の有機溶媒、水酸化ナトリウム水溶液等が供給され、撹拌混合されてカーボネートオリゴマーの重縮合反応が行われる。
重縮合反応槽中の重縮合反応液は、その後、複数の重縮合反応槽に連続的に順次導入される。これにより、カーボネートオリゴマーの重縮合反応が完結される。
重縮合工程において、連続的にカーボネートオリゴマーの重縮合反応が行われる重縮合反応槽における滞留時間は、通常12時間以下、好ましくは0.5~5時間である。
重縮合工程における重縮合反応の温度は、通常、常温付近である。反応時間は0.5~5時間、好ましくは1~3時間程度である。
重縮合反応槽における重縮合反応が完結した後、重縮合反応液は、公知の方法により、アルカリ洗浄液によるアルカリ洗浄、酸洗浄液による酸洗浄及び洗浄水による水洗浄が行われる。なお、洗浄工程の全滞留時間は、通常12時間以下、好ましくは0.5~6時間である。
ポリカーボネート樹脂単離工程では、先ず、洗浄工程において洗浄されたポリカーボネート樹脂を含む重縮合反応液は、所定の固形分濃度に濃縮された濃縮液として調製される。濃縮液におけるポリカーボネート樹脂の固形分濃度は、通常5~35質量%、好ましくは10~30質量%である。
脱塩水の温度は、通常37~67℃、好ましくは40~50℃である。また、造粒槽内で行われる造粒処理によりポリカーボネート樹脂の固形化温度は、通常37~67℃、好ましくは40~50℃である。
造粒槽から連続的に排出されるポリカーボネート樹脂粉状体を含む水スラリーは、その後、所定の分離器に連続的に導入され、水スラリーから水が分離される。
乾燥工程では、分離器において、水スラリーから水が分離されたポリカーボネート樹脂粉状体が、所定の乾燥機に連続的に供給され、所定の滞留時間で滞留させた後、連続的に抜き出される。乾燥機としては、例えば流動床型乾燥機が挙げられる。なお、複数の流動床型乾燥機を直列につなぎ、連続的に乾燥処理を行ってもよい。
乾燥機は、通常熱媒ジャケット等の加熱手段を有し、例えば、水蒸気にて、通常0.1~1.0MPa-G、好ましくは0.2~0.6MPa-Gに保持されている。これにより、乾燥機の中を流通する窒素(N2)の温度は、通常100~200℃、好ましくは120~180℃に保持されている。
溶融法によるポリカーボネート樹脂の製造方法では、ジヒドロキシ化合物とカルボニル化合物とをエステル交換反応触媒存在下、溶融状態にてエステル交換反応させることによりポリカーボネート樹脂を製造する。
ポリカーボネート樹脂の原料であるジヒドロキシ化合物としては、具体的には前記したようなジヒドロキシ化合物等の1種又は2種以上が挙げられる。
(炭酸ジエステル)
ポリカーボネート樹脂の原料である炭酸ジエステルとしては、下記式(3)で示される化合物が挙げられる。
なお、A上の置換基としては、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基、フェニル基、フェノキシ基、ビニル基、シアノ基、エステル基、アミド基、ニトロ基等が例示される。
これらの中でも、ジフェニルカーボネート(以下、「DPC」と称する場合がある。)、置換ジフェニルカーボネートが好ましい。これらの炭酸ジエステルは、単独又は2種以上を混合して用いることができる。
溶融法によるポリカーボネート樹脂の製造方法において使用されるエステル交換触媒としては、通常のエステル交換法によりポリカーボネート樹脂を製造する際に用いられる触媒が挙げられ、特には限定されない。
例えば、アルカリ金属化合物、アルカリ土類金属化合物、塩基性ホウ素化合物、塩基性リン化合物、塩基性アンモニウム化合物、アミン系化合物等の塩基性化合物が挙げられる。これらの中でも、実用的にはアルカリ金属化合物、アルカリ土類金属化合物が好ましい。これらのエステル交換触媒は、単独で使用してもよく、2種類以上を組み合わせて使用してもよい。
これらのアルカリ金属化合物の中でも、セシウム化合物が好ましく、特に、炭酸セシウム、炭酸水素セシウム、水酸化セシウムが好ましい。
アルカリ土類金属化合物としては、例えば、アルカリ土類金属の水酸化物、炭酸塩等の無機アルカリ土類金属化合物;アルカリ土類金属のアルコール類、フェノール類、有機カルボン酸類との塩;等が挙げられる。ここで、アルカリ土類金属としては、例えば、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等が挙げられる。
塩基性リン化合物としては、例えば、トリエチルホスフィン、トリ-n-プロピルホスフィン、トリイソプロピルホスフィン、トリ-n-ブチルホスフィン、トリフェニルホスフィン、トリブチルホスフィン等の3価のリン化合物、又はこれらの化合物から誘導される4級ホスホニウム塩等が挙げられる。
溶融法においては、エステル交換反応終了後に、エステル交換触媒を中和して失活させるための触媒失活剤を添加してもよい。触媒失活剤の添加により、得られたポリカーボネート樹脂の耐熱性、耐加水分解性が向上する。
触媒失活剤としては、スルホン酸やスルホン酸エステルのようなpKaが3以下の酸性化合物が好ましく、具体的には、ベンゼンスルホン酸、p-トルエンスルホン酸、ベンゼンスルホン酸メチル、ベンゼンスルホン酸エチル、ベンゼンスルホン酸プロピル、ベンゼンスルホン酸ブチル、p-トルエンスルホン酸メチル、p-トルエンスルホン酸エチル、p-トルエンスルホン酸プロピル、p-トルエンスルホン酸ブチルなどが挙げられ、これらは1種又は2種以上を用いてもよい。
中でも、p-トルエンスルホン酸、p-トルエンスルホン酸ブチルが好適に用いられる。
重縮合工程後、反応を停止させ、重縮合反応液中の未反応原料や反応副生物を脱気除去する工程や、熱安定剤、離型剤、色剤等を添加する工程、ポリカーボネート樹脂を所定の粒径に形成する工程等を適宜追加してもよい。
以下、各工程について説明する。
ポリカーボネート樹脂の原料として使用するジヒドロキシ化合物と炭酸ジエステルとは、通常窒素、アルゴン等の不活性ガスの雰囲気下、バッチ式、半回分式又は連続式の撹拌槽型の装置を用いて、原料混合溶融液として調製される。溶融混合の温度は、例えば、ジヒドロキシ化合物としてビスフェノールAを用い、炭酸ジエステルとしてジフェニルカーボネートを用いる場合は、通常120~180℃、好ましくは125~160℃である。
以下、ジヒドロキシ化合物としてビスフェノールA、炭酸ジエステルとしてジフェニルカーボネートを原料として用いる場合を例として説明する。
この際、ジヒドロキシ化合物と炭酸ジエステルとの割合は、炭酸ジエステルが過剰になるように調整され、前述の如く、ジヒドロキシ化合物1モルに対して、炭酸ジエステルは、通常1.01~1.30モル、好ましくは1.02~1.20モルの割合になるように調整される。
ジヒドロキシ化合物と炭酸ジエステルとのエステル交換反応による重縮合反応は、通常2段階以上、好ましくは3~7段階の多段方式で連続的に行われる。各段階の具体的な反応条件としては、温度:150~320℃、圧力:常圧~0.01Torr(1.3Pa)、平均滞留時間:5~150分の範囲である。
多段方式の各反応槽においては、エステル交換反応の進行とともに副生するフェノール等のモノヒドロキシ化合物をより効果的に系外に除去するために、上記の反応条件内で、段階的により高温、より高真空に設定する。
反応槽としては、例えば、撹拌槽型反応槽、薄膜反応槽、遠心式薄膜蒸発反応槽、表面更新型二軸混練反応槽、二軸横型撹拌反応槽、濡れ壁式反応槽、自由落下させながら重縮合する多孔板型反応槽、ワイヤーに沿わせて落下させながら重縮合するワイヤー付き多孔板型反応槽等が挙げられる。
また、横型撹拌反応槽とは、撹拌翼の回転軸が横型(水平方向)であるものをいう。横型撹拌反応槽の撹拌翼としては、例えば、円板型、パドル型等の一軸タイプの撹拌翼、HVR、SCR、N-SCR(三菱重工業社製)、バイボラック(住友重機械工業社製)、あるいはメガネ翼、格子翼(日立プラントテクノロジー社製)等の二軸タイプの撹拌翼が挙げられる。
溶媒として水を選択した場合、水の性状は、含有される不純物の種類及び濃度が一定であれば特に限定されないが、通常、蒸留水、脱イオン水等が好ましく用いられる。
ポリカーボネート樹脂(a)及び(b)の組成物の調製は、次の(1)~(4)の方法で行うのが好ましい。
(1)ポリカーボネート樹脂(a)とポリカーボネート樹脂(b)とを溶融混練する方法。
(2)溶融状態のポリカーボネート樹脂(a)と溶融状態のポリカーボネート樹脂(b)とを溶融混練する方法。
(3)ポリカーボネート樹脂(a)とポリカーボネート樹脂(b)とを溶液状態で混合する方法。
(4)ポリカーボネート樹脂(a)とポリカーボネート樹脂(b)とをドライブレンドする方法。
以下、各方法について説明する。
ポリカーボネート樹脂(a)のペレットもしくは粉粒体と、ポリカーボネート樹脂(b)のペレットもしくは粉粒体とを、例えば、ニーダー、二軸押出機、単軸押出機等の混合装置を用いて溶融混練する。ポリカーボネート樹脂(a)のペレットもしくは粉粒体と、ポリカーボネート樹脂(b)のペレットもしくは粉粒体は予め固体状態で混合し、その後混練してもよいし、又はどちらか一方を先に前記混合装置で溶融させ、そこへもう一方のポリカーボネート樹脂を添加し、混練してもよい。混練させる温度に特に規定はないが、200℃以上が好ましく、230℃以上がより好ましく、260℃以上がさらに好ましい。また、350℃以下が好ましく、320℃以下が特に好ましい。混練させる温度が低いとポリカーボネート樹脂(a)とポリカーボネート樹脂(b)の混合が完全ではなく、ポリカーボネート樹脂積層体を製造した際に、鉛筆硬度等にばらつきが出る虞がある。また、混練する温度が高すぎると、前記式(8)、式(9)、及び式(10)に由来する構造単位の含有量が増えすぎてしまい、ポリカーボネート樹脂積層体に異物が発生したり、色調が悪化する可能性がある。
溶融状態のポリカーボネート樹脂(a)と溶融状態のポリカーボネート樹脂(b)とを、例えば攪拌槽やスタティックミキサー、ニーダー、二軸押出機、単軸押出機等の混合装置を用いて混合する。このとき、例えば溶融重合法で得られたポリカーボネート樹脂であれば、冷却・固化することなく溶融状態で上記混合装置に導入してもよい。混合する温度としては特に規定はないが、200℃以上が好ましく、230℃以上がより好ましく、260℃以上がさらに好ましい。また、350℃以下が好ましく、320℃以下が特に好ましい。混合させる温度が低いとポリカーボネート樹脂(a)とポリカーボネート樹脂(b)の混合が完全ではなく、ポリカーボネート樹脂積層体を製造した際に、鉛筆硬度等にばらつきが出る虞がある。また、混合する温度が高すぎると、前記式(8)、式(9)、及び式(10)に由来する構造単位の含有量が増えすぎてしまい、ポリカーボネート樹脂積層体に異物が発生したり、色調が悪化する可能性がある。
ポリカーボネート樹脂(a)とポリカーボネート樹脂(b)とを溶媒に溶解して溶液とし、溶液状態で混合し、その後、ポリカーボネート樹脂組成物として単離する方法である。
溶媒としては、例えば、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、テトラクロロエタン、ジクロロプロパン、1,2-ジクロロエチレン等の塩素化脂肪族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;ニトロベンゼン、アセトフェノン等の置換芳香族炭化水素;等が挙げられる。これらの中でも、例えば、ジクロロメタン、クロロベンゼン等の塩素化された炭化水素が好適に使用される。これらの溶媒は、単独であるいは他の溶媒との混合物として使用することができる。
混合装置としては、攪拌槽、スタティックミキサー等が挙げられる。また、混合温度としてはポリカーボネート樹脂(a)とポリカーボネート樹脂(b)とが溶解する条件であれば特に規定はなく、通常使用する溶媒の沸点以下で実施される。
ポリカーボネート樹脂(a)のペレットもしくは粉粒体と、ポリカーボネート樹脂(b)のペレットもしくは粉粒体とをタンブラー、スーパーミキサー、ヘンシェルミキサー、ナウターミキサー等を用いてドライブレンドする方法である。
本発明のポリカーボネート樹脂積層体の作製方法としては特に制限はなく、例えば、次のような3つの方法が挙げられる。中でも、表面硬度等がシート表面の全面に渡って均一となる傾向がある、共押出成形法、熱圧着成形法が好ましい。
ポリカーボネート樹脂積層体を製造する場合の押出機のバレル温度は、特に制限はないが、360℃以下が好ましく、340℃以下がさらに好ましく、320℃以下が最も好ましい。また、220℃以上が好ましく、240℃以上がさらに好ましく、260℃以上が特に好ましい。バレル温度が高すぎると、溶融粘度が低くなり、積層体の成形が難しくなる場合がある。又、前記式(8)、式(9)、及び式(10)に由来する構造単位の含有量が増えすぎてしまい、ポリカーボネート樹脂積層体に異物が発生したり、色調が悪化する可能性がある。バレル温度が低すぎると溶融粘度が高くなり、樹脂圧が高くなるため、Tダイが閉塞することがある。なお、押出機には通例、特定厚みを有するTダイと称するダイが装着されており、該Tダイより、溶融された状態でポリカーボネート樹脂積層体が押出される。
その他、予め成形した表層(A)用及び樹脂層(B)用の樹脂組成物のシートを、接着剤等を用いて接着することにより、本発明のポリカーボネート樹脂積層体とすることもできる。
本発明において、これらの廃材は、適宜、表層(A)用及び樹脂層(B)用の樹脂組成物に混合して次の成形に用いることができる。ただし、このような廃材をリサイクルする場合、その使用量が過度に多く、バージン樹脂の割合が少ないと、得られるポリカーボネート樹脂積層体の表面硬度、色調、耐衝撃性等の機械的特性が損なわれる場合がある。このため、これらの廃材の使用量は、原料全体に対して30質量%以下、特に20質量%以下、例えば0.1~10質量%程度とすることが好ましい。
前述したように、表層(A)用及び樹脂層(B)用の樹脂組成物には、各種の添加剤を配合することができる。添加剤としては、例えば、安定剤、紫外線吸収剤、離型剤、難燃剤、着色剤、帯電防止剤、熱可塑性樹脂、熱可塑性エラストマー、ガラス繊維、ガラスフレーク、ガラスビーズ、炭素繊維、ワラストナイト、珪酸カルシウム、硼酸アルミニウムウィスカー等が挙げられる。中でも、安定剤、離型剤、紫外線吸収剤、難燃剤等を配合することが好ましい。
表層(A)用及び樹脂層(B)用の樹脂組成物と添加剤等の混合方法は、特に限定されない。本発明では、例えば、ペレット又は粉末等の固体状態のポリカーボネート樹脂と添加剤等を混合後、押出機等で混練する方法、溶融状態のポリカーボネート樹脂と添加剤等とを混合する方法、溶融法又は界面法における原料モノマーの重合反応の途中又は重合反応終了時に添加する方法等が挙げられる。
ポリカーボネート樹脂組成物は、成形時等における分子量の低下、色調や透明性の悪化を防止するために、安定剤を含有することが好ましい。
安定剤としては、リン系安定剤、フェノール系安定剤、硫黄系安定剤が好ましい。
リン系安定剤としては、例えば、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸及びこれらのエステル等が挙げられる。具体的には、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、2,2-メチレンビス(4,6-ジ-tert-ブチルフェニル)オクチルホスファイト、ビス(ノニルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリブチルホスフェート、トリエチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェート、4,4'-ビフェニレンジホスホスフィン酸テトラキス(2,4-ジ-tert-ブチルフェニル)、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピル等が挙げられる。
これらの安定剤は1種単独で、又は2種以上を組み合わせて使用することができる。
安定剤の含有量は、ポリカーボネート樹脂(a)及びポリカーボネート樹脂(b)の合計100質量部に対して、0.01質量部以上が好ましく、より好ましくは0.02質量部以上であり、また、1質量部以下が好ましく、より好ましくは0.5質量部以下、さらに好ましくは0.2質量部以下である。安定剤の含有量が、下限値を下回ると、分子量低下や透明性悪化の改善効果が得られない場合がある。また、安定剤の含有量が、上限値を超えると、逆に、熱や水分に対して不安定となる場合がある。
ポリカーボネート樹脂組成物は、離型剤を含有することが好ましい。
離型剤としては、脂肪族カルボン酸、脂肪族カルボン酸とアルコールとを反応させて得られる脂肪酸エステル、数平均分子量200~15,000の脂肪族炭化水素化合物、ポリシロキサン系シリコーンオイル等が挙げられる。中でも、脂肪族カルボン酸とアルコールとを反応させて得られる脂肪酸エステルが好ましい。
本発明のポリカーボネート樹脂組成物は、紫外線吸収剤を含有することが好ましい。特に、上記したリン系安定剤及び/又はフェノール系安定剤と併用することにより、耐候性が向上しやすい。
紫外線吸収剤としては、例えば、ベンゾトリアゾール化合物、ベンゾフェノン化合物、サリシレート化合物、シアノアクリレート化合物、トリアジン化合物、オギザニリド化合物、マロン酸エステル化合物、ヒンダードアミン化合物などの有機紫外線吸収剤が挙げられる。中でも、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、マロン酸エステル系紫外線吸収剤がより好ましい。
紫外線吸収剤の添加は、特に、ポリカーボネート樹脂(a)において良好であり、ポリカーボネート樹脂(b)に対するよりも耐候性の向上効果が良く、かつ色調の変化がより少ないことが認められた。
マロン酸エステル系紫外線吸収剤の具体例としては、2-(アルキリデン)マロン酸エステル類、特に2-(1-アリールアルキリデン)マロン酸エステル類が挙げられ、具体的には、クラリアントジャパン社製「PR-25」、BASF社製「B-CAP」等が挙げられる。
特に、樹脂層(B)が紫外線吸収剤を含有する場合、ポリカーボネート樹脂(a)及び(b)の合計100質量部に対しての含有量は、好ましくは0.01~1質量部、より好ましくは0.05~0.7質量部、さらに好ましくは0.1~0.5質量部である。
また、表層(A)が紫外線吸収剤を含有する場合は、ポリカーボネート樹脂(a)及び(b)の合計100質量部に対しての含有量は、好ましくは1~5質量部、より好ましくは1.5~4.5質量部、さらに好ましくは2~4質量部である。
本発明のポリカーボネート樹脂積層体は、難燃剤を含有することもできる。使用する難燃剤としては、例えば、スルホン酸金属塩系難燃剤、ハロゲン含有化合物系難燃剤、燐含有化合物系難燃剤及び珪素含有化合物系難燃剤からなる群より選ばれる少なくとも1種が挙げられる。これらの中でも、スルホン酸金属塩系難燃剤が好ましい。
スルホン酸金属塩系難燃剤としては、脂肪族スルホン酸金属塩、芳香族スルホン酸金属塩等が挙げられる。これら金属塩の金属としては、ナトリウム、リチウム、カリウム、ルビジウム、セシウムの長周期型周期表第1族金属;ベリリウム、マグネシウムのマグネシウム類;カルシウム、ストロンチウム、バリウム等の長周期型周期表第2族金属等が挙げられる。スルホン酸金属塩は、1種又は2種以上を混合して使用することもできる。スルホン酸金属塩としては、芳香族スルホンスルホン酸金属塩、パーフルオロアルカン-スルホン酸金属塩等が挙げられる。
芳香族スルホンスルホン酸金属塩の具体例としては、例えば、ジフェニルスルホン-3-スルホン酸ナトリウム、ジフェニルスルホン-3-スルホン酸カリウム、4,4'-ジブロモジフェニル-スルホン-3-スルホン酸ナトリウム、4,4'-ジブロモジフェニル-スルホン-3-スルホンのカリウム、4-クロロー4'-ニトロジフェニルスルホン-3-スルホン酸カルシウム、ジフェニルスルホン-3,3'-ジスルホン酸ジナトリウム、ジフェニルスルホン-3,3'-ジスルホン酸ジカリウム等が挙げられる。
ハロゲン含有化合物系難燃剤は、前記ポリカーボネート樹脂(a)及び(b)の合計の100質量部に対して好ましくは5~30質量部、より好ましくは10~25質量部添加される。
珪素含有化合物系難燃剤としては、例えば、シリコーンワニス、ケイ素原子と結合する置換基が芳香族炭化水素基と炭素数2以上の脂肪族炭化水素基とからなるシリコーン樹脂、主鎖が分岐構造で、かつ含有する有機官能基中に芳香族基を持つシリコーン化合物、シリカ粉末の表面に官能基を有していてもよいポリジオルガノシロキサン重合体を担持させたシリコーン粉末、オルガノポリシロキサン-ポリカーボネート共重合体等が挙げられる。
本発明のポリカーボネート樹脂積層体の難燃性が向上する理由は明確ではないが、例えば、ポリカーボネート樹脂成分に、芳香族ジヒドロキシ化合物の2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパンを原料モノマーとして使用して得られたポリカーボネート樹脂(「C-PC」と記す。)を用いる場合を例に挙げると、以下のように考えられる。
実施例で使用したポリカーボネート樹脂、ポリカーボネート樹脂積層体及びポリカーボネート樹脂シートの物性は、下記の方法により評価した。
(1-1)ポリカーボネート樹脂の鉛筆硬度
ポリカーボネート樹脂を、射出成形機(日本製鋼所社製、J50E2)により、バレル温度280℃、金型温度80℃の条件下にて、厚さ3mm、縦60mm、横60mmの成形体に射出成形した。この成形体について、ISO15184に準拠し、鉛筆硬度試験機(東洋精機製作所社製)を用いて、750g荷重にて鉛筆硬度を測定した。
(1-2)ポリカーボネート樹脂積層体の鉛筆強度
ポリカーボネート樹脂積層体について、ISO15184に準拠し、鉛筆硬度試験機(東洋精機製作所社製)を用いて、750g荷重にて鉛筆硬度を測定した。尚、ポリカーボネート樹脂積層体については表層(A)側の表面側から測定した。
ポリカーボネート樹脂を塩化メチレンに溶解し(濃度6.0g/L(リットル))、ウベローデ粘度管を用いて、20℃における比粘度(ηsp)を測定し、下記の式により粘度平均分子量(Mv)を算出した。下記式中、Cは濃度を表し、[η]は極限粘度を表す。
ηsp/C=[η](1+0.28ηsp)
[η]=1.23×10-4Mv0.83
(3-1)目視観察
ポリカーボネート樹脂積層体の表層(A)面側から、積層体の色相を目視で観察した。透明で無色に近いものを「○」、透明であるが黄色着色が若干みられるものを「△」、くすんでいて黄色に着色しているものを「×」として評価した。
(3-2)イエローインデックス(溶液YI)
ポリカーボネート樹脂積層体を塩化メチレン(林純薬工業社製、試薬特級塩化メチレン)に溶解し、7質量%の塩化メチレン溶液とした。次いで、容器内幅50mmの石英セルに該塩化メチレン溶液を入れ、色差計(スガ試験機社製、SMカラーコンピューター、SM-4-2)によりイエローインデックス(溶液YI)を測定した。数値が小さいほど色調が良好であることを示す。
(4-1)面衝撃強度
ポリカーボネート樹脂積層体について、ASTM D2794に準拠し、東洋精機製作所社製「デュポン衝撃強度測定機」を用いて、亀裂が生じたものを「破壊」として評価し、10回試験を行い、50%破壊エネルギーを求めた。その際の撃芯半径は1/16インチ、錘は133gで、温度25℃で測定した。なお、表1中の「NB」は、10回の試験で破壊しなかったことを示す。
(4-2)デュポン衝撃強度
ポリカーボネート樹脂積層体のデュポン衝撃強度の測定は、東洋精機製作所社製「デュポン衝撃試験機」を用い、ASTM D2794-64に準拠して行なった。なお、撃芯半径は1/4インチ、受台には外径70mm、内径50mmの円筒形の受台を使用した。錘は100g、300g、500g、1000g、及び2000gから各積層体の耐衝撃性に応じた適当な錘を選択して使用した。試験のn数は6乃至10であり、50%破壊高さを測定し、使用した錘とから衝撃エネルギーを算出した。なお、表22中の「NB」は、全試験において破壊しなかったことを示す。
(5-1)ポリカーボネート樹脂単層シートにおける300μm以上の異物数
厚み200μmのポリカーボネート樹脂の単層シートについて、目視および顕微鏡を用いて、直径300μm以上の異物数をカウントし、1m2当たりの個数として評価した。
(5-2)ポリカーボネート樹脂積層体における300μm以上の異物数
ポリカーボネート樹脂積層体について、目視および顕微鏡を用いて、直径300μm以上の異物数をカウントし、1m2当たりの個数として評価した。
2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン(以下、BPCと略記する場合がある。)(本州化学社製)37.60kg(約147mol)及びジフェニルカーボネート(以下、DPCと略記する場合がある。)32.20kg(約150mol)に、炭酸セシウムの水溶液を、炭酸セシウムがジヒドロキシ化合物1mol当たり2μmolとなるように添加して混合物を調製した。次に、該混合物を、攪拌機、熱媒ジャケット、真空ポンプ及び還流冷却器を具備した内容量200L(リットル)の第1反応器に投入した。
続いて、第1反応器内の圧力を13.3kPaに保持し、フェノールをさらに留去させながら、80分間、エステル交換反応を行った。
その後、系内を窒素で絶対圧で101.3kPaに復圧した後、ゲージ圧で0.2MPaまで昇圧し、予め200℃以上に加熱した移送配管を経由して、第1反応器内のオリゴマーを、第2反応器に圧送した。尚、第2反応器は、内容量は200Lであり、攪拌機、熱媒ジャケット、真空ポンプ及び還流冷却管を具備し、内圧は大気圧に、内温は240℃に制御した。
2,2-ビス(4-ヒドロキシフェニル)プロパン(BPA)に由来する構造単位のみで構成された、界面法により合成された市販のポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製、商品名「ユーピロン S-3000R」)を用いた。
このポリカーボネート樹脂(以下、PC(2)と略記する場合がある。)の粘度平均分子量(Mv)は22,000であり、鉛筆硬度はBであった。式(10)で表される化合物の含有量は0ppm、式(8)で表される化合物の含有量は0ppm、式(9)で表される化合物の含有量は0ppmであった。
BPAとBPCを45mol/55molとなるように所定量仕込んだ以外は、上記ポリカーボネート樹脂(a)と同様の方法でポリカーボネート樹脂(BPA/BPCコポリマー)を合成した。第2反応器内の最終的な内部温度は285℃であった。得られたポリカーボネート樹脂(BPA/BPCコポリマー、以下、PC(3)と略記する場合がある。)のMvは28,000であり、鉛筆硬度はF、式(10)で表される化合物の含有量は190ppm、式(8)で表される化合物の含有量は130ppm、式(9)で表される化合物の含有量は920ppmであった。
2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン(BPC)(本州化学社製)37.60kg(約147mol)及びジフェニルカーボネート(DPC)32.20kg(約150mol)に、炭酸セシウムの水溶液を、炭酸セシウムがジヒドロキシ化合物1mol当たり2μmolとなるように添加して混合物を調整した。次に該混合物を、攪拌機、熱媒ジャケット、真空ポンプ及び還流冷却器を具備した内容量200Lの第1反応器に投入した。
次に、第1反応器内を1.33kPa(10Torr)に減圧し、続いて、窒素で大気圧に復圧する操作を5回繰り返し、第1反応器の内部を窒素置換した。窒素置換後、熱媒ジャケットに温度230℃の熱媒を通じて第1反応器の内温を徐々に昇温させ、混合物を溶解させた。その後、55rpmで撹拌機を回転させ、熱媒ジャケット内の温度をコントロールして、第1反応器の内温を220℃に保った。次いで、第1反応器の内部で行われるBPCとDPCのオリゴマー化反応により副生するフェノールを留去しながら、40分間かけて第1反応器内の圧力を絶対圧で101.3kPa(760Torr)から13.3kPa(100Torr)まで減圧した。
その後、系内を窒素で絶対圧で101.3kPaに復圧した後、ゲージ圧で0.2MPaまで昇圧し、予め200℃以上に加熱した移送配管を経由して、第1反応器内のオリゴマーを、第2反応器に圧送した。尚、第2反応器は、内容量は200Lであり、攪拌機、熱媒ジャケット、真空ポンプ及び還流冷却管を具備し、内圧は大気圧に、内温は240℃に制御した。
次いで、第2反応器内を、窒素により絶対圧で101.3kPaに復圧した後、ゲージ圧で0.2MPaまで昇圧し、第2反応器の槽底からポリカーボネート樹脂をストランド状で抜き出し、水槽で冷却しながら、回転式カッターを使用してペレット化した。得られたポリカーボネート樹脂(以下、PC(11)と略記する場合がある)のMvは31,800、鉛筆硬度は2H、式(10)で表される化合物の含有量は420ppm、式(8)で表される化合物の含有量は180ppm、式(9)で表される化合物の含有量は1,850ppmであった。
BPAホモポリマーとして、ビスフェノールA(BPA)に由来するモノマー単位のみで構成された、溶融法により合成された市販のポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製 商品名「ノバレックス M7027J」)を用いた。該BPAホモポリマー(以下、PC(12)と略記する場合がある)のMvは25,600、鉛筆硬度は2Bであった。式(10)で表される化合物の含有量は0ppm、式(8)で表される化合物の含有量は0ppm、式(9)で表される化合物の含有量は0ppmであった。
原料のジヒドロキシ化合物としてBPC(本州化学社製)を360質量部、25質量%水酸化ナトリウム(NaOH)水溶液585.1質量部および水1721.5質量部をハイドロサルファイト0.41質量部の存在下に、40℃で溶解したのち20℃に冷却し、BPC水溶液を得た。このBPC水溶液8.87kg/時間と塩化メチレン4.50kg/時間とを、還流冷却器、攪拌機、冷媒ジャケットを有する1.8Lのガラス製第1反応器に導入し、ここに別途供給される常温のホスゲン0.672kg/時間とを接触させた。このときの反応温度は35℃に達した。
上記オリゴマーの塩化メチレン溶液のうち、2.60kgを内容積6.8Lのパドル翼付き反応槽に仕込み、これに希釈用塩化メチレン2.44kgを追加し、さらに25質量%水酸化ナトリウム水溶液0.278kg、水0.927kg、2質量%トリエチルアミン水溶液8.37g、p-t-ブチルフェノール2.01gを加え、10℃で攪拌し、180分間重縮合反応を行った。
得られたポリカーボネート溶液を60~75℃温水中にフィードすることで粉化し、乾燥し、粉末状ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂(以下、PC(21)と略記する場合がある)のMvは30,000、鉛筆硬度は2Hであった。式(10)で表される化合物の含有量は0ppm、式(8)で表される化合物の含有量は0ppm、式(9)で表される化合物の含有量は0ppmであった。
第2反応器の攪拌機が予め決めておいた所定の攪拌動力を変えた以外は合成例11と同様に実施した。得られたポリカーボネート樹脂(以下、PC(22)と略記する場合がある)のMvは24,000、鉛筆硬度は2H、式(10)で表される化合物の含有量は50ppm、式(8)で表される化合物の含有量は40ppm、式(9)で表される化合物の含有量は850ppmであった。
BPAホモポリマーとして、ビスフェノールA(BPA)に由来するモノマー単位のみで構成された、溶融法により合成された市販のポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製 商品名「ノバレックス M7022J」)を用いた。該BPAホモポリマー(以下、PC(23)と略記する場合がある)のMvは20,400、鉛筆硬度は2Bであった。式(10)で表される化合物の含有量は0ppm、式(8)で表される化合物の含有量は0ppm、式(9)で表される化合物の含有量は0ppmであった。
原料のジヒドロキシ化合物としてBPCの代わりに、BPC(本州化学社製)25.95kg、及びBPA(三菱化学社製)8.65kgを使用し、第2反応器の攪拌機が予め決めておいた所定の攪拌動力を変えた以外は合成例11と同様にして実施し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂(以下、PC(24)と略記する場合がある)のMvは21,200、鉛筆硬度はH、式(10)で表される化合物の含有量は80ppm、式(8)で表される化合物の含有量は70ppm、式(9)で表される化合物の含有量は1,200ppmであった。
2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン(BPC)(本州化学社製)181.8kg及びジフェニルカーボネート(DPC)157.7kgに、炭酸セシウムの水溶液を、炭酸セシウムがジヒドロキシ化合物1mol当たり2.0μmolとなるように添加して混合物を調整した。次に該混合物を、攪拌機、熱媒ジャケット、真空ポンプ及び還流冷却器を具備した内容量400Lの第1反応器に投入した。
合成例1、2及び3で得た、BPCホモポリマー(PC(1))、BPAホモポリマー(PC(2))及びBPA/BPCコポリマー(PC(3))を、表1に記載の割合で使用して、田辺プラスチック社製の単軸押出機(VS-40)にて、溶融混練し、単軸押出機の出口からストランド状に押し出し、水で冷却固化させた後、回転式カッターで切断してペレット化し、ポリカーボネート樹脂の組成物ペレットを得た。
単軸押出機のバレル温度は280℃であり、単軸押出機の出口における樹脂温度は300℃であった。
これらのシートをエポキシ系接着剤(ニチバン社製、商品名(アラルダイト))を用いて積層し、表1に記載の層構成の積層体を得た。
得られたポリカーボネート樹脂積層体について、前記評価項目の方法に準じて、各評価を行った。結果を表1に示した。
ポリカーボネート樹脂(a)及び(b)として、それぞれBPCホモポリマー(PC(11))とBPAホモポリマー(PC(12))とを表11に記載の割合で、1つのベント口を有する日本製鋼所社製の2軸押出機(LABOTEX30HSS-32)にて、溶融混練し、2軸押出機の出口からストランド状に押し出し、水で冷却固化させた後、回転式カッターでペレット化し、ポリカーボネート樹脂ペレットを得た。このとき、2軸押出機のバレル温度は280℃であり、2軸押出機の出口におけるポリカーボネート樹脂温度は300℃であった。なお、溶融混練時は、2軸押出機のベント口は真空ポンプに連結し、ベント口での圧力は500Paになるように制御した。
BPCホモポリマー(PC(11))を表層(A)用のφ25mm単軸押出機(創研社製)で、BPAホモポリマー(PC(12))を樹脂層(B)用のφ30mm単軸押出機(創研社製)でそれぞれ溶融させ、両単軸押出機の先端に取り付けられた二層Tダイから押し出し、ロールで冷却することにより、ポリカーボネート樹脂の積層体を得た。尚、押出成形時の成形温度及びロール温度は、表11に記載の通りである。更に実施例11と同様の方法にて各種評価を行った。その結果を表11に示した。
ポリカーボネート樹脂(a)及び(b)として、それぞれ、BPCホモポリマー(PC(21)、PC(22)もしくはPC(25))と、BPC/BPA共重合ポリマー(PC(24))と、BPAホモポリマー(PC(23))と、を表21に記載の割合で、1つのベント口を有する日本製鋼所社製の2軸押出機(LABOTEX30HSS-32)にて、溶融混練し、2軸押出機の出口からストランド状に押し出し、水で冷却固化させた後、回転式カッターでペレット化し、ポリカーボネート樹脂ペレットを得た。このとき、溶融混練時の樹脂温度は表21に記載の通りであった。また、表21に記載の割合でp-トルエンスルホン酸ブチルとイルガノックス1076を添加した。なお、溶融混練時は、2軸押出機のベント口は真空ポンプに連結し、ベント口での圧力は500Paになるように制御した。
次いで、得られた表層用ポリカーボネート樹脂単層シートを縦100mm、横100mm、厚み2mm厚の金型の内側に貼り付け、射出成形機(株式会社日本製鋼所製J50E2)を用い、バレル温度280℃、金型温度90℃の条件下にて、ポリカーボネート樹脂積層体を射出成形した。このときのコア層の組成は表21に記載の通りである。得られたポリカーボネート樹脂積層体は前記評価項目に記載の方法に準じて鉛筆硬度、溶液YI、デュポン衝撃強度等を評価した。その結果を表22に示した。
Claims (16)
- 表層(A)と樹脂層(B)を少なくとも有するポリカーボネート樹脂積層体であって、以下の条件を満足することを特徴とするポリカーボネート樹脂積層体。
(i)表層(A)が下記式(1)で表される構造単位を少なくとも有するポリカーボネート樹脂(a)と、ポリカーボネート樹脂(a)とは異なる構造単位を有するポリカーボネート樹脂(b)とを少なくとも含むポリカーボネート樹脂組成物からなる層である。
(ii)表層(A)におけるポリカーボネート樹脂(a)とポリカーボネート樹脂(b)との質量比が、45:55~99:1の範囲である。
(iii)ポリカーボネート樹脂積層体の表層(A)側から測定したISO 15184で規定される鉛筆硬度がH以上である。
- 樹脂層(B)がポリカーボネート樹脂(b)を少なくとも含むポリカーボネート樹脂組成物からなる請求項1又は2に記載のポリカーボネート樹脂積層体。
- 樹脂層(B)が、さらにポリカーボネート樹脂(a)を含むポリカーボネート樹脂組成物からなり、樹脂層(B)中のポリカーボネート樹脂(a)の割合が30~1質量%、ポリカーボネート樹脂(b)の割合が70~99質量%である請求項3に記載のポリカーボネート樹脂積層体。
- ポリカーボネート樹脂積層体中の前記式(8)で表される化合物に由来する構造単位の含有量が0.05~1,000ppmである請求項1乃至5のいずれかに記載のポリカーボネート樹脂積層体。
- ポリカーボネート樹脂積層体中の前記式(9)で表される化合物に由来する構造単位の含有量が0.02~3,500ppmである請求項1乃至7のいずれかに記載のポリカーボネート樹脂積層体。
- ポリカーボネート樹脂積層体中の前記式(10)で表される化合物に由来する構造単位の含有量が0.1~600ppmである請求項1乃至9のいずれかに記載のポリカーボネート樹脂積層体。
- ポリカーボネート樹脂積層体の厚みが、200~5,000μmである請求項1乃至10のいずれかに記載のポリカーボネート樹脂積層体。
- 表層(A)の厚みが20~1,000μmであり、樹脂層(B)の厚みが10~5,000μmである請求項1乃至11のいずれかに記載のポリカーボネート樹脂積層体。
- ポリカーボネート樹脂積層体の7質量%塩化メチレン溶液を光路長50mmで測定したイエローインデックスが、10以下である請求項1乃至12のいずれかに記載のポリカーボネート樹脂積層体。
- 表層(A)及び/又は樹脂層(B)を構成するポリカーボネート樹脂組成物がリン系安定剤、フェノール系安定剤及び硫黄系安定剤からなる群より選ばれる少なくとも1種の安定剤を0.01~1質量部含む請求項1乃至13のいずれかに記載のポリカーボネート樹脂積層体。
- 安定剤がフェノール系安定剤である請求項14に記載のポリカーボネート樹脂積層体。
- 請求項1乃至15のいずれかに記載のポリカーボネート樹脂積層体からなる携帯型表示体の保護窓、表示装置用部材、表示装置用カバー、保護具用部材又は車載用部品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280036802.7A CN103702831B (zh) | 2011-08-01 | 2012-08-01 | 聚碳酸酯树脂层积体 |
EP12820813.9A EP2740598B1 (en) | 2011-08-01 | 2012-08-01 | Polycarbonate resin laminate |
KR1020147002440A KR101948356B1 (ko) | 2011-08-01 | 2012-08-01 | 폴리카보네이트 수지 적층체 |
US14/170,995 US9522519B2 (en) | 2011-08-01 | 2014-02-03 | Polycarbonate resin laminate |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011168506 | 2011-08-01 | ||
JP2011-168506 | 2011-08-01 | ||
JP2012036053 | 2012-02-22 | ||
JP2012-036053 | 2012-02-22 | ||
JP2012-101702 | 2012-04-26 | ||
JP2012-101700 | 2012-04-26 | ||
JP2012101701A JP6199008B2 (ja) | 2011-04-27 | 2012-04-26 | ポリカーボネート樹脂及びポリカーボネート樹脂の製造方法 |
JP2012101702A JP6199009B2 (ja) | 2011-04-27 | 2012-04-26 | ポリカーボネート樹脂及びポリカーボネート樹脂の製造方法 |
JP2012-101701 | 2012-04-26 | ||
JP2012101700A JP6199007B2 (ja) | 2011-04-27 | 2012-04-26 | ポリカーボネート樹脂及びポリカーボネート樹脂の製造方法 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/170,995 Continuation US9522519B2 (en) | 2011-08-01 | 2014-02-03 | Polycarbonate resin laminate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013018835A1 true WO2013018835A1 (ja) | 2013-02-07 |
Family
ID=47629354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/069604 WO2013018835A1 (ja) | 2011-08-01 | 2012-08-01 | ポリカーボネート樹脂積層体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9522519B2 (ja) |
EP (1) | EP2740598B1 (ja) |
JP (1) | JP6207816B2 (ja) |
KR (1) | KR101948356B1 (ja) |
CN (1) | CN103702831B (ja) |
TW (1) | TWI554404B (ja) |
WO (1) | WO2013018835A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021090824A1 (ja) * | 2019-11-06 | 2021-05-14 | 三菱エンジニアリングプラスチックス株式会社 | レーザーダイレクトストラクチャリング用樹脂組成物、成形品、および、メッキ付き成形品の製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6163644B2 (ja) | 2012-03-30 | 2017-07-19 | 三菱ケミカル株式会社 | ポリカーボネート樹脂及びその組成物 |
US10240036B2 (en) * | 2015-04-30 | 2019-03-26 | Samsung Electronics Co., Ltd. | Polymer composition, molded article, and method of manufacturing the molded article |
KR102373615B1 (ko) | 2015-08-24 | 2022-03-15 | 삼성디스플레이 주식회사 | 윈도우 부재를 포함하는 표시장치 및 윈도우 부재의 제조방법 |
WO2017073508A1 (ja) | 2015-10-29 | 2017-05-04 | 帝人株式会社 | アミン耐性を有するポリカーボネート樹脂 |
US20200016877A1 (en) * | 2017-03-06 | 2020-01-16 | Mitsubishi Gas Chemical Company, Inc. | Resin laminate and card comprising resin laminate |
JP7193278B2 (ja) * | 2018-09-06 | 2022-12-20 | 積水化学工業株式会社 | 積層体 |
WO2020095981A1 (ja) * | 2018-11-08 | 2020-05-14 | 三菱エンジニアリングプラスチックス株式会社 | 芳香族ポリカーボネート樹脂組成物 |
JPWO2021090823A1 (ja) * | 2019-11-06 | 2021-05-14 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6469625A (en) | 1987-09-10 | 1989-03-15 | Daicel Chem | Polycarbonate polymer having excellent surface hardness |
JPH08183852A (ja) * | 1994-12-28 | 1996-07-16 | Nippon G Ii Plast Kk | コポリカーボネート、コポリカーボネート組成物およびこれらの製造方法 |
JP2003535948A (ja) * | 2000-06-05 | 2003-12-02 | ゼネラル・エレクトリック・カンパニイ | 透明ポリカーボネートブレンドを含む情報記録媒体 |
JP2010126594A (ja) | 2008-11-26 | 2010-06-10 | Mitsubishi Gas Chemical Co Inc | ポリカーボネート樹脂およびそれを用いた高表面硬度フィルムまたはシート |
JP2010188719A (ja) | 2009-01-22 | 2010-09-02 | Teijin Chem Ltd | ポリカーボネート樹脂積層体 |
JP2011089049A (ja) * | 2009-10-23 | 2011-05-06 | Mitsubishi Gas Chemical Co Inc | ポリカーボネート樹脂及びそれを用いた積層成形部材 |
JP2011088402A (ja) | 2009-10-26 | 2011-05-06 | Sumitomo Bakelite Co Ltd | ポリカーボネート樹脂積層体、携帯用表示体および支持基板 |
JP2011105931A (ja) * | 2009-10-22 | 2011-06-02 | Mitsubishi Chemicals Corp | ポリカーボネート樹脂 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3153008A (en) * | 1955-07-05 | 1964-10-13 | Gen Electric | Aromatic carbonate resins and preparation thereof |
JP3766527B2 (ja) * | 1997-11-20 | 2006-04-12 | 大日本印刷株式会社 | 保護層転写シートおよび印画物 |
WO2002022708A1 (fr) | 2000-09-12 | 2002-03-21 | Teijin Limited | Polycarbonates aromatiques et procede de fabrication associe |
JP5055663B2 (ja) | 2001-06-12 | 2012-10-24 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート及び樹脂組成物 |
JP4401608B2 (ja) | 2001-10-15 | 2010-01-20 | 三菱化学株式会社 | 樹脂組成物及び成形品 |
JP4808951B2 (ja) | 2004-10-14 | 2011-11-02 | 帝人化成株式会社 | 光拡散性ポリカーボネート樹脂組成物成形品 |
CN101056939A (zh) * | 2004-11-01 | 2007-10-17 | 帝人化成株式会社 | 树脂组合物以及平板显示器固定框 |
JP4799126B2 (ja) | 2004-11-05 | 2011-10-26 | 帝人化成株式会社 | 眼鏡レンズおよび眼鏡レンズ用ポリカーボネート樹脂成形材料 |
US20080254299A1 (en) * | 2007-04-13 | 2008-10-16 | General Electric Company | Scratch-resistant Layered Composite and Articles |
US20090176946A1 (en) * | 2008-01-03 | 2009-07-09 | Sabic Innovative Plastics Ip B.V. | Polycarbonate blends with high scratch resistance and ductility |
EP2554599B2 (en) | 2010-03-31 | 2024-08-28 | Mitsubishi Chemical Corporation | Polycarbonate resin composition, method for producing same and molded article of this resin composition |
WO2011125896A1 (ja) | 2010-03-31 | 2011-10-13 | 三菱化学株式会社 | ポリカーボネート樹脂組成物、その製造方法及び同樹脂組成物の成形体 |
JP6163644B2 (ja) | 2012-03-30 | 2017-07-19 | 三菱ケミカル株式会社 | ポリカーボネート樹脂及びその組成物 |
-
2012
- 2012-08-01 WO PCT/JP2012/069604 patent/WO2013018835A1/ja active Application Filing
- 2012-08-01 CN CN201280036802.7A patent/CN103702831B/zh active Active
- 2012-08-01 JP JP2012171367A patent/JP6207816B2/ja active Active
- 2012-08-01 EP EP12820813.9A patent/EP2740598B1/en active Active
- 2012-08-01 TW TW101127726A patent/TWI554404B/zh active
- 2012-08-01 KR KR1020147002440A patent/KR101948356B1/ko active IP Right Grant
-
2014
- 2014-02-03 US US14/170,995 patent/US9522519B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6469625A (en) | 1987-09-10 | 1989-03-15 | Daicel Chem | Polycarbonate polymer having excellent surface hardness |
JPH08183852A (ja) * | 1994-12-28 | 1996-07-16 | Nippon G Ii Plast Kk | コポリカーボネート、コポリカーボネート組成物およびこれらの製造方法 |
JP2003535948A (ja) * | 2000-06-05 | 2003-12-02 | ゼネラル・エレクトリック・カンパニイ | 透明ポリカーボネートブレンドを含む情報記録媒体 |
JP2010126594A (ja) | 2008-11-26 | 2010-06-10 | Mitsubishi Gas Chemical Co Inc | ポリカーボネート樹脂およびそれを用いた高表面硬度フィルムまたはシート |
JP2010188719A (ja) | 2009-01-22 | 2010-09-02 | Teijin Chem Ltd | ポリカーボネート樹脂積層体 |
JP2011105931A (ja) * | 2009-10-22 | 2011-06-02 | Mitsubishi Chemicals Corp | ポリカーボネート樹脂 |
JP2011089049A (ja) * | 2009-10-23 | 2011-05-06 | Mitsubishi Gas Chemical Co Inc | ポリカーボネート樹脂及びそれを用いた積層成形部材 |
JP2011088402A (ja) | 2009-10-26 | 2011-05-06 | Sumitomo Bakelite Co Ltd | ポリカーボネート樹脂積層体、携帯用表示体および支持基板 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2740598A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021090824A1 (ja) * | 2019-11-06 | 2021-05-14 | 三菱エンジニアリングプラスチックス株式会社 | レーザーダイレクトストラクチャリング用樹脂組成物、成形品、および、メッキ付き成形品の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201309477A (zh) | 2013-03-01 |
CN103702831B (zh) | 2016-03-23 |
US9522519B2 (en) | 2016-12-20 |
KR20140063580A (ko) | 2014-05-27 |
US20140147651A1 (en) | 2014-05-29 |
JP6207816B2 (ja) | 2017-10-04 |
TWI554404B (zh) | 2016-10-21 |
EP2740598A4 (en) | 2014-06-11 |
JP2013199107A (ja) | 2013-10-03 |
EP2740598B1 (en) | 2016-05-25 |
KR101948356B1 (ko) | 2019-02-14 |
EP2740598A1 (en) | 2014-06-11 |
CN103702831A (zh) | 2014-04-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6207816B2 (ja) | ポリカーボネート樹脂積層体 | |
EP2557123B1 (en) | Polycarbonate resin composition, method for producing same and molded article of this resin composition | |
US9771477B2 (en) | Polycarbonate resin composition, method for producing same and molded article of this resin composition | |
WO2011125906A1 (ja) | ポリカーボネート樹脂、同樹脂の組成物及び同樹脂の成形体 | |
JP6100416B2 (ja) | ポリカーボネート樹脂及びポリカーボネート樹脂組成物の製造方法 | |
JP6163644B2 (ja) | ポリカーボネート樹脂及びその組成物 | |
JP6001322B2 (ja) | ポリカーボネート樹脂組成物 | |
JP6213025B2 (ja) | ポリカーボネート樹脂及びポリカーボネート樹脂組成物 | |
JP5796424B2 (ja) | ポリカーボネート樹脂積層体及びその製造方法 | |
JP2011256368A (ja) | ポリカーボネート樹脂組成物及びポリカーボネート樹脂成形体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201280036802.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12820813 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147002440 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012820813 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |