CN114466896B - Polycarbonate resin composition - Google Patents
Polycarbonate resin composition Download PDFInfo
- Publication number
- CN114466896B CN114466896B CN202080066787.5A CN202080066787A CN114466896B CN 114466896 B CN114466896 B CN 114466896B CN 202080066787 A CN202080066787 A CN 202080066787A CN 114466896 B CN114466896 B CN 114466896B
- Authority
- CN
- China
- Prior art keywords
- glycol
- mass
- polycarbonate resin
- resin composition
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
A polycarbonate resin composition comprising, per 100 parts by mass of a polycarbonate resin (A), 0.1 to 10 parts by mass of a polycarbonate copolymer (B) obtained by bonding (B1) bisphenol A and (B2) a carbonate bond of a poly (n-propylene glycol) optionally having a substituent, and 0.005 to 0.5 parts by mass of a phosphorus stabilizer (C).
Description
Technical Field
The present invention relates to a polycarbonate resin composition, and more particularly, to: a polycarbonate resin composition which has excellent impact resistance, a good hue, and further has excellent transparency, and which is little in gas generation and mold contamination during molding, and a molded article obtained by molding the same.
Background
In order to meet the demands for thickness reduction, weight reduction, labor saving and high definition, a planar light source device is mounted in a liquid crystal display device used for personal computers, mobile phones and the like. In addition, the planar light source device includes a light guide plate having a wedge-shaped cross section with a uniform inclined surface on one surface, and a light guide plate having a flat plate shape, for the purpose of exhibiting an effect of guiding incident light uniformly and efficiently to the liquid crystal display side. In addition, a concave-convex pattern is formed on the surface of the light guide plate to provide a light scattering function.
Such a light guide plate can be obtained by injection molding of a thermoplastic resin, and the above-described concave-convex pattern can be imparted by transfer of concave-convex portions formed on the surface of the insert mold. At present, a light guide plate is molded from a resin material such as polymethyl methacrylate (PMMA), but recently, a display device reflecting a clearer image has been demanded, and a polycarbonate resin material having higher heat resistance has been substituted for the light guide plate because of a tendency to raise the temperature in the device due to heat generated in the vicinity of a light source.
Polycarbonate resins are excellent in mechanical properties, thermal properties, electrical properties, and weather resistance, but have lower light transmittance than PMMA, and therefore have a problem of low brightness when a surface light source body is constituted by a light guide plate made of polycarbonate resin and a light source. In addition, there is a recent demand for reduction in chromaticity difference between an incident portion and a position distant from the incident portion of the light guide plate, but there is a problem in that polycarbonate resin is more likely to yellow than PMMA.
Patent document 1 proposes a method of improving light transmittance and brightness by adding an acrylic resin and an alicyclic epoxy compound, patent document 2 proposes a method of improving brightness by modifying polycarbonate resin terminals and improving transferability of uneven portions to a light guide plate, and patent document 3 proposes a method of improving brightness by introducing a copolymerized polyester carbonate having an aliphatic segment and improving the transferability.
However, in the method of patent document 1, although the hue is improved by adding the acrylic resin, the transmittance and the brightness cannot be improved due to the cloudiness, and the transmittance can be improved by adding the alicyclic epoxy compound, but the effect of improving the hue is not observed. In the cases of patent document 2 and patent document 3, although the effect of improving fluidity and transferability can be expected, there is a disadvantage in that heat resistance is lowered.
On the other hand, it is known that a thermoplastic resin such as a polycarbonate resin is blended with polyethylene glycol or poly (2-methyl) ethylene glycol, and a polycarbonate resin having gamma-ray irradiation resistance is described in patent document 4, and a thermoplastic resin composition excellent in antistatic properties and surface appearance is described in patent document 5, which is blended with PMMA.
Patent document 6 proposes: by compounding a polyalkylene glycol composed of a linear alkyl group, the transmittance and hue are improved. By compounding polytetramethylene glycol, transmittance and yellowing (yellow index: YI) are improved.
Further, patent document 7 describes that: a process for producing a polycarbonate copolymer using a diol obtained by di-esterifying a polyalkylene glycol as a raw material (comonomer), wherein the diester diol of the polyalkylene glycol in the polycarbonate copolymer is unstable, has insufficient impact resistance, and is poor in hue and thermochromatic resistance.
In particular, in various mobile terminals such as smart phones and tablet terminals, the optical components such as the light guide plate have recently been thinned and enlarged at a remarkable speed, and high-temperature barrel temperature and high-speed injection have been required for molding the light guide plate. With this, there is a problem that gas generated during molding increases and mold contamination is liable to develop. Therefore, the resin composition used for these molding needs to have not only excellent optical properties but also less mold contamination due to gas generation at the time of injection molding at high temperature and excellent impact resistance.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 11-158364
Patent document 2: japanese patent laid-open No. 2001-208917
Patent document 3: japanese patent laid-open No. 2001-215336
Patent document 4: japanese patent laid-open No. 1-22959
Patent document 5: japanese patent laid-open No. 9-227785
Patent document 6: japanese patent No. 5699188
Patent document 7: japanese patent laid-open No. 2006-016497
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide: a polycarbonate resin composition which has a good hue, is excellent in transparency and impact resistance, and is little in gas generation and mold contamination during molding.
Solution for solving the problem
The present inventors have conducted intensive studies to achieve the above object, and as a result, found that: the present invention has been accomplished by the above-described findings, and it is an object of the present invention to provide a polycarbonate resin composition which has excellent impact resistance, good hue, excellent transparency, and little gas generation and mold contamination during molding, by blending a specific polycarbonate copolymer based on a carbonate bond of bisphenol a and poly-n-propylene glycol with a phosphorus stabilizer in a specific amount in a general polycarbonate resin.
The present invention relates to the following polycarbonate resin compositions and molded articles.
[1] A polycarbonate resin composition comprising, per 100 parts by mass of a polycarbonate resin (A), 0.1 to 10 parts by mass of a polycarbonate copolymer (B) obtained by bonding (B1) bisphenol A and (B2) a carbonate bond of a poly (n-propylene glycol) optionally having a substituent, and 0.005 to 0.5 parts by mass of a phosphorus stabilizer (C).
[2] The polycarbonate resin composition according to the above [1], wherein the initial YI value of the 300mm optical path length is 25 or less, and the difference (DeltaYI) between the YI value of the 300mm optical path length after being maintained at 95℃for 1000 hours and the initial YI value is 6 or less.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the weight average molecular weight (Mw) of the (B2) poly (n-propylene glycol) constituting the polycarbonate copolymer (B) is 600 to 8000.
[4] The polycarbonate resin composition according to any one of the above [1] to [3], wherein the weight average molecular weight (Mw) of the polycarbonate copolymer (B) is 5000 to 40000.
[5] The polycarbonate resin composition according to any one of the above [1] to [4], wherein the mass ratio of (B1) bisphenol A to (B2) poly (n-propylene glycol) constituting the polycarbonate copolymer (B) is 5% by mass or more and less than 50% by mass, and the mass ratio of (B1) to (B2) exceeds 50% by mass and is 95% by mass or less, based on 100% by mass of the total of (B1) and (B2).
[6]According to [1] above]～[5]The polycarbonate resin composition according to any one of the above, wherein the 3mm thick molded article based on ISO179 has a Charpy notched impact strength of 25kJ/m 2 The above.
[7] A molded article of the polycarbonate resin composition described in any one of [1] to [6 ].
[8] The molded article according to [7] above, which is an optical component.
[9] A polycarbonate resin composition which contains 0.001 to 0.5 part by mass of a stabilizer per 100 parts by mass of a polycarbonate resin (A), has an initial YI value of not more than 25 in a 300mm optical path length, and has a difference (delta YI) between the YI value of 300mm optical path length and the initial YI value of not more than 6 after the composition is held at 95 ℃ for 1000 hours.
[10] The polycarbonate resin composition according to the above [9], wherein the stabilizer is a phosphorus-based stabilizer.
[11]According to [9] above]Or [10]]The polycarbonate resin composition has a Charpy notched impact strength of 25kJ/m in a molded article of 3mm thickness based on ISO179 2 The above.
ADVANTAGEOUS EFFECTS OF INVENTION
The polycarbonate resin composition of the present invention is excellent in impact resistance, has a good hue, further excellent in transparency, and is little in gas generation and mold contamination during molding, and the molded article thus formed is excellent in impact resistance and is particularly suitable for use as an optical member having a good hue and transparency. In particular, the polycarbonate copolymer (B) using (B2) poly (n-propylene glycol) of the present invention has higher compatibility with the polycarbonate resin (a) and excellent transparency than the copolymer substituted with the same linear polytetramethylene glycol, and therefore, the proportion of the miscible polycarbonate copolymer (B) can be practically increased or the polycarbonate copolymer (B) having a higher molecular weight can be used, and therefore, the range of resin design can be widened depending on various applications.
Drawings
Fig. 1 is a plan view of a water-drop type mold used for evaluation of mold contamination in examples.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In the present specification, "to" is used in a sense that it includes the numerical values described before and after as the lower limit value and the upper limit value unless otherwise specified.
The polycarbonate resin composition of the present invention is characterized by comprising 0.1 to 10 parts by mass of a polycarbonate copolymer (B) and 0.005 to 0.5 part by mass of a phosphorus stabilizer (C) per 100 parts by mass of a polycarbonate resin (A), wherein the polycarbonate copolymer (B) is formed by (B1) bisphenol A and (B2) optionally substituted poly (n-propylene glycol) based on carbonate bond.
The components, optical members, and the like constituting the polycarbonate resin composition of the present invention are described in detail below.
[ (B1) polycarbonate copolymer (B) of bisphenol A and (B2) Poly (n-propylene glycol) based on carbonate bond
The polycarbonate copolymer (B) used in the present invention is a polycarbonate copolymer based on a carbonate bond of (B1) bisphenol A and (B2) optionally substituted poly (n-propylene glycol).
The mass ratio of (B1) bisphenol a to (B2) poly (n-propylene glycol) constituting the polycarbonate copolymer (B) is preferably 5 mass% or more and less than 50 mass% based on 100 mass% total of (B1) and (B2), and (B2) poly (n-propylene glycol) is more than 50 mass% and 95 mass% or less, more preferably (B1) 5 mass% or more and 40 mass% or less, (B2) 60 mass% or more and 95 mass% or less, still more preferably (B1) 5 mass% or more and 35 mass% or less, and (B2) 65 mass% or more and 95 mass% or less. (B2) When the amount of the poly (n-propylene glycol) is 50% by mass or less, the hue of the polycarbonate resin composition is deteriorated, and when the amount exceeds 95% by mass, cloudiness is likely to occur.
The polycarbonate copolymer (B) is represented by the following general formula (1) and is a polycarbonate copolymer composed of polycarbonate units derived from bisphenol A and polycarbonate units derived from poly-n-propylene glycol.
(in the formula (1), R a ～R f Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m, n and l represent integers. )
The polycarbonate copolymer (B) can be produced by a conventional production method such as an interfacial polymerization method or a melt polymerization method, and can be produced, for example, by a method of reacting at least (B1) bisphenol a and (B2) poly-n-propylene glycol with a carbonate precursor such as phosgene or diphenyl carbonate.
As the optionally substituted poly (n-propylene glycol) B2, various poly (n-propylene glycol) may be used, and for example, a preferred example thereof is a poly (n-propylene glycol) having an optionally substituted methylene group represented by the following general formula (2).
(in the formula (2), R a ～R f Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 6 to 600. )
As the poly (n-propylene glycol) (B2), preferable is: in the general formula (2), R b Is methyl and R a 、R c 、R d 、R e 、R f Poly- (2-methyl) n-propylene glycol being hydrogen; r is R b Is ethyl and R a 、R c 、R d 、R e 、R f Poly- (2-ethyl) n-propylene glycol being hydrogen; r is R b 、R e Is methyl and R a 、R c 、R d Poly- (2, 2-dimethyl) n-propanediol wherein Rf is hydrogen, wherein R is further preferred a ～R f Poly-n-propylene glycol (i.e., polytrimethylene glycol) that are both hydrogen atoms.
In the present specification, poly (n-propylene glycol) is sometimes referred to as polytrimethylene glycol, but both are the same in meaning and are the same compounds.
The poly (n-propylene glycol) represented by the above formula (2) (B2) may be represented by one of R a ～R f Homopolymers of the composition, in addition, also being composed of different R a ～R f A copolymer of the composition.
As a commercial product of the poly (n-propylene glycol) B2 represented by the above general formula (2), R in the above general formula (2) a ～R f As a commercially available product of poly (n-propylene glycol), i.e., polytrimethylene glycol, each having a hydrogen atom, there is mentioned a product of ALLESSA under the trade name "VELVETOL".
The poly (n-propylene glycol) represented by the above general formula (2) may be a copolymer of a linear polyalkylene glycol such as polyethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, etc., but is preferably a homopolymer of poly (trimethylene glycol), i.e., poly (n-propylene glycol), in terms of improving the transparency of the obtained molded article.
In addition to the n-propyl ether unit (P1) represented by the following general formula (3), the poly-n-propylene glycol (B2) may also contain a polyalkylene glycol copolymer having a branched alkylene ether unit (P2) selected from the units represented by the following general formulae (4-1) to (4-4).
(in the formula (3), R a ～R f The meaning is the same as that of the above general formula (2). )
(in the formulae (4-1) to (4-4), R 1 ～R 10 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R in each of the formulae (4-1) to (4-4) 1 ～R 10 At least 1 of them is an alkyl group having 1 to 3 carbon atoms. )
The branched alkylene ether units represented by the general formulae (4-1) to (4-4) may be homopolymers composed of a branched alkylene ether unit having any one of the general formulae (4-1) to (4-4), or copolymers composed of a plurality of branched alkylene ether units having a structure.
The n-propyl ether unit represented by the above general formula (3) is n-propylene glycol when it is referred to as a diol, and ethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol may be mixed in addition to n-propylene glycol, but is preferably only n-propylene glycol, and more preferably only R as described above a ～R f N-propylene glycol (i.e., trimethylene glycol) each of which is a hydrogen atom.
Trimethylene glycol can be industrially produced by the following process: a process for the hydrogenation of 3-hydroxypropionaldehyde obtained by hydroformylation of ethylene oxide; or a method of hydrogenating 3-hydroxypropanal obtained by hydrating acrolein with a Ni catalyst. In addition, recently, the production of trimethylene glycol by reducing glycerol, glucose, starch, etc. to microorganisms by a biological method has also been carried out.
When the branched alkylene ether unit represented by the above general formula (4-1) is referred to as a diol, (2-methyl) ethylene glycol, (2-ethyl) ethylene glycol, and (2, 2-dimethyl) ethylene glycol may be mentioned, and these may be mixed, but (2-methyl) ethylene glycol and (2-ethyl) ethylene glycol are preferable.
When the branched alkylene ether unit represented by the above general formula (4-2) is referred to as a diol, (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol, (3-ethyl) triethylene glycol, (2, 2-dimethyl) trimethylene glycol (i.e., neopentyl glycol), (2, 2-methylethyl) trimethylene glycol, (2, 2-diethyl) trimethylene glycol, (3, 3-dimethyl) trimethylene glycol, (3, 3-methylethyl) trimethylene glycol, and (3, 3-diethyl) trimethylene glycol may be mentioned, and these may be mixed.
When the branched alkylene ether unit represented by the above general formula (4-3) is referred to as a diol, (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol, (4-ethyl) tetramethylene glycol, (3, 3-dimethyl) tetramethylene glycol, (3, 3-methylethyl) tetramethylene glycol, (3, 3-diethyl) tetramethylene glycol, (4, 4-dimethyl) tetramethylene glycol, (4, 4-methylethyl) tetramethylene glycol, (4, 4-diethyl) tetramethylene glycol, and the like are exemplified, and these may be mixed, but (3-methyl) tetramethylene glycol is preferable.
When the branched alkylene ether unit represented by the above general formula (4-4) is referred to as a diol, (3-methyl) pentamethylene glycol, (4-methyl) pentamethylene glycol, (5-methyl) pentamethylene glycol, (3-ethyl) pentamethylene glycol, (4-ethyl) pentamethylene glycol, (5-ethyl) pentamethylene glycol, (3, 3-dimethyl) pentamethylene glycol, (3, 3-methylethyl) pentamethylene glycol, (3, 3-diethyl) pentamethylene glycol, (4, 4-dimethyl) pentamethylene glycol, (4, 4-methylethyl) pentamethylene glycol, (4, 4-diethyl) pentamethylene glycol, (5, 5-dimethyl) pentamethylene glycol, (5, 5-methylethyl) pentamethylene glycol, and the like may be mentioned, and these may be mixed.
The units represented by the general formulae (4-1) to (4-4) constituting the branched alkylene ether unit are described above for convenience by taking a diol as an example, but the units are not limited to these diols, and may be these alkylene oxides or these polyether derivatives.
Preferred poly (n-propylene glycol) copolymers (B2) are those comprising n-propyl ether units and units represented by the above general formula (4-2), and particularly those comprising trimethylene ether units and 3-methyltrimethylene ether units.
The poly (n-propylene glycol) copolymer (B2) may be a random copolymer or a block copolymer.
The copolymerization ratio of the n-propyl ether unit (P1) represented by the above general formula (3) and the branched alkylene ether unit (P2) represented by the above general formulae (4-1) to (4-4) of the poly (n-propylene glycol) copolymer (B2) is preferably 95/5 to 5/95, more preferably 93/7 to 40/60, still more preferably 90/10 to 65/35, and even more preferably is rich in the n-propyl ether unit (P1), in terms of the molar ratio of (P1)/(P2).
The molar fraction may be used 1 The H-NMR measuring apparatus measures deuterated chloroform as a solvent.
Among the above, particularly preferred poly (n-propylene glycol) (B2) is a homopolymer of n-propylene glycol having no substituent, i.e., trimethylene glycol.
The poly (n-propylene glycol) B2 may have a structure derived from a polyhydric alcohol such as 1, 4-butanediol, glycerin, sorbitol, benzene glycol, bisphenol a, cyclohexanediol, and spiro diol. These organic groups can be imparted to the main chain by adding these polyols at the time of polymerization of polyalkylene glycol. Glycerol, sorbitol, bisphenol a and the like are particularly preferably exemplified.
As the poly (n-propylene glycol) having an organic group in the structure, preferable examples include:
Poly-n-propylene glycol glycerol ether,
Poly (2-methyl) n-propylene glycol glycerol ether,
Poly (n-propylene glycol) -poly (2-methyl) n-propylene glycol glycerol ether,
Poly (n-propylene glycol) -poly (2-ethyl) poly (n-propylene glycol) glycerol ether,
Poly-n-propylene glycol sorbitol ether,
Poly (2-methyl) n-propylene glycol sorbitol ether,
Poly (n-propylene glycol) -poly (2-methyl) ethylene glycol sorbitol ether,
Bisphenol A-bis (poly-n-propylene glycol) ether,
Bisphenol A-bis (poly (2-methyl) n-propylene glycol) ether, bisphenol A-bis (poly n-propylene glycol-poly (2-methyl) ethylene glycol) ether,
Bisphenol a-bis (poly-n-propylene glycol-poly (2-ethyl) poly-n-propylene glycol) ether, and the like.
The weight average molecular weight (Mw) of the poly (n-propylene glycol) (B2) is preferably 600 to 8000, more preferably 800 or more, still more preferably 1000 or more, still more preferably 6000 or less, still more preferably 5000 or less, and particularly preferably 4000 or less. When the weight average molecular weight exceeds the upper limit, compatibility tends to be lowered. When the weight average molecular weight exceeds the lower limit, the impact properties of the composition are reduced.
The weight average molecular weight (Mw) is a molecular weight in terms of polystyrene measured by gel permeation exchange chromatography (GPC) using chloroform as a developing solvent.
Specifically, as GPC, high-speed GPC apparatus "HLC-8320", column, tosoh Co., ltd.) was used: HZ-M (4.6 mm. Times.150 mm). Times.3 pieces of the solution were connected in series and prepared by Tosoh Co., ltd.): chloroform is a value obtained by converting a molecular weight (weight average molecular weight) into polystyrene.
Among the monomers used as the raw material of the polycarbonate copolymer (B), carboxylic acid halides, carbonates, and the like can be used if examples of the carbonate precursor are given. The carbonate precursor may be used in 1 kind, and 2 or more kinds may be used in any combination and ratio.
Specific examples of the carboxylic acid halide include phosgene; bischloroformates of dihydroxy compounds, and haloformates of dihydroxy compounds, such as monochloroformates.
Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate and xylyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; a dicarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, a carbonate of a dihydroxy compound such as a cyclic carbonate, and the like.
As the polycarbonate copolymer (B), bisphenol A-poly-n-propylene glycol copolycarbonate represented by the following formula (5) is particularly preferred.
In the formula (5), m, n and l represent integers. ]
The method for producing the polycarbonate copolymer (B) is not particularly limited, and any known method can be used. Examples thereof include interfacial polymerization, melt transesterification, pyridine, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, the melt transesterification method and the interfacial polymerization method are preferable, and the melt transesterification method is more preferable.
The weight average molecular weight (Mw) of the polycarbonate copolymer (B) is preferably 5000 to 40000, more preferably 6000 or more, still more preferably 7000 or more, still more preferably 37000 or less, still more preferably 35000 or less, particularly preferably 30000 or less, and most preferably 25000 or less. When the weight average molecular weight (Mw) exceeds the upper limit, the compatibility tends to be lowered. When the weight average molecular weight exceeds the lower limit, gas tends to be generated during molding.
The weight average molecular weight (Mw) of the polycarbonate copolymer (B) can be adjusted by: selecting the Mw of (B2) poly-n-propylene glycol as one of the comonomer diol starting materials; the adjustment of the ratio of the carbonate precursor, the addition of the terminator, the adjustment of the temperature and pressure during polymerization, and the like can be performed, for example, in order to increase the Mw in the melt transesterification method, as follows: adjusting the monomer feed ratio so that the reaction ratio of diphenyl carbonate as a carbonate precursor monomer to a diol monomer is close to 1; in order to easily remove the by-product phenol from the polymerization system, the polymerization temperature is kept high, the pressure is reduced as much as possible, and the interface update by stirring is actively performed.
The weight average molecular weight (Mw) of the polycarbonate copolymer (B) is a molecular weight in terms of polystyrene measured by GPC with chloroform as a developing solvent.
Specifically, as GPC, high-speed GPC apparatus "HLC-8320", column, tosoh Co., ltd.) was used: HZ-M (4.6 mm. Times.150 mm). Times.3 pieces of the solution were connected in series and prepared by Tosoh Co., ltd.): chloroform, measurement temperature: the temperature at 25℃is a value obtained by converting the molecular weight (weight average molecular weight) into polystyrene.
The content of the polycarbonate copolymer (B) in the polycarbonate resin composition of the present invention is 0.1 to 10 parts by mass, preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, and further preferably 7 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, particularly 2 parts by mass or less, and most preferably 1 part by mass or less, based on 100 parts by mass of the polycarbonate resin (a). When the content of the polycarbonate copolymer (B) is less than 0.1 part by mass in the above-mentioned range, the hue and the thermochromatic resistance become insufficient, and when it exceeds 10 parts by mass, the material becomes cloudy and the transparency is lost.
[ polycarbonate resin (A) ]
The polycarbonate resin (a) used in the present invention is not particularly limited as long as it is other than the polycarbonate copolymer (B) described above, and various resins can be used.
The polycarbonate resin may be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonate bond is an aromatic carbon, and an aliphatic polycarbonate resin in which carbon is an aliphatic carbon, and may be used. Among them, the polycarbonate resin (a) is preferably an aromatic polycarbonate resin from the viewpoints of heat resistance, mechanical properties, electric characteristics, and the like.
Among the monomers used as the raw material of the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include:
dihydroxybenzenes such as 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene (i.e., resorcinol), and 1, 4-dihydroxybenzene;
dihydroxybiphenyls such as 2, 5-dihydroxybiphenyl, 2 '-dihydroxybiphenyl, and 4,4' -dihydroxybiphenyl;
dihydroxynaphthalenes such as 2,2 '-dihydroxy-1, 1' -binaphthalene, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, and 2, 7-dihydroxynaphthalene;
dihydroxydiaryl ethers such as 2,2 '-dihydroxydiphenyl ether, 3' -dihydroxydiphenyl ether, 4 '-dihydroxy-3, 3' -dimethyldiphenyl ether, 1, 4-bis (3-hydroxyphenoxy) benzene, and 1, 3-bis (4-hydroxyphenoxy) benzene;
2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol A),
1, 1-bis (4-hydroxyphenyl) propane,
2, 2-bis (3-methyl-4-hydroxyphenyl) propane,
2, 2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1, 1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane,
2, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
Alpha, alpha' -bis (4-hydroxyphenyl) -1, 4-diisopropylbenzene,
1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1, 1-bis (4-hydroxyphenyl) ethane,
1, 1-bis (4-hydroxyphenyl) -1-phenylethane,
1, 1-bis (4-hydroxyphenyl) -1-naphthylethane,
1, 1-bis (4-hydroxyphenyl) butane,
2, 2-bis (4-hydroxyphenyl) butane,
2, 2-bis (4-hydroxyphenyl) pentane,
1, 1-bis (4-hydroxyphenyl) hexane,
2, 2-bis (4-hydroxyphenyl) hexane,
1, 1-bis (4-hydroxyphenyl) octane,
2, 2-bis (4-hydroxyphenyl) octane,
4, 4-bis (4-hydroxyphenyl) heptane,
2, 2-bis (4-hydroxyphenyl) nonane,
1, 1-bis (4-hydroxyphenyl) decane,
1, 1-bis (4-hydroxyphenyl) dodecane,
Iso-bis (hydroxyaryl) alkanes;
1, 1-bis (4-hydroxyphenyl) cyclopentane,
1, 1-bis (4-hydroxyphenyl) cyclohexane,
1, 1-bis (4-hydroxyphenyl) -3, 3-dimethylcyclohexane,
1, 1-bis (4-hydroxyphenyl) -3, 4-dimethylcyclohexane,
1, 1-bis (4-hydroxyphenyl) -3, 5-dimethylcyclohexane,
1, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane,
1, 1-bis (4-hydroxy-3, 5-dimethylphenyl) -3, 5-trimethylcyclohexane,
1, 1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1, 1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1, 1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1, 1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Iso-bis (hydroxyaryl) cycloalkanes;
9, 9-bis (4-hydroxyphenyl) fluorene,
Bisphenols containing a xanthene ring-shaped (cardo) structure such as 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene;
4,4' -dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfide;
dihydroxydiaryl sulfoxides such as 4,4' -dihydroxydiphenyl sulfoxide and 4,4' -dihydroxy-3, 3' -dimethyldiphenyl sulfoxide;
4,4' -dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfone;
etc.
Among these, bis (hydroxyaryl) alkanes are preferred, and among them, bis (4-hydroxyphenyl) alkanes are preferred, and 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol a) is preferred in view of impact resistance and heat resistance, among others.
The aromatic dihydroxy compound may be used in 1 kind, and 2 or more kinds may be used in any combination and ratio.
Among the monomers used as the raw material of the polycarbonate resin, carboxylic acid halides, carbonates, and the like can be used if examples of the carbonate precursor are given. The carbonate precursor may be used in 1 kind, and 2 or more kinds may be used in any combination and ratio.
Specific examples of the carboxylic acid halide include phosgene; bischloroformates of dihydroxy compounds, and haloformates of dihydroxy compounds, such as monochloroformates.
Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate and xylyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; a dicarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, a carbonate of a dihydroxy compound such as a cyclic carbonate, and the like.
The method for producing the polycarbonate resin (a) is not particularly limited, and any method can be used. Examples thereof include interfacial polymerization, melt transesterification, pyridine, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, the interfacial polymerization method is also particularly preferred.
The molecular weight of the polycarbonate resin (a) is a viscosity average molecular weight (Mv) obtained by conversion from a solution viscosity measured at a temperature of 25 ℃ using methylene chloride as a solvent, and is preferably 10000 to 26000, more preferably 10500 or more, further preferably 11000 or more, particularly 11500 or more, most preferably 12000 or more, more preferably 24000 or less, further preferably 20000 or less. By setting the viscosity average molecular weight to the lower limit or more of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity average molecular weight to the upper limit or less of the above range, the reduction in fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the moldability can be improved, thereby enabling easy thin-wall molding processing.
In this case, a polycarbonate resin having a viscosity average molecular weight not within the above-mentioned suitable range may be mixed.
The viscosity average molecular weight [ Mv ]]Is as follows: determination of intrinsic viscosity [ eta ] at a temperature of 25℃by using methylene chloride as a solvent and Ubbelohde viscometer ](dl/g) is expressed by Schnell's viscosity formula, i.e., η=1.23×10 -4 Mv 0.83 And (3) the calculated value. In addition, the intrinsic viscosity [ eta ]]Is to measure the concentration [ C ] of each solution]Specific viscosity [ eta ] at (g/dl) sp ]And calculated according to the following formula.
The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrarily selected and determined, and is usually 1000ppm or less, preferably 800ppm or less, more preferably 600ppm or less. Thereby, the retention heat stability and color tone of the polycarbonate resin can be further improved. In particular, the lower limit of the polycarbonate resin produced by the melt transesterification method is usually 10ppm or more, preferably 30ppm or more, and more preferably 40ppm or more. This can suppress the decrease in molecular weight, and can further improve the mechanical properties of the resin composition.
The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group relative to the mass of the polycarbonate resin in ppm. The measurement method is a colorimetric assay by a titanium tetrachloride/acetic acid method (method described in macromol. Chem.88 (1965)) 215.
In order to improve the appearance and flowability of the molded article, the polycarbonate resin (a) may contain a polycarbonate oligomer. The polycarbonate oligomer has a viscosity average molecular weight [ Mv ] of usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Further, the polycarbonate oligomer contained is preferably 30 mass% or less of the polycarbonate resin (including the polycarbonate oligomer).
Further, the polycarbonate resin (a) may be not only a virgin material, but also a polycarbonate resin recycled from a used product (so-called recycled polycarbonate resin).
However, the recycled polycarbonate resin is preferably 80 mass% or less in the polycarbonate resin (a), and more preferably 50 mass% or less. The reason is that the recycled polycarbonate resin is highly likely to be degraded by thermal degradation, aging degradation, or the like, and therefore, if such a polycarbonate resin is used in an amount exceeding the above range, hue and mechanical properties may be degraded.
[ phosphorus stabilizer (C) ]
The polycarbonate resin composition of the present invention contains a phosphorus stabilizer (C). By containing the phosphorus stabilizer, the hue of the polycarbonate resin composition of the present invention is improved, and the thermochromatic resistance is further improved.
As the phosphorus stabilizer, any known one can be used. Specific examples thereof include phosphorus oxyacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic metal pyrophosphates such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphates of group 1 or group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; phosphate compounds, phosphite compounds, phosphonite compounds, and the like, with phosphite compounds being particularly preferred. By selecting the phosphite compound, a polycarbonate resin composition having higher discoloration resistance and continuous productivity can be obtained.
Here, the phosphite compound is of the formula: p (OR) 3 The phosphorus compound with 3 valences is shown, and R represents an organic group with 1 valences or 2 valences.
Examples of the phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) octyl phosphite, monooctyldiphenyl phosphite, dioctyl monophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, bis (2, 4-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, bis (2, 6-di-t-butylphenyl) octyl phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, tetrakis (2, 4-di-t-butylphenyl) -4,4' -biphenylene-diphosphite, and 6- [3- (3-t-butyl-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-t-butyldibenzo [ d, f ] [1,3,2] -dioxaphosphorus.
Among these phosphite compounds, the aromatic phosphite compounds represented by the following formula (1) or (2) are more preferable because they effectively improve the thermochromatic resistance of the polycarbonate resin composition of the present invention.
[ in formula (1), R 1 、R 2 And R is 3 The aryl groups may be the same or different and each represent an aryl group having 6 to 30 carbon atoms.]
[ in formula (2), R 4 And R is 5 And each is optionally the same or different and represents an aryl group having 6 to 30 carbon atoms.]
Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite and the like are preferable, and among them, tris (2, 4-di-t-butylphenyl) phosphite is more preferable. Specific examples of such organic phosphite compounds include "Adekatab 1178" manufactured by ADEKA, sumitomo Chemical Co., ltd., "Sumilizer TNP", JP-351 "manufactured by North chemical industries, inc., ADEKA," Adekatab 2112 "manufactured by BASF Corporation," Irgafos 168 "manufactured by North chemical industries, inc., and" JP-650 "manufactured by North chemical industries, inc.
Among the phosphite compounds represented by the above formula (2), a substance having a pentaerythritol diphosphite structure such as bis (2, 4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, or bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is particularly preferable. Specific examples of the organic phosphite compound include "Adekastab PEP-24G" manufactured by ADEKA, inc. "Adekastab PEP-36", and "Doverphos S-9228" manufactured by Doverchemical Co., ltd.
Among the phosphite compounds, the aromatic phosphite compounds represented by the above formula (2) are more preferable because the hue is more excellent.
The phosphorus stabilizer may be contained in 1 kind, or may be contained in 2 or more kinds in any combination and ratio.
The content of the phosphorus stabilizer (C) is 0.005 to 0.5 parts by mass, preferably 0.007 parts by mass or more, more preferably 0.008 parts by mass or more, particularly preferably 0.01 parts by mass or more, and further preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, further preferably 0.2 parts by mass or less, particularly preferably 0.1 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (a). When the content of the phosphorus stabilizer (C) is less than 0.005 parts by mass in the above-mentioned range, the hue and the thermochromatic resistance become insufficient, and when the content of the phosphorus stabilizer (C) exceeds 0.5 parts by mass, not only the thermochromatic resistance but also the wet heat stability is lowered.
[ epoxy Compound and/or oxetane Compound (D) ]
The resin composition of the present invention also preferably contains an epoxy compound and/or an oxetane compound (D). The epoxy compound and/or oxetane compound (D) can further improve the thermochromatic resistance. The content of the epoxy compound and/or oxetane compound (D) is preferably 0.0005 to 0.2 parts by mass relative to 100 parts by mass of the polycarbonate resin (a).
As the epoxy compound, a compound having 1 or more epoxy groups in 1 molecule is used. Specifically, phenyl glycidyl ether, allyl glycidyl ether, tert-butylphenyl glycidyl ether, 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylcarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-3 ',4' -epoxy-6 '-methylcyclohexylcarboxylate, 2, 3-epoxycyclohexylmethyl-3', 4 '-epoxycyclohexylcarboxylate, 4- (3, 4-epoxy-5-methylcyclohexyl) butyl-3', 4 '-epoxycyclohexylcarboxylate, 3, 4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-6' -methylcyclohexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadiene ether, bis-epoxyethylene glycol, bis-epoxycyclohexyladipate, butadiene diepoxide, tetraphenylethylene oxide, octylene phthalate, epoxy3, 3, 4-epoxycyclohexylmethyl-2, 3-epoxycyclohexane, 2-epoxymethyl-3, 4-epoxycyclohexane, 2-epoxymethyl-2-epoxycyclohexane, 2-epoxymethyl-3, 4-epoxycyclohexane, 2-epoxycyclohexane-2-methyl-2-epoxycyclohexane carboxylate, N-butyl-2, 2-dimethyl-3, 4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3, 4-epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3, 4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3, 4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3 ',4' -epoxycyclohexyl carboxylate, 4, 6-dimethyl-2, 3-epoxycyclohexyl-3 ',4' -epoxycyclohexyl carboxylate, 4, 5-epoxytetrahydrophthalic anhydride, 3-tert-butyl-4, 5-epoxytetrahydrophthalic anhydride, diethyl-4, 5-epoxy-cis-1, 2-cyclohexyl dicarboxylate, di-N-butyl-3-tert-butyl-4, 5-epoxy-cis-1, 2-cyclohexyl dicarboxylate, epoxidized soybean oil, epoxidized linseed oil, and the like.
Among these, alicyclic epoxy compounds are preferably used, and 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylcarboxylate is particularly preferred.
In addition, a polyalkylene glycol derivative having an epoxy group at one end or both ends may be preferably used. Polyalkylene glycols having epoxy groups at both ends are particularly preferred.
Examples of the polyalkylene glycol derivative having an epoxy group in the structure include polyalkylene glycol derivatives such as polyethylene glycol diglycidyl ether, poly (2-methyl) ethylene glycol diglycidyl ether, poly (2-ethyl) ethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polyethylene glycol-poly (2-methyl) ethylene glycol diglycidyl ether, polytetramethylene glycol-poly (2-methyl) ethylene glycol diglycidyl ether, and polytetramethylene glycol-poly (2-ethyl) ethylene glycol diglycidyl ether.
The epoxy compound may be used alone or in combination of 2 or more.
The content of the epoxy compound is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, still more preferably 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, still more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (a). When the content of the epoxy compound is less than 0.0005 parts by mass, the hue and the thermochromatic property tend to be insufficient, and when it exceeds 0.2 parts by mass, the thermochromatic property tends to be deteriorated, and the hue and the wet heat stability tend to be lowered.
The oxetane compound may be any compound having 1 or more oxetanyl groups in the molecule, and a mono-oxetane compound having 1 or more oxetanyl groups in the molecule and a 2-functional or more polyoxetane compound having 2 or more oxetanyl groups in the molecule may be used.
By containing the oxetane compound, a good hue and a high degree of thermochromatic resistance can be further improved.
As the monooxetane compound, a compound represented by the following general formula (3), (4) or (5) and the like can be preferably exemplified.
[ in formulae (3) to (5), R 1 Represents alkyl, R 2 Represents alkyl or phenyl, R 3 Represents a 2-valent organic group optionally having an aromatic ring, and n represents 0 or 1.]
In the above general formulae (3), (4) and (5), R 1 Alkyl is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl or ethyl, particularly preferably ethyl.
In addition, R 2 The alkyl group or phenyl group is preferably an alkyl group having 2 to 10 carbon atoms, and may be any of a chain alkyl group, a branched alkyl group, and an alicyclic alkyl group, or may be a chain or branched alkyl group having an ether bond (ether oxygen atom) in the middle of the alkyl chain. As R 2 Specific examples of (a) include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3-oxopentyl, cyclohexyl, phenyl and the like. Wherein R is 2 Preference is given to 2-ethylhexyl, phenyl, cyclohexyl.
Specific examples of the compound of the general formula (3) include 3-hydroxymethyl-3-methyl oxetane, 3-hydroxymethyl-3-ethyl oxetane, 3-hydroxymethyl-3-propyl oxetane, 3-hydroxymethyl-3-n-butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, and the like. Among them, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane and the like are particularly preferable.
As specific examples of the compound of the formula (4), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like are particularly preferable.
In the general formula (5), R 3 Examples of the organic group having a valence 2 which optionally has an aromatic ring include linear or branched alkylene groups having 1 to 12 carbon atoms such as ethylene, propylene, butylene, neopentylene, n-pentylene, n-hexylene, etc., phenylene groups, and the formula: -CH 2 -Ph-CH 2 -or-CH 2 -Ph-Ph-CH 2 - (here, ph represents a phenyl group) represented by a 2-valent group, a hydrogenated bisphenol A residue, and a hydrogenated bisphenol F residues, hydrogenated bisphenol Z residues, cyclohexanedimethanol residues, tricyclodecanedimethanol residues, and the like.
Specific examples of the compound of the general formula (5) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetan, 4' -bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] biphenyl, 1, 4-bis [ (3-ethyl-3-oxetanylmethyl) methoxymethyl ] benzene, and the like.
The oxetane compound may be used alone or in combination of 2 or more.
The content of the oxetane compound is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, still more preferably 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, still more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (a). When the content of the oxetane compound is less than 0.0005 parts by mass, the hue and the thermochromatic properties tend to be insufficient, and when it exceeds 0.2 parts by mass, the thermochromatic properties tend to deteriorate instead, and a gas during molding tends to be generated.
The epoxy compound and the oxetane compound are preferably contained in combination, and the total content of both is preferably 0.0005 to 0.2 parts by mass based on 100 parts by mass of the polycarbonate resin (a).
[ polyalkylene glycol ]
The resin composition of the present invention also preferably contains a polyalkylene glycol.
As the polyalkylene glycol compound, a polyalkylene glycol Copolymer (CP) having a branched alkylene ether unit (P2) selected from the group consisting of a linear alkylene ether unit (P1) represented by the following general formula (2) and units represented by the following general formulae (2A) to (2D) is preferably exemplified.
In the general formula (2), t represents an integer of 3 to 6.
In the general formulae (2A) to (2D), R 31 ～R 40 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R in the general formulae (2A) to (2D) 31 ～R 40 At least 1 of them is an alkyl group having 1 to 3 carbon atoms.
When the linear alkylene ether unit (P1) represented by the general formula (2) is referred to as a diol, trimethylene glycol having t of 3, tetramethylene glycol having t of 4, pentamethylene glycol having t of 5, and hexamethylene glycol having t of 6 can be exemplified. Trimethylene glycol and tetramethylene glycol are preferred, and tetramethylene glycol is particularly preferred.
Trimethylene glycol (i.e., n-propylene glycol) can be industrially produced by: a process for the hydrogenation of 3-hydroxypropionaldehyde obtained by the hydroformylation of ethylene oxide; alternatively, a method of hydrogenating 3-hydroxypropanal obtained by hydrogenating acrolein using a Ni catalyst. Trimethylene glycol can also be produced by biologically reducing glycerol, glucose, starch, etc. to microorganisms.
When the branched alkylene ether unit represented by the general formula (2A) is referred to as a diol, there may be mentioned (2-methyl) ethylene glycol (i.e., propylene glycol), (2-ethyl) ethylene glycol (i.e., butylene glycol), and (2, 2-dimethyl) ethylene glycol (i.e., neopentyl glycol).
When the branched alkylene ether unit represented by the general formula (2B) is referred to as a diol, there may be mentioned (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol, (3-ethyl) triethylene glycol, (2, 2-dimethyl) trimethylene glycol, (2, 2-methylethyl) trimethylene glycol, (2, 2-diethyl) trimethylene glycol (i.e., neopentyl glycol), (3, 3-dimethyl) trimethylene glycol, (3, 3-methylethyl) trimethylene glycol, and (3, 3-diethyl) trimethylene glycol.
When the branched alkylene ether unit represented by the general formula (2C) is referred to as a diol, (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol, (4-ethyl) tetramethylene glycol, (3, 3-dimethyl) tetramethylene glycol, (3, 3-methylethyl) tetramethylene glycol, (3, 3-diethyl) tetramethylene glycol, (4, 4-dimethyl) tetramethylene glycol, (4, 4-methylethyl) tetramethylene glycol, (4, 4-diethyl) tetramethylene glycol, and the like are exemplified, and (3-methyl) tetramethylene glycol is preferable.
When the branched alkylene ether unit represented by the general formula (2D) is referred to as a diol, (3-methyl) pentamethylene glycol, (4-methyl) pentamethylene glycol, (5-methyl) pentamethylene glycol, (3-ethyl) pentamethylene glycol, (4-ethyl) pentamethylene glycol, (5-ethyl) pentamethylene glycol, (3, 3-dimethyl) pentamethylene glycol, (3, 3-methylethyl) pentamethylene glycol, (3, 3-diethyl) pentamethylene glycol, (4, 4-dimethyl) pentamethylene glycol, (4, 4-methylethyl) pentamethylene glycol, (4, 4-diethyl) pentamethylene glycol, (5, 5-dimethyl) pentamethylene glycol, (5, 5-methylethyl) pentamethylene glycol, 5-diethyl) pentamethylene glycol, and the like are exemplified.
The units represented by the general formulae (2A) to (2D) constituting the branched alkylene ether unit (P2) are described above for convenience with reference to diols, but are not limited to these diols, and may be these alkylene oxides or these polyether derivatives.
Preferred polyalkylene glycol Copolymers (CP) are exemplified by copolymers composed of tetramethylene ether (i.e., tetramethylene glycol) units and units represented by the general formula (2A), and particularly preferably copolymers composed of tetramethylene ether (i.e., tetramethylene glycol) units and 2-methylethyl ether (i.e., propylene glycol) units and/or (2-ethyl) ethylene glycol (i.e., butylene glycol) units. Copolymers composed of tetramethylene ether units and 2, 2-dimethyltrimethylene ether units, i.e., neopentyl glycol ether units, are also preferred.
A method for producing a polyalkylene glycol Copolymer (CP) having a linear alkylene ether unit (P1) and a branched alkylene ether unit (P2) is known, and the copolymer can be produced by polycondensing the above-mentioned diol, alkylene oxide or polyether derivative thereof using a usual acid catalyst.
The polyalkylene glycol Copolymer (CP) may be a random copolymer or a block copolymer.
The terminal group of the polyalkylene glycol Copolymer (CP) is preferably a hydroxyl group. Even if one or both ends of the polyalkylene glycol Copolymer (CP) are capped with an alkyl ether, an aryl ether, an aralkyl ether, a fatty acid ester, an aryl ester, or the like, the showing performance is not affected, and an etherate or an esterified product can be similarly used.
The alkyl group constituting the alkyl ether may be any of a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a lauryl group, a stearyl group, and the like. As the alkyl ether, methyl ether, ethyl ether, butyl ether, lauryl ether, stearyl ether and the like of polyalkylene glycol can be preferably exemplified.
The aryl group constituting the aryl ether is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms, and examples thereof include phenyl, tolyl, naphthyl, and the like, and phenyl, tolyl, and the like are preferred. The aralkyl group is preferably an aralkyl group having 7 to 23 carbon atoms, more preferably 7 to 13 carbon atoms, and still more preferably 7 to 11 carbon atoms, and examples thereof include benzyl, phenethyl, and the like, and particularly preferably benzyl.
The fatty acid constituting the fatty acid ester may be either a straight chain or branched chain, and may be a saturated fatty acid or an unsaturated fatty acid.
The fatty acid constituting the fatty acid ester may be a 1-or 2-valent fatty acid having 1 to 22 carbon atoms. Examples of the 1-valent saturated fatty acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, and behenic acid. Examples of the 1-valent unsaturated fatty acid include unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of the divalent fatty acid having 10 or more carbon atoms include sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, its general acid, dodecenedioic acid, undecanedioic acid, and dodecenedioic acid.
The aryl group constituting the aryl ester is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms, and examples thereof include phenyl, tolyl, naphthyl, and the like, and phenyl, tolyl, and the like are preferred. The group to be blocked is an aralkyl group and shows good compatibility with the polycarbonate resin (a), and therefore can exert the same function as an aryl group. The aralkyl group is preferably an aralkyl group having 7 to 23 carbon atoms, more preferably 7 to 13 carbon atoms, and still more preferably 7 to 11 carbon atoms, and examples thereof include benzyl, phenethyl, and the like, and particularly preferably benzyl.
Among these, a copolymer composed of a tetramethylene ether unit and a 2-methylethylether unit, a copolymer composed of a tetramethylene ether unit and a 3-methyltetramethylene ether unit, and a copolymer composed of a tetramethylene ether unit and a 2, 2-dimethyltrimethylene ether unit are particularly preferable as the polyalkylene glycol Copolymer (CP). Examples of commercial products of such polyalkylene glycol copolymers include "Polystyrene DCB" manufactured by the company of daily oil, "PTG-L" manufactured by the company of Baotu chemical, asahi Kasei Fibers Co., ltd.
The copolymer comprising the tetramethylene ether unit and the 2, 2-dimethyltrimethylene ether unit can be produced by the method described in Japanese patent application laid-open No. 2016-125038.
As the polyalkylene glycol compound, a branched polyalkylene glycol compound represented by the following general formula (3A) or a linear polyalkylene glycol compound represented by the following general formula (3B) can be exemplified as preferable examples. The branched polyalkylene glycol compound represented by the following general formula (3A) or the linear polyalkylene glycol compound represented by the following general formula (3B) may be a copolymer of other copolymerization components, preferably a homopolymer.
In the general formula (3A), R represents an alkyl group having 1 to 3 carbon atoms. Q (Q) 1 And Q 2 Each independently represents a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, or an alkyl group having 1 to 23 carbon atoms. r represents an integer of 5 to 400.
In the general formula (3B), Q 3 And Q 4 Each independently represents a hydrogen atom, an aliphatic acyl group having 2 to 23 carbon atoms, or an alkyl group having 1 to 23 carbon atoms. p represents an integer of 2 to 6, and q represents an integer of 6 to 100.
In the general formula (3A), the integer (degree of polymerization) r is 5 to 400, preferably 10 to 200, more preferably 15 to 100, particularly preferably 20 to 50. When the polymerization degree r is less than 5, the amount of gas generated during molding increases, and there is a possibility that molding defects due to gas, such as unfilling, gas combustion, and transfer defects may occur. When the polymerization degree r exceeds 400, the effect of improving the hue of the pellets of the present invention may not be sufficiently obtained.
As the branched polyalkylene glycol compound, in the general formula (3A), preferable is: q (Q) 1 、Q 2 Polypropylene glycol (i.e., poly (2-methyl) glycol) in which R is a hydrogen atom and R is a methyl group, polybutylene glycol (i.e., poly (2-ethyl) glycol) in which R is an ethyl group, and polybutylene glycol (i.e., poly (2-ethyl) glycol) is particularly preferred.
In the general formula (3B), q (degree of polymerization) is an integer of 6 to 100, preferably 8 to 90, more preferably 10 to 80. When the polymerization degree q is less than 6, gas is generated during molding, which is not preferable. When the polymerization degree q exceeds 100, the compatibility is lowered, which is not preferable.
As the linear polyalkylene glycol compound, Q in the general formula (3B) is preferably exemplified 3 And Q 4 Polyethylene glycol having a hydrogen atom of p of 2, polytrimethylene glycol having a p of 3, polytetramethylene glycol having a p of 4, polypentamethylene glycol having a p of 5, polyhexamethylene glycol having a p of 6, and more preferably polytrimethylene glycol, polytetramethylene glycol or an ester or ether thereof.
The polyalkylene glycol compound may be used as a fatty acid ester or an etherified compound in the same manner without affecting the performance of the polyalkylene glycol compound even if one or both ends thereof are blocked with a fatty acid or an alcohol. Accordingly, Q in the general formulae (3A), (3B) 1 ～Q 4 An aliphatic acyl group or an alkyl group having 1 to 23 carbon atoms may be used.
As the fatty acid ester, any of linear or branched fatty acid esters can be used. The fatty acid constituting the fatty acid ester may be a saturated fatty acid or an unsaturated fatty acid. It is also possible to use those wherein a part of the hydrogen atoms are substituted with a substituent such as a hydroxyl group.
The fatty acid constituting the fatty acid ester may be a 1-or 2-valent fatty acid having 1 to 23 carbon atoms. Specific examples of the saturated fatty acid having a valence of 1 include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, and behenic acid. Specific examples of the 1-valent unsaturated fatty acid include unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of the divalent fatty acid having 10 or more carbon atoms include sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, its general acid, dodecenedioic acid, undecanedioic acid, and dodecenedioic acid.
The fatty acid may be used in an amount of 1 or 2 or more in combination. Fatty acids also include fatty acids having 1 or more hydroxyl groups in the molecule.
As preferable specific examples of fatty acid esters of branched polyalkylene glycols, there may be mentioned those of the general formula (3A) wherein R is methyl or Q 1 And Q 2 Polypropylene glycol stearate as C18 aliphatic acyl, R is methyl, Q 1 And Q 2 Polypropylene glycol behenate which is an aliphatic acyl group having 22 carbon atoms. Preferred specific examples of the fatty acid ester of a linear polyalkylene glycol include polyalkylene glycol monopalmitate, polyalkylene glycol dipalmitate, polyalkylene glycol monostearate,Polyalkylene glycol distearate, polyalkylene glycol (monopalmitate/monostearate), polyalkylene glycol behenate, and the like.
The alkyl group constituting the alkyl ether of the polyalkylene glycol may be any of a linear chain and a branched chain, and examples thereof include alkyl groups having 1 to 23 carbon atoms such as methyl, ethyl, propyl, butyl, octyl, lauryl, and stearyl groups. As the polyalkylene glycol compound, alkyl methyl ether, ethyl ether, butyl ether, lauryl ether, stearyl ether and the like of polyalkylene glycol can be preferably exemplified.
Examples of the commercial products of the branched polyalkylene glycol compound represented by the general formula (3A) include "UNICOL D-1000" manufactured by the daily oil company, and "UNICOL PB-1000".
The number average molecular weight of the polyalkylene glycol compound such as the polyalkylene glycol Copolymer (CP), the branched polyalkylene glycol compound represented by the general formula (3A), and the linear polyalkylene glycol compound represented by the general formula (3B) is preferably 200 to 5000, more preferably 300 or more, still more preferably 500 or more, still more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, particularly preferably less than 1000, and most preferably 800 or less. When the number average molecular weight exceeds the upper limit, compatibility tends to be lowered. When the number average molecular weight exceeds the lower limit, gas tends to be generated during molding. The number average molecular weight of the polyalkylene glycol compound is a number average molecular weight calculated based on a hydroxyl value measured in accordance with JIS K1577.
These polyalkylene glycol compounds may be used alone or in combination of 1 or more than 2.
When the resin composition of the present invention contains a polyalkylene glycol compound, the content thereof is preferably 0.001 to 1.0 part by mass, more preferably 0.01 to 0.8 part by mass, particularly preferably 0.1 to 0.5 part by mass, relative to 100 parts by mass of the polycarbonate resin (a). The content of the polyalkylene glycol compound is less than the lower limit or exceeds the upper limit, and the resulting molded article tends to have a color difference.
[ Release agent ]
The resin composition of the present invention also preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, silicone-based silicones, and the like.
Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Aliphatic carboxylic acids herein also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tricdecylic acid, montanic acid, adipic acid, azelaic acid, and the like.
The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol may be, for example, the same as the aliphatic carboxylic acid described above. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom and an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic is used as a term including alicyclic compounds.
Specific examples of the above alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2-dihydroxyperfluoropropanol, neopentyl glycol, bis (trimethylol) propane, dipentaerythritol, and the like.
The above-mentioned ester may contain an aliphatic carboxylic acid and/or an alcohol as impurities. The ester may be pure or a mixture of a plurality of compounds. Further, the aliphatic carboxylic acid and the alcohol which are combined to form one ester may be used in 1 kind, or may be used in 2 kinds or more in any combination and ratio.
Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing melittin palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and the like.
Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, fischer-Tropsch wax (Fischer Tropsch wax), and an alpha-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons as well. In addition, these hydrocarbons may also be partially oxidized.
Of these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are further preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.
The aliphatic hydrocarbon may be a single substance or a mixture of different components and molecular weights, and the main component may be used within the above-mentioned range.
Examples of the silicone-based silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, fluorinated alkyl silicone and the like.
The release agent may be contained in 1 kind, or may be contained in 2 or more kinds in any combination and ratio.
The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the polycarbonate resin (a). When the content of the release agent is less than the lower limit of the above range, the effect of releasability may be insufficient, and when the content of the release agent exceeds the upper limit of the above range, degradation of hydrolysis resistance, mold contamination at the time of injection molding, and the like may occur.
[ additives etc. ]
The polycarbonate resin composition of the present invention may contain additives other than the above, for example, antioxidants, ultraviolet absorbers, fluorescent brighteners, pigments, dyes, polymers other than polycarbonate resins, flame retardants, impact modifiers, antistatic agents, plasticizers, compatibilizers, and the like. These additives may be blended in one kind or two or more kinds.
The content of the polymer other than the polycarbonate resin (a) and the polycarbonate copolymer (B) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, based on 100 parts by mass of the total of the polycarbonate resin (a) and the polycarbonate copolymer (B).
[ method for producing polycarbonate resin composition ]
The method for producing the polycarbonate resin composition of the present invention is not limited, and known methods for producing polycarbonate resin compositions can be widely used, and the following methods are exemplified: the aromatic polycarbonate resin (a), the polycarbonate copolymer (B), the phosphorus stabilizer (C), and other components blended as needed are mixed in advance by various mixers such as a barrel mixer and a henschel mixer, and then melt-kneaded by a mixer such as a banbury mixer, a roll, a brabender powder stretcher, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The temperature of the melt kneading is not particularly limited, and is usually in the range of 240 to 320 ℃.
[ polycarbonate resin composition ]
The polycarbonate resin composition of the present invention has excellent hue, so that YI (yellowing index) is excellent, an initial YI value of 300mm optical path length is preferably 25 or less, and further, has excellent thermochromatism resistance, so that a difference (DeltaYI) between YI value of 300mm optical path length after being held at 95 ℃ for 1000 hours and initial YI value is preferably 6 or less.
The initial YI value is more preferably 24 or less, still more preferably 22 or less, still more preferably 20 or less. The ΔYI is more preferably 5 or less, and still more preferably 4 or less.
For measurement of the initial YI value and ΔYI, a long-light-path molded article (300 mm. Times.7 mm. Times.4 mm) was molded at a resin temperature of 340℃and a mold temperature of 80℃and the YI value (initial YI value) under a C light source and a 2 DEG visual field was measured at a light path length of 300mm, and the YI value after holding at 95℃for 1000 hours was measured to obtain a difference ΔYI from the initial YI value.
The polycarbonate resin composition of the present invention is excellent in impact resistance, and therefore, the Charpy notched impact strength of a molded article of 3mm thickness based on ISO179 is preferably 25kJ/m 2 The above is more preferably 30kJ/m 2 The above is more preferably 35kJ/m 2 The above.
In the present invention, the following polycarbonate resin composition may be provided.
Specifically disclosed is a polycarbonate resin composition which is characterized by containing 0.001-0.5 part by mass of a stabilizer per 100 parts by mass of a polycarbonate resin (A), wherein the initial YI value of a 300mm optical path length is 25 or less, and the difference (delta YI) between the YI value of a 300mm optical path length after being held at 95 ℃ for 1000 hours and the initial YI value is 6 or less.
The initial YI value is preferably 24 or less, more preferably 22 or less, and further preferably 20 or less. ΔYI is preferably 5 or less, more preferably 4 or less.
The stabilizer in this case is preferably a phosphorus stabilizer. The phosphorus stabilizer is as described above.
The polycarbonate resin composition preferably has a Charpy notched impact strength of 25kJ/m in a molded article of 3mm thickness based on ISO179 2 The above is more preferably 30kJ/m 2 The above is more preferably 35kJ/m 2 The above.
[ optical Member ]
The polycarbonate resin composition of the present invention can be pelletized, and the obtained pellets can be molded by various molding methods to produce optical parts. Further, the resin melt-kneaded in the extruder may be directly molded without passing through the pellet to form an optical member.
The polycarbonate resin composition of the present invention is excellent in fluidity and hue, and is particularly suitable for molding thin-walled optical parts, particularly those that are susceptible to mold contamination, by injection molding, because of little gas generation and mold contamination during molding. In the case of a molded article having a particularly thin wall, the resin temperature at the time of injection molding is preferably a resin temperature higher than 260 to 300℃which is a temperature usually suitable for injection molding of a polycarbonate resin, and the resin temperature is preferably 305 to 400 ℃. The resin temperature is more preferably 310℃or higher, still more preferably 315℃or higher, particularly preferably 320℃or higher, and still more preferably 390℃or lower. In the case of using a conventional polycarbonate resin composition, there is a problem that yellowing of a molded article tends to occur if the resin temperature at the time of molding is increased in order to mold a thin molded article, but by using the resin composition of the present invention, a molded article having a good hue and high transparency, particularly a thin optical member, can be produced even in the above temperature range.
In the case where it is difficult to directly measure the resin temperature, the resin temperature may be grasped as the barrel set temperature.
Here, the thin-walled molded article generally means a molded article having a plate-like portion with a wall thickness of 1mm or less, preferably 0.8mm or less, more preferably 0.6mm or less. Here, the plate-like portion may be a flat plate, a curved plate, or a flat surface, and the surface may have irregularities or the like, and the cross section may have an inclined surface, a wedge-shaped cross section, or the like.
As the optical member, a device or instrument using a light source such as an LED, an organic EL, a white-heat bulb, a fluorescent lamp, or a cathode tube directly or indirectly is exemplified by a light guide plate, a surface light-emitting member, and the like.
The light guide plate is a device for guiding light from a light source such as an LED in a liquid crystal backlight unit, various display devices, and lighting devices, and emits uniform light by diffusing light incident from a side surface, a back surface, or the like through irregularities generally provided on the surface. The shape is generally a flat plate, and may or may not have irregularities on the surface.
The light guide plate is preferably molded by injection molding, ultra-high speed injection molding, injection compression molding, melt extrusion molding (e.g., T-die molding), or the like.
The light guide plate molded by using the resin composition of the invention has no white turbidity and transmittance reduction, good hue and high transparency, and little molding difference caused by mold pollution.
The light guide plate using the polycarbonate resin composition of the present invention can be suitably used in the fields of liquid crystal backlight units, various display devices, and illumination devices. Examples of such devices include various mobile terminals such as mobile phones, mobile notebooks, netbooks, tablet personal computers, tablet computers, smartphones, tablet terminals, cameras, watches, portable computers, various displays, and lighting devices.
The optical member may be in the form of a film or sheet, and specific examples thereof include a light guide film.
In addition, as the optical member, a light guide for guiding light from a light source such as an LED, a lens, or the like is also suitable in a light guide member for external illumination, for example, a head lamp (head lamp), a tail lamp, a fog lamp, or the like for a vehicle such as an automobile or a motorcycle, and may be suitably used.
The light guide plate using the polycarbonate resin composition of the present invention can be suitably used in the fields of liquid crystal backlight units, various display devices, and illumination devices. Examples of such devices include various portable terminals such as mobile phones, mobile notebooks, netbooks, tablet PCs, smartphones, tablet terminals, cameras, clocks, personal computers, various displays, and lighting devices.
Examples
The present invention will be further specifically described below by way of examples. However, the present invention is not limited to the following examples.
The raw materials used in the following examples and comparative examples are shown in table 1.
TABLE 1
In table 1, the polycarbonate copolymers (B1) to (B4) and the other polycarbonate copolymer (Y1) were produced by the following production examples 1 to 5.
[ production example 1 of polycarbonate copolymer (B1) ]
A polymerization apparatus equipped with A1L three-necked flask was charged with diphenyl carbonate, which was a product of ALLESSA corporation, namely, polytrimethylene glycol, and was designated as "VELVETOL H500" (Mw: 1700), in an amount of 85% by mass, and bisphenol A in an amount of 15% by mass, in a molar ratio to diol of 1.16. As catalyst, 11. Mu. Mol (in terms of Cs) of Cs are added per 1mol of diol 2 CO 3 An aqueous solution. After drying the inside of the system for 1 hour, the inside of the polymerization apparatus was repressed with nitrogen gas. Polymerization was started from the time of immersing the double-pressure polymerization apparatus in an oil bath, and the polymerization was performed according to the temperature raising/reducing procedure shown in table 2 below, with the final temperature kept at 217 ℃ under reduced pressure of 0.13kPaA or less by a vacuum pump (f.v.), and after 140 minutes from the start of polymerization, the polymerization was completed.
The weight average molecular weight (Mw) of the bisphenol A-poly (n-propylene glycol) -polycarbonate copolymer (B1) obtained was 15400.
TABLE 2
Production example 2 of polycarbonate copolymer (B2)
A polymerization apparatus equipped with A1L three-necked flask was charged with diphenyl carbonate having a molar ratio of 1.11 relative to diol, in an equivalent amount of 85% by mass and an equivalent amount of bisphenol A of 15% by mass, under the trade name "VELVETOL H500" (Mw: 1700) manufactured by ALLESSA Co., ltd. 5.0. Mu. Mol (in terms of Cs) of Cs are added as catalyst per 1mol of diol 2 CO 3 An aqueous solution. After drying the inside of the system for 1 hour, the inside of the polymerization apparatus was repressed with nitrogen gas. Polymerization was started from the time of immersing the double-pressure polymerization apparatus in an oil bath, and the polymerization was performed by the following temperature rise/pressure reduction procedure shown in Table 3, using a vacuum pump full vacuum (F.V.) the final temperature was maintained at 217℃under reduced pressure of 0.13kPaA or less, and the polymerization was terminated 320 minutes after the initiation of the polymerization.
The weight average molecular weight (Mw) of the bisphenol A-poly (n-propylene glycol) -polycarbonate copolymer (B1) obtained was 18800.
TABLE 3
[ production example 3 of polycarbonate copolymer (B3) ]
A polymerization apparatus equipped with A1L three-necked flask was charged with diphenyl carbonate having a molar ratio of 1.10 relative to glycol, in an equivalent amount of 85% by mass and an equivalent amount of bisphenol A of 15% by mass, under the trade name "VELVETOL H500" (Mw: 1700) manufactured by ALLESSA, which is polytrimethylene glycol. 4.9. Mu. Mol (in terms of Cs) of Cs are added as catalyst per 1mol of diol 2 CO 3 An aqueous solution. After drying the inside of the system for 1 hour, the inside of the polymerization apparatus was repressed with nitrogen gas. Polymerization was started from the time of immersing the double-pressure polymerization apparatus in an oil bath, and the polymerization was performed according to the temperature raising/reducing procedure shown in table 4 below, with the final temperature kept at 217 ℃ under reduced pressure of 0.13kPaA or less by a vacuum pump (f.v.), and the polymerization was ended 350 minutes after the start of polymerization.
The weight average molecular weight (Mw) of the bisphenol A-poly (n-propylene glycol) -polycarbonate copolymer (B3) obtained was 22800.
TABLE 4
Production example 4 of polycarbonate copolymer (B4)
A polymerization apparatus equipped with A1L three-necked flask was charged with diphenyl carbonate, which was a polytrimethylene glycol, and was manufactured under the trade name "VELVETOL H500" (Mw: 1700) by ALLESSA, in an amount of 85% by mass, and bisphenol A in an amount of 15% by mass, in a molar ratio to diol of 1.07. 4.9. Mu. Mol (in terms of Cs) of Cs are added as catalyst per 1mol of diol 2 CO 3 An aqueous solution. After drying the inside of the system for 1 hour, the inside of the polymerization apparatus was repressed with nitrogen gas. Polymerization was started from the time of immersing the double-pressure polymerization apparatus in an oil bath, and the polymerization was performed according to the temperature raising/reducing procedure shown in table 5 below, with the final temperature kept at 217℃under reduced pressure of 0.13kPaA or less by a vacuum pump (F.V.), and the polymerization was ended 310 minutes after the start of polymerization.
The bisphenol A-poly (n-propylene glycol) -polycarbonate copolymer (B4) obtained had a weight average molecular weight (Mw) of 34100.
TABLE 5
[ production example 5 of polycarbonate copolymer (Y1) ]
A polymerization apparatus equipped with A1L three-necked flask was charged with diphenyl carbonate having a relative molar ratio to diol of 1.15 in an amount of 85% by mass and 15% by mass of bisphenol A, respectively, under the trade name "PTMG650" (Mw: 1950) manufactured by Mitsubishi Chemical Corporation as polytetramethylene glycol. 9.9. Mu. Mol (in terms of Cs) of Cs are added as catalyst per 1mol of diol 2 CO 3 An aqueous solution. After drying the inside of the system for 1 hour, the inside of the polymerization apparatus was repressed with nitrogen gas. Polymerization was started from the time of immersing the double-pressure polymerization apparatus in an oil bath, and the polymerization was performed according to the temperature raising/reducing procedure shown in table 6 below, with the final temperature kept at 217℃under reduced pressure of 0.13kPaA or less by a vacuum pump (F.V.), and after 140 minutes from the start of polymerization, the polymerization was completed.
The weight average molecular weight (Mw) of the bisphenol A-polytetramethylene glycol-polycarbonate copolymer (Y1) obtained was 22800.
TABLE 6
Examples 1 to 19 and comparative examples 1 to 5
[ production of pellets of resin composition ]
The above-mentioned components were compounded in the ratios (parts by mass) shown in tables 7 to 9 below, and after mixing for 20 minutes in a barrel mixer, melt-kneading was performed at a barrel temperature of 240℃by using a single screw extruder (Tanabe Plastic Machine Co., ltd., "VS-40") with a vent and a screw diameter of 40mm, and strand cutting was performed to obtain pellets.
[ strand transparency for producing pellets of resin composition ]
In the above-mentioned process for producing pellets of the resin composition, the transparency of the strand melt-kneaded and extruded was visually determined by using an extruder according to the following criteria.
A: the extruded strands are extremely high in transparency and the polycarbonate resin is extremely compatible with the polycarbonate copolymer (B), polytetramethylene glycol, and other polycarbonate copolymers.
B: the extruded strands have high transparency and good compatibility of the polycarbonate resin with the polycarbonate copolymer (B), polytetramethylene glycol, and other polycarbonate copolymers.
C: the extruded strands were slightly cloudy, and the polycarbonate resin had poor compatibility with the polycarbonate copolymer (B), polytetramethylene glycol, and other polycarbonate copolymers.
D: the extruded strands are strongly cloudy, and the compatibility of the polycarbonate resin with the polycarbonate copolymer (B), polytetramethylene glycol, and other polycarbonate copolymers is extremely poor.
[ flowability evaluation (Q value) ]
The obtained pellets were dried at 120℃for 5 hours or more, and then the composition was measured for the Q value (unit:. Times.10) of flow rate per unit time using an advanced flow rate tester under a load of 160kgf at 280℃by the method described in JIS K7210 appendix C -2 cm 3 /second), flowability was evaluated. The orifice used was 1mm in diameter by 10mm in length.
The higher the Q value, the more excellent the fluidity
Impact resistance evaluation (Charpy impact Strength)
Drying the obtained granule at 120deg.C for 5 hr, and injectingAn impact resistance test piece having a thickness of 3mm was produced by an injection molding machine (NEX 80III, manufactured by Nikkin resin Co., ltd.) under the conditions of a cylinder temperature of 250 ℃, a mold temperature of 80 ℃ and a molding cycle of 45 seconds based on ISO179-1, 2. The test piece thus obtained was subjected to notch cutting with a depth of 2mm at R0.25mm, and the Charpy notched impact strength (kJ/m) was measured at a temperature of 23 ℃ 2 )。
[ evaluation of mold contamination (mold deposit) ]
Evaluation of contamination in injection Molding (mold smudge)
The pellets obtained in the above were dried at 120℃for 5 hours, and then injection molded by 200 shots using a drop mold as shown in FIG. 1 under conditions of a cylinder temperature of 340℃and a molding cycle of 10 seconds and a mold temperature of 40℃by an injection molding machine (SE 7M manufactured by Sumitomo mechanical industries Co., ltd.) to determine the state of contamination by white deposit generated on the metal mirror surface on the mold fixing side after completion of the molding by visual evaluation according to the following criteria.
A: the mold has little attachment and excellent mold pollution resistance.
B: the mold deposit was small, but a small amount of mold contamination resistance was observed.
C: mold deposit was large and mold contamination was observed.
D: mold fouling was observed significantly with a lot of mold attachments.
The water-drop type mold of fig. 1 is: the resin composition is introduced from the gate G to produce a mold designed in such a manner that the gas easily slides at the tip P portion. The gate G has a width of 1mm and a thickness of 1mm, and in FIG. 1, the gate G has a width h1 of 14.5mm, a length h2 of 7mm, a length h3 of 27mm, and a thickness of the molded part of 3mm.
[ hue (YI) and ΔYI (evaluation of thermochromic resistance) ]
The pellets thus obtained were dried at 120℃for 5 to 7 hours by a hot air circulating dryer, and then molded into long-path molded articles (300 mm. Times.7 mm. Times.4 mm) at a resin temperature of 340℃and a mold temperature of 80℃by an injection molding machine (HSP 100A made by Sodic k).
For this long optical path molded article, YI value (yellowing index) was measured at an optical path length of 300 mm. For the measurement, a long-path spectral transmission colorimeter (ASA 1, C light source, 2℃field of view, manufactured by Nippon Denshoku Co., ltd.) was used.
Then, the long optical path molded article was held at 95℃for 1000 hours, and then YI value was measured at an optical path length of 300mm to obtain a difference DeltaYI from the initial YI value, and the thermochromatic property was evaluated.
The above evaluation results are shown in tables 7 to 9 below.
TABLE 7
TABLE 8
TABLE 9
Industrial applicability
The polycarbonate resin composition of the present invention is excellent in impact resistance, has a good hue, is excellent in transparency, and is extremely suitable for various molded articles, particularly optical parts, because of little gas generation and mold contamination during molding.
Claims (10)
1. A polycarbonate resin composition comprising, per 100 parts by mass of a polycarbonate resin (A), 0.1 to 10 parts by mass of a polycarbonate copolymer (B) and 0.005 to 0.5 part by mass of a phosphorus stabilizer (C),
the polycarbonate copolymer (B) is formed by (B1) bisphenol A and (B2) poly (n-propylene glycol) optionally having substituent(s) based on carbonate bond,
the mass ratio of (B1) bisphenol A to (B2) poly (n-propylene glycol) constituting the polycarbonate copolymer (B) is 5 mass% or more and less than 50 mass%, based on 100 mass% of the total of (B1) and (B2), and (B1) is more than 50 mass% and 95 mass% or less.
2. The polycarbonate resin composition according to claim 1, wherein the initial YI value of the 300mm optical path length is 25 or less, and the difference (DeltaYI) between the YI value of the 300mm optical path length after being maintained at 95℃for 1000 hours and the initial YI value is 6 or less.
3. The polycarbonate resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the (B2) poly-n-propylene glycol constituting the polycarbonate copolymer (B) is 600 to 8000.
4. The polycarbonate resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the polycarbonate copolymer (B) is 5000 to 40000.
5. The polycarbonate resin composition according to claim 3, wherein the weight average molecular weight (Mw) of the polycarbonate copolymer (B) is 5000 to 40000.
6. The polycarbonate resin composition according to any one of claims 1, 2 and 5, wherein the 3mm thick molded article based on ISO179 has a Charpy notched impact strength of 25kJ/m 2 The above.
7. The polycarbonate resin composition according to claim 3, wherein the 3mm thick molded article based on ISO179 has a Charpy notched impact strength of 25kJ/m 2 The above.
8. The polycarbonate resin composition according to claim 4, wherein the 3mm thick molded article based on ISO179 has a Charpy notched impact strength of 25kJ/m 2 The above.
9. A molded article of the polycarbonate resin composition according to any one of claims 1 to 8.
10. The molded article according to claim 9, which is an optical component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-173919 | 2019-09-25 | ||
| JP2019173919 | 2019-09-25 | ||
| PCT/JP2020/033188 WO2021059902A1 (en) | 2019-09-25 | 2020-09-02 | Polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114466896A CN114466896A (en) | 2022-05-10 |
| CN114466896B true CN114466896B (en) | 2023-05-30 |
Family
ID=75166579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080066787.5A Active CN114466896B (en) | 2019-09-25 | 2020-09-02 | Polycarbonate resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7457728B2 (en) |
| CN (1) | CN114466896B (en) |
| TW (1) | TW202116918A (en) |
| WO (1) | WO2021059902A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7348426B1 (en) | 2022-02-28 | 2023-09-20 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
| WO2024024943A1 (en) * | 2022-07-28 | 2024-02-01 | 三菱ケミカル株式会社 | Polycarbonate resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016118586A (en) * | 2014-12-18 | 2016-06-30 | 花王株式会社 | Electrophotographic toner |
| CN107148449A (en) * | 2015-01-07 | 2017-09-08 | 三菱工程塑料株式会社 | Thin walled optical part poly carbonate resin composition and thin walled optical part |
| JP2018178075A (en) * | 2017-04-18 | 2018-11-15 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical component and optical component |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63227627A (en) * | 1987-03-17 | 1988-09-21 | Idemitsu Petrochem Co Ltd | Production of polycarbonate based elastomer |
| JPH01252630A (en) * | 1988-04-01 | 1989-10-09 | Hodogaya Chem Co Ltd | Modified polyoxytetramethylene glycol and its production |
| JP4731134B2 (en) | 2004-07-01 | 2011-07-20 | 出光興産株式会社 | Method for producing polycarbonate copolymer and polycarbonate copolymer |
| JP5699188B2 (en) | 2013-07-26 | 2015-04-08 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for thin optical parts and thin optical parts |
| JP6101745B2 (en) * | 2015-01-07 | 2017-03-22 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for thin optical parts and thin optical parts |
| EP3778773B1 (en) * | 2018-03-27 | 2022-08-31 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
-
2020
- 2020-09-02 WO PCT/JP2020/033188 patent/WO2021059902A1/en active Application Filing
- 2020-09-02 CN CN202080066787.5A patent/CN114466896B/en active Active
- 2020-09-02 JP JP2021548735A patent/JP7457728B2/en active Active
- 2020-09-14 TW TW109131434A patent/TW202116918A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016118586A (en) * | 2014-12-18 | 2016-06-30 | 花王株式会社 | Electrophotographic toner |
| CN107148449A (en) * | 2015-01-07 | 2017-09-08 | 三菱工程塑料株式会社 | Thin walled optical part poly carbonate resin composition and thin walled optical part |
| JP2018178075A (en) * | 2017-04-18 | 2018-11-15 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical component and optical component |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114466896A (en) | 2022-05-10 |
| WO2021059902A1 (en) | 2021-04-01 |
| JPWO2021059902A1 (en) | 2021-04-01 |
| TW202116918A (en) | 2021-05-01 |
| JP7457728B2 (en) | 2024-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6101856B1 (en) | Polycarbonate resin composition for thin optical parts and thin optical parts | |
| CN111936578B (en) | Polycarbonate resin composition | |
| CN110719936B (en) | Polycarbonate resin composition for optical member and optical member | |
| CN114466896B (en) | Polycarbonate resin composition | |
| JP6912639B2 (en) | Polycarbonate resin composition for optical components | |
| JP2017171811A (en) | Polycarbonate resin composition | |
| CN110546204B (en) | Polycarbonate resin composition for optical member and optical member | |
| JP2019090043A (en) | Polycarbonate resin composition for optical component, and optical component | |
| JP2019090044A (en) | Polycarbonate resin composition for optical component, and optical component | |
| JP2018095803A (en) | Polycarbonate resin composition for optical components | |
| JP2018095725A (en) | Polycarbonate resin composition for optical components | |
| JP7163537B1 (en) | Polycarbonate resin composition | |
| JP6522493B2 (en) | Polycarbonate resin composition for optical parts and optical parts | |
| JP7347962B2 (en) | Polycarbonate resin composition | |
| KR102642651B1 (en) | Polycarbonate resin composition for optical component and optical component | |
| JP6490490B2 (en) | Polycarbonate resin composition and thin optical component | |
| JP2018095812A (en) | Polycarbonate resin composition for optical components | |
| JP7309452B2 (en) | Polycarbonate resin composition | |
| JP6446601B1 (en) | Polycarbonate resin composition for optical parts and optical parts | |
| JP2022144176A (en) | Polycarbonate resin composition and molded article | |
| JP2022144172A (en) | Polycarbonate resin composition and molded article | |
| CN117062875A (en) | Polycarbonate resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |