WO2015151742A1 - 被塗装用ポリカーボネート樹脂成形材料、成形品及び塗装成形品 - Google Patents
被塗装用ポリカーボネート樹脂成形材料、成形品及び塗装成形品 Download PDFInfo
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- C08J7/04—Coating
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to a polycarbonate resin molding material for coating, a molded article, and a coated molded article.
- Polycarbonate resins are tough and excellent in impact resistance and electrical properties, and the resulting molded products are also excellent in dimensional stability, so they are widely used in various fields such as the electrical / electronic equipment field and the automobile field. Expected. For example, it is widely used as a raw material resin for the production of housings for electric and electronic devices, automotive parts, or precision molded parts. In particular, in automotive parts applications, resin materials such as polycarbonate resins are widely used because it is possible to suppress exhaust gas and reduce fuel consumption by reducing the weight. At that time, automotive exterior parts are required to have high impact resistance from the viewpoint of safety in a car collision.
- Patent Documents 1 and 2 each include two types of polycarbonate resins each having a specific structural unit and a specific molecular weight, and physical properties such as Dupont impact strength are within a predetermined range, surface hardness, impact resistance,
- a polycarbonate resin composition having excellent transparency is disclosed.
- Patent Document 3 discloses a solvent belonging to the group consisting of an ester solvent, an aromatic hydrocarbon solvent, a ketone solvent, and ethylene glycol monobutyl ether, which has an adverse effect by dissolving the resin constituting the resin material.
- Patent Document 3 discloses a method for improving a reduction in impact resistance of a resin material due to coating by improving the paint.
- a polycarbonate resin molding material that has high impact resistance even after coating without depending on the type of paint used, and also has good coating film adhesion.
- the present invention provides a polycarbonate resin molding material for coating which does not show a significant decrease in impact resistance even after coating, and is excellent in coating film adhesion, a molded product including the same, and a coated molded product. For the purpose.
- the inventors of the present invention include a polycarbonate resin (A) containing a polycarbonate-polyorganosiloxane copolymer and a copolymer (B) having a structural unit derived from butadiene, and molding.
- A polycarbonate resin
- B copolymer having a structural unit derived from butadiene
- the present inventors have found that the coating film adhesion is excellent and has completed the present invention. That is, the present invention relates to the following [1] to [11].
- R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O— or —CO—; R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an ary
- a and b each independently represent an integer of 0 to 4.
- n represents the average number of repetitions.
- [2] The above [1], wherein the content of the polyorganosiloxane block part containing the repeating unit represented by the general formula (II) in the component (A-1) is 0.75 to 15% by mass. Polycarbonate resin molding material for coating.
- the component (B-2) is at least one selected from methyl methacrylate-butadiene-styrene terpolymer (MBS) and methyl methacrylate-butadiene terpolymer (MB).
- MBS methyl methacrylate-butadiene-styrene terpolymer
- MBS methyl methacrylate-butadiene terpolymer
- the component (B) includes the component (B-1) and the component (B-2), and the content of the component (B-1) is 100 parts by mass of the component (A).
- the polycarbonate resin molding material for coating according to any one of the above [3] to [5], which is 8 to 100 parts by mass and the content of the component (B-2) is more than 0 parts by mass and 25 parts by mass or less.
- a molded article comprising the polycarbonate resin molding material for coating according to any one of [1] to [6].
- a coated molded product obtained by coating the molded product according to [7].
- the coated molded article according to [8] which is painted with a paint containing an organic solvent.
- a polycarbonate resin molding material for coating of the present invention is a polycarbonate having a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II) -The polyorganosiloxane block in the whole molding material, comprising the polycarbonate resin (A) containing the polyorganosiloxane copolymer (A-1) and the copolymer (B) having a structural unit derived from butadiene.
- the content of the portion is 0.50 to 10% by mass, and the content of the structural unit derived from the butadiene in the entire molding material is 3 to 10% by mass.
- the “polycarbonate resin molding material for coating” refers to a polycarbonate resin molding material capable of molding a molded article to be coated, which is subjected to various coatings.
- “coating” is a concept including various coatings such as roll coating, curtain flow coating, dipping method, spray coating, electrostatic coating, electrodeposition coating, and UV coating, as well as plating and vapor deposition.
- R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O— or —CO—; R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an ary
- the polycarbonate resin (A) (hereinafter also referred to as “component (A)”) used in the present invention is a polycarbonate-polyorganosiloxane copolymer from the viewpoint of avoiding a decrease in impact resistance after coating of the obtained molded product.
- component (A) (hereinafter also referred to as “PC-POS (A-1)” or “(A-1) component”).
- the component (A) may contain an aromatic polycarbonate resin (A-2) other than the component (A-1) to the extent that the effects of the present invention are not impaired.
- PC-POS is a polycarbonate-poly having a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II) It is an organosiloxane copolymer.
- R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O— or —CO—; R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an ary
- PC-POS (A-1) may be used alone or in combination of two or more. Further, the type of the repeating unit represented by the general formula (I) in PC-POS (A-1) may be only one type, may be included in two or more types, and two or more types are copolymerized. May be. The same applies to the repeating unit represented by formula (II) in PC-POS (A-1).
- examples of the halogen atom independently represented by R 1 and R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- examples of the alkyl group independently represented by R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups (“various” means linear and all branched ones). And the same applies hereinafter), various pentyl groups, and various hexyl groups.
- examples of the alkoxy group independently represented by R 1 and R 2 include a case where the alkyl group moiety is the alkyl group.
- R 1 and R 2 are each preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
- Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and the like, and an alkylene group having 1 to 5 carbon atoms is preferable.
- Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group.
- the cycloalkylene group represented by X is preferably a cycloalkylene group having 5 to 10 carbon atoms, and examples thereof include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.
- Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferable.
- a cycloalkylidene group having 5 to 8 carbon atoms is more preferred.
- Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.
- Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.
- a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.
- examples of the halogen atom independently represented by R 3 and R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- examples of the alkyl group and alkoxy group independently represented by R 3 and R 4 include the same groups as those for R 1 and R 2 .
- Examples of the aryl group independently represented by R 3 and R 4 include a phenyl group and a naphthyl group.
- R 3 and R 4 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. More preferred is a methyl group.
- n is an average number of repetitions, preferably 30 to 500, more preferably 30 to 150, and still more preferably 30 to 120. If the average number of repetitions n is 30 or more, the impact resistance of the obtained molded product and coated molded product is better. If the average number of repetitions n is 500 or less, it is easy to avoid the difficulty in handling when producing the copolymer due to the viscosity of the raw material POS becoming too high.
- the structure of the polyorganosiloxane block including the repeating structure represented by the general formula (II) is preferably represented by the following general formula (II ′).
- R 3 to R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl having 6 to 12 carbon atoms. Indicates a group.
- Y represents a single bond or a divalent organic residue containing —C ( ⁇ O) —, an aliphatic group or an aromatic group.
- n is the average number of repetitions.
- R 3 to R 6 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- Y is preferably a residue of a phenol compound having an alkyl group, more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.
- a structure of the polyorganosiloxane block containing the repeating structure represented by general formula (II) it is also preferable that it is what is represented by following formula (II '').
- R 3 to R 6 and Y are the same as those in the general formula (II ′), and preferred ones are also the same.
- the sum of p and q is n. p and q are each preferably n / 2.
- m represents 0 or 1.
- Z ' represents a single bond, -R 7 O -, - R 7 COO -, - R 7 NH -, - COO- or -S- shown, the R 7 is a straight, branched or cyclic alkylene group, an aromatic An aryl-substituted alkylene group, an arylene group or a diarylene group which may have an alkoxy group on the ring is shown.
- ⁇ represents a divalent group derived from a diisocyanate compound, a divalent group derived from a dicarboxylic acid, or a divalent group derived from a dicarboxylic acid halide. Specific examples of the divalent group derived from the diisocyanate compound, the divalent group derived from the dicarboxylic acid, and the divalent group derived from the dicarboxylic acid halide will be described later.
- the content of the polyorganosiloxane block portion containing the repeating unit represented by the general formula (II) in PC-POS (A-1) is preferably 0.75 to 15% by mass, more preferably 2.0%. It is ⁇ 13 mass%, more preferably 2.5 to 10 mass%, particularly preferably 3.0 to 8.0 mass%. If the content is 0.75% by mass or more, the impact resistance of the obtained molded product and coated molded product is better. On the other hand, when the content is 15% by mass or less, the handling property during the production of PC-POS (A-1) is better.
- the viscosity average molecular weight (Mv) of PC-POS (A-1) is preferably 10,000 to 30,000, more preferably 12,000 to 28,000, still more preferably 15,000 to 25,000. It is. When the viscosity average molecular weight of the component (A-1) is within this range, it is easy to balance fluidity and impact resistance.
- PC-POS (A-1)
- it can be easily produced by referring to a known method for producing PC-POS, for example, the method described in JP 2010-241943 A or the like. it can.
- an aromatic polycarbonate oligomer produced in advance and a polyorganosiloxane having a reactive group at its terminal (such as polyorganosiloxanes represented by the following general formulas (2) and (3)) are water-insoluble. It is dissolved in a basic organic solvent (methylene chloride, etc.), and an alkaline compound aqueous solution (sodium hydroxide aqueous solution, etc.) of a dihydric phenol (bisphenol A, etc.) represented by the following general formula (1) is added.
- Interfacial polycondensation reaction is performed using an amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) in the presence of a molecular weight regulator (terminal terminator) (monohydric phenol such as pt-butylphenol).
- amine such as triethylamine
- quaternary ammonium salt such as trimethylbenzylammonium chloride
- terminal terminator dihydric phenol such as pt-butylphenol
- the content of the polyorganosiloxane block part containing the repeating unit represented by the general formula (II) in the PC-POS (A-1) component is adjusted by adjusting the amount of the polyorganosiloxane used. can do.
- the mixture is allowed to stand to separate into an aqueous phase and a water-insoluble organic solvent phase [separation step], and the water-insoluble organic solvent phase is washed (preferably a basic aqueous solution, an acidic aqueous solution, water PC-POS can be obtained by sequentially washing) [washing step], and concentrating [concentration step], pulverizing [pulverizing step] and drying [drying step].
- the use ratio of the PC-POS (A-1) component with the polyorganosiloxane block content adjusted to the polycarbonate resin (A) made of an aromatic polycarbonate resin (A-2) other than (A-1) is adjusted. By doing, content of the polyorganosiloxane block part in (A) component can be adjusted.
- PC-POS is a copolymer of a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), and phosgene, carbonate ester or chloroformate. Can also be manufactured.
- R 1 and R 2 , X, a and b are the same as those in the general formula (I).
- R 3 to R 6 are the same as those in general formula (II ′), and n is the same as that in general formula (II).
- Y ′ is the same as Y in the general formula (II ′).
- m 0 or 1
- Z represents a halogen atom, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —R 7 NHR 8 , —COOH or —SH
- R 7 is linear or branched A chain or cyclic alkylene group, an aryl-substituted alkylene group optionally having an alkoxy group on the aromatic ring, an arylene group, or a diarylene group
- R 8 represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxy group; Show.
- the diarylene group is a group in which two arylene groups are linked directly or via a divalent organic group, and specifically has a structure represented by —Ar 1 —W—Ar 2 —. It is a group.
- Ar 1 and Ar 2 represent an arylene group
- W represents a single bond or a divalent organic group. Specific examples and preferred examples of W are the same as X in the general formula (I).
- the linear or branched alkylene group represented by R 7 includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and the cyclic alkylene group has 5 to 15 carbon atoms, preferably a carbon number. Examples include 5 to 10 cycloalkylene groups.
- the alkylene moiety of the aryl-substituted alkylene group represented by R 7 includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
- Examples of the aryl moiety of the aryl-substituted alkylene group represented by R 7 include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.
- Examples of the arylene group represented by R 7 , Ar 1, and Ar 2 include arylene groups having 6 to 14 ring carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group.
- Y ′ represents a single bond or a divalent organic residue containing —C ( ⁇ O) —, an aliphatic group or an aromatic group and bonded to Si and O or Si and Z.
- R 3 to R 6 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- n is the same as described above, and m represents 0 or 1.
- Z is preferably —R 7 OH, —R 7 COOH, —R 7 NH 2 , —COOH or —SH.
- R 7 is as defined above, and preferred ones are also the same.
- R 8 is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
- the dihydric phenol represented by the general formula (1) which is a raw material of PC-POS, is not particularly limited, but 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable.
- dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophene) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,
- the polyorganosiloxane represented by the general formula (2) is a phenol having an olefinically unsaturated carbon-carbon bond (preferably vinylphenol, allylphenol, eugenol, isopropenylphenol, etc.) with a predetermined polymerization degree ( n: the number of repetitions) can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain.
- the phenols are more preferably allylphenol or eugenol.
- polyorganosiloxane represented by the general formula (2) those in which R 3 to R 6 are all methyl groups are preferable.
- examples of the polyorganosiloxane represented by the general formula (2) include compounds represented by the following general formulas (2-1) to (2-10).
- R 3 to R 6 , n and R 8 are as defined above, and preferred ones are also the same.
- c represents a positive integer and is usually an integer of 1 to 6.
- the phenol-modified polyorganosiloxane represented by the general formula (2-1) is preferable from the viewpoint of ease of polymerization.
- ⁇ , ⁇ -bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (2-2)
- ⁇ , ⁇ -bis [3- (4-hydroxy-2-methoxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by (2-3)
- the phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example. First, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopolysiloxane. At this time, ⁇ , ⁇ -dihydrogen polyorganosiloxane having a desired average number of repetitions can be synthesized by changing the charging ratio of cyclotrisiloxane and disiloxane.
- this ⁇ , ⁇ -dihydrogen polyorganosiloxane is subjected to an addition reaction with a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol, to thereby obtain a desired compound.
- a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol
- a phenol-modified polyorganosiloxane having an average number of repetitions can be produced.
- PC-POS is obtained by copolymerizing a dihydric phenol represented by the general formula (1), a polyorganosiloxane represented by the following general formula (3), and phosgene, carbonate ester or chloroformate. It may be manufactured by.
- the polyorganosiloxane represented by the general formula (3) is a reaction product of the polyorganosiloxane represented by the general formula (2) and a diisocyanate compound, dicarboxylic acid or dicarboxylic acid halide.
- R 3 to R 6 , m, p, q, Y ′, Z and Z ′ are as defined above, and preferred ones are also the same.
- ⁇ represents a divalent group derived from a diisocyanate compound, a divalent group derived from a dicarboxylic acid, or a divalent group derived from a dicarboxylic acid halide.
- the component (A) is an aromatic polycarbonate resin (A-2) other than the component (A-1) (hereinafter also referred to as “component (A-2)”) to the extent that the effects of the present invention are not impaired. ) May be included.
- the component (A-2) is obtained by using an aromatic dihydric phenol-based compound and contains a polyorganosiloxane block part containing a repeating unit represented by the general formula (II) contained in the component (A). Can be used to adjust the amount.
- the viscosity average molecular weight (Mv) of the aromatic polycarbonate resin as the component (A-2) is preferably 10,000 to 30,000, more preferably 12,000 to 28,000, still more preferably 15,000. ⁇ 25,000.
- the aromatic polycarbonate resin (A-2) does not have a repeating structure represented by the general formula (II), and the main chain is composed of repeating units represented by the following general formula (III). It is preferable that Such an aromatic polycarbonate resin is not particularly limited, and various known aromatic polycarbonate resins can be used.
- R 9 and R 10 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- X ′ is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO -, -SO 2- , -O- or -CO- is shown.
- d and e each independently represents an integer of 0 to 4.
- R 9 and R 10 include the same as R 1 and R 2, and preferred ones are also the same.
- R 9 and R 10 are more preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
- Specific examples of X ′ include the same as X described above, and preferable examples are also the same.
- d and e are each independently preferably 0 to 2, more preferably 0 or 1.
- the aromatic polycarbonate resin is prepared by reacting with an aromatic dihydric phenol compound and phosgene in the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, and then a tertiary amine or quaternary ammonium.
- Conventional methods such as the interfacial polymerization method in which a polymerization catalyst such as a salt is added and polymerized, and the pyridine method in which an aromatic dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgene is directly introduced are used. What is obtained by the manufacturing method of an aromatic polycarbonate can be used.
- a molecular weight regulator terminal terminator
- branching agent a branching agent and the like are used as necessary.
- said aromatic dihydric phenol type compound what is represented by the following general formula (III ') is mentioned.
- aromatic dihydric phenol compound examples include, for example, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4- Bis (hydroxyphenyl) alkanes such as hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone and the like.
- bis (hydroxyphenyl) alkane dihydric phenol is preferable, and bisphenol A is more preferable.
- the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 10,000 to 30,000, more preferably 12,000 to 28,000, and further preferably 15,000 to 25,000. When the viscosity average molecular weight of the component (A) is within this range, the balance between fluidity and impact resistance is more excellent.
- the content of the component (A-1) in the component (A) is preferably 5 to 100% by mass from the viewpoint of preferably adjusting the content of the polyorganosiloxane block portion in the component (A) to the above range. More preferably, it is 10 to 100% by mass, and further preferably 15 to 100% by mass.
- the component (A-1) is 5% by mass or more, it is not necessary to increase the content of the polyorganosiloxane block portion in the component (A-1), which is preferable for the production of PC-POS.
- the polycarbonate resin molding material for coating of the present invention contains a copolymer having a structural unit derived from butadiene (hereinafter also simply referred to as “component (B)”) as component (B). Since the polycarbonate resin molding material for coating contains the component (B), the impact resistance is improved, so that no significant decrease in impact resistance is seen even after coating, and the coating film adhesion is improved. It is possible to obtain a polycarbonate resin molding material for coating which is also excellent.
- the component (B) includes a copolymer (B-1) having a structural unit derived from butadiene, acrylonitrile and styrene and having no structural unit derived from methyl methacrylate, and , Preferably containing at least one selected from copolymers (B-2) having structural units derived from butadiene and methyl methacrylate, more preferably containing at least (B-1) component, (B-1 More preferably, the component (B) and the component (B-2) are included.
- the impact resistance after coating is further improved.
- ABS acrylonitrile-butadiene-styrene terpolymer
- ABS commercially available products of ABS as the component (B-1) include Santac AT-05, Clarastic SXH-330 (above, manufactured by Nippon A & L Co., Ltd.), Toyolac 500, 700 (manufactured by Toray Industries, Inc.), PA -756 (manufactured by Kitami Jitsugyo Co., Ltd.), HR181 (KUMHO, manufactured by PETROCHEMICAL), and the like.
- the copolymer (B-2) having a structural unit derived from butadiene and methyl methacrylate includes methyl methacrylate-butadiene-styrene terpolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene quaternary copolymer. Examples thereof include a polymer (MABS) and a methyl methacrylate-butadiene binary copolymer (MB).
- the component (B-2) is at least one selected from methyl methacrylate-butadiene-styrene terpolymer (MBS) and methyl methacrylate-butadiene terpolymer (MB).
- MBS methyl methacrylate-butadiene-styrene terpolymer
- MB methyl methacrylate-butadiene terpolymer
- it is a seed, more preferably MBS.
- MBS Commercially available products of MBS include Metabrene C223A (manufactured by Mitsubishi Rayon Co., Ltd.), Denka TH Polymer (manufactured by Denki Kagaku Kogyo Co., Ltd.), Kane Ace B (manufactured by Kaneka Co., Ltd.), Paraloid EXL2620 (manufactured by Dow Chemical), etc. Can be mentioned.
- Examples of commercially available products of MABS include Denka CL polymer, Denka TE polymer, Denka TP polymer (manufactured by Denki Kagaku Kogyo Co., Ltd.) and the like.
- Examples of commercially available MBs include Kane Ace M-711 (manufactured by Kaneka Corporation), Paraloid EXL2603, Paraloid EXL2690 (manufactured by Dow Chemical).
- the component (B) components may be used individually by 1 type, and may use 2 or more types together.
- the component (B) contains ABS as the component (B-1), and the component (B) includes the components (B-1) and (B More preferably, the component (B-1) is ABS, and the component (B-2) is MBS.
- ABS and MBS are used in combination, there is little reduction in impact resistance after painting, and a coated molded article having good impact resistance can be obtained.
- the content of the component (B) with respect to 100 parts by mass of the component (A) is preferably 8 to 125 parts by mass, more preferably 9 to 70 parts by mass, and still more preferably. Is 9 to 50 parts by mass, particularly preferably 25 to 45 parts by mass.
- the content of the component (B) is 8 to 125 parts by mass with respect to 100 parts by mass of the component (A)
- the impact resistance after coating becomes better.
- the preferred contents of the component (B-1) and the component (B-2) with respect to 100 parts by mass of the component (A) are as follows.
- the content of each component is in the following range, the impact resistance of the obtained molded article and coated molded article becomes better.
- the content of the component (B-1) is preferably 8 to 100 parts by mass with respect to 100 parts by mass of the component (A). Content is more than 0 mass part and 25 mass parts or less.
- the content of the component (B-1) is 8 to 50 parts by mass
- the content of the component (B-2) is 1 to 20 parts by mass
- the content of the component (B-1) is particularly preferably 24 to 40 parts by mass.
- the content of the component is 1 to 5 parts by mass.
- the content of the polyorganosiloxane block portion containing the repeating unit represented by the general formula (II) is 0.50 to 10% by mass in the total molding material.
- the content is preferably 0.50 to 8.0% by mass, more preferably 0.70 to 5.0% by mass, and still more preferably 0.70 to 2.0% by mass.
- the content is less than 0.50% by mass, the impact resistance of the obtained molded product and coated molded product is insufficient.
- the said content is 10 mass% or less, it is preferable at the point of economical efficiency.
- the content of the polyorganosiloxane block portion in the molding material is a value calculated by nuclear magnetic resonance (NMR) measurement.
- the content of the structural unit derived from butadiene in the entire molding material is 1 to 10% by mass.
- the content of the structural unit derived from butadiene is less than 1% by mass, the resulting molded article and the coated molded article have insufficient impact resistance, and when it exceeds 10% by mass, the fluidity of the molding material decreases.
- the polycarbonate resin molding material for coating of the present invention preferably has a content of the structural unit derived from butadiene in the total molding material of 2 to 9% by mass, more preferably 3 to 8% by mass. %.
- the polycarbonate resin molding material for coating of the present invention may contain a resin component other than the components (A) and (B) as long as the effects of the present invention are not impaired.
- the resin component include acrylonitrile-styrene binary copolymer (AS), acrylonitrile-acrylic acid ester-styrene terpolymer (AAS), acrylonitrile- (ethylene / propylene / diene copolymer) -styrene copolymer Examples include coalescence (AES).
- the polycarbonate resin molding material for coating of the present invention can appropriately contain other components to the extent that the effects of the present invention are not significantly impaired.
- other components include additives such as antioxidants, ultraviolet absorbers, mold release agents, flame retardants, flame retardant aids, inorganic fillers, and colorants (dyes and pigments).
- the polycarbonate resin molding material for coating of the present invention can be obtained by blending the above components (A) and (B) and other components used as necessary, and kneading.
- the mixing and kneading at this time are premixed by a commonly used equipment such as a ribbon blender, a drum tumbler, etc., and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw screw. It can be carried out by a method using an extruder, a kneader or the like.
- the heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.
- components other than polycarbonate resin (A) can also be previously added as polycarbonate master (A) and melt-kneading, ie, a masterbatch.
- the molded article of the present invention contains the polycarbonate resin molding material for coating of the present invention.
- the molded article of the present invention is a composition obtained by melt-kneading the polycarbonate resin molding material for coating of the present invention using the above-described melt-kneading molding machine, or by using a pellet obtained from the composition as a raw material. It is obtained by molding by a method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, a foam molding method or the like.
- a pellet-shaped forming raw material is produced by the melt kneading method, and then a molded product is formed by using injection molding or injection compression molding using the pellet.
- a gas injection molding method for preventing the appearance of sink marks or reducing the weight can be employed.
- the molded product of the present invention is excellent in impact resistance, coating film adhesion, and solvent resistance.
- a test piece having a thickness of 1 mm was dropped under the conditions of a temperature of 23 ° C., a core diameter of 12.7 mm, a cradle diameter of 48 mm, a weight mass of 500 g, and a weight height of 100 cm.
- the number of test pieces in which cracking occurs is preferably 1 or less, and more preferably 0.
- the impact resistance test of the molded product can be performed by the method described in the examples.
- the coated molded product of the present invention is obtained by coating the molded product of the present invention.
- a coating method Roll coating, curtain flow coating, a dipping method, spray coating, electrostatic coating, electrodeposition coating, UV coating, etc. are mentioned. Further, a method such as plating or vapor deposition may be used.
- coat According to the coating method, the shape of a coating molded product, etc., it can select suitably.
- a resin paint containing a colorant various resin components such as an epoxy resin, a urethane resin, a phenol resin, and an acrylic resin, and water or an organic solvent can be used.
- the resin component may be a curable resin containing a main agent and a curing agent.
- a paint containing an organic solvent is preferable.
- the impact resistance of the molded product after coating tends to decrease due to the influence of the organic solvent or the like.
- the organic solvent contained in the paint is at least one selected from ketone-based and ester-based solvents
- the molded product since the molded product has an impregnation action, the impact resistance of the molded product is significantly reduced.
- the molded article of the polycarbonate resin molding material for coating of the present invention shows a significant decrease in impact resistance even when it is coated with a paint containing at least one selected from ketone-based and ester-based solvents as the organic solvent. There is a remarkable effect of not.
- a molded product can be thinned without worrying about a decrease in impact resistance due to coating
- various products to which the coated molded product of the present invention is applied for example, smartphones, tablet PCs, notebook computer cases, automobiles It is possible to reduce the size and weight of interior parts, exterior parts for automobiles, radio cassettes and other portable electrical products.
- the coated molded article of the present invention is a test piece having a thickness of 1 mm, a drop weight impact on the conditions of a temperature of 23 ° C., a striker diameter of 12.7 mm, a cradle diameter of 48 mm, a weight mass of 500 g and a weight height of 100 cm.
- the number of test pieces in which cracks occur is preferably 1 or less, and more preferably 0.
- the impact resistance test of the coated molded product can be performed in the same manner as the impact resistance test of the molded product.
- the thickness of the coating film in the coated molded product is usually 0.1 to 100 ⁇ m. From the viewpoint of preventing cracking due to the coating film being too thick, the coating film thickness is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m.
- the polycarbonate resin molding material for coating of the present invention, a molded product including the same, and a molded molded product include a smartphone, a tablet, a notebook PC casing, an automotive interior part, an automotive exterior part, a radio cassette, and other portable electrical products. Can be suitably used.
- Preparation Example 1 Manufacture of polycarbonate oligomer> Add 2,000 ppm of sodium dithionite to 5.6% by mass sodium hydroxide aqueous solution to bisphenol A (BPA) to be dissolved later, and add bisphenol A to the bisphenol A concentration of 13.5% by mass. It melt
- BPA bisphenol A
- This bisphenol A aqueous solution of sodium hydroxide 40L (hereinafter, L is an abbreviation for liters) / hr, methylene chloride at a flow rate of 15 L / hr, phosgene at a flow rate of 4.0 kg / hr, an inner diameter of 6 mm and a tube length of 30 m It was continuously passed through the mold reactor.
- the tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
- the reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and bisphenol A aqueous sodium hydroxide solution 2.8 L / hr, 25 mass.
- the reaction was carried out by adding 0.64 L / hr of a 0.07 L / hr aqueous sodium hydroxide solution, 17 L / hr water, and 1 wt% triethylamine aqueous solution.
- the reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
- the polycarbonate oligomer thus obtained had a concentration of 329 g / L and a chloroformate group concentration of 0.74 mol / L.
- PC-PDMS Copolymer 1 Production Example 1 ⁇ Production of Polycarbonate-Polydimethylsiloxane Copolymer (PC-PDMS Copolymer 1)> In a 50 L tank reactor equipped with a baffle plate, a paddle type stirring blade and a cooling jacket, 15 L of the polycarbonate oligomer solution prepared in Preparation Example 1 above, 9.0 L of methylene chloride, and the average number of repeating n of dimethylsiloxane repeating units are 90.
- PDMS polydimethylsiloxane
- a methylene chloride solution of pt-butylphenol (PTBP) (137 g of PTBP dissolved in 2.0 L of methylene chloride), a sodium hydroxide aqueous solution of bisphenol A (577 g of sodium hydroxide and sodium dithionite 2 A solution in which 1012 g of bisphenol A was dissolved in an aqueous solution in which 0.0 g was dissolved in 8.4 L of water was added, and a polymerization reaction was performed for 50 minutes.
- PTBP pt-butylphenol
- PC-PDMS copolymer polycarbonate-polydimethylsiloxane copolymer
- aqueous phase containing excess bisphenol A and sodium hydroxide.
- the organic phase was isolated.
- the methylene chloride solution of the PC-PDMS copolymer thus obtained was washed successively with 15% by volume of 0.03 mol / L sodium hydroxide aqueous solution and 0.2 mol / L hydrochloric acid, and then washed. Washing with pure water was repeated until the electrical conductivity in the later aqueous phase became 0.01 ⁇ S / m or less.
- the methylene chloride solution of the PC-PDMS copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure to produce PC-PDMS copolymer 1.
- the content of the PDMS block portion determined by nuclear magnetic resonance (NMR) of the obtained PC-PDMS copolymer 1 was 6.0% by mass, the viscosity number was 47.5, and the viscosity average molecular weight Mv was 17,700. It was.
- Examples 1-2 and Comparative Examples 1-4 Each component was mixed in the ratio shown in Table 1, and granulated at a resin temperature of 280 ° C. using a vented 50 mm ⁇ single screw extruder to obtain pellets made of a polycarbonate resin molding material for coating.
- the pellets obtained by the above method are injection molded using an injection molding machine (model number; IS100EN, manufactured by Toshiba Machine Co., Ltd.) under molding conditions of a cylinder temperature of 240 ° C. and a mold temperature of 40 ° C., and various tests for evaluation. I got a piece.
- Example 1 From the comparison between Example 1 and Comparative Example 1, in the molded article of the polycarbonate resin molding material containing the component (A-1) and the component (B) so that the POS block portion has a predetermined content, The number of test pieces cracked in the impact resistance test after painting has decreased by four. On the other hand, in comparison with Comparative Examples 1 and 2, in the molded article of the polycarbonate resin molding material that does not contain the component (B), even if the component (A-1) is contained, the impact resistance test after coating is conducted. The number of cracked specimens is only reduced by two.
- the polycarbonate resin molding material contains the (A-1) component and the (B) component having a POS block portion at the same time. It can be seen that the characteristics are greatly improved.
- the impact resistance after coating is improved by adding the components (A-1), (B-1) and (B-2) at the same time as compared with the case where each component is added separately. It can be seen that is greatly improved.
- the polycarbonate resin molding material for coating of the present invention does not show a significant decrease in impact resistance even when it is coated, and has good coating film adhesion.
- the polycarbonate resin molding material for coating of the present invention since the impact resistance after painting is good even in the thin molded product, it is possible to reduce the size and weight of various molded products. It is suitably used for notebook PC casings, automotive interior parts, automotive exterior parts, radio cassettes and other portable electrical products.
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Abstract
Description
中でも自動車部品用途においては、軽量化により排ガスの抑制や低燃費化が期待できることから、ポリカーボネート樹脂をはじめとする樹脂製素材が汎用されている。その際、自動車外装用部品においては、自動車衝突時の安全性の観点から、高い耐衝撃性が求められる。例えば特許文献1,2には、それぞれ特定の構造単位と特定の分子量を有する2種のポリカーボネート樹脂を含有し、かつデュポン衝撃強度等の物性が所定の範囲である、表面硬度、耐衝撃性、及び透明性に優れるポリカーボネート樹脂組成物が開示されている。
そこで特許文献3には、樹脂製素材を構成する樹脂を溶解させて悪影響を及ぼすような、エステル系溶剤、芳香族炭化水素系溶剤、ケトン系溶剤及びエチレングリコールモノブチルエーテルからなる群に属する溶剤の合計含有量が一定未満であるプライマー塗料、及び該プライマー塗料をポリカーボネートポリマーアロイ等からなる基材に塗装した塗装品が提案されている。
特許文献3は、塗装を施すことによる樹脂製素材の耐衝撃性の低下を、塗料の改良により改善する方法を開示したものである。しかしながら、使用する塗料の種類に依存せず塗装後にも高い耐衝撃性を有し、さらには塗膜密着性も良好なポリカーボネート樹脂成形材料が望まれる。
すなわち、本発明は、下記[1]~[11]に関する。
[2]前記(A-1)成分中の前記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロック部分の含有量が0.75~15質量%である上記[1]に記載の被塗装用ポリカーボネート樹脂成形材料。
[3]前記(B)成分が、ブタジエン、アクリロニトリル及びスチレンに由来する構成単位を有しかつメチルメタクリレートに由来する構成単位を有さない共重合体(B-1)、並びに、ブタジエン及びメチルメタクリレートに由来する構成単位を有する共重合体(B-2)から選ばれる少なくとも1種を含む上記[1]又は[2]に記載の被塗装用ポリカーボネート樹脂成形材料。
[4]前記(B-1)成分が、アクリロニトリル-ブタジエン-スチレン3元共重合体(ABS)である上記[3]に記載の被塗装用ポリカーボネート樹脂成形材料。
[5]前記(B-2)成分が、メチルメタクリレート-ブタジエン-スチレン3元共重合体(MBS)及びメチルメタクリレート-ブタジエン2元共重合体(MB)から選ばれる少なくとも1種である上記[3]又は[4]に記載の被塗装用ポリカーボネート樹脂成形材料。
[6]前記(B)成分が前記(B-1)成分及び前記(B-2)成分を含み、前記(A)成分100質量部に対して、前記(B-1)成分の含有量が8~100質量部であり、前記(B-2)成分の含有量が0質量部超25質量部以下である上記[3]~[5]のいずれかに記載の被塗装用ポリカーボネート樹脂成形材料。
[7]上記[1]~[6]のいずれかに記載の被塗装用ポリカーボネート樹脂成形材料を含む成形品。
[8]上記[7]に記載の成形品に塗装を施した塗装成形品。
[9]有機溶剤を含む塗料により塗装された上記[8]に記載の塗装成形品。
[10]前記有機溶剤がケトン系及びエステル系溶剤から選ばれる少なくとも1種である上記[9]に記載の塗装成形品。
[11]厚さ1mmの試験片において、温度23℃、撃芯直径12.7mm、受け台直径48mm、錘質量500g、錘高さ100cmの条件で落錘衝撃試験を5回行った際に、割れが発生する試験片の数が1個以下である上記[8]~[10]のいずれかに記載の塗装成形品。
本発明の被塗装用ポリカーボネート樹脂成形材料は、下記一般式(I)で表される繰り返し単位からなるポリカーボネートブロック及び下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックを有するポリカーボネート-ポリオルガノシロキサン共重合体(A-1)を含有するポリカーボネート樹脂(A)と、ブタジエンに由来する構成単位を有する共重合体(B)とを含み、全成形材料中の前記ポリオルガノシロキサンブロック部分の含有量が0.50~10質量%であり、全成形材料中の前記ブタジエンに由来する構成単位の含有量が3~10質量%であることを特徴とする。
なお本発明において「被塗装用ポリカーボネート樹脂成形材料」とは、各種塗装が施される、被塗装物である成形品を成形しうるポリカーボネート樹脂成形材料をいう。また本発明において「塗装」とは、ロールコート、カーテンフローコート、浸漬法、スプレー塗装、静電塗装、電着塗装、UV塗装等の各種塗装のほか、めっきや蒸着等も含む概念である。
本発明に用いられるポリカーボネート樹脂(A)(以下、「(A)成分」ともいう)は、得られる成形品の塗装後の耐衝撃性の低下を避ける観点から、ポリカーボネート-ポリオルガノシロキサン共重合体(A-1)(以下「PC-POS(A-1)」又は「(A-1)成分」ともいう)を含有することを特徴とする。なお後述するように、(A)成分としては、本発明の効果を損なわない程度に(A-1)成分以外の芳香族ポリカーボネート樹脂(A-2)が含まれていてもよい。
PC-POS(A-1)は、下記一般式(I)で表される繰り返し単位からなるポリカーボネートブロック及び下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックを有するポリカーボネート-ポリオルガノシロキサン共重合体である。
PC-POS(A-1)は、1種を単独で使用してもよいし、2種以上を併用してもよい。またPC-POS(A-1)中の一般式(I)で表される繰り返し単位の種類は、1種のみでもよく、2種以上含まれていてもよく、2種以上が共重合していてもよい。PC-POS(A-1)中の一般式(II)で表される繰り返し単位についても同様である。
R1及びR2がそれぞれ独立して示すアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、各種ブチル基(「各種」とは、直鎖状及びあらゆる分岐鎖状のものを含むことを示し、以下、同様である。)、各種ペンチル基、各種ヘキシル基が挙げられる。R1及びR2がそれぞれ独立して示すアルコキシ基としては、アルキル基部位が前記アルキル基である場合が挙げられる。
R1及びR2としては、いずれも、好ましくは炭素数1~4のアルキル基又は炭素数1~4のアルコキシ基である。
Xが表すアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基等が挙げられ、炭素数1~5のアルキレン基が好ましい。Xが表すアルキリデン基としては、エチリデン基、イソプロピリデン基等が挙げられる。Xが表すシクロアルキレン基としては、炭素数5~10のシクロアルキレン基が好ましく、シクロペンタンジイル基、シクロヘキサンジイル基、シクロオクタンジイル基等が挙げられる。Xが表すシクロアルキリデン基としては、例えば、シクロヘキシリデン基、3,5,5-トリメチルシクロヘキシリデン基、2-アダマンチリデン基等が挙げられ、炭素数5~10のシクロアルキリデン基が好ましく、炭素数5~8のシクロアルキリデン基がより好ましい。Xが表すアリールアルキレン基のアリール部位としては、フェニル基、ナフチル基、ビフェニル基、アントリル基などの環形成炭素数6~14のアリール基が挙げられる。Xが表すアリールアルキリデン基のアリール部位としては、フェニル基、ナフチル基、ビフェニル基、アントリル基などの環形成炭素数6~14のアリール基が挙げられる。
a及びbは、それぞれ独立に0~4の整数を示し、好ましくは0~2、より好ましくは0又は1である。
なお、R3及びR4としては、いずれも、好ましくは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基であり、いずれもメチル基であることがより好ましい。
R3~R6としては、いずれも、好ましくは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基である。Yとしては、好ましくはアルキル基を有するフェノール系化合物の残基であり、アリルフェノール由来の有機残基やオイゲノール由来の有機残基がより好ましい。
また、一般式(II)で表される繰り返し構造を含むポリオルガノシロキサンブロックの構造としては、下記式(II'')で表されるものであることも好ましい。
mは、0又は1を示す。
Z’は、単結合、-R7O-、-R7COO-、-R7NH-、-COO-又は-S-を示し、該R7は直鎖、分岐鎖もしくは環状アルキレン基、芳香環上にアルコキシ基を有してもよいアリール置換アルキレン基、アリーレン基又はジアリーレン基を示す。該R7の具体例については後述する。
また、βは、ジイソシアネート化合物由来の2価の基、ジカルボン酸由来の2価の基、又はジカルボン酸ハロゲン化物由来の2価の基を示す。該ジイソシアネート化合物由来の2価の基、ジカルボン酸由来の2価の基、及びジカルボン酸ハロゲン化物由来の2価の基の具体例については後述する。
なお、本発明において、粘度平均分子量(Mv)は、ウベローデ型粘度管にて、20℃における塩化メチレン溶液の極限粘度〔η〕を測定し、Schnellの式(〔η〕=1.23×10-5×Mv0.83)より算出した値である。
具体的には、予め製造された芳香族ポリカーボネートオリゴマーと、末端に反応性基を有するポリオルガノシロキサン(下記一般式(2)及び(3)で表されるポリオルガノシロキサン等)とを、非水溶性有機溶媒(塩化メチレン等)に溶解させ、下記一般式(1)で表される二価フェノール(ビスフェノールA等)のアルカリ性化合物水溶液(水酸化ナトリウム水溶液等)を加え、重合触媒として第三級アミン(トリエチルアミン等)や第四級アンモニウム塩(トリメチルベンジルアンモニウムクロライド等)を用い、分子量調節剤(末端停止剤)(p-t-ブチルフェノール等の1価フェノール)の存在下、界面重縮合反応させることにより製造できる。なお、前記ポリオルガノシロキサンの使用量を調整することなどにより、PC-POS(A-1)成分中の一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロック部分の含有量を調整することができる。
上記界面重縮合反応後、適宜静置して水相と非水溶性有機溶媒相とに分離し[分離工程]、非水溶性有機溶媒相を洗浄(好ましくは塩基性水溶液、酸性水溶液、水の順に洗浄)し[洗浄工程]、得られた有機相を濃縮[濃縮工程]、粉砕[粉砕工程]及び乾燥する[乾燥工程]ことによって、PC-POSを得ることができる。このポリオルガノシロキサンブロック含有量の調整されたPC-POS(A-1)成分と(A-1)以外の芳香族ポリカーボネート樹脂(A-2)からなるポリカーボネート樹脂(A)との使用比率を調整することにより、(A)成分中のポリオルガノシロキサンブロック部分の含有量を調整することができる。
mは0又は1を示し、Zはハロゲン原子、-R7OH、-R7COOH、-R7NH2、-R7NHR8、-COOH又は-SHを示し、R7は直鎖、分岐鎖もしくは環状アルキレン基、芳香環上にアルコキシ基を有してもよいアリール置換アルキレン基、アリーレン基、又はジアリーレン基を示し、R8はアルキル基、アルケニル基、アリール基、アラルキル基又はアルコキシ基を示す。
ジアリーレン基とは、二つのアリーレン基が直接、又は二価の有機基を介して連結された基のことであり、具体的には-Ar1-W-Ar2-で表される構造を有する基である。ここで、Ar1及びAr2は、アリーレン基を示し、Wは単結合、又は2価の有機基を示す。Wの具体例及び好適例は、前記一般式(I)におけるXと同じである。
R7が表す直鎖又は分岐鎖アルキレン基としては、炭素数1~8、好ましくは炭素数1~5のアルキレン基が挙げられ、環状アルキレン基としては、炭素数5~15、好ましくは炭素数5~10のシクロアルキレン基が挙げられる。R7が表すアリール置換アルキレン基のアルキレン部位としては、炭素数1~8、好ましくは炭素数1~5のアルキレン基が挙げられる。R7が表すアリール置換アルキレン基のアリール部位としては、フェニル基、ナフチル基、ビフェニル基、アントリル基などの環形成炭素数6~14のアリール基が挙げられる。R7、Ar1及びAr2が表すアリーレン基としては、フェニレン基、ナフチレン基、ビフェニレン基、アントリレン基などの環形成炭素数6~14のアリーレン基が挙げられる。
好ましくは、Y’は、単結合、又は-C(=O)-、脂肪族基若しくは芳香族基を含み、SiとO又はSiとZに結合している2価の有機残基を示す。R3~R6としては、いずれも、好ましくは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基である。nは上記と同じであり、mは0又は1を示す。
Zとしては、好ましくは-R7OH、-R7COOH、-R7NH2、-COOH又は-SHである。該R7は、前記定義の通りであり、好ましいものも同じである。
R8としては、好ましくは、アルキル基、アルケニル基、アリール基又はアラルキル基である。
ビスフェノールA以外の二価フェノールとしては、例えば、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシフェニル)オクタン、ビス(4-ヒドロキシフェニル)フェニルメタン、ビス(4-ヒドロキシフェニル)ジフェニルメタン、2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン、ビス(4-ヒドロキシフェニル)ナフチルメタン、1,1-ビス(4-ヒドロキシ-3-t-ブチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3-ブロモフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3-クロロフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジクロロフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジブロモフェニル)プロパン等のビス(ヒドロキシアリール)アルカン類;1,1-ビス(4-ヒドロキシフェニル)シクロペンタン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,5,5-トリメチルシクロヘキサン、2,2-ビス(4-ヒドロキシフェニル)ノルボルナン、1,1-ビス(4-ヒドロキシフェニル)シクロドデカン等のビス(ヒドロキシアリール)シクロアルカン類;4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシ-3,3’-ジメチルフェニルエーテル等のジヒドロキシアリールエーテル類;4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルフィド等のジヒドロキシジアリールスルフィド類;4,4’-ジヒドロキシジフェニルスルホキシド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホキシド等のジヒドロキシジアリールスルホキシド類;4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホン等のジヒドロキシジアリールスルホン類;4,4’-ジヒドロキシジフェニル等のジヒドロキシジフェニル類;9,9-ビス(4-ヒドロキシフェニル)フルオレン、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン等のジヒドロキシジアリールフルオレン類;1,3-ビス(4-ヒドロキシフェニル)アダマンタン、2,2-ビス(4-ヒドロキシフェニル)アダマンタン、1,3-ビス(4-ヒドロキシフェニル)-5,7-ジメチルアダマンタン等のジヒドロキシジアリールアダマンタン類;4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスフェノール、10,10-ビス(4-ヒドロキシフェニル)-9-アントロン、1,5-ビス(4-ヒドロキシフェニルチオ)-2,3-ジオキサペンタエン等が挙げられる。
これらの二価フェノールは、1種を単独で使用してもよいし、2種以上を混合して用いてもよい。
一般式(2)で表されるポリオルガノシロキサンとしては、例えば、以下の一般式(2-1)~(2-10)の化合物が挙げられる。
これらの中でも、重合の容易さの観点においては、一般式(2-1)で表されるフェノール変性ポリオルガノシロキサンが好ましい。また、入手の容易さの観点においては、一般式(2-2)で表される化合物中の一種であるα,ω-ビス[3-(o-ヒドロキシフェニル)プロピル]ポリジメチルシロキサン、一般式(2-3)で表される化合物中の一種であるα,ω-ビス[3-(4-ヒドロキシ-2-メトキシフェニル)プロピル]ポリジメチルシロキサンが好ましい。
まず、シクロトリシロキサンとジシロキサンとを酸性触媒存在下で反応させ、α,ω-ジハイドロジェンオルガノポリシロキサンを合成する。このとき、シクロトリシロキサンとジシロキサンとの仕込み比を変えることで所望の平均繰り返し数を持つα,ω-ジハイドロジェンポリオルガノシロキサンを合成することができる。次いで、ヒドロシリル化反応用触媒の存在下に、このα,ω-ジハイドロジェンポリオルガノシロキサンにアリルフェノールやオイゲノール等の不飽和脂肪族炭化水素基を有するフェノール化合物を付加反応させることで、所望の平均繰り返し数を有するフェノール変性ポリオルガノシロキサンを製造することができる。
また、この段階では、低分子量の環状ポリオルガノシロキサンや過剰量の上記フェノール化合物が不純物として残存するために、減圧下で加熱し、これらの低分子化合物を留去することが好ましい。
また、βは、ジイソシアネート化合物由来の2価の基、ジカルボン酸由来の2価の基、又はジカルボン酸ハロゲン化物由来の2価の基を示し、例えば、以下の一般式(3-1)~(3-5)で表される2価の基が挙げられる。
該(A-2)成分の芳香族ポリカーボネート樹脂の粘度平均分子量(Mv)は、好ましくは10,000~30,000であり、より好ましくは12,000~28,000、さらに好ましくは15,000~25,000である。
R9及びR10の具体例としては、前記R1及びR2と同じものが挙げられ、好ましいものも同じである。R9及びR10としては、より好ましくは、炭素数1~6のアルキル基又は炭素数1~6のアルコキシ基である。X’の具体例としては、前記Xと同じものが挙げられ、好ましいものも同じである。d及びeは、それぞれ独立に、好ましくは0~2、より好ましくは0又は1である。
上記の反応に際し、必要に応じて、分子量調節剤(末端停止剤)、分岐化剤等が使用される。
なお、上記芳香族二価フェノール系化合物としては、下記一般式(III')で表されるものが挙げられる。
該芳香族二価フェノール系化合物の具体例としては、例えば、2,2-ビス(4-ヒドロキシフェニル)プロパン〔ビスフェノールA〕、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン等のビス(ヒドロキシフェニル)アルカン系、4,4'-ジヒドロキシジフェニル、ビス(4-ヒドロキシフェニル)シクロアルカン、ビス(4-ヒドロキシフェニル)オキシド、ビス(4-ヒドロキシフェニル)スルフィド、ビス(4-ヒドロキシフェニル)スルホン、ビス(4-ヒドロキシフェニル)スルホキシド、ビス(4-ヒドロキシフェニル)ケトン等が挙げられる。
これらの中でも、ビス(ヒドロキシフェニル)アルカン系二価フェノールが好ましく、ビスフェノールAがより好ましい。
上記芳香族ポリカーボネート樹脂(A-2)は1種を単独で用いてもよいし、2種以上を併用してもよい。
(A-1)成分が5質量%以上であると、(A-1)成分中のポリオルガノシロキサンブロック部分の含有量を高くする必要がなく、PC-POSの製造上好ましい。
本発明の被塗装用ポリカーボネート樹脂成形材料は、(B)成分として、ブタジエンに由来する構成単位を有する共重合体(以下、単に「(B)成分」ともいう)を含む。被塗装用ポリカーボネート樹脂成形材料が当該(B)成分を含むことで、耐衝撃性が向上することから、塗装を施しても耐衝撃性の大幅な低下が見られず、かつ塗膜密着性にも優れる被塗装用ポリカーボネート樹脂成形材料を得ることができる。
本発明の被塗装用ポリカーボネート樹脂成形材料は、前記(A)成分100質量部に対して、好ましくは、(B-1)成分の含有量が8~100質量部、(B-2)成分の含有量が0質量部超25質量部以下である。より好ましくは、(B-1)成分の含有量が8~50質量部、(B-2)成分の含有量が1~20質量部であり、さらに好ましくは、(B-1)成分の含有量が8~45質量部、(B-2)成分の含有量が1~5質量部であり、特に好ましくは、(B-1)成分の含有量が24~40質量部、(B-2)成分の含有量が1~5質量部である。
当該含有量が0.50質量%未満であると、得られる成形品及び塗装成形品の耐衝撃性が不十分となる。また当該含有量が10質量%以下であれば経済性の点で好ましい。
ここで、成形材料中のポリオルガノシロキサンブロック部分の含有量は、核磁気共鳴(NMR)測定により算出された値である。
本発明の被塗装用ポリカーボネート樹脂成形材料には、本発明の効果を著しく損なわない程度において、適宜、その他の成分を含有させることができる。
その他の成分としては、例えば、酸化防止剤、紫外線吸収剤、離型剤、難燃剤、難燃助剤、無機充填材、着色剤(染料、顔料)等の添加剤が挙げられる。
次に、本発明の被塗装用ポリカーボネート樹脂成形材料の製造方法について説明する。
本発明の被塗装用ポリカーボネート樹脂成形材料は、前記の(A)、(B)成分、さらに必要に応じて用いられる他の成分を配合し、混練することにより得られる。
このときの配合及び混練は、通常用いられている機器、例えば、リボンブレンダー、ドラムタンブラー等で予備混合して、ヘンシェルミキサー、バンバリーミキサー、単軸スクリュー押出機、二軸スクリュー押出機、多軸スクリュー押出機、コニーダ等を用いる方法で行うことができる。
混練の際の加熱温度は、通常240~300℃の範囲で適宜選択される。
なお、ポリカーボネート樹脂(A)以外の成分は、予め、ポリカーボネート樹脂(A)と溶融混練、すなわち、マスターバッチとして添加することもできる。
本発明の成形品は、本発明の被塗装用ポリカーボネート樹脂成形材料を含むものである。
本発明の成形品は、本発明の被塗装用ポリカーボネート樹脂成形材料を、上記の溶融混練成形機を用いて溶融混練した組成物、又は、該組成物から得られたペレットを原料として、射出成形法、射出圧縮成形法、押出成形法、ブロー成形法、プレス成形法、真空成形法及び発泡成形法等により成形することにより得られる。
特に好適な方法としては、上記溶融混練方法により、ペレット状の成形原料を製造し、次いで、このペレットを用いて、射出成形、射出圧縮成形を用いることにより、成形品とする方法が挙げられる。
なお、射出成形方法としては、外観のヒケ防止のため、又は、軽量化のためのガス注入成形方法を採用することもできる。
本発明の塗装成形品は、上記本発明の成形品に塗装を施したものである。塗装方法には特に制限はなく、ロールコート、カーテンフローコート、浸漬法、スプレー塗装、静電塗装、電着塗装、UV塗装等が挙げられる。また、めっきや蒸着等の方法を用いてもよい。
塗装を施すために用いる塗料についても特に制限はなく、塗装方法や塗装成形品の形状等に応じて適宜選択することができる。例えば、着色剤と、エポキシ樹脂、ウレタン樹脂、フェノール樹脂、アクリル樹脂などの各種樹脂成分と、水や有機溶剤とを含む樹脂塗料などを用いることができる。上記樹脂成分は、主剤と硬化剤とを含む硬化性樹脂でもよい。また塗装成形品の量産性の点からは、有機溶剤を含む塗料が好ましい。
ここで、ポリカーボネート樹脂成形品を有機溶剤を含む塗料により塗装すると、該有機溶剤等の影響により塗装後の成形品の耐衝撃性が低下する傾向がある。特に塗料に含まれる有機溶剤がケトン系及びエステル系溶剤から選ばれる少なくとも1種である場合には、成形品への含浸作用があることから、該成形品の耐衝撃性の低下が著しい。しかしながら、本発明の被塗装用ポリカーボネート樹脂成形材料の成形品は、有機溶剤としてケトン系及びエステル系溶剤から選ばれる少なくとも1種を含む塗料により塗装した場合でも耐衝撃性の大幅な低下が見られないという顕著な効果を奏する。このため、塗装による耐衝撃性の低下を懸念することなく成形品を薄肉化できるので、本発明の塗装成形品が適用される各種製品、例えばスマートフォン、タブレットPC、ノートパソコンの筐体、自動車用内装部品、自動車用外装部品、ラジカセその他携帯用電気製品等の小型化、軽量化が可能となる。
<ポリカーボネートオリゴマー製造>
5.6質量%水酸化ナトリウム水溶液に後から溶解するビスフェノールA(BPA)に対して2000ppmの亜二チオン酸ナトリウムを加え、これにビスフェノールA濃度が13.5質量%になるようにビスフェノールAを溶解し、ビスフェノールAの水酸化ナトリウム水溶液を調製した。
このビスフェノールAの水酸化ナトリウム水溶液40L(以下、Lはリットルの省略である。)/hr、塩化メチレン15L/hrの流量で、ホスゲンを4.0kg/hrの流量で内径6mm、管長30mの管型反応器に連続的に通した。
管型反応器はジャケット部分を有しており、ジャケットに冷却水を通して反応液の温度を40℃以下に保った。
管型反応器を出た反応液は後退翼を備えた内容積40Lのバッフル付き槽型反応器へ連続的に導入され、ここにさらにビスフェノールAの水酸化ナトリウム水溶液2.8L/hr、25質量%水酸化ナトリウム水溶液0.07L/hr、水17L/hr、1質量%トリエチルアミン水溶液を0.64L/hr添加して反応を行った。
槽型反応器から溢れ出る反応液を連続的に抜き出し、静置することで水相を分離除去し、塩化メチレン相を採取した。
このようにして得られたポリカーボネートオリゴマーは、濃度329g/L、クロロホーメート基濃度0.74mol/Lであった。
<ポリカーボネート-ポリジメチルシロキサン共重合体(PC-PDMS共重合体1)の製造>
邪魔板、パドル型攪拌翼及び冷却用ジャケットを備えた50L槽型反応器に、上記調製例1で製造したポリカーボネートオリゴマー溶液15L、塩化メチレン9.0L、ジメチルシロキサン繰り返し単位の平均繰り返し数nが90であるo-アリルフェノール末端変性ポリジメチルシロキサン(PDMS)384g及びトリエチルアミン8.8mLを仕込み、攪拌下でここに6.4質量%水酸化ナトリウム水溶液1389gを加え、10分間ポリカーボネートオリゴマーとアリルフェノール末端変性PDMSの反応を行った。
この重合液に、p-t-ブチルフェノール(PTBP)の塩化メチレン溶液(PTBP137gを塩化メチレン2.0Lに溶解したもの)、ビスフェノールAの水酸化ナトリウム水溶液(水酸化ナトリウム577gと亜二チオン酸ナトリウム2.0gを水8.4Lに溶解した水溶液にビスフェノールA1012gを溶解させたもの)を添加し、50分間重合反応を行った。
希釈のため塩化メチレン10Lを加え10分間攪拌した後、ポリカーボネート-ポリジメチルシロキサン共重合体(PC-PDMS共重合体)を含む有機相と過剰のビスフェノールA及び水酸化ナトリウムを含む水相に分離し、有機相を単離した。
こうして得られたPC-PDMS共重合体の塩化メチレン溶液を、その溶液に対して順次、15容積%の0.03mol/L水酸化ナトリウム水溶液、0.2モル/L塩酸で洗浄し、次いで洗浄後の水相中の電気伝導度が0.01μS/m以下になるまで純水で洗浄を繰り返した。
洗浄により得られたPC-PDMS共重合体の塩化メチレン溶液を濃縮・粉砕し、得られたフレークを減圧下120℃で乾燥し、PC-PDMS共重合体1を製造した。
得られたPC-PDMS共重合体1の核磁気共鳴(NMR)により求めたPDMSブロック部分の含有量は6.0質量%、粘度数は47.5、粘度平均分子量Mvは17,700であった。
<塗膜密着性評価>
塗装した試験片表面にカッターナイフで2mm間隔に縦横に切り込みを入れ、25個の碁盤目を作成し、その碁盤目部分にセロハンテープを接着させた後、テープの端を60度の角度で瞬時に引きはがし、碁盤目の状態を確認した。なお、カッターナイフはオルファ(株)製オルファカッター替刃(小)を使用し、セロハンテープはニチバン(株)製セロハンテープ(CT-18)を使用した。
表1において、碁盤目の状態に変化がないものを、塗膜密着性が良好であるとした。
塗装前及び塗装後の成形品についてそれぞれ評価を行った。厚さ1mmの試験片において、温度23℃、撃芯直径12.7mm、受け台直径48mm、錘質量500g、錘高さ100cmの条件で落錘衝撃試験を5回行い、割れが発生した試験片の数を表1に示した。割れた試験片の数が少ないほど耐衝撃性が良好であることを示す。
表1に示す割合で各成分を混合し、ベント付き50mmφの単軸押出機を用いて樹脂温度280℃で造粒し、被塗装用ポリカーボネート樹脂成形材料からなるペレットを得た。
上記方法で得られたペレットを、射出成形機(型番;IS100EN、東芝機械(株)製)を用い、シリンダー温度240℃、金型温度40℃の成形条件で射出成形して評価用の各種試験片を得た。
次に、得られた試験片に対して、塗料(武蔵塗料(株)製、主剤;CPX79シルバー、硬化剤;H-250、有機溶剤;エステル系、主剤/硬化剤/有機溶剤(質量比)=10/1/10)を使用して塗装し、厚み9±1μmの塗膜を有する塗装試験片を得た。なお塗装乾燥条件は80℃、30分である。
得られた塗装前及び塗装後の試験片を用いて前記の性能評価を行った。結果を表1に示す。
<ポリカーボネート-ポリオルガノシロキサン共重合体(A-1)>
PC-PDMS共重合体1(製造例1に記載のポリカーボネート-ポリジメチルシロキサン共重合体)
<芳香族ポリカーボネート樹脂(A-2)>
タフロンFN1900(ビスフェノールAポリカーボネート、出光興産(株)製、粘度数51.0、粘度平均分子量Mv=19,200)
サンタックAT-05(アクリロニトリル-ブタジエン-スチレン3元共重合体(ABS)、日本エイアンドエル(株)製)
<共重合体(B-2)>
カネエースM-701(メチルメタクリレート-ブタジエン-スチレン3元共重合体(MBS)、(株)カネカ製)
これに対し、比較例1,2の対比から、(B)成分を含まないポリカーボネート樹脂成形材料の成形品においては、(A-1)成分を含有させても、塗装後の耐衝撃特性試験で割れた試験片の個数は2個減るに過ぎない。また比較例1,3の対比から、(A-1)成分を含まないポリカーボネート樹脂成形材料の成形品においては、(B)成分を含有させても、塗装後の耐衝撃特性試験で割れた試験片の個数は1個減るに過ぎない。
以上より、ポリカーボネート樹脂成形材料にPOSブロック部分を有する(A-1)成分及び(B)成分を同時に含有させることにより、それぞれを独立別個に含有させた場合と比して、塗装後の耐衝撃特性がより大きく向上することがわかる。
以上より、(A-1)成分、(B-1)成分及び(B-2)成分を同時に含有させることにより、それぞれを独立別個に含有させた場合と比して、塗装後の耐衝撃特性がより大きく向上することがわかる。
以上のとおり、本発明の被塗装用ポリカーボネート樹脂成形材料は塗装を施しても耐衝撃性の大幅な低下が見られず、塗膜密着性も良好である。
Claims (11)
- 下記一般式(I)で表される繰り返し単位からなるポリカーボネートブロック及び下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックを有するポリカーボネート-ポリオルガノシロキサン共重合体(A-1)を含有するポリカーボネート樹脂(A)と、ブタジエンに由来する構成単位を有する共重合体(B)とを含み、全成形材料中の前記ポリオルガノシロキサンブロック部分の含有量が0.50~10質量%であり、全成形材料中の前記ブタジエンに由来する構成単位の含有量が1~10質量%である被塗装用ポリカーボネート樹脂成形材料。
[式中、R1及びR2はそれぞれ独立に、ハロゲン原子、炭素数1~6のアルキル基又は炭素数1~6のアルコキシ基を示す。Xは、単結合、炭素数1~8のアルキレン基、炭素数2~8のアルキリデン基、炭素数5~15のシクロアルキレン基、炭素数5~15のシクロアルキリデン基、フルオレンジイル基、炭素数7~15のアリールアルキレン基、炭素数7~15のアリールアルキリデン基、-S-、-SO-、-SO2-、-O-又は-CO-を示す。R3及びR4はそれぞれ独立に、水素原子、ハロゲン原子又は炭素数1~6のアルキル基、炭素数1~6のアルコキシ基もしくは炭素数6~12のアリール基を示す。a及びbは、それぞれ独立に0~4の整数を示す。nは平均繰り返し数を示す。] - 前記(A-1)成分中の前記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロック部分の含有量が0.75~15質量%である請求項1に記載の被塗装用ポリカーボネート樹脂成形材料。
- 前記(B)成分が、ブタジエン、アクリロニトリル及びスチレンに由来する構成単位を有しかつメチルメタクリレートに由来する構成単位を有さない共重合体(B-1)、並びに、ブタジエン及びメチルメタクリレートに由来する構成単位を有する共重合体(B-2)から選ばれる少なくとも1種を含む請求項1又は2に記載の被塗装用ポリカーボネート樹脂成形材料。
- 前記(B-1)成分が、アクリロニトリル-ブタジエン-スチレン3元共重合体(ABS)である請求項3に記載の被塗装用ポリカーボネート樹脂成形材料。
- 前記(B-2)成分が、メチルメタクリレート-ブタジエン-スチレン3元共重合体(MBS)及びメチルメタクリレート-ブタジエン2元共重合体(MB)から選ばれる少なくとも1種である請求項3又は4に記載の被塗装用ポリカーボネート樹脂成形材料。
- 前記(B)成分が前記(B-1)成分及び前記(B-2)成分を含み、前記(A)成分100質量部に対して、前記(B-1)成分の含有量が8~100質量部であり、前記(B-2)成分の含有量が0質量部超25質量部以下である請求項3~5のいずれかに記載の被塗装用ポリカーボネート樹脂成形材料。
- 請求項1~6のいずれかに記載の被塗装用ポリカーボネート樹脂成形材料を含む成形品。
- 請求項7に記載の成形品に塗装を施した塗装成形品。
- 有機溶剤を含む塗料により塗装された請求項8に記載の塗装成形品。
- 前記有機溶剤がケトン系及びエステル系溶剤から選ばれる少なくとも1種である請求項9に記載の塗装成形品。
- 厚さ1mmの試験片において、温度23℃、撃芯直径12.7mm、受け台直径48mm、錘質量500g、錘高さ100cmの条件で落錘衝撃試験を5回行った際に、割れが発生する試験片の数が1個以下である請求項8~10のいずれかに記載の塗装成形品。
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KR20160140633A (ko) | 2016-12-07 |
JP6231420B2 (ja) | 2017-11-15 |
JP2015196697A (ja) | 2015-11-09 |
EP3127964A4 (en) | 2017-11-29 |
US10066101B2 (en) | 2018-09-04 |
KR102258871B1 (ko) | 2021-05-31 |
TW201536868A (zh) | 2015-10-01 |
CN106103589A (zh) | 2016-11-09 |
EP3127964B1 (en) | 2021-01-13 |
TWI646157B (zh) | 2019-01-01 |
US20170145211A1 (en) | 2017-05-25 |
EP3127964A1 (en) | 2017-02-08 |
CN106103589B (zh) | 2019-09-06 |
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