WO2014129483A1 - Aromatic polycarbonate resin molded body and panel - Google Patents

Abstract

A window frame member having reliable durability is provided by using an aromatic polycarbonate resin molded body, which has excellent chemical resistance, mechanical characteristics and the like, as a frame member for glazing, thereby enabling primer-mediated urethane bonding without performing a hard coat treatment that has been conventionally required. An aromatic polycarbonate resin molded body which is obtained by injection molding an aromatic polycarbonate resin composition that contains, as resin components, (A) an aromatic polycarbonate resin, (B-1) a rubbery polymer/aromatic vinyl/vinyl cyanide copolymer, (B-2) an aromatic vinyl/vinyl cyanide copolymer and (C) a polyolefin resin at an injection rate of 10-100 cm³/s and at a surface advancing coefficient, which is defined below, of 40-200 cm³/s·cm. Surface advancing coefficient: the value obtained by dividing the above-mentioned injection rate by the thickness of a mold cavity into which the resin composition is injected

Description

Aromatic polycarbonate resin molded body and panel

The present invention relates to an aromatic polycarbonate resin molded article which is suitable as a molding material for a glazing window frame member and excellent in chemical resistance, mechanical properties and the like.
The present invention also relates to a panel having a frame member made of the aromatic polycarbonate resin molded body, a panel installation structure, and a vehicle including the panel installation structure.

In recent years, in the field of automobiles and the like, various studies have been made on resin windows (glazing) instead of glass for the purpose of weight reduction.

Glazing is usually composed of a transparent window (panel body according to the present invention) and a window frame (frame member according to the present invention) at the periphery thereof, and is generally manufactured by integral molding by injection molding, including the window frame. Has been.

FIG. 1 is a view showing a glazing panel used for a panoramic roof of an automobile, FIG. 1a is a rear view (a rear side or a rear side, a plane which is a vehicle compartment side when attached to an automobile), and FIG. FIG. 1c is a partial cross-sectional view showing a structure for attaching the glazing to the automobile roof.

The panel 1 is composed of a panel body 2 and a frame member 3 provided on the peripheral edge of the rear surface of the panel body 2. When the panel 1 is attached to the automobile roof, as shown in FIG. 1c, the frame member 3 is adhered to the vehicle body frame 4 with an adhesive 5 such as urethane, and rubber is provided in the gap between the panel 1 and the vehicle body frame 4. A sealing member (weather strip) 6 made of metal is fitted and fixed.

Conventionally, as a molding material for such a glazing window frame member (frame member 3 in FIG. 1), a resin composition in which an inorganic filler is blended with a polycarbonate resin / ABS resin composite resin is used (for example, a patent). Reference 1).

Since the polycarbonate resin / ABS resin composite resin has poor chemical resistance, when the frame member is bonded to the vehicle frame with a urethane-based adhesive, the frame member is affected by the primer applied to the adhesive application surface. Thus, there is a problem that high adhesion or adhesion and durability reliability cannot be obtained. For this reason, in a polycarbonate resin / ABS resin frame member, a hard coat is applied (a hard coating is formed) to prevent deterioration due to a primer. In this case, a hard coat process is required for the frame member, which is disadvantageous in terms of production efficiency and manufacturing cost. Furthermore, there is a concern that long-term durability and reliability may deteriorate under wet heat environment or weather resistance test due to an increase in layer structure.

In order to improve the chemical resistance of polycarbonate resin, it is known to blend polyethylene resin. However, polyethylene resin has poor compatibility with polycarbonate resin, and depending on the dispersion state of polyethylene resin, the desired chemical resistance may not be obtained, or the flowability and residence heat stability may be increased by blending polyethylene resin. There is a problem in characteristics that impair the mechanical characteristics and a problem in appearance such as whitening.

Patent Document 2 discloses a multicolor molded resin window member having a transparent window layer and a window frame laminated around the transparent window layer, and the adhesion between the transparent window layer and the window frame is within a specific range. Thus, a multicolor molded resin window member excellent in safety in which the transparent window layer does not brittlely break when an impact is applied has been proposed. Patent Document 2 exemplifies a polycarbonate resin composition in which a polycarbonate resin, an ABS resin, an AS resin, and a polyethylene resin and talc are blended as a constituent material of the window frame. In Patent Document 2, since an injection compression molding method is employed as a method for molding the polycarbonate resin composition, the polyethylene resin in the composition is difficult to be oriented in the molded body. For this reason, since the domain of the polyethylene resin as in the present invention cannot be formed on the surface layer portion of the molded article, there is a problem that sufficient chemical resistance by the polyethylene resin cannot be exhibited. That is, since there is no problem of improving chemical resistance in Patent Document 2, there is no technical idea of forming a polyethylene-based resin domain in the surface layer portion of the molded body.

JP 2003-320548 A JP 2011-20441 A

The present invention solves the above-mentioned conventional problems, and uses an aromatic polycarbonate resin molded article excellent in chemical resistance, mechanical properties and the like as a glazing frame member, so that a primer is interposed without performing a hard coat treatment. It is an object of the present invention to provide a technology capable of realizing a panel installation structure with high durability and reliability by urethane bonding.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an aromatic polycarbonate resin (A) and a rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B) as resin components. -1), preferably an aromatic polycarbonate resin composition containing an aromatic vinyl / vinyl cyanide copolymer (B-2) and a polyolefin resin (C), by injection molding under predetermined conditions. It has been found that an aromatic polycarbonate resin molded article can solve the above problems.

The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] Fragrance comprising aromatic polycarbonate resin (A), rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), and polyolefin resin (C) as resin components A group polycarbonate resin composition is injection molded under the conditions of an injection rate of 10 to 100 cm ³ / s defined below and a surface progression coefficient of 40 to 200 cm ³ / s · cm defined below. An aromatic polycarbonate resin molded product.
Injection rate: Resin composition volume per unit time injected from the discharge nozzle of the injection molding machine into the mold cavity Surface progression coefficient: Value obtained by dividing the above injection rate by the thickness of the mold cavity into which the resin composition is injected

[2] The aromatic polycarbonate resin composition contains, as a resin component, an aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), aromatic vinyl / An aromatic polycarbonate resin molded article comprising a vinyl cyanide copolymer (B-2) and a polyolefin resin (C).

[3] The domain formed by the polyolefin-based resin (C) is dispersed and present in a surface layer portion having a depth of 30 μm from the surface of the molded body, and the resin composition at the time of the injection molding of the surface layer portion [1] or [2], wherein the area of the domain in the cross section along the flow direction is 10 to 100 μm ² and the area / major axis ratio is 0.5 to 5 μm. The aromatic polycarbonate resin molded article described.

[4] The aromatic polycarbonate resin composition contains, as a resin component, 45 to 88% by mass of an aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1). 2 to 40% by weight, aromatic vinyl / vinyl cyanide copolymer (B-2) 0 to 35% by weight and polyolefin resin (C) 1 to 15% by weight, The aromatic polycarbonate resin molded article according to any one of [1] to [3].

[5] The aromatic polycarbonate resin composition has an aromatic polycarbonate resin (A) of 45 to 88% by mass, a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) of 2 to 40% by mass. % Of the inorganic filler (D) 30 with respect to a total of 100 parts by mass of the aromatic vinyl / vinyl cyanide copolymer (B-2) 0 to 35% by mass and the polyolefin resin (C) 1 to 15% by mass. The aromatic polycarbonate resin molded article according to [4], comprising not more than part by mass.

[6] The polyolefin resin (C) is a polyethylene resin having a density of 0.85 to 0.90 g / cm ³ and a melt flow rate (MFR) at 190 ° C. of 1 to 20 g / 10 min. The aromatic polycarbonate resin molded article according to any one of [1] to [5], which is characterized.

[7] The aromatic polycarbonate resin molded article according to any one of [1] to [6], wherein the polyolefin resin (C) contains 0.01 to 2% by mass of an oligomer component.

[8] The rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) contains a butadiene component, and the rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B -1) and the aromatic vinyl / vinyl cyanide copolymer (B-2), the content of the butadiene component is 5 to 50% by mass, [2] to [7 ] The aromatic polycarbonate resin molding in any one of Claims 1-4.

[9], wherein the aromatic polycarbonate resin composition is 280 ° C., a melt volume rate of 2.16kg load (MVR) is 10 cm ³ / 10min or more, any one of [1] to [8] The aromatic polycarbonate resin molded article described in 1.

[10] The content of the inorganic filler (D) in the aromatic polycarbonate resin composition is such that the aromatic polycarbonate resin (A), rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B- 1) 1 to 30 parts by mass with respect to 100 parts by mass in total of the aromatic vinyl / vinyl cyanide copolymer (B-2) and the polyolefin resin (C), [5] The aromatic polycarbonate resin molded article according to any one of to [9].

[11] A panel comprising a panel body having a front surface and a rear surface, and a frame member provided at a peripheral edge of the rear surface of the panel body, the panel body supported by the panel support via the frame member, A panel comprising an aromatic polycarbonate resin as a main component resin and the frame member comprising the molded article of the aromatic polycarbonate resin according to any one of [1] to [10].

[12] The panel according to [11], wherein the panel body and the frame member are laminated and integrated by multicolor molding.

[13] A hard coating is formed on one or both of a front surface of the panel body and a region other than a portion bonded to the panel support on the rear surface of the panel body. The panel according to [11] or [12].

[14] The panel according to any one of [11] to [13], which is used for a window member of a vehicle.

[15] A panel installation structure, wherein the panel according to any one of [11] to [14] is supported on a panel support through a primer layer and a urethane-based adhesive layer.

[16] The panel installation structure according to [15], wherein the panel support is made of a metal material.

[17] A vehicle comprising the panel installation structure according to [16].

The aromatic polycarbonate resin molded product of the present invention is excellent in chemical resistance, mechanical properties and the like. For this reason, if it is the window frame member for glazing which consists of an aromatic polycarbonate resin molding of this invention, the urethane adhesion | attachment via a primer will be attained, without performing the hard-coat process currently performed conventionally. Therefore, according to this invention, the window frame member excellent in adhesiveness and adhesiveness, and its durability reliability can be provided at low cost under good production efficiency.

It is a figure which shows the panel for glazing used for the panorama roof of a motor vehicle. 1a is a rear view, FIG. 1b is a cross-sectional view taken along the line BB of FIG. 1a, and FIG. 1c is a partial cross-sectional view showing a structure for attaching the glazing to the automobile roof. It is sectional drawing of the panel edge part which shows another example of embodiment of the panel of this invention. It is a figure which shows the shape of the molded article as a test piece for a shaping | molding shrinkage rate measurement. 3a is a front view and FIG. 3b is a side view. It is a schematic diagram which shows the chemical-resistance evaluation test method. 4A is a side view showing a state in which the test piece is subjected to bending, FIG. 4B is a plan view thereof, and FIG. 4C is a bottom surface portion thereof. It is a schematic diagram which shows a urethane shear test method. 5a and 5b are perspective views of the test piece, and FIGS. 5c and 5d are cross-sectional views of the shear test piece to which these are bonded. It is a figure which shows the panel for the curvature of 2 color molded products in an Example, and surface layer part SEM observation. 6a is a rear view, FIG. 6b is a cross-sectional view taken along line BB of FIG. 6a, and FIG. 6c is a schematic view showing a filling region. 7a is an SEM photograph of a cross section of the surface layer of the ISO multipurpose test piece of Example 10. FIG. FIG. 7 b is a SEM photograph of the cross section of the surface layer of the ISO multipurpose test piece of Example 11. FIG. 7 c is a SEM photograph of a cross section of the surface layer of the ISO multipurpose test piece of Example 12. FIG. 8 a is a SEM photograph of a cross section of the surface layer of the I part of the frame member of Example 13. FIG. 8b is an SEM photograph of a cross section of the surface layer of the same II part. It is a figure which shows the shape of the molded article as a test piece for urethane peeling tests and urethane shear tests of Comparative Example 4. 9a is a front view and FIG. 9b is a side view.

Hereinafter, embodiments of the present invention will be described in detail.

Hereinafter, the surface layer portion in the range of 30 μm in depth from the surface of the aromatic polycarbonate resin molded body of the present invention is simply referred to as “surface layer portion of molded body” or “surface layer portion”. A range from the surface of the cross section along the flow direction of the resin composition during injection molding of the surface layer portion to a depth of 30 μm is referred to as a “surface layer section”. The area of the domain of the polyolefin-based resin (C) formed in the surface layer portion in the surface layer section is referred to as “domain area”, and the domain major axis and major axis diameter in the surface layer section are defined as “domain major axis”. ”And“ major axis diameter of domain ”. The minor axis and minor axis diameter of the domain in the surface layer section are referred to as “domain minor axis” and “domain minor axis diameter”.
In the present invention, the major axis diameter of a domain refers to the longest diameter of the domain, and the minor axis diameter refers to the shortest diameter among the diameters perpendicular to the major axis diameter.

[Aromatic polycarbonate resin composition]
In the present invention, as a resin component used for injection molding, an aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), and a polyolefin resin (C) An aromatic polycarbonate resin composition (hereinafter, may be referred to as “the aromatic polycarbonate resin composition of the present invention”) is described.
The aromatic polycarbonate resin composition of the present invention may further contain an aromatic vinyl / vinyl cyanide copolymer (B-2) as a resin component.

The aromatic polycarbonate resin composition of the present invention is preferably an aromatic polycarbonate resin (A) (hereinafter sometimes referred to as “component (A)”) 45 to 88% by mass, rubbery polymer / aromatic vinyl. / Vinyl cyanide copolymer (B-1) (hereinafter sometimes referred to as “component (B-1)”) 2 to 40% by mass, aromatic vinyl / vinyl cyanide copolymer (B— 2) (hereinafter sometimes referred to as “component (B-2)”) 0 to 35 mass% and polyolefin resin (C) (hereinafter sometimes referred to as “component (C)”) 1 to 15 mass % Of the inorganic filler (D) in which 100 parts by mass of (A), (B-1), (B-2), and (C) are combined). ) 0 to 30 parts by mass.

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) is a linear or branched thermoplastic obtained by using an aromatic dihydroxy compound and a carbonate precursor as raw materials, or using a small amount of a polyhydroxy compound in combination with these. It is a polymer or a copolymer.

As aromatic dihydroxy compounds, for example, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol) A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5) -Dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3 -Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis ( 4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxy) Bis (hydroxy) such as phenyl) -1,1,1,3,3,3-hexachloropropane and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Aryl) alkanes.

As aromatic dihydroxy compounds other than the above, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes exemplified by 3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) ) Cardio structure-containing bisphenols exemplified by fluorene and the like; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like; 4,4′- Dihydroxydiphenyl sulfide, 4,4'-dihydroxy Dihydroxy diaryl sulfides exemplified by -3,3′-dimethyldiphenyl sulfide; dihydroxy diaryls exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Sulfoxides; dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Can be mentioned.

Among the above, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. Two or more aromatic dihydroxy compounds may be used in combination.

Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like. Specific examples thereof include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl such as dimethyl carbonate and diethyl carbonate. Carbonates; dihaloformates of dihydric phenols and the like. Two or more of these carbonate precursors may be used in combination.

The aromatic polycarbonate resin (A) used in the present invention may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, In addition to polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7 -Dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably based on the aromatic dihydroxy compound. 0.1 to 2 mol%.

Examples of the method for producing the aromatic polycarbonate resin include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Although there is no restriction | limiting in the manufacturing method of aromatic polycarbonate resin (A) used by this invention, Interfacial polymerization method or melt transesterification method is advantageous industrially.

The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is usually 10,000 from the viewpoint of mechanical strength and fluidity (ease of moldability) as a viscosity average molecular weight (Mv) converted from solution viscosity. 50,000 to 50,000, preferably 12,000 to 40,000, more preferably 14,000 to 30,000, and particularly preferably 18,000 to 27,000. Two or more aromatic polycarbonate resins having different viscosity average molecular weights may be mixed to adjust the viscosity average molecular weight. Moreover, you may mix and use the aromatic polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

Viscosity average molecular weight (Mv) refers to the intrinsic viscosity ([η]) (unit dl / g) at a temperature of 20 ° C. using methylene chloride as a solvent and an Ubbelohde viscometer, and the Schnell viscosity formula: It means a value calculated from the equation η = 1.23 × 10 ⁻⁴ M ^0.83 . The intrinsic viscosity ([η]) is a value calculated from the following equation by measuring the specific viscosity (η _sp ) at each solution concentration (C) (g / dl).

The terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) used in the present invention is usually 1,000 ppm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit of the terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) used in the present invention is preferably 10 ppm or more, particularly 20 ppm or more, more preferably 30 ppm or more, and particularly preferably 40 ppm or more. By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. The terminal group hydroxyl group concentration is preferably 1,000 ppm or less because the heat resistance and residence heat stability of the resin composition tend to be further improved.

The terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the aromatic polycarbonate resin, and the measuring method is described in the colorimetric determination (Macromol. Chem. 88215 (1965) by the titanium tetrachloride / acetic acid method. Method).

The aromatic polycarbonate resin (A) used in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The aromatic polycarbonate oligomer has a viscosity average molecular weight (Mv) of usually 1,500 to 9,500, preferably 2,000 to 9,000. The amount of the aromatic polycarbonate oligomer used is preferably 30% by mass or less with respect to the aromatic polycarbonate resin, because it tends to suppress impact resistance, residence heat stability, and moist heat resistance deterioration.

In the present invention, not only virgin resin but also aromatic polycarbonate resin regenerated from used products, so-called material recycled aromatic polycarbonate resin may be used as the aromatic polycarbonate resin. Used products include, for example, optical recording media such as optical discs, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, etc.・ Construction materials such as corrugated sheet. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The ratio of the regenerated aromatic polycarbonate resin used is usually 80% by mass or less, preferably 50% by mass or less, based on the virgin resin.

[Rubber Polymer / Aromatic Vinyl / Vinyl Cyanide Copolymer (B-1)]
The rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) used in the present invention comprises at least an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of the rubber polymer. It is a copolymer obtained by polymerizing a monomer and, if necessary, further polymerizing another monomer copolymerizable with each of the above monomers. In the component (B-1), it is not necessary that the two or more monomers described above are all graft-polymerized with the rubber component to form a graft copolymer. Examples of the method for producing the rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) include known methods such as emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization.

The rubbery polymer component in the component (B-1) is not particularly limited as long as it is a polymer showing rubbery properties. Examples thereof include one or more of diene rubber, acrylic rubber, ethylene / propylene rubber, silicone rubber, polyurethane rubber and the like. Among these, diene rubber or acrylic rubber is preferable from the viewpoint of balance between performance and cost.

Examples of the diene rubber include polybutadiene, polyisoprene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, butadiene / (meth) acrylic acid lower alkyl ester copolymer, butadiene / styrene / (meth) acrylic acid. Examples include lower alkyl ester copolymers. Examples of the (meth) acrylic acid lower alkyl ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The proportion of (meth) acrylic acid lower alkyl ester in butadiene / (meth) acrylic acid lower alkyl ester copolymer or butadiene / styrene / (meth) acrylic acid lower alkyl ester copolymer is 30% by mass of rubber mass. The following is preferable.

Examples of the acrylic rubber include alkyl acrylate rubber, and the alkyl group usually has 1 to 8 carbon atoms. Specific examples of the alkyl acrylate rubber include ethyl acrylate, butyl acrylate, ethyl hexyl acrylate and the like. In the alkyl acrylate rubber, a crosslinkable ethylenically unsaturated monomer (crosslinking agent) may be used. Examples of the crosslinking agent include alkylene diol, di (meth) acrylate, polyester di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. Furthermore, examples of the acrylic rubber include a core-shell type polymer having a crosslinked diene rubber as a core.

Among these rubbery polymers, in the present invention, in particular, since they are excellent in maintaining impact resistance in a low temperature environment, polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, butadiene / (meta ) A butadiene-based rubber such as an acrylic acid lower alkyl ester copolymer and a butadiene / styrene / (meth) acrylic acid lower alkyl ester copolymer is preferred.

Examples of the aromatic vinyl monomer in the component (B-1) include styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, methyl-α-methylstyrene, divinylbenzene, diphenylstyrene, and vinylxylene. 1 type, or 2 or more types, etc. are mentioned. Of these, styrene or α-methylstyrene is preferred.

Examples of the vinyl cyanide monomer in the component (B-1) include one or more of acrylonitrile, methacrylonitrile, crotonnitrile, cinnamate nitrile and the like. Of these, acrylonitrile or methacrylonitrile is preferred.

The component (B-1) may be polymerized with an aromatic vinyl monomer and another monomer copolymerizable with the vinyl cyanide monomer. Examples of other monomers used here include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid. (Meth) acrylic acid alkyl ester compounds such as propyl methacrylate, butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate; α, β-unsaturated acid glycidyl ester compounds such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate One or more of maleimide compounds such as maleimide, N-methylmaleimide, N-butylmaleimide and N-phenylmaleimide; Of these, (meth) acrylic acid alkyl ester compounds are preferred.

(B-1) The ratio of each of the above components in the component is as follows. The proportion of the rubbery polymer component is usually 31 to 65% by mass, preferably 31 to 55% by mass. The proportion of the aromatic vinyl component is usually 25 to 60% by mass, preferably 30 to 60% by mass. The proportion of the vinyl cyanide component is usually 5 to 25% by mass, preferably 5 to 20% by mass. The proportion of other monomer components copolymerizable with these is usually 0 to 30% by mass, preferably 0 to 25% by mass. The mass ratio of the vinyl cyanide component to the total mass of the aromatic vinyl component and the vinyl cyanide component is usually 10 to 45 mass%, preferably 15 to 40 mass%.

Specific examples of the component (B-1) include an ABS resin comprising styrene, butadiene and acrylonitrile; a heat-resistant ABS resin in which a part or most of the styrene of the ABS resin is replaced with α-methylstyrene or maleimide; -(Heat resistant) AES resin or (Heat resistant) AAS resin replaced with propylene rubber or polybutyl acrylate; (Heat resistant) ABS resin where butadiene is replaced with silicone rubber or silicone / acrylic composite rubber. Among these, ABS resin is preferable.

As the component (B-1), one type may be used alone, or two or more types may be mixed and used.

[Aromatic vinyl / vinyl cyanide copolymer (B-2)]
The aromatic vinyl / vinyl cyanide copolymer (B-2) used in the present invention comprises at least an aromatic vinyl monomer and a vinyl cyanide monomer in the absence of a rubbery polymer. It is a copolymer obtained by polymerizing and, if necessary, further polymerizing another monomer copolymerizable with each of the above monomers. A typical example is an AS resin made of styrene and acrylonitrile.

As the aromatic vinyl monomer, vinyl cyanide monomer and other copolymerizable monomers in component (B-2), for example, used in component (B-1) above Monomer components to be used.

(B-2) The ratio of each of the above components in the component is as follows. The proportion of the aromatic vinyl component is usually 45 to 90% by mass, preferably 45 to 80% by mass. The proportion of the vinyl cyanide component is usually 5 to 50% by mass, preferably 10 to 45% by mass. The ratio of the other monomer component is usually 0 to 30% by mass, preferably 0 to 25% by mass. The mass ratio of the vinyl cyanide component to the total mass of the aromatic vinyl component and the vinyl cyanide component is usually 10 to 45 mass%, preferably 15 to 40 mass%.

Component (B-2) may be used alone or in combination of two or more.

[Polyolefin resin (C)]
Examples of the polyolefin resin (C) include polyethylene resins and polypropylene resins. Polyethylene resins include high density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, ethylene- A glycidyl (meth) acrylate copolymer etc. are mentioned. Examples of the polypropylene resin include polypropylene resin, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like.

Among these polyolefin resins, polyolefin resins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene resin are preferable because they can provide particularly high chemical resistance. Polyethylene resins such as density polyethylene, low density polyethylene, and linear low density polyethylene are preferred.

Hereinafter, among the polyolefin resins, polyethylene resins will be described.

Polyethylene resin is a copolymer of ethylene and a monomer copolymerizable with ethylene. The copolymerizable monomer is not particularly limited, and examples thereof include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. , Vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, or esters thereof, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or acid anhydrides thereof, or one or more of them These may be copolymerized in the main chain, and those that can be graft-polymerized may be graft-polymerized.

These polyethylene resins can be produced by a usual method.

Among them, a preferable polyethylene resin is a copolymer of ethylene and one or more of α-olefins having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms. Preferred polyethylene resins include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-hexene copolymer, Examples thereof include ethylene-4-methyl-1-pentene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, and the like. Particularly, a linear polyethylene system in which a copolymer component is introduced into the main chain. Resins are preferred.

If the content of ethylene in the polyethylene resin is too small, the handling becomes worse due to a decrease in melting point and the cost increases, and if it is too large, whitening occurs due to molding shrinkage due to crystallization. Accordingly, the ethylene content in the polyethylene resin is preferably 90 to 40 mol%, particularly 85 to 50 mol%.

The polyethylene resin used in the present invention is a polyethylene resin as described above, and a low density polyethylene resin having a density of 0.85 to 0.90 g / cm ³ is preferable. When the density of the polyethylene resin exceeds 0.90 g / cm ³ , there are problems of whitening due to domain voids, delamination, and a decrease in chemical resistance due to poor dispersion of the polyethylene resin. By using a low-density polyethylene resin having a density of 0.90 g / cm ³ or less, the flowability and dispersibility of the aromatic polycarbonate resin (A) are improved, crystallinity is reduced, and shrinkage during molding is achieved. The rate becomes close to the shrinkage rate of the aromatic polycarbonate resin (A), and the formation of voids tends to be suppressed. By using the low-density polyethylene-based resin as described above, the area of the polyethylene-based resin domain of the molded body surface layer portion is 10 to 100 μm ² and the area / major axis diameter ratio is easily 0.5 to 5 μm. Since the domain of the system resin is uniform and is easily dispersed in layers, the layered peeling of the molded body is prevented, and further, good chemical resistance tends to be obtained.
If the density of the polyethylene resin is smaller than 0.85 g / cm ³ , the physical properties may be lowered. Therefore, it is preferable to use a polyethylene resin having a density of 0.85 g / cm ³ or more. The density of the polyethylene resin is particularly preferably 0.86 to 0.90 g / cm ³ , particularly preferably 0.87 to 0.89 g / cm ³ .

In the present invention, the density of the polyethylene resin is a value measured in accordance with ISO 1183 D method.

The polyethylene resin having a density of 0.85 to 0.90 g / cm ³ used in the present invention is simply referred to as “low density polyethylene”.

The polyethylene resin used in the present invention preferably has a molecular weight distribution (Mw / Mn) represented by a ratio of a mass average molecular weight (Mw) to a number average molecular weight (Mn) of 1.0 to 3.0. If the molecular weight distribution (Mw / Mn) is larger than 3.0, there may be a problem that impact resistance is lowered, and if it is smaller than 1.0, the moldability may be inferior. A more preferable molecular weight distribution (Mw / Mn) of the polyethylene resin is 1.3 to 2.5, and more preferably 1.5 to 2.0.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyethylene resin were determined by dissolving the sample with 135 ° C. o-dichlorobenzene (0.5 g / L dibutylhydroxytoluene added) and then a metal filter with a pore size of 2 μm. And filtered by SEC (size exclusion chromatography) under the following conditions.

<SEC conditions>
Apparatus: GPCV2000 (1) manufactured by Waters
Detector: RI (built-in device)
Mobile phase: Special grade reagent ODCB (o-dichlorobenzene)
Flow rate: 1.0 mL / min Injection: 0.1% by mass × 515.5 μL
Column: TSKgel GMH6-HT (7.8 mm ID × 30 cmL × 4)
Column temperature: 135 ° C
Calibration sample: monodisperse PST (polystyrene)
Calibration method: PE (polyethylene) conversion (General calibration curve method)
Calibration curve approximation formula: cubic equation For the sample, a calibration curve created using monodisperse PST was converted into PE using the concept of general-purpose calibration curve. The coefficient used was Kpst = 1. 38 × 10 ⁻⁴ , αpst = 0.70, Kpe = 4.77 × 10 ⁻⁴ , αpe = 0.70.

The molecular weight distribution of the polyethylene resin used in the present invention is preferably sharper, and the half-value width of the molecular weight distribution is preferably 0.5 to 1.0, particularly preferably 0.6 to 0.8.
If the half-value width of the molecular weight distribution of the polyethylene resin is larger than the above upper limit, the composition tends to be non-uniform, resulting in unevenness in the form of the domain described later, and it becomes impossible to exhibit stable chemical resistance, or the interface Appearance defects such as peeling (peeling between the matrix of the aromatic polycarbonate resin (A) and the domain of the polyolefin resin (C)) and whitening are likely to occur.
The smaller the half-value width of the molecular weight distribution, the better. However, since a polyethylene resin having a small half-value width of the molecular weight distribution is expensive, the lower limit is usually about 0.5.

The crystallinity of the polyethylene resin used in the present invention is preferably 5 to 25%, particularly preferably 10 to 20%. If the crystallinity of the polyethylene resin is lower than the above lower limit, the effect of improving chemical resistance cannot be sufficiently exerted, and if it is higher than the upper limit, the shrinkage increases, resulting in poor appearance such as whitening and interfacial peeling. Is likely to occur.

In the aromatic polycarbonate resin molded product of the present invention obtained by injection molding the aromatic polycarbonate resin composition of the present invention, the crystallinity of the polyethylene resin in the molded product is more than the crystallinity of the polyethylene resin used. A low state is preferable. The degree of crystallinity of the polyethylene resin present in the surface layer portion of the aromatic polycarbonate resin molding obtained by injection molding is 50 to 80%, particularly 55 to 75% of the degree of crystallinity of the polyethylene resin used as a raw material. It is preferable that the number is decreased. In other words, the crystallinity of the polyethylene resin present in the surface layer portion of the aromatic polycarbonate resin molding obtained by injection molding is 20 to 50% relative to the crystallinity of the raw polyethylene resin, in particular, It is preferably reduced by 25 to 45% (hereinafter, the rate at which the crystallinity of the polyethylene resin decreases after injection molding is referred to as “crystallinity reduction rate”). This is due to the following reason.

In the present invention, the chemical resistance is enhanced when the polyethylene resin takes the form of a domain as described below.
In the present invention, by performing injection molding under the conditions satisfying the injection rate and surface progression coefficient described later, the domain of the polyethylene resin particularly in the surface layer portion of the molded body is stretched by the shearing force received in the injection molding process. Thus, when the resin composition is oriented in the flow direction, the crystallinity is considered to decrease. That is, after injection molding, the crystallinity of the polyethylene resin becomes smaller than that before injection molding. This means that the domain of the polyethylene resin is stretched during the injection molding process and is effective in improving chemical resistance. Means to form. For this reason, it is preferable that the crystallinity degree of the polyethylene resin in at least the surface layer portion of the aromatic polycarbonate resin molded body of the present invention is reduced by the above ratio by injection molding.
Usually, in order to improve chemical resistance, it is considered that a higher degree of crystallinity is preferable, but surprisingly, in the present invention, injection molding is performed under conditions that satisfy an injection rate and a surface progression coefficient described later. The chemical resistance can be further improved by reducing the crystallinity of the polyethylene resin in the molded body, preferably the molded body surface layer, to some extent, and forming a specific domain dispersion state. .

When the crystallinity reduction rate of the polyethylene resin in the surface layer part of the aromatic polycarbonate resin molded body of the present invention is smaller than the lower limit, the chemical resistance of the polyethylene resin domain is sufficiently stretched during the injection molding process. If a domain effective in improving the above is not formed and the above-described upper limit is exceeded, the crystallinity is too low, and stable chemical resistance may not be obtained.

The crystallinity of the polyethylene resin of the aromatic polycarbonate resin molded article thus obtained is preferably 7 to 16%, and more preferably 9 to 14%. Higher chemical resistance can be achieved by forming a polyethylene-based resin domain having such a crystallinity in a molded body, preferably a surface layer of the molded body.

The crystallinity of the polyethylene resin can be calculated according to a conventional method from the measurement result of the heat of fusion by DSC (differential scanning calorimeter). When measuring the crystallinity of the polyethylene-based resin in the molded product, the frozen and pulverized molded product is dissolved in dichloromethane (room temperature x 2 hours), and insoluble matter is collected by suction filtration (3 μm PTFE filter). It can obtain | require from the measurement result of DSC melting calorie | heat amount performed with respect to the collect | recovered insoluble matter. In calculating the crystallinity from the heat of fusion, the mass of components other than the polyethylene resin in the insoluble material is taken into consideration.

The polyethylene resin used in the present invention has a melt flow rate (MFR) at 190 ° C. of 1 to 20 g / 10 min, preferably 1 to 10 g / 10 min, and preferably 1.3 to 8 g / 10 min. More preferred. When the MFR of the polyethylene resin is smaller than the above range, the dispersibility is poor, and a large domain is likely to be formed. If the MFR of the polyethylene resin is larger than the above range, the aromatic polycarbonate resin (A) constituting the matrix, the rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), if necessary Since the difference in flowability from the blended aromatic vinyl / vinyl cyanide copolymer (B-2) becomes large, the domain has a structure that is excessively stretched. Decrease is likely to occur.

In particular, using a polyethylene resin with an MFR of 1 to 5 g / 10 min, the domain structure of the polyethylene resin has a minor axis diameter of 0.5 to 5 μm and an average aspect ratio (major axis diameter / minor axis diameter) as described later. By controlling so that the area of the domain is 2 to 200, and the area of the domain is 10 to 100 μm ² and the area / major axis diameter ratio is 0.5 to 5, the formation of large domains and their delamination are suppressed, Suppresses the formation of voids due to peeling between the matrix of the aromatic polycarbonate resin (A) and the polyethylene resin, thereby obtaining an excellent impact resistance improvement effect. Chemical properties can be improved.

The MFR of polyethylene resin is a value measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with ISO 1133.

The polyethylene resin used in the present invention may have been subjected to a thickening treatment with a peroxide in order to satisfy the above-mentioned preferred MFR. Examples of the peroxide used for the thickening treatment include hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, and peroxyketal. These may be used alone or in combination of two or more. It is preferable to select an optimum peroxide in consideration of the reactivity of the peroxide at the kneading temperature and the kneading time.

The thickening treatment with peroxide is a treatment to reduce MFR by heating and kneading the peroxide as described above to a polyethylene resin, thereby increasing the viscosity of the polyethylene resin with MFR outside the above preferred range. Thus, the MFR can be adjusted to a suitable range.

If the amount of peroxide used for the thickening treatment is too large, an excessive crosslinking reaction proceeds, the resin is cured and the dispersibility deteriorates, and if it is too small, a sufficient thickening effect cannot be obtained. The amount of peroxide used for the thickening treatment is preferably 50 to 2,000 ppm (mass basis), particularly 100 to 1,000 ppm, based on the polyethylene resin.
The temperature at the time of heat-kneading in the thickening treatment is preferably 150 to 250 ° C., particularly 170 to 230 ° C. If the temperature is too high, the resin is thermally deteriorated, resulting in a decrease in physical properties. If the temperature is too low, the load during kneading increases, the reaction does not proceed sufficiently, and the effect of the crosslinking reaction is not recognized.

Specifically, the thickening treatment is performed by feeding a polyethylene resin and a predetermined amount of peroxide into a kneader such as a biaxial kneader, uniaxial kneader, or Brabender, and melt-kneading and extruding at a predetermined temperature. Done.

The polyolefin resin (C) preferably contains an oligomer component. The oligomer component can be contained in a desired amount by appropriately adjusting the production conditions such as the catalyst type, the catalyst amount, the polymerization temperature, the polymerization time, and the polymerization pressure in the polymerization process of the polyolefin resin (C). In addition, in the granulation stage after polymerization, when additives such as antioxidants and heat stabilizers are blended, it is possible to incorporate a desired amount in the polyolefin resin by blending oligomer components at the same time. .

The content of the oligomer component is preferably 0.01 to 2% by mass in the polyolefin resin (C), more preferably 0.05 to 1% by mass, and still more preferably 0.1 to 0.5% by mass. %. When the oligomer component content is less than the above lower limit, the dispersibility of the polyolefin-based resin (C) is poor, and it becomes easy to form a large domain, so that it is difficult to achieve the preferred dispersion state of the present invention, and whitening and delamination are likely to occur. In some cases, the chemical resistance improving effect cannot be fully exhibited. When the content of the oligomer component exceeds the above upper limit, the oligomer component is selectively oriented on the surface layer of the molded product, so that surface layer peeling is likely to occur, and appearance defects may occur or physical properties may be deteriorated. There is.
The oligomer component in the polyolefin resin (C) refers to a component extracted when chloroform extraction is performed at 23 ° C. for 1 hour.

The above-mentioned polyolefin resin (C) such as low density polyethylene may be used alone or in combination of two or more.

[Resin component]
In the present invention, the component (A), the component (B-1), the component (B-2) and the component (C) described above are contained in an amount of 45 to 88% by mass of the component (A) and 2 to It is preferable to use 40% by mass, (B-2) component 0 to 35% by mass, and (C) component 1 to 15% by mass in a total amount of 100% by mass (hereinafter referred to as (B-1 The component (B) and the component (B-2) are referred to as “component (B)”, and the sum of the component (A), the component (B-1), the component (B-2), and the component (C) It may be referred to as “the resin component of the present invention”).

In the resin component of the present invention, if the aromatic polycarbonate resin as the component (A) is less than 45% by mass, the mechanical properties such as the original impact resistance of the aromatic polycarbonate resin and heat resistance cannot be obtained. When the content exceeds 88% by mass, the proportion of other components is relatively reduced, and the chemical resistance and fluidity tend to be lowered.
The ratio of the aromatic polycarbonate resin (A) in the resin component of the present invention is more preferably 48 to 84% by mass, still more preferably 50 to 80% by mass.

The cyanide contained in the rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) and aromatic vinyl / vinyl cyanide copolymer (B-2) in the resin component of the present invention. The vinyl component functions to improve chemical resistance. The rubbery polymer component functions to improve impact resistance. The aromatic vinyl component functions to improve fluidity and other performance balances.
Since the component (B) has a function of pulling the polyolefin-based resin (C) such as low-density polyethylene, the component (B) is finely dispersed in the aromatic polycarbonate resin (A), so that The domain of the component (C) is finely dispersed, and the effect of improving the chemical resistance is effectively exhibited by the uniform fine dispersion of the component (C).
Among the components (B), the vinyl cyanide component functions to improve the compatibility between the component (B) and the aromatic polycarbonate resin (A), and the component (B) is finely dispersed as described above (C) It has the effect of finely dispersing the components.
The rubbery polymer component such as the butadiene component in the component (B-1) is effective in improving the impact resistance, but even if its content is too large, the effect of improving the impact resistance has reached its peak, rather it is retained. There is a problem that thermal stability and fluidity are lowered.

Therefore, in the resin component of the present invention, the component (B-1) and the component (B-2) are contained in a balanced manner, and the sum of the component (B-1) and the component (B-2) It is preferable that the rubbery polymer component such as a butadiene component is controlled to an amount capable of obtaining sufficient impact resistance without impairing the residence heat stability and fluidity.
From such a viewpoint, the proportion of the component (B-1) in the resin component of the present invention is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 5 to 25% by mass, -2) The proportion of the component is preferably 0 to 35% by mass, more preferably 1 to 30% by mass, still more preferably 5 to 30% by mass, and the sum of the component (B-1) and the component (B-2) That is, the ratio of the component (B) is preferably 10 to 50% by mass, particularly preferably 15 to 45% by mass. When the amount of the component (B) is larger than this range, the elastic modulus, heat distortion temperature, and residence heat stability tend to decrease, and when the amount is smaller, the effect of improving the fluidity due to the component (B) tends to be impaired.

The proportion of the rubbery polymer component such as a butadiene component in the component (B) is preferably 5 to 50% by mass, particularly 7 to 40% by mass, and particularly preferably 10 to 30% by mass. If the proportion of the rubbery polymer component such as the butadiene component in the component (B) is less than the above lower limit, the toughness, elongation and impact resistance will be reduced. Tend to be impaired.

The proportion of the vinyl cyanide component in the component (B) is preferably 10 to 40% by mass, particularly 12 to 30% by mass, and particularly preferably 15 to 25% by mass. When the proportion of the vinyl cyanide component in the component (B) is less than the above lower limit, the effect of improving the compatibility between the component (B) and the aromatic polycarbonate resin (A) is lowered, so that the component (B) is finely dispersed. As a result, the component (C) is difficult to finely disperse, and the chemical resistance improving effect may be impaired. Since the fine dispersion effect of the component (B) decreases as the improvement effect increases at a certain ratio or more, if the proportion of the vinyl cyanide component exceeds the above upper limit, the residence heat stability and impact resistance tend to be reduced.

The proportion of each component contained in the components (B-1) and (B-2) can be specified from the absorbance ratio of the IR spectrum obtained by IR analysis. In the analysis, a characteristic absorption wavelength of each component contained in the components (B-1) and (B-2) is selected, and a calibration curve created using a sample whose component ratio is known is used.
When specifying from among the polycarbonate resin composition, the components (B-1) and (B-2) isolated by methanol decomposition of the polycarbonate resin composition are specified by performing IR analysis similar to the above. can do. When decomposing methanol, it is necessary to appropriately select conditions under which the components (B-1) and (B-2) are not altered by heating.

Polyolefin resin (C) such as low density polyethylene has an effect of improving chemical resistance. The proportion of the polyolefin resin (C) in the resin component of the present invention is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 3 to 10% by mass.

When the proportion of the polyolefin resin (C) in the resin component of the present invention is less than 1% by mass, the effect of improving the chemical resistance by the polyolefin resin (C) cannot be sufficiently obtained, and when it exceeds 15% by mass. In addition, the content of other components may be relatively reduced, and the mechanical characteristics, residence heat stability, and heat distortion temperature may be impaired. Such as poor appearance and chemical resistance may be impaired.

[Inorganic filler (D)]
The aromatic polycarbonate resin composition of this invention can mix | blend an inorganic filler (D). By blending the inorganic filler (D), the elastic modulus can be controlled and shrinkage during molding can be suppressed. In particular, in the case of a multicolor molded body, it is possible to adjust warpage and improve dimensional accuracy.
The inorganic filler (D) functions to improve the fine dispersion of the domain by breaking the domain shape of the polyolefin resin (C).

Examples of the inorganic filler (D) include glass fillers such as glass fibers (chopped strands), milled glass fibers (short glass fibers), glass flakes, and glass beads; carbon such as carbon fibers, short carbon fibers, carbon nanotubes, and graphite. Fillers such as potassium titanate and aluminum borate; silicate compounds such as wollastonite, talc, mica, kaolinite, zonotlite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. Preferred are glass fiber, milled glass fiber, wollastonite, talc, mica, etc. Among them, wollastonite and talc are preferable for improving the appearance, and rigidity and residence heat stability are preferred. Luo glass fiber is preferable. These inorganic fillers (D) may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The shape of the inorganic filler (D) is preferably fibrous, needle-like, plate-like, or spherical, and when considering the reduction in molding shrinkage or linear expansion, the fibrous, needle-like, or plate-like inorganic filler is More preferred.

As the size of the inorganic filler, the minor axis diameter is 0.01 to 100 μm, more preferably 0.05 to 50 μm, and still more preferably 0.1 to 20 μm. If the minor axis diameter of the inorganic filler is smaller than 10 nm, the domain shape of the polyolefin resin (C) cannot be sufficiently broken, and pearly luster may remain in the molded product. When the minor axis diameter of the inorganic filler is larger than 100 μm, the distance between the inorganic fillers becomes large, and the domain of the polyolefin resin (C) becomes difficult to finely disperse, so that pearly luster remains between the inorganic fillers. There is. As will be described later, in particular, the short axis diameter of the inorganic filler is preferably equal to the short axis diameter of the domain of the polyolefin resin (C) in order to effectively eliminate the pearl luster.

The minor axis diameter of the inorganic filler is the length of the portion where the interval between the parallel plates is the smallest when the inorganic filler is sandwiched between two parallel plates, and the inorganic filler is fibrous. It corresponds to the fiber diameter, if it is plate-like, it corresponds to the plate thickness, and if it is spherical, it corresponds to its diameter.

The minor axis diameter (average minor axis diameter) of the inorganic filler was determined by observing a cross section in the injection direction of the obtained injection molded product with a scanning electron microscope (SEM), and selecting the minor axis of 50 inorganic fillers arbitrarily selected. It can also be determined as a number average value of measured diameter values. An average fiber diameter as a product standard of the fibrous inorganic filler supplied as a product can be a short axis diameter. The same applies to plate-like and spherical inorganic fillers.

The aspect ratio (= major axis diameter / minor axis diameter) of the inorganic filler is not particularly limited, but is preferably 2 to 500. The major axis diameter is the length of the portion where the interval between the parallel plates is the widest when the inorganic filler is sandwiched between two parallel plates. If the inorganic filler is fibrous, the fiber length If it is plate-shaped, it corresponds to the major axis of the plate surface, and if it is spherical, it corresponds to its diameter. If the aspect ratio of the inorganic filler is too large, the difference in molding shrinkage between the orientation direction of the inorganic filler and the direction perpendicular thereto becomes too large, and thus distortion is likely to occur, and if it is too small, the effect of suppressing linear expansion is not sufficient.

Similarly to the short axis diameter, the aspect ratio can be obtained as a number average value by measuring the short axis diameter and the long axis diameter of the inorganic filler by SEM observation, calculating the aspect ratio for each inorganic filler. . An aspect ratio as a product standard of an inorganic filler supplied as a product can also be adopted.

The content of the inorganic filler (D) is 0 to 30 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 28 parts by weight, still more preferably 2 to 2 parts by weight based on 100 parts by weight of the resin component of the present invention. 25 parts by mass, particularly preferably 3 to 20 parts by mass. By including the inorganic filler (D), the molding shrinkage tends to be easily optimized, and the dimensional accuracy can be sufficiently increased. Furthermore, when a multicolor molded product is used, the amount of warpage tends to be easily adjusted. When content of an inorganic filler (D) exceeds the said upper limit, problems, such as a deterioration of a moldability and embrittlement, may arise.

[Other resins]
The aromatic polycarbonate resin composition of the present invention contains other resins other than the resin component of the present invention, for example, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and one or more kinds of polystyrene. By including these other resins, the following effects can be obtained.
Polyethylene terephthalate: improved chemical resistance Polybutylene terephthalate: improved chemical resistance, improved fluidity polystyrene: improved fluidity

Hereinafter, the polyester resin that the aromatic polycarbonate resin composition of the present invention may contain will be described.

As the polyester resin used in the present invention, any conventionally known polyester resin can be used, and among them, an aromatic polyester resin is preferable. Here, the aromatic polyester resin refers to a polyester resin having an aromatic ring in a polymer chain unit, and includes, for example, an aromatic dicarboxylic acid component and a diol (and / or its ester or halide) component as main components. These are polymers or copolymers obtained by polycondensation of these.

Examples of the aromatic dicarboxylic acid component include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2, 2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4 , 4′-dicarboxylic acid, diphenylisopropylidene-4,4′-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4′-dicarboxylic acid, Pyridine-2,5-dicarboxylic acid, succinic acid, adipic acid, sebacic acid, suberic acid, Zerain acid, and dimer acid.

The aromatic dicarboxylic acid component may be used alone or in combination of two or more in any proportion, and among these aromatic dicarboxylic acids, terephthalic acid is preferred. As long as the effects of the present invention are not impaired, an alicyclic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, sebacic acid, dimer acid, etc. may be used in combination with these aromatic dicarboxylic acids. Good.

Examples of the diol component include aliphatic glycols, polyoxyalkylene glycols, alicyclic diols, aromatic diols, and the like. Aliphatic glycols include, for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, etc. Among these, aliphatic glycols having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms are preferable.

Examples of the polyoxyalkylene glycols include glycols having an alkylene group having 2 to 4 carbon atoms and a plurality of oxyalkylene units such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, Examples include tritetramethylene glycol.

Examples of the alicyclic diols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, hydrogenated bisphenol A, and the like. Aromatic diols include 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, xylylene glycol and the like.

Other diol components include esters of the diols described above, and halogenated diols such as halides such as adducts of tetrabromobisphenol A and alkylene oxides (such as ethylene oxide and propylene oxide) of tetrabromobisphenol A. These diol components may be used alone or in combination of two or more in any proportion. If the amount is small, long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be used.

As the aromatic polyester resin used in the present invention, polyalkylene terephthalate is preferable. The polyalkylene terephthalate refers to a resin containing an alkylene terephthalate structural unit, and may be a copolymer of an alkylene terephthalate structural unit and another structural unit.

Examples of the polyalkylene terephthalate used in the present invention include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and poly (cyclohexane-1,4). -Dimethylene-terephthalate), polytrimethylene terephthalate and the like.

Examples of the polyalkylene terephthalate used in the present invention include, besides the above, an alkylene terephthalate copolymer having an alkylene terephthalate structural unit as a main structural unit, and a polyalkylene terephthalate mixture having polyalkylene terephthalate as a main component. Furthermore, what contains or copolymerized elastomer components, such as polyoxytetramethylene glycol (PTMG), can also be used.

Examples of the alkylene terephthalate copolyester include a copolyester composed of two or more diol components and terephthalic acid, and a copolyester composed of a diol component, terephthalic acid, and a dicarboxylic acid other than terephthalic acid. When two or more kinds of diol components are used, they may be selected and determined as appropriate from the above-mentioned diol components, but the monomer unit copolymerized with alkylene terephthalate which is the main constituent unit is within 25% by mass. It is preferable because heat resistance is improved.

Examples of the polyalkylene terephthalate copolyester include ethylene glycol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polyethylene terephthalate) and 1,4-butanediol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymer). In addition to the alkylene terephthalate copolyester having an alkylene terephthalate structural unit as the main structural unit, such as polymerized polybutylene terephthalate), 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymer, and the like can be mentioned. An alkylene terephthalate copolyester having an alkylene terephthalate structural unit as a main structural unit is preferred.

As the polyester resin used in the present invention, when an alkylene terephthalate copolyester is used, the above-mentioned isophthalic acid copolymerized polybutylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate, and the like are preferable. Therefore, it is preferable that the isophthalic acid component is within 25% by mass.

<Polyethylene terephthalate>
As the polyester resin, it is particularly preferable to use polyethylene terephthalate. Polyethylene terephthalate is the ratio of oxyethylene oxyterephthaloyl units consisting of terephthalic acid and ethylene glycol (hereinafter sometimes referred to as “ET units”) to the total repeating units (hereinafter sometimes referred to as “ET ratio”). .) Is preferably a polyethylene terephthalate resin of 90 equivalent% or more. The polyethylene terephthalate in the present invention may contain constituent repeating units other than ET units in a range of less than 10 equivalent%. The polyethylene terephthalate in the present invention is produced using terephthalic acid or its lower alkyl ester and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

Diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol and neopentyl glycol, cyclohexanedimethanol And aromatic dihydroxy compound derivatives such as bisphenol A, bisphenol A, and bisphenol S.

A raw material containing terephthalic acid or an ester-forming derivative thereof and ethylene glycol as described above is subjected to esterification or transesterification in the presence of an esterification catalyst or transesterification catalyst, and bis (β-hydroxyethyl) terephthalate and Then, an oligomer thereof is formed, and then a melt polycondensation is performed under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer to obtain a polymer.

The esterification catalyst is not particularly required because terephthalic acid serves as an autocatalyst for the esterification reaction. The esterification reaction can be carried out in the presence of an esterification catalyst and a polycondensation catalyst described later, and can be carried out in the presence of a small amount of an inorganic acid or the like. As the transesterification catalyst, alkali metal salts such as sodium and lithium, alkaline earth metal salts such as magnesium and calcium, and metal compounds such as zinc and manganese are preferably used. Compounds are particularly preferred.

As the polycondensation catalyst, compounds soluble in a reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound, and a tin compound are used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferable from the viewpoints of color tone and transparency. These polycondensation catalysts may be used in combination with a stabilizer in order to suppress the decomposition reaction during polymerization. Examples of the stabilizer include phosphate esters such as trimethyl phosphate, triethyl phosphate and triphenyl phosphate, and triphenyl phosphate. Phosphites such as phyto, trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl phosphate acidic phosphate, phosphorous compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid Or 2 or more types are preferable.

The usage ratio of the above catalyst is usually in the range of 1 to 2000 ppm, preferably 3 to 500 ppm as the mass of the metal in the catalyst in all the polymerization raw materials. The proportion of the stabilizer used is usually in the range of 10 to 1,000 ppm, preferably 20 to 200 ppm, as the mass of phosphorus atoms in the stabilizer in the total polymerization raw material. The catalyst and the stabilizer can be supplied at any stage of the esterification reaction or transesterification reaction in addition to the preparation of the raw slurry. Further, it can be supplied at the beginning of the polycondensation reaction step.

The intrinsic viscosity of the polyethylene terephthalate used in the present invention may be appropriately selected and determined, but is usually 0.5 to 2 dl / g, particularly 0.6 to 1.5 dl / g, particularly 0.7 to 1.0 dl. / G is preferable. By setting the intrinsic viscosity to 0.5 dl / g or more, particularly 0.7 dl / g or more, the mechanical properties, residence heat stability, chemical resistance, and heat-and-moisture resistance tend to be improved in the resin composition of the present invention. And preferred. On the contrary, it is preferable that the intrinsic viscosity is 2 dl / g or less, particularly 1.0 dl / g or less because the fluidity of the resin composition tends to be improved.

In the present invention, the intrinsic viscosity of polyethylene terephthalate is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (mass ratio 1/1).

The concentration of the terminal carboxyl group of the polyethylene terephthalate used in the present invention is usually 1 to 60 μeq / g, preferably 3 to 50 μeq / g, more preferably 5 to 40 μeq / g. By setting the terminal carboxyl group concentration to 60 μeq / g or less, the mechanical properties of the resin composition tend to be improved. By setting the terminal carboxyl group concentration to 1 μeq / g or more, the heat resistance and retention of the resin composition are increased. It tends to improve thermal stability and hue, which is preferable.

The terminal carboxyl group concentration of polyethylene terephthalate can be determined by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

The polyethylene terephthalate used in the present invention is preferably the one obtained by subjecting the above-described polyethylene terephthalate to a polycondensation catalyst deactivation treatment.
That is, a resin composition obtained by combining a polyester resin with an aromatic polycarbonate resin has poor thermal stability, and is transesterified between the aromatic polycarbonate resin and the polyester resin by being held at a high temperature in the cylinder during the molding process. Causes reaction, and generation of decomposition gas due to the reaction causes bubbles and appearance of molded products called silver; poor molecular weight of aromatic polycarbonate resin impact resistance, heat distortion resistance, etc. In addition, a change in viscosity of the aromatic polycarbonate resin composition due to residence at high temperature results in a loss of molding stability during injection molding, resulting in short shots and burrs of the molded product. In addition, there is a problem of a decrease in melt tension.
The problem of this residence heat deterioration is caused by the polycondensation catalyst contained in the polyethylene terephthalate used in the production process of polyethylene terephthalate and provided as a product. Therefore, by using polyethylene terephthalate in which this polycondensation catalyst is deactivated as polyethylene terephthalate, it is possible to suppress residence heat deterioration.

There is no restriction | limiting in particular as a deactivation processing method of the polycondensation catalyst of a polyethylene terephthalate, A conventionally well-known deactivation process can be given according to the used polycondensation catalyst. Examples of the deactivation treatment method include the following methods.

Deactivation treatment method of polycondensation catalyst 1: Hot water (steam) treatment of germanium catalyst Polyethylene terephthalate is treated with hot water (steam) to deactivate the germanium catalyst in the polyethylene terephthalate.
Deactivation treatment method 2 of polycondensation catalyst: Addition of phosphorus compound to titanium catalyst A phosphorus compound is added to polyethylene terephthalate to deactivate the titanium catalyst in the polyethylene terephthalate.
The deactivation treatment method for the polycondensation catalyst of polyethylene terephthalate is an example of the deactivation treatment that can be employed in the present invention, and the deactivation treatment according to the present invention is not limited to the above method.

<Polybutylene terephthalate>
Polybutylene terephthalate may be used as the polyester resin. The polybutylene terephthalate refers to a resin having a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded. In the present invention, it is preferable to use polybutylene terephthalate in which 50 mol% or more of dicarboxylic acid units are terephthalic acid units and 50 mol% or more of diol components are 1,4-butanediol units. The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. The proportion of 1,4-butanediol units in all diol units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. When the terephthalic acid unit or the 1,4-butanediol unit is in the above range, the moldability is good because the crystallization rate is in an appropriate range.

As described above, polybutylene terephthalate may contain dicarboxylic acid units other than terephthalic acid. There are no particular restrictions on dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; . These dicarboxylic acid units can be introduced into the polymer skeleton by using a dicarboxylic acid or a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

As described above, polybutylene terephthalate may contain a diol unit other than 1,4-butanediol. Diols other than 1,4-butanediol are not particularly limited. For example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene Aliphatic diols such as glycol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1- Cycloaliphatic diols such as cyclohexane dimethylol and 1,4-cyclohexane dimethylol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) Nyl) sulfone and other aromatic diols;

The polybutylene terephthalate further contains hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid; Monofunctional compounds such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane , Trimethylolpropane, glycerol, pentaerythritol and the like trifunctional or higher polyfunctional compounds; and the like.

Although there is no restriction | limiting in particular about the intrinsic viscosity of the polybutylene terephthalate used for this invention, a lower limit may be determined from a viewpoint of mechanical properties, and an upper limit may be determined from a viewpoint of moldability. The intrinsic viscosity of polybutylene terephthalate is preferably 0.70 to 3.0 dl / g, more preferably 0.80 to 1.5 dl / g, and particularly preferably 0.80 to 1.2 dl / g. . When the intrinsic viscosity is within the above range, good mechanical properties can be exhibited and good moldability can be obtained. The intrinsic viscosity is a value measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (mass ratio).
In the present invention, two or more polybutylene terephthalates having different intrinsic viscosities may be used in combination.

The terminal carboxyl group concentration of the polybutylene terephthalate used in the present invention is preferably 120 eq / ton or less, more preferably 2 to 80 eq / ton, and particularly preferably 5 to 60 eq / ton. When the terminal carboxyl group concentration is 120 eq / ton or less, hydrolysis resistance and fluidity are improved. The terminal carboxyl group concentration is preferably 2 eq / ton or more from the viewpoint of productivity. The terminal carboxyl group concentration can be determined by dissolving polybutylene terephthalate in benzyl alcohol and titrating with an aqueous solution of 0.1 N (mol / L) sodium hydroxide, and the above value is the carboxyl per 10 ⁶ g. It is a group equivalent.

When the aromatic polycarbonate resin composition of the present invention contains a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, the content thereof is 20 parts by mass or less, for example, 1 with respect to 100 parts by mass of the resin component of the present invention described above. It is preferable that the amount be ˜15 parts by mass.

When the content ratio of the polyester resin is not less than the above lower limit value, the effect of improving the chemical resistance by blending the polyester resin can be sufficiently obtained, and by being not more than the above upper limit value, the aromatic polycarbonate resin ( Good physical properties such as impact resistance and thermal stability can be obtained without impairing the original properties such as A).

[Other additives]
In the aromatic polycarbonate resin composition of the present invention, in addition to the above-described resin component of the present invention, other resins, and inorganic filler (D), the usual polycarbonate resin composition is within the range not impairing the effects of the present invention. Various other additives contained in may be contained.

Various additives that can be contained include antioxidants, heat stabilizers, mold release agents, UV absorbers, dyes and pigments, flame retardants, impact resistance improvers, antistatic agents, antifogging agents, lubricants and antiblocking agents. , Fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the resin composition according to the present invention will be specifically described.

<Antioxidant>
Examples of the antioxidant include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like. Two or more of these may be used in combination.

Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

The content of the antioxidant is usually 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and when it exceeds 1 part by mass, the effect reaches a peak and is not economical.

<Heat stabilizer>
As the heat stabilizer, at least one ester in the molecule is a phosphite compound esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms, phosphorous acid and tetrakis ( And at least one selected from 2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite.

Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2,4 -Dinolylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (octylphenyl) phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, octyl Diphenyl phosphite, dilauryl phenyl phosphite, diisodecyl phenyl phosphite, bis (nonylphenyl) phenyl phosphite, diisooctylphenyl phosphite, diisodecyl pentaerythritol Rudiphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphite , (2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-di-tert-butylphenyl) ) (1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) ) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanedio) Phosphite, (4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylphenyl) ( 1,2-ethanediol) phosphite, (2,4-di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl) (1,2- Ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) ( 1,4-butanediol) phosphite, diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphat Bis (3-methylphenyl) pentaerythritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethyl) Phenyl) pentaerythritol diphosphite, bis (2,3,6-trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3-tert-butylphenyl) penta Erythritol diphosphite, bis (4-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) Ruphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol Examples thereof include diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, and dinaphthyl pentaerythritol diphosphite.

Organophosphate metal salt compounds can also be used as heat stabilizers. Specific examples include a mixture of a zinc salt of distearyl acid phosphate and a zinc salt of monostearyl acid phosphate.

In the present invention, a phosphine compound can also be used as a heat stabilizer. The phosphine compound is not particularly limited, and includes all organic derivatives of phosphine and salts thereof. Examples thereof include various phosphine compounds, phosphine oxides, phosphonium salts with halogen ions, and diphosphine. In particular, an aliphatic or aromatic phosphine compound can be preferably used. Any of primary, secondary, and tertiary phosphine compounds can be used, with tertiary phosphine compounds being particularly preferred, and tertiary aromatic phosphine compounds being more preferred.

The tertiary phosphine compound has a general formula R ₃ P (wherein R represents an aliphatic or aromatic hydrocarbon group which may have a substituent, and three Rs are the same or different from each other). May be expressed. R is preferably a phenyl group. Examples of the substituent for R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-amyl group, isoamyl group, n-hexyl group, isohexyl group, Examples thereof include alkyl groups such as cyclopentyl group and cyclohexyl group, and alkoxy groups such as methoxy group and ethoxy group.

Specific examples of the tertiary aromatic phosphine compound include triphenylphosphine, tri-m-tolylphosphine, tri-o-tolylphosphine, tri-p-tolylphosphine, tris-p-methoxyphenylphosphine, and the like. Specifically, triphenylphosphine is preferably used, but other phosphine compounds may be used in combination.

Furthermore, phosphate compounds and phosphonate compounds can also be used as heat stabilizers. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, dioctyl phosphate, di (2-ethylhexyl) phosphate, diisooctyl phosphate, dinonyl phosphate, diisononyl phosphate, didecyl phosphate, diisodecyl phosphate, dilauryl Examples include phosphate, ditridecyl phosphate, dimethylphenyl phosphate, 1,3-phenylene-bis (dixylenyl) phosphate, and the like.

The content of the heat stabilizer is usually 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the heat stabilizer is less than 0.001 part by mass, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by mass, the hydrolysis resistance may deteriorate.

<Release agent>
The release agent includes at least one selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. Compounds.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable 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 preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same aliphatic carboxylic acid as that described above can be used. Examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.

The above ester compound may contain an aliphatic carboxylic acid and / or alcohol as an impurity, or may be a mixture of a plurality of compounds.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol 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 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. These hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

The content of the releasing agent is usually 0.001 to 2 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the release agent is less than 0.001 part by mass, the effect of releasability may not be sufficient. When the content exceeds 2 parts by mass, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

<Ultraviolet absorber>
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. In these, an organic ultraviolet absorber is preferable. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- On], at least one selected from the group of [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylene- Bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H-benzotriazole) -2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

The content of the ultraviolet absorber is usually 0.01 to 3 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the ultraviolet absorber is less than 0.01 parts by mass, the effect of improving the weather resistance may be insufficient, and when it exceeds 3 parts by mass, a problem such as mold deposit may occur.

<Colorant>
Examples of the colorant include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability. These colorants are preferably used in the form of a masterbatch in order to improve the dispersibility in the resin composition.

The content of the colorant is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the resin component of the present invention. When the content of the dye / pigment exceeds 5 parts by mass, the impact resistance may not be sufficient.

<Flame Retardant>
Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-potassium sulfonate, potassium perfluorobutane sulfonate, polyorganosiloxane flame retardants, etc., but phosphate ester flame retardants are particularly preferred .

Specific examples of phosphate ester flame retardants include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

The content of the flame retardant is usually 1 to 30 parts by mass, preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the flame retardant is less than 1 part by mass, the flame retardancy may not be sufficient, and when it exceeds 30 parts by mass, the heat resistance may decrease.

<Anti-dripping agent>
Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemicals, Inc. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

The content of the anti-dripping agent is usually 0.02 to 4 parts by mass, preferably 0.03 to 3 parts by mass with respect to 100 parts by mass of the resin component of the present invention. When the content of the dripping inhibitor exceeds 5 parts by mass, the appearance of the molded product may be deteriorated.

[Method for producing aromatic polycarbonate resin composition]
Regarding the kneading conditions for producing the aromatic polycarbonate resin composition of the present invention, the physical properties and blending ratios of the components (A), (B), and (C) used, and the types and blends of the inorganic filler (D) used. Depending on the ratio, the presence or absence of other additives, etc., it cannot be generally stated, but for example, the following conditions can be adopted.

The resin component of the present invention, the inorganic filler (D) used as necessary, other resins and additives, etc., are blended and blended at a cylinder temperature of 200 to 300 ° C. and a screw rotation speed of 80 to 400 rpm. Knead. As an addition method in the case of adding the inorganic filler (D), the resin component and the inorganic filler (D) may be kneaded by batch supply to the kneading machine, but may be a fibrous form such as glass fiber or wollastonite. In the case of the needle-like inorganic filler (D), the inorganic filler is broken by strong needling, and the performance as the filler may be reduced. Inorganic mineral-based inorganic fillers such as talc, wollastonite, mica, etc. degrade and degrade the aromatic polycarbonate resin (A) by increasing the time of contact with the aromatic polycarbonate resin (A) under heating.

In the present invention, in order to suppress such degradation and degradation of the aromatic polycarbonate resin (A), it is preferable that the melt kneading time of the resin component of the present invention and the inorganic filler (D) is short.

Therefore, it is preferable to add the inorganic filler (D) to the resin component that has been previously subjected to the melt-kneading process using the side feed method, and then to extrude it as a strand through a light kneading zone. The extruded strand is cooled, cut and pelletized. In particular, when glass fiber or wollastonite is used as the inorganic filler (D), it is preferable to use a side feed method in order to suppress breakage due to kneading.

In kneading, the screw rotation speed and the discharge amount are balanced, the resin pressure in the die is set to about 1 to 50 MPa, and the resin pressure is kept constant, and the shear stress is effectively applied, so that the aromatic polycarbonate resin (A ), The dispersibility of the component (C) component and the inorganic filler (D) blended as necessary. Even if the resin is not filled in the cylinder, sufficient shear stress is not applied, the component (C) tends to form a large domain, and the inorganic filler (D) is not uniformly dispersed. Variations and appearance defects are likely to occur.

[Production method of polycarbonate resin molded product]
The molding method for producing a polycarbonate resin molded product from the aromatic polycarbonate resin composition of the present invention includes a general injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a multicolor injection molding method, and a multicolor injection compression method. Examples thereof include a molding method, a gas assist injection molding method, a molding method using a heat insulating mold, a molding method using a high-speed heating / cooling mold, an insert molding method, and an IMC (in-mold coating) molding method. Of these, the injection molding method is particularly preferable.
The aromatic polycarbonate resin composition of the present invention can be formed into a composite molded product by multicolor composite molding with other thermoplastic resin compositions.

[Physical properties of aromatic polycarbonate resin composition]
<MVR>
The aromatic polycarbonate resin composition of the present invention, 280 ° C., we are preferable melt volume rate of 2.16kg load (MVR) is ^{5 cm} 3 / 10min or more. MVR is insufficient fluidity is less than ^{5 cm} 3 / 10min, tends to moldability is inferior. MVR of the aromatic polycarbonate resin composition of the present invention, more preferably ⁸ ~ 100cm 3 / 10min, more preferably ¹⁰ ~ 75cm 3 / 10min. If the MVR is excessively high, the impact resistance is lowered, and the function required for the window frame cannot be performed, or the staying heat stability is lowered, and the physical properties may be lowered due to deterioration during molding.

Specifically, the MVR of the aromatic polycarbonate resin composition is measured by the method described in the Examples section below.

<High-speed surface impact resistance>
The aromatic polycarbonate resin composition of the present invention was subjected to a high-speed surface impact test at 23 ° C. and a punching speed of 10 m / sec performed on a molded article having a thickness of 3 mm obtained by molding the aromatic polycarbonate resin composition of the present invention. It is preferable that the absorbed energy at the puncture point is 7 J or more, particularly 15 J or more.
If the absorbed energy value is less than 7 J, the high-speed surface impact resistance required as a glazing window frame member described later may not be satisfied. The larger the absorbed energy value, the better the high-speed surface impact resistance, which is preferable, but usually the upper limit of the window frame member is about 70J.

Specifically, the absorbed energy value of the molded product is measured by the method described in the section of Examples described later.

[Aromatic polycarbonate resin molding]
The aromatic polycarbonate resin molded article of the present invention comprises the above-described aromatic polycarbonate resin composition of the present invention having an injection rate of 10 to 100 cm ³ / s defined below and a surface progression coefficient of 40 to 40 defined below. It is formed by injection molding under the condition of 200 cm ³ / s · cm.
Injection rate: Resin composition volume per unit time injected from the discharge nozzle of the injection molding machine into the mold cavity Surface progression coefficient: Value obtained by dividing the above injection rate by the thickness of the mold cavity where the resin composition is injected The thickness of the mold cavity is the thickness of the mold cavity when the resin composition is injected. For example, as in the case of injection compression molding, after the resin composition is injected, the thickness of the resin is filled. When the mold is clamped inside, the mold cavity thickness in the resin flow portion when the filling resin is flowing in the mold is indicated.

The injection rate and the surface progression coefficient are conditions for forming the domain of the component (C) effective for improving chemical resistance, which will be described later. The injection rate is 10 to 100 cm ³ / s, preferably 12 It is ˜80 cm ³ / s, more preferably 15 to 70 cm ³ / s.

In order to improve the chemical resistance of the aromatic polycarbonate resin molded article, the size of the domain of the component (C) is large to some extent, and a large number of layers are dispersed in the surface layer portion (the long axis of the domain is long). Although it is preferable for obtaining good chemical resistance by suppressing the penetration of chemicals, if the injection rate is smaller than the lower limit, in the injection molding process, the domain of component (C) is finely dispersed without applying shear. As a result, the size (area) of the domain is reduced and the major axis is shortened. That is, since the domain is short and small, a sufficient chemical resistance improvement effect cannot be obtained. When the injection rate is larger than the above upper limit, the shearing force when the resin composition is filled in the mold cavity is too large. As a result, the domain of the component (C) is shredded, so the domain size (area) is small. In addition, since the major axis is also shortened, it does not disperse in a layered form and cannot exert an effect on chemical resistance.

The surface progression coefficient is 40 to 200 cm ³ / s · cm, preferably 40 to 180 cm ³ / s · cm, more preferably 45 to 170 cm ³ / s · cm.

When the surface progression coefficient is smaller than the lower limit, in the injection molding process, the domain of the component (C) is finely dispersed without being sheared, so the size (area) of the formed domain is reduced, And the long axis becomes shorter. That is, since the domain is short and small, a sufficient chemical resistance improvement effect cannot be obtained, and in addition, there is a high risk of appearance defects such as hot water wrinkles. When the surface progression coefficient is larger than the above upper limit, the shearing force when the resin composition is filled in the mold cavity is too large, so that the domain of the component (C) is shredded, so that the domain size (area) is small. In addition to the fact that the major axis is shortened, it does not disperse into a layer and cannot exert its effect on chemical resistance. In addition, appearance defects such as jetting (resin flow pattern) may occur. High risk.

The shape of the mold cavity corresponds to the shape of the molded body.Therefore, if the molded body is not plate-shaped and there are steps or irregularities, or even if it is plate-shaped, The thickness of the mold cavity varies depending on the part. In the present invention, the thickness of the mold cavity at a location where chemical resistance of the obtained molded body is required (as in the case of injection compression molding, after the resin composition is injected, the resin is being filled. When performing mold clamping, conditions may be set so that the surface progression coefficient determined by the mold cavity thickness in the resin flow portion when the filling resin is flowing in the mold satisfies the above range, for example, There is no problem even when the thickness of the mold cavity is thick at a location where chemical resistance is not required and the surface progression coefficient is outside the above range.
In the present invention, at least a part of the part requiring chemical resistance in the molded body is injection molded under the conditions of an injection rate of 10 to 100 cm ³ / s and a surface progression coefficient of 40 to 200 cm ³ / s · cm. Preferably, 50% or more, more preferably 70% or more, and still more preferably 80% or more of the area of the part where chemical resistance in the molded body is required, has an injection rate of 10 to 100 cm ³ / It is sufficient that the injection molding is performed under the conditions of s and a surface progression coefficient of 40 to 200 cm ³ / s · cm.

In the present invention, the reason why the injection rate and the surface progression coefficient are within the predetermined ranges as the conditions during injection molding is as follows.
Generally, the injection speed is often defined as the injection condition, but the injection speed is influenced by the shape in the molded body (that is, in the mold cavity), except in the case of a fixed shape such as a flat plate or strip. Therefore, the injection force cannot evaluate the shear force that the resin composition receives in the molded body (that is, in the mold cavity) at the time of injection molding.
Even the cylinder moving speed (injection speed of the molding machine) changes the capacity of the resin composition to be filled depending on the cylinder diameter of the molding machine, and as a result, the traveling speed of the resin composition in the mold cavity also varies. After all, the shear force cannot be evaluated.
Therefore, in the present invention, the injection rate is adopted as a parameter for eliminating these effects.
Even if the mold cavity is filled with the same injection rate, the traveling speed of the melt front (the tip of the resin composition flowing in the mold cavity) varies depending on the thickness of the mold cavity. . If the melt front traveling speed is different, the shearing method in the surface layer portion is different, so that the orientation state of the domain of the component (C) is different.
Therefore, in the present invention, in addition to the above injection rate, a surface progression coefficient is defined as a parameter for evaluating the degree of shearing force resulting from the traveling speed of the melt front.

In the above-mentioned Patent Document 2, only the injection speed is described, and the injection rate and the surface progression coefficient specified in the present invention are unknown, but at least the surface progression coefficient is less than 40 cm ³ / s · cm, Insufficient shear force to form a chemical effective domain

The aromatic polycarbonate resin molded body of the present invention is formed by injection molding the above-described aromatic polycarbonate resin composition of the present invention under conditions that satisfy the above injection rate and surface progression coefficient. In addition to general injection molding methods, it includes various injection molding methods such as ultra-high-speed injection molding methods, injection compression molding methods, multicolor injection molding methods, multicolor injection compression molding methods, and gas assist injection molding methods. It is an injection molding method in a broad sense.
The aromatic polycarbonate resin molded body of the present invention may be a composite molded body by multicolor composite molding of the aromatic polycarbonate resin composition of the present invention and another thermoplastic resin composition.

[(C) Component Domain Shape]
In the aromatic polycarbonate resin molded body of the present invention, in order to effectively obtain the chemical resistance improving effect by the component (C), the component (C) is finely and dispersed in at least the surface layer portion of the molded body. It is important that
In terms of the effect of improving the chemical resistance of the aromatic polycarbonate resin molded product, the aromatic polycarbonate resin molded product of the present invention is the component (C) in the surface layer part having a depth of 30 μm from the surface. It is preferable that the domain formed by the polyethylene resin satisfies the following dimensional conditions.
The surface layer portion of the aromatic polycarbonate resin molded body is a surface layer portion on the surface where chemical resistance is required in the usage of the molded body, and does not need to be the entire surface of the molded body. Usually, if it is a plate-shaped molded object, the surface layer part of the one or both, preferably both plate surfaces is pointed out.

<Short shaft diameter>
The short axis diameter of the domain is preferably 0.5 to 5 μm, more preferably 1 to 4 μm, and still more preferably 1.2 to 3 μm.
If the minor axis diameter of the domain is smaller than the lower limit, the domain layer becomes too thin to exhibit a sufficient effect on chemical resistance, or interface peeling tends to occur. When the short axis diameter of the domain is larger than the above upper limit, the domain is not dispersed in a layered manner, so that a sufficient effect on chemical resistance cannot be exhibited, and appearance defects such as whitening may occur. The short axis diameter of the domain refers to the shortest diameter among the diameters perpendicular to the long axis diameter described later.

<Area>
The area of the domain is preferably 10 to 100 μm ² , more preferably 20 to 90 μm ² , still more preferably 30 to 80 μm ² .
When the area of the domain is smaller than the above lower limit, even if the domain is dispersed in a layer form, it may be too fine to exhibit a sufficient effect on chemical resistance. If the area of the domain is larger than the above upper limit, the domain will become too large and will not disperse in layers, so that it will not exert a sufficient effect on chemical resistance, or it will be a long layer dispersion and appearance such as interface peeling Defects and defects such as delamination are likely to occur.

<Area / major axis ratio>
The area / major axis ratio of the domain is preferably 0.5 to 5 μm, more preferably 1 to 4 μm, and still more preferably 1.2 to 3 μm.
If the area / major axis diameter ratio of the domain is smaller than the above lower limit, the domain will be layered, but it will be a thin layer with a very small minor axis diameter and will not exhibit a sufficient effect on chemical resistance, There is a risk of causing appearance defects such as peeling and defects such as layered peeling. If the area / major axis diameter ratio of the domain is larger than the above upper limit, the domain is difficult to be layered and cannot exert a sufficient effect on chemical resistance, and appearance defects such as whitening may occur. The major axis diameter of a domain refers to the longest diameter of the domain.

<Aspect ratio>
The domain aspect ratio (major axis diameter / minor axis diameter ratio) is preferably 1 to 100, more preferably 3 to 60, and even more preferably 5 to 40.
If the aspect ratio of the domain is smaller than the above lower limit, large voids that can scatter visible light are likely to be formed, which may lead to whitening and impairing the chemical resistance improving effect. The oriented polyethylene domain tends to produce a strong pearl luster.

It is effective for disappearance of pearl luster that there is no great difference in the minor axis diameter of both the domain of component (C) and the inorganic filler (D), and the minor axis diameter ratio (minor axis of the inorganic filler (D) (Diameter / short axis of domain) is preferably 0.1 to 100, particularly 1 to 25, and particularly 1 to 15.

The short axis diameter, long axis diameter, aspect ratio, and area of this domain are values measured and calculated as follows.

The cut surface in the flow direction of the molded body can be observed with an SEM, and the obtained SEM observation photograph can be binarized from the cut surface in the surface layer within a range of 30 μm from the surface, and measured with image analysis software. . The minor axis diameter, major axis diameter, aspect ratio, and area are calculated as an average value of 700 or more domains extracted by image analysis software.

In the present invention, as described above, the thickness of the orientation layer of the polyethylene-based resin domain in the molded body in which the domains of the component (C) are finely and dispersed in layers is 30 μm or more from the surface of the molded body. Preferably, it is 100 μm or more, more preferably 500 μm or more, and particularly preferably 1 mm or more. The upper limit of the thickness of the alignment layer is preferably 1.8 mm, more preferably 1.5 mm, and still more preferably 1.2 mm. Usually, there is often no orientation at a depth of about 2 mm from the surface. By making the thickness of the alignment layer in the above range, the chemical resistance tends to be more improved, which is preferable.

In the present invention, the aromatic polycarbonate resin composition of the present invention is injection-molded under the conditions satisfying the above-described injection rate and surface progression coefficient, so that the shape or dimension effective for improving the chemical resistance as described above is obtained. Although the domain can be formed, more detailed molding conditions are the properties of the aromatic polycarbonate resin (A), (B) component and polyolefin resin (C) used, the blending ratio thereof, and the inorganic filler (D) used. For example, it is preferable to make the following adjustments, for example, depending on the type and content thereof and the presence or absence of other additives.

The pellets of the aromatic polycarbonate resin composition of the present invention produced under the above-mentioned preferred conditions are previously dried at 80 to 120 ° C. for 3 to 20 hours, for example, at 100 ° C. for 5 hours. When drying is performed at a lower temperature, the drying time is further increased. As the injection molding conditions, the cylinder temperature is set to 230 to 340 ° C., and the mold temperature is adjusted to 40 to 120 ° C., and injection molding is performed so as to satisfy the above injection rate and surface progression coefficient. Since many inorganic fillers (D) promote the deterioration of the resin, it is preferable to shorten the residence time in the cylinder of the injection molding machine at the time of molding, or to set the cylinder temperature to a low level within the range where there is no problem in molding. . When measuring in a cylinder, it is desirable to measure at a rotation speed of 40 to 150 rpm with a back pressure of 1 to 20 MPa in order to suppress entrainment of bubbles. Since the injection speed condition greatly depends on the shape of the target molded product, the injection speed is controlled step by step according to the mold shape. When injection is performed at a high injection speed, molding defects such as silver may occur due to deterioration of the resin or vaporization of low molecular weight components due to shearing heat generation.

In the present invention, after adopting such molding conditions, the domain shape of the molded product sample is examined for each blending of the aromatic polycarbonate resin composition, and further, the molding conditions are fine-tuned to obtain the desired domain shape. Can be realized. That is, if the area / major axis diameter ratio of the domain is too small, the shear stress is too strong, or the fluidity of the polyethylene resin is too high, and the domain size is too small due to fine dispersion. There is a case. In the former case, the injection rate may be decreased, the surface progression coefficient may be decreased, the resin temperature may be decreased, and the like. In the latter case, the collection of domains may be achieved by increasing the injection rate and the surface progression coefficient. Also, if the domain area / major axis diameter ratio is too large, the shear stress is too weak, or the fluidity of the polyethylene resin is too low, so the injection rate is increased and the surface progression coefficient is increased. You can raise it. In addition, if the domain aspect ratio is too small, the shear stress is too weak, or the domain is relaxed before solidification, so increase the injection rate, increase the surface progression coefficient, and lower the mold temperature. It is sufficient to increase the resin temperature. In addition, when the aspect ratio of the domain is too large, the shear stress is excessively applied, or the stretched domain is quenched before being relaxed, so that the injection rate is decreased and the surface progression coefficient is decreased. The mold temperature may be set higher or the resin temperature may be lowered.

[panel]
The panel of the present invention is a panel comprising a panel main body having a front surface and a rear surface, and a frame member provided at a peripheral edge portion of the rear surface of the panel main body, and supported by a panel support through the frame member. The panel body is made of an aromatic polycarbonate resin as a main component resin, and the frame member is made of the molded article of the aromatic polycarbonate resin of the present invention.

The panel of the present invention generally has a structure shown in FIGS. 1a to 1c.

[Panel body]
If the constituent material of the panel main body 1 is a transparent resin, it can be suitably selected from conventionally well-known arbitrary things. Here, the term “transparent” is generally 5% or more, preferably 10% or more, and more preferably 20% as a total light transmittance in a plate-shaped molded article having a smooth surface thickness of 3 mm measured according to JIS K7105. This means that the Haze value is usually 10% or less, preferably 5% or less, and more preferably 3% or less. In a transparent resin containing a dye or pigment, the amount of the dye or pigment used is usually 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, more preferably 100 parts by weight of the resin. 0.005 to 0.5 parts by mass.

Examples of the transparent resin include polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, poly Methacryl methacrylate resin, polyphenyl ether resin, polycarbonate resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, poly Ether sulfone, Styrenic thermoplastic elastomer, Olefin thermoplastic elastomer, Polyamide thermoplastic elastomer, Polyester thermoplastic elastomer, Polyurethane thermoplastic elastomer, etc. Thermoplastic elastomers are Kyora. In the present invention, among these, an aromatic polycarbonate resin is used as the main constituent resin from the viewpoint of impact resistance and heat resistance. The main constituent resin means that the ratio of the aromatic polycarbonate resin is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly 80 to 100% by mass.

Resin used together when aromatic polycarbonate resin is the main constituent resin includes polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polymethacryl methacrylate resin, polyester resin, etc. May be an alloy or a copolymer as long as it maintains transparency.

As the aromatic polycarbonate resin, those exemplified as the component (A) contained in the aromatic polycarbonate resin composition of the present invention can be used. The aromatic polycarbonate resin constituting the panel body and the aromatic polycarbonate resin (A) contained in the aromatic polycarbonate resin composition of the present invention forming the frame member may be the same or different. Good.

In addition to dyes or pigments, any conventionally known additive can be added to the constituent material of the panel body. Examples thereof include release agents, heat stabilizers, antioxidants, ultraviolet absorbers, Examples include flame retardants and anti-dripping agents. As these additives, those exemplified as other additives that can be blended in the aromatic polycarbonate resin composition of the present invention can be used, and the blending amounts thereof are also the same.

[Dimensions, shapes, etc.]
In the panel of the present invention, the dimensions and shapes of the frame member and the panel body are appropriately designed according to the application.

Generally, the thickness of the panel body is about 2 to 10 mm, preferably 3 to 8 mm, and the thickness of the frame member is about 0.5 to 5 mm, preferably 1 to 4 mm. The ratio of the thickness of the panel body to the thickness of the frame member is preferably 0.75 to 5.0, particularly about 1.5 to 4.0.

Usually, the outer edge part of this frame member is set back from the outer edge part of the panel body toward the center of the panel body. As described above, when the outer edge portion of the frame member is retracted to the center side of the panel body from the outer edge portion of the panel body, the back of the resin tends to be prevented when the frame member is molded. However, if this retreat width is too large, the design and solvent resistance are impaired, so the retreat width from the outer edge of the panel body of the frame member (d ₁ in FIG. 1 and FIG. 2 described later) is 0.1 to 10 mm. A degree, in particular 0.5 to 5 mm, especially 0.5 to 2 mm is preferred.

The panel body may be a flat plate shape, or may be curved so that the surface side opposite to the frame member forming surface is convex as shown in FIG.

パ ネ ル Panel is generally rectangular, but is not limited to a rectangular shape.

For example, when the panel has a substantially rectangular shape, the size is not particularly limited and is appropriately selected and determined according to the application. Usually, when the panel is used as an automobile window material, the panel is used. The area inside the frame member of the main body is about 400 cm ² to 2 m ² , and the width of the frame member is about 30 to 200 mm. In particular, the area inside the frame member of the panel body is preferably 800 cm ² to 1 m ² , and the width of the frame member is preferably 30 to 150 mm.

When the panel body has a substantially rectangular shape and is curved so as to be convex toward the front surface side, the curved height of the most convex portion on the front surface may be appropriately selected and determined according to the application. Usually, R in the long side length direction (longitudinal direction) of the panel body is about 5,000 R to 20,000 R, particularly about 10,000 R to 20,000 R, and R in the short side length direction (short side direction) is 1, The value is preferably about 000R to 15,000R, particularly about 5,000R to 10,000R.

An uneven portion may be formed in the boundary portion (joint surface) between the rear surface of the panel main body and the frame member, and the coupling strength between the panel main body and the frame member may be increased with an uneven fitting structure. The frame member may be provided with a mounting shape for mounting other components.

The frame member is not limited to a rectangular section having the same thickness in the width direction (inner side from the outer edge of the panel (the center side of the panel body)), and the inner side (the center side of the panel body 2). ), The thickness may decrease continuously or stepwise.
An example of such a panel is a panel 1A provided with a trapezoidal frame member 3A shown in FIG.
Thus, by thinning the thickness of the frame member 3A toward the center of the panel body 2, the panel body 2 and the frame member 3A are integrally formed by injection molding. When forming and then injection-molding the frame member 3A, the shrinkage stress of the frame member 3A is relaxed, and the distortion of the panel body 2 is easily prevented. To the relaxation effect of the shrinkage stress and favorable, in the panel 1A has a frame member 3A as shown in FIG. 2, the total width L ₁ and the thickness of the thickness t ₂ and the frame member 3A of frame member 3A it is in the following relationship with the width L ₂ of the portion smaller is desirable.
L ₂ / t ₂ ≧ 1.75
1> L ₂ / L ₁ ≧ 0.25

[Panel manufacturing method]
The panel of the present invention is manufactured, for example, by the following method.
(1) The panel body and the frame member are integrally formed by multicolor injection molding.
(2) One of the panel main body and the frame member is integrally molded by insert injection molding using one previously molded by injection molding.
In particular, in the point of preventing warpage of the integrally molded panel and the molten resin of the frame member from being mixed into the transparent window member during the integral molding, the frame member is laminated and integrated by the method of injection molding later during the integral molding. It is preferable to do.
In any of the above methods, in the injection molding of the frame member, the injection molding is performed under the conditions satisfying the above-described injection rate and surface progression coefficient.

[Hard coating]
In the panel of the present invention, a hard coat (hard film) as a protective film may be provided in order to mainly prevent damage and deterioration of the panel body. The hard coating is formed on one or both of the front surface side of the panel body opposite to the frame member and the inner region of the frame member on the rear surface of the panel body, but at least on the front surface of the panel body. Preferably it is formed.

Since the aromatic polycarbonate resin molded article of the present invention is excellent in chemical resistance, the frame member made of the aromatic polycarbonate resin molded article of the present invention needs to be provided with a hard coating for preventing resin deterioration due to the primer. Reduced.
Therefore, in the present invention, it is preferable that a hard coating is formed on one or both of the front surface of the panel main body and the region other than the portion bonded to the panel support on the rear surface of the panel main body. . Moreover, it is mentioned as one of the preferable aspects that the hard film is formed in one or both of the front surface of a panel main body, and the area | region which is not in contact with the said frame member of the rear surface of this panel main body. In such a case, the hard coating treatment on the frame member is not necessary, which is advantageous in terms of production efficiency and manufacturing cost, and further increases the layer structure, so that long-term durability under humid heat environment and weather resistance test Deterioration of reliability and reliability can also be suppressed.

The thickness of the hard coating is preferably 1/100 or less of the thickness of the panel body, and usually 1 to 50 μm, particularly 5 to 20 μm. When the thickness of the hard coating is too thin, the function as the protective layer of the panel body may be impaired in terms of weather resistance and scratch resistance. When the thickness of the hard coating is too thick, the possibility of aging breakage tends to increase due to the difference in linear expansion from the panel body.

The hard coating may be a single layer, but may have a multilayer structure of at least two layers in order to enhance the protective function or weather resistance. In the multilayer structure, it is preferable to set the hardness of the outermost layer to the maximum. As the hard coating having a multilayer structure, for example, it has at least one function among a functional layer of each of heat ray shielding, ultraviolet absorption, thermochromic, photochromic, electrochromic, primer layer, colored decoration layer, etc. Preferably it is.

The constituent material of the hard coating is preferably a transparent resin. As such a transparent resin, a known material known as a hard coating agent can be used as appropriate. For example, various hard coating agents such as silicone, acrylic, silazane, and urethane can be used. I can do it. In these, in order to improve adhesiveness and a weather resistance, the 2-coat type hard coat which provides a primer layer before apply | coating a hard-coat agent is preferable. Examples of the coating method include spray coating, dip coating, flow coating, spin coating, and bar coating. Moreover, the method by a film insert, the method of apply | coating and transferring the functional film suitable for a transfer film, etc. can be employ | adopted.

As the hard coating, a surface protective layer described in JP2011-121304A is also effective.

A functional film having various functions (heat ray shielding, ultraviolet absorption, thermochromic, photochromic, electrochromic functions) may be formed on the outermost layer of the hard coating.

A transparent resin layer may be provided between the surface of the panel body and the hard coating.

When the panel of the present invention is used as a back door panel, it is necessary to have a function of preventing fogging and removing fogging of the rear glass. Therefore, it is preferable to form a conductive film or an antifogging film on the frame member forming surface side of the panel body. The conductive film may be further provided with a hard film as a hard coat function on the outer surface side, but the antifogging film is preferably the outermost layer of the film attached to the panel body.

[Panel installation structure]
As shown in FIG. 1c, the panel installation structure of the present invention is characterized in that the panel of the present invention is supported on a panel support such as a vehicle body frame via a primer layer and a urethane-based adhesive layer. The primer layer is preferably provided between the panel support and the urethane adhesive layer and between the urethane adhesive layer and the frame member. The primer is preferably applied to both the adhesive surface of the panel support and the adhesive surface of the frame member.

[Primer]
In this invention, it is preferable that a urethane type adhesive layer is provided through the primer layer with respect to the surface of a frame member so that the performance of the urethane type adhesive mentioned later may fully be exhibited.

The panel of the present invention is firmly bonded to the panel support by having a primer layer between the frame member and the urethane adhesive layer. It is preferable that the frame member and the urethane-based adhesive layer are attached via a primer layer.

As such a primer, a primer composition containing an isocyanate component and a solvent is preferably exemplified.

The isocyanate component is not particularly limited as long as it is a compound having at least two isocyanate groups at its end. Specifically, for example, 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diene, for example. Isocyanate (XDI), hexamethylene diisocyanate (HMDI), hydrogenated (hydrogenated) MDI, hydrogenated TDI, hydrogenated XDI, isophorone diisocyanate (IPDI), aromatic aliphatic polyisocyanate, aromatic polyisocyanate, triphenylmethanetri An isocyanate, a tris (isocyanate phenyl) thiophosphate, etc. are mentioned. These may be used alone or in combination of two or more.
Among these, tris (isocyanate phenyl) thiophosphate is preferable from the viewpoint of excellent adhesiveness. In particular, the tris (isocyanatephenyl) thiophosphate is preferably contained in an amount of 6 to 24% by mass, more preferably 10 to 20% by mass, based on the total mass of the primer. If it is within this range, the viscosity does not become too high and the storage stability tends to be excellent.

The solvent used in the primer composition is not particularly limited as long as it is inert with respect to the isocyanate component, and various conventionally known solvents can be used.
Specifically, aromatic hydrocarbons such as benzene, xylene and toluene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran and dioxane Ethers etc. are mentioned, These may be used independently and may use 2 or more types together.
Of these, methyl ethyl ketone and ethyl acetate are preferred for reasons such as low boiling point and quick drying.
The solvent is preferably used after sufficiently dried or dehydrated.

The content of the solvent is not particularly limited and is appropriately determined depending on the type of the isocyanate component, but is preferably about 500 to 1,000 parts by mass with respect to 100 parts by mass of the isocyanate component.

It is preferable that the primer composition further contains an isocyanate silane compound. The isocyanate silane compound is a compound having an isocyanate group and a hydrolyzable silicon-containing group. The isocyanate silane compound can be obtained, for example, by reacting an isocyanate group-containing compound with a compound having a functional group capable of reacting with an isocyanate group and a hydrolyzable silicon-containing group. Specific examples of the isocyanate silane compound include compounds obtained by reacting diisocyanates such as MDI and TDI with silane coupling agents such as aminoalkoxysilane and mercaptoalkoxysilane.

An isocyanate silane compound obtained by reacting an isocyanate group-containing compound with a silane coupling agent having an imino group in which a phenyl group or a derivative thereof is directly bonded to a nitrogen atom is also preferably used. The isocyanate group-containing compound is preferably an aliphatic or alicyclic polyisocyanate. The isocyanate group-containing compound is preferably obtained by reacting the silane coupling agent with a reaction ratio of NCO / NH = 3/1 to 3/2.

The content of the isocyanate silane compound in the primer composition is preferably 0.1 to 50% by mass, and more preferably 30 to 50% by mass.

In one preferred embodiment, the primer composition further contains a phosphate.
Although it does not specifically limit as a phosphate, Specifically, an aluminum phosphate, zinc phosphate, tripolyaluminum dihydrogen phosphate etc. are illustrated suitably. In particular, aluminum dihydrogen triphosphate is preferably used.

Such a phosphate may be subjected to various treatments. In particular, phosphates surface-treated with Si and / or Zn, especially aluminum dihydrogen phosphate polysurface-treated with Si and / or Zn, can ensure extremely good adhesion, More favorable results can be obtained. The phosphate is preferably subjected to a dehydration treatment.

The content of the phosphate in the primer composition is preferably about 5 to 100 parts by mass with respect to 100 parts by mass of the isocyanate component. If it is this range, the effect of adding a phosphate is fully acquired, and a phosphate can fully be disperse | distributed and favorable adhesiveness can be acquired. In view of these characteristics, the content of the phosphate is more preferably about 30 to 60 parts by mass.

It is one of the preferred embodiments that the primer composition further contains carbon black. The carbon black content in the primer composition is preferably 5 to 30% by mass, more preferably 5 to 15% by mass. Within this range, the storage stability and the flexibility of the primer coating are excellent.

The said primer composition can contain a curing catalyst as needed.
Specific examples of the catalyst include amine catalysts such as triethylenediamine, pentamethylenediethylenetriamine, morpholine amine, and triethylamine, tin such as dilauric acid-di-n-octyltin, dibutyltin dilaurate, and stannous octoate. And system catalysts.
The content of the curing catalyst in the primer composition is not particularly limited, but is usually about 0.1 to 1 part by mass with respect to 100 parts by mass of the isocyanate component.

One of the preferred embodiments of the primer composition is a primer composition containing 6 to 24% by mass of tris (isocyanatephenyl) thiophosphate, 5 to 30% by mass of carbon black, and a solvent. This primer composition is excellent in adhesiveness to resin.
Another preferred embodiment of the primer composition is a primer composition containing an isocyanate component, a phosphate, and a solvent. This primer composition is excellent in adhesiveness to the coated plate.

The method for producing the primer composition is not particularly limited, and examples thereof include a method of mixing the above-described components with a roll, a kneader, an extruder, a universal stirrer, or the like.

Examples of the commercially available primer suitable for the present invention include, for example, Primer M (RC-50E) or M (RC-50KE) for painted surfaces and resin, manufactured by Yokohama Rubber Co., Ltd.

In any surface of the frame member and the panel support, it is preferable to clean the surface before applying the primer or before applying the adhesive for forming the urethane-based adhesive layer. For such cleaning, isopropanol or the like is suitable. is there.

[Urethane adhesive]
In the present invention, a urethane adhesive having excellent strength, fatigue characteristics, heat aging resistance, and the like as an elastic body is used for bonding the frame member and the panel support. As urethane-based adhesives, either moisture-curing one-component urethane adhesives or two-component urethane adhesives can be used, but high strength, low cost, and fast curing speed (solidification: set speed and curing) : Means a curing speed), and a moisture-curable one-component urethane adhesive is preferable. In particular, a high curing rate is advantageous in terms of bonding a lightweight frame member or a frame member and a panel support as compared with glass or the like. A resin-made frame member has a weak pressure-bonding force due to its own weight as compared with glass or the like, and therefore requires a step of applying pressure.

The moisture-curing one-component urethane adhesive, which is a suitable urethane adhesive, will be further described. The urethane prepolymer used in the moisture curable one-component urethane adhesive is not particularly limited, and for example, a urethane prepolymer obtained by reacting a polyol compound and an isocyanate group-containing compound can be used.

The polyol compound used in the urethane prepolymer is an alcohol obtained by substituting a plurality of hydrocarbon hydrogens with hydroxy groups. Examples thereof include a product obtained by addition polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to an active hydrogen-containing compound having two or more active hydrogens in the molecule.

Examples of the active hydrogen-containing compound include polyhydric alcohols, amines, alkanolamines, polyhydric phenols, and the like.
Specific examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol and the like.
Specific examples of amines include ethylenediamine and hexamethylenediamine.
Specific examples of alkanolamines include ethanolamine and propanolamine.
Specific examples of polyhydric phenols include resorcin and bisphenols.

Specific examples of the polyol compound include polyether-based polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polyolefins such as polybutadiene polyol and polyisoprene polyol. Examples include polyols; adipate type polyols; lactone type polyols; polyester type polyols such as castor oil. These may be used alone or in combination of two or more.

The polyol compound preferably has an average molecular weight of about 1,000 to 10,000, more preferably about 2,000 to 5,000.

As an isocyanate group containing compound used for the said urethane prepolymer, the various thing used for manufacture of a normal polyurethane resin can be used. For example, TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, diisocyanate having a norbornane skeleton (NBDI) ), And their modified products.
These may be used alone or in combination of two or more.

Among these isocyanate group-containing compounds, TDI and MDI are preferable. Since these polyisocyanates are general-purpose, they are inexpensive and easily available.

The ratio of the number of isocyanate groups in the isocyanate group-containing compound to the number of hydroxy groups in the polyol compound (NCO / OH) is the ratio of mixing the polyol compound and the isocyanate group-containing compound in the production of the urethane prepolymer. It is preferably 0 or more, more preferably 1.5 to 2.0.

The urethane adhesive can suitably contain a plasticizer. By blending a plasticizer, the viscosity of the resulting urethane composition can be adjusted and workability can be improved.
Examples of the plasticizer include tetrahydrophthalic acid, azelaic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and esters thereof. Derivatives of: polyester, polyether, epoxy, paraffin, naphthenic and aromatic process oils.
Of these, ester plasticizers such as phthalate ester plasticizers and adipate ester plasticizers are preferred.

Specifically, as the phthalate ester plasticizer, for example, dioctyl phthalate (DOP), dioctyl tin laurate (DOTL), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), diisodecyl Examples include phthalate (DIDP), diisononyl phthalate (DINP), dimethyl phthalate, and diethyl phthalate. Of these, diisononyl phthalate and diisodecyl phthalate are preferred.
Examples of the adipate ester plasticizer include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate, adipate propylene glycol polyester, and adipate butylene glycol polyester. Of these, diisononyl adipate is preferred.

Other plasticizers include, for example, dibutyl sebacate, diisodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) ) Phosphate, tricresyl phosphate, tributyl trimellitate (TBTM), trioctyl trimellitate (TOTM), alkyl epoxystearate, epoxidized soybean oil; acrylic oligomers such as butyl acrylate having a molecular weight of 500 to 10,000 It is done.
These may be used alone or in combination of two or more.

The content of the plasticizer to be added as desired in the urethane-based adhesive is preferably 20 to 70 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the urethane prepolymer. . If the content of the plasticizer is within this range, it is preferable because the viscosity can be adjusted and the workability can be improved without impairing the thixotropy of the resulting urethane adhesive.

It is preferable that the urethane adhesive contains calcium carbonate. By blending calcium carbonate, workability can be improved by adjusting the viscosity of the resulting urethane adhesive.
Examples of calcium carbonate include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and the like.
As calcium carbonate, a surface-treated calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol-added isocyanate compound, or the like can also be used. Of these, the surface is treated with a fatty acid, a fatty acid ester, a higher alcohol-added isocyanate compound, or the like. The treated one is particularly preferred. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.

The content of calcium carbonate to be added in the urethane-based adhesive, if desired, is preferably 1 to 50 parts by mass, more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the urethane prepolymer. . If the content of calcium carbonate is within this range, it is preferable because the workability can be improved by adjusting the viscosity of the obtained urethane adhesive.

In addition to the above components, the urethane-based adhesive is within the range that does not impair the purpose of the present invention, if necessary, other additives, such as curing catalysts such as tertiary amine catalysts, carbon black, and calcium carbonate. It can contain a filler, a thixotropy imparting agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersant, a dehydrating agent, and an ultraviolet absorber.

Fillers other than calcium carbonate are organic or inorganic in various shapes, such as silica (white carbon), clay talc, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, quicklime, carbonates ( For example, magnesium carbonate, zinc carbonate, flour), alumina hydrate (for example, hydrous aluminum hydroxide), diatomaceous earth, barium sulfate (for example, precipitated barium sulfate), mica, alumina sulfate, lithopone, asbestos, graphite, two Molybdenum sulfide, pumice powder, glass powder, silica sand, zeolite; surface treated products of these fatty acids, resin acids, fatty acid esters, higher alcohol addition isocyanate compounds, etc .; glass balloons; resin balloons;

Examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.) and the like.

Examples of the pigment include inorganic pigments and organic pigments.
Inorganic pigments include, for example, zinc white, titanium oxide, dial, chrome oxide, iron black, complex oxides (eg, titanium yellow, zinc-iron brown, titanium / cobalt green, cobalt green, cobalt blue, copper -Chromium black, copper-iron black) oxides; Chromates such as yellow lead and molybdate orange; Ferrocyanides such as bitumen; Sulfides such as cadmium yellow, cadmium red and zinc sulfide; Barium sulfate Sulfates such as: Hydrochloric acid; Silicates such as ultramarine; Carbonates such as calcium carbonate; Phosphate such as manganese violet; Hydroxides such as yellow iron oxide; Carbon such as carbon black; Aluminum powder, bronze powder Metal powders such as; titanium-coated mica; and the like.

Examples of the organic pigment include monoazo lakes (for example, Lake Red C, Permanen Red 2B, Brilliant Carmine 6B), monoazo (for example, Toluidine Red, Naphthol Red, Fast Yellow G, Benzimidazole Bordeaux, Benzimidazolone Brown). ), Disazo type (for example, disazo yellow aromatic polycarbonate resin molding, disazo yellow HR, pyrazolone red), condensed azo type (for example, condensed azo yellow, condensed azo red, condensed azo brown), metal complex azo type (for example, nickel azo yellow) Azo pigments such as copper phthalocyanine blue, copper phthalocyanine green, brominated copper phthalocyanine green, and the like; dyes such as basic dye lakes (for example, rhodamine 6 lake); Laquinone (eg, flavanthrone yellow, dianslaquinolyl red, indanthrene blue), thioindigo (eg, thioindigo Bordeaux), perinone (eg, perinone orange), perylene (eg, perylene scarlet, perylene) Red, perylene maroon), quinacridone (eg, quinacridone red, quinacridone magenta, quinacridone scarlet), dioxazine (eg, dioxazine violet), isoindolinone (eg, isoindolinone yellow), quinophthalone (eg, quinophthalone). Yellow), isoindoline (for example, isoindoline yellow), pyrrole (for example, pyrrole red) condensed polycyclic pigments; copper azomethine yellow and other metal complex salts azomethine; Click; daylight fluorescent pigments; and the like.

Examples of the dye include zinc oxide, zinc sulfide, chromium oxide, and a valve.
Examples of the antioxidant include N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), 2,2,4-trimethyl-1,3- Examples thereof include dihydroquinoline (TMDQ), N-phenyl-1-naphthylamine (PAN), and hindered phenol compounds.
Examples of the antioxidant include hindered phenol compounds such as butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA); triphenyl phosphite: and the like.
Examples of the antistatic agent include ionic compounds such as quaternary ammonium salts and amines; hydrophilic compounds such as polyglycols and ethylene oxide derivatives; and the like.
Examples of the flame retardant include chloroalkyl phosphate, dimethylmethylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, diethyl bishydroxyethylamino phosphate, neopentyl bromide polyether, brominated polyether, and the like.

Examples of the adhesion-imparting agent include terpene resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin, various silane coupling agents and the like.
Examples of the dispersing agent include fatty acid metal salts such as calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminum stearate, calcium linoleate, magnesium hydroxystearate; ethyl stearate, ethyl laurate, oleic acid And fatty acid esters such as butyl, dioctyl adipate, and stearic acid monoglyceride.
Examples of the dehydrating agent include methylsutearoxy polysiloxane.
Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, hindered phenol UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, and oxalic acid anilide UV absorbers. Agents, formamidine ultraviolet absorbers, triazine ring ultraviolet absorbers, nickel complex ultraviolet absorbers and the like.

As a commercial product of a moisture curing type one-component urethane adhesive suitable for the present invention, for example, Hamatite WS-222 (trade name) manufactured by Yokohama Rubber Co., Ltd. is exemplified.

The thickness of the urethane-based adhesive layer is not particularly limited, but is preferably 2 to 10 mm, more preferably 2.5 to 9 mm, and still more preferably 3 to 8 mm in order to achieve better adhesion and buffering properties. A range is preferable. This thickness is the thickness after completion of the reaction of the urethane-based adhesive. If the thickness of the urethane-based adhesive layer is too thick, the absolute amount of the urethane-based adhesive layer will increase, resulting in insufficient fixing of the member or increased displacement (creep) over time. There is a case. When the thickness of the urethane-based adhesive layer is too thin, the durability of the urethane-based adhesive layer tends to be insufficient, and there is a possibility that peeling from the interface occurs.

The more preferable thickness of the urethane-based adhesive layer depends on the size of the applied panel, that is, the maximum length. When the maximum panel length exceeds 1 m, the thickness of the urethane adhesive layer is preferably 2 to 8 mm, particularly 3 to 7 mm per 1 m of the maximum panel length.

The application of the urethane adhesive for forming the urethane adhesive layer is performed according to the method of applying the urethane adhesive used. In order to accelerate solidification and curing after application of the urethane-based adhesive, the members bonded with the adhesive may be heat-treated. Examples of such heat treatment include induction heating, infrared heating, microwave heating, and heating medium heating such as hot air.

[Panel support]
The panel support body on which the panel of the present invention is supported via a frame member is preferably made of a metal material.
When the panel of the present invention is a window member such as a building, the panel support is a metal frame of a window part, and is made of various steel materials or non-ferrous materials, such as steel materials (steel plates), aluminum alloys, magnesium alloys, A titanium alloy etc. are illustrated. Of these, steel materials and aluminum alloys are preferred. The surface of the metal frame may have a coating of other materials on the frame member joint surface of the panel. For example, a coating such as hot dipping, electroplating, or other coating may be formed.

When the panel of the present invention is a glazing of a vehicle, the body frame is a panel support and is usually made of steel or aluminum alloy.

[Usage]
The aromatic polycarbonate resin molded body of the present invention is used for applications requiring chemical resistance, mechanical strength, etc., for example, vehicle exteriors such as glazing for vehicle window members, bonnets, pillars, trunk lids, canopies, spoilers, trims, etc. Parts, cup holders, vehicle interior parts such as bezels, instrument panels, (mobile) phones, smartphones, PDAs, (portable) DVD players, (portable) personal computers, (portable) gaming machines, (portable) It is suitably used for housings and parts of electrical / electronic devices such as touch panels and cameras, OA related parts such as printers and copiers, lighting equipment parts, signboards, display boards, window frames, sashes and other building material parts.
In particular, the panel and panel installation structure of the present invention are useful as windows for buildings, glazing for vehicles, and the like.
As glazing for vehicles, it can be applied to roofs such as side doors, back doors, sliding doors, hoods, sunroofs, panoramic roofs, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Materials used]
In the following Examples and Comparative Examples, the materials used for the production of the aromatic polycarbonate resin composition are as follows.

<(A) component>
Aromatic polycarbonate resin (A-1): “Iupilon (registered trademark) S-3000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (viscosity average molecular weight: 21,000)
Aromatic polycarbonate resin (A-2): “Iupilon (registered trademark) H-4000FN” (viscosity average molecular weight: 14,000) manufactured by Mitsubishi Engineering Plastics
<(B) component>
ABS resin: “Techno ABS DP611” manufactured by Techno Polymer Co., Ltd. (acrylonitrile / butadiene / styrene = 16/40/44 mass%)
AS resin: “SANREX 290FF” manufactured by Techno Polymer Co., Ltd. (acrylonitrile / styrene = 24/76% by mass)
<(C) component>
Low density polyethylene (C-1): ethylene-propylene-hexene copolymer (ethylene content: 50 to 55 mol%, density: 0.88 g / cm ³ , Mw / Mn: 1.8, half width of molecular weight distribution) : 0.697, MFR: 2.2 g / 10 min, crystallinity: 18%, oligomer component content: 0.22% by mass (23 ° C. × 1 hour chloroform extraction))
Polyethylene resin (C-2): “Novatec HD HJ360” manufactured by Nippon Polyethylene Co., Ltd. (density: 0.95 g / cm ³ , Mw / Mn: 4.6, half-value width of molecular weight distribution: 1.155, MFR: 5.5 g) / 10 min, oligomer component content: 0% by mass (not detected by chloroform extraction at 23 ° C. for 1 hour))

<Inorganic filler (D)>
Talc: “HICON-TALC R10” manufactured by Matsumura Sangyo Co., Ltd. (average particle size: 4.3 μm, particle top size: 20 μm, bulk density: 0.76 g / ml, particle size: opening ratio of 500 μm, 98% by mass on sieve) (Particle shape: cylindrical, average shaft diameter: 1.2 mm, average shaft length: 1.5 mm, binder type: water-soluble polyester)
Glass fiber: “ECS-03T-187” manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter: 13 μm, average length of 3 mm chopped strand)
Milled glass fiber: “MF06JB1-20” manufactured by Asahi Fiber Glass Co., Ltd. (milled glass fiber having an average fiber diameter of 10 μm and an average length of 60 μm)
Wollastonite: “NYGLOS4” manufactured by Sakai Kogyo Co., Ltd. (average particle size: 4.5 μm, average length 50 μm, surface treatment: aminosilane)

<Other resins>
Polyethylene terephthalate (PET): “Novapex GG501H” manufactured by Mitsubishi Chemical Corporation

<Other additives>
Thermal stabilizer A: “ADEGA STAB AO50” manufactured by ADEKA (stearyl-β- (3,5-di-tent-butyl-4-hydroxyphenyl) propionate)
Thermal stabilizer B: “ADEGA STAB AS2112” manufactured by ADEKA (Tris (2,4-di-tert-butylphenyl) phosphite)
Heat stabilizer C: “JP-518Zn” manufactured by Johoku Chemical Industry Co., Ltd. (organic phosphate metal salt: mixture of zinc salt of distearyl acid phosphate and zinc salt of monostearyl acid phosphate)
Colorant: “Royal Black 904G” manufactured by Koshigaya Kasei Kogyo Co., Ltd. (carbon black masterbatch of 40% by mass of carbon black and 60% by mass of polystyrene)

[Primer / urethane adhesive]
In the following examples and comparative examples, the primers and urethane adhesives used in the urethane peel test and the urethane shear test are as follows.
Primer: “Body Primer M (RC-50E)” manufactured by Yokohama Rubber Co., Ltd.
Urethane adhesive: “Hamatite WS-222” manufactured by Yokohama Rubber Co., Ltd.

[Evaluation methods]
Evaluation methods of various physical properties and performances in the following examples and comparative examples are as follows.

<MVR>
The pellets of each resin composition were dried at 100 ° C. for 4 hours or more, and then measured according to ISO 1133 at a measurement temperature of 280 ° C. and a measurement load of 2.16 kgf.

<Flowability (Q value)>
After the pellets of each resin composition are dried at 100 ° C. for 4 hours or longer, the unit of the composition is 280 ° C. and the load is 160 kgf using a high load type flow tester according to the method described in Appendix C of JIS K7210. The flow rate Q value per unit (unit: × 10 ⁻² cm ³ / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high.

<Heat deformation temperature>
After drying the pellet of each resin composition at 100 ° C. for 5 hours, an ISO multipurpose test piece (4 mm) was molded with “J220EVP” (clamping force 220 t) manufactured by Nippon Steel Works under the following conditions. .
Mold: Mold with four ISO specimens Molding conditions:
Resin temperature at molding: 280 ° C
Mold temperature: 80 ℃
Filling time: 2.0 seconds Injection rate: 42.87 cm ³ / s
Surface progression coefficient: 107.2 cm ³ / s · cm
Holding pressure: 50% of the peak pressure at the time of injection is 10 seconds. Cooling time: 20 seconds. This ISO multi-purpose test piece was processed by the method prescribed by ISO to prepare a test piece for measuring heat distortion temperature. Using the obtained test piece, the heat distortion temperature (deflection temperature under load) was measured under the condition of a load of 0.45 MPa in accordance with ISO75-1 and ISO75-2.

<Impact strength>
The above-mentioned ISO multipurpose test piece was processed by a method specified by ISO to prepare a notched test piece. The notched Charpy impact strength (unit: kJ / m ² ) was measured under the environment of 23 ° C. using the obtained test piece in accordance with ISO 179.

<Bending strength and flexural modulus>
The ISO multipurpose test piece was processed by a method prescribed by ISO to prepare a test piece for a bending test. Using the obtained test piece, bending strength and bending elastic modulus were measured according to ISO 178 standard.

<Mold shrinkage>
After drying the pellets of each resin composition at 100 ° C. for 5 hours, a flat test piece 11 shown in FIGS. 3a and 3b was molded with “J220EVP” (clamping force 220 t) manufactured by Nippon Steel Works under the following conditions. did.
Mold: 100mm x 100mm x 3mm thickness Molding conditions:
Resin temperature at molding: 280 ° C
Mold temperature: 80 ℃
Filling time: 1.5 seconds Injection rate: 23.59 cm ³ / s
Surface progression coefficient: 78.62 cm ³ / s · cm
Holding pressure: 50% of the peak pressure at the time of injection is 10 seconds Cooling time: 20 seconds Mold shrinkage is a percentage of the mold cavity dimension obtained by subtracting the dimension of the dry molded product from the mold cavity dimension (% ) And was obtained as follows.
The prepared flat plate was allowed to stand for 24 hours or more under constant temperature and humidity conditions of 25 ° C. and 50% humidity, and then the dimension parallel to the 70 mm square flow direction (MD) printed on the flat plate and perpendicular to the flow direction. The dimension of (TD) was measured, and the percentage of the dimension on the mold was calculated to obtain the respective mold shrinkage rates of MD and TD.

<Chemical resistance>
The above ISO standard tensile test piece was annealed at 100 ° C. for 2 hours in order to remove residual strain at the time of molding. Thereafter, as shown in FIGS. 4a, 4b, and 4c, a spacer 22 having a height of 13.1 mm or 12.4 mm and supporting cylinders 24a and 24b having a diameter of 10 mm are used to fix the fixing frame 23 by 0.21% or 0. In a state where a deflection with a deformation rate of 38% is applied, gasoline is applied as a test chemical to the convex side of the test piece 21 (X part in FIG. 4c), and in this state, constant temperature and constant at 23 ° C. and humidity 50% are obtained. Left in wet conditions. Thereafter, the appearance of the test piece was observed and evaluated according to the following criteria. In addition, by ISO527 tensile test, to measure the elongation at break _{E x.}
(Evaluation criteria for appearance)
A: Appearance No change C: Apart occurrence of cracks or breakage, except that no coating a gasoline after was loaded deflection under the same conditions as described above was left in the same conditions, to measure the elongation at break E _o by ISO527 tensile test .
(E _x / E _o × 100) was calculated as a retention rate (%) with respect to the breaking elongation E _o .

Here, the deformation rate is defined as: L is the linear distance connecting the test piece 21 and the contacts A and B between the cylinders 24a and 24b that support the test piece 21, the thickness of the test piece is a, and the deflection amount is δ. = 6aδ / L ² is calculated.
The deflection amount δ is calculated by the following equation.
δ = ([height of supporting cylinder] + [thickness of test piece] − [height of spacer])
The distance L between the jig support points is 101 mm, the thickness a of the test piece 21 is 4 mm, the height of the spacer 22 is 13.1 mm or 12.4 mm, and the height (diameter) of the support cylinders 24a and 24b is 10 mm.

The retention of elongation at break was measured for 5 test pieces and evaluated according to the following criteria.
(Evaluation criteria for retention rate of elongation at break)
A: Retention rate of breaking elongation of all test pieces is 80% or more B: Retention rate of breaking elongation of 4 test pieces out of 5 is 80% or more C: Three test pieces out of 5 Retention rate of breaking elongation of 80% or more D: Out of 5 pieces, 2 or less test pieces with breaking elongation retention rate of 80% or more

<Stability thermal stability>
The pellets of each resin composition were dried at 100 ° C. for 5 hours, and then molded with “J220EVP” (clamping force 220 t) manufactured by Nippon Steel Works under the following conditions.
Mold: Mold with four ISO specimens Molding conditions:
Resin temperature at molding: 280 ° C
Mold temperature: 80 ℃
Filling time: 2.0 seconds Injection rate: 42.87 cm ³ / s
Surface progression coefficient: 107.2 cm ³ / s · cm
Holding pressure: 50 seconds of the peak pressure at the time of injection for 10 seconds At this time, the residence time is adjusted using the cooling time, and the time from when the pellets are put into the cylinder until injection molding is taken as the residence time. With the residence time (5 minutes, 10 minutes, and 20 minutes), the presence or absence of silver generation in the obtained molded product was visually confirmed and evaluated according to the following criteria.
(Evaluation criteria for silver generation)
A: No silver occurs in all molded products B: Silver occurs in some molded products C: Silver occurs in all molded products

<High-speed surface impact>
Using a high-speed impact tester “Hydroshot HITS-P10” manufactured by Shimadzu Corporation, a high-speed surface impact test was performed on the above-mentioned 100 mm × 100 mm × 3 mm thickness flat plate test piece under the following test conditions. Absorbed energy (unit: J) was measured.
(Test conditions)
Striker diameter: 12.8 mm (1/2 inch)
Specimen support: 25.6 mm (1 inch)
Impact speed: 10m / s
Test temperature: Room temperature (23 ° C)

<Urethane peeling test>
A strip-shaped test with a width of 25 mm from the above-mentioned 100 mm × 100 mm × 3 mm thick flat plate specimen obtained by injection molding with an injection rate of 23.59 cm ³ / s and a surface progression coefficient of 78.62 cm ³ / s · cm. After the piece was cut out and the surface was degreased with isopropyl alcohol, a primer was applied and cured for 30 minutes. Thereafter, a urethane adhesive is applied in a strip shape in the longitudinal direction to the primer application surface of the strip-shaped test piece, and at room temperature (23 ° C.) so that the urethane adhesive layer becomes 10 mm wide and 5 mm thick using a spacer. Curing treatment was performed for 1 week.
Pull up the end of the urethane adhesive layer of the peel test piece thus prepared, pull up the urethane adhesive layer while inserting the blade of the cutter at the boundary between the urethane adhesive layer and the strip-shaped test piece. A peeling test for peeling was performed. When the adhesive strength by the urethane-based adhesive is low, it peels off at the interface between the urethane-based adhesive layer and the strip-shaped test piece. When this adhesive strength is high, the urethane-based adhesive layer or the strip-shaped test piece. Any one of these will break and peel. Since it is preferable that the urethane adhesive layer part is broken and peeled off, this urethane peelability was evaluated according to the following criteria.
(Evaluation criteria for urethane peelability)
A: Of the peeled surface, the fracture surface of the urethane-based adhesive layer is 50% or more. C: Of the peeled surface, the fracture surface of the urethane-based adhesive layer is less than 50%.

<Urethane shear test>
A strip-shaped test with a width of 25 mm from the above-mentioned 100 mm × 100 mm × 3 mm thick flat plate test piece obtained by injection molding with an injection rate of 23.59 cm ³ / s and a surface progression coefficient of 78.62 cm ³ / s · cm. A piece (hereinafter referred to as “resin test piece”) was cut out. A steel strip test piece (hereinafter referred to as “steel test piece”) having the same size as the strip test piece was prepared. As shown in FIG. 5a, the surfaces of the resin test piece 31 and the steel test piece 32 were degreased with isopropyl alcohol, and then a primer 33 was applied to the adhesion surface of both the test pieces 31 and 32, followed by curing for 30 minutes. Next, as shown in FIG. 5 b, a urethane adhesive 34 was applied to the surface of the resin test piece 31 on which the primer 33 was applied in a strip shape in the longitudinal direction. Next, as shown in FIG. 5 c, the surface of the steel test piece 32 covered with the primer 33 is covered, and a spacer 35 is used to make the urethane adhesive 34 layer 10 mm wide and 5 mm thick at room temperature (23 ° C.). Weekly curing adhesion treatment was performed.
As shown in FIG. 5d, the shear test piece thus produced was pulled in the opposite direction, and the shear test was performed until the test pieces 31 and 32 were separated. It was evaluated with.
(Evaluation criteria for urethane shearability)
A: The urethane adhesive layer breaks.
C: The resin test piece breaks.

<Appearance>
The appearances of the ISO multipurpose test piece and the 100 × 100 × 3 mm-thick flat plate test piece were visually confirmed and evaluated according to the following evaluation criteria.
(Appearance evaluation criteria)
A: No whitening B: Whitening C: Significant whitening

<War of two-color molded product>
Warpage was evaluated using the two-color molded product shown in FIGS. 6A to 6C simulating a panoramic roof of an automobile. 6A to 6C, reference numeral 51 denotes a test sample panel, which includes a panel main body 52 and a frame member 53 provided on the peripheral edge thereof. The outer dimensions of the panel body 52 are 750 mm × 465 mm, and the wall thickness is 5 mm. The width of the short side of the frame member 53 is 97 mm, the width of one of the long sides is 75 mm, the width of the other is 90 mm, and the thickness is 3 .5 mm. The frame member 53 is provided at a position 3 mm inside from the outer edge of the panel main body 52 (that is, d ₂ = 3 mm in FIG. 6B). The panel body 52 is curved such that the surface (front surface) opposite to the surface on which the frame member 53 is formed is convex toward the front surface, and the longitudinal direction (long side) is 10,000 R, short. The hand direction (short side) is a curved surface of 5,000R. 6A and 6C, G indicates a gate portion, and a broken line indicates a weld line.

As the molding material for the panel body, aromatic polycarbonate resin: “Iupilon (registered trademark) S-2000UR” (viscosity average molecular weight: 24,000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. is used. The panel of the sample for a test was shape | molded by the following method using what is shown to.
First, a panel body material pre-dried at 120 ° C. for 5 hours is injection-molded (injection temperature) into a cavity formed between a fixed mold and a first movable mold that are temperature-controlled at a mold temperature of 90 ° C. 320 ° C.) to form a panel body. The injection speed was a single speed of 50 mm / sec, and the injection holding pressure switching position was 2 mm. Molding was performed with a valve gate type hot runner. The gate position is a portion corresponding to the center in the width direction at the center of the width 75 mm on the long side of the frame member 53. Injection compression molding was performed, the mold was opened by 2 mm before injection, and 700 t was re-clamped at the injection holding pressure switching position. The holding time for re-clamping at this time was 15 seconds. Next, after the panel body is cooled for 60 seconds, the first movable mold is opened, and the second movable mold that is controlled to a mold temperature of 90 ° C. is held with the panel body held in the first movable mold. The molding material for the frame member preliminarily dried at 100 ° C. for 5 hours is injected into the cavity formed between the second movable mold and the panel body at a single speed of 40 mm / sec. Filled (injection resin temperature 270 ° C.). The injection holding pressure switching position was set to 35 mm. A holding pressure of 25 MPa was applied for 5 seconds to form a frame member. Molding was performed with a valve gate type hot runner. The number of gates of the valve gate was 6, and all the gates were opened at the same time, and resin filling was started at the same time. After the cooling time of 60 seconds, the second movable mold was opened, and the panel in which the molded panel body and the frame member were integrated was removed.

The 6-point gate average injection rate at the time of injection molding of the frame member portion is 26.67 cm ³ / s, and the 6-point gate average surface progression coefficient is 76.21 cm ³ / s · cm. As described above, since the six valve gates are simultaneously opened and filled with resin, the injection rate differs slightly depending on the cavities carried by the respective gates. The result of calculating the actual injection rate and surface progression coefficient of each part from the filling amounts of the filling regions I to VI between the weld lines, which each gate shown in FIG. 6c plays, is as follows.
Part I, Part IV: Ejection rate: 24.67 cm ³ / s
Surface progression coefficient: 70.49 cm ³ / s · cm
Part II, Part V: Injection rate: 22.97 cm ³ / s
Surface progression coefficient: 65.63 cm ³ / s · cm
Part III, Part VI: Injection rate: 32.38 cm ³ / s
Surface progression coefficient: 92.50 cm ³ / s · cm

The obtained two-color molded product panel is placed on a surface plate having flatness with the frame member side down, and the curved height of the central portion (total height of the two-color molded product) is measured. The warpage of the two-color molded product was evaluated based on the evaluation criteria.
(Criteria for warpage of two-color molded products)
AA: The difference in bending height between the two-color molded product and the design value is less than 5 mm A: The difference in bending height between the two-color molded product and the design value is 5 mm or more and less than 10 mm B: The two-color molded product and the design value The difference in curve height is 10 mm or more and less than 20 mm

[Examples 1 to 9, Comparative Examples 1 and 2]
Each component shown in Tables 1 and 2 is uniformly mixed in the ratio shown in Tables 1 and 2 with a tumbler-mixer, then fed to a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Co., Ltd.), and melt kneaded. The resulting composition was quenched in a water tank and pelletized using a pelletizer to obtain resin composition pellets. When glass fiber and wollastonite were used, they were fed from the side feeder to the extruder. Using the obtained resin composition pellets, the above-described evaluations were performed, and the results are shown in Tables 1 and 2.

From Tables 1 and 2, the aromatic polycarbonate resin composition of the present invention is excellent in chemical resistance, mechanical properties, fluidity and residence heat stability, and the present invention is formed by injection molding this aromatic polycarbonate resin composition. It can be understood that the aromatic polycarbonate resin molded article can be firmly bonded to the primer-treated surface with a urethane-based adhesive.
On the other hand, in the comparative example 1 which does not contain (C) component, it is inferior to chemical resistance, and is inferior to urethane adhesiveness. Comparative Example 1 has poor residence heat stability. In Comparative Example 2 in which polyethylene terephthalate is blended in place of the component (C), the effect of improving chemical resistance is slightly recognized, but the effect is not sufficient particularly under high strain addition conditions. Comparative Example 2 is inferior in urethane adhesion because the domain shape of polyethylene does not have a fine layered dispersion, but is considered to be a large approximate circular shape, approximate elliptical shape, or amoeba shape.

[Examples 10 to 12, Comparative Example 3]
The pellets of the aromatic polycarbonate resin composition produced in Example 1 were dried at 100 ° C. for 5 hours, and then ISO multipurpose with “J180AD-2M” (clamping force 180 t) manufactured by Nippon Steel Works under the following conditions. A test piece (4 mm) was molded.
Mold: Mold with four ISO specimens Molding conditions:
Resin temperature at molding: 270 ° C
Mold temperature: 80 ℃
Filling time: 0.8 seconds, 1.2 seconds, 2.3 seconds, or 4.3 seconds Injection rate: shown in Table 3 Surface progression coefficient: shown in Table 3 Holding pressure: 50% of the peak pressure during injection 10 seconds Cooling time: 20 seconds

The surface layer portion of each ISO multipurpose test piece was observed by SEM by the following method to examine the form of the domain formed of the low density polyethylene (C-1). The results are shown in Table 3.
SEM observation: An ultra-thin slice having a thickness of 100 nm was cut out with a diamond knife from a cross section parallel to the flow direction of the resin composition at the center of the ISO multipurpose test piece, using “UC7” manufactured by Leica. The obtained ultrathin sections were stained with osmium tetroxide (OsO ₄ ) for 30 minutes and with ruthenium tetroxide (RuO ₄ ) for 70 minutes in a 15 ° C. environment, and then accelerated using “SU8020” manufactured by Hitachi High-Tech. SEM observation was performed on the surface layer portion having a depth of 30 μm from the surface under the condition of a voltage of 1 kV.
Measurement of domain morphology: SEM observation photographs were binarized and measured by the above-described method using image analysis software “Image-Pr Plus (ver 6.2J)” (Media Cybernetics).

7a, 7b, and 7c show SEM photographs of the surface layer portions of the ISO multipurpose test pieces of Examples 10, 11, and 12. FIG.
In this photograph, the flow direction is from right to left. The light gray portion is the matrix of the aromatic polycarbonate resin, and the ABS resin and / or AS resin is present in a lighter gray circle to ellipse. The part observed in black lines to layers is a polyethylene domain.
Each ISO multipurpose test piece was evaluated for the above-mentioned <chemical resistance>, and the results are shown in Table 3.

In Comparative Example 3, the injection rate and the surface progression coefficient were large, and the shearing force was excessively applied during molding, so the domain was short and broken. In Comparative Example 3, since the area of the domain was reduced, the chemical resistance was deteriorated and the elongation at break was lowered. Further, in Comparative Example 3, in the evaluation of chemical resistance at a deformation rate of 0.38%, fine cracks were also generated in the appearance.

With respect to the ISO multipurpose test piece obtained in Example 11, the crystallinity of the low density polyethylene (C-1) constituting the domain was determined by DSC. The crystallinity was 10 to 12%, and was measured before molding. It was confirmed that the crystallinity was reduced to 56-67% compared to low density polyethylene (C-1) (crystallinity: 18%).

[Example 13]
Of the two long sides of the frame member of the panel formed by the evaluation of <warpage of two-color molded product> described above, using the pellet of the aromatic polycarbonate resin composition produced in Example 1 as the molding material of the frame member SEM observation of the surface layer portion (surface opposite to the surface in contact with the panel body) was performed on the 90 mm width portion (I portion) and the 75 mm width portion (II portion) in the same manner as in Examples 10-12. The domain morphology was measured and the results are shown in Table 4.
The SEM photograph of the surface layer part of I part is shown in FIG. 8a, and the SEM photograph of the surface part part of II part is shown in FIG. 8b. Also in this photograph, as in Examples 10 to 12, it can be seen that the polyethylene domains are appropriately oriented along the flow direction of the resin composition.

The above-mentioned <urethane peeling test> and <urethane shear test> were performed on this frame member portion, and the results are shown in Table 4.

[Comparative Example 4]
The pellets of the aromatic polycarbonate resin composition produced in Example 1 were dried at 100 ° C. for 5 hours, and then “J180AD-2M” (clamping force 180 t) manufactured by Nippon Steel Works under the following conditions. The flat test piece 60 shown in FIG.
Mold: 150 mm x 100 mm x 10 mm thickness Molding conditions:
Resin temperature at molding: 270 ° C
Mold temperature: 80 ℃
Filling time: 5.4 seconds Injection rate: as shown in Table 5 Surface progression coefficient: as shown in Table 5 Holding pressure: 50% of the peak pressure during injection is 10 seconds Cooling time: 40 seconds

About the center part of the obtained flat plate-shaped test piece, SEM observation of the surface layer part was performed by the same method as in Example 10, the polyethylene domain form was measured, and the results are shown in Table 5. This flat test piece was subjected to the aforementioned <urethane peeling test> and <urethane shear test>, and the results are shown in Table 5.

In Comparative Example 4, the surface progression coefficient was small, and the shearing force was not so much applied to the domain at the time of molding, so the domain was not sufficiently stretched. For this reason, the domains are not oriented in layers, and the ratio of the domain area to the major axis diameter is increased, resulting in poor chemical resistance, and the surface of the strip-shaped test piece peels off in the urethane peel test, resulting in material destruction. have done.

From the results of Examples 10 to 14 and Comparative Examples 3 and 4, by adjusting the injection rate and the surface progression coefficient, a polyethylene domain effective for improving chemical resistance can be formed on the surface layer portion of the molded body. It can be seen that excellent chemical resistance and urethane adhesion can be obtained.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2013-030083 filed on Feb. 19, 2013, which is incorporated by reference in its entirety.

1, 1A, 51 Panel 2, 52 Panel body 3, 3A, 53 Frame member 4 Body frame 5 Adhesive 6 Seal member 11, 60 Test piece 12 Gate part 21 Test piece 22 Spacer 23 Fixed frame 24a, 24b Support column 31 Resin Test piece 32 Steel test piece 33 Primer 34 Urethane adhesive 35 Spacer

Claims (17)

1. Aromatic polycarbonate resin comprising, as resin components, aromatic polycarbonate resin (A), rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), and polyolefin resin (C) A fragrance obtained by injection-molding a composition under the conditions of an injection rate of 10 to 100 cm ³ / s defined below and a surface progression coefficient of 40 to 200 cm ³ / s · cm defined below. Group polycarbonate resin moldings.
   Injection rate: Resin composition volume per unit time injected from the discharge nozzle of the injection molding machine into the mold cavity Surface progression coefficient: Value obtained by dividing the above injection rate by the thickness of the mold cavity into which the resin composition is injected
2. The aromatic polycarbonate resin composition contains, as a resin component, an aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), aromatic vinyl / vinyl cyanide. An aromatic polycarbonate resin molded article comprising a copolymer (B-2) and a polyolefin resin (C).
3. The domain formed by the polyolefin-based resin (C) is dispersed in the surface layer portion having a depth of 30 μm from the surface of the molded body, and the flow direction of the resin composition at the time of injection molding of the surface layer portion 3. The aromatic polycarbonate according to claim 1, wherein the area of the domain in a cross section along the line is 10 to 100 μm ² and the area / major axis ratio is 0.5 to 5 μm. Resin molded body.
4. The aromatic polycarbonate resin composition comprises, as resin components, aromatic polycarbonate resin (A) 45 to 88% by mass, rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) 2 to 40 2. The composition according to claim 1, comprising 0 to 35% by mass of an aromatic vinyl / vinyl cyanide copolymer (B-2) and 1 to 15% by mass of a polyolefin resin (C). 4. The aromatic polycarbonate resin molded article according to any one of items 1 to 3.
5. The aromatic polycarbonate resin composition contains 45 to 88% by mass of the aromatic polycarbonate resin (A), 2 to 40% by mass of the rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), aromatic 30 parts by mass or less of the inorganic filler (D) with respect to 100 parts by mass in total of the vinyl group / vinyl cyanide copolymer (B-2) 0 to 35% by mass and the polyolefin resin (C) 1 to 15% by mass. The aromatic polycarbonate resin molded article according to claim 4, comprising:
6. The polyolefin resin (C) is a polyethylene resin having a density of 0.85 to 0.90 g / cm ³ and a melt flow rate (MFR) at 190 ° C. of 1 to 20 g / 10 min. The aromatic polycarbonate resin molded article according to any one of claims 1 to 5.
7. The aromatic polycarbonate resin molded article according to any one of claims 1 to 6, wherein the polyolefin resin (C) contains 0.01 to 2% by mass of an oligomer component.
8. The rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B-1) contains a butadiene component, and the rubber polymer / aromatic vinyl / vinyl cyanide copolymer (B-1). The content of the butadiene component in the total of the vinyl chloride and aromatic vinyl / vinyl cyanide copolymer (B-2) is 5 to 50% by mass, according to any one of claims 2 to 7. The aromatic polycarbonate resin molded article according to Item.
9. Of the aromatic polycarbonate resin composition, 280 ° C., wherein the melt volume rate of 2.16kg load (MVR) is 10 cm ³ / 10min or more, according to any one of claims 1 to 8 Aromatic polycarbonate resin molding.
10. The content of the inorganic filler (D) in the aromatic polycarbonate resin composition is such that the aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), 10. The amount of 1 to 30 parts by mass, based on a total of 100 parts by mass of the aromatic vinyl / vinyl cyanide copolymer (B-2) and the polyolefin resin (C). The aromatic polycarbonate resin molded article according to any one of the above items.
11. A panel body comprising a panel body having a front surface and a rear surface and a frame member provided at a peripheral edge of the rear surface of the panel body, the panel body being an aromatic polycarbonate, supported by a panel support via the frame member A panel comprising a resin as a main component resin and the frame member comprising the aromatic polycarbonate resin molded article according to any one of claims 1 to 10.
12. The panel according to claim 11, wherein the panel body and the frame member are laminated and integrated by multicolor molding.
13. The hard coating is formed in one or both of the front surface of the said panel main body, and the area | regions other than the part adhere | attached with the said panel support body of the rear surface of this panel main body, It is characterized by the above-mentioned. Or the panel of 12.
14. The panel according to any one of claims 11 to 13, wherein the panel is used for a window member of a vehicle.
15. 15. A panel installation structure comprising the panel according to any one of claims 11 to 14 supported on a panel support through a primer layer and a urethane adhesive layer.
16. The panel installation structure according to claim 15, wherein the panel support is made of a metal material.
17. A vehicle comprising the panel installation structure according to claim 16.

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