JP5521797B2 - Multicolor molded resin window material - Google Patents

Description

  The present invention relates to a multicolor molded resin window member, and in particular, from a polycarbonate resin transparent window layer and a window frame layer made of a polycarbonate resin composition laminated around a transparent window portion constituted by the transparent window layer. The present invention relates to a multicolor molded resin window member that is free from the problem of brittle fracture of a transparent window layer or a window frame layer laminate.

  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 portion and a window frame outside thereof, and is generally produced by multicolor molding (laminate) including injection molding including injection molding. For this reason, conventionally, in order to obtain a multicolor molded resin window member free from the problem of delamination by multicolor molding, studies have been made to improve the adhesion between the transparent window portion and the window frame portion.

  Conventionally, as a constituent material of a transparent window portion of glazing, polycarbonate resin has been used because it is excellent in transparency, excellent in impact resistance, and is not easily broken as compared with other transparent resins as well as glass windows. . On the other hand, as a constituent material of the window frame, a resin (composition) having a high elastic modulus and excellent adhesion to a polycarbonate resin is used. For example, an alloy resin of polycarbonate and polyethylene terephthalate reinforced with glass fiber. Etc. are used (for example, patent document 1).

Such glazing is required to satisfy various characteristics in terms of safety. In particular, in glazing for automobiles, it is resistant to occupant protection when an impact is applied in an accident or the like. It is required to have excellent impact properties, and in particular, it does not cause brittle fracture when an impact is applied. In other words, if it is a ductile fracture that causes plastic deformation in response to an impact, the damage to the occupant is small, but in a brittle fracture that breaks due to the impact and the fragments are scattered, the damage to the occupant and the passenger compartment is increased. In order to improve the impact resistance, it is desired that the material does not break against an impact, and that when it breaks, it causes ductile fracture instead of brittle fracture.
Polycarbonate resin causes ductile fracture in response to impact, and is also suitably used as a window material from this point.

JP 2005-103907 A

  As described above, in the conventional glazing, studies have been made to increase the adhesion strength between the transparent window portion and the window frame portion. However, as a result of our investigation, as a result of increasing the adhesion strength in this way, when an impact is applied to glazing, deformation of the polycarbonate resin layer, which is a transparent window, is suppressed by the resin of the window frame, As a result, it has been found that the ductile property of the polycarbonate resin is not exhibited and brittle fracture occurs.

  The present invention solves the above-mentioned conventional problems, and is a multicolor molded resin window member having glazing, that is, a transparent window layer and a window frame layer laminated around the glazing, and is brittle fracture against impact. It is an object of the present invention to provide a multicolor molded resin window member that is less prone to cause trouble and is excellent in safety.

  The present inventors diligently studied to solve the above problems. Specifically, in glazing using a polycarbonate resin for the transparent window layer, when the window frame layer is composed of a polycarbonate resin composition mainly composed of polycarbonate resin, the adhesion strength, the strength as glazing, and the impact We examined the destruction situation when.

  As a result, by making the adhesion between the transparent window layer and the window frame layer within a specific range, an impact is applied after ensuring the integrity retention strength (preventing peeling of the window frame layer during normal use) as glazing. It was found that the window frame layer was peeled off to prevent brittle fracture of the transparent window layer and to cause ductile fracture effective for protecting passengers in the vehicle. Moreover, as a result of examining the constituent material of the window frame layer for achieving such specific adhesion strength, a polycarbonate resin composition containing a polyolefin resin, particularly preferably a polycarbonate resin composition containing a specific amount of a polyethylene resin, It was found to be suitable.

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

(1) A multicolor molded resin window member having a transparent window layer constituting a transparent window part and a window frame layer provided by being laminated on at least a part of the transparent window layer around the transparent window part, The transparent window layer is made of a polycarbonate resin (A), and the window frame layer includes a polycarbonate resin (A) and a resin (B) having no reactivity and / or interaction (excluding intermolecular force). made from the composition, an adhesion strength between the transparent window layer and the window frame layer 35～90MPa, in falling weight impact test at the boundary between the window frame layer laminated portion and the non-laminated part of the transparent window layer, the A multicolor molded resin window member characterized in that the transparent window layer does not brittlely break.

( 2 ) The multicolor molded resin window member according to ( 1 ), wherein the resin (B) is a polyolefin resin.

( 3 ) Content of resin (B) in polycarbonate resin composition which comprises the said window frame layer is 6-20 mass%, The multicolor molding resin as described in ( 1 ) or ( 2 ) characterized by the above-mentioned. Window member.

( 4 ) The multicolor molded resin window member according to ( 2 ) or ( 3 ), wherein the resin (B) is a polyethylene resin.

( 5 ) The multicolor molding resin according to any one of ( 1 ) to ( 4 ), wherein the polycarbonate resin composition constituting the window frame layer contains 0.1 to 10% by mass of an inorganic filler. Window member.

( 6 ) The multicolor molded resin window member according to any one of (1) to ( 5 ), wherein the window frame layer is laminated on the transparent window layer around the entire periphery of the transparent window portion.
(7) The multicolor molded resin window member according to any one of (1) to (6), wherein the window frame layer is injection compression molded.

  According to the present invention, it is a multicolor molded resin window member having a transparent window layer and a window frame layer laminated around the transparent window layer, and is effective in protecting an occupant and the like, not brittle fracture when an impact is applied. A multicolor molded resin window member excellent in safety that causes ductile fracture is provided.

  Such a multi-color molded resin window member of the present invention is excellent in impact resistance and safety, and is a panoramic roof, sun roof, rear window, front side window, side door window, back door window, slide door window, hood of an automobile. In addition to windows for roofs or similar parts, bullet trains, trains, airplanes, ships, windows for amusement parks and theme parks, they are useful for various window applications such as windows in buildings.

(A) A figure is a front view which shows the two-color molded product shape | molded by the Example and the comparative example, (b) A figure is A-A 'sectional drawing in (a) figure. It is typical sectional drawing which shows the falling weight impact test method in an Example and a comparative example. (A) A figure is a perspective view of the sample for a measurement of adhesion power in an example and a comparative example, and (b) figure is a typical sectional view showing the adhesion power measurement test method.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The multicolor molded resin window member of the present invention is a multicolor having a transparent window layer constituting a transparent window part and a window frame layer provided by being laminated on at least a part of the transparent window layer around the transparent window part. In a molded resin window member, the adhesive force between the transparent window layer and the window frame layer is 35 to 90 MPa, and in the falling weight impact test at the boundary between the laminated portion of the transparent window layer and the window frame layer, The layer is characterized by not brittle fracture.

In the present invention, the transparent window layer is made of a polycarbonate resin (A), and the window frame layer contains a polycarbonate resin (A) and a resin (B) having no reactivity and / or interaction (excluding intermolecular force). It consists of a resin composition . The resin (B) is preferably a polyolefin resin, particularly a polyethylene resin.

[Polycarbonate resin (A)]
The polycarbonate resin (A) suitably used as the constituent material of the transparent window layer according to the present invention and the polycarbonate resin (A) of the polycarbonate resin composition used as the constituent material of the window frame layer are aromatic polycarbonates. Examples thereof include resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, and aromatic polycarbonate resins are preferable.

  The aromatic polycarbonate resin is a linear or branched thermoplastic polymer 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 therewith, or It is a copolymer.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetra Bromobisphenol 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 ( , 5-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 -Hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, bis such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane And (hydroxyaryl) alkanes.

  Moreover, 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-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Cardo structure-containing bisphenols exemplified by methylphenyl) fluorene; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; '-Dihydroxydiphenyl sulfide, 4,4'-dihydride Dihydroxy diaryl sulfides exemplified by xy-3,3′-dimethyldiphenyl sulfide; dihydroxy exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Diaryl sulfoxides; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Is 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. These aromatic dihydroxy compounds may be used individually by 1 type, and may use 2 or more types together.

  On the other hand, 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; dimethyl carbonate, diethyl carbonate and the like. Dialkyl carbonates; dihaloformates of dihydric phenols, and the like. These carbonate precursors may be used alone or in combination of two or more.

  The aromatic polycarbonate resin 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 -Dichloro isatin, 5-bromo isatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. These polyfunctional aromatic compounds may be used individually by 1 type, and may use 2 or more types together. 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 polycarbonate resin (A) 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 polycarbonate resin (A) used by this invention, Interfacial polymerization method or melt transesterification method is advantageous industrially.

  The molecular weight of the polycarbonate resin (A) used in the present invention is usually 10,000 to 50 as the viscosity average molecular weight (Mv) converted from the solution viscosity from the viewpoint of mechanical strength and fluidity (ease of moldability). , Preferably 12,000 to 40,000, more preferably 14,000 to 35,000, and particularly preferably 16,000 to 32,000. Two or more types of 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 polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

Here, the viscosity average molecular weight (Mv) is methylene chloride as a solvent, an Ubbelohde viscometer is used, and the intrinsic viscosity (η) (unit dl / g) at a temperature of 20 ° C. is obtained. : Means a value calculated from the equation of 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).

  Further, the terminal hydroxyl group concentration of the polycarbonate resin (A) used in the present invention is usually 1000 ppm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, further 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. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the heat resistance and residence heat stability of the resin composition tend to be further improved.

  In addition, the unit of the terminal hydroxyl group density | concentration displays the mass of the terminal hydroxyl group with respect to polycarbonate resin mass in ppm, and the measuring method is the colorimetric determination (Macromol. Chem. 88 215 (1965) by the titanium tetrachloride / acetic acid method. ).

  In addition, the polycarbonate resin (A) used in the present invention may contain a polycarbonate oligomer, preferably an aromatic polycarbonate oligomer, in order to improve the appearance of the molded product and the fluidity. The viscosity average molecular weight (Mv) of the polycarbonate oligomer is usually 1,500 to 9,500, preferably 2,000 to 9,000. The content of the polycarbonate oligomer in the polycarbonate resin (A) is usually 30% by mass or less.

  Furthermore, in the present invention, as the polycarbonate resin (A), not only a virgin resin but also a polycarbonate resin regenerated from a used product, that is, a so-called material recycled polycarbonate resin may be used. Used products include, for example, optical recording media such as optical disks, 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 used proportion of the regenerated polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, based on the virgin resin.

In the present invention, the transparent window layer is preferably composed of the polycarbonate resin (A) as described above, but the constituent material of the transparent window layer is not limited to the polycarbonate resin (A) alone, and the polycarbonate resin (A ) And antioxidants, heat stabilizers, mold release agents, dyes, pigments, reinforcing agents, flame retardants, impact modifiers, and weather resistance improvements contained in the polycarbonate resin composition as a constituent material of the window frame layer described below. Even if one or more of various additives such as an agent, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and a fungicide are blended. Good.
In that case, the compounding quantity of these additives with respect to polycarbonate resin (A) is the compounding quantity of various additives with respect to the resin component (total of polycarbonate resin (A) and resin (B)) in the polycarbonate resin composition mentioned later. It is the same.

[Polycarbonate resin composition]
A polycarbonate resin composition suitable as a constituent material of the window frame layer according to the present invention includes a polycarbonate resin (A) and a resin having no reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (A) ( B), and various additives as necessary.

  Examples of the polycarbonate resin (A) in the polycarbonate resin composition include the above-described polycarbonate resin (A). This polycarbonate resin (A) does not necessarily need to be the same polycarbonate resin as the polycarbonate resin (A) which comprises a transparent window layer, and may differ. Moreover, it is the same kind of polycarbonate resin, and the molecular weight and the terminal hydroxyl group concentration may be different. Moreover, not only what consists of 1 type of polycarbonate resin but what consists of 2 or more types of polycarbonate resin may be sufficient.

{Resin (B) not having reactivity and / or interaction (excluding intermolecular force) with polycarbonate resin (A)}
“Reactivity and / or interaction (excluding intermolecular force) with respect to polycarbonate resin (A)” of resin (B) having no reactivity and / or interaction (excluding intermolecular force) with polycarbonate resin (A) “Do not have” means that it does not have a functional group that causes a chemical reaction such as transesterification with the terminal or side chain of the polycarbonate resin (that is, has no reactivity) and / or the terminal or side of the polycarbonate resin. It indicates that it does not have a functional group that causes hydrogen bond or ionic bond with the chain (that is, it has no interaction).

  The resin (B) is not particularly limited as long as it does not have reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (A), and various resins can be exemplified. However, polyolefin resins such as polypropylene resins and polyethylene resins are preferable.

  That is, by mixing a polycarbonate resin (A) with a resin (B) that has no reactivity and / or interaction (excluding intermolecular force) with respect to such a polycarbonate resin (A), the polycarbonate resin is made transparent. Although the adhesion strength of the window frame layer to the window layer can be reduced and the adhesion strength can be controlled within a desired range, the multicolor molded resin window member that is glazing has chemical resistance in joining with the vehicle body. Securing is also required. By using a polycarbonate resin composition containing a polyolefin-based resin as the resin (B), it is possible to improve the chemical resistance of the window frame layer as well as controlling the adhesion force.

<Polyolefin resin>
There is no restriction | limiting in particular as an olefin resin as resin (B), A various thing can be mentioned. For example, ethylene-based resins such as ethylene homopolymers, ethylene-based copolymers with other α-olefins such as propylene and 1-butene; propylene homopolymers and propylene-based main components , Propylene resins such as copolymers with other α-olefins such as ethylene and 1-butene; homopolymers of 1-butene, other α such as ethylene and propylene based on 1-butene -Butene-based resins such as copolymers with olefins and the like. Thus, the olefin resin may be a homopolymer or a copolymer. In the case of a copolymer, the olefin resin may be a random copolymer or a block copolymer.

Among these, from the point of incompatibility with the polycarbonate resin, an ethylene-based resin is preferable. Specific examples include, for example, ethylene homopolymer, propylene mainly composed of ethylene, and other α such as 1-butene. -Ethylene-based resins such as copolymers with olefins and the like can be mentioned, and particularly preferred are copolymers with other α-olefins such as propylene and 1-butene mainly composed of ethylene.
If the resin is incompatible with the polycarbonate resin, a sea-island structure of the polycarbonate resin and the ethylene resin is formed in the polycarbonate resin composition, and the ethylene resin phase and the polycarbonate resin of the transparent window layer are formed. The adhesion strength can be adjusted by non-adhesion.

  The polymerization method of the olefin resin may be any polymerization method as long as a resinous material can be obtained, but the gas phase method and the solution method are particularly preferable.

(Ethylene resin)
In the present invention, the ethylene resin suitably used as the resin (B) 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. , Isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, or esters thereof. Further, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or acid anhydrides thereof may be used as long as the effects of the present invention are not impaired.
These monomers and acid anhydrides may be copolymerized with an ethylene main chain, and those capable of graft polymerization may be graft polymerized.

  These ethylene resins can be produced by a usual method.

  Among these, preferred ethylene-based resins are copolymers of ethylene and one or more of α-olefins having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and ethylene-propylene copolymers, Ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-heptene copolymer, ethylene Examples include -1-octene copolymers, and linear ethylene resins in which a copolymer component is introduced into the main chain are particularly preferable.

  If the ethylene content in the ethylene-based resin is too low, handling deteriorates due to a decrease in melting point and the cost increases, and if it is too high, whitening occurs due to molding shrinkage due to crystallization. Therefore, the ethylene content in the ethylene-based resin is preferably 90 to 40 mol%, particularly 85 to 50 mol%.

The ethylene resin used in the present invention is preferably an ethylene resin as described above and a low density ethylene resin having a density of 0.85 to 0.92 g / cm ³ .

When the density of this ethylene-based resin exceeds 0.92 g / cm ³ , the chemical resistance may be deteriorated due to whitening phenomenon on the surface of the resin molded product, delamination, or poor dispersion of the ethylene-based resin. Conversely, by using a low density ethylene-based resin having a density of 0.92 g / cm ³ or less, the flowability and dispersibility with respect to the polycarbonate resin are improved, the crystallinity is reduced, and the shrinkage rate at the time of molding is reduced. It becomes close to the shrinkage rate of the polycarbonate resin, and the formation of voids tends to be suppressed. In addition, since relatively small domains are formed and delamination is prevented, and the domains of the ethylene-based resin are uniformly dispersed, good chemical resistance is obtained, which is preferable.
However, if the density is smaller than 0.85 g / cm ³ , the physical properties may be lowered.
Accordingly, the density of the ethylene-based resin to be used is preferably 0.86 to 0.92 g / cm ³ , and particularly preferably 0.88 to 0.90 g / cm ³ .

In the present invention, the density of the ethylene-based resin is a value measured according to the ISO 1183 D method. Hereinafter, the ethylene resin having a density of 0.85 to 0.92 g / cm ³ used in the present invention may be simply referred to as “low density polyethylene”.

  In the low density polyethylene used in the present invention, if the molecular weight distribution (Mw / Mn) represented by the ratio of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is too large, the impact resistance may be lowered. On the contrary, if it is too small, the moldability may be inferior. Therefore, this molecular weight distribution (Mw / Mn) is preferably 1.3 to 4, and more preferably 1.5 to 3.5.

  The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the low density polyethylene are measured by gel permeation chromatography (GPC: Gel Permeation Chromatography). Specifically, it is as described in the section of Examples described later.

  The melt flow rate of the low density polyethylene used in the present invention, specifically, the melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with ISO 1133 may be selected and determined as appropriate. However, if the MFR is too low (that is, if the value of the MFR is too small), the dispersibility is lowered and a large domain is easily formed, so that whitening and delamination are likely to occur. On the other hand, even if it is too high (that is, even if the MFR value is too large), it takes a structure in which the domain is greatly stretched, so that appearance defects and physical properties are likely to deteriorate due to pearl luster.

  Therefore, the low density polyethylene used in the present invention preferably has the above MFR of 0.1 to 50 g / 10 min, and more preferably 0.2 to 30 g / 10 min.

{Resin component}
Content (composition) of resin (B) having no reactivity and / or interaction (excluding intermolecular force) with the aforementioned polycarbonate resin (A) and polycarbonate resin (A) in the polycarbonate resin composition for forming a window frame layer The content in the product) is preferably from 80 to 94% by mass for the polycarbonate resin (A), and preferably from 6 to 20% by mass for the resin (B), preferably a polyolefin resin, more preferably an ethylene resin.

If the ratio of the polycarbonate resin (A) in the polycarbonate resin composition is higher than the above upper limit and the ratio of the resin (B) is lower than the lower limit, the adhesion strength between the transparent window layer and the window frame layer becomes too high. When the impact is received, the ductility characteristic of the polycarbonate resin cannot be sufficiently obtained. On the contrary, the ratio of the polycarbonate resin (A) is less than the above lower limit and the resin (B) is more transparent than the above upper limit. The adhesion strength between the window layer and the window frame layer becomes too weak, and the product cannot be realized.
More preferable content (content in the composition) is 85 to 94% by mass of the polycarbonate resin and 6 to 15% by mass of the resin (B), and particularly preferably 80 to 90% by mass of the polycarbonate resin (A) and the resin ( B) 10 to 20% by mass.
The total content of the polycarbonate resin (A) and the resin (B) in the polycarbonate resin composition is preferably 85% by mass or more.

{Other ingredients}
The polycarbonate resin composition for forming a window frame layer according to the present invention is contained in an ordinary polycarbonate resin composition in addition to the above-described polycarbonate resin (A) and resin (B) within a range not impairing the effects of the present invention. Various other additives may be contained.

  Various additives that can be included include inorganic fillers, antioxidants, heat stabilizers, mold release agents, UV absorbers, dyes and pigments, flame retardants, anti-dripping agents, reinforcing agents, impact resistance improvers, and weather resistance. Examples thereof include an improving agent, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a fluidity improving agent, a plasticizer, a dispersant, and an antibacterial agent. Two or more of these may be used in combination.

  Hereinafter, an example of an additive suitable for the polycarbonate resin composition according to the present invention will be specifically described.

<Inorganic filler>
The polycarbonate resin composition for forming a window frame layer is preferably blended with an inorganic filler for the purpose of improving mechanical strength such as rigidity, dimensional stability, and heat resistance. Examples of the inorganic filler include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads; carbon fillers such as carbon fibers, short carbon fibers, carbon nanotubes, and graphite; Examples include whiskers such as potassium titanate and aluminum borate; silicate compounds such as talc, mica, wollastonite, kaolinite, zonotolite, sepiolite, attabalgite, montmorillonite, bentonite and smectite; silica, alumina, calcium carbonate and the like. These inorganic fillers may be used alone or in combination of two or more.

  The particle size and the like of these inorganic fillers may be appropriately selected and determined. For example, when a fibrous inorganic filler is used, the mass average fiber length is usually 1.5 from the viewpoint of strength and dispersibility. -10 mm, preferably 1.8-5 mm. Moreover, the average fiber diameter is 1-20 micrometers normally, for example, in the case of glass fiber, it is preferable that it is 10 micrometers-20 micrometers from the point which raises the breakage and physical property balance of glass fiber further.

  The content of the inorganic filler in the polycarbonate resin composition may be appropriately selected and determined. However, if the amount is too small, the effect of blending the inorganic filler cannot be sufficiently obtained, and warping as a molded product increases. On the other hand, if the amount is too large, the moldability deteriorates, and there is a case where the molded product warps in the reverse direction. Therefore, the content is preferably 0.1 to 10% by mass, particularly 1 to 10% by mass, and particularly preferably 2 to 8% by mass in the polycarbonate resin composition.

<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 the sum of the polycarbonate resin (A) and the resin (B) having no reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (hereinafter referred to as “resin component”). The amount 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. 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, phosphite compound (a), phosphorous acid (at least one ester in the molecule esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms) and at least one selected from the group of b) and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).

  Specific examples of the phosphite compound (a) include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4 -Di-tert-butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl Phosphite, distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Rudiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Examples include erythritol diphosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in combination of two or more.

  Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

  Content of a heat stabilizer is 0.001-1 mass part normally with respect to 100 mass parts of resin components, Preferably it is 0.01-0.5 mass part. 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 is at least one compound 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 15000, and polysiloxane silicone oils. Is mentioned.

  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. On the other hand, 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.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  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. These may be used alone or in combination of two or more.

  Examples of the aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, micro wax, 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. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, paraffin wax and polyethylene wax are more preferable, and 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.

  Content of a mold release agent is 0.001-2 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.01-1 mass part. 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>
Specific 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. Of these, organic ultraviolet absorbers are preferred. 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], and at least one selected from the group of [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferable.

  Specific examples of the benzotriazole compound include methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol condensate. 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-chloro Benzotriazole, 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′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-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].

  Content of a ultraviolet absorber is 0.01-3 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.1-1 mass part. 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.

<Dye and pigment>
Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include carbon black; sulfide pigments such as 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, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; heterocyclic dyes such as anthraquinone and quinoline; and methyl dyes and the like. Two or more of these may be used in combination.

  Among these, carbon black, titanium oxide, anthraquinone series, quinoline series, phthalocyanine series compounds and the like are preferable from the viewpoint of thermal stability.

  The content of the dye / pigment 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. 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-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant 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.

  Content of a flame retardant is 1-30 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 3-25 mass parts, More preferably, it is 5-20 mass parts. 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 resin and to couple | bond together resins and to form 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.

  Content of a dripping inhibitor is 0.02-5 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.03-3 mass parts. When the compounding amount of the dripping inhibitor exceeds 5 parts by mass, the appearance of the molded product may be deteriorated.

  The polycarbonate resin composition for forming a window frame layer according to the present invention includes a polycarbonate resin (A) and a resin that does not have reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (A) (B In this case, examples of the other resin or rubber component include acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer. Rubber-reinforced styrene resin such as polymer (ABS resin), styrene resin such as polystyrene resin, and polyacrylic acid (core) / acrylonitrile-styrene copolymer (shell) used in the examples described later And a core / shell type graft copolymer comprising The content of these other resins or rubber components is sufficient to ensure the effects of using the polycarbonate resin (A) and the resin (B) in combination, and the resin components (the polycarbonate resin (A) and the resin (B). )) With respect to 100 parts by weight, preferably 30 parts by weight or less, more preferably 27 parts by weight or less, especially 20 parts by weight or less, and particularly preferably 10 parts by weight or less. In order to obtain the effect by blending, it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more.

  Among them, in the present invention, the above-described resin component and rubber other than the polycarbonate resin (A) and the resin (B) which does not have reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (A). As a component, it is preferable to use a rubber-reinforced styrene resin from the viewpoint of moldability, surface property of the obtained window frame layer, and the like.

  The rubber-reinforced styrene resin is obtained by graft polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of a rubbery polymer. And (a2) an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the absence of a rubbery polymer. It contains a (co) polymer obtained by (co) polymerizing the body. Hereinafter, “(co) polymerization” means “homopolymerization and / or copolymerization”.

  Examples of the rubbery polymer used in the above (a1) include polybutadiene, butadiene-styrene copolymer, butadiene- (meth) acrylic acid ester copolymer (here, “(meth) acrylic acid” means “acrylic acid and / or Or methacrylic acid.), Styrene-butadiene-styrene block copolymer, polymer comprising at least one styrene polymer block and at least one butadiene polymer block, styrene-isoprene-styrene block copolymer Butadiene-based (co) polymers such as styrene-isoprene block copolymers, hydrogenated products of the butadiene-based (co) polymers, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, Ethylene-butene copolymer, ethylene-butene-nonconjugated diene copolymer, ureta Rubber, acrylic rubber, silicone rubber, silicone - acrylic IPN rubbers, etc. These may be used alone or in admixture of two or more.

  Examples of the aromatic vinyl compound used in the above (a1) and (a2) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, brominated styrene, hydroxystyrene, and the like. Can be used alone or in combination of two or more.

  Other vinyl monomers copolymerizable with the aromatic vinyl compound used in the above (a1) and (a2) include vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide compounds, carboxyl group-containing unsaturated compounds Functional group-containing unsaturated compounds such as acid anhydride group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, substituted or unsubstituted amino group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds. Can be mentioned.

Examples of the vinylcyan compound include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more.
Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. Can be used in combination.

  Examples of maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. These may be used alone or in combination of two or more. Can do. The maleimide compound may be introduced by a method in which maleic anhydride is copolymerized and then imidized.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combinations of two or more. Can be used together.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.
Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples thereof include methyl-1-propene, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide, and the like can be used alone or in combination of two or more.

Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, and acrylamine. , Methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and these can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used alone or in combination of two or more.

  Among the rubber-reinforced styrene resins used in the present invention, AS resins and ABS resins are preferable, and it is particularly preferable to use both in combination. The content of these rubber-reinforced styrenic resins is sufficient to ensure the effect of using the polycarbonate resin (A) and the resin (B) in combination, and the resin components (the polycarbonate resin (A) and the resin (B) 30 parts by mass or less, more preferably 27 parts by mass or less with respect to 100 parts by mass. By blending these, effects such as improvement in surface appearance and improvement in physical properties due to notch sensitivity reduction are sufficiently obtained. When obtaining, it is preferable to set it as 10 mass parts or more, especially 15 mass parts or more, especially 20 mass parts or more. In addition, when AS resin and ABS resin are used in combination, the combined ratio is determined by using AS resin in order to obtain sufficient effects such as improvement in surface appearance and improvement in physical properties due to notch sensitivity reduction. : ABS resin = 1: 0.1 to 10 (weight ratio), particularly preferably 1: 0.5 to 5 (weight ratio).

  The method for producing the rubber-reinforced styrene resin used in the present invention is arbitrary, and those produced by any conventionally known method can be used. Specific examples of the production method include emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and a polymerization method using a combination thereof. In addition, the method of adding each component when producing the rubber-reinforced styrene resin may be a method in which a vinyl monomer such as an aromatic vinyl compound is added all at once in the presence of the total amount of the above-mentioned rubbery polymer. A method may be used in which the monomers are divided or added continuously, or a method in which these are combined.

  In the case of producing a rubber-reinforced styrene resin by emulsion polymerization, the polymerization initiator, chain transfer agent, emulsifier, water and the like to be used are not particularly limited, and any conventionally known one can be used.

  Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butyl peroxylaurate, and t-butyl. 1 type, or 2 or more types, such as peroxymonocarbonate, is mentioned. In addition, as a polymerization initiation aid, redox systems such as various reducing agents, sugar-containing pyrophosphate / iron formulations, sulfoxylate formulations, and the like can also be used.

  Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, tetraethyl thiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol, and terpinolenes. Or 2 or more types are mentioned.

  Examples of the emulsifier include higher alcohol sulfates, alkylbenzene sulfonic acid metal salts such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, anionic surfactants such as rosinate and phosphate, Furthermore, 1 type (s) or 2 or more types, such as a well-known nonionic surfactant, are mentioned.

  In emulsion polymerization, the target polymer powder is usually obtained by washing and drying a powder obtained by coagulation with a coagulant or the like. As the coagulant in this case, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, and acids such as sulfuric acid, hydrochloric acid, acetic acid and citric acid can be used. Further, depending on the required performance, washing may be carried out after adding an alkali component and neutralizing after coagulation, or washing after adding an acid component and neutralizing treatment.

In the case of producing a rubber-reinforced styrene resin by solution polymerization, thermal polymerization may be performed without using a polymerization initiator, or polymerization may be performed using a polymerization initiator. As the polymerization initiator used here, one or more organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide and the like are preferably used.
As a chain transfer agent, 1 type (s) or 2 or more types, such as mercaptans, (alpha) -methylstyrene dimer, terpinolenes, are used, for example.

  These polymerization initiators, chain transfer agents and the like are also preferably used in bulk polymerization and bulk / suspension polymerization.

  Polymers obtained by polymerizing vinyl monomers in the absence of rubbery polymer (component (a2)) are also known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, and the like. All of the above-described reagents can be used for the reagents used in these polymerization methods.

{Production method}
The polycarbonate resin composition for forming a window frame layer includes a polycarbonate resin (A), a resin (B) having no reactivity and / or interaction (excluding intermolecular force) with the polycarbonate resin (A), and as necessary. It can be produced by appropriately selecting any conventionally known method using other additives to be added.

  Specifically, the polycarbonate resin (A), the resin (B), and additives to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender The resin composition can be produced by melt-kneading with a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like. Moreover, it is also possible to produce a resin composition without mixing each component in advance, or by mixing only some components in advance and supplying them to an extruder using a feeder and melt-kneading them.

[Molding method of multicolor molded resin window member]
The multicolor molded resin window member of the present invention comprises a polycarbonate resin (A) for forming a transparent window layer (this polycarbonate resin (A) may further be a polycarbonate resin composition containing various additives) and a window. It can be manufactured by injection molding using a polycarbonate resin composition for forming a frame layer according to a conventional method. Examples of the injection molding method for producing the multicolor molded resin window member of the present invention include a multicolor injection molding method, a multicolor injection compression molding method, and an insert molding method.

  For example, in the case of injection compression molding, first, a resin molded product of the transparent window layer is molded by injection molding. Next, before injecting the resin composition for forming the window frame layer on the transparent window layer, the movable core is retracted, and the space between the surface of the transparent window layer and the mold cavity surface is expanded. The polycarbonate resin composition for forming a window frame layer is filled, the movable core is advanced, and pressure is applied (compressed) to the resin molded product on which the window frame layer is formed.

  As a result, it is possible to reduce the pressure at the time of filling, and to make uniform the pressure difference in the mold between the vicinity of the gate portion and the vicinity of the flow end portion of the thermoplastic resin filled in the mold. That is, the holding pressure generated by the advancement of the movable core can transmit a sufficiently uniform pressure to the entire molded product, so that the anisotropy of adhesion can be reduced. As a result, the influence of the direction of the load is reduced. In addition, when obtaining the resin molded product of a transparent window layer, it is also possible to carry out injection compression molding. In that case, since a transparent window layer with few distortions is obtained, it is preferable.

  Here, as the injection compression molding method, for example, a mold-clamping compression molding method using opening and closing of a movable or fixed plate (platen) to which a mold is attached in an injection molding machine, a compression cylinder of a molding machine platen, a ball screw, etc. Any conventionally known method such as a core compression molding method used can be used.

  Here, the mold-clamping compression molding method specifically refers to, for example, injecting resin into a cavity formed with the mold parting surfaces of both the fixed side and the movable side platens opened by a predetermined interval, and then In this method, the parting surfaces are brought into contact with each other by the clamping force and compressed.

  The core compression molding method specifically refers to, for example, in the mold clamping before injection, each parting surface of the mold is brought into contact, a resin is injected with a predetermined mold clamping force, and then compressed. Is the method. In the step of compressing after injection, the movable side core is advanced and compressed in a direction in which the volume of the cavity is reduced by a compression mechanism installed in a molding machine, a mold or the like. Here, examples of the compression mechanism include a compression cylinder and a ball screw.

In addition, there is no restriction | limiting in particular in the dimension of the multicolor molding resin window member of this invention, What is necessary is just to select and determine suitably according to the use. Usually, as a window material for automobiles, the area of the transparent window layer portion is about 400 cm ^{2 to 2} m ² , the width of the window frame layer portion is about 30 to 200 mm, the thickness of the transparent window layer is about 3 to 15 mm, The thickness of the frame layer is about 1 to 10 mm. Among them, the area of the transparent window layer portion is 800 cm ^{2 to 1} m ² , the width of the window frame layer portion is 30 to 150 mm, the thickness of the transparent window layer is 3 to 8 mm, and the thickness of the window frame layer is 2 to 5 mm. Is preferred.
The window frame layer is preferably formed all around the transparent window layer.

[Adhesion]
In the multicolor molded resin window member of the present invention, the adhesion between the transparent window layer and the window frame layer is 35 to 90 MPa, preferably 45 to 85 MPa. If the adhesion between the two layers is less than 35 MPa, the adhesion is too weak, and the transparent window layer and the window frame layer easily peel off, which does not hold as a product. When the adhesive force between the transparent window layer and the window frame layer exceeds 90 MPa, the adhesive force is too strong, and when subjected to impact, the ductile fracture of the polycarbonate resin of the transparent window layer is inhibited, resulting in brittle fracture, which is not preferable. .

  Here, the adhesion between the transparent window layer and the window frame layer is a value measured as follows.

First, a multicolor molded resin window member is molded, and a plate-like sample is obtained by cutting from a portion where the thickness of each layer is constant in the laminated portion of the transparent window layer and the window frame layer.
The cutting part may be appropriately selected and determined. However, for the test to be described later, when this sample is a multicolor molded product manufactured by, for example, injection molding, the resin flow direction (MD in the window frame layer) It is preferable to obtain it from a part where the (direction) is clearly known, specifically, for example, a part near the gate or a part avoiding the weld part. At this time, at least one of the side surfaces (surface composed of both the transparent window layer and the window frame layer) of the plate-like sample obtained by cutting the multicolor molded product manufactured by injection molding is the above-mentioned MD. A plate-like sample is obtained so as to be a plane perpendicular to the direction.

Then, on the side surface of the plate-like sample, which is a plane perpendicular to the MD direction, the center of the blade is centered using a rotating notch blade along the interface (adhesion interface) between the transparent window layer and the window frame layer. Place at the interface of the layers, rotate and cut to provide a 120 ° angle notch.
At this time, as shown in FIG. 3A described later, the surface forming the notch provided by the above-described cutting and the side surface intersect to form an acute angle portion. If both layers are thick, even if the above-mentioned notch is provided, the acute angle portion may not be formed. In this case, the notch is provided after cutting the layer or reducing the layer thickness in advance. May be. On the other hand, when both layers are thin, the thickness may be provided, specifically, the thickness may be increased by using a highly rigid material such as a metal or other resin so that the thickness is sufficient for the test.

Next, after cutting the side surface portion of the plate-like sample provided with this notch at a position where the length from the tip of the notch recess in both layers is 5 mm, a long product having a notch in the longitudinal direction was obtained. The long product is cut into a width of 3 mm so that the contact area is 3 mm × 5 mm to obtain a measurement sample (sample 20 in FIG. 3A).
The measurement sample described above is a standard measurement sample for measuring the adhesion between the transparent window layer and the window frame layer in the present invention. If such a sample is difficult to collect depending on the shape of the window, the above-described measurement sample is used. What is necessary is just to correct | amend the difference of the adhesion area with a measurement sample from the value of the adhesion strength calculated | required with the following method.

  As shown in FIG. 3 (b), this measurement sample is self-supported with a notch facing downward on a non-flexible plate surface such as an iron plate, and in accordance with a bending test (JIS K7171), Apply force downward from the top with an indenter (jig). The jig is placed on the sample so as to push the adhesion interface. When force is applied to the jig from the top, it peels along the flow direction of the resin at the contact interface, and the stress when these two layers are peeled is defined as contact force (MPa).

The calculation of the adhesion force is the same as the bending stress, and is obtained by the following formula.
σ = 3FL / 2bh ²
(Here, σ: adhesion, F: load, L: sample thickness, b: sample width (3 mm), h: sample height (7 mm))
A more specific method for measuring the adhesion strength will be described later in the Examples section.

[Falling weight impact test]
In the multicolor molded resin window member of the present invention, in the falling weight impact test at the boundary between the window frame layer laminated portion and the non-laminated portion of the transparent window layer, the transparent window layer does not break brittlely, but if it breaks, ductile fracture It is characterized by being.

  Here, the falling weight impact test at the boundary portion between the window frame layer laminated portion and the non-laminated portion of the transparent window layer is a surface impact test performed as follows. The details are described in the Examples section.

  First, a multicolor molded resin window member is molded, including a portion where the transparent window layer and the window frame layer are laminated, and a portion where the window frame layer is not laminated (only the transparent window layer). A plate-like sample of 100 mm square is obtained by cutting around the boundary.

  The plate-like sample is placed horizontally with the transparent window layer on the upper side and the window frame layer on the lower side, and a surface impact test is performed (see FIG. 2). The result is observed visually, and when the sample is broken into pieces or cracked into two or more of the part where the window frame layer is laminated and the part where it is not laminated, it is called `` brittle fracture '' and the transparent window layer A case of penetration without cracking or indentation without cracking is evaluated as “ductile fracture”.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

  In addition, the compounding component of the resin composition used in the Example and the comparative example is as follows.

Polycarbonate resin (1): Aromatic polycarbonate resin “Iupilon (registered trademark) S-2000UR” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight (Mv) 24500

Polycarbonate resin (2): Aromatic polycarbonate resin “Iupilon (registered trademark) S-3000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight (Mv) 22500

Polycarbonate resin (3): Aromatic polycarbonate resin “Iupilon (registered trademark) H-4000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight (Mv) 15500

Polycarbonate resin (4): Aromatic polycarbonate resin “Iupilon (registered trademark) E-2000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight (Mv) 28000

Polyethylene resin (1): Ethylene-propylene copolymer “HF310 (trade name)” manufactured by Nippon Polyethylene Co., Ltd. 98 mol% ethylene, density 0.950 g / cm ³ , Mw / Mn 25, MFR 0.06 g / 10 min

Polyethylene resin (2): ethylene-propylene-hexene copolymer “Kernel KS240T (trade name)” manufactured by Nippon Polyethylene Co., Ltd., 50 to 55 mol% in ethylene content, density 0.88 g / cm ³ , Mw / Mn 2.5 , MFR2.2g / 10min

ABS-based resin: Technopolymer acrylonitrile-butadiene-styrene copolymer “Techno ABSDP-611”

AS-based resin: Acrylonitrile-styrene copolymer “SAN-290FFDN” manufactured by Techno Polymer Co., Ltd.

Rubber-like elastic body: Core / shell type graft copolymer "Staffyroid MG1011 (trade name)" made of polyalkyl acrylate (core) / acrylonitrile-styrene copolymer (shell) manufactured by Ganz Kasei Co., Ltd.

Glass fiber: “ECS03T-571 (trade name)” manufactured by Nippon Electric Glass Co., Ltd. Average fiber diameter: 13 μm, average fiber length: 3 mm

Wollastonite: “Nygros 4 (trade name)” manufactured by Nyco Minerals, Inc. Average particle size 3.4 μm

Talc: “High filler # 5000PJ (trade name)” manufactured by Matsumura Sangyo Co., Ltd. Average particle size 1.8 μm, bulk density 0.12 g / ml

Carbon black: Oil furnace carbon black “# 1000” manufactured by Mitsubishi Chemical Corporation

[Examples 1, 2, 4 and Comparative Examples 2, 3]
After uniformly mixing the polycarbonate resin, polyethylene resin, carbon black and rubber-like elastic body (only Example 2) with a tumbler mixer at the ratio shown in Table 1, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30XCT) , L / D = 42, barrel number 12), cylinder temperature 280 ° C., screw rotation speed 250 rpm, feed from barrel 1 (uppermost barrel) to extruder, melt knead, and barrel 7 The glass fiber or wollastonite was fed to the extruder at a ratio shown in Table 1 from (the seventh barrel from the upstream side) and melt-kneaded to prepare pellets of the resin composition.

[Examples 3, 5, and 6]
After uniformly mixing polycarbonate resin, polyethylene resin, AS resin, ABS resin, carbon black and talc with a tumbler mixer at the ratio shown in Table 1, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30XCT, Using L / D = 42, barrel number 12), pellets of the resin composition were prepared by feeding to the extruder from barrel 1 at a cylinder temperature of 280 ° C. and a screw rotation speed of 200 rpm, and melt-kneading.

These pellets were used as a polycarbonate resin composition for forming a window frame layer.
Moreover, about the transparent window layer, the polycarbonate resin (1) independent pellet (Iupilon S-2000UR) was used.
Moreover, in the comparative example 1, the window frame layer also used this polycarbonate resin (1) single pellet (Iupilon S-2000UR).

  Two-color molding was performed using an “ENGEL DUO COMBI 700” molding machine (clamping force 700 t, opposed reversal type). The molding temperature was 300 ° C. for the transparent window layer, the temperature shown in Table 1 for the window frame layer, and the mold temperature was 90 ° C. Moreover, filling was performed at a single speed of an injection speed of 50 mm / sec, and the injection holding pressure switching position was set to 2 mm. Molding was performed with a valve gate type hot runner. Both the transparent window layer and the window frame layer were subjected to injection compression molding, and both the transparent window layer and the window frame layer were opened by 3 mm before injection. After completion of injection, re-clamping was performed at 700 t, and the holding time of re-clamping was 15 seconds for the transparent window layer and 10 seconds for the window frame layer.

  After injecting the window frame layer first, the transparent window layer was injected, and then 60 seconds was taken as the cooling time. Although the molding cycle was not always constant due to the sample removal time, it was performed in about 180 seconds. The hot runner temperature was the same as the molding temperature. In addition, the hot air drying was performed at 120 degreeC for 6 hours before shaping | molding.

The obtained two-color molded product has a size of 750 mm (curvature R: 10000) × 450 (curvature R: 5000) mm, and the thickness is 5 mm for the transparent window layer and 3 mm for the window frame layer around the transparent window layer. It was. The shape of the molded product 1 is shown in FIG. In FIG. 1, 11 is a transparent window layer and 12 is a window frame layer.
Molding was performed continuously for 10 shots, and the following drop weight impact test, adhesion force measurement, and adhesion evaluation as a product were performed on the 10th shot sample.
These results are shown in Table 1.

<Falling weight impact test>
As shown in FIG. 2, the two-color molded product 1 includes 11 parts of a transparent window layer and 12 parts of a window frame layer, and the boundary 13 between the laminated part of the window frame layer 12 and the non-laminated part of the transparent window layer 11 is the center (center). A sample 10 having a size of 100 mm × 100 mm was cut out so as to be a line. Such a portion was a slightly curved plate. The plate-like body sample 10 was allowed to stand for 1 week in an environment of 23 ° C. × 50% RH, and then the state was adjusted. Went. As the striker 14, "M800" was used, and both sides of the sample 10 were sandwiched and fixed using a ring-shaped cradle (ring inner diameter 80 mm) 16. Reference numeral 15 denotes a dummy spacer. The collision speed of the striker 14 was 5 m / sec, and the measurement temperature was 23 ° C. The result was observed visually.

  When the sample 10 is broken into pieces or cracked into two or more at the boundary 13 between the laminated portion and the non-laminated portion, it is referred to as “brittle fracture”. ) Was evaluated as “ductile fracture”.

<Measurement of adhesion>
The peripheral portion where the transparent window layer 11 and the window frame layer 12 were laminated from the two-color molded product 1 was cut out to 50 mm × 50 mm, and then a 120 ° notch was made along the direction perpendicular to the resin flow direction. A cut piece was made. The notch depth was 2 mm. After notching, as shown to Fig.3 (a), it cut into 3 mm width x 7 mm length, and obtained the test piece. The area of the contact surface 17 between the transparent window layer 11 and the window frame layer 12 is 3 mm × 5 mm = 15 mm ² .

The sample 20 was measured in a bending test mode using a “universal material testing machine 5544” (manufactured by Instron) and a 2 kN load cell. The test speed was 2 mm / min. As shown in FIG.3 (b), the sample 20 was made to stand on the iron plate 21, and it was set to 8 mm which is sample thickness between spans. A load F was applied from the jig 22, the load when the sample 20 was peeled off between the transparent window layer 11 and the window frame layer 12 was read, and the adhesion was calculated by the following equation. When it did not peel, it was set as “−”.
σ = 3FL / 2bh ²
(Here, σ: adhesion, F: load, L: sample thickness (8 mm), b: sample width (3 mm), h: sample height (7 mm))

<Evaluation of adhesion as a product>
The obtained two-color molded product 1 is slanted with the curved surface up so that the angle of the plate surface is about 45 ° with respect to the horizontal plane, and the curved surface is manually formed around the center of the molded product from the transparent window layer side. The test of pressing and applying a load to deform was performed 10 times.
Thereafter, the appearance was visually observed, and the peeled state of the window frame layer was confirmed around the portion where the load was applied. The degree of peeling was evaluated in the following three stages.
○: No peeling is observed.
Δ: Slight peeling was observed at the boundary between the window frame layer and the transparent window layer (whitening was observed).
X: The window frame layer peeled from the transparent window layer.

  From Table 1, it can be seen that according to the present invention, a multicolor molded resin window member excellent in safety and exhibiting ductile fracture against impact is provided.

1 Two-color molded product 10 Sample 11 Transparent window layer 12 Window frame layer 13 Boundary 14 Striker 15 Spacer 16 Ring-shaped cradle (part)
17 Contact surface 18 Notch 20 Sample 21 Iron plate 22 Jig

Claims (7)

A transparent window layer constituting the transparent window portion, a multicolor molding resin window member having a window frame layer are stacked in at least a portion of the transparent window layer of the transparent window portion surrounding transparent window The layer is made of a polycarbonate resin (A), and the window frame layer is made of a polycarbonate resin composition containing the polycarbonate resin (A) and a resin (B) having no reactivity and / or interaction (excluding intermolecular force). becomes a contact force between the transparent window layer and the window frame layer 35～90MPa, in falling weight impact test at the boundary between the window frame layer laminated portion and the non-laminated part of the transparent window layer, the transparent window layer Is a multicolor molded resin window member characterized in that it does not brittlely break. The multicolor molded resin window member according to claim 1 , wherein the resin (B) is a polyolefin resin. The multicolor molded resin window member according to claim 1 or 2 , wherein the content of the resin (B) in the polycarbonate resin composition constituting the window frame layer is 6 to 20% by mass. The multicolor molded resin window member according to claim 2 or 3 , wherein the resin (B) is a polyethylene resin. The multicolor molded resin window member according to any one of claims 1 to 4 , wherein the polycarbonate resin composition constituting the window frame layer contains 0.1 to 10% by mass of an inorganic filler. The multicolor molded resin window member according to any one of claims 1 to 5 , wherein the window frame layer is laminated on the transparent window layer around the entire periphery of the transparent window portion. The window frame layer, a multicolor molded resin window member according to any one of claims 1 to 6, characterized in that it is injection compression molding.

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