JP3875908B2 - Molded product - Google Patents

Description

【０１３７】
【表２】

【０１３８】
実施例１〜１４のダイレクト蒸着用樹脂組成物の成型品は、アイゾット衝撃強度が高く、耐候性が良好であり、また、ダイレクト蒸着後の拡散反射率が低くて光輝性に優れるものであった。さらには、熱板溶着の際の糸曳き長さが短く、熱板溶着性にも優れていた。
【０１３９】
一方、比較例１〜９の熱可塑性樹脂組成物の成型品は、アイゾット衝撃強度、耐候性、ダイレクト蒸着後の光輝性のいずれかの項目において劣るものであった。
【０１４０】
また、実施例１および比較例１、２、７より、また、実施例１１および比較例８より、グラフト共重合体（Ａ）中に含まれるポリオルガノシロキサン中の３個以上のシロキサン結合を有するケイ素原子の比率が大きくなるにしたがってダイレクト蒸着後の拡散反射率が上昇し、光輝性が悪化する傾向があった。
【０１４１】
特に、実施例１〜８、１０〜１４のように全ゴム状重合体１００質量％中の粒子径５００ｎｍ以上のゴムの比率が４質量％以下である場合には、これまで知られてない高いアイゾット衝撃強度、耐候性、ダイレクト蒸着後の光輝性を発現できる。
【０１４２】
【発明の効果】
本発明によれば、ダイレクト蒸着後に美麗な光輝外観が得られ、しかも、高いレベルの耐衝撃性等の機械的強度と耐候性とを有し、ＰＭＭＡ樹脂やポリカーボネート樹脂などの透明樹脂との熱板溶着性にも優れたダイレクト蒸着用樹脂組成物を用いた成型品を提供することができる。
【０１４３】
特に、耐衝撃性、耐候性とダイレクト蒸着後の光輝性のバランスは、従来知られているゴム変性熱可塑性樹脂組成物を用いた成型品と比べて非常に優れており、本発明の成型品は各種工業用製品としての利用価値が極めて高い。[0001]
BACKGROUND OF THE INVENTION
  The present invention provides a metallic layer such as aluminum or chromium directly by metallization such as a vacuum deposition method or a sputtering method without providing a surface treatment or undercoat in order to obtain a molded product subjected to a bright treatment. Can be formed, so-calledUsing a resin composition for direct vapor depositionRegarding molded products.
[0002]
[Prior art]
Thermoplastic resin molded products for automobile parts and various electrical equipment casings are plated with a metal layer such as copper, chromium, nickel, etc. to improve design and other functionality, and aluminum, chromium, etc. In some cases, a metallization treatment is performed in which a metal layer is formed on the surface of a molded product by a vacuum deposition method, a sputtering method, or the like.
[0003]
Conventionally, when a surface metallization treatment is performed on such a resin molded product by a vacuum deposition method or a sputtering method, an undercoat treatment layer is formed by painting or plasma polymerization treatment in order to eliminate unevenness on the surface of the molded product and obtain smoothness. After that, it was necessary to form a metal layer (several tens to several hundreds of nm) by a vacuum deposition method or the like. Usually, a silicon-based top coat layer is then formed for the purpose of protecting the metal layer. As described above, the metallization treatment of the molded thermoplastic resin product requires a large number of steps, a dedicated device, and a high-cost treatment agent, but recently, a pretreatment step for forming an undercoat treatment layer. A so-called “direct vapor deposition method” has been carried out.
[0004]
The design of the glitter molded product obtained by this “direct vapor deposition method” varies greatly depending on the type of resin material and the surface state of the resin molded product. In the direct vapor deposition method, in particular, obtaining a beautiful brilliant appearance without surface haze was one of the important issues.
[0005]
For such a field, for example, in Japanese Patent Application Laid-Open No. 2001-2869, a vinyl polymer is added to a rubbery polymer (polyorganosiloxane polymer, acrylate polymer, etc.) having a specific particle size distribution. Rubber-containing graft copolymer obtained by graft polymerization of polymer (styrene, acrylonitrile), aromatic vinyl monomer and vinyl cyanide monomer, and other copolymerizable unsaturation used as required A thermoplastic resin composition having excellent direct vapor deposition properties containing a hard copolymer obtained by copolymerizing a monomer is disclosed.
[0006]
Incidentally, automotive tail lamps, stop lamps, head lamps, and the like are generally configured by a lens made of a transparent resin such as PMMA (polymethyl methacrylate) resin or PC (polycarbonate) resin, and a housing that supports the lens. In recent years, since such an automotive lamp housing is often exposed to sunlight outdoors, a material excellent in weather resistance is desired. Also, when joining the lens made of transparent resin and the housing, press the heated plate to the bonding part to be bonded together for several seconds to heat and melt together, quickly remove the hot plate and bond the two together, So-called hot plate welding is becoming common. In the hot plate welding method, a part of both materials may adhere to the hot hot plate, and there may be a phenomenon of pulling the thread when the hot plate is removed. Less is important.
[0007]
As a material in such a field, for example, JP-A-10-310676 discloses vinyl cyanide in the presence of at least one rubbery polymer selected from the group consisting of crosslinked acrylic rubber and polyorganosiloxane rubber. Graft polymer 10 obtained by graft polymerization of at least one monomer unit selected from monomers, aromatic monomers, (meth) acrylate monomers, and other vinyl monomers Heat comprising 100 parts by weight and a copolymer consisting of aromatic vinyl monomer units, vinyl cyanide monomer units, and other vinyl monomer units, 0 to 90 parts by weight A thermoplastic resin composition for sheet welding is disclosed.
[0008]
However, the thermoplastic resin composition excellent in direct vapor deposition disclosed in Japanese Patent Application Laid-Open No. 2001-2869 is not necessarily sufficient for the recent required level for high glitter. Furthermore, in applications such as lamp housings for automobiles, it is necessary to have a high level of weather resistance for molded products. It is possible to express a higher level of glitter by further reducing the amount of the large particle diameter rubber component specifically proposed in Japanese Patent Application Laid-Open No. 2001-2869. It is difficult to say that the brightness, impact resistance, and weather resistance of the direct vapor deposition process are satisfied at the same time. Also, the hot plate weldability is often not very good.
[0009]
On the other hand, the thermoplastic resin compositions disclosed in the examples of JP-A-10-310676 have good impact resistance and weather resistance, but a metal layer such as aluminum or chromium is formed by a direct vapor deposition method. In such a case, it cannot always be said that sufficient glitter is obtained, and the recent required level may not be reached.
[0010]
[Problems to be solved by the invention]
  The present invention provides a beautiful brilliant appearance after direct vapor deposition, has a high level of impact resistance and weather resistance, and is excellent in hot plate weldability with transparent resins such as PMMA resin and PC resin.Using a resin composition for direct vapor depositionThe purpose is to provide a molded product.
[0011]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by using a graft copolymer containing a specific composite rubber-like polymer, and have reached the present invention.
[0012]
That is, the above object of the present invention can be solved by the following present invention.
[0013]
(1) A polyorganosiloxane in which silicon atoms having three or more siloxane bonds are 1 mol% or less (including 0) with respect to all silicon atoms in polydimethylsiloxane and a (meth) acrylic acid ester polymer Graft copolymer (A) formed by graft polymerizing a vinyl polymer composed of one or more monomer components to the composite rubber-like polymer (G)A molded product characterized in that the surface of a molded product of the resin composition for direct vapor deposition containing metal is metallized by direct vapor deposition.
[0014]
(2)The resin composition for direct vapor depositionThe above (1) further includes a vinyl (co) polymer (B) obtained by polymerizing a monomer containing at least one of an aromatic alkenyl compound, a vinyl cyanide compound and a (meth) acrylic acid alkyl ester. )ofMolded product.
[0015]
(3)The resin composition for direct vapor deposition(1) or (2) comprising 5 to 100 parts by mass of the graft copolymer (A) and 95 to 0 parts by mass (100 parts by mass in total) of the vinyl-based (co) polymer (B).Molded product.
[0016]
(4)The resin composition for direct vapor depositionFurther, the above (1) or (2) comprising polycarbonate and / or polyester (C)Molded product.
[0017]
(5)The resin composition for direct vapor depositionGraft copolymer (A) 5 to 80 parts by mass, vinyl-based (co) polymer (B) 75 to 0 parts by mass, polycarbonate and / or polyester (C) 95 to 20 parts by mass (total 100 parts by mass) (4) includingMolded product.
[0018]
(6) In the total rubbery polymer including the composite rubbery polymer (G), the proportion of the rubbery polymer having a particle diameter of 500 nm or more is 4% by mass.Less thanAny one of (1) to (5)Molded product.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
  The present inventionUse inThe thermoplastic resin composition for direct vapor deposition includes polyorganosiloxane and (meth) acrylic in which silicon atoms having three or more siloxane bonds are 1 mol% or less (including 0) based on all silicon atoms in polydimethylsiloxane. A composite rubber-like polymer (G) composed of an acid ester polymer includes a graft copolymer (A) obtained by graft polymerization of a vinyl polymer composed of one or more monomer components. . Further, if necessary, a vinyl-based (co) polymer (B) obtained by polymerizing a monomer containing at least one of an aromatic alkenyl compound, a vinyl cyanide compound and an alkyl (meth) acrylate. Polycarbonate and / or polyester (C) may be contained.
[0022]
The molded product of the thermoplastic resin composition of the present invention is a molded product of a metal layer such as aluminum or chromium by a vacuum deposition method or a sputtering method without performing a special pretreatment such as formation of an undercoat treatment layer. Surface metallization treatment formed on the surface can be performed. The glitter molded article obtained by this direct vapor deposition method has a beautiful glitter appearance with no surface haze because the thermoplastic resin molded article of the present invention is excellent in surface smoothness.
[0023]
  Also,thisThe thermoplastic resin composition for direct vapor deposition is excellent in both impact resistance and weather resistance.
[0024]
Furthermore, the molded article made of the thermoplastic resin composition for direct vapor deposition according to the present invention can be bonded to a transparent resin such as PC resin or PMMA resin by a hot plate welding method. In addition, the stringing phenomenon hardly occurs at that time, the appearance of the bonded portion is excellent, and the bonding strength is sufficiently high.
[0025]
Therefore, the thermoplastic resin composition of the present invention is suitable for, for example, a vehicle lamp housing and the present invention can efficiently produce a vehicle lamp excellent in glitter, appearance, weather resistance, and impact resistance. it can.
[0026]
Hereinafter, the present invention will be described in detail.
[0027]
As described above, the thermoplastic resin composition for direct vapor deposition of the present invention contains the graft copolymer (A) described later, and further, if necessary, an aromatic alkenyl compound, a vinyl cyanide compound or ( A vinyl (co) polymer (B), polycarbonate and / or polyester (C) obtained by polymerizing a monomer containing any one or more of (meth) acrylic acid alkyl esters may be contained.
[0028]
The content of each of these components is excellent in impact strength, weather resistance, and glitter after direct vapor deposition of the resulting resin composition. Therefore, when the total is 100 parts by mass, the graft copolymer (A) 5 ~ 100 parts by weight, vinyl (co) polymer (B) 95-0 parts by weight, graft copolymer (A) 5-80 parts by weight, vinyl (co) polymer (B) 75 ˜0 parts by mass, polycarbonate and / or polyester (C) is preferably 95 to 20 parts by mass. Especially, when using a vinyl type (co) polymer (B), it is preferable that it is 20 mass parts or more, especially 30 mass parts or more, and 90 mass parts or less, It is especially preferable that it is 80 mass parts or less. . Moreover, when using a polycarbonate and / or polyester (C), it is preferable that it is 20 mass parts or more, especially 30 mass parts or more, and it is 90 mass parts or less, It is especially preferable that it is 80 mass parts or less.
[0029]
  In addition, the present inventionUse inIn the resin composition for direct vapor deposition, other thermoplastic resins which will be described later may be blended within a range that does not significantly impede various performances aimed at by the present invention.
[0030]
The graft copolymer (A) used in the present invention is a polyorganosiloxane in which silicon atoms having three or more siloxane bonds are 1 mol% or less (including 0) based on all silicon atoms in polydimethylsiloxane. It is obtained by graft polymerization of a vinyl polymer composed of one or more monomer components onto a composite rubber-like polymer (G) composed of a (meth) acrylate polymer. . A graft copolymer (A) may be used independently, or may use 2 or more types together, and can be arbitrarily selected by a use.
[0031]
In the polyorganosiloxane constituting the graft copolymer (A) according to the present invention, silicon atoms having 3 or more siloxane bonds are 1 mol% or less (including 0) with respect to all silicon atoms in the polydimethylsiloxane. is there. When it is 1 mol% or less, the impact strength of the finally obtained thermoplastic resin composition is excellent. Moreover, since both the impact strength of the thermoplastic resin composition obtained and the glitter after direct vapor deposition become favorable, it is more preferable that it is 0.8 mol% or less.
[0032]
At that time, it is preferable to use a polyorganosiloxane containing a vinyl polymerizable functional group. The siloxane unit containing a vinyl polymerizable functional group in the polyorganosiloxane can be sufficiently combined with the polyorganosiloxane and the (meth) acrylic ester rubber, and the thermoplastic resin composition molded article finally obtained The polyorganosiloxane hardly bleeds out on the surface of the film, and the glossiness after direct vapor deposition of the molded product becomes good. Therefore, it is preferably 0.3 mol% or more. In addition, since the final thermoplastic resin composition has both excellent impact resistance and glitter after direct vapor deposition, 0.5 mol of siloxane units containing a vinyl polymerizable functional group in the polyorganosiloxane. % Or more is more preferable.
[0033]
Moreover, since the impact resistance of the thermoplastic resin composition finally obtained is excellent, the siloxane unit containing the vinyl polymerizable functional group in polyorganosiloxane is preferably 3 mol% or less. In addition, since the finally obtained thermoplastic resin composition has excellent impact resistance and brightness after direct vapor deposition, the content of siloxane units containing vinyl polymerizable functional groups in the polyorganosiloxane is 2 mol% or less. In particular, it is more preferably 1 mol% or less.
[0034]
As the polyorganosiloxane, in particular, a silicon atom having 3 or more siloxane bonds is 1 mol% or less with respect to all silicon atoms in the polydimethylsiloxane, and a siloxane unit containing a vinyl polymerizable functional group is 0.3 to 0.3%. It is preferable to use a polyorganosiloxane composed of 3 mol% and dimethylsiloxane units 97 to 99.7 mol%.
[0035]
Examples of the dimethylsiloxane used in the production of the polyorganosiloxane include a dimethylsiloxane-based cyclic body having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These are used alone or in admixture of two or more.
[0036]
The siloxane containing a vinyl polymerizable functional group used in the production of polyorganosiloxane contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. In consideration of the reactivity with dimethylsiloxane, it is preferable to use various alkoxysilane compounds containing a vinyl polymerizable functional group. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and other methacryloyloxysiloxanes, tetramethyltetravinylcyclotetrasiloxane and other vinylsiloxanes, p-vinylphenyldimethoxymethylsilane, and γ-mercaptopropyl And mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.These siloxanes containing vinyl polymerizable functional groups are used alone or as a mixture of two or more.
[0037]
The size of the polyorganosiloxane particles is not particularly limited, but for the purpose of improving the glitter after direct vapor deposition of the thermoplastic resin composition finally obtained, the mass average particle diameter may be 600 nm or less, particularly 200 nm or less. preferable.
[0038]
In order to produce polyorganosiloxane, first, an emulsifier and water are added and emulsified into a mixture of dimethylsiloxane and siloxane containing a vinyl polymerizable functional group to obtain a latex. Next, the latex is microparticulated using a homomixer that microparticulates with a shearing force generated by high-speed rotation, a homogenizer that microparticulates with a jet output from a high-pressure generator, or the like. Use of a high-pressure emulsifier such as a homogenizer is preferable because the particle size distribution of the polyorganosiloxane latex becomes small. Then, the latex after the micronization is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. The polymerization is stopped by cooling the reaction solution and further neutralizing with an alkaline substance such as caustic soda, caustic potash or sodium carbonate.
[0039]
The acid catalyst may be added in advance by mixing the acid catalyst with a siloxane mixture, an emulsifier and water, or by dropping a high-temperature aqueous acid solution at a constant rate into the latex in which the siloxane mixture is finely divided. However, since it is easy to control the particle diameter of the resulting polyorganosiloxane, a method in which the latex in which the siloxane mixture is made fine is dropped into a high-temperature acid aqueous solution at a constant rate is preferable.
[0040]
The polymerization time is preferably 2 hours or longer, particularly 5 hours or longer when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form a fine particle for polymerization. In the method in which the latex in which the siloxane mixture is atomized is dropped into the aqueous solution of the acid catalyst, it is preferable to hold the latex for about 1 hour after the end of the dropping of the latex.
[0041]
The polymerization temperature is preferably 50 ° C. or higher, particularly 80 ° C. or higher. The upper limit of the polymerization temperature is not particularly defined, but is usually about 95 ° C.
[0042]
The emulsifier used is preferably an anionic emulsifier such as sodium alkylbenzene sulfonate or sodium polyoxyethylene nonylphenyl ether sulfate, and among them, a sulfonic acid emulsifier such as sodium alkylbenzene sulfonate or sodium lauryl sulfonate is preferred. . These emulsifiers may be used alone or in combination of two or more. The amount of the emulsifier is usually 0.05 parts by mass or more with respect to 100 parts by mass of the siloxane mixture because the dispersion state is stable and an emulsified state with a fine particle size can be maintained. The color of the molded product is hardly affected by the color of the thermoplastic resin composition and the deterioration of the thermoplastic resin composition resulting from it, and therefore it is preferably 5 parts by mass or less with respect to 100 parts by mass of the siloxane mixture.
[0043]
Examples of the acid catalyst used for polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts may be used singly or in combination of two or more. As the acid catalyst, aliphatic substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable because it is excellent in stabilizing action of the polyorganosiloxane latex. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the effect of the color of the emulsifier used in the polyorganosiloxane latex on the color of the thermoplastic resin composition molded product can be reduced. The addition amount may be determined as appropriate, but is usually about 0.1 to 20 parts by mass with respect to 100 parts by mass of the siloxane mixture.
[0044]
The (meth) acrylic acid ester polymer constituting the composite rubber-like polymer (G) contains at least one (meth) acrylic acid alkyl ester monomer or (meth) acrylic acid alkyl ester monomer. It is obtained by polymerizing a monomer mixture. The (meth) acrylic acid ester polymer may contain a monomer other than the (meth) acrylic acid alkyl ester monomer.
[0045]
Examples of the (meth) acrylic acid alkyl ester monomer include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Examples include methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Especially, since the impact resistance of the obtained resin composition is excellent, it is preferable to use n-butyl acrylate. These may be used alone or in combination of two or more.
[0046]
The polymerization can be performed according to a known method. Moreover, you may use a graft crossing agent and a crosslinking agent so that it may mention later.
[0047]
Although it does not restrict | limit especially as a method to manufacture the composite rubber-like polymer (G) used by this invention, Hetero-aggregation or co-enlargement of the separate latex of a polyorganosiloxane and a (meth) acrylic acid ester type polymer And a method of polymerizing a monomer (including a mixture) that forms one or more other polymers in the presence of any one or more latexes to form a composite. Among them, the resulting resin composition is excellent in impact resistance and glitter after direct vapor deposition, so that the (meth) acrylic acid ester monomer (including the mixture) as described above is present in the presence of latex polyorganosiloxane. A method of polymerizing is preferred.
[0048]
Moreover, it is also possible to use a graft crossing agent and a crosslinking agent as needed. Examples of the grafting and crosslinking agents that can be used include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, and 1,3 dimethacrylate. -Butylene glycol diester, 1,4-butylene glycol diester dimethacrylic acid, etc. are mentioned. These may be used alone or in combination of two or more. Although the addition amount may be determined as appropriate, since the resulting resin composition is excellent in impact resistance and glitter after direct vapor deposition, it is based on 100 parts by weight of (meth) acrylic acid ester monomer (including mixture). It is preferable that it is about 0.3-6 mass parts.
[0049]
A monomer mixture composed of these (meth) acrylic acid alkyl esters and, if necessary, a graft cross-linking agent or a crosslinking agent, in a polyorganosiloxane in a latex state, or continuously, or The polyorganosiloxane / (meth) acrylic acid ester-based composite rubbery polymer (G) can be obtained by intermittent supply and radical polymerization.
[0050]
The ratio of the polyorganosiloxane / (meth) acrylic acid ester polymer constituting the composite rubber-like polymer (G) is excellent in impact resistance of the resulting resin composition. The meth) acrylate polymer (monomer mixture) is preferably 99% by mass or less, and the resin composition obtained has an excellent balance between impact resistance and glitter after direct vapor deposition. It is preferable that they are 90 mass% or less of organosiloxane and 10 mass% or more of (meth) acrylic acid ester polymer (monomer mixture). When the amount of polyorganosiloxane in the composite rubber-like polymer (G) is within this range, the resulting resin composition is excellent in impact resistance and glitter after direct vapor deposition. The amount of the polyorganosiloxane in the composite rubber-like polymer (G) is preferably 2% by mass or more, more preferably 3% by mass or more, and 50% by mass or less, particularly preferably 10% by mass or less. More preferred.
[0051]
The mass average particle diameter of the composite rubber-like polymer (G) is not particularly limited, but is preferably less than 400 nm, more preferably 300 nm or less, because the resulting resin composition has excellent glitter appearance after direct vapor deposition. . Further, the lower limit of the mass average particle diameter of the composite rubber-like polymer (G) is not particularly defined, but is usually about 30 nm.
[0052]
Further, since a molded product having a high level of glittering appearance can be obtained, the rubber-like weight having a particle diameter of 500 nm or more per 100% by mass of the total rubber-like polymer in the resin composition containing the composite rubber-like polymer (G). The proportion of coalescence is preferably 4% by mass or less (including 0% by mass), particularly 3% by mass or less, and more preferably 2% by mass or less.
[0053]
The graft polymer (A) is a composite of the above-described composite rubber-like polymer (G), and is a vinyl monomer, preferably an aromatic alkenyl compound, a (meth) acrylic acid alkyl ester, or a vinyl cyanide compound. These monomer components can be produced by emulsion graft polymerization.
[0054]
Among the monomer components, examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene and the like. Examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Among these, since the impact resistance of the obtained thermoplastic resin composition is excellent, it is preferable to use a mixture of styrene and acrylonitrile as the monomer component. The content of styrene in 100% by mass of the mixture is preferably 10% by mass or more, and preferably 90% by mass or less. On the other hand, since the resulting thermoplastic resin composition is excellent in glitter after direct vapor deposition, it is preferable to use methyl methacrylate alone or a mixture containing preferably 50% by mass or more of methyl methacrylate as a monomer component. .
[0055]
The mass ratio of the rubber-like polymer (G) to be subjected to emulsion graft polymerization and the vinyl monomer is that the finally obtained thermoplastic resin composition is excellent in impact resistance, and the glitter after direct vapor deposition is also good. The rubber-like polymer (G) is preferably 10% by mass or more, and the vinyl monomer is preferably 90% by mass or less. In addition, the mass ratio of the rubber-like polymer (G) to be subjected to emulsion graft polymerization and the vinyl monomer is excellent in impact resistance of the finally obtained thermoplastic resin composition, so that the rubber-like polymer (G ) Is 80% by mass or less, and the vinyl monomer is preferably 20% by mass or more. When emulsion graft polymerization is performed at such a mass ratio, the finally obtained thermoplastic resin composition has excellent impact resistance and fluidity, and glitter after direct vapor deposition.
[0056]
In particular, the mass ratio of the rubber-like polymer (G) to be subjected to emulsion graft polymerization and the vinyl monomer is such that the rubber-like polymer (G) is 30% by mass or more and the vinyl monomer is 70% by mass or less. Moreover, it is preferable that rubber-like polymer (G) is 70 mass% or less, and a vinyl-type monomer is 30 mass% or less. When emulsion graft polymerization is performed at such a mass ratio, the finally obtained thermoplastic resin composition exhibits a good balance between good impact resistance and direct vapor deposition appearance excellent in glitter.
[0057]
The graft polymer (A) can be produced by performing radical polymerization using an emulsifier. Further, in the monomer component, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component, such as mercaptan compounds, terpene compounds, α-methylstyrene dimers, and the like may be added. . The polymerization conditions are not particularly limited, and can be appropriately selected as necessary.
[0058]
As the radical polymerization initiator used in producing the (meth) acrylic acid ester polymer or graft polymer (A) of the composite rubber-like polymer (G), a peroxide, an azo initiator, or an oxidation is used. A redox initiator combined with an agent / reducing agent can be used. Among them, it is preferable to use a redox initiator, and in particular, redox in which ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longarit, hydroperoxide are combined. It is preferable to use a system initiator.
[0059]
Although it does not restrict | limit especially as an emulsifier used when manufacturing the (meth) acrylic acid ester type polymer and graft polymer (A) of the above-mentioned composite rubber-like polymer (G), it is in stability of the latex at the time of emulsion polymerization. Excellent, because the polymerization rate is increased, various carboxylates such as sodium sarcosine, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, rosin acid soap, alkyl sulfate, sodium alkylbenzene sulfonate, polyoxyethylene nonyl phenyl ether sulfate It is preferable to use an anionic emulsifier such as sodium ester. These are properly used according to the purpose. Further, the emulsifier used for the preparation of the rubbery polymer may be used as it is, and may not be added at the time of emulsion graft polymerization.
[0060]
The graft copolymer (A) latex obtained by emulsion graft polymerization can be used for, for example, a wet method in which a coagulant is dissolved in hot water to coagulate in a slurry state, or a graft copolymer in a heated atmosphere. The graft copolymer (A) can be recovered as a graft copolymer (A) by a method such as a spray drying method in which the graft copolymer (A) is recovered semi-directly by spraying the polymer (A) latex.
[0061]
As the coagulant used in the wet recovery method, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate can be used. The coagulant used is selected in combination with the emulsifier used in the polymerization. That is, when only a carboxylic acid soap such as a fatty acid soap or a rosin acid soap is used as an emulsifier, the graft polymer (A) can be recovered using any coagulant. In the case where an emulsifier exhibiting a stable emulsifying power is contained even in an acidic region, the above-mentioned inorganic acid is insufficient, and a metal salt needs to be used as a coagulant.
[0062]
In order to make the graft copolymer (A) in a dry state from the slurry-like graft copolymer (A) obtained by the wet recovery method, first, the remaining emulsifier residue is eluted in water and washed. After the slurry is dehydrated with a centrifugal or press dehydrator, etc. and then dried with an air dryer, etc., after being subjected to a process such as a method of simultaneously performing dehydration and drying with a press dehydrator or extruder, etc., the dried graft copolymer The coalescence (A) can be obtained in the form of powder or particles. At this time, the product discharged from the press dehydrator or the extruder can be directly sent to an extruder or a molding machine for producing the thermoplastic resin composition to obtain a molded product.
[0063]
The vinyl (co) polymer (B) that can be used in the thermoplastic resin composition of the present invention is a monomer containing at least one of an aromatic alkenyl compound, a vinyl cyanide compound, and a (meth) acrylic acid alkyl ester. It is a (co) polymer obtained by polymerizing (including a mixture). By including the vinyl (co) polymer (B), effects other than the object of the present invention, such as improving the molding processability of the resulting thermoplastic resin composition and imparting heat resistance, are imparted. Can be selected according to its purpose.
[0064]
The vinyl (co) polymer (B) is a copolymer obtained by polymerizing a monomer mixture containing monomers other than an aromatic alkenyl compound, a vinyl cyanide compound and an alkyl (meth) acrylate. For example, a copolymer obtained by polymerizing a monomer mixture composed of an aromatic alkenyl compound, a vinyl cyanide compound and an N-substituted maleimide is also preferable.
[0065]
As the aromatic alkenyl compound, the vinyl cyanide compound, and the (meth) acrylic acid alkyl ester constituting these, those similar to those used in the aforementioned graft polymerization can be used.
[0066]
Examples of monomer components other than these include maleimide monomers and maleic anhydride. Examples of the maleimide monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide and the like.
[0067]
Specific examples of the vinyl (co) polymer (B) include acrylonitrile-styrene copolymer (SAN) resin, polymethyl methacrylate (PMMA) resin, styrene-methyl methacrylate copolymer (MS) resin, and acrylonitrile. Preferred are resins such as -α methylstyrene copolymer (αSAN) resin, styrene-acrylonitrile-N-phenylmaleimide terpolymer (SAM) resin, polystyrene resin, acrylonitrile-styrene-methyl methacrylate terpolymer. The vinyl (co) polymer (B) may be used alone or in combination of two or more.
[0068]
The vinyl (co) polymer (B) can be of any molecular weight.
[0069]
The polycarbonate (C) that can be used in the thermoplastic resin composition of the present invention is obtained from a dihydroxydiarylalkane, and may be arbitrarily branched. By containing the polycarbonate (C), the heat resistance and impact resistance of the resulting thermoplastic resin composition can be improved.
[0070]
The dihydroxyarylalkane may have an alkyl group, a chlorine atom or a bromine atom in the ortho position with respect to the hydroxy group. As the dihydroxydiarylalkane, 4,4'-dihydroxy-2,2'-diphenylpropane (bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene and the like are preferable.
[0071]
Polycarbonate (C) having an arbitrary molecular weight can be used.
[0072]
The polycarbonate (C) can be produced by a known method, and is generally produced by reacting a dihydroxy compound or a polyhydroxy compound with phosgene or a diester of carbonic acid.
[0073]
The branched polycarbonate is produced, for example, by substituting a part of the dihydroxy compound, for example, 0.2 to 2 mol% with a polyhydroxy compound. Examples of the polyhydroxy compound include 1,4-bis (4 ′, 4,2-dihydroxytriphenylmethyl) -benzene, fluorodalcinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane, 1,3,5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri (4-hydroxyphenyl) -ethane, 2,2-bis [4,4 ′-(4,4′-dihydroxyphenyl) cyclohexyl] propane and the like.
[0074]
Polycarbonate (C) may be used independently or may use 2 or more types together.
[0075]
The polyester (C) that can be used in the thermoplastic resin composition of the present invention is mainly composed of polyalkylene terephthalate, and has an aromatic dicarboxylic acid having 8 to 22 carbon atoms and an alkylene glycol having 2 to 22 carbon atoms. It is preferable to contain 50% by mass or more of cycloalkylene glycol. By containing polyester (C), the moldability and chemical resistance of the resin composition can be improved.
[0076]
Further, the polyester (C) may preferably contain 80% by mass or less of an aliphatic dicarboxylic acid, for example, adipic acid or sebacic acid as a structural unit, if desired. The polyester (C) may contain a polyalkylene glycol such as polyethylene glycol as a structural unit.
[0077]
Polyester (C) to be used is particularly preferably polyethylene terephthalate, polytetramethylene terephthalate, or the like.
[0078]
Polyester (C) having an arbitrary molecular weight can be used.
[0079]
Polyester (C) may be used independently or may use 2 or more types together.
[0080]
Moreover, when using these polycarbonate and polyester, each may be used independently and may be used together in arbitrary ratios as needed.
[0081]
In the resin composition for direct vapor deposition of the present invention, if necessary, other thermoplastic resins can be blended within a range that does not significantly disturb the various performances targeted by the present invention.
[0082]
Other thermoplastic resins are not particularly limited, for example, polyolefins such as polyvinyl chloride, polyethylene, polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene. (SIS) and other styrene elastomers, various olefin elastomers, various polyester elastomers, polyacetal resins, modified polyphenylene ethers (modified PPE resins), ethylene-vinyl acetate copolymers, PPS resins, PES resins, PEEK resins, polyarylate , Liquid crystal polyester resin, polyamide resin (nylon), ABS resin other than the present invention, ASA resin, and styrene-acrylonitrile-silicone (SAS) resin. These other thermoplastic resins may be used alone or in combination of two or more.
[0083]
It is preferable that the usage-amount of these other thermoplastic resins is 80 mass parts or less in 100 mass parts of thermoplastic resin compositions.
[0084]
  The present inventionUse inThe thermoplastic resin composition is composed of a graft copolymer (A), vinyl (co) polymer (B), polycarbonate and / or polyester (C), if necessary, and other thermoplastic resins in a V-type blender or Henschel. It can be produced by mixing and dispersing using a mixer or the like, and melt-kneading the mixture using an extruder or a Banbury mixer, a kneader such as a pressure kneader, or a roll.
[0085]
The obtained thermoplastic resin composition is left as it is or after blending additives such as dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers as necessary, It can be used as a raw material for producing molded products. This thermoplastic resin composition is made into a target molded article by various molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method.
[0086]
The molded product of the thermoplastic resin composition of the present invention subjected to primary processing by the above-described various molding methods, as described above, without performing a special pretreatment such as formation of an undercoat treatment layer, Surface metallizing treatment such as aluminum or chromium can be performed by sputtering. The bright surface that has been subjected to metallization may be used as it is, but in order to protect it from the occurrence of scratches caused by dust or the like, it is possible to perform a top coat process in which a silicon-based film is formed by coating or the like.
[0087]
Examples of industrial applications of the thermoplastic resin composition of the present invention include vehicle parts, particularly home lamp parts such as head lamp and tail lamp housings, lighting equipment housings, OA equipment housings, interior members, and the like.
[0088]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these. In the following examples and comparative examples,% and parts are based on mass unless otherwise specified.
[0089]
[Production Example 1] Production of polyorganosiloxane (L-1) latex
98 parts of octamethylcyclotetrasiloxane
2 parts γ-methacryloyloxypropyldimethoxymethylsilane
Were mixed to obtain 100 parts of a siloxane-based mixture. to this,
0.67 parts sodium dodecylbenzenesulfonate
300 parts of ion exchange water
After adding an aqueous solution consisting of 2 and stirring at 10000 rpm for 2 minutes with a homomixer, 200 kg / cm is added to the homogenizer.²At a pressure of 1 to obtain a stable premixed organosiloxane latex.
[0090]
Meanwhile, in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device,
10 parts of dodecylbenzenesulfonic acid
90 parts of ion exchange water
Was added to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid.
[0091]
While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours. After the completion of the addition, the temperature was maintained for 1 hour, and then cooled to 40 ° C. or lower. Next, this reaction product was neutralized to pH 7 with an aqueous caustic soda solution to complete the polymerization.
[0092]
The polyorganosiloxane (L-1) latex thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. Further, the mass average particle diameter of the polyorganosiloxane (L-1) in the latex was 50 nm, and the ratio of the rubbery polymer having a particle diameter of 500 nm or more was almost 0%. In addition, siloxane units containing vinyl polymerizable functional groups in polydimethylsiloxane were 0.65 mol%, and silicon atoms having three or more siloxane bonds were 0 mol% with respect to all silicon atoms in polydimethylsiloxane. It was.
[0093]
[Production Example 2] Production of polyorganosiloxane (L-2) latex
95.5 parts octamethylcyclotetrasiloxane
γ-methacryloyloxypropyldimethoxymethylsilane 0.5 part
4 parts of tetraethoxysilane
Were mixed to obtain 100 parts of a siloxane-based mixture. to this,
1 part dodecylbenzenesulfonic acid
Sodium dodecylbenzenesulfonate 1 part
200 parts of ion exchange water
After adding an aqueous solution consisting of 2 and stirring at 10000 rpm for 2 minutes with a homomixer, 200 kg / cm in a homogenizer²At a pressure of 1 to obtain a stable premixed organosiloxane latex.
[0094]
This premixed organosiloxane latex is put into a reactor equipped with a cooling tube, a jacket heater and a stirrer, heated at 80 ° C. for 5 hours with stirring and mixing, then cooled to about 20 ° C. and left as it is for 48 hours. did. The reaction was then neutralized with aqueous sodium hydroxide to pH 7.0 to complete the polymerization.
[0095]
The polyorganosiloxane (L-2) latex thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 36.5%. The mass average particle diameter of the polyorganosiloxane (L-2) in the latex was 160 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more was 0.3%. In addition, siloxane units containing a vinyl polymerizable functional group in polydimethylsiloxane are 0.3 mol%, and silicon atoms having three or more siloxane bonds are 1.5 mol% with respect to all silicon atoms in polydimethylsiloxane. Met.
[0096]
[Production Example 3] Production of polyorganosiloxane (L-3) latex
Polymerization was conducted in the same manner as in Production Example 1 except that the composition of the siloxane mixture used was 96 parts octamethylcyclotetrasiloxane, 2 parts γ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts tetraethoxysilane. The proportion of particles having a mass average particle size of 50 nm and a particle size of 500 nm or more is approximately 0%, the methacrylosiloxane unit is 0.7 mol%, and the silicon atom having 3 or more siloxane bonds is 1. It was 2 mol%.
[0097]
[Production Example 4] Production of polyorganosiloxane / acrylic ester composite rubber-based graft polymer (A-1)
Produced in Production Example 1 in a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer
Polyorganosiloxane latex (L-1, solid content) 8 parts
Emar NC-35 (polyoxyethylene alkylphenyl ether sulfate; manufactured by Kao Corporation) 0.2 part
148.5 parts of ion-exchanged water
After mixing and mixing
42 parts of n-butyl acrylate
Allyl methacrylate 0.3 parts
1,3-butylene glycol dimethacrylate 0.1 part
t-Butyl hydroperoxide 0.11 parts
A mixture consisting of was added.
[0098]
The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C.
Ferrous sulfate heptahydrate 0.000075 parts
Ethylenediaminetetraacetic acid disodium salt 0.000225 parts
Rongalit 0.2 parts
10 parts of ion exchange water
An aqueous solution consisting of was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state was maintained for 1 hour, and the polymerization of the acrylate component was completed to obtain a latex of a composite rubber-like polymer of polyorganosiloxane (L-1) and acrylic acid-n-butyl rubber.
[0099]
The mass average particle diameter of the composite rubber-like polymer is 120 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more is 0.1% in 100% by mass of the composite rubber-like polymer (solid content). It was.
[0100]
Furthermore, after the liquid temperature inside the reactor has decreased to 70 ° C.,
Longarit 0.25 parts
10 parts of ion exchange water
An aqueous solution consisting of
Acrylonitrile 2.5 parts
Styrene 7.5 parts
t-Butyl hydroperoxide 0.05 parts
Was added dropwise over 2 hours to polymerize. After the completion of the dripping, after maintaining the temperature at 60 ° C. for 1 hour,
Ferrous sulfate heptahydrate 0.001 part
Ethylenediaminetetraacetic acid disodium salt 0.003 parts
Rongalit 0.2 parts
Emar NC-35 (Kao Corporation) 0.2 parts
10 parts of ion exchange water
An aqueous solution consisting of
Acrylonitrile 10 parts
30 parts of styrene
t-Butyl hydroperoxide 0.2 parts
The mixture consisting of was dropped over 2 hours and polymerized. After the completion of dropping, after maintaining the temperature at 60 ° C. for 0.5 hour
Cumene hydroperoxide 0.05 parts
Is added, and the temperature is maintained at 60 ° C. for 0.5 hours, followed by cooling and graft polymerization of acrylonitrile and styrene onto a composite rubber-like polymer composed of polyorganosiloxane (L-1) and butyl acrylate rubber. A graft polymer latex was obtained.
[0101]
Next, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of a graft polymer latex was gradually dropped into the solution to solidify. Then, the precipitate was dehydrated, washed and dried to obtain a polyorganosiloxane / acrylic acid ester composite rubber-based graft polymer (A-1).
[0102]
[Production Example 5] Production of polyorganosiloxane / acrylic acid ester composite rubber graft polymer (A-2)
In Production Example 4, the first stage mixture was
Acrylonitrile 5 parts
15 parts of styrene
t-Butyl hydroperoxide 0.1 parts
To the second stage mixture,
Methyl methacrylate 28.5 parts
1.5 parts of methyl acrylate
t-Butyl hydroperoxide 0.15 parts
Polymerization was carried out in the same manner except for the above, and a composite rubber-like polymer composed of polyorganosiloxane (L-1) and butyl acrylate rubber was converted into acrylonitrile and styrene in the first stage, and methyl methacrylate and acrylic in the second stage. A graft polymer latex obtained by graft polymerization of methyl acid was obtained.
[0103]
Subsequently, coagulation, dehydration, washing and drying were carried out in the same manner as in Production Example 4 to obtain a polyorganosiloxane / acrylic acid ester composite rubber graft polymer (A-2).
[0104]
[Production Example 6] Production of polyorganosiloxane / acrylic acid ester composite rubber-based graft polymer (A-3)
Produced in Production Example 1 in a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer
Polyorganosiloxane latex (L-1, solid content) 2 parts
Emar NC-35 (polyoxyethylene alkylphenyl ether sulfate; manufactured by Kao Corporation) 0.2 part
148.5 parts of ion-exchanged water
After mixing and mixing
48 parts of n-butyl acrylate
Allyl methacrylate 1.08 parts
1,3-butylene glycol dimethacrylate 0.36 parts
t-butyl hydroperoxide 0.11 parts
A mixture consisting of was added.
[0105]
The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C.
Ferrous sulfate heptahydrate 0.000075 parts
Ethylenediaminetetraacetic acid disodium salt 0.000225 parts
Rongalit 0.2 parts
10 parts of ion exchange water
An aqueous solution consisting of was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state was maintained for 1 hour, and the polymerization of the acrylate component was completed to obtain a latex of a composite rubber-like polymer of polyorganosiloxane (L-1) and acrylic acid-n-butyl rubber.
[0106]
The mass average particle diameter of the composite rubber-like polymer is 145 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more is 0.3% in 100 mass% of the composite rubber-like polymer (solid content). It was.
[0107]
Graft polymerization was carried out in the same manner as in Production Example 4 except that the obtained composite rubber was used, and the composite rubber-like polymer composed of polyorganosiloxane (L-1) and acrylic acid-n-butyl rubber was added to acrylonitrile, A graft polymer latex obtained by graft polymerization of styrene was obtained.
[0108]
Subsequently, coagulation, dehydration, washing and drying were performed in the same manner as in Production Example 4 to obtain a polyorganosiloxane / acrylic acid ester composite rubber graft polymer (A-3).
[0109]
[Production Example 7] Production of polyorganosiloxane / acrylic acid ester composite rubber-based graft polymer (a-4)
Produced in Production Example 2 in a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer
Polyorganosiloxane latex (L-2)
(30 parts as solid content) 82.1 parts
Additional ion exchange water (total 295 parts) 242.9 parts
Was charged with nitrogen, and the temperature was raised to 50 ° C.
N-butyl acrylate 37.5 parts
Allyl methacrylate 2.5 parts
t-Butyl hydroperoxide 0.3 parts
The mixture consisting of was added and stirred for 30 minutes. Then
Ferrous sulfate heptahydrate 0.0003 parts
Ethylenediaminetetraacetic acid disodium salt 0.001 part
Rongalit 0.17 parts
5 parts of ion exchange water
An aqueous solution consisting of was added to initiate radical polymerization. Thereafter, the inner temperature was maintained at 70 ° C. for 2 hours to complete the polymerization of the acrylate component to obtain a composite rubber-like polymer latex of polyorganosiloxane (L-2) and butyl acrylate.
[0110]
The mass average particle diameter of the composite rubber-like polymer was 190 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more was 3% in 100 mass% of the composite rubber-like polymer (solid content).
[0111]
To this composite rubber latex,
9 parts acrylonitrile
21 parts of styrene
t-Butyl hydroperoxide 0.3 parts
The mixture consisting of the above was dropped at an internal temperature of 70 ° C. over 45 minutes, and then maintained at 70 ° C. for 4 hours to complete graft polymerization onto the composite rubber-like polymer.
[0112]
Next, this graft polymer latex was put into the same amount of 12% aqueous calcium chloride solution (water temperature: 60 ° C.) with stirring, and then kept at 80 ° C. for 5 minutes and further at 95 ° C. for 5 minutes. It solidified. The precipitate was separated, washed and dehydrated, and then dried at 85 ° C. for 24 hours to obtain a polyorganosiloxane / acrylic acid ester composite rubber-based graft polymer (a-4).
[0113]
[Production Example 8] Production of polyorganosiloxane / acrylic acid ester composite rubber-based graft polymer (a-5)
Polymerization was carried out in the same manner as in Production Example 4 except that the polyorganosiloxane (L-1) used was changed to (L-3), and a polyorganosiloxane / acrylic ester composite rubber-based graft polymer (a-5) Got.
[0114]
At this time, the mass average particle diameter of the composite rubber-like polymer was 120 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more in 100 mass% of the composite rubber-like polymer was 2%.
[0115]
[Production Example 9] Production of polyorganosiloxane-based graft copolymer (a-6) In Production Example 4, 50 parts (solid content) of the composite rubber-like polymer to be used was converted to 50 polyorganosiloxane (L-1, solid content). Polymerization was carried out in the same manner except for changing to part, to obtain a polyorganosiloxane graft copolymer (a-6).
[0116]
[Production Example 10] Production of diene-based graft polymer (a-7)
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device,
50 parts of polybutadiene latex (mass average particle diameter 120 nm, ratio of particles having a particle diameter of 500 nm or more is 0.2%, solid content)
At room temperature,
140 parts of water (including water contained in rubbery polymer latex)
0.6 parts of glucose
0.01 parts of anhydrous sodium pyrophosphate
Ferrous sulfate heptahydrate 0.005 parts
Sodium hydroxide 0.1 part
Was added, and the atmosphere was replaced with nitrogen under stirring. to this,
Acrylonitrile 15 parts
35 parts of styrene
t-dodecyl mercaptan 0.5 part
Cumene hydroperoxide 0.3 parts
The mixture consisting of was added dropwise over 180 minutes, and the internal temperature was controlled so as not to exceed 65 ° C. After completion of dripping
Cumene hydroperoxide 0.12 parts
Was added and held for an additional hour to cool.
[0117]
The resulting latex is then
Anti-aging agent (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage W-400) 1 part
Was added to a 1.2% sulfuric acid aqueous solution (water temperature: 70 ° C.) in the same amount as the graft polymer latex, solidified, further heated to 90 ° C. and held for 5 minutes, and then dehydrated and washed. And dried to obtain a milky white powder diene graft polymer (a-7).
[0118]
[Production Example 11] Production of acrylic ester-based graft copolymer (a-8)
In Production Example 4, polymerization was carried out in the same manner except that polyorganosiloxane (L-1) was not used and the amount of acrylic acid-n-butyl used was 50 parts, and an acrylic ester graft copolymer ( a-8) was obtained.
[0119]
At this time, the mass average particle diameter of the rubber-like polymer was 110 nm, and the ratio of particles having a particle diameter of 500 nm or more was almost 0%.
[0120]
[Production Example 12] Production of acrylic ester-based graft copolymer (a-9)
10 parts of a polybutadiene latex having a solid content of 35% (pH 10, gel content 85%, mass average particle diameter 80 nm, solid content) is composed of 81.5% acrylic acid-n-butyl units and 18.5% methacrylic acid units. Add 0.2 parts (solid content) of an acid group-containing copolymer latex having a solid content of 33% and a mass average particle size of 80 nm with stirring, and continue stirring for 30 minutes to enlarge the diene rubber having a mass average particle size of 380 nm. A polymer latex was obtained. to this,
Dipotassium alkenyl succinate
(Latest ASK manufactured by Kao Corporation, the same as the actual amount below) 0.3 parts
175 parts of water (including water in enlarged butadiene polymer latex)
Under stirring,
40 parts of n-butyl acrylate
Allyl methacrylate 0.16 parts
1,8-butylene glycol dimethacrylate 0.08 parts
Tertiary butyl hydroperoxide 0.1 part
A mixture consisting of was added.
[0121]
The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reaches 50 ° C,
Ferrous sulfate heptahydrate 0.00015 parts
Ethylenediaminetetraacetic acid disodium salt 0.00045 parts
Rongalit 0.24 parts
5.0 parts of water
After adding an aqueous solution consisting of the above, the internal temperature was raised to 75 ° C. to initiate radical polymerization. This state was maintained for 1 hour to complete polymerization of the acrylate component, and a latex of a composite rubber-based rubbery polymer of an enlarged butadiene-based polymer and n-butyl acrylate rubber was obtained. The composite rubber-based rubber polymer latex had a mass average particle diameter of 300 nm and a ratio of particles having a particle diameter of 500 nm or more was 51%.
[0122]
next,
Rongalit 0.15 parts
0.65 part of dipotassium alkenyl succinate
10 parts of water
An aqueous solution consisting of
6.3 parts of acrylonitrile
Styrene 18.7 parts
Tertiary butyl hydroperoxide 0.11 parts
The mixture was added dropwise over 1 hour for polymerization. 5 minutes after the end of dropping,
Ferrous sulfate heptahydrate 0.001 part
Ethylenediaminetetraacetic acid disodium salt 0.003 parts
Rongalit 0.15 parts
5 parts of water
An aqueous solution dissolved in
6.3 parts of acrylonitrile
Styrene 18.7 parts
Tertiary butyl hydroperoxide 0.19 parts
Normal octyl mercaptan 0.014 parts
A mixture consisting of was dropped and polymerized over 1 hour. After completion of dropping, the temperature is maintained at 75 ° C. for 10 minutes, and then cooled, and when the internal temperature reaches 60 ° C.,
0.2 parts of antioxidant (Antage W500 manufactured by Kawaguchi Chemical Industry Co., Ltd.)
0.2 parts of dipotassium alkenyl succinate
5 parts of water
A dispersion consisting of was added. Through the above operation, a latex of a graft copolymer obtained by graft-polymerizing acrylonitrile / styrene onto a composite rubber-based rubbery polymer of an enlarged butadiene-based polymer and n-butyl acrylate rubber was obtained.
[0123]
Next, the polymerized latex was poured into a 0.6% aqueous solution of sulfuric acid heated to 45 ° C., which is 1.2 times the total latex, with stirring, and the polymer was coagulated. Next, the liquid temperature was raised to 65 ° C. and held for 5 minutes, and then the liquid temperature was raised to 90 ° C. Next, after separating the precipitate, the recovered material was poured into 10 times the amount of water and stirred for 10 minutes to carry out a washing treatment. This dispersion was dehydrated in a centrifugal dehydrator and further dried at 80 ° C. for 16 hours to obtain a graft copolymer (a-9).
[0124]
The mass average particle size and particle size distribution of the polymer in the latex described in the production examples were measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES.
[0125]
[Production Example 13] Production of vinyl-based (co) polymer (B-1)
Known suspension polymerization of acrylic resin (B-1) comprising 99 parts of methyl methacrylate and 1 part of methyl acrylate and having a reduced viscosity of 0.25 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution Manufactured by.
[0126]
[Production Example 14] Production of vinyl-based (co) polymer (B-2)
A known suspension polymerization of acrylonitrile-styrene copolymer (B-2) comprising 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of 0.60 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Manufactured by.
[0127]
[Production Example 15] Production of vinyl-based (co) polymer (B-3)
An acrylonitrile-styrene-N-phenylmaleimide ternary comprising 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide and having a reduced viscosity of 0.65 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Copolymer (B-3) was produced by known continuous solution polymerization.
[0128]
[Production Example 16] Production of vinyl-based (co) polymer (B-4)
An acrylonitrile-α-methylstyrene copolymer (B-4) comprising 25 parts of acrylonitrile and 75 parts of α-methylstyrene and having a reduced viscosity of 0.50 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. is known. Was prepared by continuous solution polymerization.
[0129]
[Examples 1 to 13 and Comparative Examples 1 to 9]
Graft polymers (A-1) to (A-3), (a-4) to (a-9), vinyl (co) polymers (B-1) to (B-4) produced in Production Examples Polycarbonate (C-1, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S2000F), polyester (C-2, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Toughpet N1300) are shown in Tables 1 and 2. (Numerical values in the table are based on mass) Further, 0.4 parts of ethylenebisstearylamide was added to 100 parts of these resin components, and then mixed using a Henschel mixer. Or it supplied to the deaeration type extruder (Nippon Steel Works Co., Ltd. TEX-30) heated at 260 degreeC, and knead | mixed, and the pellet was obtained.
[0130]
Then, using the obtained pellets, the Izod impact strength, weather resistance, glitter after direct vapor deposition, and hot plate weldability of the thermoplastic resin composition were measured and evaluated. The results are shown in Tables 1 and 2.
[0131]
(1) Izod impact strength
The measurement was carried out by a method according to ASTM D256, a notched, ¼ ”-thick test piece, which was left in a 23 ° C. atmosphere for 12 hours or longer, and then measured.
[0132]
(2) Weather resistance
A white colored plate of 100 mm × 100 mm × 3 mm was treated with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes) for 1,000 hours. And the weather resistance was evaluated by the degree of color change (ΔE) measured with a color difference meter in that case.
[0133]
(3) Brightness after direct vapor deposition
Using an injection molding machine “IS80FP” manufactured by Toshiba Machine Co., Ltd., a 100 mm × 100 mm × 3 mm plate was molded as a sample under the conditions of a cylinder set temperature of 230 ° C., a mold temperature of 70 ° C., and an injection speed of 99%. Next, the degree of vacuum reached 1 × 10 by vacuum deposition.^-6An aluminum vapor deposition film having a thickness of about 50 nm was formed at a Torr, a current value of 400 mA, and a film formation rate of 1.5 nm / s. And on this aluminum vapor deposition film, SiO₂The top coat layer was vacuum deposited.
[0134]
About the molded product which performed direct vapor deposition in this way, the regular reflectance (%) and the diffuse reflectance (%) were measured using a reflectometer (Murakami Color Research Laboratory "HR-100"). Evaluation of glitter was performed.
[0135]
(4) Hot plate weldability
A hot plate processed with a fluororesin is heated to a surface temperature of 300 ° C., a test sheet (30 mm × 100 mm × 3 mm) is brought into contact with the hot plate for 30 seconds, and then the test sheet is pulled up vertically. The stringing length was measured to evaluate the hot plate weldability. A stringing length of less than 1 mm was marked with ◎, a stringing length of 1 mm or more and less than 5 mm was marked with ◯, and a stringing length of 5 mm or more was marked with x.
[0136]
[Table 1]

[0137]
[Table 2]

[0138]
  Examples 1-14ofOf the resin composition for direct vapor depositionMolded productHas high Izod impact strength, good weather resistance, low diffuse reflectance after direct vapor deposition, and excellent glitter. Furthermore, the stringing length at the time of hot plate welding was short, and the hot plate weldability was also excellent.
[0139]
  Meanwhile, the thermoplastic resin compositions of Comparative Examples 1 to 9Molded productWas inferior in any of the items of Izod impact strength, weather resistance, and glitter after direct vapor deposition.
[0140]
Further, from Example 1 and Comparative Examples 1, 2, and 7, and from Example 11 and Comparative Example 8, the polyorganosiloxane contained in the graft copolymer (A) has three or more siloxane bonds. As the ratio of silicon atoms increased, the diffuse reflectance after direct deposition increased, and the glittering property tended to deteriorate.
[0141]
In particular, when the ratio of rubber having a particle diameter of 500 nm or more in 100% by mass of the total rubber-like polymer is 4% by mass or less as in Examples 1 to 8 and 10 to 14, it is not known so far. Izod impact strength, weather resistance, and glitter after direct deposition can be expressed.
[0142]
【The invention's effect】
  According to the present invention, a beautiful brilliant appearance is obtained after direct vapor deposition, and has a high level of mechanical strength such as impact resistance and weather resistance, and heat with a transparent resin such as PMMA resin or polycarbonate resin. Resin composition for direct vapor deposition with excellent plate weldabilityMolded product usingCan be provided.
[0143]
  In particular, the balance between impact resistance, weather resistance and glitter after direct deposition is,Conventionally known rubber-modified thermoplastic resin compositionsMolded products usingCompared with the present invention,Molded productIs for industrial useProductThe utility value is extremely high.

Claims (6)

A composite rubber comprising a polyorganosiloxane in which silicon atoms having three or more siloxane bonds are 1 mol% or less (including 0) with respect to all silicon atoms in polydimethylsiloxane and a (meth) acrylate polymer The surface of the molded product of the resin composition for direct vapor deposition containing the graft copolymer (A) formed by graft polymerization of a vinyl polymer composed of one or more kinds of monomer components on the polymer-like polymer (G) Molded product characterized by being metallized by direct vapor deposition . A resin composition for direct vapor deposition is further obtained by polymerizing a monomer containing any one or more of an aromatic alkenyl compound, a vinyl cyanide compound, and a (meth) acrylic acid alkyl ester. The molded article according to claim 1, comprising a coalescence (B). The resin composition for direct vapor deposition contains 5 to 100 parts by mass of the graft copolymer (A) and 95 to 0 parts by mass (100 parts by mass in total) of the vinyl (co) polymer (B). The molded product according to claim 1 or 2. The molded article according to claim 1 or 2, wherein the resin composition for direct vapor deposition further contains polycarbonate and / or polyester (C). The resin composition for direct vapor deposition contains 5 to 80 parts by mass of the graft copolymer (A), 75 to 0 parts by mass of the vinyl (co) polymer (B), and 95 to 20 of the polycarbonate and / or polyester (C). The molded product according to claim 4, comprising a mass part (100 mass parts in total). The total rubbery polymer comprising a composite rubber-like polymer (G), any one of claims 1 to 5, wherein the ratio of the particle diameter 500nm or more rubber-like polymer is not more than 4 wt% molded article according to.