JP2004263034A - Methacrylic resin composition and laminate using the same - Google Patents

Abstract

An object of the present invention is to provide a methacrylic resin composition which is excellent in impact resistance, lubricity and matting property and is suitable as a coating layer of a laminate.
A methacrylic resin composition comprising a methacrylic resin (A), acrylic multilayer polymer particles (B), and silicone fine particles (C) having an average particle diameter of 0.2 to 20 μm, and the methacrylic resin. The above problem is solved by a laminate having a layer made of the composition.
[Selection diagram] None

Description

【００５７】
＜実施例２＞
実施例１のメタクリル系樹脂組成物のペレットを被覆層の樹脂、塩ビ樹脂（信越ポリマー製ＥＸ−２８２Ｅ）を基材層の樹脂として、それぞれサブ押出機（２３０℃；Ｌ／Ｄ＝３２；３０ｍｍφ）、メイン押出機（１９０℃；Ｌ／Ｄ＝３２；４０ｍｍφ）から押出すことによって共押出しを行った。積層シートの厚みはポリシングロールのクリアランスで調整し、被覆層の厚みは吐出量で調整した。得られた積層シートの基材層および被覆層の厚みはそれぞれ２．０ｍｍおよび２００μｍであった。
積層シートにはフローマークや界面白化等の欠点は無く、被覆層と基材層の接着も十分であった。
【００５８】
＜実施例３〜８＞
基材層の樹脂の種類とメイン押出機の温度を表２のように変更した以外は実施例２と同様に行った。
いずれの積層シートにもフローマークや界面白化等の欠点は無く、被覆層と基材層の接着も十分であった。
【００５９】
【表２】

【００６０】
以上、本発明の実施例１と比較例１および２を比較すると、シリコーン微粒子を添加しない点で本発明と異なる比較例１は動摩擦係数が大きく、多層構造重合体粒子添加しない点で本発明と異なる比較例２は耐衝撃性が低く、シリコーン微粒子に替えてマイカを使用した比較例３は表面性が劣り、いずれも本発明の目的を達成できない。一方、実施例１は動摩擦係数、耐衝撃性、表面平滑性のいずれも改善されている。
さらに、実施例２〜８の積層シートは被覆層と基材層の接着も十分である。
【００６１】
【発明の効果】
本発明によれば、耐衝撃性、滑性および艶消し性に優れたメタクリル系樹脂組成物が得られ、該メタクリル系樹脂組成物は、シート、フィルム、他の熱可塑性樹脂からなる基材層を有する積層体の被覆層として好適に使用することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a methacrylic resin composition excellent in impact resistance, lubricity and matting property, and a laminate having a coating layer made of the methacrylic resin composition.
[0002]
[Prior art]
Methacrylic resins have a beautiful appearance and weather resistance and are easy to mold, so that they are widely used in applications such as electric parts, vehicle parts, decorative articles, signboards, and building materials. In general, methacrylic resins have a problem of relatively poor impact resistance, but improvements have been made by a method of adding multilayer polymer particles containing a rubber component (see Patent Document 1 and the like).
In addition, methacrylic resins are used as a coating layer of a multilayer molded article because of their excellent weather resistance and design properties (see Patent Document 2 and the like). When a multilayer molded article is produced, a profile extrusion method is often used. However, the profile extrusion requires a good lubricity due to a large number of contact portions with a mold.
Generally, as a method for improving the lubricity of a resin material, a method of adding a lubricant such as silicone oil or fluorine-based oil, silica (see Patent Document 3), kaolin, clay, calcium carbonate (see Patent Document 4), silicic acid A method of adding fine inorganic particles such as aluminum, silicic acid, calcium phosphate, alumina and zeolite, and a method of adding organic particles (see Patent Document 5) are known.
[0003]
[Patent Document 1]
US Patent No. 3,808,180 (Claims)
[Patent Document 2]
JP-A-10-338792 (Claims)
[Patent Document 3]
JP-A-63-72730 (Claims)
[Patent Document 4]
JP-A-64-1515 (Claims)
[Patent Document 5]
JP-A-9-165519 (Claims)
[0004]
[Problems to be solved by the invention]
However, the method of adding a lubricant to improve the lubricity may impair the physical properties of the resin material, fail to maintain its effect, or cause contamination by bleed-out. The method of adding fine particles reduces impact resistance, impairs smoothness due to the formation of an uneven surface, or causes a defect called plate-out due to poor dispersion of fine particles during extrusion, and appearance May be defective. In particular, in the method using inorganic particles, since hard particles are used, metal parts such as nozzles, dies, and dies are worn during molding, and defects such as bumps and die lines occur due to low compatibility with the base resin. Problems.
[0005]
[Means for Solving the Problems]
The present inventors have conducted various studies in order to solve the above problems, as a result of using a methacrylic resin, a methacrylic resin composition composed of multilayer polymer particles, and silicone fine particles, impact resistance, They have found that a methacrylic resin composition having excellent lubricity and matting properties can be obtained, and have completed the present invention.
[0006]
According to the invention, the object is
Methacrylic resin composition comprising a total of 100 parts by mass of methacrylic resin (A) 60 to 98% by mass and multilayer polymer particles (B) 40 to 2% by mass and silicone fine particles (C) 0.1 to 5 parts by mass. Thing;
(1) A rubber layer mainly composed of an alkyl acrylate unit having an alkyl group having 1 to 8 carbon atoms and / or a diene-based monomer unit in at least one inner layer of the multilayer structure polymer particles (B). Acrylic multi-layer polymer particles having a hard layer mainly composed of alkyl methacrylate units having 1 to 8 carbon atoms in the outermost layer in the outermost layer;
(2) The silicone fine particles (C) are non-melting elastomers in which siloxane units mainly composed of organosiloxane are bonded three-dimensionally, have an average particle diameter of 0.2 to 20 μm, and have a standard deviation of Not more than 4 μm;
This is achieved by a methacrylic resin composition characterized in that:
[0007]
Furthermore, the present invention relates to a film or sheet comprising the above methacrylic resin composition, a base layer comprising another thermoplastic resin, and a laminate having at least one layer comprising the above methacrylic resin composition. .
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The methacrylic resin (A) used in the present invention is not particularly limited, but is a methacrylic thermoplastic resin comprising at least 80% by mass of methyl methacrylate units and at most 20% by mass of vinyl monomer units copolymerizable therewith. It is preferred that
[0009]
The compounding ratio of the methacrylic resin (A) used in the present invention is 60 to 98% by mass, preferably 70 to 98% by mass, based on the total of the methacrylic resin (A) and the multilayer polymer particles (B). 95% by mass.
[0010]
The multilayered polymer particles (B) used in the present invention comprise, in at least one inner layer of the multilayered polymer particles, an alkyl acrylate unit having an alkyl group having 1 to 8 carbon atoms and / or a diene monomer. Acrylic multi-layer polymer particles having a rubber layer mainly composed of body units and having, as an outermost layer, a hard layer mainly composed of alkyl methacrylate units having an alkyl group of 1 to 8 carbon atoms.
[0011]
The acrylate having 1 to 8 carbon atoms in the alkyl group used in the polymerization for forming the rubber layer is not particularly limited, but includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Examples include alkyl acrylates such as 2-ethylhexyl acrylate and octyl acrylate, and these are used alone or in combination of two or more. Among them, butyl acrylate or 2-ethylhexyl acrylate is preferable.
[0012]
The diene-based monomer used in the polymerization for forming the rubber layer is not particularly limited, and includes, for example, 1,3-butadiene and isoprene.
[0013]
In the above polymerization for forming the rubber layer, other copolymerizable monofunctional monomers can be copolymerized in addition to these main components, if necessary. Other monofunctional monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylic acid. Methacrylic acid esters such as octyl acrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, isobornyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; acrylonitrile And the like, and used alone or in combination of two or more.
[0014]
When these other copolymerizable monofunctional monomers are used, preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, based on all the monomers used for forming the rubber layer. It is used in the range of 0.5 to 20% by mass.
[0015]
In order to impart rubber elasticity to a polymer comprising an acrylate ester and / or a diene monomer having 1 to 8 carbon atoms in the alkyl group used in the polymerization for forming the rubber layer, crosslinking is optionally performed. The reactive monomer and / or the graft copolymerizable monomer can be copolymerized. The crosslinkable monomer and the graft copolymerizable monomer are not particularly limited as long as they can impart rubber elasticity. For example, polyfunctional (meth) such as hexanediol diacrylate and hexanediol dimethacrylate are used. Crosslinkable monomers such as acrylates; graft copolymerizable monomers such as allyl carboxylate such as allyl acrylate and allyl methacrylate are preferably used.
[0016]
When the above-mentioned crosslinkable monomer and / or graft copolymerizable monomer is used, it is preferably 0.2 to 15% by mass based on all monomers used for forming the polymer of the rubber layer. %, More preferably in the range of 0.5 to 10% by mass.
[0017]
In the multilayer polymer particles used in the present invention, a part of the rubber layer can be formed in the presence of a molecular weight modifier in order to impart excellent properties such as impact resistance to the multilayer polymer particles.
[0018]
The molecular weight regulator to be used is not particularly limited, but for example, mercaptans such as n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol; terpinolene, dipentene, t-terpinene And halogenated hydrocarbons such as chloroform and carbon tetrachloride. These are used alone or as a mixture of two or more. Among these, alkyl mercaptans such as n-octyl mercaptan are preferably used.
[0019]
The amount of the molecular weight modifier added to the monomer for forming the rubber layer is not particularly limited, but is used for forming the polymer of the rubber layer from the viewpoint of sufficiently exhibiting handleability and impact resistance. It is preferably used in the range of 0 to 3% by mass, more preferably 0 to 1.5% by mass, based on all the monomers to be prepared.
[0020]
The alkyl methacrylate having 1 to 8 carbon atoms in the alkyl group used in the polymerization for forming the hard layer of the multilayer polymer particles is not particularly limited. Examples thereof include methyl methacrylate, ethyl methacrylate, and methacryl. Examples thereof include methacrylates such as propyl acrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, and may be used alone or in combination of two or more. Among them, methyl methacrylate is preferred.
[0021]
In the polymerization for forming the hard layer, other copolymerizable monofunctional monomers can be copolymerized in addition to these main components, if necessary. Other monofunctional monomers that can be copolymerized include decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and isozobornyl methacrylate. Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; acrylonitrile; And used alone or in combination of two or more.
[0022]
When these other copolymerizable monofunctional monomers are used, preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, based on all the monomers used for forming the hard layer. It is used in the range of 0.5 to 20% by mass.
[0023]
The multilayer polymer particles used in the present invention generally have a layer structure called a core / shell, that is, an inner layer / outer layer structure in which an inner layer is covered by an outer layer, and have two or three layers. Or four or more layers. In the case of a two-layer structure, it has a rubber layer (center layer) / hard layer (outermost layer) structure, and in the case of a three-layer structure, it has a hard layer (center layer) / rubber layer (intermediate layer) / hard layer (most layer). Outer layer), rubber layer (center layer) / rubber layer (intermediate layer) / hard layer (outermost layer) or rubber layer (center layer) / hard layer (intermediate layer) / hard layer (outermost layer). In the case of a layer structure, for example, it has a configuration of a rubber layer (center layer) / hard layer (intermediate layer) / rubber layer (intermediate layer) / hard layer (outermost layer).
[0024]
The acrylic multilayer polymer that can be particularly preferably used in the present invention,
(1) a rubber layer (a) obtained by polymerizing a monomer mainly containing an alkyl acrylate having 1 to 8 carbon atoms in the presence of a molecular weight modifier,
(2) a rubber layer (b) mainly composed of acrylic acid alkyl ester units having 1 to 8 carbon atoms in the alkyl group,
(3) Hard layer mainly composed of methyl methacrylate units (c)
And the rubber layer (a), the rubber layer (b) and the hard layer (c) are multilayer polymer particles arranged in this order from the inside.
[0025]
The polymerization method for producing the multilayer structure polymer particles used in the present invention is not particularly limited, and, for example, by following a normal emulsion polymerization, spherical multilayer structure polymer particles can be easily obtained. . After the emulsion polymerization, the multi-layered polymer particles can be separated and obtained from the polymer latex according to a known method, for example, by an acid precipitation method, a salting out method, a freeze coagulation method, a spray drying method, or the like.
[0026]
In the present invention, the particle size of the multilayer polymer particles is not particularly limited, but is preferably in the range of 150 to 700 nm, and more preferably in the range of 200 to 650 nm. If the particle diameter is too small, the handleability in the process of the multilayer polymer particles tends to decrease, and if too large, the impact resistance improving effect in the methacrylic resin composition tends to decrease, which is not preferable. .
[0027]
The particle size of the multilayer structure polymer particles, for example, the average diameter measurement of the multilayer structure polymer particles based on electron microscopic observation of the multilayer structure polymer particles, a method such as dynamic light scattering method measurement for the multilayer structure polymer particles Can be determined by
[0028]
The mixing ratio of the multilayer polymer particles (B) used in the present invention is 2 to 40% by mass based on the total of the methacrylic resin (A) and the multilayer polymer particles (B), and is preferably. 5 to 30% by mass. If it is less than 2% by mass, the effect of improving the impact resistance is small, and if it exceeds 30% by mass, the inherent properties of the methacrylic resin may be impaired.
[0029]
The silicone fine particles used in the present invention are siloxane units mainly composed of an organosiloxane such as dimethylsiloxane, methylphenylsiloxane, methyloctylsiloxane, methylcyclohexylsiloxane, diphenylsiloxane, methyl (3,3,3-trifluoropropyl) siloxane. Is a three-dimensionally bonded, non-meltable elastomeric material. The average particle size is from 0.2 to 20 μm, preferably from 0.5 to 15 μm. When the average particle diameter is smaller than 0.2 μm, the matting performance may be reduced, and when the average particle diameter is larger than 20 μm, the surface uniformity may be impaired, which is not preferable. The standard deviation is 4 μm or less, preferably 3 μm or less. If the standard deviation is larger than 4 μm, particles having a large particle diameter may be present, which may undesirably impair the surface uniformity.
[0030]
The particle shape of the silicone fine particles used in the present invention may be a true sphere or an irregular shape, but a true sphere is particularly preferable when surface smoothness is required.
[0031]
When the methacrylic resin composition of the present invention is used as a coating layer of a multilayer molded article, it is necessary to select the particle size of the silicone fine particles in consideration of the thickness of the coating layer. If the thickness and the particle size of the coating layer are equal to or more than or slightly smaller, the surface uniformity may be impaired.
[0032]
The method for producing the silicone fine particles used in the present invention is not particularly limited. For example, as described in JP-A-59-68333, a curable polymer containing a specific linear organosiloxane block or A method in which the curable polymer composition is cured in a spray state to obtain spherical particles is preferable. The method of mechanically pulverizing the crosslinked silicone resin is not preferable because it is difficult to control the shape and the particle diameter.
[0033]
The mixing ratio of the silicone fine particles (C) used in the present invention is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the methacrylic resin (A) and the multilayer polymer particles (B). And preferably in the range of 0.5 to 3 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving lubricity is small, and if it exceeds 3 parts by mass, the effect of improving lubricity with respect to the added amount is small, and the inherent properties of the methacrylic resin may be impaired.
[0034]
The amount of the multilayer polymer particles (B) and the amount of the silicone fine particles (C) in the methacrylic resin composition are represented by the following formula:
[Equation 2]
-20> B-50C
[0036]
(B in the above formula represents parts by mass of the multilayer polymer particles (B) with respect to 100 parts by mass in total of the methacrylic resin (A) and the multilayer polymer particles (B), and C represents the methacrylic resin (A ) And the multilayer polymer particles (B) represent 100 parts by mass of the silicone fine particles (C) with respect to 100 parts by mass in total.)
It is preferable to satisfy the following. If the above expression is not satisfied, a sufficient lubrication improving effect may not be obtained.
[0037]
The method for melt-mixing the methacrylic resin, the multilayer polymer particles, and the silicone fine particles is not particularly limited, and a known method generally used for melt-mixing resins can be applied. As a melt-kneading device at that time, a heating roll machine, a heating kneader machine, a screw-type extruder (extruder) or the like can be used.
[0038]
Upon melt mixing in the above, a methacrylic resin, a multilayer structure polymer particles, and a methacrylic resin composition comprising silicone fine particles, within a range that does not impair the effects of the present invention, a pigment, an antiblocking agent, a stabilizer, and an antistatic. It is possible to add additives such as an agent and a plasticizer. Among these additives, examples of the stabilizer include an antioxidant, a heat stabilizer, and an ultraviolet absorber.
[0039]
Since the methacrylic resin composition of the present invention has a matting property, it is suitably used for a molded article having a matting property on its surface, especially for a film or sheet. The mattness of the surface is preferably 80% or less at a 60-degree specular gloss.
[0040]
The methacrylic resin composition of the present invention can obtain a molded article by any molding method generally used for molding a resin, such as injection molding, extrusion molding, compression molding, blow molding, calender molding, and cast molding. it can.
[0041]
In addition, the methacrylic resin composition of the present invention has excellent adhesiveness to other resins, and thus is suitably used for various laminates. The base resin constituting the base layer of the laminate is not particularly limited as long as it is another thermoplastic resin (including a thermoplastic composition) other than the methacrylic resin composition of the present invention. Examples include vinyl resin, methacrylic resin, polycarbonate resin, vinylidene fluoride resin, ABS resin, AES resin, acrylonitrile-styrene (AS) resin, and the like, and one or more of these may be combined.
[0042]
The method for producing the laminate is not particularly limited, and can be in accordance with a general method for producing a laminate. When a laminate sheet is obtained, for example, a coextrusion method or a lamination method Etc. can be adopted. Among these, the co-extrusion method is excellent in that the fluids of the respective layers can be combined and laminated and integrated, so that the adhesion between the respective layers is good and the molding distortion of the respective layers is similar. In co-extrusion, using two or more ordinary extruders, for example, an extruder of 40 mmφ, 60 mmφ, 90 mmφ, etc. for forming a base layer, and a coating layer made of the methacrylic resin composition of the present invention. For forming, it is common to use a smaller extruder of 20 mmφ, 30 mmφ, 45 mmφ or the like. The extrusion temperature can be performed in a normal temperature range.
[0043]
In the case of the laminating method, for example, a film is prepared in advance from the methacrylic resin composition of the present invention, and the film is overlapped with an extruded base sheet at a polishing roll portion at an extruder outlet. A laminate can be made. In this case, it is desirable to select conditions such as a roll temperature or the like that prevent air from being mixed at the time of superposition and improve the adhesion. In addition, at the time of co-extrusion or lamination, you may laminate | stack through an adhesive layer as needed.
[0044]
In the laminated sheet as described above, the thickness of the entire laminated sheet is not particularly limited, but is generally 0.5 to 10 mm. The thickness of the coating layer composed of the methacrylic resin composition of the present invention may be at least the minimum thickness necessary for exhibiting the desired performance, and from that viewpoint, it is preferably at least 1 μm. In the context, it is generally between 30 and 300 μm.
[0045]
Although the form of the surface of the laminated sheet is not particularly limited, for example, a flat surface, a curved surface, a curved surface (for example, a corrugated sheet) or the like can be adopted.
[0046]
In addition, a laminate other than a sheet can be manufactured by, for example, a profile extrusion method, a method of secondary forming a laminated sheet, or the like.
[0047]
【Example】
Next, examples of the present invention will be described, but the present invention is not limited thereto. The measurement of physical properties in Reference Examples and Examples was performed by the following methods (1) to (5).
[0048]
(1) Particle size of multilayer structure polymer particles The average particle size of the multilayer structure polymer particles is determined by a dynamic light scattering method using a laser particle size analyzer (“PAR-III” manufactured by Otsuka Electronics Co., Ltd.). Was measured.
(2) Measurement of dynamic friction coefficient According to JIS K7125, a dynamic friction coefficient was measured using a stainless steel plate (SUS430) as a mating material.
(3) Impact resistance Using a No. 2 test piece, an Izod impact value was measured by edgewise impact of a notch A according to JIS K7110.
(4) Glossiness A 60-degree specular glossiness was measured according to JIS K7105.
(5) A test piece was cut out from the laminated sheet in which the thickness of the coating layer of the laminated sheet was formed, the cross section was polished, and the cross section was measured using an optical microscope.
[0049]
As the silicone fine particles (C), “Tospearl 2000B” (non-melting spherical elastomer composed of organosiloxane units, average particle diameter 6.0 μm) manufactured by GE Toshiba Silicone Co., Ltd. was used.
[0050]
<Reference Example 1> (Production Example of Multilayer Structure Polymer Particle (B))
147 parts by mass of ion-exchanged water are charged into a polymerization tank made of glass lining equipped with a condenser, a thermometer, and a stirrer, and 0.015 parts by mass of sodium alkyldiphenylether disulfonate and 0.001 part by mass of sodium carbonate are dissolved. The temperature was raised to 80 ° C. while stirring. Separately, 44.06 parts by mass of butyl acrylate (hereinafter abbreviated as BA), 0.90 parts by mass of 1,4-butanediol diacrylate, and 0.05 parts by mass of n-octyl mercaptan are charged into a stainless steel container. To prepare a monomer mixture (I). After 10% by mass of the monomer mixture (I) was added to the reaction vessel at a time, 0.045 parts by mass of potassium persulfate (hereinafter abbreviated as KPS) was added as a polymerization initiator to initiate polymerization. Thirty minutes after the addition of KPS, an emulsifier-dissolved monomer mixture (II) obtained by dissolving 0.20 part by mass of sodium dioctylsulfosuccinate (hereinafter abbreviated as SDOSS) in 90% by mass of the remaining monomer mixture (I) was 0.83%. Polymerization was carried out by continuously supplying at a supply rate of mass% / min. Next, after the supply of the emulsifier-dissolved monomer mixture (II) is completed, the mixture is maintained at 80 ° C. for 30 minutes with stirring, and 0.045 parts by mass of KPS is further added. Then, 44.1 parts by mass of BA and 0.1 ml of allyl methacrylate are added. An emulsifier-dissolved monomer mixture (III) comprising 9 parts by mass and SDOSS 0.23 parts by mass was continuously supplied at a supply rate of 0.64% by mass / min to carry out polymerization. After the supply of the emulsifier-dissolved monomer mixture (III) was completed, the mixture was kept at 80 ° C. for 60 minutes with stirring, and after 0.01 part by mass of KPS was added, 9.50 parts by mass of methyl methacrylate and 0 part of methyl acrylate were added. The emulsifier-dissolved monomer mixture (4) consisting of .50 parts by mass and SDOSS 0.05 parts by mass was continuously supplied at a supply rate of 0.5% by mass / min to carry out polymerization. After the supply of the emulsifier-dissolved monomer mixture (4) was completed, the mixture was kept at 80 ° C. for 60 minutes with further stirring to complete the polymerization. The particle diameter of the multilayer polymer particles in the latex thus obtained was 350 nm.
[0051]
The obtained latex was cooled at −30 ° C. for 12 hours to coagulate, then the coagulated product was taken out, washed with warm water of 40 ° C., dehydrated by a centrifugal dehydrator, and dried under reduced pressure and vibration at 50 ° C. for 12 hours. Thus, multilayer polymer particles were obtained. The obtained multilayer polymer particles had a core / shell type three-layer structure in which an acrylic rubber containing a BA unit as a main component was used as an inner layer and a methacrylic resin was used as a hard outermost layer.
[0052]
<Example 1>
82 parts by mass of a methacrylic resin (Kuraray's Parapet G) dried at 70 ° C. for 4 hours, 18 parts by mass of multilayered polymer particles (B), and 2 parts by mass of silicone fine particles (GE Toshiba Silicone Tospearl 2000B) in a tumbler. Charged and mixed. This mixture was melt-kneaded using a single screw extruder (manufactured by Chuo Kikai Seisakusho; L / D = 28, 40 mmφ), extruded into strands, and cut to produce milky white methacrylic resin composition pellets. . The obtained pellets were dried at 70 ° C. for 4 hours and injection molded to obtain a 3.2 mm thick sheet-like molded product. No irregularities were visually observed on the surface of the molded article. The dynamic friction coefficient was 0.38, the Izod impact value was 38 J / m, and the glossiness was 77%.
[0053]
<Comparative Example 1>
The procedure was performed in the same manner as in Example 1 except that no silicone fine particles were added. No irregularities were visually observed on the surface of the molded article. The coefficient of kinetic friction was 0.48, the Izod impact value was 42 J / m, and the glossiness was 86%.
[0054]
<Comparative Example 2>
The procedure was performed in the same manner as in Example 1 except that the multilayer polymer particles (B) were not added. No irregularities were visually observed on the surface of the molded article. The dynamic friction coefficient was 0.36, the Izod impact value was 13 J / m, and the glossiness was 67%.
[0055]
<Comparative Example 3>
The procedure was performed in the same manner as in Example 1 except that mica (Y-4000M manufactured by Kirara) was added instead of the silicone fine particles. Irregularities were visually observed on the surface of the molded product. The coefficient of kinetic friction was 0.39, the Izod impact value was 28 J / m, and the glossiness was 80%.
[0056]
[Table 1]

[0057]
<Example 2>
The pellets of the methacrylic resin composition of Example 1 were used as the resin for the coating layer, and the PVC resin (EX-282E made by Shin-Etsu Polymer) was used as the resin for the base layer, and each was a sub-extruder (230 ° C .; L / D = 32; 30 mmφ). ), Co-extrusion was performed by extruding from a main extruder (190 ° C .; L / D = 32; 40 mmφ). The thickness of the laminated sheet was adjusted by the clearance of the polishing roll, and the thickness of the coating layer was adjusted by the discharge amount. The thicknesses of the base layer and the coating layer of the obtained laminated sheet were 2.0 mm and 200 μm, respectively.
The laminated sheet had no defects such as flow marks and whitening of the interface, and the adhesion between the coating layer and the base material layer was sufficient.
[0058]
<Examples 3 to 8>
The procedure was performed in the same manner as in Example 2 except that the kind of the resin of the base material layer and the temperature of the main extruder were changed as shown in Table 2.
None of the laminated sheets had defects such as flow marks and whitening of the interface, and the adhesion between the coating layer and the base material layer was sufficient.
[0059]
[Table 2]

[0060]
As described above, when Example 1 of the present invention is compared with Comparative Examples 1 and 2, Comparative Example 1 which is different from the present invention in that silicone fine particles are not added has a large kinetic friction coefficient and does not contain multilayer polymer particles. Comparative Example 2, which is different, has low impact resistance, and Comparative Example 3, which uses mica instead of silicone fine particles, has poor surface properties, and none of them can achieve the object of the present invention. On the other hand, in Example 1, the dynamic friction coefficient, impact resistance, and surface smoothness were all improved.
Further, the laminated sheets of Examples 2 to 8 have sufficient adhesion between the coating layer and the base material layer.
[0061]
【The invention's effect】
According to the present invention, a methacrylic resin composition having excellent impact resistance, lubricity and matting property can be obtained, and the methacrylic resin composition can be used as a sheet, film, or base layer made of another thermoplastic resin. Can be suitably used as a coating layer of a laminate having

Claims (8)

Methacrylic resin composition comprising a total of 100 parts by mass of methacrylic resin (A) 60 to 98% by mass and multilayer polymer particles (B) 40 to 2% by mass and silicone fine particles (C) 0.1 to 5 parts by mass. Thing;
(1) A rubber layer mainly composed of an alkyl acrylate unit having an alkyl group having 1 to 8 carbon atoms and / or a diene-based monomer unit in at least one inner layer of the multilayer structure polymer particles (B). Acrylic multi-layer polymer particles having a hard layer mainly composed of alkyl methacrylate units having 1 to 8 carbon atoms in the outermost layer in the outermost layer;
(2) The silicone fine particles (C) are non-melting elastomers in which siloxane units mainly composed of organosiloxane are bonded three-dimensionally, have an average particle diameter of 0.2 to 20 μm, and have a standard deviation of Not more than 4 μm;
A methacrylic resin composition, characterized in that: Acrylic multi-layer polymer particles (B)
(1) a rubber layer (a) obtained by polymerizing a monomer mainly containing an alkyl acrylate having 1 to 8 carbon atoms in the presence of a molecular weight modifier,
(2) a rubber layer (b) mainly composed of acrylic acid alkyl ester units having 1 to 8 carbon atoms in the alkyl group,
(3) Hard layer mainly composed of methyl methacrylate units (c)
The methacrylic polymer according to claim 1, wherein the methacrylic polymer is a multilayer polymer particle having a structure in which at least three layers of (a), (b), and (c) are arranged in this order from the inside. -Based resin composition. The methacrylic resin composition according to claim 1 or 2, wherein the amount of the multilayer polymer particles (B) and the amount of the silicone fine particles (C) in the methacrylic resin composition are represented by the following formulas.
(Equation 1)

(B in the above formula represents parts by mass of the multilayer polymer particles (B) with respect to 100 parts by mass in total of the methacrylic resin (A) and the multilayer polymer particles (B), and C represents the methacrylic resin (A ) And the multilayer polymer particles (B) represent 100 parts by mass of the silicone fine particles (C) with respect to 100 parts by mass in total.) A film or sheet comprising the methacrylic resin composition according to claim 1. The film or sheet according to claim 4, wherein the 60-degree specular gloss is 80% or less. A laminate having a base layer made of another thermoplastic resin and at least one layer made of the methacrylic resin composition according to any one of claims 1 to 3. The laminate according to claim 6, wherein the thermoplastic resin is a vinyl chloride resin. The laminate according to claim 6 or 7, which has a form of a laminate sheet.