WO2012133789A1 - 高耐傷性ポリオレフィン樹脂組成物成形体 - Google Patents
高耐傷性ポリオレフィン樹脂組成物成形体 Download PDFInfo
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- WO2012133789A1 WO2012133789A1 PCT/JP2012/058612 JP2012058612W WO2012133789A1 WO 2012133789 A1 WO2012133789 A1 WO 2012133789A1 JP 2012058612 W JP2012058612 W JP 2012058612W WO 2012133789 A1 WO2012133789 A1 WO 2012133789A1
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- polyolefin resin
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
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- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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Definitions
- the present invention relates to a polyolefin resin composition and a molded body of the polyolefin resin composition. From another point of view, the present invention relates to a polyolefin resin composition molded body and a polyolefin resin composition coating layer in which the presence of scratches is not noticeable even when the surface is scratched, and a molded body or coating of such a polyolefin resin. The present invention relates to a polyolefin resin composition that can be advantageously used in the production of a layer.
- Polyolefin resin compositions prepared by adding various pigments (eg, white pigments, black pigments) to polyolefin resins and, if necessary, chromatic pigments and various additives, have been conventionally used in various containers and various products (eg, , Daily products, electrical products, automobile members, building members), and are widely used by being molded into a shape such as a member for exterior or interior, or a sheet. Further, such a polyolefin resin composition is formed as a coating film on the surface of various molded bodies such as metal molded bodies and ceramic molded bodies (eg, concrete products), and the appearance of these molded bodies is improved, or It is also used for the purpose of covering the rough surface or the uneven surface of these molded bodies so that they are not noticeable.
- various pigments eg, white pigments, black pigments
- the colored polyolefin resin molding used for various purposes is used for other members (especially metal members and ceramic members (eg, glass, concrete), etc.) even when used for a long time or for a short time.
- scratches occur on the surface of the molded body.
- the scratches generated on the surface of the polyolefin resin molded body are conspicuous because the difference in the brightness and the color difference between the scratched portion and the portion without the scratch increase, and therefore the appearance of the polyolefin resin molded body is significantly deteriorated. .
- Patent Document 1 even if a pulverized product of a polyolefin resin product (especially a used thermoplastic resin product) containing various pigments is used as a raw material as a polyolefin resin, a white pigment (especially white dioxide) Titanium pigments) and chromatic pigments are added in a certain range, and the melt-molding method is used, which is almost the same as when an unused polyolefin resin (generally called a virgin polyolefin resin) is used. It is disclosed that a polyolefin resin product that exhibits an equivalent appearance of color can be produced. However, there is no disclosure about the relationship between the scratch resistance of polyolefin resin products or the conspicuousness of scratches generated on the surface and the type and amount of added white pigment or chromatic pigment.
- the present invention is a case where an unused polyolefin resin (virgin material) is used as a raw material resin material, or a case where a polyolefin resin (recycled material) recovered from a used thermoplastic resin product is used.
- the surface of the molded body or coating layer formed from those polyolefin resins has high scratch resistance (in the present specification, the expression “high scratch resistance” is not only difficult to be scratched but also scratched. It is also an object of the present invention to provide a polyolefin resin composition capable of exhibiting that the scratches are not conspicuous.
- the inventor of the present invention can recognize the scratches generated on the surface of a molded body or coating layer obtained by molding a polyolefin resin composition prepared using a pigment conventionally used as an additive pigment for polyolefin resin ( We have come up with the idea that it can be improved by changing the type and amount of pigment to be added, and various experiments were conducted based on the idea.
- a pigment for addition to polyolefin resin white titanium dioxide and carbon black or black pigment that is iron black are combined, and these are added in a larger amount than the conventionally used addition amount, and if necessary
- a polyolefin resin composition prepared by adding a chromatic pigment is used as a molding material to form a molding or coating layer after heating and melting, even if the surface of the molding or coating layer is damaged, I found that the scratches were less noticeable.
- the present invention is an invention completed based on such novel findings by the inventors of the present invention.
- the present invention firstly contains white titanium dioxide pigment and black pigment in an amount of 1.1 to 6 parts by weight and 0.1 to 5 parts by weight, respectively, with respect to 100 parts by weight of the polyolefin resin. It exists in the polyolefin resin composition whose total amount of a titanium pigment and a black pigment is 2.0 mass parts or more.
- the present invention contains white titanium dioxide pigment and black pigment in an amount of 1.1 to 6 parts by weight and 0.1 to 5 parts by weight, respectively, with respect to 100 parts by weight of the polyolefin resin.
- a white titanium dioxide pigment and a black pigment are respectively added to 100 parts by mass of a metal molded body or a ceramic molded body and a polyolefin resin formed on the surface of the molded body.
- a laminate comprising a polyolefin resin composition layer which is contained in an amount of 0.1 to 5 parts by mass and the total amount of the white titanium dioxide pigment and the black pigment is 2.0 parts by mass or more.
- molded articles produced using the polyolefin resin composition of the present invention and various molded articles whose surfaces are coated with the polyolefin resin composition of the present invention are used in consideration of severe use forms such as frequent occurrence of scratches.
- severe use forms such as frequent occurrence of scratches.
- Preferred embodiments of the polyolefin resin composition of the present invention are as follows.
- the content of the white titanium dioxide pigment is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- the black pigment contains carbon black, and the carbon black is contained in an amount in the range of 0.1 to 1.0 part by mass with respect to 100 parts by mass of the polyolefin resin.
- the black pigment contains iron black, and iron black is contained in an amount in the range of 1.0 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- the white titanium dioxide pigment and the black pigment are contained in a total amount of 3.0 to 7.0 parts by mass in 100 parts by mass of the polyolefin resin.
- a chromatic pigment is contained in an amount in the range of 0.05 to 3.0 parts by mass (preferably in an amount in the range of 0.5 to 3.0 parts by mass).
- Polyolefin resin is an unused polyolefin resin (virgin material).
- the polyolefin resin is a polyolefin resin (recycled material) obtained by using a waste of a molded polyolefin resin as a raw material.
- polyolefin resin examples include polypropylene and polyethylene, and polypropylene is preferred.
- Polypropylene which is generally distributed in the market and used as a raw material for producing various components, is a block copolymer of propylene and a relatively small amount of ethylene (propylene-ethylene block copolymer). There are often. Accordingly, such a propylene-ethylene block copolymer is preferable as the polypropylene used in the present invention.
- an unused polyolefin resin (generally referred to as virgin polyolefin resin or virgin material) can be used.
- This unused polyolefin resin may contain a small amount of additives necessary for resin production.
- pulverized products of molded products of polyolefin resins that were not rejected due to defects in molded product production various products (for example, automobile interior parts, automobile exterior parts, electrical product members, office work) It is also possible to use a pulverized product (generally referred to as a recycled material) of a molded article of polyolefin resin that is used as a product and then discarded.
- the white titanium dioxide pigment (also referred to as titanium white) used in the present invention is not particularly limited, but is preferably rutile titanium dioxide or anatase titanium dioxide generally used in various applications. As described above, the white titanium dioxide pigment used in the present invention is a large amount (1.1 to 6 parts by weight, preferably 1.2 to 6 parts by weight, more preferably 1.5 parts by weight based on 100 parts by weight of the polyolefin resin. (6 parts by mass).
- Black pigment examples of the black pigment used in the present invention include carbon black and iron black. As described above, the black pigment is used in an amount in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin. In addition, the usage-amount of a black pigment and the usage-amount of a white titanium dioxide pigment are those sum total, and it is necessary to set it as 2.0 mass parts or more with respect to 100 mass parts of polyolefin resin. Carbon black and iron black can be used alone or in combination. Among black pigments, carbon black has a strong light shielding effect and is preferable for improving the conspicuousness of scratches. However, since fine carbon black tends to aggregate, it needs to be handled with care.
- thermosetting resin fragments pulverized products
- various deposits such thermoplastic resins are added to molded products made from recycled materials.
- the main component is carbon black, which has high light shielding properties so that the presence of these contaminants may not be noticeable. It is preferable to mix a black pigment. Iron black, on the other hand, is inferior to carbon black in terms of light shielding properties, but has excellent dispersibility in the resin composition, and color matching (toning) required when used in combination with white titanium dioxide pigments and chromatic pigments. ) Can be advantageously used.
- iron black alone or a black pigment mainly composed of iron black is used. It is preferable to use it.
- the amount of carbon black used is preferably in the range of 0.01 to 0.30 in terms of the ratio (carbon black / white titanium dioxide pigment) to the amount of white titanium dioxide pigment used.
- the amount of iron black used is preferably in the range of 0.1 to 3 in terms of the ratio (iron black / white titanium dioxide pigment) to the amount of white titanium dioxide pigment used.
- the polyolefin resin composition of the present invention can contain a chromatic pigment in addition to the white titanium dioxide pigment and the black pigment as necessary.
- chromatic pigments inorganic chromatic pigments such as petals, ultramarine blue, cobalt blue, titanium yellow, cobalt yellow, cobalt blue, cobalt green, and quinacridone red, polyazo yellow, anthraquinone red, anthraquinone yellow, polyazo red, Organic chromatic pigments such as Azo Lake Yellow, Phthalocyanine Blue, Phthalocyanine Green, Isoindolinone Yellow, Permanent Red, Para Red, Toluidine Maroon, Bend Gin Yellow, First Sky Blue, Brilliant Carmine 6B, depending on the purpose, alone or in combination Used.
- both the white titanium dioxide pigment and the black pigment are dispersed in a highly dispersed state.
- a known dispersant such as higher fatty acid, higher fatty acid amide, higher fatty acid metal salt (metal soap), glycerin ester, polyethylene wax, polypropylene wax and the like.
- a particularly preferred dispersant is magnesium stearate.
- the polyolefin resin composition of the present invention can further contain various elastomers and known additives as necessary.
- known additives include fillers (eg, talc), lubricants, antistatic agents, surfactants, nucleating agents, ultraviolet absorbers, antioxidants, and flame retardants.
- Examples of molded articles produced using the polyolefin resin composition of the present invention include automobile interior parts such as passenger cars, trucks and buses, exterior parts for household appliances such as vacuum cleaners and washing machines, furniture, and office supplies. And you can list daily necessities.
- the polyolefin resin composition of the present invention is also useful as a coating layer formed on the surface of a metal molded body or a ceramic molded body (eg, a concrete member such as a concrete building member).
- the thickness is usually in the range of 0.5 to 6 mm (especially 1 to 4 mm, more preferably 1.5 to 3.5 mm).
- the thickness is preferably in the above-mentioned thickness range.
- Example 1 Manufacture 1 of a sheet-like molded body colored in gray from a virgin material 100 parts by mass of a polypropylene resin substrate (unused propylene-ethylene block copolymer: virgin material), white titanium dioxide pigment (4.40 parts by mass), iron black (1.44 parts by mass), red pigment (valve) Handle, 0.08 parts by mass), yellow pigment (titanium yellow, 0.56 parts by mass), blue pigment (ultraviolet, 0.40 parts by mass), and other additives (dispersant, lubricant, etc.) 30 parts by mass) were mixed, heated and melted, and injection molded to prepare a test sheet piece (color plate, 100 mm ⁇ 100 mm ⁇ 3.35 mm) colored in gray having an embossed surface.
- a test sheet piece color plate, 100 mm ⁇ 100 mm ⁇ 3.35 mm
- Example 2 (Production 1 of gray sheet-like molded body from virgin material) A gray test sheet piece having an embossed surface was prepared in the same manner as in Example 1 except that none of the chromatic pigments (red pigment, yellow pigment, and blue pigment) was added.
- Example 1 Manufacture 1 of a sheet-like molded body colored in gray from a virgin material
- a test sheet piece colored in gray having an embossed surface was prepared in the same manner as in Example 1 except that the addition amount of the pigment was changed as follows.
- Example 3 (Production 1 of a sheet-like molded product colored brown from virgin material) 100 parts by mass of a polypropylene resin substrate (unused propylene-ethylene block copolymer: virgin material), white titanium dioxide pigment (1.92 parts by mass), iron black (2.80 parts by mass), red pigment (valve) Handle, 0.48 parts by mass), yellow pigment (titanium yellow, 1.28 parts by mass), blue pigment (ultraviolet, 0.32 parts by mass), and other additives (dispersant, lubricant, etc.) 30 parts by mass) were mixed, heated and melted, and injection molded to prepare a test sheet piece colored brown with an embossed surface.
- a polypropylene resin substrate unused propylene-ethylene block copolymer: virgin material
- white titanium dioxide pigment (1.92 parts by mass
- iron black (2.80 parts by mass
- red pigment (valve) Handle 0.48 parts by mass
- yellow pigment titanium yellow, 1.28 parts by mass
- blue pigment ultraviolet, 0.32 parts by mass
- Example 2 (Production 1 of a sheet-like molded body colored brown from virgin material) A test sheet piece colored in brown having an embossed surface was prepared in the same manner as in Example 3 except that the addition amount of the pigment was changed as follows.
- White titanium dioxide pigment 0.24 parts by mass
- iron black 0.35 parts by mass
- red pigment 0.06 parts by mass
- yellow pigment 0.16 parts by mass
- blue pigment 0.04 parts by mass
- Example 4 Manufacture 2 of gray sheet-shaped molded product from virgin material
- white titanium dioxide pigment 3.76 parts by mass
- iron black 19.2 Parts by weight
- red pigment petal, 0.08 parts by weight
- yellow pigment titanium yellow, 0.64 parts by weight
- blue pigment ultraviolet, 0.48 parts by weight
- a lubricant total 0.30 parts by mass
- Example 5 (Production 2 of gray sheet-like molded body from virgin material) A gray test sheet piece having an embossed surface was prepared in the same manner as in Example 4 except that none of the chromatic pigments (red pigment, yellow pigment, and blue pigment) was added.
- Example 3 Manufacture 2 of a sheet-like molded body colored in gray from a virgin material
- a test sheet piece colored in gray having an embossed surface was prepared in the same manner as in Example 4 except that the addition amount of the pigment was changed as follows.
- White titanium dioxide pigment 0.47 parts by mass
- iron black 0.24 parts by mass
- red pigment 0.01 parts by mass
- yellow pigment 0.08 parts by mass
- blue pigment 0.06 parts by mass
- Example 6 Manufacture 2 of a sheet-like molded product colored brown from virgin material
- a mixture of 80 parts by mass of a polypropylene resin substrate (unused propylene-ethylene block copolymer: virgin material) and 20 parts by mass of talc was mixed with white titanium dioxide pigment (1.04 parts by mass), iron black (3.84). Parts by weight), red pigment (petal, 0.56 parts by weight), yellow pigment (titanium yellow, 1.20 parts by weight), blue pigment (ultraviolet, 0.16 parts by weight), and other additives (dispersants) And a lubricant (total 0.30 parts by mass) were mixed, heated and melted, and injection molded to prepare a test sheet piece colored brown with an embossed surface.
- Example 7 (Production 1 of gray sheet-shaped molded product from recycled material) To 100 parts by weight of white polypropylene dioxide (polypropylene resin base material used in household electrical appliances made of propylene-ethylene block copolymer, each containing white and black pigments of 1.0% by mass or less) Titanium pigment (4.100 parts by mass), black pigment (carbon black, 0.170 parts by mass), red pigment (valve, 0.050 parts by mass), yellow pigment (titanium yellow, 0.330 parts by mass), blue After mixing pigment (ultraviolet, 0.350 parts by mass) and other additives (dispersant, lubricant, etc., total 0.30 parts by mass), the mixture is heated and melted and injection molded to provide an embossed surface. A test sheet piece colored in gray was prepared.
- Example 8 (Production 1 of a sheet-like molded product colored brown from recycled material)
- After mixing a total of 0.30 parts by mass of an agent, etc. it was heated and melted and injection molded to prepare a test sheet piece colored brown with an embossed surface.
- Example 9 Manufacture 2 of a sheet-like molded product colored in gray from a recycled material
- a white titanium dioxide pigment is added to a mixture of 80 parts by mass of polypropylene resin base material (a pulverized household electrical product made of the same propylene-ethylene block copolymer used in Example 7) and 20 parts by mass of talc.
- Example 10 Manufacture of a sheet-like molded product colored brown from recycled material 2
- a white titanium dioxide pigment is added to a mixture of 80 parts by mass of polypropylene resin base material (a pulverized household electrical product made of the same propylene-ethylene block copolymer used in Example 7) and 20 parts by mass of talc. (2.030 parts by mass), black pigment (carbon black, 0.460 parts by mass), red pigment (valve, 0.570 parts by mass), yellow pigment (titanium yellow, 1.930 parts by mass), and other Additives (dispersant, lubricant, etc., 0.30 parts by mass in total) were mixed, heated and melted, and injection molded to prepare a brown colored test sheet piece having an embossed surface.
- polypropylene resin base material a pulverized household electrical product made of the same propylene-ethylene block copolymer used in Example 7
- talc. 2.030 parts by mass
- black pigment carbon black, 0.460 parts by mass
- red pigment valve, 0.
- Table 1 shows the brightness difference and the color difference obtained by the measurement of the method (1).
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Abstract
Description
(2)黒色顔料がカーボンブラックを含み、カーボンブラックがポリオレフィン樹脂100質量部に対して0.1~1.0質量部の範囲の量にて含まれる。
(3)黒色顔料が鉄黒を含み、鉄黒がポリオレフィン樹脂100質量部に対して1.0~5質量部の範囲の量にて含まれる。
(4)白色二酸化チタン顔料と黒色顔料とが合計でポリオレフィン樹脂100質量部に3.0~7.0質量部の範囲の量にて含まれる。
(5)さらに有彩色顔料を0.05~3.0質量部の範囲の量(好ましくは、0.5~3.0質量部の範囲の量)にて含有する。
(6)ポリオレフィン樹脂が未使用のポリオレフィン樹脂(バージン材)である。
(7)ポリオレフィン樹脂がポリオレフィン樹脂成形体の廃棄物を原料として得たポリオレフィン樹脂(リサイクル材)である。
本発明で用いられるポリオレフィン樹脂の例としては、ポリプロピレンおよびポリエチレンを挙げることができるが、ポリプロピレンであることが好ましい。なお、市場において一般的に流通していて、各種部材の製造原料として用いられるポリプロピレンは、主要量のプロピレンと相対的に少量のエチレンとのブロック共重合体(プロピレン-エチレンブロック共重合体)であることが多い。従って、本発明で用いるポリプロピレンとしては、そのようなプロピレン-エチレンブロック共重合体が好ましい。
本発明で用いられる白色二酸化チタン顔料(チタンホワイトとも呼ぶ)には特別の限定はないが、各種の用途にて一般的に用いられるルチル型二酸化チタン、あるいはアナターゼ型二酸化チタンであることが好ましい。本発明で使用する白色二酸化チタン顔料は、前述のように、ポリオレフィン樹脂100質量部に対して多量(1.1~6質量部、好ましくは1.2~6質量部、さらに好ましくは1.5~6質量部)にて用いることが特徴である。
本発明で用いられる黒色顔料の例としては、カーボンブラック及び鉄黒を挙げることができる。黒色顔料は、前述のように、ポリオレフィン樹脂100質量部に対して0.1~5質量部の範囲の量にて用いられる。なお、黒色顔料の使用量と白色二酸化チタン顔料の使用量とはそれらの合計で、ポリオレフィン樹脂100質量部に対して2.0質量部以上とする必要がある。カーボンブラックと鉄黒は、それぞれ単独でも用いられるが、混合して用いることもできる。
黒色顔料のうちでもカーボンブラックは、強い光遮蔽作用があり、傷の目立ちにくさを改良するには好ましいが、微細なカーボンブラックは凝集しやすいため、その取り扱いに注意を必要とする。なお、リサイクル材には、通常、熱硬化性樹脂の破片(粉砕物)や各種の付着物が混入している場合が多く、リサイクル材を原料として製造した成形体に、そのような熱可塑性樹脂の破片や各種付着物が混入して、成形体の見かけを悪くすることがあるため、それらの混入物の存在を目だたせないためにも、光遮蔽性の高いカーボンブラックを主成分とする黒色顔料を配合することが好ましい。一方、鉄黒は、光遮蔽性についてはカーボンブラックには劣るものの、樹脂組成物中での分散性に優れ、また白色二酸化チタン顔料や有彩色顔料と併用する場合に必要な色合わせ(調色)に有利に用いることができる。このため、バージン材を樹脂原料とする樹脂成形体の製造において、その成形体に発生した傷の目立ちにくさを向上させるためには、鉄黒単独、あるいは鉄黒を主成分とする黒色顔料を用いることが好ましい。
カーボンブラックの使用量は、白色二酸化チタン顔料の使用量との比(カーボンブラック/白色二酸化チタン顔料)で表わした場合で、0.01~0.30の範囲にあることが好ましい。一方、鉄黒の使用量は、白色二酸化チタン顔料の使用量との比(鉄黒/白色二酸化チタン顔料)で表わした場合で、0.1~3の範囲にあることが好ましい。
ポリプロピレン樹脂基材(未使用のプロピレン-エチレンブロック共重合体:バージン材)100質量部に、白色二酸化チタン顔料(4.40質量部)、鉄黒(1.44質量部)、赤色顔料(弁柄、0.08質量部)、黄色顔料(チタンイエロー、0.56質量部)、青色顔料(群青、0.40質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つグレーに着色された試験シート片(カラープレート、100mm×100mm×3.35mm)を作成した。
有彩色顔料(赤色顔料、黄色顔料、そして青色顔料)をいずれも添加しなかった以外は実施例1と同様にして、エンボス表面を持つグレーの試験シート片を作成した。
顔料の添加量を下記のように変えた以外は実施例1と同様にして、エンボス表面を持つグレーに着色された試験シート片を作成した。
白色二酸化チタン顔料:0.55質量部、鉄黒:0.18質量部、赤色顔料:0.01質量部、黄色顔料:0.07質量部、青色顔料:0.05質量部
ポリプロピレン樹脂基材(未使用のプロピレン-エチレンブロック共重合体:バージン材)100質量部に、白色二酸化チタン顔料(1.92質量部)、鉄黒(2.80質量部)、赤色顔料(弁柄、0.48質量部)、黄色顔料(チタンイエロー、1.28質量部)、青色顔料(群青、0.32質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つブラウンに着色された試験シート片を作成した。
顔料の添加量を下記のように変えた以外は実施例3と同様にして、エンボス表面を持つブラウンに着色された試験シート片を作成した。
白色二酸化チタン顔料:0.24質量部、鉄黒:0.35質量部、赤色顔料:0.06質量部、黄色顔料:0.16質量部、青色顔料:0.04質量部
ポリプロピレン樹脂基材(未使用のプロピレン-エチレンブロック共重合体:バージン材)80質量部とタルク20質量部との混合物に、白色二酸化チタン顔料(3.76質量部)、鉄黒(1.92質量部)、赤色顔料(弁柄、0.08質量部)、黄色顔料(チタンイエロー、0.64質量部)、青色顔料(群青、0.48質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つグレーに着色された試験シート片を作成した。
有彩色顔料(赤色顔料、黄色顔料、そして青色顔料)をいずれも添加しなかった以外は、実施例4と同様にして、エンボス表面を持つグレーの試験シート片を作成した。
顔料の添加量を下記のように変えた以外は実施例4と同様にして、エンボス表面を持つグレーに着色された試験シート片を作成した。
白色二酸化チタン顔料:0.47質量部、鉄黒:0.24質量部、赤色顔料:0.01質量部、黄色顔料:0.08質量部、青色顔料:0.06質量部
ポリプロピレン樹脂基材(未使用のプロピレン-エチレンブロック共重合体:バージン材)80質量部とタルク20質量部との混合物に、白色二酸化チタン顔料(1.04質量部)、鉄黒(3.84質量部)、赤色顔料(弁柄、0.56質量部)、黄色顔料(チタンイエロー、1.20質量部)、青色顔料(群青、0.16質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つブラウンに着色された試験シート片を作成した。
顔料の添加量を下記のように変えた以外は実施例6と同様にして、エンボス表面を持つブラウンに着色された試験シート片を作成した。
白色二酸化チタン顔料:0.13質量部、鉄黒:0.48質量部、赤色顔料:0.07質量部、黄色顔料:0.15質量部、青色顔料:0.02質量部
ポリプロピレン樹脂基材(使用済のプロピレン-エチレンブロック共重合体製の家庭用電気製品の粉砕物、白色顔料と黒色顔料の含有量は、それぞれ1.0質量%以下)100質量部に、白色二酸化チタン顔料(4.100質量部)、黒色顔料(カーボンブラック、0.170質量部)、赤色顔料(弁柄、0.050質量部)、黄色顔料(チタンイエロー、0.330質量部)、青色顔料(群青、0.350質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つグレーに着色された試験シート片を作成した。
ポリプロピレン樹脂基材(実施例7で用いたものと同じ使用済のプロピレン-エチレンブロック共重合体製の家庭用電気製品の粉砕物)100質量部に、白色二酸化チタン顔料(2.250質量部)、黒色顔料(カーボンブラック、0.440質量部)、赤色顔料(弁柄、0.500質量部)、黄色顔料(チタンイエロー、1.800質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つブラウンに着色された試験シート片を作成した。
ポリプロピレン樹脂基材(実施例7で用いたものと同じ使用済のプロピレン-エチレンブロック共重合体製の家庭用電気製品の粉砕物)80質量部とタルク20質量部の混合物に、白色二酸化チタン顔料(4.000質量部)、黒色顔料(カーボンブラック、0.160質量部)、赤色顔料(弁柄、0.040質量部)、黄色顔料(チタンイエロー、0.430質量部)、青色顔料(群青、0.370質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つグレーに着色された試験シート片を作成した。
ポリプロピレン樹脂基材(実施例7で用いたものと同じ使用済のプロピレン-エチレンブロック共重合体製の家庭用電気製品の粉砕物)80質量部とタルク20質量部の混合物に、白色二酸化チタン顔料(2.030質量部)、黒色顔料(カーボンブラック、0.460質量部)、赤色顔料(弁柄、0.570質量部)、黄色顔料(チタンイエロー、1.930質量部)、そして他の添加剤(分散剤や潤滑剤等、合計0.30質量部)を混合した後、加熱溶融し、射出成形することによって、エンボス表面を持つブラウンに着色された試験シート片を作成した。
(1)傷の目立ちやすさの評価方法
実施例1~10そして比較例1~4のそれぞれで作成された試験シート片(カラープレート)の表面に、底面にサンドペーパー(#80サンドペーパー)を貼り付けた重り(荷重2kg)を配置し、その重りをカラープレートの表面と接触させながら、一往復させて、カラープレートの表面に傷を発生させた。
次に、傷のない領域と傷を発生させた領域との間の明度差と色差を測定した。測定は、倉敷紡績株式会社製の分光光度計(光源:D-65 10度視野)を用いて、明度L*、色相a*及び色相b*(CIE1976)を測定することにより実施した。なお、測定は3回の測定の平均値である。
上記(1)の方法の測定により得られた明度差と色差とを表1に示す。
表1にまとめた評価結果から、本発明に従うポリオレフィン樹脂組成物を用いて作成したシート状成形体(試験シート片)は、ポリオレフィン原材料としてバージン材を用いた場合でも、リサイクル材を用いた場合でも、そしてフィラー(タルク)を配合した場合でも、フィラー(タルク)を配合しなかった場合でも、試験シート片表面の傷のない領域と傷が発生した領域との明度の差や色差が小さく、従って傷が目立ちにくいことがわかる。一方、白色二酸化チタン顔料と黒色顔料の含有量を一般的な量としたポリオレフィン樹脂組成物から成形した試験シート片の場合には、試験片表面の傷のない領域と傷が発生した領域との明度の差や色差が大きく、従って傷が目立ちやすいことが分かる。
Claims (15)
- ポリオレフィン樹脂100質量部に対して白色二酸化チタン顔料そして黒色顔料を、それぞれ1.1~6質量部そして0.1~5質量部の範囲の量にて含有し、かつ白色二酸化チタン顔料と黒色顔料との合計量が2.0質量部以上であるポリオレフィン樹脂組成物。
- ポリオレフィン樹脂100質量部に対して白色二酸化チタン顔料の含有量が1.5~6質量部の範囲にある請求項1に記載のポリオレフィン樹脂組成物。
- 黒色顔料がカーボンブラックを含み、カーボンブラックがポリオレフィン樹脂100質量部に対して0.1~1.0質量部の範囲の量にて含まれる請求項1に記載のポリオレフィン樹脂組成物。
- 黒色顔料が鉄黒を含み、鉄黒がポリオレフィン樹脂100質量部に対して1.0~5質量部の範囲の量にて含まれる請求項1に記載のポリオレフィン樹脂組成物。
- 白色二酸化チタン顔料と黒色顔料とが合計でポリオレフィン樹脂100質量部に3.0~7.0質量部の範囲の量にて含まれる請求項1に記載のポリオレフィン樹脂組成物。
- さらに有彩色顔料を0.05~3.0質量部の範囲の量にて含有する請求項1に記載のポリオレフィン樹脂組成物。
- 有彩色顔料の含有量が0.5~3.0質量部の範囲の量である請求項6に記載のポリオレフィン樹脂組成物。
- ポリオレフィン樹脂が未使用のポリオレフィン樹脂である請求項1乃至6の内のいずれかの1項に記載のポリオレフィン樹脂組成物。
- ポリオレフィン樹脂がポリオレフィン樹脂成形体の廃棄物を原料として得たポリオレフィン樹脂である請求項1乃至6の内のいずれかの1項に記載のポリオレフィン樹脂組成物。
- ポリオレフィン樹脂100質量部に対して白色二酸化チタン顔料そして黒色顔料を、それぞれ1.1~6質量部そして0.1~5質量部の範囲の量にて含有し、かつ白色二酸化チタン顔料と黒色顔料との合計量が2.0質量部以上であるポリオレフィン樹脂組成物から成形したポリオレフィン樹脂組成物成形体。
- ポリオレフィン樹脂組成物がさらに有彩色顔料を0.05~3.0質量部の量にて含有する請求項10に記載のポリオレフィン樹脂組成物成形体。
- シート状成形体である請求項10に記載のポリオレフィン樹脂組成物成形体。
- 表面にエンボス面を持つシート状成形体である請求項10に記載のポリオレフィン樹脂組成物成形体。
- 金属成形体もしくはセラミック成形体そして該成形体の表面に形成されたポリオレフィン樹脂100質量部に対して白色二酸化チタン顔料そして黒色顔料を、それぞれ1.1~6質量部そして0.1~5質量部の量にて含有し、かつ白色二酸化チタン顔料と黒色顔料との合計量が2.0質量部以上であるポリオレフィン樹脂組成物層からなる積層体。
- ポリオレフィン樹脂組成物層にさらに有彩色顔料が0.05~3.0質量部の量にて含まれている請求項14に記載の積層体。
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WO2022153939A1 (ja) * | 2021-01-13 | 2022-07-21 | 住友化学株式会社 | オレフィン樹脂組成物及びそれを含む成形体 |
WO2022153940A1 (ja) * | 2021-01-13 | 2022-07-21 | 住友化学株式会社 | プロピレン系樹脂組成物 |
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ES2897986T3 (es) | 2016-05-20 | 2022-03-03 | Sumitomo Chemical Co | Objeto moldeado por inyección |
CN106398085A (zh) * | 2016-09-09 | 2017-02-15 | 博硕科技(江西)有限公司 | 耐刮擦无卤阻燃tpe注塑料及其制备方法 |
CN109988363B (zh) * | 2019-03-21 | 2022-01-07 | 武汉金发科技有限公司 | 一种聚丙烯复合材料及其制备方法 |
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