JP6586339B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition, a molded article, a sheet, a laminated sheet and a resin sheet obtained therefrom, a molded article obtained therefrom, and a method for producing the molded article.

  Currently, polycarbonate sheets satisfying VTM-0 having good transparency and flame retardancy are used in home appliances, OA, automobiles, industrial materials, construction fields, and the like. However, since the polycarbonate itself has low solvent resistance, it cannot be used for applications that require solvent resistance. Therefore, a sheet material made of polypropylene having good solvent resistance, which is highly transparent and satisfies the flame retardancy VTM-0 (thickness 0.2 mm) is desired.

  Patent Document 1 discloses that flame retardancy is exhibited in fibers, sheets, and films by blending a small amount of a weather-resistant NOR-type hindered amine with a polymer material, but it is transparent and VTM-0. There is no description of a polypropylene material from which a sheet film can be obtained.

  Patent Document 2 describes that the flame retardancy of a film is improved by adding a phosphate ester (1% by mass) to polypropylene / NOR hindered amine (1 to 1.5% by mass). (Examples 1-4). However, the flame retardancy is JIS No. A polypropylene material that has passed the vertical combustion test method of the L-1091A4 method and that satisfies the advanced VTM-0 has not been obtained.

  Patent Document 3 discloses a flame retardant sheet having a three-layer structure of A layer (surface layer) / B layer (intermediate layer) / C layer (surface layer), polyethylene A / random polypropylene as layer A, and homopolypropylene / random polypropylene as layer B. / NOR type hindered amine (3% by mass) / phosphate ester (10% by mass), flame retardant sheet using block polypropylene for C layer is disclosed (Example 3), but flame retardancy is VTM-2 There is no polypropylene material that can obtain a transparent and more highly satisfying sheet satisfying VTM-0. In particular, the compatibility between the phosphoric acid ester and polypropylene is very poor. Therefore, when 10 mass% of the phosphoric acid ester is blended, melt kneading itself becomes difficult. In addition, there is a problem that the phosphoric acid ester bleeds out on the surface of the sheet and a problem that the phosphoric acid ester is phase-separated to become cloudy and not transparent.

  For such problems, Patent Document 4 contains a cyclic resin (10 to 18% by mass) in a polyolefin resin (63 to 70% by mass) and a phosphoric acid compound (10 to 15% by mass). It is disclosed that bleeding of the phosphoric acid compound is suppressed, the composition has good transparency, and the flame retardancy is good in the VTM test (Examples 1 to 6). However, since the processing temperature of cycloolefin resin is very high compared with the processing temperature of polyolefin resin, there is concern about thermal decomposition of polypropylene, which is not realistic. In addition, the cycloolefin-based resin is very expensive and is not realistic as a blend material with a polyolefin material that requires low cost.

In Patent Document 5, as a method for suppressing bleeding out of a phosphoric acid derivative flame retardant, a polymer containing an OH group such as ethylene vinyl alcohol (EVOH) and a phosphoric acid derivative such as phosphoric acid or a phosphate compound are difficult. A method of suppressing the bleed-out of a phosphoric acid derivative flame retardant by performing a dehydration reaction of a flame retardant and bonding with a covalent bond is disclosed.
However, in Example 1, the high-density polyethylene / EVOH / monoammonium phosphate mixture is produced by melt-kneading with reaction, but there is a concern that bleed-out of unreacted components may occur. There is a method in which a chemical reaction between a polymer containing an OH group and a phosphoric acid derivative flame retardant is performed in advance to produce a flame retardant resin component and then melt-kneaded with a polyolefin resin, but the number of steps increases and the cost increases. Moreover, the material which has the high flame retardance of VTM-0 is not disclosed.

  That is, a sheet material made of polypropylene having high transparency and satisfying flame retardancy VTM-0 (thickness 0.2 mm) has not been reported yet.

Japanese translation of PCT publication No. 2002-507238 JP 2004-83913 A JP 2014-139001 A JP 2011-241368 A JP 2004-83788 A

  The objective of this invention is providing the resin composition which can obtain the polypropylene-type sheet | seat which has the outstanding flame retardance.

In a sheet comprising a resin composition containing polypropylene resin / phosphate ester / NOR hindered amine, when a large amount of phosphate ester is blended in order to obtain highly flame retardant VTM-0, the phosphate ester and the polypropylene resin Due to the low compatibility with the resin, the phosphoric acid ester is phase-separated, making melt kneading difficult, and there is a problem that flame retardancy is lowered.
Attempts were made to blend the cycloolefin resin described in Patent Document 4 as a compatibilizing agent for phosphate ester. However, since the kneading and processing temperature is increased, lowering the molecular weight by thermal decomposition of the polypropylene resin and the heat of NOR type hindered amine Decomposition occurred and high flame retardancy was not obtained.
Although a polymer containing an OH group described in Patent Document 5 was tried as a compatibilizing agent for phosphate ester, the phosphate ester did not react with the OH group of EVOH. Moreover, since the compatibility of EVOH and phosphate ester was low, phosphate ester bleeded out, transparency and appearance were bad, and high flame retardance was not obtained.

  As a result of intensive studies by the present inventors, a specific amount of a specific ethylene-vinyl acetate copolymer as a compatibilizer is blended in a resin composition comprising a polypropylene resin, a phosphorus flame retardant, and a NOR-type hindered amine. It has been found that phase separation of the flame retardant is reduced and melt kneading becomes possible, and the present invention has been completed.

（式（２０）中、Ｒ_１〜Ｒ_５は、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基又はハロゲン原子である。Ｒ_１〜Ｒ_５は同一でも異なっていてもよい。ｎは０〜３０の整数である。）
１２．前記式（２０）中のｎが０〜１０である１１に記載の樹脂組成物。
１３．前記（Ｃ）成分がトリフェニルホスフェート、レゾルシノールビス−ジキシレニルフォスフェート及びレゾルシノールビス−ジフェニルフォスフェートから選ばれる少なくとも１つである１〜８のいずれかに記載の樹脂組成物。
１４．前記（Ｃ）成分がトリフェニルホスフェート及びレゾルシノールビス−ジキシレニルフォスフェートから選ばれる少なくとも１つである１〜８のいずれかに記載の樹脂組成物。
１５．前記（Ｃ）成分がレゾルシノールビス−ジキシレニルフォスフェートである１〜８のいずれかに記載の樹脂組成物。
１６．前記（Ａ）成分がホモポリプロピレン及びランダムポリプロピレンから選ばれる少なくとも１つである１〜１５のいずれかに記載の樹脂組成物。
１７．前記（Ａ）成分がホモポリプロピレンである１〜１５のいずれかに記載の樹脂組成物。
１８．前記（Ａ）成分のＭＦＲが０．５〜３０ｇ／１０分である１〜１７のいずれかに記載の樹脂組成物。
１９．前記（Ｄ）成分中にカーボネート結合が含まれる１〜１８のいずれかに記載の樹脂組成物。
２０．前記（Ａ）成分の含有量が４６．０〜９１．８質量％である１〜１９のいずれかに記載の樹脂組成物。
２１．前記（Ｂ）成分の含有量が５質量％以上である１〜２０のいずれかに記載の樹脂組成物。
２２．前記（Ｂ）成分の含有量が３０質量％以下である１〜２１のいずれかに記載の樹脂組成物。
２３．前記（Ｂ）成分の含有量が２０質量％以下である１〜２１のいずれかに記載の樹脂組成物。
２４．前記（Ｃ）成分の含有量が５質量％以上である１〜２３のいずれかに記載の樹脂組成物。
２５．前記（Ｃ）成分の含有量が１５質量％以上である１〜２３のいずれかに記載の樹脂組成物。
２６．前記（Ｃ）成分の含有量が２０質量％以下である１〜２５のいずれかに記載の樹脂組成物。
２７．前記（Ｃ）成分の含有量が１０質量％以下である１〜２４のいずれかに記載の樹脂組成物。
２８．１〜２７のいずれかに記載の樹脂組成物を成形してなる成形体。
２９．１〜２７のいずれかに記載の樹脂組成物を成形してなるシート。
３０．２９に記載のシートにポリプロピレンを積層した積層シート。
３１．１〜２７のいずれかに記載の樹脂組成物からなる溶融樹脂を急冷して成形された樹脂シート。
３２．前記急冷を表面温度が露点以上５０℃以下に保たれた冷却ロールを用いて行う３１に記載の樹脂シート。
３３．２９に記載のシート、３０に記載の積層シート、又は３１もしくは３２に記載の樹脂シートを用いて附形して得られた成形品。
３４．前記シート、前記積層シート、又は前記樹脂シートを成形用金型の内面に装着し、成形用樹脂を供給して一体化して得られたものである３３に記載の成形品。
３５．前記成形品は、前記シート、前記積層シート、又は前記樹脂シートが非平面状に成形された成形品であり、
前記成形品は、前記シート、前記積層シート、又は前記樹脂シートを成形用金型の内面に合致するように附形し、得られた附形品を前記成形用金型の面に装着し、成形用樹脂を供給して一体化して得られたものである３３に記載の成形品。
３６．被覆される芯材を配設したチャンバーボックス内を減圧状態とし、前記前記シート、前記積層シート、又は前記樹脂シートを加熱軟化させ、前記チャンバーボックス内を加圧して、前記加熱軟化させた前記シート、前記積層シート、又は前記樹脂シートを前記芯材に押圧して被覆し、一体化して得られたものである３３に記載の成形品。
３７．基体の少なくとも一部に成形体を設ける成形物の製造方法であって、複数の冷却ロールに巻装された鏡面エンドレスベルトと鏡面冷却ロールとを備え、前記鏡面エンドレスベルトと前記鏡面冷却ロールの表面温度が露点以上５０℃以下に保たれた装置を用い、前記鏡面冷却ロールと前記鏡面エンドレスベルトとの間に、Ｔダイ押出機に１〜２７のいずれかに記載の樹脂組成物からなる溶融樹脂をより押し出して導入し、圧接してシート状に成形するとともに、前記鏡面エンドレスベルトに前記鏡面エンドレスベルトの表面温度より低い温度の冷却水を吹き付けることによって急冷して透明な樹脂シートを製造する工程と、前記樹脂シートを非平面状に成形して前記基体の少なくとも一部に設ける工程と、を実施する成形物の製造方法。 According to the present invention, the following resin composition and the like are provided.
1. The resin composition which contains the following (A)-(D) component in the following ratio.
(A) Polypropylene resin 16.0-95.8 mass%
(B) ethylene vinyl acetate copolymer 1-40 mass% whose content of the structural unit derived from vinyl acetate is 10-90 mass%
(C) 3 to 40% by mass of a phosphorus-based flame retardant that is liquid at 150 to 300 ° C.
(D) NOR type hindered amine compound 0.2 to 4.0 mass%
2. 2. The resin composition according to 1, which satisfies the following formula (1).
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content (mass%) of the component (C) in the resin composition, and Y is the component (B) in the total amount of the components (A) to (D). (The content (% by mass) of structural units derived from vinyl acetate.)
3. 3. The resin composition according to 1 or 2, wherein the content of the structural unit derived from vinyl acetate in the component (B) is 30% by mass or more.
4). The resin composition according to 1 or 2, wherein the content of the structural unit derived from vinyl acetate in the component (B) is 40% by mass or more.
5. The resin composition in any one of 1-4 whose content of the structural unit derived from the vinyl acetate in the said (B) component is 70 mass% or less.
6). The resin composition in any one of 1-5 whose mass ratio ((B) / (C)) of content of the said (B) component and the said (C) component is 1 or more.
7. The resin composition in any one of 1-6 whose MFR of the said (B) component is 0.5-30 g / 10min.
8). The resin composition in any one of 1-7 whose phosphorus content in the said (C) component is 8 mass% or more.
9. The resin composition according to any one of 1 to 8, wherein the component (C) is at least one selected from a phosphate ester compound, a phosphazene compound, and a phosphonate ester compound.
10. The resin composition according to any one of 1 to 8, wherein the component (C) is a phosphate ester compound.
11. The resin composition according to any one of 1 to 8, wherein the component (C) is a compound represented by the following formula (20).

(In formula (20), R _{1 to} R ₅ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or a halogen atom. R _{1 to} R ₅ may be the same or different. Is an integer from 0 to 30.)
12 12. The resin composition according to 11, wherein n in the formula (20) is 0-10.
13. The resin composition according to any one of 1 to 8, wherein the component (C) is at least one selected from triphenyl phosphate, resorcinol bis-dixylenyl phosphate, and resorcinol bis-diphenyl phosphate.
14 The resin composition according to any one of 1 to 8, wherein the component (C) is at least one selected from triphenyl phosphate and resorcinol bis-dixylenyl phosphate.
15. The resin composition according to any one of 1 to 8, wherein the component (C) is resorcinol bis-dixylenyl phosphate.
16. The resin composition according to any one of 1 to 15, wherein the component (A) is at least one selected from homopolypropylene and random polypropylene.
17. The resin composition according to any one of 1 to 15, wherein the component (A) is homopolypropylene.
18. The resin composition according to any one of 1 to 17, wherein the MFR of the component (A) is 0.5 to 30 g / 10 minutes.
19. The resin composition according to any one of 1 to 18, wherein a carbonate bond is contained in the component (D).
20. The resin composition according to any one of 1 to 19, wherein the content of the component (A) is 46.0 to 91.8% by mass.
21. The resin composition according to any one of 1 to 20, wherein the content of the component (B) is 5% by mass or more.
22. The resin composition according to any one of 1 to 21, wherein the content of the component (B) is 30% by mass or less.
23. The resin composition in any one of 1-21 whose content of the said (B) component is 20 mass% or less.
24. The resin composition according to any one of 1 to 23, wherein the content of the component (C) is 5% by mass or more.
25. The resin composition according to any one of 1 to 23, wherein the content of the component (C) is 15% by mass or more.
26. The resin composition in any one of 1-25 whose content of the said (C) component is 20 mass% or less.
27. The resin composition according to any one of 1 to 24, wherein the content of the component (C) is 10% by mass or less.
A molded article formed by molding the resin composition according to any one of 28.1 to 27.
The sheet | seat formed by shape | molding the resin composition in any one of 29.1-27.
A laminated sheet obtained by laminating polypropylene on the sheet according to 30.29.
A resin sheet formed by quenching a molten resin comprising the resin composition according to any one of 31.1 to 27.
32. 32. The resin sheet according to 31, wherein the rapid cooling is performed using a cooling roll whose surface temperature is maintained at a dew point or higher and 50 ° C. or lower.
A molded product obtained by forming using the sheet according to 33.29, the laminated sheet according to 30, or the resin sheet according to 31 or 32.
34. 34. The molded product according to 33, wherein the molded product is obtained by mounting the sheet, the laminated sheet, or the resin sheet on an inner surface of a molding die and supplying and integrating the molding resin.
35. The molded product is a molded product in which the sheet, the laminated sheet, or the resin sheet is molded in a non-planar shape,
The molded product is shaped such that the sheet, the laminated sheet, or the resin sheet matches the inner surface of the molding die, and the obtained molded product is attached to the surface of the molding die, 34. The molded product according to 33, which is obtained by supplying and integrating a molding resin.
36. The sheet in which the inside of the chamber box in which the core material to be coated is disposed is in a reduced pressure state, the sheet, the laminated sheet, or the resin sheet is heated and softened, the inside of the chamber box is pressurized and the heat softened 34. The molded product according to 33, wherein the laminate sheet or the resin sheet is obtained by pressing the core material to cover and integrate the core material.
37. A method of manufacturing a molded article in which a molded body is provided on at least a part of a substrate, comprising a mirror endless belt wound around a plurality of cooling rolls and a mirror cooling roll, and the surface of the mirror endless belt and the mirror cooling roll. A molten resin comprising a resin composition according to any one of 1 to 27 in a T-die extruder between a mirror surface cooling roll and the mirror surface endless belt using an apparatus maintained at a dew point of 50 ° C. or lower. A process of producing a transparent resin sheet by rapidly cooling by spraying cooling water having a temperature lower than the surface temperature of the mirror endless belt onto the mirror endless belt. And a step of forming the resin sheet into a non-planar shape and providing the resin sheet on at least a part of the base body.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the polypropylene-type sheet | seat which has the outstanding flame retardance can be provided.

It is a schematic block diagram of an example of the manufacturing apparatus for manufacturing the molding of this invention.

[Resin composition]
The resin composition of the present invention contains the following components (A) to (D) in the following proportions.
(A) Polypropylene resin 16.0-95.8 mass%
(B) ethylene vinyl acetate copolymer 1-40 mass% whose content of the structural unit derived from vinyl acetate is 10-90 mass%
(C) 3 to 40% by mass of a phosphorus-based flame retardant that is liquid at 150 to 300 ° C.
(D) NOR type hindered amine compound 0.2 to 4.0 mass%

The resin composition of the present invention can be melt-kneaded by having the above-described configuration, and has high flame retardancy (VTM-0).
Hereinafter, each component will be described.

((A) component)
Examples of the polypropylene resin as the component (A) include homopolypropylene, block polypropylene, and random polypropylene. Solvent resistance can be imparted by blending the component (A) polypropylene resin.
Homopolypropylene is a homopolymer of propylene, block polypropylene is a block copolymer of ethylene and propylene, and random polypropylene is a random copolymer of ethylene and propylene. These can be obtained by a conventionally known method. Moreover, 1 type may be used independently and may be used in combination of 2 or more type.
There are no particular limitations on the stereoregularity expressed by the isotactic pentad fraction or the like, the melt characteristics such as the melt tension and the swell ratio. In order to improve transparency, an additive such as a crystal nucleating agent may be added.

The MFR (230 ° C., 2.16 kg load) of the polypropylene resin (for example, homopolypropylene, block polypropylene or random polypropylene) of the component (A) is preferably 0.5 to 30 g / 10 minutes, more preferably 1 to It is 20 g / 10 minutes, and more preferably 2 to 10 g / 10 minutes. You may mix and use the polypropylene resin from which MFR differs.
The MFR of the component (A) is measured at 230 ° C. and a load of 2.16 kg according to the method of JIS K7210.

  If it is 0.5 g / 10 min or more, melt shear heat generation during melt-kneading can be prevented, and thermal decomposition of the component (C) and the component (D) can be suppressed, so that excellent flame retardancy can be secured. In addition, there is no significant difference in melt viscosity from component (B) (for example, a combination of a polypropylene resin having an MFR of less than 0.5 and an ethylene-vinyl acetate copolymer having a high MFR), resulting in a decrease in compatibility. In addition, phase separation during melt kneading is suppressed, and excellent transparency, flame retardancy, and solvent resistance can be secured.

  If it is 30 g / 10 min or less, sheet molding can be performed without any problem. Moreover, since it is moderate fluidity | liquidity, there is no molten drip cotton ignition at the time of a flame retardance test, and the outstanding flame retardance can be ensured. In addition, the difference in melt viscosity from the ethylene-vinyl acetate copolymer of component (B) is not significantly different (for example, a combination of an ethylene-vinyl acetate copolymer having a low MFR and a polypropylene resin having a high MFR). A decrease in solubility and phase separation during melt-kneading are suppressed, and excellent transparency, flame retardancy, and solvent resistance can be ensured.

  When homopolypropylene is used, the molded body is excellent in strength and rigidity. Moreover, when homopolypropylene or random polypropylene is used, it is excellent in transparency when it is used as a sheet.

(Other resin and processing aid ingredients)
The resin composition of this invention can add conventionally well-known resin and a process adjuvant component as needed in the range which does not impair the effect of this invention.

  For the purpose of imparting impact resistance, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polyolefin thermoplastic elastomer (TPO), or styrenic thermoplastic elastomer is used as necessary, as well as transparency and flame retardancy. Can be used in an appropriate amount within a range where it does not decrease (about 5% by mass or less).

  Examples of these resins include SBR [polystyrene-polybutadiene rubber], SBS [polystyrene-polybutadiene block-polystyrene], SEBS [polystyrene-poly (ethylene / butylene) block-polystyrene], SIR [polystyrene-polyisoprene rubber], SIS. [Polystyrene-polyisoprene block-polystyrene], SEEPS [polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene], SEP [polystyrene-poly (ethylene / propylene) block], SEPS [polystyrene-poly (ethylene / propylene) Block-polystyrene] and the like. Among these, hydrogenated butadiene block copolymers, block TPO, SEBS, SEPS and the like are particularly preferably used.

  Examples of commercially available products include Clayton series such as Dynalon 6200 manufactured by JSR Corporation, R-110MP manufactured by Prime Polymer Co., Ltd., Clayton G1651 manufactured by Shell Chemical Co., Ltd., and Septon Series such as Septon 2104 manufactured by Kuraray Co., Ltd. And Tuftec H series manufactured by Asahi Kasei Chemicals Corporation.

  Further, for the purpose of increasing the strength and rigidity, a polypropylene resin, a polyethylene resin, a polybutene resin, a polypentene resin, a thermoplastic elastomer, etc., modified with maleic anhydride, etc. An appropriate amount can be used within a range where flame retardancy does not decrease (about 5% by mass or less).

In addition, for the purpose of improving flame retardancy, an appropriate amount of flame retardant resin can be added as necessary.
Examples of the flame-retardant resin include Noryl PPO640 manufactured by SABIC, which is polyphenylene ether, and A1020LP manufactured by Unitika Co., Ltd., which is nylon 6.
The addition amount of the flame retardant resin is preferably in a range where the transparency does not decrease (about 10% by mass or less).

In addition, for the purpose of improving processability and impact resistance, mineral oil softeners should be added in an appropriate amount within a range where flame retardancy and transparency do not deteriorate (about 5% by mass or less) as necessary. Can do.
Mineral oil softeners are high-boiling petroleum fractions, those with paraffin chain carbon number of 50% or more of the total carbon number are paraffinic, those with 30-40% naphthenic ring carbon number are naphthenic, aromatic Those having a group carbon number of 30% or more are called aromatic mineral oil softeners.

  As the mineral oil softener, a mineral oil softener for rubber used for rubber is preferable. The mineral oil softener for rubber is a mixture in which an aromatic ring, a naphthene ring, and a paraffin chain are combined. As this mineral oil softener for rubber becomes more pollutant when the aromatic component increases, the weather resistance also decreases, so that the non-aromatic paraffinic and naphthenic rubber mineral oil softener, In particular, the mineral oil softener for paraffin rubber is preferable because it is colorless and transparent. Also, a liquid or low molecular weight synthetic softener can be used together with the mineral oil softener. Examples of commercially available products include process oils PW90, PW100, and PW380 manufactured by Idemitsu Kosan Co., Ltd.

  The content (% by mass) of the component (A) in the resin composition is 16.0 to 95.8% by mass, preferably 46.0 to 91.8% by mass, and more preferably 50 to 90% by mass. %.

((B) component)
The (B) component ethylene-vinyl acetate copolymer is a copolymer obtained from ethylene and vinyl acetate, and is a compatibilizer between the (A) component polypropylene resin and the (C) component phosphorus flame retardant. Acts as Since the component (B) uniformly disperses the phosphorus-based flame retardant of the component (C) in the composition, the resin composition can be melt-kneaded and excellent flame retardancy can be obtained. Moreover, the bleeding out of the phosphorus flame retardant of the component (C) in the resin composition is suppressed, and the transparency can be improved.

The MFR of the ethylene-vinyl acetate copolymer (B) is preferably 0.5 to 30 g / 10 minutes, more preferably 1 to 20 g / 10 minutes, and further preferably 3 to 10 g / 10 minutes. It is.
The MFR of the component (B) is measured at 190 ° C. and a 2.16 kg load according to the method of JIS K 6924-1.

  If it is 0.5 or more, shear heat generation during melt-kneading can be prevented, and thermal decomposition of the component (C) and the component (D) can be suppressed, so that excellent flame retardancy can be secured. In addition, the difference in melt viscosity from the polypropylene resin of the component (A) is not significantly different (for example, a combination of an ethylene-vinyl acetate copolymer having a low MFR and a polypropylene resin having a high MFR). Phase separation during melt-kneading is suppressed, and excellent transparency, flame retardancy, and solvent resistance can be secured.

  If it is 30 or less, the strand can be drawn without problems and can be extruded. In addition, there is no significant difference in melt viscosity from the polypropylene resin of component (A) (for example, a combination of an ethylene-vinyl acetate copolymer having a high MFR and a polypropylene resin having a low MFR) and excellent compatibility. Excellent in transparency, flame retardancy and solvent resistance.

  The content (% by mass) of the ethylene-vinyl acetate copolymer as the component (B) in the resin composition is 1 to 40% by mass, as 5% by mass or more, 30% by mass or less, or 20% by mass or less. Also good. (B) Content of a component becomes like this. Preferably it is 3-30 mass%, More preferably, it is 5-20 mass%.

  If the amount is 1% by mass or more, the component amount of the vinyl acetate structural unit having a high polarity is suitable for the compatibility of the phosphorus-based flame retardant of the component (C) having a high polarity, and melt kneading becomes possible. Further, if it is 40% by mass or less, the vinyl acetate structural unit having a high polarity is not excessive but is an appropriate amount, so that the compatibility with the polypropylene resin of the component (A) having a low polarity becomes moderately high, and melt kneading is possible. It becomes possible.

  The ethylene-vinyl acetate copolymer (B) has a content of structural units derived from vinyl acetate of 10 to 90% by mass, and may be 30% by mass or more, 40% by mass or more, or 70% by mass or less. Good. Content of the structural unit derived from vinyl acetate becomes like this. Preferably it is 20-80 mass%, More preferably, it is 30-70 mass%, More preferably, it is 40-60 mass%. Hereinafter, the “content of structural units derived from vinyl acetate” may be simply referred to as “content of vinyl acetate”.

  If the content of vinyl acetate is 10% by mass or more, the component amount of the highly polar vinyl acetate structural unit is appropriate for the compatibility of the highly polar (C) component phosphorus flame retardant, and melt kneading is possible It becomes. If the content of vinyl acetate is 90% by mass or less, the ethylene-vinyl acetate copolymer is not a lump and can be produced by a continuous melt extruder.

  The content of structural units derived from vinyl acetate in the component (B) is measured according to JIS K6924-1.

Moreover, it is preferable that the vinyl acetate content of the (B) component ethylene-vinyl acetate copolymer and the (C) component phosphorus flame retardant content satisfy the relationship of the formula (1).
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content (mass%) of the component (C) in the resin composition, and Y is vinyl acetate in the component (B) in the total amount of components (A) to (D). The content (% by mass) of the structural unit derived from

  When the formula (1) is satisfied, since there are relatively many highly polar vinyl acetate structural units, the compatibility with the highly polar (C) component phosphorus flame retardant increases, and as a result, the highly polar (C) Since the compatibility of the component phosphorus flame retardant and the low polarity (A) component polypropylene resin is excellent, the kneadability is excellent.

  By satisfying the content of the ethylene-vinyl acetate copolymer of the component (B) and the content of vinyl acetate, the component (B) is composed of the polypropylene resin of the component (A) and the phosphorus system of the component (C). Acts as a compatibilizer with the flame retardant, uniformly disperses the component (C) in the composition, and improves the compatibility of the components (A) and (B), so that the resin composition can be melt kneaded. It becomes possible, and excellent flame retardancy can be obtained.

  In addition, as shown below, by limiting the content of the ethylene-vinyl acetate copolymer of component (B), the content of vinyl acetate, the ratio of (B) / (C), etc., component (C) The compatibility of (A) is further increased, the bleeding out of the component (C) in the resin composition is suppressed, and the compatibility of the component (A) is further increased, whereby the transparency of the sheet can be improved.

  Specifically, the content (% by mass) of the ethylene-vinyl acetate copolymer as the component (B) is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and still more preferably 1 ˜20 mass%.

  When the content is 5% by mass or more, since there are a relatively large number of highly polar vinyl acetate structural units, phase separation of the (C) component phosphorus flame retardant and bleeding out of the (C) component phosphorus flame retardant may occur. There is no. That is, since the phosphorus flame retardant of component (C) is more uniformly mixed, the transparency of the sheet is excellent. Moreover, if it is 30 mass% or less, since the vinyl acetate structural unit with a high polarity is an appropriate amount, it is excellent in compatibility with the polypropylene resin of the component (A) having a low polarity and is kneaded uniformly without phase separation. And the molded article is excellent in flame retardancy, transparency and solvent resistance.

Further, the ratio (B) / (C) of the content (mass%) of the ethylene-vinyl acetate copolymer of the component (B) and the content (mass%) of the phosphorus flame retardant of the component (C) is: It is preferably 1 or more. If it is 1 or more, since there are a relatively large number of highly polar vinyl acetate structural units, there is no risk of phase separation of the phosphorus flame retardant of component (C) and bleeding out of the phosphorus flame retardant of component (C). . That is, since the phosphorus flame retardant of component (C) is more uniformly mixed, the transparency of the sheet is excellent.
(B) / (C) is preferably 1.2 or more, more preferably 1.5 or more.

  Moreover, content of the structural unit derived from vinyl acetate becomes like this. Preferably it is 30-70 mass%, More preferably, it is 35-65 mass%, More preferably, it is 40-60 mass%.

  If the vinyl acetate content is 30% by mass or more, there are relatively many highly polar vinyl acetate structural units, which may cause phase separation of highly polar phosphorus-based flame retardants and bleed-out of phosphorus-based flame retardants. Absent. That is, since the phosphorus-based flame retardant is mixed more uniformly, the transparency of the sheet is excellent.

  If it is 70% by mass or less, the vinyl acetate structural unit having a high polarity is not excessive but is in an appropriate amount, so that it has excellent compatibility with the polypropylene resin of the component (A) having a low polarity and is uniformly kneaded without phase separation. can do. That is, the molded product is excellent in flame retardancy, transparency and solvent resistance.

  Moreover, if it is 70 mass% or less, free acetic acid will not generate | occur | produce at the time of thermoforming, and it can prevent that the metal part of an apparatus is corroded and a health hazard is carried out to an operator. In addition, the crosslinking reaction and gelation caused by the elimination of acetic acid can be suppressed, and the product quality is not adversely affected.

As the ethylene-vinyl acetate copolymer of component (B), those obtained by a conventionally known method can be used. Examples of commercially available products of component (B) include Soabrene from Nippon Synthetic Chemical Industry Co., Ltd., Everflex from Mitsui DuPont Polychemical Co., Ltd., Revaprene from LANXESS, and the like.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

((C) component)
The phosphorus flame retardant as the component (C) is a flame retardant having a liquid at 150 ° C. to 300 ° C., that is, a melting point of 300 ° C. or less. If a flame retardant that is solid at the time of melt kneading (for example, a flame retardant having no melting point) is used, the flame retardant is not liquid at the time of melt kneading, so it is not uniformly dispersed in component (A) or (B) There is a risk that physical properties may be lowered or flame retardancy may be reduced.

  The phosphorus flame retardant as the component (C) is not particularly limited as long as the above conditions are satisfied, and those obtained by a conventionally known method or commercially available products can be used. A phosphoric acid ester compound, a phosphazene compound, or a phosphonic acid ester compound is preferable, and among them, a phosphoric acid ester having excellent transparency is most preferable.

Phosphate ester compounds include trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl Monomer phosphate compounds such as diphenyl phosphate (CDP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP), bisphenol A bis-crecresyl phosphate Phosphorus oxychloride and dihydric phenolic compounds such as phosphate, biphenol bis-diphenyl phosphate, biphenol bis-dixylenyl phosphate, and phenol (or alkyl phosphate) Aromatic condensed phosphoric acid ester compounds such as a reaction product of Knoll) and the like.
Among these, triphenyl phosphate (TPP), tricresyl phosphate (TCP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP) , Biphenol bis-diphenyl phosphate, biphenol bis-dixylenyl phosphate, more preferably triphenyl phosphate (TPP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, Resorcinol bis-dixylenyl phosphate is preferred.

As the phosphazene compound, 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3 , 3,5,5-hexa (n-propoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (iso-propoxy) cyclotriphosphazene, 1,1,3,3,5,5 -Hexa (n-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (iso-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (phenoxy) cyclo Triphosphazene, 1,1,3,3,5,5-hexa (p-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (m-tolyloxy) cyclotriphosphazene, 1 1,3,3,5,5-hexa (o-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-ethylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-hexa (4-n-propylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-iso-propylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-hexa (4-t-butylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-t-octylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-hexa (2,3-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,4-dimethylphenoxy) cyclotriphosphazene, 1,1,3 , 5,5-hexa (2,5-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,6-dimethylphenoxy) cyclotriphosphazene, 1,3,5-tris (Methoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3 , 5-Tris (n-butoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tri (Phenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3 5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy)- 1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris (Ethoxy) -1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (p- Ryloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1, 3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (N-butoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene 1,3,5-tris (methoxy) -1,3,5-tris (4-t-butylphenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) ) -1,3,5-tris (4-t-octylphenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-t-butylphenoxy) cyclo Examples include triphosphazene and 1,3,5-tris (n-propoxy) -1,3,5-tris (4-t-octylphenoxy) cyclotriphosphazene.
Among these, 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3 3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1 , 3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, more preferably 1,1,3, 3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3 - tris (phenoxy) a cyclotriphosphazene, more preferably 1,1,3,3,5,5 hexa (phenoxy) cyclotriphosphazene.

式（１０）中、Ｒ^１〜Ｒ^５は、水素原子、又は置換基を有していてもよい炭化水素基であり、Ｒ^１〜Ｒ^５はそれぞれ同一でも異なっていてもよい。
炭化水素基としては、鎖状（直鎖及び分岐鎖のいずれでもよい）及び環状（単環、縮合多環、架橋環及びスピロ環のいずれでもよい）のいずれであってもよく、例えば、側鎖を有する環状炭化水素基が挙げられる。また、炭化水素基は、飽和及び不飽和のいずれでもよい。
炭化水素基としては、例えばアルキル基、シクロアルキル基、アリル基、アリール基、アルキルアリール基、アリールアルキル基等が挙げられる。 Examples of the phosphonic acid ester include those represented by the following formula (10).

In formula (10), R < ¹ > -R < ⁵ > is a hydrocarbon group which may have a hydrogen atom or a substituent, and R < ¹ > -R < ⁵ > may be the same or different, respectively.
The hydrocarbon group may be any of a chain (which may be either a straight chain or a branched chain) or a cyclic (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring). Examples thereof include a cyclic hydrocarbon group having a chain. Further, the hydrocarbon group may be either saturated or unsaturated.
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

Specific examples of the phosphonic acid ester represented by the above formula include compounds represented by the following formulas (10) -1 to (10) -8.

  Among these, Preferably it is Formula (10) -1-(10) -6, More preferably, it is Formula (10) -1-(10) -3, More preferably, it is Formula (10) -1. .

Content (mass%) of the phosphorus flame retardant of the (C) component in a resin composition is 3-40 mass%, 5 mass% or more, 15 mass% or more, 20 mass% or less, or 10 mass%. It is good also as follows. (C) Content (mass%) of a component becomes like this. Preferably it is 5-35 mass%, More preferably, it is 15-30 mass%.
If it is 3 mass% or more, the high flame retardance of VTM-0 will be obtained. If the content is 40% by mass or less, the content of the phosphorus-based flame retardant of the component (C), which has a low compatibility with the polypropylene resin of the component (A), is an appropriate amount. If a specific amount of the polymer is contained, there is no phase separation of the phosphorus flame retardant of component (C), and uniform melt-kneading can be performed.

The phosphorus flame retardant as the component (C) preferably has a phosphorus content of 8% by mass or more, more preferably 9% by mass or more, or 10% by mass or more.
When the phosphorus content is 8% by mass or more, the phosphorus atom having sufficient flame retardancy is sufficiently contained, so that the flame retardancy is excellent.
The phosphorus content is measured by absorptiometry.

式（２０）中、Ｒ_１〜Ｒ_５は水素原子、炭素数１〜１０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基又はハロゲン原子であり、Ｒ_１〜Ｒ_５は同一でも異なっていてもよい。ｎは０〜３０の整数であり、好ましくは０〜１０の整数である。 The phosphorus flame retardant as the component (C) is preferably represented by the following formula (20). When this compound is used, the sheet is excellent in transparency and bleed resistance.

In Formula (20), R _{1 to} R ₅ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. A group or a halogen atom, and R _{1 to} R ₅ may be the same or different. n is an integer of 0 to 30, preferably an integer of 0 to 10.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl and the like.
Examples of the cycloalkyl group include cyclohexyl.
Examples of the aryl group include phenyl, cresyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl and the like.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The phosphorus-based flame retardant component (C) has the following compound No. 1 from the viewpoint of achieving both flame retardancy and transparency. 1, 2 or 3 is preferred, and compound No. 2 or 3 is more preferable. 2 is more preferable.
Compound No. 1 (triphenyl phosphate) is, for example, TPP, Compound No. 2 (resorcinol bis-dixylenyl phosphate) is, for example, PX-200, compound no. As 3 (resorcinol bis-diphenyl phosphate), for example, CR-733S manufactured by Daihachi Chemical Industry Co., Ltd. can be used.

  When the phosphoric acid ester compound of the formula (20) is used, both flame retardancy VTM-0 and transparency can be achieved.

Content (mass%) of the phosphoric acid ester compound of Formula (20) becomes like this. Preferably it is 3-20 mass%, More preferably, it is 4-15 mass%, More preferably, it is 5-10 mass%. If it is 3 mass% or more, highly flame-retardant VTM-0 will be obtained and transparency will also be favorable. Moreover, if it is 20 mass% or less, since the content of the phosphoric acid ester compound of the (C) component having low compatibility with the polypropylene resin of the (A) component is an appropriate amount, the phosphoric acid ester compound of the (C) component Phase separation and bleed-out, resulting in a transparent and highly flame retardant VTM-0.
As the component (C), one type may be used alone, or two or more types may be used in combination.

((D) component)
The NOR-type hindered amine compound (stabilizer) as the component (D) is well known as a light stabilizer, but is also known to have a function as a flame retardant.

The alkoxyimino group of the NOR (alkoxyimino group) type hindered amine stabilizer is an NH type in which the imino group part of the piperidine ring remains NH, and NCH ₃ type in which H is replaced by a methyl group, -Alkoxyl group (> N-OR) structure, and these groups easily capture radicals of alkyl peroxy radicals (RO _2. ) And exhibit a flame retardant effect.
In the case of an N-methyl type hindered amine stabilizer or an NH type hindered amine stabilizer instead of the NOR type hindered amine stabilizer, flame retardancy may be reduced.

  Said alkoxyl group (OR) is not limited to the alkoxyl group which oxygen couple | bonded with the alkyl group, R contains a cycloalkyl group, an aralkyl group, and an aryl group other than an alkyl group. As specific examples of these alkoxyl groups, a methoxy group, a propoxy group, a cyclohexyloxy group, and an octyloxy group are preferable, and in particular, a propoxy group, a cyclohexyloxy group, an octyloxy group, and the like have an increased molecular weight. It is preferable from the point which can suppress the bleed out from a film.

  The NOR type hindered amine stabilizer used in the present invention is not particularly limited as long as it is a compound having a structure of an N-alkoxyl group (> N-OR). Specific examples include NOR-type hindered amine stabilizers described in JP-T-2002-507238, WO 2005/082852, WO 2008/003605, and the like.

  The component (D) is preferably a compound containing a carbonate bond. When a carbonate bond is included, the flame retardancy and bleed resistance are excellent.

Moreover, the following compounds are mentioned as an example of a specific compound.
(A) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine (b) bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate (c) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine ( d) Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate (e) 4,4′-hexamethylenebis (amino-2,2,6,6-tetramethyl) Piperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2, endcapped with 2-chloro-4,6-bis (dibutylamino) -s-triazine. 6,6-Tetramethylpiperidin-4-yl) butylamino] -s-triazine is an oligomeric compound (f) 4,4′-hexamethylenebis (amino-2,2,6,6) -Tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6, end-capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine Oligomeric compound (g) 2,4-bis [(1-cyclohexyloxy-2,2,6,6) which is a condensable product with 6-tetramethylpiperidin-4-yl) butylamino] -s-triazine -Piperidin-4-yl) -6-chloro-s-triazine (h) peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine and 2,4,6-trichloro-s A reaction product (N, N ′, N ′ ″-tris {2,4-bis) of triazine, cyclohexane and N, N′-ethane-1,2-diylbis (1,3-propanediamine) [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazin-6-yl} -3,3′-ethylenediiminodipropylamine)
(I) Bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (J) 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one (K) Bis (1-stearyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate

Examples of commercially available products include Flamestab NOR116FF, TINUVIN NOR371, TINUVIN 123S, TINUVIN XT850FF, TINUVIN XT855FF, and ADEKA LA-81 manufactured by BASF Corporation.
The NOR type hindered amine stabilizer (D) may be used alone or in combination of two or more.

The content (mass%) of the NOR-type hindered amine stabilizer (D) is 0.2 to 4 mass%, preferably 0.5 to 3 mass%, more preferably 1 to 2 mass%. It is.
If it is 0.2 mass% or more, highly flame-retardant VTM-0 will be obtained. Further, if it is 4% by mass or less, there is no problem such as fusion and coloring of pellets and sheets at the time of melt-kneading and molding by the component (D) that acts as a plasticizer, and high-quality pellets and sheets are obtained, Moreover, the high cost by adding a large amount of expensive NOR type hindered amine stabilizers can be avoided.

(Other additives)
In addition to the above components (A) to (D), the resin composition of the present invention may be added with conventionally known additives, processing aids and the like as necessary within the range not impairing the effects of the present invention. it can. Examples of these additives include antioxidants, weathering agents, lubricants, antistatic agents, nucleating agents, metal deactivators, and fillers.

Examples of the antioxidant include phenolic compounds, phosphorus compounds, and thioether compounds.
Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4- Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tertiarybutyl-m-cresol) 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- m-cresol), 2,2′-ethylidenebis (4,6-ditertiarybutylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tertiarybutylphenol), , 1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanate Nurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert-butyl) -4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [(3 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tertiary 3-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, And reethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. You may use these in mixture of 2 or more types.

  Examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tertiary 3butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphos Phyto, bis (2,4-dicumylphenyl) pentae Thritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6 Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis) tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl ) Oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol phosphite. You may use these in mixture of 2 or more types.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). These may be used as a mixture of two or more.

As the weathering agent, an ultraviolet absorber, a hindered amine light stabilizer, or the like can be used.
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzo Triazol, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4- 2- (2′-hydroxyphenyl) benzotriazole such as 3-octyl-6- (benzotriazolyl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiary amylphenyl-3,5-ditertiary Benzoates such as butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxanilide Substituted oxanilides such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl Cyanoacrylates such as ru-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2, And triaryltriazines such as 4-ditertiarybutylphenyl) -s-triazine. You may use these in mixture of 2 or more types.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6 6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) he Sun / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6 , 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane. You may use these in mixture of 2 or more types.

As the lubricant, fatty acid amides, fatty acid esters, fatty acids, fatty acid metal salt systems and the like can be used.
Examples of aliphatic amide lubricants include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, ethylene bis lauric acid amide, and the like. It is done. You may use these in mixture of 2 or more types.
Aliphatic ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, palmitic acid Isopropyl, octyl palmitate, octyl palm fatty acid, octyl stearate, beef tallow fatty acid octyl ester, lauryl lauryl, stearyl stearate, behenyl behenate, cetyl myristate, 28-30 carbon linear and unbranched saturated Monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerol ester, montanic acid and butylene glycol ester, montanic acid and trimethylolethane ester Esters of montanic acid and trimethylolpropane, esters of montanic acid and pentaerythritol, glycerol monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, Examples thereof include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate and the like. You may use these in mixture of 2 or more types.

Among the fatty acid lubricants, as saturated fatty acids, specifically, lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) , Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid ( Hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid and the like, and in particular, lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid.
Among the fatty acid lubricants, as the unsaturated fatty acid, specifically, myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid) ), Ricinoleic acid (octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid ( 9,11,13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid), and the like. You may use these in mixture of 2 or more types.

  Examples of the fatty acid metal salt lubricant include lithium salts, calcium salts, magnesium salts, and aluminum salts of fatty acids of the above fatty acid lubricants. You may use these in mixture of 2 or more types.

As the antistatic agent, fatty acid partial esters such as cationic, anionic, nonionic, amphoteric, and glycerin fatty acid monoesters can be used.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate , (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate Alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, monoglyceride stearate , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. You may use these in mixture of 2 or more types.

As the nucleating agent, sorbitols, phosphorus-based, rosins, petroleum resins and the like can be used.
Examples of sorbitols such as alkyl-substituted benzylidene sorbitol include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, and 1,3-o-methyl. Benzylidene 2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethylbenzylidene) sorbitol . Examples of phosphorus-based compounds include bis (4-t-butylphenyl) sodium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) sodium phosphate, and organic phosphate-based composite products. Other examples include sodium benzoate, aluminum pt-butylbenzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin clay, talc, rosins, petroleum resins and the like. You may use these in mixture of 2 or more types.

As the metal deactivator, triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like can be used.
Specifically, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, decanedicarboxylic acid disali Tyroylbidazide, bisbenzylidenehydrazide oxalate, N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide, melamine, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5-t-butyl) phenyl- 5-methyl] phosphite and the like. You may use these in mixture of 2 or more types.

  As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whisker and the like can be used.

  In addition, an antiblocking agent, a coloring agent, an antiblooming agent, a surface treatment agent, an antibacterial agent, an anti-fogging agent (silicone oil described in JP-A-2009-120717, a monoamide compound of a higher aliphatic carboxylic acid, and a higher aliphatic carboxyl An anti-smudge agent such as a monoester compound obtained by reacting an acid with a monovalent to trivalent alcohol compound) may be added.

  The addition amount of the additive and the processing aid is usually 0.05 to 5% by mass in the resin composition.

The resin composition of the present invention may consist essentially of the components (A) to (D) and optional addition components. Moreover, you may consist only of (A) component-(D) component or only (A) component-(D) component and arbitrary addition components.
“Substantially only composed of the component (A) to the component (D) and the optional additive component” means that 95% by mass to 100% by mass (preferably 98% by mass to 100% by mass) of the composition is (A ) Component to (D) component, or (A) component to (D) component and an optional additive component.
In addition, the composition of this invention may contain an unavoidable impurity other than (A) component-(D) component and arbitrary addition components in the range which does not impair the effect of this invention.

[Method for Producing Resin Composition]
The resin composition of this invention can be manufactured by melt-kneading each component by arbitrary methods. Examples thereof include a method of using a high-speed stirrer represented by a Henschel mixer, a batch kneader represented by a Banbury mixer, a single or biaxial continuous kneader, a roll mixer and the like alone or in combination.

[Molded body, sheet]
By molding the resin composition of the present invention, a molded body such as a sheet can be produced.
As the molding method, a conventionally known molding method can be employed, and examples thereof include injection molding, sheet molding, extrusion molding, profile extrusion molding, and hot press molding. Among these, the method of forming a sheet using a melt extruder is preferable from the viewpoint of excellent appearance of the obtained molded product and economical efficiency. These molding conditions are not particularly limited.

The molded body of the present invention has flame retardancy that passes UL94 VTM-0 (thickness 0.2 mm).
The molded article of the present invention can be suitably used for applications that require the characteristics of polypropylene, such as tracking resistance, electrical insulation and chemical resistance. Specifically, among the molded products, transparent thin molded products are, for example, computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electrical / electronic devices, personal digital assistants, home appliance parts, automobile parts, industrial materials. It is preferably used for building materials and the like. In particular, the transparent thin molded article is preferably a display film, a decorative film, an insulating sheet, a masking sheet, and a curing sheet. Furthermore, a decorative sheet, a battery case, a plastic frame, and the like for which a demand for a transparent thin-walled molded body has been increasing in recent years can also be cited as suitable applications.

[Laminated sheet]
A laminated sheet can be obtained by laminating polypropylene on the sheet of the present invention. By laminating polypropylene, the sheet of the present invention can be prevented from coming into direct contact with the sheet forming line, and adhesion of the phosphorus-based flame retardant can be prevented.
Moreover, a weather resistance and a flame retardance can be provided by adding a NOR type hindered amine compound (stabilizer) to polypropylene. The NOR type hindered amine compound is the same as described above.

[Resin sheet]
The resin sheet of the present invention can be obtained by rapidly cooling and molding the molten resin comprising the resin composition of the present invention. By rapid cooling, even if the sheet is molded into a complicated shape, the sheet is not whitened, and excellent design properties can be imparted. Moreover, transparency can be further improved.
In this case, it is preferable to perform rapid cooling using a cooling roll whose surface temperature is maintained at a dew point or higher and 50 ° C. or lower. By doing in this way, whitening of a sheet | seat can further be prevented.

In addition, the above molding uses a mirror endless belt wound around a plurality of cooling rolls and a mirror cooling roll, and uses an apparatus in which the surface temperatures of the mirror endless belt and the mirror cooling roll are kept at a dew point or higher and 50 ° C. or lower. Can be done.
In this case, a molten resin made of a resin composition is introduced between a mirror surface cooling roll and a mirror surface endless belt by a T-die extruder, pressed into a sheet shape, and the mirror surface endless belt has a temperature lower than the surface temperature of the belt. The sheet is manufactured by spraying temperature cooling water and quenching.

  The obtained sheet is formed into a non-planar shape and provided on at least a part of the substrate. Even if it is molded into a complicated shape, whitening of the sheet can be prevented, and even a molded product having a complicated shape can be well-decorated without deteriorating the appearance.

An example of the manufacturing apparatus is shown in FIG.
The manufacturing apparatus shown in FIG. 1 includes an extruder T-die 12, a first cooling roll 13, a second cooling roll 14, a third cooling roll 15, a fourth cooling roll 16, a metal endless belt 17, and a cooling water spray nozzle 18. A water tank 19, a water absorption roll 20, and a peeling roll 21.
A method for manufacturing the sheet 11 by rapid cooling using the manufacturing apparatus configured as described above will be described below.

  First, the surface temperature of the metal endless belt 17 and the fourth cooling roll 16 that directly contacts and cools the extruded molten resin is maintained at a dew point of 50 ° C. or less, preferably 30 ° C. or less. Temperature control of each cooling roll 13, 14, 15, 16 is performed in advance.

  Here, if the surface temperature of the fourth cooling roll 16 and the metal endless belt 17 is equal to or lower than the dew point, condensation may occur on the surface, and uniform film formation may be difficult. On the other hand, when the surface temperature is higher than 50 ° C., the transparency of the obtained sheet 11 is lowered, and α crystals are increased, which may make it difficult to perform thermoforming. Accordingly, the surface temperature is 14 ° C., for example.

Next, the molten resin (excluding the nucleating agent) extruded from the T die 12 of the extruder is sandwiched between the metal endless belt 17 and the fourth cooling roll 16 on the first cooling roll 13. In this state, the molten resin is pressed by the first and fourth cooling rolls 13 and 16 and rapidly cooled at 14 ° C.
At this time, the elastic material 22 is compressed and elastically deformed by the pressing force between the first cooling roll 13 and the fourth cooling roll 16.
The rapidly cooled sheet is press-contacted by the cooling rolls 13 and 16 at the portion where the elastic material 22 is elastically deformed, that is, the arc portion corresponding to the central angle θ1 of the first cooling roll 13. The surface pressure at this time is usually 0.1 MPa or more and 20 MPa or less.

The sheet press-contacted as described above and sandwiched between the fourth cooling roll 16 and the metal endless belt 17 continues with the metal endless belt 17 at an arc portion corresponding to the substantially lower half circumference of the fourth cooling roll 16. The sheet is sandwiched between the fourth cooling rolls 16 and pressed in a planar shape, and further cooled rapidly by blowing cooling water to the back side of the metal endless belt 17 by the cooling water blowing nozzle 18. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less, and the temperature of the cooling water is 8 ° C., for example.
The sprayed cooling water is collected in the water tank 19, and the collected water is discharged from the drain outlet 19A.

After the sheet pressure contact and cooling by the fourth cooling roll 16 as described above, the sheet that is in close contact with the metal endless belt 17 is moved onto the second cooling roll 14 as the metal endless belt 17 rotates. Here, the sheet guided by the peeling roll 21 and pressed to the second cooling roll 14 side is pressed by the metal endless belt 17 at the arc portion corresponding to the substantially upper half circumference of the second cooling roll 14 as described above. And cooled again at a temperature of 30 ° C. or lower. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less.
In addition, the water adhering to the back surface of the metal endless belt 17 is removed by the water absorption roll 20 provided during the movement from the fourth cooling roll 16 to the second cooling roll 14.

  The sheet cooled on the second cooling roll 14 is peeled off from the metal endless belt 17 by the peeling roll 21 and wound up at a predetermined speed by a winding roll (not shown).

[Molding]
A molded product (sheet), a laminated sheet or a resin sheet (hereinafter, these may be referred to as “sheets”) of the present invention can be formed into a molded product. The attachment is usually performed by thermoforming.

When performing decorative molding using the molded article of the present invention, it can be performed by insert molding. By providing the molded product of the present invention on a part of the substrate by insert molding, it is possible to satisfactorily decorate a complex-shaped substrate.
Specifically, the insert formation is characterized in that a sheet or the like is formed into a non-planar shape, the sheet or the like is shaped so as to match the inner surface of the molding die, and the shaped product is attached to the inner surface of the molding die. And is integrated by supplying molding resin.

Further, the decorative molding can be performed by in-mold molding. By providing the molded product of the present invention on a part of the base body by in-mold molding, a complex-shaped base body can be favorably decoratively molded.
Specifically, in-mold formation is performed by mounting a sheet or the like on the inner surface of a molding die and supplying a molding resin to be integrated.

The decorative molding can also be performed by coating molding. By providing the molded product of the present invention on a part of the substrate by coating, a complex-shaped substrate can be favorably decorated.
Specifically, in coating formation, the inside of the chamber box in which the core material to be coated is placed in a reduced pressure state, the sheet is heated and softened, and the pressure inside the chamber box is pressed and the softened sheet is pressed against the core material. Then, it is coated and integrated.

[Modification]
In addition to the above-described insert molding, in-mold molding, and coating molding, various methods capable of providing a sheet or the like on a part of the substrate, such as a transfer molding method in which the sheet is peeled off after coating to leave only ink, can be used. Moreover, a sheet | seat etc. may provide not only the structure provided only in one part of the surface of the molded object but a some molded object.

  The improvement of the design property by obtaining transparency is obtained. Furthermore, a printing layer or a vapor deposition layer may be provided, and a sheet or the like may be formed and insert-molded as a molded body, or a printed layer may be provided on a molded body obtained by forming a sheet or the like.

As a molded object, it is good also as a layer structure shown below.
(A) Polypropylene layer (sheet of the present invention) / substrate (B) polypropylene layer (sheet of the present invention) / printing layer / substrate (C) printed layer / polypropylene layer (sheet of the present invention) / substrate (D) polypropylene layer (Sheet of the present invention) / printing layer / polypropylene layer B (base material layer) / substrate (E) printed layer / polypropylene layer (sheet of the present invention) / printing layer / substrate (F) polypropylene layer (sheet of the present invention) / Printing layer / metal thin film layer / substrate (G) polypropylene layer (sheet of the present invention) / deposition layer / substrate (H) vapor deposition layer / polypropylene layer (sheet of the present invention) / substrate (I) polypropylene layer (of the present invention) Sheet) / deposition layer / polypropylene layer B (base material layer) / substrate (J) printing layer / polypropylene layer (sheet of the present invention) / printing layer / substrate (K) polypropylene layer (sheet of the present invention) / easy contact Layer / print layer / substrate (L) (sheet of the present invention) Polypropylene layer / adhesion layer / vapor deposited layer / substrate

In the layer configuration (B), the printed layer is protected by the polypropylene layer located on the surface side, and good design properties by the printed layer can be stably provided for a long period of time.
In the configuration of (C), even when the printing layer is weak against heat at the time of insert molding, for example, a good printing layer can be formed without being denatured by heat at the time of insert molding.
In the layer structure of (D), since a base material layer is provided, it is not deformed by heat at the time of insert molding, a good printing layer can be formed, and the polypropylene layer can prevent peeling of printing, and thus a design such as decoration Can be easily improved.
In the layer configuration (E), high design properties can be provided by providing a plurality of printing layers.
In the layer configuration of (F), high designability can be provided by providing a metal thin film layer having reflection characteristics such as an aluminum layer.
In the layer configuration (G), the vapor deposition layer is protected by the polypropylene layer located on the surface side, and good design properties by the vapor deposition layer can be stably provided for a long period of time.
In the configuration of (H), even when the vapor deposition layer is weak to heat at the time of insert molding, for example, a good vapor deposition layer can be formed without being denatured by the heat at the time of insert molding.
In the layer structure of (I), since the base material layer is provided, it is not deformed by heat at the time of insert molding, a good vapor deposition layer can be formed, and the polypropylene layer can prevent the vapor deposition layer from peeling off. It is easy to improve the design.
In the layer configuration (J), high designability can be provided by providing a plurality of vapor deposition layers.
In the layer configuration (K), since the easy adhesion layer is provided between the polypropylene layer and the printing layer, the ink adhesion of the printing layer can be improved.
In the layer configuration of (L), since the easy adhesion layer is provided between the polypropylene layer and the vapor deposition layer, the adhesion strength of the metal or metal oxide of the vapor deposition layer can be improved.
Furthermore, you may provide another layer in the said layer structure.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited at all by these Examples.
The components used in Examples and Comparative Examples are shown below. In addition, although [(X ') component] does not correspond to X component used by this invention, it shows that it is a component corresponding to X component.

[(A) component]
Homopolypropylene A [MFR = 0.5 g / 10 min (230 ° C., 2.16 kg), Prime Polymer Co., Ltd. E-105GM]
Homopolypropylene B [MFR = 3.0 g / 10 min (230 ° C., 2.16 kg), Prime Polymer F-133A, Inc.]
Homopolypropylene D [MFR = 30 g / 10 min (230 ° C., 2.16 kg), Prime Polymer F109V, Inc.]
Random polypropylene A [MFR = 7.0 g / 10 min (230 ° C., 2.16 kg), Prime Polymer F-744NP]
・ Random polypropylene B [MFR = 25 g / 10 min (230 ° C., 2.16 kg), F329RA manufactured by Prime Polymer Co., Ltd.]
-Ethylene-propylene block copolymer G [MI = 3 g / 10 min (210 ° C., 2.16 kg), J-466HP manufactured by Prime Polymer Co., Ltd.]

[Component (B)]
Ethylene vinyl acetate copolymer A [MFR = 1 g / 10 min (190 ° C., 2.16 kg), vinyl acetate content 40% by mass, repaprene 400 manufactured by LANXESS]
-Ethylene vinyl acetate copolymer B [MFR = 1.7 g / 10 min (190 ° C., 2.16 kg), vinyl acetate content 50 mass%, repaprene 500 manufactured by LANXESS]
-Ethylene vinyl acetate copolymer C [MFR = 3.8 g / 10 min (190 ° C., 2.16 kg), vinyl acetate content 70 mass%, repaprene 700 manufactured by LANXESS]
-Ethylene vinyl acetate copolymer D [MFR = 5.0g / 10min (190 degreeC, 2.16kg), vinyl acetate content 24 mass%, NUC NUC-3195]

[(B ′) component]
-Ethylene vinyl acetate copolymer G [MFR = 5.5g / 10min (190 degreeC, 2.16kg), vinyl acetate content 6 mass%, NUC-3660 by NUC]
・ Cycloolefin polymer [MFR = 10 g / 10 min (260 ° C., 2.16 kg), glass transition temperature 123 ° C., ZEONEX 330R manufactured by Nippon Zeon Co., Ltd.]
Styrene elastomer [MFR = 2.0 g / 10 min (230 ° C., 2.16 kg), styrene / ethylene / butylene ratio = 67/33, Tuftec H1043 manufactured by Asahi Kasei Chemicals Corporation]
-Ethylene-vinyl alcohol copolymer [MFR = 12 g / 10 min (210 ° C., 2.16 kg), ethylene content 44 mol%, Nippon Synthetic Chemical Industry Co., Ltd., Soarnol A4412]

[Component (C)]
Phosphate ester A (Compound No. 1): Triphenyl phosphate [manufactured by Daihachi Chemical Industry Co., Ltd. TPP, melting point 49 ° C., phosphorus content 9.5%]
Phosphoric acid ester B (Compound No. 2): Resorcinol bis-dixylenyl phosphate [PX-200 manufactured by Daihachi Chemical Industry Co., Ltd., melting point 92 ° C., phosphorus content 9.0%]
-Phosphate ester C (Compound No. 3): Resorcinol bis-diphenyl phosphate [Daihachi Chemical Industries, Ltd. CR-733S, liquid at 23 ° C., phosphorus content 10.5%]
Phosphate ester D (Compound No. 4): Biphenol bis-diphenyl phosphate [FP-900 manufactured by ADEKA Corporation, liquid at 23 ° C., phosphorus content 9.5%]
-Phosphate ester E (Compound No. 5): Biphenol bis-dixylenyl phosphate [PX-202, manufactured by Daihachi Chemical Industry Co., Ltd., melting point 170 ° C., phosphorus content 9.0%]
Phosphate ester F (Compound No. 6): Bisphenol A bis-diphenyl phosphate [FP-600 manufactured by ADEKA Corporation, liquid at 23 ° C., phosphorus content 8.8%]
-Phosphazene compound [Fabumi Pharmaceutical Co., Ltd. Rabitol FP-110, melting point 109 ° C., phosphorus content 13%]
・ Phosphonic acid ester compound [Nonen 73, manufactured by Maruhishi Oil Chemical Co., Ltd., melting point 100 ° C., phosphorus content 10%]

[(C ′) component]
-Phosphoric acid amine salt compound [FP2100JC manufactured by ADEKA Corporation, no melting point, phosphorus content 20%]

[(D) component]
NOR type hindered amine stabilizer A [Flamstab NOR116FF manufactured by BASF]
NOR type hindered amine stabilizer B [TINUVIN NOR371 made by BASF]
NOR type hindered amine stabilizer C [TINUVIN123S manufactured by BASF]
-NOR type hindered amine stabilizer D [TINUVIN XT855FF manufactured by BASF]
NOR type hindered amine stabilizer E [LA-81 manufactured by ADEKA Corporation]

[(D ′) component]
・ N-methyl type hindered amine stabilizer [LA-52 manufactured by ADEKA Corporation]
-NH type hindered amine stabilizer [LA-57 manufactured by ADEKA Corporation]

[Additive]
(Dispersant / Lubricant)
Glycerin monostearate [GS95P made by Lion Corporation]
(Phenolic antioxidant)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane [ADEKA STAB AO60 manufactured by ADEKA Corporation]
(Phosphorus antioxidant)
Tris (2,4-di-t-butylphenyl) phosphite [ADEKA STAB 2112 manufactured by ADEKA Corporation]

Examples 1-5, 11-17, 29, 30
1. Production of Resin Composition and Pellet Components (A) to (D) and other components were mixed and melt-kneaded by a twin screw extruder to produce a pellet made of the resin composition, and the pellet was formed into a sheet. Hereinafter, each step will be described.
(1) Premixing Each component was mix | blended with the composition shown in Tables 1-5, and it premixed with the Henschel mixer.
In Examples 1 to 5, 11 to 17, GS95P (0.3 parts by mass) and ADK STAB AO60 (0. 0 parts) were added to 100 parts by mass of the total amount of components (A) to (D) and other flame retardants / fillers. 1 part by mass) and ADK STAB 2112 (0.2 part by mass) were added as additives.
The unit of the compounding quantity in Tables 1-5 is the mass%.
(2) Melt-kneading The obtained pre-mixture was kneaded at 200-230 ° C. using a biaxial kneader (trade name CTM35, manufactured by CTI Co., Ltd.) to prepare a composition, and pelletized using a strand cut. .

2. Molding In Examples 1 to 5 and 11 to 17, sheets were manufactured as follows using a press molding machine PY-50 / 50A manufactured by Kodaira Seisakusho. That is, 9 g of the pellets obtained above were heated to 200 ° C. and pressurized at a pressure of 30 tons for 1 minute. Subsequently, it pressed for 3 minutes with the pressure of 30 tons with the water cooling press, and the press sheet of thickness 0.2mm was obtained.

In Examples 29 and 30, a sheet was produced under the following conditions using the pellets obtained above and using the production apparatus shown in FIG.
・ Extruder diameter: 90 mm
・ T die width: 800mm
・ Seat take-off speed: 10 m / min
The surface temperature of the fourth cooling roll and the metal endless belt 17: 14 ° C.
・ Cooling water temperature: 8 ℃
・ Cooling water spray rate: 200 liters / min

3. Evaluation The following evaluation was performed about the resin composition and molded object (sheet) which were obtained above. The results are shown in Tables 1-5.

(1) Kneadability In the melt kneading described above, kneadability was evaluated as follows. That is, the case where the compatibility between the polypropylene-based resin and the phosphorus-based flame retardant was low at the time of melt-kneading and the following production failure phenomenon occurred was evaluated as x.
-Polypropylene resin pellets or melt were ejected from the open vent or vacuum vent.
・ Discharge amount became unstable, surging phenomenon occurred, and strand breakage occurred.
・ Phosphorus flame retardant eluted in the water tank (bleed out) and contaminated the discharged water.
A resin having a high melting point such as a cycloolefin polymer was used and kneaded at a high temperature (280 ° C.), and the flame retardant, the ethylene-vinyl acetate copolymer and the like were thermally decomposed and intensely colored.
The case where there was no problem described above was marked as “Good”.

(2) Flame retardancy (UL94-VTM test)
A press sheet having a thickness of 0.2 mm obtained by press molding was cut into a width of 50 mm and a length of 200 mm to prepare a sample. Using the HVUL plastic UL combustion test chamber manufactured by Atlas, the manufactured sample was subjected to a 20 mm vertical combustion test according to the UL94-VTM test standard. About five samples, the combustion rank was given according to UL94-VTM specification from the combustion time of the 1st time and the 2nd time, the presence or absence of the ignition of cotton, etc., respectively.
The combustion rank “VTM-0” is the highest, and the flame retardancy decreases as “VTM-1” and “VTM-2”. Those not corresponding to any of “VTM-0” to “VTM-2” were designated as “not-VTM”.

(3) Transparency Transparency was evaluated by the internal haze value. The lower the internal haze value, the more transparent.
Since the internal haze value excludes the influence of the sheet surface roughness and measures the transparency inside the sheet, the haze is measured in a state where silicone is applied to the sheet surface and both surfaces are sandwiched between glass plates. The internal haze is measured by dividing the haze value of the glass only from this haze value. In addition, the measurement of haze was measured according to test standard JISK7136 using Nippon Denshoku Industries Co., Ltd. haze meter NDH-200.

(4) Bleed test evaluation Using a constant temperature dryer DO-600FA manufactured by AS ONE Co., Ltd., the sheet was treated for 7 days in a state of 40 ° C and humidity of 30 to 40% to perform bleed evaluation.
The internal haze value before and after the above treatment was measured, and the changed value was evaluated. When the change value is large, the bleed is large. When the change value is small, the bleed is small.

(5) Elongation rate, surface area, and whitening of the sheet molded body These evaluation methods are as follows.
The sheet is heated to a surface temperature of 145 ° C. with an infrared heater, and the ratio of the size of the surface area Y after molding to the surface area X before molding (Y / X) is 2.42 in vacuum and compressed air. It was thermoformed by pressing and cooling. The elongation percentage was calculated by measuring the length of a preprinted 1 mm square grid pattern after molding. For whitening, one side of the thermoformed product was painted with a black paint, and the whitening was evaluated visually from the side opposite to the painted surface. In the evaluation of whitening, a case where black appears to be clear is indicated as ◯, and a case where black appears as whitened is indicated as x.

Examples 6-10, 18-28, Comparative Examples 1-16
In the same manner as in Example 1, the components are blended in the compositions shown in Tables 1 to 4 to produce resin compositions and pellets. Additives are also added as in Example 1. Moreover, it shape | molds similarly to Example 1, and evaluates about the resin composition and molded object (sheet | sheet) which are obtained. Expected results are shown in Tables 1-4.

From Tables 1 to 5, it can be seen that the resin composition of the present invention can be melt-kneaded without problems and has high flame retardancy (VTM-0). In Comparative Examples 1 to 16, it can be seen that the melt-kneading is impossible or the flame retardancy is lowered even if the melt-kneading is possible.
Moreover, it turns out that the sheet | seat obtained from the specific thing among the resin compositions of this invention has improved transparency, there is no generation | occurrence | production of a bleed, and an external appearance is favorable.
In addition, the sheet formed with an extruder equipped with a quenching belt type cooling using the resin composition of the present invention is more transparent than the sheet formed with an extruder equipped with a conventionally known air knife type cooling. And the sheet molded product is not whitened.

  Molded articles obtained from the resin composition of the present invention include computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electric / electronic devices, personal digital assistants, home appliance parts, automobile parts, industrial materials and building materials. Can be used for etc.

DESCRIPTION OF SYMBOLS 11 Sheet | seat 12 T die 13 1st cooling roll 14 2nd cooling roll 15 3rd cooling roll 16 4th cooling roll 17 Metal endless belt 18 Cooling water spray nozzle 19 Water tank 19A Drain outlet 20 Water absorption roll 21 Peeling roll 22 Elastic material

Claims (37)

Below the (A) ~ (D) component viewed including in the following proportions,
(A) to (D) component only, or
(A) to (D) components, and only one or more additives selected from dispersants, lubricants and antioxidants,
A resin composition that may contain inevitable impurities .
(A) Polypropylene resin 16.0-95.8 mass%
(B) ethylene vinyl acetate copolymer 1-40 mass% whose content of the structural unit derived from vinyl acetate is 10-90 mass%
(C) 3 to 40% by mass of a phosphorus-based flame retardant that is liquid at 150 to 300 ° C.
(D) NOR type hindered amine compound 0.2 to 4.0 mass% The resin composition of Claim 1 which satisfy | fills following formula (1).
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content (mass%) of the component (C) in the resin composition, and Y is the component (B) in the total amount of the components (A) to (D). (The content (% by mass) of structural units derived from vinyl acetate.)   The resin composition according to claim 1 or 2, wherein the content of the structural unit derived from vinyl acetate in the component (B) is 30% by mass or more.   The resin composition according to claim 1 or 2, wherein the content of the structural unit derived from vinyl acetate in the component (B) is 40% by mass or more.   Content of the structural unit derived from the vinyl acetate in the said (B) component is 70 mass% or less, The resin composition in any one of Claims 1-4.   The resin composition according to any one of claims 1 to 5, wherein a mass ratio ((B) / (C)) of the content of the component (B) and the component (C) is 1 or more.   The MFR of the said (B) component is 0.5-30 g / 10min, The resin composition in any one of Claims 1-6.   The resin composition according to any one of claims 1 to 7, wherein a phosphorus content in the component (C) is 8% by mass or more.   The resin composition according to claim 1, wherein the component (C) is at least one selected from a phosphate ester compound, a phosphazene compound, and a phosphonate ester compound.   The said (C) component is a phosphate ester compound, The resin composition in any one of Claims 1-8. The resin composition according to claim 1, wherein the component (C) is a compound represented by the following formula (20).

(In formula (20), R _{1 to} R ₅ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or a halogen atom. R _{1 to} R ₅ may be the same or different. Is an integer from 0 to 30.)   The resin composition according to claim 11, wherein n in the formula (20) is 0 to 10.   The resin composition according to any one of claims 1 to 8, wherein the component (C) is at least one selected from triphenyl phosphate, resorcinol bis-dixylenyl phosphate, and resorcinol bis-diphenyl phosphate.   The resin composition according to any one of claims 1 to 8, wherein the component (C) is at least one selected from triphenyl phosphate and resorcinol bis-dixylenyl phosphate.   The resin composition according to any one of claims 1 to 8, wherein the component (C) is resorcinol bis-dixylenyl phosphate.   The resin composition according to claim 1, wherein the component (A) is at least one selected from homopolypropylene and random polypropylene.   The resin composition according to claim 1, wherein the component (A) is homopolypropylene.   The resin composition according to any one of claims 1 to 17, wherein the MFR of the component (A) is 0.5 to 30 g / 10 minutes.   The resin composition according to any one of claims 1 to 18, wherein a carbonate bond is contained in the component (D).   The resin composition according to any one of claims 1 to 19, wherein the content of the component (A) is 46.0 to 91.8% by mass.   21. The resin composition according to claim 1, wherein the content of the component (B) is 5% by mass or more.   Content of the said (B) component is 30 mass% or less, The resin composition in any one of Claims 1-21.   Content of the said (B) component is 20 mass% or less, The resin composition in any one of Claims 1-21.   The resin composition according to any one of claims 1 to 23, wherein the content of the component (C) is 5% by mass or more.   The resin composition according to any one of claims 1 to 23, wherein the content of the component (C) is 15% by mass or more.   26. The resin composition according to claim 1, wherein the content of the component (C) is 20% by mass or less.   The resin composition according to any one of claims 1 to 24, wherein the content of the component (C) is 10% by mass or less.   The molded object formed by shape | molding the resin composition in any one of Claims 1-27.   A sheet formed by molding the resin composition according to claim 1.   A laminated sheet obtained by laminating polypropylene on the sheet according to claim 29. A resin sheet formed by cooling a molten resin comprising the resin composition according to claim 1. The resin sheet according to claim 31, wherein the cooling is performed using a cooling roll whose surface temperature is maintained at a dew point or higher and 50 ° C. or lower.   A molded product obtained by forming using the sheet according to claim 29, the laminated sheet according to claim 30, or the resin sheet according to claim 31 or 32.   34. The molded article according to claim 33, wherein the molded article is obtained by mounting the sheet, the laminated sheet, or the resin sheet on an inner surface of a molding die, and supplying and integrating the molding resin. The molded product is a molded product in which the sheet, the laminated sheet, or the resin sheet is molded in a non-planar shape,
The molded product is shaped such that the sheet, the laminated sheet, or the resin sheet matches the inner surface of the molding die, and the obtained molded product is attached to the surface of the molding die, 34. The molded product according to claim 33, which is obtained by supplying and integrating a molding resin.   The sheet in which the inside of the chamber box in which the core material to be coated is disposed is in a reduced pressure state, the sheet, the laminated sheet, or the resin sheet is heated and softened, the inside of the chamber box is pressurized and the heat softened 34. The molded article according to claim 33, wherein the laminated sheet or the resin sheet is obtained by pressing the core material to cover and integrate. A method of manufacturing a molded article in which a molded body is provided on at least a part of a substrate, comprising a mirror endless belt wound around a plurality of cooling rolls and a mirror cooling roll, and the surface of the mirror endless belt and the mirror cooling roll. It consists of the resin composition in any one of Claims 1-27 from a T-die extruder between the said mirror surface cooling roll and the said mirror surface endless belt using the apparatus maintained at the dew point or more and 50 degrees C or less. the molten resin is introduced out press, as well as formed into a sheet in pressure contact, a transparent resin sheet is quenched by blowing cooling water temperature is lower than the surface temperature of the mirror surface endless belt to said mirror surface endless belt The manufacturing method of the molded article which implements the process to manufacture and the process to shape | mold the said resin sheet in non-planar shape, and to provide in at least one part of the said base | substrate.

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