JP2021036057A - (meth)acrylic resin composition, resin molding, illumination lamp cover, and illumination signboard - Google Patents
(meth)acrylic resin composition, resin molding, illumination lamp cover, and illumination signboard Download PDFInfo
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Abstract
Description
本発明は、(メタ)アクリル樹脂組成物、樹脂成形体、照明灯カバー及び照明看板に関する。 The present invention relates to a (meth) acrylic resin composition, a resin molded product, a lighting lamp cover, and a lighting signboard.
メタクリル酸メチルを主成分とする(メタ)アクリル樹脂は透明性及び耐侯性に優れ、且つ、機械的強度、熱的性質、成形加工性等の樹脂物性においても比較的バランスのとれた性能を有している。特に、照明材料、看板、装飾部材、建築部材等の多くの用途では、高い難燃性を有する(メタ)アクリル樹脂が使用されている。
また、最近では、屋内外に設置される照明看板用途や照明用途に難燃性(メタ)アクリル樹脂が用いられることがある。この場合、蛍光灯やLED等の光源の形状を、照明看板や照明灯カバーで隠蔽するために、適度な光拡散性を発現するための乳半色を有する(メタ)アクリル樹脂が要望されている。
The (meth) acrylic resin containing methyl methacrylate as a main component has excellent transparency and weather resistance, and also has relatively well-balanced performance in resin physical properties such as mechanical strength, thermal properties, and moldability. doing. In particular, (meth) acrylic resin having high flame retardancy is used in many applications such as lighting materials, signboards, decorative members, and building members.
Recently, flame-retardant (meth) acrylic resin may be used for lighting signboards and lighting applications installed indoors and outdoors. In this case, in order to conceal the shape of a light source such as a fluorescent lamp or LED with a lighting signboard or a lighting cover, a (meth) acrylic resin having a milky half color for exhibiting appropriate light diffusivity is desired. There is.
難燃性(メタ)アクリル樹脂製品に、光拡散性を発現するための乳半色を付与する技術として、例えば特許文献1や特許文献2には、ハロゲン化リン酸エステルを含有する難燃性メタクリル樹脂板が提案されており、特許文献2には光拡散剤として有機系もしくは無機系の微粒子を用いることが記載されている。
また、特許文献3や特許文献4には、メタクリル系樹脂、リン系難燃剤、光拡散剤として硫酸バリウムおよび酸化チタンを含有する難燃メタクリル系樹脂板が提案されている。
As a technique for imparting a milky half color to exhibit light diffusivity to a flame-retardant (meth) acrylic resin product, for example, Patent Document 1 and Patent Document 2 describe flame-retardant phosphate containing a halide phosphate. A methacrylic resin plate has been proposed, and Patent Document 2 describes that organic or inorganic fine particles are used as a light diffusing agent.
Further, Patent Document 3 and Patent Document 4 propose a flame-retardant methacrylic resin plate containing a methacrylic resin, a phosphorus-based flame retardant, and barium sulfate and titanium oxide as a light diffusing agent.
しかしながら、特許文献1〜4で開示されている、単に有機系もしくは無機系の微粒子を添加・含有して、乳半色を発現させた難燃性メタクリル樹脂板では、光拡散剤自体がメタクリル樹脂の難燃性を低下させてしまうため、難燃性が不十分であった。すなわち、従来技術では難燃性と乳半色を両立した(メタ)アクリル樹脂を得ることは困難であった。 However, in the flame-retardant methacrylic resin plate disclosed in Patent Documents 1 to 4 in which organic or inorganic fine particles are simply added and contained to express a milky half color, the light diffusing agent itself is a methacrylic resin. The flame retardancy was insufficient because it reduced the flame retardancy of the resin. That is, it has been difficult to obtain a (meth) acrylic resin having both flame retardancy and a milky half color by the prior art.
本発明の目的は、適度な光拡散性と、高い難燃性を有する(メタ)アクリル樹脂組成物、及び該(メタ)アクリル樹脂組成物を成形してなる樹脂成形体を提供することにある。 An object of the present invention is to provide a (meth) acrylic resin composition having appropriate light diffusivity and high flame retardancy, and a resin molded product obtained by molding the (meth) acrylic resin composition. ..
本発明は以下の態様を有する。
[1](メタ)アクリル重合体(P)とリン系難燃剤(C)と樹脂粒子(F)とを含有する(メタ)アクリル樹脂組成物であって、
前記樹脂粒子(F)の分散粒子径が0.5μm以上10μm以下であり、
前記(メタ)アクリル重合体(P)が、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖に有するメタクリル酸エステル(M1)由来の繰り返し単位と、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖中に有するアクリル酸エステル(M2)由来の繰り返し単位とを含有する(メタ)アクリル樹脂組成物。
[2]前記(メタ)アクリル重合体(P)が、ビニル基を2個以上有する単量体(B)由来の構造単位を含有する、[1]に記載の(メタ)アクリル樹脂組成物。
[3]前記樹脂粒子(F)が、スチレン単量体由来の繰り返し単位を、該樹脂粒子(F)の総質量に対して、80質量%以上含有するスチレン系微粒子である、[1]又は[2]に記載の(メタ)アクリル樹脂組成物。
[4]前記スチレン系微粒子が、ゲルパーミエーションクロマトグラフィー(GPC)で測定した重量平均分子量(Mw)が4万以上30万以下である、[3]に記載の(メタ)アクリル樹脂組成物。
[5]前記スチレン系微粒子が、ゲルパーミエーションクロマトグラフィー(GPC)で測定した重量平均分子量(Mw)が5万以上15万以下である、[3]又は[4]に記載の(メタ)アクリル樹脂組成物。
[6]前記樹脂粒子(F)の中に、略球状の樹脂粒子が存在する[3]〜[5]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[7]前記樹脂粒子(F)の分散粒子径が0.5μm以上5.0μm以下であり、
前記略球状の樹脂粒子の分散粒子径が0.01μm以上0.3μm以下である[6]に記載の(メタ)アクリル樹脂組成物。
[8]前記樹脂粒子(F)の分散粒子径が1.0μm以上2.0μm以下であり、
前記略球状の樹脂粒子の分散粒子径が0.01μm以上0.1μm以下である[6]に記載の(メタ)アクリル樹脂組成物。
[9]前記(メタ)アクリル重合体(P)100質量部に対する、前記樹脂粒子(F)の量が0.5質量部以上4.0質量部以下である、[1]〜[8]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[10]前記(メタ)アクリル重合体(P)が、(メタ)アクリル重合体(P)の総質量に対し、
前記メタクリル酸エステル(M1)由来の繰り返し単位を10質量%以上80質量%以下と、前記アクリル酸エステル(M2)由来の繰り返し単位を0.50質量%以上20質量%以下とを含有する。[1]〜[9]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[11]前記(メタ)アクリル重合体(P)が、ビニル基を2個以上有する単量体(B)由来の構造単位を0.05質量%以上0.40質量%以下で含有する[2]〜[9]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[12]前記リン系難燃剤(C)が、リン酸エステル又はホスホン酸エステルである、[1]〜[11]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[13]前記リン系難燃剤(C)が、ハロゲン含有リン酸エステル又はハロゲン含有ホスホン酸エステルである、[1]〜[11]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[14]前記(メタ)アクリル重合体(P)100質量部に対する、前記リン系難燃剤(C)の量が5.0質量部以上35質量部以下である、[1]〜[13]のいずれか一項に記載の(メタ)アクリル樹脂組成物。
[15][1]〜[14]のいずれか一項に記載の(メタ)アクリル樹脂組成物を成形してなる樹脂成形体。
[16](メタ)アクリル重合体(P)とリン系難燃剤(C)と樹脂粒子(F)とを含有する(メタ)アクリル樹脂組成物を成形してなる樹脂成形体であって、DIN 5036にて測定した拡散率が60%以上99%以下であり、且つ、JIS K6911A法にて燃焼試験を行った場合に3分未満で自消する不燃性を有する樹脂成形体。
[17]JIS K6911A法にて燃焼試験を行った場合に1.5分未満で自消する不燃性を有し、且つ、前記樹脂粒子(F)の分散粒子径が1.0μm以上2.0μm以下であり、前記樹脂粒子(F)が、スチレン単量体由来の繰り返し単位を、該樹脂粒子(F)の総質量に対して、80質量%以上含有するスチレン系微粒子である、[16]に記載の樹脂成形体。
[18]UL94で規定される垂直燃焼試験においてV−0の難燃性を有し、樹脂成形体の厚みが4mm以上である、[16]又は[17]に記載の樹脂成形体。
[19][15]〜[18]のいずれか一項に記載の樹脂成形体を含む照明灯カバー。[20][15]〜[18]のいずれか一項に記載の樹脂成形体を含む照明看板。
The present invention has the following aspects.
[1] A (meth) acrylic resin composition containing a (meth) acrylic polymer (P), a phosphorus-based flame retardant (C), and resin particles (F).
The dispersed particle size of the resin particles (F) is 0.5 μm or more and 10 μm or less.
The (meth) acrylic polymer (P) is a repeating unit derived from a methacrylic acid ester (M1) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain, and aromatic hydrocarbons. A (meth) acrylic resin composition containing a repeating unit derived from an acrylic acid ester (M2) having a hydrogen group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain.
[2] The (meth) acrylic resin composition according to [1], wherein the (meth) acrylic polymer (P) contains a structural unit derived from a monomer (B) having two or more vinyl groups.
[3] The resin particles (F) are styrene-based fine particles containing 80% by mass or more of the repeating unit derived from the styrene monomer with respect to the total mass of the resin particles (F), [1] or The (meth) acrylic resin composition according to [2].
[4] The (meth) acrylic resin composition according to [3], wherein the styrene-based fine particles have a weight average molecular weight (Mw) of 40,000 or more and 300,000 or less as measured by gel permeation chromatography (GPC).
[5] The (meth) acrylic according to [3] or [4], wherein the styrene-based fine particles have a weight average molecular weight (Mw) of 50,000 or more and 150,000 or less as measured by gel permeation chromatography (GPC). Resin composition.
[6] The (meth) acrylic resin composition according to any one of [3] to [5], wherein substantially spherical resin particles are present in the resin particles (F).
[7] The dispersed particle size of the resin particles (F) is 0.5 μm or more and 5.0 μm or less.
The (meth) acrylic resin composition according to [6], wherein the dispersed particle size of the substantially spherical resin particles is 0.01 μm or more and 0.3 μm or less.
[8] The dispersed particle size of the resin particles (F) is 1.0 μm or more and 2.0 μm or less.
The (meth) acrylic resin composition according to [6], wherein the dispersed particle size of the substantially spherical resin particles is 0.01 μm or more and 0.1 μm or less.
[9] Of [1] to [8], the amount of the resin particles (F) is 0.5 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (P). The (meth) acrylic resin composition according to any one of the above.
[10] The (meth) acrylic polymer (P) is based on the total mass of the (meth) acrylic polymer (P).
The repeating unit derived from the methacrylic acid ester (M1) is contained in an amount of 10% by mass or more and 80% by mass or less, and the repeating unit derived from the acrylic acid ester (M2) is contained in an amount of 0.50% by mass or more and 20% by mass or less. The (meth) acrylic resin composition according to any one of [1] to [9].
[11] The (meth) acrylic polymer (P) contains a structural unit derived from the monomer (B) having two or more vinyl groups in an amount of 0.05% by mass or more and 0.40% by mass or less [2]. ] To [9], the (meth) acrylic resin composition according to any one of the items.
[12] The (meth) acrylic resin composition according to any one of [1] to [11], wherein the phosphorus-based flame retardant (C) is a phosphoric acid ester or a phosphonic acid ester.
[13] The (meth) acrylic resin composition according to any one of [1] to [11], wherein the phosphorus-based flame retardant (C) is a halogen-containing phosphoric acid ester or a halogen-containing phosphonic acid ester.
[14] Of [1] to [13], the amount of the phosphorus-based flame retardant (C) is 5.0 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (P). The (meth) acrylic resin composition according to any one of the above.
[15] A resin molded product obtained by molding the (meth) acrylic resin composition according to any one of [1] to [14].
[16] A resin molded product obtained by molding a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), a phosphorus-based flame retardant (C), and resin particles (F), and is a DIN. A nonflammable resin molded product having a diffusivity of 60% or more and 99% or less measured by 5036 and self-extinguishing in less than 3 minutes when a combustion test is performed by the JIS K6911A method.
[17] It has nonflammability that self-extinguishes in less than 1.5 minutes when a combustion test is performed by the JIS K6911A method, and the dispersed particle size of the resin particles (F) is 1.0 μm or more and 2.0 μm. [16] The resin particles (F) are styrene-based fine particles containing 80% by mass or more of the repeating unit derived from the styrene monomer with respect to the total mass of the resin particles (F). [16] The resin molded body according to.
[18] The resin molded product according to [16] or [17], which has a flame retardancy of V-0 in a vertical combustion test defined by UL94 and has a thickness of 4 mm or more.
[19] An illuminating lamp cover including the resin molded product according to any one of [15] to [18]. [20] A lighting signboard containing the resin molded product according to any one of [15] to [18].
本発明により、照明看板・照明材料として適度な光拡散性と、高い難燃性を有する樹脂成形体、及び該樹脂成形体を得るための(メタ)アクリル樹脂組成物を得ることができる。 According to the present invention, it is possible to obtain a resin molded product having appropriate light diffusivity and high flame retardancy as a lighting signboard / lighting material, and a (meth) acrylic resin composition for obtaining the resin molded product.
以下、本発明を詳細に説明する。
本発明において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」からなる群から選ばれる少なくとも1種を意味する。「(メタ)アクリル酸」は、「アクリル酸」及び「メタクリル酸」からなる群から選ばれる少なくとも1種を意味する。
Hereinafter, the present invention will be described in detail.
In the present invention, "(meth) acrylate" means at least one selected from the group consisting of "acrylate" and "methacrylate". "(Meta) acrylic acid" means at least one selected from the group consisting of "acrylic acid" and "methacrylic acid".
また、「単量体」は未重合の化合物を意味し、「繰り返し単位」は単量体が重合することによって形成された該単量体に由来する単位を意味する。繰り返し単位は、重合反応によって直接形成された単位であってもよく、ポリマーを処理することによって該単位の一部が別の構造に変換されたものであってもよい。「構造単位」とは、(メタ)アクリル樹脂組成物の製造に用いる単量体に由来する単位を意味する。「質量%」は全体量100質量%中に含まれる所定の成分の含有量を意味する。 Further, "monomer" means an unpolymerized compound, and "repeating unit" means a unit derived from the monomer formed by polymerizing the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or a part of the unit may be converted into another structure by processing a polymer. "Structural unit" means a unit derived from a monomer used in the production of a (meth) acrylic resin composition. "Mass%" means the content of a predetermined component contained in 100% by mass of the total amount.
<(メタ)アクリル樹脂組成物>
本発明の(メタ)アクリル樹脂組成物は、後述する(メタ)アクリル重合体(P)、後述するリン系難燃剤(C)及び後述する樹脂粒子(F)を含有する。
<(Meta) acrylic resin composition>
The (meth) acrylic resin composition of the present invention contains a (meth) acrylic polymer (P) described later, a phosphorus-based flame retardant (C) described later, and resin particles (F) described later.
前記(メタ)アクリル樹脂組成物中のリン系難燃剤(C)の含有量は、特に限定されないが、(メタ)アクリル重合体(P)100質量部に対して、5.0質量部以上35質量部以下とすることができる。 The content of the phosphorus-based flame retardant (C) in the (meth) acrylic resin composition is not particularly limited, but is 5.0 parts by mass or more and 35 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic polymer (P). It can be less than or equal to parts by mass.
(メタ)アクリル重合体(P)100質量部に対するリン系難燃剤(C)の含有量が5.0質量部以上で難燃性に優れた樹脂成形体が得られる。また、(メタ)アクリル重合体(P)100質量部に対するリン系難燃剤(C)の含有量が35質量部以下で耐熱性に優れた樹脂成形体が得られる。(メタ)アクリル重合体(P)100質量部に対するリン系難燃剤(C)の含有量は6.0質量部以上が好ましく、23質量部以下が好ましい。 A resin molded product having excellent flame retardancy can be obtained when the content of the phosphorus-based flame retardant (C) is 5.0 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic polymer (P). Further, a resin molded product having excellent heat resistance can be obtained when the content of the phosphorus-based flame retardant (C) is 35 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (P). The content of the phosphorus-based flame retardant (C) with respect to 100 parts by mass of the (meth) acrylic polymer (P) is preferably 6.0 parts by mass or more, and preferably 23 parts by mass or less.
前記(メタ)アクリル樹脂組成物中の樹脂粒子(F)の含有量は、特に限定されないが、(メタ)アクリル重合体(P)100質量部に対して0.5質量部以上4.0質量部以下を含有することで、適度な拡散率及び乳半色の色調を有する樹脂成形体が得られる。樹脂粒子(F)の含有量の下限が0.5質量部以上であれば、樹脂成形体に適度な拡散率と乳半色の色調を付与できることから好ましく、0.6質量部以上がより好ましい。また樹脂粒子(F)の含有量の上限が4.0質量部以下であれば、樹脂成形体の難燃性を維持できることから好ましく、3.0質量部以下がより好ましい。 The content of the resin particles (F) in the (meth) acrylic resin composition is not particularly limited, but is 0.5 parts by mass or more and 4.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (P). By containing a portion or less, a resin molded body having an appropriate diffusivity and a milky half-color tone can be obtained. When the lower limit of the content of the resin particles (F) is 0.5 parts by mass or more, it is preferable because an appropriate diffusivity and a milky half-color tone can be imparted to the resin molded product, and 0.6 parts by mass or more is more preferable. .. Further, when the upper limit of the content of the resin particles (F) is 4.0 parts by mass or less, it is preferable because the flame retardancy of the resin molded product can be maintained, and 3.0 parts by mass or less is more preferable.
<(メタ)アクリル重合体(P)>
本発明における(メタ)アクリル樹脂組成物は、下記の(メタ)アクリル重合体(P)を構成成分の1つとして含む。前記(メタ)アクリル重合体(P)を構成成分の1つとして含むことにより、後述する他の構成成分との相乗効果により、適度な光拡散性と高い難燃性を有する樹脂成形体を得ることが可能となる。
<(Meta) acrylic polymer (P)>
The (meth) acrylic resin composition in the present invention contains the following (meth) acrylic polymer (P) as one of the constituent components. By containing the (meth) acrylic polymer (P) as one of the constituent components, a resin molded product having appropriate light diffusivity and high flame retardancy can be obtained by a synergistic effect with other constituent components described later. It becomes possible.
本発明において、(メタ)アクリル重合体(P)は、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖に有するメタクリル酸エステル(M1)由来の繰り返し単位と、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖中に有するアクリル酸エステル(M2)由来の繰り返し単位とを含有する。さらに、ビニル基を2個以上有する単量体(B)由来の構造単位を含有することが好ましい。
本明細書において「側鎖」とは、エステル部分を意味する。
前記メタクリル酸エステル(M1)、前記アクリル酸エステル(M2)及び前記単量体(B)の詳細については後述する。
In the present invention, the (meth) acrylic polymer (P) is a repeating unit derived from a methacrylic acid ester (M1) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain. It contains an aromatic hydrocarbon group or a repeating unit derived from an acrylic acid ester (M2) having an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain. Further, it is preferable to contain a structural unit derived from the monomer (B) having two or more vinyl groups.
As used herein, the term "side chain" means an ester moiety.
Details of the methacrylic acid ester (M1), the acrylic acid ester (M2), and the monomer (B) will be described later.
さらに、(メタ)アクリル重合体(P)は、該(メタ)アクリル重合体(P)の総質量に対し、前記メタクリル酸エステル(M1)由来の繰り返し単位10質量%以上80質量%以下、前記アクリル酸エステル(M2)由来の繰り返し単位0.50質量%以上20質量%以下と前記単量体(B)由来の構造単位0.05質量%以上0.40質量%以下を含有することにより、樹脂成形体の難燃性をより優れたものにできる。 Further, the (meth) acrylic polymer (P) contains 10% by mass or more and 80% by mass or less of the repeating unit derived from the methacrylic acid ester (M1) with respect to the total mass of the (meth) acrylic polymer (P). By containing 0.50% by mass or more and 20% by mass or less of the repeating unit derived from the acrylic acid ester (M2) and 0.05% by mass or more and 0.40% by mass or less of the structural unit derived from the monomer (B). The flame retardancy of the resin molded body can be made more excellent.
メタクリル酸エステル(M1)由来の繰り返し単位の含有量の下限は、樹脂粒子(F)の分散安定が良好となることで、樹脂成形体の難燃性と光拡散性が良好となり、さらに樹脂成形体の耐熱性が良好となることから、(メタ)アクリル重合体(P)の総質量に対し、10質量%以上が好ましい。また、含有量の上限は、樹脂成形体の耐候性が良好となることから80質量%以下が好ましい。 The lower limit of the content of the repeating unit derived from the methacrylic acid ester (M1) is that the dispersion stability of the resin particles (F) is good, so that the flame retardancy and light diffusivity of the resin molded product are good, and further, the resin molding is performed. Since the heat resistance of the body is improved, 10% by mass or more is preferable with respect to the total mass of the (meth) acrylic polymer (P). The upper limit of the content is preferably 80% by mass or less because the weather resistance of the resin molded product is good.
アクリル酸エステル(M2)由来の繰り返し単位の含有量の下限は、樹脂粒子(F)の分散安定が良好となることで、樹脂成形体の難燃性と光拡散性が良好となり、さらに樹脂成形体の耐熱性が良好となることから、(メタ)アクリル重合体(P)の総質量に対し、0.50質量%以上が好ましく、1.0質量%以上がより好ましく、2.0質量%以上がさらに好ましい。含有量の上限は、樹脂成形体の耐熱性が良好となることから20質量%以下が好ましく、5.0質量%以下がより好ましく、4.0質量%以下がさらに好ましい。 The lower limit of the content of the repeating unit derived from the acrylic acid ester (M2) is that the dispersion stability of the resin particles (F) is good, so that the flame retardancy and light diffusivity of the resin molded product are good, and further, the resin molding is performed. Since the heat resistance of the body becomes good, 0.50% by mass or more is preferable, 1.0% by mass or more is more preferable, and 2.0% by mass is more preferable with respect to the total mass of the (meth) acrylic polymer (P). The above is more preferable. The upper limit of the content is preferably 20% by mass or less, more preferably 5.0% by mass or less, and further preferably 4.0% by mass or less because the heat resistance of the resin molded product becomes good.
メタクリル酸エステル(M1)由来の繰り返し単位と、アクリル酸エステル(M2)由来の繰り返し単位の含有量の合計の下限は特に限定されないが、樹脂粒子(F)の分散安定が良好となることで、樹脂成形体の難燃性と光拡散性が良好となり、さらに樹脂成形体の耐熱性が良好となることから、(メタ)アクリル重合体(P)の総質量に対し、15質量%以上が好ましく、20質量%以上がより好ましい。含有量の上限は、樹脂成形体の難燃性を良好に維持できることから80質量%以下が好ましい。 The lower limit of the total content of the repeating unit derived from the methacrylic acid ester (M1) and the repeating unit derived from the acrylic acid ester (M2) is not particularly limited, but the dispersion stability of the resin particles (F) is improved. Since the flame retardancy and light diffusivity of the resin molded product are improved and the heat resistance of the resin molded product is further improved, 15% by mass or more is preferable with respect to the total mass of the (meth) acrylic polymer (P). , 20% by mass or more is more preferable. The upper limit of the content is preferably 80% by mass or less because the flame retardancy of the resin molded product can be maintained satisfactorily.
また、前記(メタ)アクリル重合体(P)は、メタクリル酸メチル由来の繰り返し単位を含むことにより、樹脂成形体の透明性や機械強度を良好にできる。(メタ)アクリル重合体(P)中のメタクリル酸メチル由来の繰り返し単位の含有量の下限は特に限定されるものではないが、樹脂成形体の透明性や機械強度が良好となることから、(メタ)アクリル重合体(P)の総質量に対し、20質量%以上が好ましい。また、含有量の上限は特に限定されるものではないが、樹脂成形体の難燃性を良好に維持できることから85質量%以下が好ましい。 Further, the (meth) acrylic polymer (P) contains a repeating unit derived from methyl methacrylate, so that the transparency and mechanical strength of the resin molded product can be improved. The lower limit of the content of the repeating unit derived from methyl methacrylate in the (meth) acrylic polymer (P) is not particularly limited, but since the transparency and mechanical strength of the resin molded product are improved, ( 20% by mass or more is preferable with respect to the total mass of the meta) acrylic polymer (P). The upper limit of the content is not particularly limited, but is preferably 85% by mass or less because the flame retardancy of the resin molded product can be maintained satisfactorily.
前記単量体(B)由来の構造単位の含有量の下限は特に限定されないが、樹脂成形体の難燃性が良好となることから、(メタ)アクリル重合体(P)の総質量に対し、0.05質量%以上が好ましい。また、含有量の上限は特に限定されないが、樹脂成形体の耐衝撃性や機械強度が良好となることから0.40質量%以下が好ましい。尚、具体的な単量体(B)については後述する。
(メタ)アクリル重合体(P)の製造方法としては、例えば、塊状重合法、溶液重合法、乳化重合法及び懸濁重合法が挙げられる。これらの中で、(メタ)アクリル重合体の製造コスト、溶剤使用等による環境負荷及び生産性の観点で、塊状重合が好ましい。
The lower limit of the content of the structural unit derived from the monomer (B) is not particularly limited, but since the flame retardancy of the resin molded product is improved, the total mass of the (meth) acrylic polymer (P) is increased. , 0.05% by mass or more is preferable. The upper limit of the content is not particularly limited, but is preferably 0.40% by mass or less because the impact resistance and mechanical strength of the resin molded product are improved. The specific monomer (B) will be described later.
Examples of the method for producing the (meth) acrylic polymer (P) include a massive polymerization method, a solution polymerization method, an emulsion polymerization method and a suspension polymerization method. Among these, bulk polymerization is preferable from the viewpoint of the production cost of the (meth) acrylic polymer, the environmental load due to the use of a solvent, and the productivity.
<メタクリル酸エステル(M1)、アクリル酸エステル(M2)>
本発明において、(メタ)アクリル重合体(P)は、芳香族炭化水素又は炭素数3〜20の脂環式炭化水素を側鎖に有するメタクリル酸エステル(M1)由来の繰り返し単位、及び芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖中に有するアクリル酸エステル(M2)由来の繰り返し単位を含む。(以下、必要に応じて、メタクリル酸エステル(M1)とアクリル酸エステル(M2)を合わせて、「(メタ)アクリル酸エステル(M)」と略する。)
<Methacrylic acid ester (M1), acrylic acid ester (M2)>
In the present invention, the (meth) acrylic polymer (P) is a repeating unit derived from a methacrylic acid ester (M1) having an aromatic hydrocarbon or an alicyclic hydrocarbon having 3 to 20 carbon atoms in a side chain, and an aromatic. It contains a repeating unit derived from an acrylic acid ester (M2) having a hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain. (Hereinafter, if necessary, the methacrylic acid ester (M1) and the acrylic acid ester (M2) are combined and abbreviated as "(meth) acrylic acid ester (M)".)
(メタ)アクリル酸エステル(M)は熱が加わると、側鎖が脱離し、(メタ)アクリル酸構造単位に転化する。この(メタ)アクリル酸構造単位がリン系難燃剤(C)に作用して、相互作用することにより、樹脂組成物が燃焼するときの炭化物(チャー)の生成量が増大する。その結果、樹脂成形体の難燃性が向上する。一方、(メタ)アクリル酸エステル(M)から脱離した側鎖は、酸素を消費して燃焼場が酸素不足の状態になるため、樹脂組成物の難燃性を更に高める。
また、後述する単量体(B)が加わることで、炭化物(チャー)の生成が更に促進される。
さらに、アクリル酸エステル(M2)は、後述するリン系難燃剤(C)と相互作用して、リン系難燃剤(C)が有する難燃性向上効果を相乗的に高める効果を有するので、樹脂成形体の難燃性を向上できる。
When heat is applied to the (meth) acrylic acid ester (M), the side chain is detached and converted into a (meth) acrylic acid structural unit. This (meth) acrylic acid structural unit acts on the phosphorus-based flame retardant (C) and interacts with each other, so that the amount of carbide (char) produced when the resin composition burns increases. As a result, the flame retardancy of the resin molded product is improved. On the other hand, the side chain desorbed from the (meth) acrylic acid ester (M) consumes oxygen and the combustion field becomes oxygen-deficient, further enhancing the flame retardancy of the resin composition.
Further, the addition of the monomer (B) described later further promotes the formation of carbide (char).
Further, the acrylic acid ester (M2) has an effect of interacting with the phosphorus-based flame retardant (C) described later and synergistically enhances the flame retardant improving effect of the phosphorus-based flame retardant (C). The flame retardancy of the molded product can be improved.
(メタ)アクリル酸エステル(M)の具体例としては、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ボルニル、(メタ)アクリル酸ノルボルニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸アダマンチル、(メタ)アクリル酸ジメチルアダマンチル、メタクリル酸メチルシクロヘキシル、(メタ)アクリル酸ノルボルニルメチル、(メタ)アクリル酸メンチル、(メタ)アクリル酸フェンチル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸ジシクロペンテニル、(メタ)アクリル酸ジシクロペンテニルオキシエチル、(メタ)アクリル酸シクロデシル、(メタ)アクリル酸4−t−ブチルシクロヘキシル、(メタ)アクリル酸トリメチルシクロヘキシル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェノキシエチル等の(メタ)アクリル酸エステル、及びそれらの誘導体が挙げられるが、これらに限定されるものではない。これらは単独で又は2種以上を併せて使用できる。 Specific examples of the (meth) acrylic acid ester (M) include cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. Dimethyladamantyl (meth) acrylate, cyclohexyl methacrylate, (meth) norbornylmethyl acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclodecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate , (Meta) acrylic acid esters such as phenoxyethyl (meth) acrylic acid, and derivatives thereof, but are not limited thereto. These can be used alone or in combination of two or more.
本発明の(メタ)アクリル樹脂組成物において、前記メタクリル酸エステル(M1)には、難燃性及び耐熱性の向上効果に優れる観点から、メタクリル酸シクロヘキシル及びメタクリル酸イソボルニルからなる群から選ばれる少なくとも1種の単量体を用いることができる。 In the (meth) acrylic resin composition of the present invention, the methacrylic acid ester (M1) is at least selected from the group consisting of cyclohexyl methacrylate and isobornyl methacrylate from the viewpoint of excellent effects of improving flame retardancy and heat resistance. One kind of monomer can be used.
本発明の(メタ)アクリル樹脂組成物において、前記アクリル酸エステル(M2)には、樹脂成形体の難燃性及び耐候性の向上効果に優れ、樹脂粒子(F)の分散安定性の向上効果に優れる観点から、アクリル酸シクロヘキシル及びアクリル酸イソボルニルからなる群から選ばれる少なくとも1種の単量体を用いることができる。 In the (meth) acrylic resin composition of the present invention, the acrylic acid ester (M2) has an excellent effect of improving the flame retardancy and weather resistance of the resin molded product, and has an effect of improving the dispersion stability of the resin particles (F). From the viewpoint of excellent properties, at least one monomer selected from the group consisting of cyclohexyl acrylate and isobornyl acrylate can be used.
<単量体(B)>
単量体(B)はビニル基を2個以上有する単量体であり、(メタ)アクリル重合体(P)の構成成分の一つである。(メタ)アクリル樹脂組成物に単量体(B)を含有させることにより、樹脂成形体の難燃性を、より向上することができる。
<Polymer (B)>
The monomer (B) is a monomer having two or more vinyl groups, and is one of the constituents of the (meth) acrylic polymer (P). By containing the monomer (B) in the (meth) acrylic resin composition, the flame retardancy of the resin molded product can be further improved.
単量体(B)としては、例えば、エチレングリコールジ(メタ)アクリレート、1,2−プロピレングリコールジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート等のアルカンジオールジ(メタ)アクリレートが挙げられる。これらは単独で又は2種以上を併せて使用できる。 Examples of the monomer (B) include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,6-hexanediol di. Examples thereof include alkanediol di (meth) acrylates such as (meth) acrylates, neopentyl glycol di (meth) acrylates, and tricyclodecanedimethanol di (meth) acrylates. These can be used alone or in combination of two or more.
上述した単量体(B)の中でも、炭素数10〜14の単量体(B)は、原料の取り扱い性が良好であることから、(メタ)アクリル樹脂組成物を製造するときの作業性が向上する。 Among the above-mentioned monomers (B), the monomer (B) having 10 to 14 carbon atoms has good handleability as a raw material, and therefore has good workability when producing a (meth) acrylic resin composition. Is improved.
さらに、単量体(B)が、エチレングリコールジ(メタ)アクリレート及びネオペンチルグリコールジ(メタ)アクリレートからなる群から選ばれる少なくとも1種の単量体であれば、原料の取り扱い性が優れることに加え、樹脂成形体の難燃性をより優れたものとできる点から好ましい。 Further, if the monomer (B) is at least one monomer selected from the group consisting of ethylene glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate, the handleability of the raw material is excellent. In addition to this, it is preferable because the flame retardancy of the resin molded product can be made more excellent.
<共重合可能な単量体>
本発明においては、必要に応じて(メタ)アクリル重合体(P)中に、メタクリル酸メチル又は(メタ)アクリル酸エステル(M)と共重合可能な単量体を、(メタ)アクリル重合体(P)の総質量に対し、0〜10質量%の範囲で共重合させることができる。
<Copolymerizable monomer>
In the present invention, if necessary, a monomer copolymerizable with methyl methacrylate or (meth) acrylic acid ester (M) is contained in the (meth) acrylic polymer (P) in the (meth) acrylic polymer. It can be copolymerized in the range of 0 to 10% by mass with respect to the total mass of (P).
(メタ)アクリル酸エステル(M)と共重合可能な単量体としては、例えば、(メタ)アクリル酸エチル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸i−ブチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸、マレイン酸、イタコン酸等の不飽和カルボン酸、無水マレイン酸、無水イタコン酸等の酸無水物、N−フェニルマレイミド、N−シクロヘキシルマレイミド等のマレイミド誘導体、酢酸ビニル、安息香酸ビニル等のビニルエステル、塩化ビニル、塩化ビニリデン及びそれらの誘導体、メタクリルアミド、アクリロニトリル等の窒素含有単量体、(メタ)アクリル酸グリシジルアクリレート等のエポキシ基含有単量体並びにスチレン、α−メチルスチレン等の芳香族ビニル化合物が挙げられる。 Examples of the monomer copolymerizable with (meth) acrylic acid ester (M) include ethyl (meth) acrylic acid, isopropyl (meth) acrylic acid, t-butyl (meth) acrylic acid, and (meth) acrylic acid. Unsaturated carboxylic acids such as i-butyl, (meth) acrylic acid n-butyl, (meth) acrylic acid, maleic acid, and itaconic acid, acid anhydrides such as maleic anhydride and itaconic acid anhydride, N-phenylmaleimide, N. -Maleimide derivatives such as cyclohexyl maleimide, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl chloride, vinylidene chloride and their derivatives, nitrogen-containing monomers such as methacrylamide and acrylonitrile, glycidyl acrylate (meth) acrylate and the like. Examples thereof include epoxy group-containing monomers and aromatic vinyl compounds such as styrene and α-methylstyrene.
<リン系難燃剤(C)>
本発明では、樹脂成形体の難燃性を高めるために、(メタ)アクリル樹脂組成物がリン系難燃剤(C)を構成成分の一つとして含む。難燃性向上効果を有するリン系難燃剤(C)と前記(メタ)アクリル酸エステル(M)との併用で難燃相乗効果が得られ、樹脂成形体の難燃性を向上できる。
<Phosphorus flame retardant (C)>
In the present invention, the (meth) acrylic resin composition contains a phosphorus-based flame retardant (C) as one of the constituent components in order to enhance the flame retardancy of the resin molded product. A flame retardant synergistic effect can be obtained by using a phosphorus-based flame retardant (C) having a flame retardancy improving effect in combination with the (meth) acrylic acid ester (M), and the flame retardancy of the resin molded product can be improved.
リン系難燃剤(C)としては、リン酸エステル系化合物(以下、「リン酸エステル」と略する。)やホスホン酸エステル系化合物(以下、「ホスホン酸エステル」と略する。)を挙げることができる。
リン系難燃剤(C)としては、ハロゲン非含有リン酸エステル系化合物(以下、「ハロゲン非含有リン酸エステル」と略する。)、ハロゲン含有リン酸エステル系化合物(以下、「ハロゲン含有リン酸エステル」と略する。)、ハロゲン非含有ホスホン酸エステル系化合物(以下、「ハロゲン非含有ホスホン酸エステル」と略する。)、ハロゲン含有ホスホン酸エステル系化合物(以下、「ハロゲン含有ホスホン酸エステル」と略する。)を挙げることができる。具体的には、以下の化合物を例示できるが、これらに限定されるものではない。これらの化合物は、単独使用で又は2種以上を併せて使用できる。
Examples of the phosphorus-based flame retardant (C) include a phosphoric acid ester-based compound (hereinafter, abbreviated as “phosphate ester”) and a phosphonic acid ester-based compound (hereinafter, abbreviated as “phosphonic acid ester”). Can be done.
Examples of the phosphorus-based flame retardant (C) include a halogen-free phosphoric acid ester-based compound (hereinafter, abbreviated as “halogen-free phosphoric acid ester”) and a halogen-containing phosphoric acid ester-based compound (hereinafter, “halogen-containing phosphoric acid”). (Abbreviated as "ester"), halogen-free phosphonic acid ester-based compound (hereinafter, abbreviated as "halogen-free phosphonic acid ester"), halogen-containing phosphonic acid ester-based compound (hereinafter, "halogen-containing phosphonic acid ester". It is abbreviated as.). Specific examples thereof include, but are not limited to, the following compounds. These compounds can be used alone or in combination of two or more.
リン酸エステルとしては、例えば、トリメチルフォスフェート、トリエチルフォスフェート、トリフェニルフォスフェート等のハロゲン非含有リン酸エステル;トリス(クロロエチル)フォスフェート、トリス(クロロプロピル)フォスフェート、トリス(ジクロロプロピル)フォスフェート、トリス(ジブロモプロピル)フォスフェート、ビス(2,3−ジブロモプロピル)−2,3−ジクロロプロピルフォスフェート、ビス(クロロプロピル)オクチルフォスフェート等のハロゲン含有リン酸エステル;及びハロゲン含有アルキルポリフォスフェート等のハロゲン原子を含有するポリリン酸エステル(含ハロゲン縮合リン酸エステル)、およびそれらの誘導体化合物が挙げられるが、これらに限定されるものではない。これらは単独で使用又は2種以上を併せて使用できる。 Examples of the phosphoric acid ester include halogen-free phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, and triphenyl phosphate; tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, and tris (dichloropropyl) phosphate. Halogen-containing phosphates such as fate, tris (dibromopropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) octyl phosphate; and halogen-containing alkylpoly Examples thereof include, but are not limited to, polyphosphates containing halogen atoms such as phosphate (halogen-containing condensed phosphoric acid esters) and derivative compounds thereof. These can be used alone or in combination of two or more.
ハロゲン非含有リン酸エステルとしては、具体的には、城北化学(株)製の「JAMP−2」、「JAMP−4」、「JAMP−8」、「JAMP−12」、「JP−501」、「JP−502」、「JP−504」、「JP−504A」、「JP−506−H」、「JP−508」、「JP−512」、「JP−513」、「JP−518−O」、「JP−524−R」、「LB−58」、「DBP」、大八化学工業(株)製の、「TMP」、「TEP」、「TPP」、「TCP」、「TXP」、「CDP」、「PX−110」、「#41」、「CR−733S」、「CR−741」、「PX−200」、「DAIGUARD−400/580/610」等の市販品を用いることができる。 Specific examples of the halogen-free phosphoric acid ester include "JAMP-2", "JAMP-4", "JAMP-8", "JAMP-12", and "JP-501" manufactured by Johoku Chemical Co., Ltd. , "JP-502", "JP-504", "JP-504A", "JP-506-H", "JP-508", "JP-512", "JP-513", "JP-518-" "O", "JP-524-R", "LB-58", "DBP", "TMP", "TEP", "TPP", "TCP", "TXP" manufactured by Daihachi Chemical Industry Co., Ltd. , "CDP", "PX-110", "# 41", "CR-733S", "CR-741", "PX-200", "DAIGUARD-400 / 580/610", etc. Can be done.
ハロゲン含有リン酸エステルとしては、具体的には、大八化学工業(株)製の「TMCPP」、「CRP」、「CR−900」、「DAIGUARD−540」、「CR−504L」、「CR−570」等の市販品を用いることができる。 Specific examples of the halogen-containing phosphoric acid ester include "TMCPP", "CRP", "CR-900", "DAIGUARD-540", "CR-504L", and "CR" manufactured by Daihachi Chemical Industry Co., Ltd. Commercially available products such as "-570" can be used.
ホスホン酸エステルとしては、例えば、ジメチルビニルホスホナート、ジエチルビニルホスホナート、ジフェニルビニルホスホナート、ジフェニルビニルホスフィンオキシド等、およびそれらの誘導体化合物や、それらの縮合物が挙げられるが、これらに限定されるものではない。これらは単独で使用又は2種以上を併せて使用できる。 Examples of the phosphonic acid ester include, but are limited to, dimethylvinylphosphonate, diethylvinylphosphonate, diphenylvinylphosphonate, diphenylvinylphosphine oxide and the like, derivative compounds thereof, and condensates thereof. It's not a thing. These can be used alone or in combination of two or more.
ホスホン酸エステルとしては、具体的には、片山化学工業(株)製の「Vシリーズ」、丸菱油化工業(株)製の「ノンネン73」等の市販品を用いることができる。 Specifically, as the phosphonate ester, commercially available products such as "V series" manufactured by Katayama Chemical Industry Co., Ltd. and "Non Nen 73" manufactured by Maruhishi Yuka Kogyo Co., Ltd. can be used.
<樹脂粒子(F)>
本発明の樹脂成形体は、樹脂粒子(F)を含む(メタ)アクリル樹脂組成物を用いて製造される。樹脂粒子(F)を光拡散剤として用いることにより、樹脂成形体は高い難燃性を維持しつつ適度な光拡散性を発現できる。
樹脂粒子(F)の構造としては、例えば、グラフトポリマーが挙げられる。
樹脂粒子(F)の形態としては、例えば、粉末、ビ−ズ、ペレット及び液体が挙げられる。
<Resin particles (F)>
The resin molded product of the present invention is produced using a (meth) acrylic resin composition containing resin particles (F). By using the resin particles (F) as a light diffusing agent, the resin molded product can exhibit appropriate light diffusing property while maintaining high flame retardancy.
Examples of the structure of the resin particles (F) include a graft polymer.
Examples of the form of the resin particles (F) include powders, beads, pellets and liquids.
本発明においては、(メタ)アクリル樹脂組成物中の樹脂粒子(F)の分散粒子径を0.5μm以上10μm以下の範囲に制御することが好ましい。分散粒子径の下限が0.5μm以上であれば、樹脂成形体に適度な光拡散性を付与できること、及び樹脂粒子(F)を過剰に含有させる必要がないので高輝度の拡散光が得られることから好ましく、1.0μm以上がより好ましい。分散粒子径の上限が10μm以下であれば、樹脂粒子(F)が(メタ)アクリル樹脂組成物中に均一に分散するので樹脂成形体の難燃性を良好に維持できること、拡散光の輝度を良好に維持できること及び樹脂成形体の表面外観が良好となることから好ましく、5.0μm以下がより好ましく、2.0μm以下がさらに好ましい。 なお、「分散粒子径」とは、(メタ)アクリル樹脂組成物又はシート状の樹脂成形体からウルトラミクロトーム等を用いて切り出した小片を、透過型電子顕微鏡を用いて樹脂粒子の中心近傍を通る断面において観察された、任意の樹脂粒子又は凝集粒子30個について、樹脂粒子の一次粒子径又は凝集粒子の二次粒子径の最大粒径を測定し、平均した値である。なお、凝集粒子とは、樹脂粒子(一次粒子)が接触して形成された二次粒子のことをいう。 In the present invention, it is preferable to control the dispersed particle size of the resin particles (F) in the (meth) acrylic resin composition to a range of 0.5 μm or more and 10 μm or less. When the lower limit of the dispersed particle size is 0.5 μm or more, it is possible to impart appropriate light diffusivity to the resin molded product, and since it is not necessary to excessively contain the resin particles (F), high-luminance diffused light can be obtained. Therefore, it is preferable, and 1.0 μm or more is more preferable. When the upper limit of the dispersed particle size is 10 μm or less, the resin particles (F) are uniformly dispersed in the (meth) acrylic resin composition, so that the flame retardancy of the resin molded product can be maintained well, and the brightness of the diffused light can be improved. It is preferable because it can be maintained well and the surface appearance of the resin molded product is good, more preferably 5.0 μm or less, and further preferably 2.0 μm or less. The "dispersed particle size" refers to a small piece cut out from a (meth) acrylic resin composition or a sheet-shaped resin molded body using an ultramicrotome or the like and passes near the center of the resin particle using a transmission electron microscope. The maximum particle size of the primary particle size of the resin particles or the secondary particle size of the agglomerated particles was measured and averaged for 30 arbitrary resin particles or agglomerated particles observed in the cross section. The agglomerated particles refer to secondary particles formed by contacting resin particles (primary particles).
分散粒子径を制御する方法としては、スチレン系樹脂粒子を構成するスチレン単量体由来の繰り返し単位の含有量や、スチレン単量体と共重合させるコモノマーの種類、前記(メタ)アクリル重合体(P)に含有される前記(メタ)アクリル酸エステル(M)由来の繰り返し単位の種類・含有量、スチレン系樹脂粒子を重合する際の重合条件、(メタ)アクリル樹脂組成物に含有される前のスチレン系樹脂粒子の粒子径などを調整するなど、公知の方法を採用することができる。 As a method for controlling the dispersed particle size, the content of the repeating unit derived from the styrene monomer constituting the styrene resin particles, the type of the comonomer to be copolymerized with the styrene monomer, and the (meth) acrylic polymer ( The type and content of the repeating unit derived from the (meth) acrylic acid ester (M) contained in P), the polymerization conditions when polymerizing the styrene resin particles, and before being contained in the (meth) acrylic resin composition. A known method can be adopted, such as adjusting the particle size of the styrene-based resin particles.
スチレン系樹脂粒子の粉末、ビ−ズの製造方法としては、分散安定剤を用いて水中に分散させた単量体混合物を重合させ、次いで洗浄脱水処理の後に真空乾燥して粉体を得る方法が挙げられる。また、スチレン系樹脂粒子のペレットの製造方法としては、例えば、上記の方法で得られた粉体を押出しすることによってペレットを得る方法や、単量体混合物を反応器内で塊状重合させ、未反応の単量体を分離除去しながら押出しすることによってペレットを得る方法が挙げられる。重合形式としては、ラジカル重合、懸濁重合、アニオン重合等の公知の重合形式を用いることができる。 As a method for producing powder and beads of styrene-based resin particles, a method of polymerizing a monomer mixture dispersed in water using a dispersion stabilizer, and then vacuum-drying after washing and dehydrating treatment to obtain a powder. Can be mentioned. Further, as a method for producing pellets of styrene-based resin particles, for example, a method of obtaining pellets by extruding the powder obtained by the above method, or a method of bulk polymerization of a monomer mixture in a reactor has not been performed. Examples thereof include a method of obtaining pellets by extruding while separating and removing the monomer of the reaction. As the polymerization format, known polymerization formats such as radical polymerization, suspension polymerization, and anionic polymerization can be used.
樹脂粒子(F)の種類としては、特に限定されるものではないが、公知の熱可塑性樹脂を用いることができる。公知の熱可塑性樹脂としては、例えば、(メタ)アクリル系樹脂粒子、スチレン系樹脂粒子、MS系樹脂(メタクリル−スチレン共重合樹脂)粒子、及びシリコーン系樹脂粒子、ポリエチレン系樹脂粒子、ポリプロピレン系樹脂粒子、ポリエステル系樹脂粒子、ポリアミド系樹脂粒子が挙げられる。これらは1種又は2種以上を併用して使用することができる。中でも、スチレン系樹脂粒子又は(メタ)アクリル樹脂粒子は、屈折率を調整しやすく、(メタ)アクリル樹脂組成物中の分散安定性が良いことから、樹脂成形体の光拡散性を制御しやすく、耐候性が良好となるので好ましい。
前記(メタ)アクリル系樹脂粒子は、(メタ)アクリル重合体(P)中のメタクリル酸エステル(M1)由来の繰り返し単位及びアクリル酸エステル(M2)由来の繰り返し単位に高い親和性を有するので、(メタ)アクリル樹脂組成物中への分散安定性がより良好となり。樹脂成形体の光拡散効果と難燃性をより優れたものにできる。
前記スチレン系樹脂粒子としては、スチレン単量体由来の繰り返し単位を、前記樹脂粒子(F)の総質量に対して、80質量%以上含有する樹脂粒子が、樹脂微粒子の屈折率を高くして、樹脂成形体の光拡散効果を向上できる観点から好ましい。
添加するスチレン系樹脂粒子の屈折率としては、(メタ)アクリル重合体(P)との屈折率差が、0.01以上3.0以下の範囲にあることが好ましい。屈折率差が、0.01以上あれば、樹脂成形体が適度な光拡散性を発現できることから好ましく、0.03以上がより好ましい。屈折率差が、2.5以下であれば、樹脂成形体は、光源から適度な光路長にわたって光拡散性を維持できることから好ましく、2.0以下がより好ましい。
なお、本明細書において「屈折率」は、ISO 13468に準拠し、23℃でナトリウムD線を用いてアッベ屈折計を用いて測定できる。
The type of the resin particles (F) is not particularly limited, but a known thermoplastic resin can be used. Known thermoplastic resins include, for example, (meth) acrylic resin particles, styrene resin particles, MS resin (methacryl-styrene copolymer resin) particles, silicone resin particles, polyethylene resin particles, and polypropylene resin. Examples thereof include particles, polyester-based resin particles, and polyamide-based resin particles. These can be used alone or in combination of two or more. Among them, the styrene resin particles or the (meth) acrylic resin particles are easy to adjust the refractive index and have good dispersion stability in the (meth) acrylic resin composition, so that it is easy to control the light diffusivity of the resin molded body. , It is preferable because the weather resistance is good.
Since the (meth) acrylic resin particles have a high affinity for the repeating unit derived from the methacrylic acid ester (M1) and the repeating unit derived from the acrylic acid ester (M2) in the (meth) acrylic polymer (P), The dispersion stability in the (meth) acrylic resin composition becomes better. The light diffusing effect and flame retardancy of the resin molded product can be improved.
As the styrene-based resin particles, the resin particles containing 80% by mass or more of the repeating unit derived from the styrene monomer with respect to the total mass of the resin particles (F) increase the refractive index of the resin fine particles. , Preferable from the viewpoint of improving the light diffusion effect of the resin molded body.
As for the refractive index of the styrene resin particles to be added, it is preferable that the difference in the refractive index from the (meth) acrylic polymer (P) is in the range of 0.01 or more and 3.0 or less. When the difference in refractive index is 0.01 or more, the resin molded product can exhibit appropriate light diffusivity, which is preferable, and 0.03 or more is more preferable. When the difference in refractive index is 2.5 or less, the resin molded product is preferable because it can maintain the light diffusivity over an appropriate optical path length from the light source, and more preferably 2.0 or less.
In this specification, the "refractive index" is based on ISO 13468 and can be measured using an Abbe refractometer using a sodium D line at 23 ° C.
前記スチレン系微粒子としては、ゲルパーミエーションクロマトグラフィー(GPC)で測定した重量平均分子量(Mw)が4万以上30万以下の重合体を用いることが好ましい。重量平均分子量の下限は、(メタ)アクリル樹脂組成物中の樹脂粒子(F)の分散粒子径を0.5μm以上とする点から4万以上が好ましく、1.0μm以上とする点から5万以上がより好ましい。一方、重量平均分子量の上限は(メタ)アクリル樹脂組成物中の樹脂粒子(F)の分散粒子径を10μm以下とする点から30万以下が好ましく、分散粒子径を5.0μm以下とする点から15万以下がより好ましい。 As the styrene-based fine particles, it is preferable to use a polymer having a weight average molecular weight (Mw) of 40,000 or more and 300,000 or less as measured by gel permeation chromatography (GPC). The lower limit of the weight average molecular weight is preferably 40,000 or more from the viewpoint that the dispersed particle size of the resin particles (F) in the (meth) acrylic resin composition is 0.5 μm or more, and 50,000 from the viewpoint of 1.0 μm or more. The above is more preferable. On the other hand, the upper limit of the weight average molecular weight is preferably 300,000 or less from the viewpoint that the dispersed particle size of the resin particles (F) in the (meth) acrylic resin composition is 10 μm or less, and the dispersed particle size is 5.0 μm or less. To 150,000 or less is more preferable.
本発明の樹脂成形体は、前記樹脂粒子(F)の中に、略球状の樹脂粒子が存在する形態をとることができる。「略球状」とは角のない形状のことをいう。樹脂粒子(F)中に略球状の樹脂粒子が存在することにより、樹脂成形体の難燃性は良好となる傾向がある。 なお、樹脂粒子(F)中に略球状の樹脂粒子が存在するとは、透過型電子顕微鏡を用いて、不特定に選択した樹脂粒子(F)について、該樹脂粒子の中心近傍を通る断面を観察したときに、樹脂粒子(F)中の1μm×1μmの視野に、略球状の樹脂粒子が5〜20個存在している状態をいう。 The resin molded product of the present invention can take a form in which substantially spherical resin particles are present in the resin particles (F). "Approximately spherical" refers to a shape without corners. The presence of substantially spherical resin particles in the resin particles (F) tends to improve the flame retardancy of the resin molded product. The presence of substantially spherical resin particles in the resin particles (F) means that the resin particles (F) selected unspecifiedly are observed in a cross section near the center of the resin particles using a transmission electron microscope. This refers to a state in which 5 to 20 substantially spherical resin particles are present in a 1 μm × 1 μm field of view in the resin particles (F).
前記樹脂粒子(F)の分散粒子径が0.5μm以上5.0μm以下のときに、前記略球状の樹脂粒子の分散粒子径を0.01μm以上0.3μm以下の範囲とすることができる。このような形態は、重量平均分子量(Mw)が4万以上30万以下のスチレン系微粒子を用いて、得ることができる。
前記樹脂粒子(F)の分散粒子径が1.0μm以上2.0μm以下のときに、前記略球状の樹脂粒子の分散粒子径を0.01μm以上0.1μm以下の範囲とすることができる。このような形態は、重量平均分子量(Mw)が5万以上15万以下のスチレン系微粒子を用いて、得ることができる。
なお、前記略球状の樹脂粒子の形態や分散粒子径は、前述した樹脂粒子(F)の分散粒子径の測定方法と同様の方法を用いて観察できる。
When the dispersed particle size of the resin particles (F) is 0.5 μm or more and 5.0 μm or less, the dispersed particle size of the substantially spherical resin particles can be in the range of 0.01 μm or more and 0.3 μm or less. Such a form can be obtained by using styrene-based fine particles having a weight average molecular weight (Mw) of 40,000 or more and 300,000 or less.
When the dispersed particle size of the resin particles (F) is 1.0 μm or more and 2.0 μm or less, the dispersed particle size of the substantially spherical resin particles can be in the range of 0.01 μm or more and 0.1 μm or less. Such a form can be obtained by using styrene-based fine particles having a weight average molecular weight (Mw) of 50,000 or more and 150,000 or less.
The morphology and the dispersed particle size of the substantially spherical resin particles can be observed by using the same method as the method for measuring the dispersed particle size of the resin particles (F) described above.
上述した樹脂粒子(F)としては、市販品を用いてもよいし、公知の方法で単量体から製造してもよい。
(メタ)アクリル樹脂粒子の市販品としては、例えば、三菱レイヨン(株)製のメタブレンシリーズ(W−341)、綜研化学(株)製のケミスノーMR−2G、MS−300X、旭化成ケミカルズ(株)製のデルペットシリーズ(SRB215)等の市販品を挙げられる。
スチレン系樹脂粒子の市販品としては、例えば、スチレン、p−メチルスチレン、p−クロロスチレン、クロロメチルスチレン、α−メチルスチレン等のスチレン系単量体由来の粒子が挙げられる。これらスチレン系樹脂粒子は、架橋されていても、架橋されていなくても良い。具体的には、綜研化学社製のSXシリーズ(SX−130H、SX−200H、SX−350H)、積水化成品工業社製のSBXシリーズ(SBX−6、SBX−8、SBX−12)等の市販品を挙げられる。
市販の樹脂粒子(F)を用いる場合、樹脂粒子(F)の平均粒径は特に限定されるものではないが、樹脂成形体が使用される目的に応じて選択すればよい。例えば、市販の樹脂粒子として、0.5〜20μm程度の平均粒径を有する樹脂粒子を入手することができる。平均粒径の下限は0.5μm以上であれば、樹脂成形体中の樹脂粒子(F)の分散性が良好となり、適度な拡散率及び乳半色の色調を有する樹脂成形体が得られる観点から好ましい。平均粒径の上限は20μm以下であれば、樹脂成形体の難燃性や、樹脂成形体を光拡散板として用いた時の輝度、及び表面円滑性等の外観の観点から好ましい。なお、上記平均粒径とは、(メタ)アクリル樹脂組成物に含有される前の、樹脂粒子(F)単独での測定であり、コールターカウンター法による重量平均径として計測できる。
As the resin particles (F) described above, a commercially available product may be used, or the resin particles (F) may be produced from a monomer by a known method.
Commercially available products of (meth) acrylic resin particles include, for example, Metablen series (W-341) manufactured by Mitsubishi Rayon Co., Ltd., Chemisnow MR-2G, MS-300X manufactured by Soken Kagaku Co., Ltd., and Asahi Kasei Chemicals Co., Ltd. ), Such as the Delpet series (SRB215).
Examples of commercially available styrene-based resin particles include particles derived from styrene-based monomers such as styrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, and α-methylstyrene. These styrene-based resin particles may or may not be crosslinked. Specifically, the SX series (SX-130H, SX-200H, SX-350H) manufactured by Soken Chemical Co., Ltd., the SBX series (SBX-6, SBX-8, SBX-12) manufactured by Sekisui Plastics Co., Ltd., etc. Commercially available products can be mentioned.
When commercially available resin particles (F) are used, the average particle size of the resin particles (F) is not particularly limited, but may be selected according to the purpose for which the resin molded product is used. For example, as commercially available resin particles, resin particles having an average particle size of about 0.5 to 20 μm can be obtained. When the lower limit of the average particle size is 0.5 μm or more, the dispersibility of the resin particles (F) in the resin molded product is good, and a resin molded product having an appropriate diffusivity and a milky half-color tone can be obtained. Is preferable. When the upper limit of the average particle size is 20 μm or less, it is preferable from the viewpoint of flame retardancy of the resin molded product, brightness when the resin molded product is used as a light diffusing plate, surface smoothness, and the like. The average particle size is a measurement of the resin particles (F) alone before being contained in the (meth) acrylic resin composition, and can be measured as a weight average diameter by the Coulter counter method.
<樹脂成形体>
本発明の樹脂成形体は、上述した(メタ)アクリル重合体(P)とリン系難燃剤(C)と樹脂粒子(F)とを含有する(メタ)アクリル樹脂組成物を成形して得られる。
樹脂成形体の難燃性は、一般にはDIN 5036にて測定する拡散率と所謂トレードオフの関係にあり、拡散率の向上に伴って難燃性が低下する傾向にある。すなわち、本発明の樹脂成形体は、相反する特性である難燃性と拡散率とを両立させているという顕著な特性を有した樹脂成形体である。
<Resin molded product>
The resin molded product of the present invention is obtained by molding a (meth) acrylic resin composition containing the above-mentioned (meth) acrylic polymer (P), a phosphorus-based flame retardant (C), and resin particles (F). ..
The flame retardancy of a resin molded product generally has a so-called trade-off relationship with the diffusivity measured by DIN 5036, and the flame retardancy tends to decrease as the diffusivity increases. That is, the resin molded product of the present invention is a resin molded product having a remarkable characteristic that both flame retardancy and diffusivity, which are contradictory characteristics, are compatible with each other.
本発明において、樹脂成形体の拡散率は、DIN 5036に準拠して測定した拡散率の値を用いることができる。本発明の樹脂成形体の拡散率は60%以上99%以下の範囲とすることができる。照明看板用途・照明用途において蛍光灯やLED等の照明灯カバーとして用いたときに、樹脂成形体の拡散率の下限が60%以上であれば、光源の形状を隠蔽できる観点から好ましい。また拡散率の上限が99%以下であれば、十分な明るさを確保できる観点から好ましい。樹脂成形体の拡散率の値は、後述する(メタ)アクリル樹脂組成物の組成、光拡散剤の種類・含有量等を調整することにより、所望の値に制御できる。
上述した樹脂成形体は、例えば、本発明の要件を満たす(メタ)アクリル樹脂組成物を、公知の方法により成形することにより製造することができる。
In the present invention, the value of the diffusivity measured according to DIN 5036 can be used as the diffusivity of the resin molded product. The diffusion rate of the resin molded product of the present invention can be in the range of 60% or more and 99% or less. When used as a lighting cover for fluorescent lamps, LEDs, etc. in lighting signboard applications and lighting applications, if the lower limit of the diffusivity of the resin molded body is 60% or more, it is preferable from the viewpoint that the shape of the light source can be hidden. Further, when the upper limit of the diffusion rate is 99% or less, it is preferable from the viewpoint of ensuring sufficient brightness. The value of the diffusivity of the resin molded product can be controlled to a desired value by adjusting the composition of the (meth) acrylic resin composition described later, the type and content of the light diffusing agent, and the like.
The above-mentioned resin molded product can be produced, for example, by molding a (meth) acrylic resin composition satisfying the requirements of the present invention by a known method.
さらに、本発明の樹脂成形体は、JIS K 6911 耐燃性A法試験において3分未満で自消する不燃性を有する。樹脂成形体が、前記試験で3分未満で自消する難燃性を有するなら、火災発生時の延焼や類焼を防止できるので安全性の観点から好ましく、蛍光灯やLED等の照明灯カバーでの使用に加え、さらにガソリンスタンド等の照明看板等での使用に適している。このような樹脂成形体は、例えば、本発明の要件を満たす(メタ)アクリル樹脂組成物を用いて、公知の方法により成形することにより製造できる。 Further, the resin molded product of the present invention has a nonflammability that self-extinguishes in less than 3 minutes in the JIS K 6911 flame resistance method A test. If the resin molded body has a flame retardancy that self-extinguishes in less than 3 minutes in the above test, it is preferable from the viewpoint of safety because it can prevent the spread of fire and other types of fire in the event of a fire. In addition to the use of, it is also suitable for use in lighting signs such as gas stations. Such a resin molded product can be produced, for example, by molding by a known method using a (meth) acrylic resin composition satisfying the requirements of the present invention.
さらに、本発明の樹脂成形体は、前記樹脂粒子(F)として、分散粒子径が1.0μm以上2.0μm以下であり、スチレン単量体由来の繰り返し単位を、該樹脂粒子(F)の総質量に対して、80質量%以上含有するスチレン系微粒子を用いるときに、JIS K6911A法にて燃焼試験を行った場合に1.5分未満で自消する不燃性を有することができる。 Further, in the resin molded product of the present invention, the dispersed particle diameter of the resin particles (F) is 1.0 μm or more and 2.0 μm or less, and the repeating unit derived from the styrene monomer is used as the resin particles (F). When styrene-based fine particles containing 80% by mass or more with respect to the total mass are used, it can have nonflammability that self-extinguishes in less than 1.5 minutes when a combustion test is performed by the JIS K6911A method.
さらに、本発明の樹脂成形体は、該樹脂成形体の厚みを4mm以上とすることで、UL94で規定される垂直燃焼試験においてV−0の難燃性を有することができる。樹脂成形体が前記試験においてUL94/V−0の難燃性を有するなら、火災発生時に接炎しても、樹脂成形体の燃焼が継続しないので安全性の観点から好ましく、蛍光灯やLED等の照明灯カバーやガソリンスタンド等の照明看板等での使用に加え、さらに鉄道車両や自動車等の移動体内の照明看板等での使用に適している。このような樹脂成形体は、例えば、本発明の要件を満たす(メタ)アクリル樹脂組成物において、(メタ)アクリル重合体(P)100質量部に対して、リン系難燃剤(C)の量を15質量部以上とし、樹脂微粒子(F)の含有量を3.0質量部以下とすることにより製造できる。
なお、本明細書において厚みは、シックネスゲージで測定できる。
Further, the resin molded product of the present invention can have a flame retardancy of V-0 in the vertical combustion test defined by UL94 by setting the thickness of the resin molded product to 4 mm or more. If the resin molded body has a flame retardancy of UL94 / V-0 in the above test, it is preferable from the viewpoint of safety because the resin molded body does not continue to burn even if it comes into contact with a flame in the event of a fire. In addition to being used for lighting signs such as lighting covers and gas stations, it is also suitable for use in lighting signs inside moving bodies such as railroad vehicles and automobiles. In such a resin molded product, for example, in a (meth) acrylic resin composition satisfying the requirements of the present invention, the amount of the phosphorus-based flame retardant (C) is based on 100 parts by mass of the (meth) acrylic polymer (P). Is 15 parts by mass or more, and the content of the resin fine particles (F) is 3.0 parts by mass or less.
In this specification, the thickness can be measured with a thickness gauge.
本樹脂成形体の形状は限定されないが、一実施形態として、板状の樹脂板とすることができる。樹脂板の厚みは、特に限定されないが、1mm以上30mm以下とすることができる。樹脂板厚みの下限が1mm以上であれば、樹脂成形体の強度を十分なものでできる。樹脂板厚みの上限が30mm以下であれば、樹脂成形体の成型性が良好となる。
<照明灯カバー、照明看板>
本発明の照明灯カバーは、上述した、本発明の樹脂成形体を含む。
本発明の照明看板は、上述した、本発明の樹脂成形体を含む。
ここで、「本発明の樹脂成形体を含む」とは、本発明の(メタ)アクリル樹脂組成物又は樹脂成形体を、照明灯カバー又は照明看板の「主成分の材料」として含むことを意味する。ここで、「主成分の材料」とは、照明灯カバー又は照明看板が単一の材料からなる場合には、その材料のことを示し、複数の材料からなる場合には、構成する材料のうち最も質量分率の高い材料のことを示す。
The shape of the resin molded product is not limited, but as one embodiment, a plate-shaped resin plate can be used. The thickness of the resin plate is not particularly limited, but can be 1 mm or more and 30 mm or less. When the lower limit of the resin plate thickness is 1 mm or more, the strength of the resin molded product can be made sufficient. When the upper limit of the resin plate thickness is 30 mm or less, the moldability of the resin molded product is good.
<Lighting cover, lighting signboard>
The illumination lamp cover of the present invention includes the resin molded product of the present invention described above.
The lighting signboard of the present invention includes the resin molded product of the present invention described above.
Here, "including the resin molded product of the present invention" means that the (meth) acrylic resin composition or the resin molded product of the present invention is included as the "main component material" of the lighting lamp cover or the lighting signboard. To do. Here, the "main component material" indicates the material when the lighting cover or the lighting signboard is made of a single material, and when it is made of a plurality of materials, it is among the constituent materials. Indicates the material with the highest mass fraction.
<樹脂成形体の製造法>
本発明の樹脂成形体の製造方法は特に限定されるものではなく、例えば、後述するセルキャスト法や連続キャスト法等の公知の注型重合法を用いて製造できる。注型重合法は、周辺を樹脂チューブ等のガスケットでシールして所定間隔で対向配置された2枚の無機ガラス板または金属板(SUS板)からなる鋳型に、(メタ)アクリル樹脂組成物を得るための重合性原料を注入して重合させることにより(メタ)アクリル樹脂組成物を形成し、得られた(メタ)アクリル樹脂組成物を鋳型から剥離して樹脂成形体を得る方法である。 注型重合用の鋳型は特に限定されず、公知の鋳型を用いることができる。板状の樹脂成形物を得るための鋳型としては、例えば、セルキャスト用の鋳型と連続キャスト用の鋳型が挙げられる。
セルキャスト用の鋳型としては、例えば、無機ガラス板、クロムメッキ金属板、ステンレス鋼板等の2枚の板状体を所定間隔で対向配置し、その縁部にガスケットを配置して、板状体とガスケットにより密封空間を形成させたものが挙げられる。
連続キャスト用の鋳型としては、例えば、同一方向へ同一速度で走行する一対のエンドレスベルトの対向する面と、エンドレスベルトの両側辺部においてエンドレスベルトと同一速度で走行するガスケットとにより密封空間を形成させたものが挙げられる。
注型重合法を用いた場合の重合方法としては、例えば、前述のアクリル重合体の製造方法と同様に、公知の方法を用いることができる。
鋳型の空隙の間隔は所望の厚さの樹脂板が得られるように適宜調整されるが、一般的には1〜30mmである。
<Manufacturing method of resin molded product>
The method for producing the resin molded product of the present invention is not particularly limited, and for example, it can be produced by using a known casting polymerization method such as a cell casting method or a continuous casting method described later. In the casting polymerization method, the (meth) acrylic resin composition is placed in a mold consisting of two inorganic glass plates or metal plates (SUS plates) arranged opposite to each other at predetermined intervals by sealing the periphery with a gasket such as a resin tube. This is a method of forming a (meth) acrylic resin composition by injecting and polymerizing a polymerizable raw material for obtaining the resin, and peeling the obtained (meth) acrylic resin composition from a mold to obtain a resin molded product. The mold for casting polymerization is not particularly limited, and a known mold can be used. Examples of the mold for obtaining a plate-shaped resin molded product include a mold for cell casting and a mold for continuous casting.
As a mold for cell casting, for example, two plate-like bodies such as an inorganic glass plate, a chrome-plated metal plate, and a stainless steel plate are arranged to face each other at predetermined intervals, and a gasket is arranged at the edge thereof to form a plate-like body. And the one in which a sealed space is formed by a gasket.
As a mold for continuous casting, for example, a sealed space is formed by facing surfaces of a pair of endless belts traveling in the same direction at the same speed and gaskets traveling at the same speed as the endless belts on both sides of the endless belt. The ones that have been made can be mentioned.
As the polymerization method when the cast polymerization method is used, for example, a known method can be used in the same manner as the above-mentioned method for producing an acrylic polymer.
The spacing between the voids of the mold is appropriately adjusted so as to obtain a resin plate having a desired thickness, but is generally 1 to 30 mm.
以下に本発明を、実施例を用いて説明する。以下において、「部」は「質量部」を示す。 Hereinafter, the present invention will be described with reference to examples. In the following, "part" means "part by mass".
また、実施例及び比較例で使用した化合物の略号は以下のとおりである。
・MMA:メタクリル酸メチル
・IBXMA:メタクリル酸イソボルニル
・IBXA:アクリル酸イソボルニル
・TBMA:メタクリル酸t−ブチル
・BA:アクリル酸n−ブチル
・EDMA:エチレングリコールジメタクリレート
・CR−570:ハロゲン含有縮合リン酸エステル(商品名、大八化学工業(株)製)・St系粒子:市販のスチレン系樹脂粒子(GPC重量平均分子量(Mw):9.1万、スチレン単位の含有量:100質量%)
・Stペレット:市販のスチレン系ペレット(GPC重量平均分子量(Mw):20.0万、スチレン単位の含有量:100質量%)
・架橋粒子A:市販のスチレン系樹脂粒子(商品名:KSR−3A、綜研化学(株)製、スチレン単位の含有量:100質量%)
・架橋粒子B:市販のスチレン系樹脂粒子(商品名:SBX−12、積水化成品工業(株)製、スチレン単位の含有量:100質量%)
・架橋粒子C:市販のスチレン系樹脂粒子(商品名:SX−130H、綜研化学(株)製)
・シリカ粒子:市販のシリカ粒子(商品名:シーホスターP100、(株)日本触媒製、スチレン単位の含有量:0質量%)
The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
MMA: Methyl methacrylate ・ IBXMA: Isobornyl methacrylate ・ IBXA: Isobornyl acrylate ・ TBMA: t-butyl methacrylate ・ BA: n-butyl methacrylate ・ EDMA: Ethylene glycol dimethacrylate ・ CR-570: Halogen-containing condensed phosphorus Acid ester (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.) ・ St-based particles: Commercially available styrene-based resin particles (GPC weight average molecular weight (Mw): 91,000, styrene unit content: 100% by mass)
-St pellets: Commercially available styrene-based pellets (GPC weight average molecular weight (Mw): 200,000, styrene unit content: 100% by mass)
-Crosslinked particles A: Commercially available styrene resin particles (trade name: KSR-3A, manufactured by Soken Kagaku Co., Ltd., styrene unit content: 100% by mass)
-Crosslinked particles B: Commercially available styrene resin particles (trade name: SBX-12, manufactured by Sekisui Plastics Co., Ltd., styrene unit content: 100% by mass)
-Crosslinked particles C: Commercially available styrene resin particles (trade name: SX-130H, manufactured by Soken Chemical Co., Ltd.)
-Silica particles: Commercially available silica particles (trade name: Seahoster P100, manufactured by Nippon Shokubai Co., Ltd., content of styrene unit: 0% by mass)
尚、実施例及び比較例における評価は以下の方法により実施した。
(1)樹脂粒子(F)の分散粒子径
樹脂粒子(F)の分散粒子径とは、(メタ)アクリル樹脂組成物又は樹脂成形体中に含有される樹脂粒子の平均粒径である。(メタ)アクリル樹脂組成物を切断、又はシート状の樹脂成形体を主平面に対して垂直方向に切断した後に、ウルトラミクロトーム(ライカ製、商品名:EM−ULTRACUTUCT)を用いて小片を切り出した。次いで、透過型電子顕微鏡(JEM−1011、日本電子(株)製、倍率1万倍)を用いて得られた小片を観察して、樹脂粒子の中心近傍を通る断面において、任意の樹脂粒子又は凝集粒子を30個選択して、樹脂粒子の一次粒子径又は凝集粒子の二次粒子径の最大粒径を測定し、その平均値として算出した。画像から判断するため、画像解析ソフトを用いて算出した。 (2)略球状の樹脂粒子の分散粒子径
略球状の樹脂粒子の分散粒子径とは、樹脂粒子(F)中に含有される樹脂粒子の平均粒径である。上述した樹脂粒子(F)の分散粒子径と同様の方法で、透過型電子顕微鏡を用いて、不特定に選択した樹脂粒子(F)について、該樹脂粒子の中心近傍を通る断面を観察したときに、樹脂粒子(F)中の1μm×1μmの視野に観察される任意の略球状の樹脂粒子を30個選択して、該樹脂粒子の最大粒径を測定し、その平均値として算出した。画像から判断するため、画像解析ソフトを用いて算出した。
The evaluation in Examples and Comparative Examples was carried out by the following method.
(1) Dispersed particle size of the resin particles (F) The dispersed particle size of the resin particles (F) is the average particle size of the resin particles contained in the (meth) acrylic resin composition or the resin molded body. After cutting the (meth) acrylic resin composition or cutting the sheet-shaped resin molded product in the direction perpendicular to the main plane, small pieces were cut out using an ultramicrotome (manufactured by Leica, trade name: EM-ULTRACUTUCT). .. Next, the small pieces obtained by using a transmission electron microscope (JEM-1011, manufactured by JEOL Ltd., magnification 10,000 times) are observed, and in a cross section passing near the center of the resin particles, any resin particles or Thirty agglomerated particles were selected, the maximum particle size of the primary particle size of the resin particles or the secondary particle size of the agglomerated particles was measured, and the average value was calculated. It was calculated using image analysis software in order to judge from the image. (2) Dispersed particle size of substantially spherical resin particles The dispersed particle size of substantially spherical resin particles is the average particle size of the resin particles contained in the resin particles (F). When the cross section of the unspecified resin particles (F) passing near the center of the resin particles is observed by using a transmission electron microscope in the same manner as the dispersed particle size of the resin particles (F) described above. In addition, 30 arbitrary substantially spherical resin particles observed in a field of 1 μm × 1 μm in the resin particles (F) were selected, the maximum particle size of the resin particles was measured, and the average value was calculated. It was calculated using image analysis software in order to judge from the image.
(3)拡散性
厚さ3mmの板状の樹脂成形体を用いて以下の評価を行った。樹脂成形体を、点灯した45Wの蛍光灯から1.5mの距離のところに設置し、樹脂成形体を通して蛍光灯のランプ形状が確認できるかどうかの評価を行った。
○:蛍光灯のランプ形状は確認できない。
△:蛍光灯のランプ形状が極僅かに確認できる。
×:蛍光灯のランプ形状が明らかに確認できる。
(3) Diffusibility The following evaluation was performed using a plate-shaped resin molded product having a thickness of 3 mm. The resin molded body was installed at a distance of 1.5 m from the lit 45 W fluorescent lamp, and it was evaluated whether or not the lamp shape of the fluorescent lamp could be confirmed through the resin molded body.
◯: The lamp shape of the fluorescent lamp cannot be confirmed.
Δ: The lamp shape of the fluorescent lamp can be confirmed very slightly.
X: The lamp shape of the fluorescent lamp can be clearly confirmed.
(4)拡散率
厚さ3mmの板状の樹脂成形体を用いて以下の評価を行った。変角光度計((株)村上色彩技術研究所製、商品名:GP−200)を用い、試料に0°で光を入射したときの、試料に対して5°、20°、70°の角度における透過光の輝度値を測定し、拡散率を算出した。
(4) Diffusion rate The following evaluation was performed using a plate-shaped resin molded product having a thickness of 3 mm. Using a variable-angle photometer (manufactured by Murakami Color Technology Laboratory Co., Ltd., trade name: GP-200), when light is incident on the sample at 0 °, it is 5 °, 20 °, 70 ° with respect to the sample. The brightness value of the transmitted light at an angle was measured, and the diffusion rate was calculated.
(5)不燃性(JIS)
難燃性の指標として、JIS K 6911−1979の耐燃性試験A法に準拠して、樹脂成形体の試験片を作製し、前記試験片の不燃性を評価した。試験片の自消までに要した時間(自消時間)を測定し、以下の基準を用いて判定した。
○:試験片の自消時間が3分未満である。
×:試験片の自消時間が3分以上又は試験片は自消しない。
(5) Nonflammable (JIS)
As an index of flame retardancy, a test piece of a resin molded product was prepared in accordance with the flame resistance test A method of JIS K 6911-1979, and the nonflammability of the test piece was evaluated. The time required for self-extinguishing of the test piece (self-extinguishing time) was measured, and the judgment was made using the following criteria.
◯: The self-extinguishing time of the test piece is less than 3 minutes.
X: The self-extinguishing time of the test piece is 3 minutes or more, or the test piece is not self-erasing.
(6)難燃性(UL94)
難燃性の指標として、UL94垂直燃焼試験法に準拠して、樹脂成形体の試験片(長さ127mm×幅12.7mm)を作製し、前記試験片の難燃性を評価した。さらに、表1に示す基準を用いて判定した。
(6) Flame retardant (UL94)
As an index of flame retardancy, a test piece (length 127 mm × width 12.7 mm) of a resin molded product was prepared in accordance with the UL94 vertical combustion test method, and the flame retardancy of the test piece was evaluated. Further, the judgment was made using the criteria shown in Table 1.
[実施例1]
(1)シラップの製造
冷却管、温度計及び攪拌機を備えた反応器(重合釜)にMMA68.0部、IBXMA20.0部、IBXA3.0部、TBMA8.0部及びBA1.0部の混合物を供給し、撹拌しながら窒素ガスでバブリングした後、加熱を開始した。反応器の内温が60℃になった時点で、ラジカル重合開始剤として2,2’−アゾビス−(2,4−ジメチルバレロニトリル)0.1部を添加し、更に反応器の内温が100℃になるまで加熱した後、13分間保持した。次いで、反応器の内温が室温になるまで冷却してシラップを得た。シラップの総質量に対し、シラップ中の重合体の含有量は30質量%、単量体組成物の含有量は70質量%であった。
[Example 1]
(1) Manufacture of syrup A mixture of 68.0 parts of MMA, 20.0 parts of IBXMA, 3.0 parts of IBXA, 8.0 parts of TBMA and 1.0 part of BA is placed in a reactor (polymerization kettle) equipped with a cooling tube, a thermometer and a stirrer. After feeding and bubbling with nitrogen gas while stirring, heating was started. When the internal temperature of the reactor reached 60 ° C., 0.1 part of 2,2'-azobis- (2,4-dimethylvaleronitrile) was added as a radical polymerization initiator, and the internal temperature of the reactor was further increased. After heating to 100 ° C., the mixture was held for 13 minutes. Then, the reactor was cooled to room temperature to obtain syrup. The content of the polymer in the syrup was 30% by mass and the content of the monomer composition was 70% by mass with respect to the total mass of the syrup.
(2)注型重合
上記のシラップ100部、単量体(B)としてEDMA0.15部、リン系難燃剤(C)としてCR−570の10.7部、樹脂粒子(F)としてSt系粒子1.7部を添加して、重合性組成物を得た。次いで、重合性組成物を、対向する2枚のSUS板の間のSUS板端部に塩化ビニル樹脂製ガスケットを配置して設けられた、空隙間隔4.1mmの空間に流し込み、82℃で30分、次いで130℃で30分加熱して、重合性組成物を硬化させて(メタ)アクリル樹脂組成物を得た。(メタ)アクリル樹脂組成物の組成を表3に示す。次いでSUS板ごと(メタ)アクリル樹脂組成物を冷却した後に、SUS板を取り除き、厚さ3mmの板状の樹脂成形体を得た。樹脂成形体中のリン系難燃剤(C)の含有量は(メタ)アクリル重合体(P)100質量部に対して10.7質量部であった。樹脂成形体の評価結果を表4に示す。なお、表4中、「−」は測定を行わなかったことを意味する。
(2) Cast Polymerization 100 parts of the above syrup, 0.15 part of EDMA as the monomer (B), 10.7 parts of CR-570 as the phosphorus flame retardant (C), and St-based particles as the resin particles (F). 1.7 parts were added to obtain a polymerizable composition. Next, the polymerizable composition was poured into a space having a gap spacing of 4.1 mm provided by arranging a vinyl chloride resin gasket at the end of the SUS plate between the two opposing SUS plates, and the mixture was poured at 82 ° C. for 30 minutes. Then, the mixture was heated at 130 ° C. for 30 minutes to cure the polymerizable composition to obtain a (meth) acrylic resin composition. The composition of the (meth) acrylic resin composition is shown in Table 3. Next, after cooling the (meth) acrylic resin composition together with the SUS plate, the SUS plate was removed to obtain a plate-shaped resin molded product having a thickness of 3 mm. The content of the phosphorus-based flame retardant (C) in the resin molded product was 10.7 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (P). Table 4 shows the evaluation results of the resin molded product. In Table 4, "-" means that the measurement was not performed.
[実施例2〜5]
重合性組成物の組成を表2記載のとおりに変更した以外は、実施例1と同様の方法で(メタ)アクリル樹脂組成物、及び樹脂成形体を製造した。得られた(メタ)アクリル樹脂組成物の組成を表3に示す。得られた樹脂成形体の評価結果を表4に示す。
[Examples 2 to 5]
A (meth) acrylic resin composition and a resin molded product were produced in the same manner as in Example 1 except that the composition of the polymerizable composition was changed as shown in Table 2. The composition of the obtained (meth) acrylic resin composition is shown in Table 3. Table 4 shows the evaluation results of the obtained resin molded product.
[実施例6〜7]
重合性組成物の組成を表2記載のとおりに変更し、且つ樹脂成形体の板厚を表4記載のとおりに変更した以外は、実施例1と同様の方法で(メタ)アクリル樹脂組成物、及び樹脂成形体を製造した。得られた(メタ)アクリル樹脂組成物の組成を表3に示す。得られた樹脂成形体の評価結果を表4に示す。
[Examples 6 to 7]
The (meth) acrylic resin composition was changed in the same manner as in Example 1 except that the composition of the polymerizable composition was changed as shown in Table 2 and the plate thickness of the resin molded product was changed as shown in Table 4. , And a resin molded product were manufactured. The composition of the obtained (meth) acrylic resin composition is shown in Table 3. Table 4 shows the evaluation results of the obtained resin molded product.
[比較例1〜3]
重合性組成物の組成を表2記載のとおりとした以外は、実施例1と同様の方法で(メタ)アクリル樹脂組成物、及び樹脂成形体を得た。得られた(メタ)アクリル樹脂組成物の組成を表3に示す。得られた樹脂成形体の評価結果を表4に示す。
[Comparative Examples 1 to 3]
A (meth) acrylic resin composition and a resin molded product were obtained in the same manner as in Example 1 except that the composition of the polymerizable composition was as shown in Table 2. The composition of the obtained (meth) acrylic resin composition is shown in Table 3. Table 4 shows the evaluation results of the obtained resin molded product.
[実施例8、比較例4]
重合性組成物の組成を表2記載のとおりとした以外は、実施例1と同様の方法で(メタ)アクリル樹脂組成物、及び樹脂成形体を得た。得られた(メタ)アクリル樹脂組成物の組成を表3に示す。得られた樹脂成形体の評価結果を表4に示す。
[Example 8, Comparative Example 4]
A (meth) acrylic resin composition and a resin molded product were obtained in the same manner as in Example 1 except that the composition of the polymerizable composition was as shown in Table 2. The composition of the obtained (meth) acrylic resin composition is shown in Table 3. Table 4 shows the evaluation results of the obtained resin molded product.
比較例1で得られた樹脂成形体は、(メタ)アクリル重合体(P)がメタクリル酸エステル(M1)及びアクリル酸エステル(M2)由来の繰り返し単位を含まないため、難燃性(JIS)が不良であった。
比較例2で得られた樹脂成形体は樹脂粒子(F)を含まないため、光拡散性が不良であった。
比較例3で得られた樹脂成形体は樹脂粒子(F)の分散粒子径が10μmを超えるため、難燃性と光拡散性が不良であった。
比較例4で得られた樹脂成形体は樹脂粒子(F)の代わりに、シリカ粒子(幹粒子)を用いたため、難燃性が不良であった。
The resin molded product obtained in Comparative Example 1 is flame-retardant (JIS) because the (meth) acrylic polymer (P) does not contain repeating units derived from methacrylic acid ester (M1) and acrylic acid ester (M2). Was defective.
Since the resin molded product obtained in Comparative Example 2 did not contain the resin particles (F), the light diffusivity was poor.
The resin molded product obtained in Comparative Example 3 had poor flame retardancy and light diffusivity because the dispersed particle size of the resin particles (F) exceeded 10 μm.
Since the resin molded product obtained in Comparative Example 4 used silica particles (stem particles) instead of the resin particles (F), the flame retardancy was poor.
本発明により、照明看板や照明灯カバーとして、適度な難燃性、光拡散性、及び、着色特性を有する乳半色の樹脂成形体、及び該樹脂成形体を得るための樹脂組成物を得ることができる。 INDUSTRIAL APPLICABILITY According to the present invention, a milky semi-colored resin molded product having appropriate flame retardancy, light diffusivity, and coloring characteristics as a lighting signboard or a lighting lamp cover, and a resin composition for obtaining the resin molded product are obtained. be able to.
Claims (20)
前記樹脂粒子(F)の分散粒子径が0.5μm以上10μm以下であり、
前記(メタ)アクリル重合体(P)が、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖に有するメタクリル酸エステル(M1)由来の繰り返し単位と、芳香族炭化水素基又は炭素数3〜20の脂環式炭化水素基を側鎖中に有するアクリル酸エステル(M2)由来の繰り返し単位とを含有する(メタ)アクリル樹脂組成物。 A (meth) acrylic resin composition containing a (meth) acrylic polymer (P), a phosphorus-based flame retardant (C), and resin particles (F).
The dispersed particle size of the resin particles (F) is 0.5 μm or more and 10 μm or less.
The (meth) acrylic polymer (P) is a repeating unit derived from a methacrylic acid ester (M1) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain, and aromatic hydrocarbons. A (meth) acrylic resin composition containing a repeating unit derived from an acrylic acid ester (M2) having a hydrogen group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in a side chain.
前記略球状の樹脂粒子の分散粒子径が0.01μm以上0.3μm以下である請求項6に記載の(メタ)アクリル樹脂組成物。 The dispersed particle size of the resin particles (F) is 0.5 μm or more and 5.0 μm or less.
The (meth) acrylic resin composition according to claim 6, wherein the dispersed particle size of the substantially spherical resin particles is 0.01 μm or more and 0.3 μm or less.
前記略球状の樹脂粒子の分散粒子径が0.01μm以上0.1μm以下である請求項6に記載の(メタ)アクリル樹脂組成物。 The dispersed particle size of the resin particles (F) is 1.0 μm or more and 2.0 μm or less.
The (meth) acrylic resin composition according to claim 6, wherein the dispersed particle size of the substantially spherical resin particles is 0.01 μm or more and 0.1 μm or less.
前記メタクリル酸エステル(M1)由来の繰り返し単位を10質量%以上80質量%以下と、前記アクリル酸エステル(M2)由来の繰り返し単位を0.50質量%以上20質量%以下とを含有する。請求項1〜9のいずれか一項に記載の(メタ)アクリル樹脂組成物。 The (meth) acrylic polymer (P) is based on the total mass of the (meth) acrylic polymer (P).
The repeating unit derived from the methacrylic acid ester (M1) is contained in an amount of 10% by mass or more and 80% by mass or less, and the repeating unit derived from the acrylic acid ester (M2) is contained in an amount of 0.50% by mass or more and 20% by mass or less. The (meth) acrylic resin composition according to any one of claims 1 to 9.
DIN 5036にて測定した拡散率が60%以上99%以下であり、且つ、JIS K6911A法にて燃焼試験を行った場合に3分未満で自消する不燃性を有する樹脂成形体。 A resin molded product obtained by molding a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), a phosphorus-based flame retardant (C), and resin particles (F).
A nonflammable resin molded product having a diffusivity of 60% or more and 99% or less measured by DIN 5036 and self-extinguishing in less than 3 minutes when a combustion test is performed by the JIS K6911A method.
前記樹脂粒子(F)の分散粒子径が1.0μm以上2.0μm以下であり、
前記樹脂粒子(F)が、スチレン単量体由来の繰り返し単位を、該樹脂粒子(F)の総質量に対して、80質量%以上含有するスチレン系微粒子である、請求項16に記載の樹脂成形体。 It has nonflammability that self-extinguishes in less than 1.5 minutes when a combustion test is performed by the JIS K6911A method, and
The dispersed particle size of the resin particles (F) is 1.0 μm or more and 2.0 μm or less.
The resin according to claim 16, wherein the resin particles (F) are styrene-based fine particles containing 80% by mass or more of the repeating unit derived from the styrene monomer with respect to the total mass of the resin particles (F). Molded body.
樹脂成形体の厚みが4mm以上である、請求項16又は17に記載の樹脂成形体。 It has a flame retardancy of V-0 in the vertical combustion test specified by UL94 and has a flame retardancy of V-0.
The resin molded product according to claim 16 or 17, wherein the thickness of the resin molded product is 4 mm or more.
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