JP5371036B2 - Expandable styrene resin particles and method for producing the same - Google Patents
Expandable styrene resin particles and method for producing the same Download PDFInfo
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本発明は発泡性スチレン系樹脂粒子及び其の製造方法に関し、詳しくは自己消火性を有するなどの難燃性に優れると共に、残存スチレン単量体の含有量が極めて少ない発泡粒子成形体を成形可能な発泡性スチレン系樹脂粒子及び其の製造方法に関する。 The present invention relates to an expandable styrene resin particle and a method for producing the same, and more specifically, it is excellent in flame retardancy such as having self-extinguishing properties and can be molded into an expanded particle molded body having a very small content of residual styrene monomer. The present invention relates to a foamable styrene resin particle and a method for producing the same.
近年、シックハウス(室内空気汚染)問題を引き起こさないために、各種製品に含まれている特定の揮発性有機化合物(VOC)の低減が強く要求されている。発泡性スチレン系樹脂粒子(以下、単に発泡性樹脂粒子ともいう。)は主にスチレン単量体を重合してなるが、このスチレン単量体は厚生労働省が室内濃度指針を定める揮発性有機化合物に指定されている。このような背景から、スチレン系樹脂発泡粒子成形体についても建材用途や自動車部材を中心に、大気中へのスチレン単量体の放散量の低減が必要となり、発泡性樹脂粒子中に残存する、重合時に重合されなかったスチレン単量体(以下、残存スチレン単量体ともいう。)の低減が進められてきた。しかしながら、建材や自動車分野においては、今まで以上の残存スチレン単量体の低減が要求されており、具体的には残存量が50ppmを切るような従来にない低いレベルまで、残存スチレン単量体を低減することが望まれている。 In recent years, there has been a strong demand for reduction of specific volatile organic compounds (VOC) contained in various products in order not to cause a sick house (indoor air pollution) problem. Expandable styrene-based resin particles (hereinafter also simply referred to as expandable resin particles) are mainly formed by polymerizing styrene monomers. These styrene monomers are volatile organic compounds that the Ministry of Health, Labor and Welfare establishes indoor concentration guidelines. Is specified. From such a background, it is necessary to reduce the amount of styrene monomer diffused into the atmosphere, mainly for building materials and automotive parts, and to remain in the foamable resin particles for the styrene resin foamed particle molded body. Reduction of the styrene monomer which was not polymerized at the time of superposition | polymerization (henceforth a residual styrene monomer) has been advanced. However, in the field of building materials and automobiles, there is a demand for a reduction in the residual styrene monomer more than ever, and specifically, the residual styrene monomer to an unprecedented low level where the residual amount is less than 50 ppm. It is desired to reduce the above.
発泡性樹脂粒子中の残存スチレン単量体を低減させるための従来の方法として、一般には、重合温度を高くする方法や、重合開始剤を多くする方法、重合時間を長くする方法などが行われてきた。更に、特許文献1のように、2種類の重合開始剤を用いて、2段階の温度で重合を行い、1段階の低温部で分子量を増大させ、高温部で残存スチレン単量体を低減させることが行われている。 As a conventional method for reducing the residual styrene monomer in the expandable resin particles, a method for increasing the polymerization temperature, a method for increasing the polymerization initiator, a method for increasing the polymerization time, etc. are generally performed. I came. Further, as in Patent Document 1, using two kinds of polymerization initiators, polymerization is performed at two stages of temperature, the molecular weight is increased at one stage of the low temperature part, and the residual styrene monomer is reduced at the high temperature part. Things have been done.
一方、スチレン系樹脂発泡粒子成形体(以下、単に発泡粒子成形体ともいう。)が建材用途や自動車部材で使用される場合には、難燃性の付与が求められ、そのためには難燃剤が添加される。その場合、一般的には難燃効果の高さからハロゲン系難燃剤が使用されるが、ハロゲン系難燃剤の存在下でスチレン系単量体の重合を進めると、ハロゲン系難燃剤が重合時の連鎖移動剤や重合禁止剤として働くので、残存スチレン単量体を低減させることが困難になるという問題がある。 On the other hand, when a styrene-based resin expanded particle molded body (hereinafter, also simply referred to as a expanded particle molded body) is used in building materials or automotive parts, it is required to impart flame retardancy. Added. In that case, a halogen flame retardant is generally used because of its high flame retardant effect. However, if the polymerization of styrene monomer in the presence of the halogen flame retardant proceeds, the halogen flame retardant is not polymerized. Therefore, there is a problem that it becomes difficult to reduce the residual styrene monomer.
ハロゲン系難燃剤の存在下でスチレン単量体を重合する場合における、残存スチレン単量体を効果的に低減させる方法として、例えば、特許文献2に記載の方法がある。特許文献2には、2種類の重合開始剤を用いて2段階の温度で重合を行い、低温部で特殊な重合開始剤を使用することにより、残存スチレン単量体を低減する方法が開示されている。 As a method for effectively reducing the residual styrene monomer in the case of polymerizing the styrene monomer in the presence of a halogen-based flame retardant, for example, there is a method described in Patent Document 2. Patent Document 2 discloses a method of reducing residual styrene monomer by performing polymerization at two stages using two kinds of polymerization initiators and using a special polymerization initiator at a low temperature part. ing.
前記特許文献2には、残存スチレン単量体を検出限界以下にすることができたとの実施例がある。しかし、本発明者がこの方法を検証したところ、残存スチレン単量体を低減させることは可能ではあったが、50ppm未満という極めて低いレベルを達成することはできなかった。さらに、このような分野においては発泡粒子成形体には残存スチレン単量体量が極めて少ないことに加えて高い機械的強度が要求されるが、ハロゲン系難燃剤存在下で残存スチレン単量体を50ppm未満に低減しようとすると、ポリマー鎖の切断によって分子量低下が生じ、この発泡性樹脂粒子から得られる発泡粒子成形体は機械的強度が低下してしまうという問題が新たに発生してしまう。 In Patent Document 2, there is an example that the residual styrene monomer can be made below the detection limit. However, when the present inventors verified this method, it was possible to reduce the residual styrene monomer, but it was not possible to achieve a very low level of less than 50 ppm. Further, in such a field, the foamed particle molded body is required to have a high mechanical strength in addition to an extremely small amount of residual styrene monomer. If it is attempted to reduce it to less than 50 ppm, the molecular weight is lowered due to breakage of the polymer chain, and a new problem arises that the foamed particle molded body obtained from the expandable resin particles has a reduced mechanical strength.
本発明者は、ハロゲン系難燃剤を含みながらも、残存スチレン単量体量が極めて少なくかつ分子量が高い発泡性樹脂粒子を得るために、残存スチレン単量体量が極めて少ないスチレン系樹脂粒子を予め製造し、この樹脂粒子にブタンなどの発泡剤と共にハロゲン系難燃剤を含浸させる方法を試みた。この方法により得られた発泡性樹脂粒子は、残存スチレン単量体量が極めて少なくかつ分子量が高いものであったが、残存スチレン単量体によるスチレン系樹脂の可塑化効果が発現しなくなり、さらに、難燃剤が粒子の表面部分に多く存在することにより、発泡時の伸びが悪くなるので、発泡性に劣るものであった。さらに、得られた発泡粒子は表層部分の気泡が細かくなり、また、難燃剤含浸と同時に発泡性樹脂粒子中に多量の水分も含浸されてしまうために、この発泡性樹脂粒子を発泡させた予備発泡粒子は気泡構造が不均一なものであった。その結果、上記可塑化効果低下と相俟って、得られた発泡粒子は融着性にも劣るものとなり、さらに得られる発泡粒子成形体は機械的物性や外観にも劣るものであった。 In order to obtain expandable resin particles having an extremely small amount of residual styrene monomer and a high molecular weight while containing a halogen-based flame retardant, the present inventor selected styrene resin particles having an extremely small amount of residual styrene monomer. An attempt was made to pre-manufacture and impregnate the resin particles with a halogen-based flame retardant together with a blowing agent such as butane. The expandable resin particles obtained by this method had a very small amount of residual styrene monomer and a high molecular weight, but the plasticizing effect of the styrene resin by the residual styrene monomer was not expressed, and The presence of a large amount of flame retardant on the surface portion of the particles deteriorates the elongation at the time of foaming, so that the foamability is poor. Furthermore, since the foamed particles thus obtained have fine air bubbles in the surface layer, and a large amount of moisture is impregnated in the foamable resin particles simultaneously with the flame retardant impregnation, the foamed resin particles are preliminarily foamed. The foamed particles had a nonuniform cell structure. As a result, coupled with the decrease in the plasticizing effect, the obtained expanded particles were inferior in fusibility, and the obtained expanded expanded particles were inferior in mechanical properties and appearance.
本発明の目的は、前記問題点に鑑み、ハロゲン系難燃剤を含みながらも、残存スチレン単量体が極度に少なくかつ分子量が十分に高い発泡性樹脂粒子であって、発泡性に優れ、得られた予備発泡粒子は融着性に優れ、難燃性及び十分な機械的強度を有しかつ外観にも優れる発泡粒子成形体を得ることができる、従来は存在しなかった発泡性スチレン系樹脂粒子を提供し、更にその製造方法を提供することにある。 In view of the above problems, an object of the present invention is an expandable resin particle having an extremely small amount of residual styrene monomer and a sufficiently high molecular weight while containing a halogen-based flame retardant. The obtained pre-expanded particles have excellent fusibility, flame retardant properties, sufficient mechanical strength, and can provide a foamed particle molded body having excellent appearance. It is to provide particles and a method for producing the same.
本発明によれば、以下に示す発泡性スチレン系樹脂粒子、発泡性スチレン系樹脂粒子の製造方法が提供される。
[1] 難燃剤を含む発泡性スチレン系樹脂粒子において、前記難燃剤がハロゲン系難燃剤であり、該発泡性スチレン系樹脂粒子中に、下記一般式(3)式で表されるアミン系化合物が含浸されており、該発泡性スチレン系樹脂粒子中のスチレン単量体の含有量が50ppm未満(0ppmを含む。)であると共に、該発泡性スチレン系樹脂粒子を構成するスチレン系樹脂の重量平均分子量が20万超であり、該発泡性スチレン系樹脂粒子が炭素数5の飽和炭化水素を含む発泡剤を含有し、該発泡性スチレン系樹脂粒子に対する炭素数5の飽和炭化水素の含有量が1〜8重量%であり、下記(1)及び(2)の条件のうち少なくとも一方の条件を満足することを特徴とする発泡性スチレン系樹脂粒子。
(1)該発泡性スチレン系樹脂粒子を嵩密度25kg/m3に発泡させた場合に、発泡粒子の平均気泡径が20〜150μmとなると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が20μm以上となる。
(2)該発泡性スチレン系樹脂粒子を嵩密度50kg/m3に発泡させた場合に、発泡粒子の平均気泡径が15〜120μmとなると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が15μm以上となる。
NR1R2R3 (3)
(但し、一般式(3)において、Nは窒素原子、R1、R2、R3は炭素数1〜22のアルキル基又はシクロアルキル基である。)
[2] 前記難燃剤が臭素化ビスフェノール系化合物であることを特徴とする前記1に記載の発泡性スチレン系樹脂粒子。
[3] 前記臭素化ビスフェノール系化合物がアリルエーテル基を有することを特徴とする前記2に記載の発泡性スチレン系樹脂粒子。
[4] 電解質を含む水性媒体中に、スチレン単量体の含有量が50ppm未満(0ppmを含む。)であると共に重量平均分子量が20万超のスチレン系樹脂粒子を分散させ、該水性媒体中に難燃剤、炭素数5の飽和炭化水素を含む発泡剤、及び下記一般式(3)式で表されるアミン系化合物を添加して、該スチレン系樹脂粒子に発泡剤と共に難燃剤を含浸させる、発泡性スチレン系樹脂粒子の製造方法であって、前記難燃剤がハロゲン系難燃剤であり、前記電解質の濃度は水性媒体1Lに対して0.02〜5モルであり、前記炭素数5の飽和炭化水素の添加量がスチレン系樹脂樹脂粒子100重量部に対して1〜15重量部、前記難燃剤の添加量がスチレン系樹脂樹脂粒子100重量部に対して0.3〜5重量部、前記アミン系化合物の添加量がスチレン系樹脂樹脂粒子100重量部に対して0.001〜0.1重量部であることを特徴とする発泡性スチレン系樹脂粒子の製造方法。
NR1R2R3 (3)
(但し、一般式(3)において、Nは窒素原子、R1、R2、R3は炭素数1〜22のアルキル基又はシクロアルキル基である。)
According to this invention, the manufacturing method of the expandable styrene resin particle and the expandable styrene resin particle shown below is provided.
[1] In the expandable styrene resin particles containing a flame retardant, the flame retardant is a halogen flame retardant, and the amine compound represented by the following general formula (3) in the expandable styrene resin particles And the content of the styrene monomer in the expandable styrene resin particles is less than 50 ppm (including 0 ppm), and the weight of the styrene resin constituting the expandable styrene resin particles The average molecular weight is more than 200,000, and the expandable styrene resin particles contain a blowing agent containing a saturated hydrocarbon having 5 carbon atoms, and the content of saturated hydrocarbons having 5 carbon atoms with respect to the expandable styrene resin particles 1 to 8% by weight, and satisfying at least one of the following conditions (1) and (2): Expandable styrenic resin particles.
(1) When the expandable styrene-based resin particles are expanded to a bulk density of 25 kg / m 3 , the average cell diameter of the expanded particles is 20 to 150 μm, and the surface layer is within 50 μm in the radial direction from the surface of the expanded particle cross section. The average bubble diameter of the part is 20 μm or more.
(2) When the expandable styrene-based resin particles are expanded to a bulk density of 50 kg / m 3 , the average cell diameter of the expanded particles is 15 to 120 μm, and the surface layer is within 50 μm in the radial direction from the surface of the expanded particle cross section. The average bubble diameter of the part is 15 μm or more.
NR 1 R 2 R 3 (3)
(However, in the general formula (3), N is a nitrogen atom, R 1, R 2, R 3 is an alkyl group or a cycloalkyl group having from 1 to 22 carbon atoms.)
[2] The expandable styrenic resin particles as described in 1 above, wherein the flame retardant is a brominated bisphenol compound.
[3] The expandable styrenic resin particles as described in 2 above, wherein the brominated bisphenol compound has an allyl ether group.
[4] In an aqueous medium containing an electrolyte, styrene resin particles having a styrene monomer content of less than 50 ppm (including 0 ppm) and a weight average molecular weight of more than 200,000 are dispersed in the aqueous medium. A flame retardant, a blowing agent containing a saturated hydrocarbon having 5 carbon atoms, and an amine compound represented by the following general formula (3) are added to impregnate the styrene resin particles with the flame retardant together with the blowing agent. The method for producing expandable styrene resin particles, wherein the flame retardant is a halogen flame retardant, the concentration of the electrolyte is 0.02 to 5 mol with respect to 1 L of an aqueous medium, and the carbon number is 5 The amount of saturated hydrocarbon added is 1 to 15 parts by weight with respect to 100 parts by weight of styrene resin resin particles, and the amount of flame retardant added is 0.3 to 5 parts by weight with respect to 100 parts by weight of styrene resin resin particles. Addition of the amine compound An additive amount is 0.001-0.1 weight part with respect to 100 weight part of styrene resin resin particles, The manufacturing method of expandable styrene resin particles characterized by the above-mentioned.
NR 1 R 2 R 3 (3)
(However, in General formula (3), N is a nitrogen atom, R1, R2, and R3 are a C1-C22 alkyl group or a cycloalkyl group.)
本発明の発泡性スチレン系樹脂粒子は、難燃剤を有効量含みながらも、スチレン単量体の含有量が極めて少なく、かつ発泡性樹脂粒子を構成するスチレン系樹脂の重量平均分子量が高いものである。さらに、本発明の発泡性スチレン系樹脂粒子は、発泡させたときに特定の範囲の気泡径でかつ均一な気泡構造を有し、かつ表層部の気泡が適度な大きさの気泡径を有する発泡粒子となることにより、発泡性に優れるものである。さらにまた、本発明の発泡性樹脂粒子を発泡してなる発泡粒子は型内成形時に融着性に優れ、その発泡粒子成形体は、自己消火性を有するなどの難燃性に優れながらも、低VOCであり、かつ機械的強度や外観にも優れるものであり、建材や自動車部材として好適に使用できるものである。
本発明の発泡性スチレン系樹脂粒子の製造方法によれば、前記発泡性スチレン系樹脂粒子を安定して、効率よく製造することができる。
The expandable styrene resin particles of the present invention contain an effective amount of a flame retardant, have a very low content of styrene monomer, and have a high weight average molecular weight of the styrene resin constituting the expandable resin particles. is there. Furthermore, the expandable styrene resin particles of the present invention have a uniform cell structure with a specific range of cell diameters when foamed, and the cells in the surface layer have an appropriate cell size. By forming particles, it has excellent foamability. Furthermore, the foamed particles formed by foaming the foamable resin particles of the present invention are excellent in fusibility during in-mold molding, and the foamed particle molded body is excellent in flame retardancy such as having self-extinguishing properties, It has a low VOC, is excellent in mechanical strength and appearance, and can be suitably used as a building material or an automobile member.
According to the method for producing expandable styrene resin particles of the present invention, the expandable styrene resin particles can be stably and efficiently produced.
以下、本発明の発泡性スチレン系樹脂粒子、及び其の製造方法について詳細に説明する。
本発明の発泡性スチレン系樹脂粒子(発泡性樹脂粒子)を構成する樹脂は、スチレン単量体を主成分とするものである。スチレン単量体と共重合可能なモノマー成分としては、例えば、アクリル酸メチル,アクリル酸エチル,アクリル酸プロピル,アクリル酸ブチル,アクリル酸−2−エチルヘキシル等のアクリル酸の炭素数が1〜10のアルキルエステル等;メタクリル酸メチル,メタクリル酸エチル,メタクリル酸プロピル,メタクリル酸ブチル,メタクリル酸−2−エチルヘキシル等のメタクリル酸の炭素数が1〜10のアルキルエステル等;α−メチルスチレン,o−メチルスチレン,m−メチルスチレン,p−メチルスチレン,ビニルトルエン,p−エチルスチレン,2,4−ジメチルスチレン,p−メトキシスチレン,p−フェニルスチレン,o−クロロスチレン,m−クロロスチレン,p−クロロスチレン,2,4−ジクロロスチレン,p−n−ブチルスチレン,p−t−ブチルスチレン,p−n−ヘキシルスチレン,p−オクチルスチレン,スチレンスルホン酸,スチレンスルホン酸ナトリウム等;アクリロニトリル,メタクリロニトリル等のニトリル基含有不飽和化合物等が挙げられる。また、スチレン単量体誘導体のモノマーを単独で、または二種以上を組み合わせてスチレン単量体と共重合することができる。
尚、本明細書において、スチレン単量体を主成分とするとは、スチレン系樹脂粒子を重合する際のスチレン系モノマーの全重量に対して、スチレン単量体の重量が50重量%以上であることをいう。
Hereinafter, the expandable styrene resin particles of the present invention and the production method thereof will be described in detail.
The resin constituting the expandable styrene-based resin particles (expandable resin particles) of the present invention is mainly composed of a styrene monomer. Examples of the monomer component copolymerizable with the styrene monomer include acrylic acid having 1 to 10 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl esters and the like; alkyl esters having 1 to 10 carbon atoms of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; α-methylstyrene, o-methyl Styrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-ethylstyrene, 2,4-dimethylstyrene, p-methoxystyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chloro Styrene, 2,4-dichlorostyrene, pn- Methylstyrene, p-t-butylstyrene, p-n-hexyl styrene, p- octyl styrene, styrene sulfonic acid, sodium styrene sulfonate and the like; acrylonitrile, methacrylonitrile group-containing unsaturated compounds such as nitrites and the like. Moreover, the monomer of a styrene monomer derivative can be copolymerized with a styrene monomer individually or in combination of 2 or more types.
In this specification, the styrene monomer as the main component means that the weight of the styrene monomer is 50% by weight or more based on the total weight of the styrene monomer when polymerizing the styrene resin particles. That means.
本発明の発泡性樹脂粒子は、難燃性が発現するのに有効な量の難燃剤を含むものである。建材用途や自動車部材用途などの用途によって要求される難燃性のレベルが異なり、さらに難燃剤の種類や発泡剤の種類、量などによっても、難燃剤の有効量は変わるが、発泡粒子成形体が自動車部材用途に使用される場合には、難燃剤の含有量は、0.3重量%以上であることが好ましく、より好ましくは0.5重量%以上であり、建材用途に使用される場合には、0.7重量%以上であることが好ましい。該含有量の上限は難燃性の観点からは特に限定されるものではないが、得られる発泡粒子成形体の外観が悪化しやすいため、その上限は3重量%が好ましく、より好ましくは2重量%であり、更に好ましくは1.5重量%である。
The expandable resin particles of the present invention contain an amount of a flame retardant effective for exhibiting flame retardancy . The required flame retardant level varies depending on the application such as building materials and automotive parts, and the effective amount of the flame retardant varies depending on the type of flame retardant and the type and amount of the flame retardant. Is used for automobile parts, the content of the flame retardant is preferably 0.3% by weight or more, more preferably 0.5% by weight or more. Is preferably 0.7% by weight or more. The upper limit of the content is not particularly limited from the viewpoint of flame retardancy, but since the appearance of the obtained foamed particle molded body is likely to deteriorate, the upper limit is preferably 3% by weight, more preferably 2% by weight. %, More preferably 1.5% by weight.
本発明においては、少量で良好な難燃性を発揮する難燃剤として、ハロゲン系難燃剤が有効である。ハロゲン系難燃剤の例としては、1,2,3,4−テトラブロモブタン、1,2,4−トリブロモブタン、テトラブロモペンタン、テトラブロモビスフェノールA、2,2−ビス(4−アリルオキシ−3,5−ジブロモフェニル)プロパン、2,2−ビス(4−ヒドロキシエトキシ−3,5−ジブロモフェニル)プロパン、2,2−ビス(4−(2,3−ジブロモ)プロピルオキシ−3,5−ジブロモフェニル)プロパン、ペンタブロモジフェニルエーテル、ヘキサブロモジフェニルエーテル、オクタブロモジフェニルエーテル、デカブロモジフェニルエーテル、トリブロモフェノール、ジブロムエチルベンゼン、1,2,3,4,5,6−ヘキサブロモシクロヘキサン、1,2,5,6,9,10−ヘキサブロモシクロドデカン、オクタブロモシクロヘキサデカン、1−クロロ−2,3,4,5,6−ペンタブロモシクロヘキサン、トリス−(2,3−ジブロモプロピル)−ホスフェートのようなジブロムプロパノールのエステルもしくはアセタール、トリブロモフェノール、トリブロモスチレン、トリブロモフェノールアリルエーテルなどが挙げられる。これらの中では、発泡粒子への含浸性に優れ、難燃性にも優れることから、テトラブロモビスフェノールA、2,2−ビス(4−アリルオキシ−3,5−ジブロモフェニル)プロパン、2,2−ビス(4−ヒドロキシエトキシ−3,5−ジブロモフェニル)プロパン、2,2−ビス(4−(2,3−ジブロモ)プロピルオキシ−3,5−ジブロモフェニル)プロパンなどの臭素化ビスフェノールA系化合物が、好ましく、より好ましくは、2,2−ビス(4−アリルオキシ−3,5−ジブロモフェニル)プロパン等のアリルエーテル基を有する臭素化ビスフェノールA系化合物である。 In the present invention, a halogen-based flame retardant is effective as a flame retardant exhibiting good flame retardancy in a small amount. Examples of halogen flame retardants include 1,2,3,4-tetrabromobutane, 1,2,4-tribromobutane, tetrabromopentane, tetrabromobisphenol A, 2,2-bis (4-allyloxy- 3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4- (2,3-dibromo) propyloxy-3,5 -Dibromophenyl) propane, pentabromodiphenyl ether, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tribromophenol, dibromoethylbenzene, 1,2,3,4,5,6-hexabromocyclohexane, 1,2, 5,6,9,10-hexabromocyclododecane, octab Dibrompropanol esters or acetals such as mocyclohexadecane, 1-chloro-2,3,4,5,6-pentabromocyclohexane, tris- (2,3-dibromopropyl) -phosphate, tribromophenol, tri Examples thereof include bromostyrene and tribromophenol allyl ether. Among these, tetrabromobisphenol A, 2,2-bis (4-allyloxy-3,5-dibromophenyl) propane, 2,2 are excellent because they are excellent in impregnation into expanded particles and flame retardancy. -Brominated bisphenol A systems such as bis (4-hydroxyethoxy-3,5-dibromophenyl) propane and 2,2-bis (4- (2,3-dibromo) propyloxy-3,5-dibromophenyl) propane The compound is preferably a brominated bisphenol A compound having an allyl ether group such as 2,2-bis (4-allyloxy-3,5-dibromophenyl) propane.
また、難燃助剤として、例えば、スチレン単量体の重合時に実質的に分解しない、ジクミルパーオキサイドなどの過酸化物や、2,3−ジメチル−2,3−ジフェニルブタンなどの化合物を添加することができる。 Further, as a flame retardant aid, for example, a peroxide such as dicumyl peroxide that does not substantially decompose during polymerization of a styrene monomer, or a compound such as 2,3-dimethyl-2,3-diphenylbutane is used. Can be added.
前記難燃剤の含有量は、次のように測定される。
先ず、発泡性樹脂粒子約5gをクロロホルム300mLに溶解し、その後メタノール2000mLに入れて、析出ポリマーを除去する。その後、抽出液を濃縮、蒸発乾固して添加物を取り出す。次に、取り出した添加物を液クロマトグラフ(カラム:TOSO G2000HHR、溶媒:クロロホルム)により定性定量する。
The content of the flame retardant is measured as follows.
First, about 5 g of expandable resin particles are dissolved in 300 mL of chloroform, and then placed in 2000 mL of methanol to remove the precipitated polymer. Thereafter, the extract is concentrated and evaporated to dryness to remove the additive. Next, the taken-out additive is qualitatively quantified with a liquid chromatograph (column: TOSO G2000HHR, solvent: chloroform).
本発明の発泡性樹脂粒子においては、スチレン単量体の含有量が50ppm未満(0ppmを含む。)である。シックハウス問題を考慮するとスチレン単量体の含有量は少なければ少ないほど良い。かかる観点から、好ましくは40ppm以下(0ppmを含む。)であり、より好ましくは30ppm以下(0ppmを含む。)である。 In the expandable resin particles of the present invention, the content of the styrene monomer is less than 50 ppm (including 0 ppm). Considering the sick house problem, the smaller the styrene monomer content, the better. From this viewpoint, it is preferably 40 ppm or less (including 0 ppm), and more preferably 30 ppm or less (including 0 ppm).
前記発泡性樹脂粒子中の残存スチレン単量体の含有量は、発泡性樹脂粒子をジメチルホルムアミド(DMF)に溶解させガスクロマトグラフにより定量する。尚、後述する樹脂粒子の残存スチレン単量体の含有量についても同様に測定する。
ガスクロマトグラフによる定量は具体的には以下の手順にて行う。
1.100mLのメスフラスコにシクロペンタノール約5gを小数点以下第3位まで精秤し(このときの重量をWiとする)、DMFを加えて全体を100mLとする。このDMF溶液をさらにDMFで100倍に希釈し内部標準溶液とする。
2.測定対象となる発泡性樹脂粒子から、測定用試料約1gを小数点以下第3位まで精秤し、このときの重量をWS(g)とする。
3.精秤した試料を約18mLのDMFに溶解させ、前記1で作製した内部標準溶液をホールピペットにて正確に2mL加える。
4.この溶液をマイクロシリンジにて1μL採集し、ガスクロマトグラフに導入し、クロマトグラムを得る。得られたクロマトグラムより残存スチレン単量体及び内部標準のピーク面積を求め、以下の(2)式により残存スチレン単量体の含有量を求める。
The content of the residual styrene monomer in the expandable resin particles is determined by gas chromatograph by dissolving the expandable resin particles in dimethylformamide (DMF). In addition, it measures similarly about content of the residual styrene monomer of the resin particle mentioned later.
Specifically, quantification by a gas chromatograph is performed according to the following procedure.
1. In a 100 mL volumetric flask, weigh about 5 g of cyclopentanol to the third decimal place (weigh the weight at this time) and add DMF to make a total of 100 mL. This DMF solution is further diluted 100 times with DMF to make an internal standard solution.
2. From the expandable resin particles to be measured, about 1 g of the measurement sample is precisely weighed to the third decimal place, and the weight at this time is WS (g).
3. The accurately weighed sample is dissolved in about 18 mL of DMF, and 2 mL of the internal standard solution prepared in 1 above is accurately added with a whole pipette.
4). 1 μL of this solution is collected with a microsyringe and introduced into a gas chromatograph to obtain a chromatogram. The peak area of the residual styrene monomer and the internal standard is obtained from the obtained chromatogram, and the content of the residual styrene monomer is obtained from the following formula (2).
残存スチレン単量体含有量(重量%)=[(Wi/10000)×2]×[An/Ai]×Fn÷WS×100・・・(2)
(但し、Wi:内部標準溶液を作成したときのシクロペンタノール重量(g)、WS:DMFに溶解させた試料重量(g)、An:ガスクロマトグラフ測定時の各有機揮発性成分物質のピーク面積、Ai:ガスクロマトグラフ測定時の内部標準物質のピーク面積、Fn:あらかじめ作成した検量線より求めた各有機揮発性成分の補正係数。)
Residual styrene monomer content (% by weight) = [(Wi / 10000) × 2] × [An / Ai] × Fn ÷ WS × 100 (2)
(Wi: cyclopentanol weight (g) when the internal standard solution was prepared, WS: sample weight (g) dissolved in DMF, An: peak area of each organic volatile component substance at the time of gas chromatograph measurement) Ai: Peak area of internal standard substance at the time of gas chromatograph measurement, Fn: Correction coefficient of each organic volatile component obtained from a calibration curve prepared in advance.)
また、上記ガスクロマトグラフ分析の条件は以下の通りである。
使用機器:(株)島津製作所製のガスクロマトグラフGC−6AM
カラム材質:内径3mm、長さ5000mmのガラスカラム
カラム充填剤:〔液相名〕FFAP(遊離脂肪酸)、〔液相含浸率〕10重量%、〔担体名〕ガスクロマトグラフ用珪藻土ChromosorbW、〔担体粒度〕60/80メッシュ、〔担体処理方法〕AW−DMCS(水洗・焼成・酸処理・シラン処理)、〔充填量〕90mL
注入口温度:200℃
カラム温度:120℃
検出部温度:200℃
キャリヤーガス:N2、流量40m/min.
検出器:FID(水素炎イオン化検出器)
検出限界:20重量ppm
The conditions for the gas chromatographic analysis are as follows.
Equipment used: Gas chromatograph GC-6AM manufactured by Shimadzu Corporation
Column material: Glass column with an inner diameter of 3 mm and a length of 5000 mm Column filler: [Liquid phase name] FFAP (free fatty acid), [Liquid phase impregnation rate] 10 wt%, [Carrier name] Diatomaceous earth Chromosorb W for gas chromatography, [Carrier particle size] ] 60/80 mesh, [carrier treatment method] AW-DMCS (washing, baking, acid treatment, silane treatment), [filling amount] 90 mL
Inlet temperature: 200 ° C
Column temperature: 120 ° C
Detector temperature: 200 ° C
Carrier gas: N 2 , flow rate 40 m / min.
Detector: FID (hydrogen flame ionization detector)
Detection limit: 20 ppm by weight
本発明においては、発泡性樹脂粒子を構成するスチレン系樹脂の重量平均分子量は20万超であり、好ましくは21万以上、より好ましくは22万以上、更に好ましくは24万以上である。該重量平均分子量が20万超であれば、得られる発泡粒子成形体は、建材や自動車部材の用途に使用可能な機械的強度を有するものとなる。一方、機械的強度の観点からは該重量平均分子量の上限は特に限定されるものではないが、分子量が高すぎると発泡性樹脂粒子の発泡性や発泡粒子の融着性が低下するため、その上限は通常40万程度である。 In the present invention, the weight average molecular weight of the styrene resin constituting the expandable resin particles is more than 200,000, preferably 210,000 or more, more preferably 220,000 or more, and further preferably 240,000 or more. When the weight average molecular weight is more than 200,000, the obtained foamed particle molded article has mechanical strength that can be used for building materials and automotive parts. On the other hand, from the viewpoint of mechanical strength, the upper limit of the weight average molecular weight is not particularly limited, but if the molecular weight is too high, the foamability of the foamable resin particles and the fusibility of the foamed particles are reduced. The upper limit is usually about 400,000.
前記重量平均分子量は、発泡性樹脂粒子10mgをテトラヒドロフラン(THF)10mlに溶解させ、ゲルパーミエーションクロマトグラフィー(GPC)分析法により測定し、標準ポリスチレンで校正した値である。尚、後述する樹脂粒子の重量平均分子量についても同様に測定する。
上記GPC分析条件の詳細は以下の通りである。
使用機器:東ソー製SC−8020型
カラム:昭和電工社製ShodexAC−80M2本を直列に連結
カラム温度:40℃
流速:1.0ml/分
検出器:東ソー社製紫外可視光検出機UV−8020型
The weight average molecular weight is a value obtained by dissolving 10 mg of expandable resin particles in 10 ml of tetrahydrofuran (THF), measuring by gel permeation chromatography (GPC) analysis, and calibrating with standard polystyrene. In addition, it measures similarly about the weight average molecular weight of the resin particle mentioned later.
The details of the GPC analysis conditions are as follows.
Equipment used: Tosoh SC-8020 type column: Showa Denko Shodex AC-80M connected in series Column temperature: 40 ° C
Flow rate: 1.0 ml / min Detector: UV-visible light detector UV-8020 manufactured by Tosoh Corporation
本発明の発泡性樹脂粒子は、炭素数5の飽和炭化水素を少なくとも含む発泡剤を含有するものである。炭素数5の飽和炭化水素は、スチレン系樹脂に対する可塑化効果が高いため、残存スチレン単量体の低減に伴うスチレン系樹脂に対する可塑化効果の低下を補うことができる。従って、発泡性に優れる発泡性樹脂粒子となり、得られる発泡粒子も融着性に優れるものとなる。 The expandable resin particle of the present invention contains a foaming agent containing at least a saturated hydrocarbon having 5 carbon atoms. Since the saturated hydrocarbon having 5 carbon atoms has a high plasticizing effect on the styrene resin, it can compensate for the decrease in the plasticizing effect on the styrene resin accompanying the reduction of the residual styrene monomer. Therefore, it becomes foamable resin particles having excellent foamability, and the resulting foamed particles also have excellent fusion properties.
前記炭素数5の飽和炭化水素としては、ノルマルペンタン、イソペンタン、ネオペンタン、シクロペンタン等の飽和炭化水素が挙げられ、これらの1種類を単独で、又は2種以上を併用して使用できる。 Examples of the saturated hydrocarbon having 5 carbon atoms include saturated hydrocarbons such as normal pentane, isopentane, neopentane, and cyclopentane, and these can be used alone or in combination of two or more.
また、本発明の発泡性樹脂粒子は、他の発泡剤を含有することができる。他の発泡剤としては、プロパン、ノルマルブタン、イソブタン等の脂肪族炭化水素;塩化メチル,ジクロルフルオロメタン等のハロゲン化炭化水素;さらには二酸化炭素,窒素,アンモニア等の無機ガス等の物理発泡剤が挙げられる。上記炭素数5の飽和炭化水素と共に、これらの発泡剤は1種類を単独で、又は2種以上を併用して使用できる。 Moreover, the expandable resin particle of this invention can contain another foaming agent. Other foaming agents include aliphatic hydrocarbons such as propane, normal butane and isobutane; halogenated hydrocarbons such as methyl chloride and dichlorofluoromethane; and physical foaming such as inorganic gases such as carbon dioxide, nitrogen and ammonia. Agents. Along with the saturated hydrocarbon having 5 carbon atoms, these blowing agents can be used alone or in combination of two or more.
前記炭素数5の飽和炭化水素の含有量は1〜8重量%である。炭素数5の飽和炭化水素の含有量が少なすぎると、スチレン系樹脂に対する可塑化効果が発現しなくなり、十分な融着性が達成できないばかりか、高発泡倍率の発泡粒子を得ることができない虞がある。更に、発泡性粒子の製造時に難燃剤が樹脂中に十分に含浸されていない虞があるため、目的の難燃性を達成できない虞がある。一方、含有量が多すぎると、全体に均一な気泡構造が得られにくく、成形性を低下させてしまう粗大な気泡が混じる可能性が高くなる。かかる観点から、該含有量は1.2〜7重量%が好ましく、1.4〜6重量%がより好ましい。
更に、発泡剤の合計含有量は、所望の発泡倍率と難燃性とのバランスを考慮して適宜決定するものであるが、通常は3〜10重量%が好ましく、3.5〜8重量%がより好ましく、4〜7重量%が更に好ましい。
The content of the saturated hydrocarbon having 5 carbon atoms is 1 to 8% by weight. If the content of the saturated hydrocarbon having 5 carbon atoms is too small, the plasticizing effect on the styrenic resin will not be exhibited, and sufficient fusing property cannot be achieved, and expanded particles with a high expansion ratio may not be obtained. There is. Furthermore, since the flame retardant may not be sufficiently impregnated in the resin during the production of the expandable particles, the target flame retardancy may not be achieved. On the other hand, if the content is too large, it is difficult to obtain a uniform cell structure on the whole, and there is a high possibility that coarse cells that deteriorate moldability are mixed. From this viewpoint, the content is preferably 1.2 to 7% by weight, and more preferably 1.4 to 6% by weight.
Furthermore, the total content of the foaming agent is appropriately determined in consideration of the desired balance between foaming ratio and flame retardancy, but usually 3 to 10% by weight is preferable, and 3.5 to 8% by weight. Is more preferable, and 4 to 7 weight% is still more preferable.
前記炭素数5の飽和炭化水素及び全発泡剤の発泡性樹脂粒子中における含有量は、ガスクロマトグラフにて各発泡剤成分の含有量を測定することにより求めることができる。尚、後述する発泡粒子における、炭素数5の飽和炭化水素及び全発泡剤の含有量についても同様に含有量を測定することができる。
ガスクロマトグラフ分析の条件は以下の通りである。
使用機器:(株)島津製作所製のガスクロマトグラフGC−8A
カラム材質:内径3mm、長さ4000mmのガラスカラム
カラム充填剤:〔液相名〕DOP−B、〔液相含浸率〕30重量%、〔担体名〕ガスクロマトグラフ用珪藻土ChromosorbP、〔担体粒度〕60/80メッシュ、担体処理方法〕AW(酸処理)
注入口温度:100℃
カラム温度:50℃
検出部温度:100℃
キャリヤーガス:N2、流量50m/min.
検出器:FID(水素炎イオン化検出器)
定量:内部標準法
The content of the saturated hydrocarbon having 5 carbon atoms and the total foaming agent in the foamable resin particles can be determined by measuring the content of each foaming agent component with a gas chromatograph. The content of the saturated hydrocarbon having 5 carbon atoms and the total foaming agent in the foamed particles to be described later can also be measured in the same manner.
The conditions for gas chromatographic analysis are as follows.
Equipment used: Gas Chromatograph GC-8A manufactured by Shimadzu Corporation
Column material: Glass column with an inner diameter of 3 mm and a length of 4000 mm Column filler: [Liquid phase name] DOP-B, [Liquid phase impregnation rate] 30 wt%, [Carrier name] Diatomaceous earth Chromosorb P for gas chromatograph, [Carrier particle size] 60 / 80 mesh, carrier treatment method] AW (acid treatment)
Inlet temperature: 100 ° C
Column temperature: 50 ° C
Detector temperature: 100 ° C
Carrier gas: N 2 , flow rate 50 m / min.
Detector: FID (hydrogen flame ionization detector)
Quantification: Internal standard method
なお、本発明の発泡性樹脂粒子は、気泡形成剤として、メタクリル酸メチル系共重合体,ポリエチレンワックス,タルク,エチレンビスステアリルアミド,メチレンビスステアリルアミド,エチレン−酢酸ビニル共重合体樹脂等を含有することができる。 The foamable resin particles of the present invention contain a methyl methacrylate copolymer, polyethylene wax, talc, ethylene bisstearyl amide, methylene bisstearyl amide, ethylene-vinyl acetate copolymer resin, and the like as a bubble forming agent. can do.
さらに、本発明の発泡性樹脂粒子には、帯電防止剤,導電化剤,セル核剤,粒度分布調整剤等の一般的に発泡性スチレン系樹脂粒子の製造に使用されている添加剤が適宜添加されていてもよく、ブタジエンゴム,スチレン・ブタジエンゴム等のゴム成分が混合されていてもよい。
また、本発明の発泡性樹脂粒子には、硬化牛脂、ヤシ油、大豆硬化油、グリセリンステアレートなどのトリグリセリド類、グリセリンジアセトモノラウレートなどのアセチル化モノグリセライド類、流動パラフィン、αオレフィンなどを可塑剤として含有させることができ、これらの可塑剤は、樹脂粒子中に予め混合しておくか、或いは難燃剤と共に樹脂粒子中に含浸させればよい。
また、ソルベントカラーなどの着色剤を樹脂粒子中に予め樹脂に混合させたり、或いは難燃剤と共に樹脂粒子中に含浸させることもできる。
Further, the expandable resin particles of the present invention may be appropriately added with additives generally used in the production of expandable styrene resin particles such as an antistatic agent, a conductive agent, a cell nucleating agent, and a particle size distribution adjusting agent. It may be added, and rubber components such as butadiene rubber and styrene / butadiene rubber may be mixed.
The foamable resin particles of the present invention are plasticized with hard beef tallow, coconut oil, soybean hardened oil, triglycerides such as glyceryl stearate, acetylated monoglycerides such as glycerin diacetomonolaurate, liquid paraffin, α-olefin and the like. These plasticizers may be mixed in advance in the resin particles or impregnated in the resin particles together with the flame retardant.
Further, a colorant such as a solvent color can be mixed with the resin in advance in the resin particles, or impregnated in the resin particles together with the flame retardant.
本発明の発泡性樹脂粒子は、該発泡性樹脂粒子を発泡させたときに、発泡粒子の気泡構造が下記(1)及び(2)の条件のうち少なくとも一方の条件を満足し、発泡粒子全体に均一な気泡構造を有すると共に、表層部分の気泡が細かすぎることがないスチレン系樹脂発泡粒子(以下、単に発泡粒子ともいう。)となるものである。
(1)嵩密度25kg/m3に発泡させた場合に、発泡粒子全体の平均気泡径が20〜150μmであると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が20μm以上の発泡粒子となる発泡性樹脂粒子。
(2)嵩密度50kg/m3に発泡させた場合に、発泡粒子全体の平均気泡径が15〜120μmであると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が15μm以上の発泡粒子となる発泡性樹脂粒子。
In the expandable resin particles of the present invention, when the expandable resin particles are expanded, the cell structure of the expanded particles satisfies at least one of the following conditions (1) and (2): The styrene-based resin expanded particles (hereinafter also simply referred to as expanded particles) that have a uniform cell structure and in which the air bubbles in the surface layer portion are not too fine.
(1) When foamed to a bulk density of 25 kg / m 3 , the average cell diameter of the entire expanded particle is 20 to 150 μm, and the average cell diameter of the surface layer portion within 50 μm in the radial direction from the surface of the expanded particle cross section is 20 μm. Expandable resin particles that become the above expanded particles.
(2) When foamed to a bulk density of 50 kg / m 3 , the average cell diameter of the entire expanded particle is 15 to 120 μm, and the average cell diameter of the surface layer portion within 50 μm in the radial direction from the surface of the expanded particle cross section is 15 μm. Expandable resin particles that become the above expanded particles.
本発明の発泡性樹脂粒子は、発泡性樹脂粒子中の残存スチレン単量体の含有量が極めて少ないこと、及び難燃剤の後含浸により、難燃剤が発泡性樹脂粒子表面付近へ偏在しているものである。本発明は、これにより発生する課題、即ち型内成形時に発泡粒子、特にその表層部分が伸びにくくなるという課題を、発泡性樹脂粒子中に特定の発泡剤を含有させると共に、発泡させたときに特定の気泡構造となるようにすることにより解決したものである。 In the expandable resin particles of the present invention, the flame retardant is unevenly distributed near the surface of the expandable resin particles due to the extremely low content of the residual styrene monomer in the expandable resin particles and the post-impregnation of the flame retardant. Is. In the present invention, when the foaming resin particles contain a specific foaming agent and foamed, the foamed particles, particularly the problem that the surface layer portion thereof is difficult to stretch during molding in mold, This is solved by having a specific bubble structure.
本発明において、発泡粒子の気泡構造を上記(1)及び(2)の条件で判定するのは、建材や自動車部材用途において要求される発泡粒子成形体の密度は、主に25kg/m3前後や50kg/m3前後のものが使用されることが多いからである。
従って、上記(1)の条件を満足すれば、見掛け密度が25kg/m3前後の発泡粒子成形体を製造する際に、所期の効果が達成される。さらに、嵩密度25kg/m3まで発泡可能な発泡性粒子は、あまり発泡させずに、嵩密度50kg/m3程度に発泡して使用されることがある。そこで、上記(1)の条件を満足し、かつ上記(2)の条件も満足する発泡性樹脂粒子であれば、約25〜約50kg/m3の広い密度範囲において所期の効果が達成される。
In the present invention, the cell structure of the expanded particles is determined under the above conditions (1) and (2) because the density of the expanded molded body required for building materials and automotive parts is mainly around 25 kg / m 3. This is because those of around 50 kg / m 3 are often used.
Therefore, if the condition (1) is satisfied, the desired effect can be achieved when producing a foamed particle molded body having an apparent density of about 25 kg / m 3 . Furthermore, the expandable particles that can be expanded to a bulk density of 25 kg / m 3 may be used after being expanded to a bulk density of about 50 kg / m 3 without causing much foaming. Therefore, if the expandable resin particles satisfy the condition (1) and satisfy the condition (2), the desired effect can be achieved in a wide density range of about 25 to about 50 kg / m 3. The
また、嵩密度50kg/m3程度までの発泡性しか必要とされない発泡性樹脂粒子は、低嵩密度まで発泡する発泡能力は要求されないので、発泡剤含有量を低減することによりその発泡性が調整される場合がある。このような場合には、嵩密度25kg/m3までは発泡できないが、50kg/m3に発泡させたときに上記(2)の条件を満足すれば、50kg/m3前後の密度の発泡粒子成形体を製造する際に、所期の効果を達成できる。 In addition, foamable resin particles that only require foamability up to a bulk density of about 50 kg / m 3 do not require foaming ability to foam to a low bulk density, so the foamability is adjusted by reducing the foaming agent content. May be. In such a case, until a bulk density 25 kg / m 3 is not able to foam, to satisfy the above condition (2) when foamed in 50kg / m 3, 50kg / m 3 foam particles before and after the density The desired effect can be achieved when the molded body is manufactured.
前記発泡粒子全体の平均気泡径が前記範囲未満になると、成形後の発泡粒子成形体の収縮が大きくなり、一方、該平均気泡径が前記範囲よりも大きくなると、得られる発泡粒子成形体の機械的強度が低下するため所期の発泡粒子成形体が得られなくなる。
かかる観点から、嵩密度25kg/m3に発泡させた場合には、該平均気泡径が30〜120μmとなることが好ましく、より好ましくは40〜100μmである。嵩密度50kg/m3に発泡させた場合には、25〜100μmとなることが好ましく、より好ましくは30〜80μmである。
When the average cell diameter of the entire foamed particles is less than the above range, shrinkage of the foamed particle molded body after molding becomes large. On the other hand, when the average cell diameter is larger than the above range, the resulting foamed particle molded body machine The desired strength of the foamed particle molded body cannot be obtained because the mechanical strength is lowered.
From this viewpoint, when foamed to a bulk density of 25 kg / m 3 , the average cell diameter is preferably 30 to 120 μm, more preferably 40 to 100 μm. When foamed to a bulk density of 50 kg / m 3 , it is preferably 25 to 100 μm, more preferably 30 to 80 μm.
また、前記発泡粒子全体の平均気泡径が前記範囲内であっても、前記表層部の平均気泡径が前記範囲未満であると、気泡が細かすぎて気泡膜が薄くなることから、型内成形時の伸びが悪くなって粒子間隙が目立つ外観が悪い発泡粒子成形体となってしまう上に、得られる発泡粒子成形体の機械的強度、特に曲げ強さが低下してしまう。かかる観点から、嵩密度25kg/m3に発泡させた場合には、表層部の平均気泡径は30μm以上が好ましく、40μm以上となることがより好ましく、その上限は、150μmが好ましく、より好ましくは100μmである。嵩密度50kg/m3に発泡させた場合には、表層部の平均気泡径は25μm以上が好ましく、30μm以上となることがより好ましく、その上限は、120μmが好ましく、より好ましくは80μmである。 Further, even if the average bubble diameter of the entire expanded particles is within the above range, if the average bubble diameter of the surface layer portion is less than the above range, the bubbles are too fine and the bubble film becomes thin. In addition to the poor elongation at the time and the appearance with conspicuous particle gaps, the foamed particle molded body has a poor appearance, and the mechanical strength, particularly the bending strength, of the obtained foamed particle molded body is lowered. From this viewpoint, when foamed to a bulk density of 25 kg / m 3 , the average cell diameter of the surface layer is preferably 30 μm or more, more preferably 40 μm or more, and the upper limit is preferably 150 μm, more preferably 100 μm. When foamed to a bulk density of 50 kg / m 3 , the average cell diameter of the surface layer is preferably 25 μm or more, more preferably 30 μm or more, and the upper limit is preferably 120 μm, more preferably 80 μm.
発泡時に上記気泡構造を有する発泡粒子となる発泡性樹脂粒子は、電解質を特定濃度で含む水性媒体中で、難燃剤と共に下記特定の発泡剤と下記特定のアミン化合物とを樹脂粒子に含浸させることにより製造することができる。特定の発泡剤により難燃剤を樹脂粒子中に均一に含浸させることで表面付近への偏在を防ぎ、電解質により樹脂粒子中への水性媒体の含浸を防ぎかつアミン化合物が樹脂粒子中に存在することにより、発泡時に表層部の気泡の微細化を防止することができる。 The foamable resin particles that become foamed particles having the above-mentioned cell structure when foamed are obtained by impregnating resin particles with the following specific foaming agent and the following specific amine compound together with a flame retardant in an aqueous medium containing an electrolyte at a specific concentration. Can be manufactured. Uniform impregnation of the flame retardant into the resin particles with a specific foaming agent prevents uneven distribution near the surface, prevents impregnation of the aqueous medium into the resin particles with the electrolyte, and the amine compound is present in the resin particles Thus, it is possible to prevent the bubbles in the surface layer from being refined during foaming.
嵩密度25kg/m3の発泡粒子は、例えば、攪拌羽根を備えた容積30Lの円筒状の小型発泡機に、発泡性樹脂粒子750gを投入し、攪拌しながらスチームを導入して加熱を行い、発泡粒子の体積が30Lレベルに到達したところで加熱をやめてエアーを導入し流動性が得られるまで乾燥を行い発泡機から取り出すことにより、得ることができる。また、嵩密度50kg/m3の発泡粒子は、前記小型発泡機への発泡性樹脂粒子の投入量を1500gに変更して発泡させることによって得ることができる。 The foamed particles with a bulk density of 25 kg / m 3 are, for example, charged with 750 g of expandable resin particles in a cylindrical small-sized foaming machine having a volume of 30 L equipped with stirring blades, and heated by introducing steam while stirring. When the volume of the foamed particles reaches the 30 L level, heating is stopped, air is introduced, drying is performed until fluidity is obtained, and the foamed particles are taken out from the foaming machine. Further, expanded particles having a bulk density of 50 kg / m 3 can be obtained by changing the amount of expandable resin particles introduced into the small-sized foaming machine to 1500 g and expanding the expanded resin particles.
なお、嵩密度を正確に25kg/m3に合わせることができない場合には、発泡条件を変えて異なる嵩密度を有する発泡粒子を得て、それぞれの平均気泡径を求め、平均気泡径と嵩密度との関係をグラフ上にプロットし、それらの相関をもとにして25kg/m3における値を求めればよい。嵩密度50kg/m3に発泡させる場合も同様である。 When the bulk density cannot be accurately adjusted to 25 kg / m 3 , foaming particles having different bulk densities are obtained by changing the foaming conditions, and the average bubble diameters are obtained. Is plotted on a graph, and a value at 25 kg / m 3 may be obtained based on the correlation between them. The same applies when foaming to a bulk density of 50 kg / m 3 .
前記発泡粒子の嵩密度(kg/m3)は次のようにして測定される。水を入れたメスシリンダーを用意し、該メスシリンダーに相対湿度50%、23℃、1atmの条件にて2日放置した500個以上の発泡粒子(発泡粒子群の重量W1)を入れ、発泡粒子を水没させてその水位上昇分から発泡粒子群の体積V1(cm3)を求める。この体積V1(cm3)にてメスシリンダーに入れた発泡粒子群の重量W1(g)を割り算して(kg/m3)に単位換算して(W1/V1×1000)、発泡粒子の見掛け密度(kg/m3)を求める。この見掛け密度(kg/m3)を1.6で除することにより発泡粒子の嵩密度(kg/m3)を求める。 The bulk density (kg / m 3 ) of the expanded particles is measured as follows. Prepare a graduated cylinder containing water, and put in the graduated cylinder 500 or more expanded particles (weight W1 of the expanded particle group) left for 2 days under conditions of relative humidity 50%, 23 ° C., 1 atm. Is submerged and the volume V1 (cm 3 ) of the expanded particle group is determined from the rise in the water level. By dividing the weight W1 (g) of the expanded particle group placed in the graduated cylinder by this volume V1 (cm 3 ), the unit is converted to (kg / m 3 ) (W1 / V1 × 1000), and the expanded particle appearance The density (kg / m 3 ) is determined. The apparent density (kg / m 3 ) is divided by 1.6 to obtain the bulk density (kg / m 3 ) of the expanded particles.
発泡粒子の平均気泡径は、次のように測定される。
発泡粒子の中心部を通るように発泡粒子を2分割し、走査型電子顕微鏡にて切断面の拡大写真を撮影する。次に、写真上に発泡粒子の表面から中心付近を通り反対側の表面まで達する直線を引き、直線と交わっている気泡数を数え、直線の長さ(実際の長さ)を気泡数で除して、気泡1個当たりの気泡径を求め、これを個々の発泡粒子の気泡径(μm)とする。この操作を発泡粒子10個について同様に行ない、得られる測定値の平均値を本発明における発泡粒子の平均気泡径(μm)とする。
The average cell diameter of the expanded particles is measured as follows.
The expanded particle is divided into two so as to pass through the center of the expanded particle, and an enlarged photograph of the cut surface is taken with a scanning electron microscope. Next, draw a straight line from the surface of the foam particle to the surface on the opposite side on the photo, count the number of bubbles intersecting the straight line, and divide the length of the straight line (actual length) by the number of bubbles. Then, the bubble diameter per bubble is obtained, and this is set as the bubble diameter (μm) of each expanded particle. This operation is similarly performed for 10 expanded particles, and the average value of the measured values obtained is defined as the average cell diameter (μm) of the expanded particles in the present invention.
発泡粒子表層部の平均気泡径は、次のように測定される。
発泡粒子の中心部を通るように発泡粒子を2分割し、走査型電子顕微鏡にて切断面を写真撮影する。写真上に発泡粒子の表面から断面の中心まで任意に4本の直線を引く。4本の直線の夫々と交わっている気泡のうち、発泡粒子表面から中心方向へ50μmまでの範囲に位置する気泡の数をカウントし(ただし、表面から50μmまでの範囲に気泡の一部が含まれればその気泡もカウントする。また、気泡の大きさによってはカウントされる気泡数が1個の場合もあり得る。)、粒子の表面から、カウントされた気泡のうち最も粒子の中心側に位置する気泡の粒子の表面とは反対側の気泡膜までの直線の長さ(実際の長さ)をその気泡数で除して、発泡粒子表層部の気泡1個当たりの気泡径(μm)を求める。同様にして他の直線についても気泡径を求め、これらの気泡径の平均を個々の発泡粒子の表層部の平均気泡径(μm)とする。この操作を発泡粒子10個について同様に行い、得られる測定値の平均値を本発明における発泡粒子表層部の平均気泡径(μm)とする。
The average cell diameter of the surface layer portion of the expanded particle is measured as follows.
The foam particles are divided into two so as to pass through the center of the foam particles, and the cut surface is photographed with a scanning electron microscope. Four arbitrary straight lines are drawn on the photograph from the surface of the expanded particle to the center of the cross section. Of the bubbles intersecting with each of the four straight lines, count the number of bubbles located in the range of 50 μm from the surface of the expanded particle to the center (however, some of the bubbles are included in the range of 50 μm from the surface) (The number of bubbles counted may be one depending on the size of the bubble.) From the surface of the particle, it is located closest to the center of the particle among the counted bubbles. Divide the length (actual length) of the straight line up to the bubble film on the opposite side of the surface of the bubble particle to be divided by the number of bubbles to obtain the bubble diameter (μm) per bubble in the surface layer of the expanded particle Ask. Similarly, the bubble diameter is obtained for other straight lines, and the average of these bubble diameters is defined as the average bubble diameter (μm) of the surface layer portion of each expanded particle. This operation is similarly performed for 10 expanded particles, and the average value of the measured values obtained is defined as the average cell diameter (μm) of the surface layer portion of the expanded particles in the present invention.
次に、本発明のスチレン系発泡性樹脂粒子の製造方法について説明する。
本発明のスチレン系発泡性樹脂粒子の製造方法においては、先ずスチレン単量体の含有量が50ppm未満(0ppmを含む。)、好ましくは40ppm以下(0ppmを含む。)、より好ましくは30ppm以下(0ppmを含む。)であると共に、重量平均分子量が20万超、好ましくは21万以上、より好ましくは22万以上、更に好ましくは24万以上のスチレン系樹脂粒子(樹脂粒子)を準備する。
該樹脂粒子は、従来公知の方法、例えば、重合温度を高くする方法や、重合開始剤を多くする方法、重合時間を長くする方法、更には、複数の重合開始剤重合温度を段階的に上げる方法などを応用して製造することができる。また、上記のような樹脂粒子中の残存スチレン単量体の含有量が低く、かつスチレン系樹脂の重量平均分子量が高い樹脂粒子を効率よく製造できることから、発泡剤が存在しない条件下でスチレン系樹脂粒子を重合することが好ましい。
なお、重合開始剤が過度に残存している場合には、難燃剤の含浸時に残存単量体の重合が更に進み残存スチレン単量体の含有量が低くなったり、難燃剤と開始剤とが反応して分子量が低くなったりすることがある。樹脂粒子中に重合開始剤を過度に残存させないことにより、目的とする発泡性樹脂粒子中の残存スチレン単量体の含有量、スチレン系樹脂の重量平均分子量を、使用する樹脂粒子中の残存スチレン単量体の含有量、重量平均分子量とほぼ変わらぬ値にすることができる。
さらに、該樹脂粒子は、発泡剤を含まないものであっても、或いは難燃剤含浸時に必要な炭素数5の飽和炭化水素添加量以外の量の発泡剤を含むものであってもよいが、所期の発泡性樹脂粒子を効率よく製造できることから、発泡剤を含まない樹脂粒子を使用することが好ましい。
Next, the manufacturing method of the styrene-type expandable resin particle of this invention is demonstrated.
In the method for producing styrene-based expandable resin particles of the present invention, the content of styrene monomer is first less than 50 ppm (including 0 ppm), preferably 40 ppm or less (including 0 ppm), more preferably 30 ppm or less ( And styrene resin particles (resin particles) having a weight average molecular weight of more than 200,000, preferably 210,000 or more, more preferably 220,000 or more, and further preferably 240,000 or more.
The resin particles may be produced by a conventionally known method, for example, a method for increasing the polymerization temperature, a method for increasing the polymerization initiator, a method for increasing the polymerization time, or a stepwise increase in the polymerization temperature of a plurality of polymerization initiators. It can be manufactured by applying a method or the like. Further, since the resin particles having a low content of the residual styrene monomer in the resin particles as described above and a high weight average molecular weight of the styrene resin can be efficiently produced, the styrenic resin is used under the condition that no blowing agent is present. It is preferable to polymerize the resin particles.
If the polymerization initiator remains excessively, the polymerization of the residual monomer further proceeds when impregnated with the flame retardant, and the content of the residual styrene monomer decreases, or the flame retardant and the initiator It may react to lower the molecular weight. By not excessively leaving the polymerization initiator in the resin particles, the content of the residual styrene monomer in the target expandable resin particles, the weight average molecular weight of the styrene resin, the residual styrene in the resin particles to be used The monomer content and the weight average molecular weight can be made substantially unchanged.
Furthermore, the resin particles may contain no foaming agent, or may contain an amount of foaming agent other than the amount of saturated hydrocarbon addition of 5 carbon atoms required at the time of impregnation with the flame retardant, Since desired foamable resin particles can be efficiently produced, it is preferable to use resin particles that do not contain a foaming agent.
次に、水性媒体中に、前記特定の樹脂粒子を分散させ、該水性媒体中に前記難燃剤、炭素数5の飽和炭化水素を含む少なくとも含む前記発泡剤、及び下記一般式(3)式で表されるアミン系化合物を添加して、該樹脂粒子に発泡剤と共に難燃剤を含浸させる。
NR1R2R3 (3)
(但し、一般式(3)において、Nは窒素原子、R1、R2、R3は炭素数1〜22のアルキル基又はシクロアルキル基である。)
Next, the specific resin particles are dispersed in an aqueous medium, and the foaming agent containing at least the flame retardant, a saturated hydrocarbon having 5 carbon atoms in the aqueous medium, and the following general formula (3): The amine compound represented is added, and the resin particles are impregnated with a flame retardant together with a foaming agent.
NR 1 R 2 R 3 (3)
(However, in the general formula (3), N is a nitrogen atom, R 1, R 2, R 3 is an alkyl group or a cycloalkyl group having from 1 to 22 carbon atoms.)
本発明方法で用いる水性媒体としては、水又は水と水溶性溶媒(例えば、アルコールなど)との混合媒体が挙げられる。中でも入手し易いことや経済性の観点から水が好ましい。 Examples of the aqueous medium used in the method of the present invention include water or a mixed medium of water and a water-soluble solvent (for example, alcohol). Among these, water is preferable from the viewpoint of easy availability and economical efficiency.
樹脂粒子の平均粒子径は、難燃剤等を含浸させやすく、優れた外観を有する発泡粒子成形体が得られることから、0.3〜3mmが好ましく、0.4〜2mmがより好ましく、0.6〜1.2mmが更に好ましい。 The average particle diameter of the resin particles is preferably from 0.3 to 3 mm, more preferably from 0.4 to 2 mm, since it is easy to impregnate a flame retardant and the like and a foamed particle molded body having an excellent appearance is obtained. More preferably, it is 6 to 1.2 mm.
水性媒体への樹脂粒子の配合量は、難燃剤等を含浸させやすいことから、水性媒体100重量部に対して、60〜110重量部が好ましく、80〜100重量部がより好ましい。該配合量が少なすぎると生産性が低下してしまい、多すぎると樹脂粒子同士が溶融、融着して凝槐物になる等の問題が生じやすい。 The blending amount of the resin particles in the aqueous medium is preferably 60 to 110 parts by weight and more preferably 80 to 100 parts by weight with respect to 100 parts by weight of the aqueous medium because the flame retardant is easily impregnated. If the blending amount is too small, the productivity is lowered. If the blending amount is too large, the resin particles are likely to be fused and fused to form a coagulated product.
前記難燃剤の配合量は、前記難燃剤含有量の発泡性樹脂粒子を得るために、樹脂粒子100重量部に対して、0.3〜5重量部が好ましく、0.5〜3重量部がより好ましい。該配合量が少なすぎると、難燃性を有する発泡粒子成形体を得ることが難しくなり、多すぎると難燃剤の含浸性が損なわれて凝槐物になりやすく、得られる成形体の外観も悪化してしまう。 The amount of the flame retardant blended is preferably 0.3 to 5 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of the resin particles in order to obtain expandable resin particles having the flame retardant content. More preferred. When the blending amount is too small, it becomes difficult to obtain a foamed particle molded body having flame retardancy. When the blending amount is too large, the impregnation property of the flame retardant is impaired and a coagulated product is easily obtained. It will get worse.
前記炭素数5の飽和炭化水素の配合量は、樹脂粒子100重量部に対して、1〜15重量部である。該配合量が少なすぎると、難燃剤を樹脂粒子中に十分に含浸させにくくなり、さらに、上記の理由から高発泡倍率の発泡粒子が得られにくくなる。一方、配合量が多すぎると、得られる発泡粒子の成形性が低下する。かかる観点から、前記炭素数5の飽和炭化水素の配合量は、1.5〜8重量部がより好ましい。 The amount of the saturated hydrocarbon having 5 carbon atoms is 1 to 15 parts by weight with respect to 100 parts by weight of the resin particles. When the blending amount is too small, it becomes difficult to sufficiently impregnate the resin particles with the flame retardant, and further, it becomes difficult to obtain expanded particles having a high expansion ratio for the above-described reason. On the other hand, when there are too many compounding quantities, the moldability of the foamed particle obtained will fall. From this viewpoint, the blending amount of the saturated hydrocarbon having 5 carbon atoms is more preferably 1.5 to 8 parts by weight.
前記アミン系化合物の配合量は、樹脂粒子100重量部に対して、0.001〜0.1重量部である。該配合量がこの範囲を外れると、発泡粒子表層部の気泡の微細化を防止することができなくなり、発泡させた場合に上記気泡構造を有する発泡粒子となる発泡性樹脂粒子を得ることが難しくなる。かかる観点から、アミン系化合物の添加量は、樹脂粒子100重量部に対して、0.002〜0.05重量部がより好ましい。 The compounding amount of the amine compound is 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the resin particles. When the blending amount is out of this range, it becomes impossible to prevent the foaming of the foamed particle surface layer from becoming finer, and it is difficult to obtain foamable resin particles that become foamed particles having the above-mentioned cell structure when foamed. Become. From this viewpoint, the amount of the amine compound added is more preferably 0.002 to 0.05 parts by weight with respect to 100 parts by weight of the resin particles.
難燃剤の含浸温度は、80〜140℃が好ましく、より好ましくは100〜120℃である。含浸温度が低すぎると生産性が低下し、高すぎると難燃剤が分解しやすいため、発泡性樹脂粒子を構成するスチレン系樹脂の重量平均分子量が低下する虞がある。
含浸時間は、4〜36時間が好ましく、より好ましくは6〜24時間である。含浸時間短すぎると各成分の含浸が不十分になり、長すぎると生産性が低下する虞がある。
The impregnation temperature of the flame retardant is preferably 80 to 140 ° C, more preferably 100 to 120 ° C. If the impregnation temperature is too low, the productivity is lowered, and if it is too high, the flame retardant is easily decomposed, so that the weight average molecular weight of the styrene resin constituting the expandable resin particles may be lowered.
The impregnation time is preferably 4 to 36 hours, more preferably 6 to 24 hours. If the impregnation time is too short, the impregnation of each component becomes insufficient, and if it is too long, the productivity may decrease.
また、難燃剤等を樹脂粒子中に含浸させるために、水性媒体に懸濁剤を添加することが好ましい。懸濁剤としては、例えばポリビニルアルコール,メチルセルロース,ポリビニルピロリドン等の水溶性高分子、ピロリン酸マグネシウム,第3燐酸カルシウム等の難溶性無機塩等を用いることができ、これらと界面活性剤を併用してもよい。なお、難溶性無機塩を用いる場合には、アルキルスルホン酸ソーダ,ドデシルベンゼンスルホン酸ソーダ等のアニオン性界面活性剤を併用するのが好ましい。 In order to impregnate the resin particles with a flame retardant or the like, it is preferable to add a suspending agent to the aqueous medium. As the suspending agent, for example, a water-soluble polymer such as polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone, a sparingly soluble inorganic salt such as magnesium pyrophosphate and tricalcium phosphate, and the like can be used. May be. In the case of using a hardly soluble inorganic salt, it is preferable to use an anionic surfactant such as sodium alkyl sulfonate or sodium dodecylbenzene sulfonate together.
懸濁剤の添加量は、樹脂粒子100重量部に対し0.01〜5.0重量部が好ましい。前記した難溶性無機塩とアニオン性界面活性剤との併用系では、それぞれ樹脂粒子100重量部に対して難溶性無機塩を0.05〜3.0重量部、アニオン性界面活性剤を0.0001〜0.5重量部添加することが好ましい。 The addition amount of the suspending agent is preferably 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the resin particles. In the combined system of the above-described hardly soluble inorganic salt and anionic surfactant, 0.05 to 3.0 parts by weight of the hardly soluble inorganic salt and 0.1% of the anionic surfactant are added to 100 parts by weight of the resin particles, respectively. It is preferable to add 0001 to 0.5 parts by weight.
必要に応じて、過硫酸カリウムなどを懸濁助剤として用いても良い。また、イオン強度や水素イオン濃度を調整するために炭酸ナトリウム、炭酸水素ナトリウム、リン酸カルシウムや水酸化ナトリウム、水酸化カルシウムなどを懸濁助剤として用いてもよい。 If necessary, potassium persulfate or the like may be used as a suspension aid. Also, sodium carbonate, sodium hydrogen carbonate, calcium phosphate, sodium hydroxide, calcium hydroxide or the like may be used as a suspension aid in order to adjust the ionic strength or hydrogen ion concentration.
本発明方法においては、前記水性媒体に電解質を添加する。水性媒体に電解質を添加して水性媒体のイオン濃度を調整することにより樹脂粒子中への水の含浸を防ぐことができる。電解質の添加量は、水性媒体1Lに対して0.02〜5モルであり、好ましくは0.03〜0.5モルである。 In the method of the present invention, an electrolyte is added to the aqueous medium. By adding an electrolyte to the aqueous medium and adjusting the ion concentration of the aqueous medium, impregnation of water into the resin particles can be prevented. The addition amount of the electrolyte is 0.02 to 5 mol, preferably 0.03 to 0.5 mol, with respect to 1 L of the aqueous medium.
前記電解質は、水溶液中でイオン解離する物質であればよく、例えば、塩化リチウム、塩化ナトリウム、塩化マグネシウム、塩化カリウム、塩化カルシウム、塩化アンモニウム、硫酸ナトリウム、硫酸マグネシウム、硫酸カリウム、硫酸アルミニウム、硫酸アンモニウム、硝酸ナトリウム、硝酸マグネシウム、硝酸カリウム、硝酸カルシウム、炭酸ナトリウム、炭酸マグネシウム、炭酸カリウム、炭酸カルシウム、炭酸アンモニウム等の無機塩類、或は酢酸カリウム、酢酸ナトリウム、ベヘミン酸ナトリウム、安息香酸ナトリウム、琥珀酸二ナトリウム等の水に可溶なカルボン酸のアルカリ金属塩等が挙げられる。特に塩化ナトリウムは、少量の添加重量で本発明の発泡性樹脂粒子を容易に得ることができ、また工業的に安価に大量に入手できるので好ましい。 The electrolyte may be any substance that ionically dissociates in an aqueous solution. For example, lithium chloride, sodium chloride, magnesium chloride, potassium chloride, calcium chloride, ammonium chloride, sodium sulfate, magnesium sulfate, potassium sulfate, aluminum sulfate, ammonium sulfate, Inorganic salts such as sodium nitrate, magnesium nitrate, potassium nitrate, calcium nitrate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, or potassium acetate, sodium acetate, sodium behemate, sodium benzoate, disodium oxalate Examples thereof include alkali metal salts of carboxylic acids that are soluble in water. In particular, sodium chloride is preferred because the expandable resin particles of the present invention can be easily obtained with a small amount of addition, and can be obtained in large quantities at low cost industrially.
以下に、実施例及び比較例をあげて本発明をさらに詳述する。但し、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
(実施例1)
(スチレン系樹脂粒子の製造)
内容積50Lの攪拌機付き密閉容器に純水17000gを入れ、懸濁剤として第三リン酸カルシウム(太平化学産業株式会社製)を60g、界面活性剤としてαオレフィンスルフォン酸ソーダ(ライオン株式会社社製 商品名:リポランLB−440=固形分37%水溶液)を2.3g、懸濁助剤として過硫酸カリウムを0.17g添加して水性懸濁液を作製した後に、過酸化ベンゾイル(25%水分含有品)40g、t−ブチルパーオキシ−2−エチルヘキシルモノカーボネート20g、スチレン単量体15000gを攪拌しながら仕込んだ。攪拌回転数を230rpmにして90℃まで加温後、100℃まで5時間かけて昇温し、その後120℃で6時間重合を行った。得られたスチレン系樹脂粒子懸濁液から遠心分離器で脱水し乾燥させた後に篩によって0.5mm〜1.4mmの範囲以外を取り除き、スチレン系樹脂粒子Aを得た。
Example 1
(Manufacture of styrene resin particles)
17000 g of pure water is put into a sealed container with a stirrer having an internal volume of 50 L, 60 g of tribasic calcium phosphate (made by Taihei Chemical Sangyo Co., Ltd.) is used as a suspending agent, and α-olefin sulfonic acid soda (manufactured by Lion Corporation) is used as a surfactant. : Lipolane LB-440 = Solid content 37% aqueous solution) 2.3 g, 0.17 g of potassium persulfate as a suspension aid was added to prepare an aqueous suspension, and then benzoyl peroxide (product containing 25% water) ) 40 g, 20 g of t-butylperoxy-2-ethylhexyl monocarbonate and 15000 g of styrene monomer were charged with stirring. The mixture was heated to 90 ° C. with a stirring speed of 230 rpm, then heated to 100 ° C. over 5 hours, and then polymerized at 120 ° C. for 6 hours. The obtained styrene-based resin particle suspension was dehydrated with a centrifuge and dried, and then a portion other than the range of 0.5 mm to 1.4 mm was removed by a sieve to obtain styrene-based resin particles A.
(難燃剤含有発泡性スチレン系樹脂粒子の製造)
内容積3Lの攪拌機付き密閉容器に純水1000gを入れ、懸濁剤として第三リン酸カルシウム(太平化学産業株式会社製)を9g、界面活性剤としてαオレフィンスルフォン酸ソーダ(ライオン株式会社製 商品名:リポランLB−440=固形分37%水溶液)を0.27g、難燃剤として2,2,−ビス[4−アリルオキシ−3,5−ジブロモフェニル]プロパン(帝人化成株式会社製 商品名:ファイヤーガード3200)を9.9g、電解質として塩化ナトリウムを8.77g(0.15mol/L相当)、アミン系化合物としてトリオクチルアミンを0.045g添加し、さらに上記で製造したスチレン系樹脂粒子Aを900g投入した。攪拌回転数を400rpmにして100℃まで昇温し、ポンプにて発泡剤として混合ペンタン32.4gと混合ブタン48.6gを30分かけて添加した。100℃到達から3時間後、120℃に昇温し6時間保持したのち、4時間かけて30℃まで冷却した。その後、遠心分離器にて脱水、流動乾燥装置にて表面水分を除去し、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Production of flame retardant-containing expandable styrene resin particles)
1000 g of pure water is put into a sealed container with a stirrer with an internal volume of 3 L, 9 g of tribasic calcium phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.) as a suspending agent, and α-olefin sulfonic acid soda (manufactured by Lion Corporation) as a surfactant. Lipolane LB-440 = Solid content 37% aqueous solution) 0.27 g, 2,2, -bis [4-allyloxy-3,5-dibromophenyl] propane (made by Teijin Chemicals Ltd., trade name: Fireguard 3200) as a flame retardant 9.9 g), sodium chloride 8.77 g (equivalent to 0.15 mol / L) as an electrolyte, trioctylamine 0.045 g as an amine compound, and 900 g of the styrene resin particles A produced above were added. did. The stirring rotation speed was set to 400 rpm, the temperature was raised to 100 ° C., and 32.4 g of mixed pentane and 48.6 g of mixed butane were added as a blowing agent over 30 minutes with a pump. Three hours after reaching 100 ° C., the temperature was raised to 120 ° C. and held for 6 hours, and then cooled to 30 ° C. over 4 hours. Thereafter, dehydration was performed with a centrifugal separator, and surface moisture was removed with a fluid drying device, to obtain flame retardant-containing expandable styrene resin particles.
(実施例2)
実施例1で用いたアミン類をジラウリルモノメチルアミン0.18gとし、発泡剤の添加量を混合ペンタン28.8gと混合ブタン43.2gにしたこと以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Example 2)
The amines used in Example 1 and dilauryl monomethylamine 0.18 g, except for the amount of mixed pentane 28.8g mixed butane 43.2g of blowing agent in the same manner as in Example 1, a flame retardant Contained expandable styrene resin particles were obtained.
(実施例3)
実施例1で用いた電解質を硝酸ナトリウム17gとし、難燃剤を2,2−ビス[4’(2’’,3’’−ジブロモアルコキシ)−3’,5’−ジブロモフェニル]−プロパン(第一工業製薬株式会社製 商品名:SR−130)11.7gとし、アミン系化合物をトリオクチルアミン0.018gとし、発泡剤の添加量を混合ペンタン48.6gと混合ブタン32.4gにしたこと以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Example 3)
The electrolyte used in Example 1 was 17 g of sodium nitrate, and the flame retardant was 2,2-bis [4 ′ (2 ″, 3 ″ -dibromoalkoxy) -3 ′, 5′-dibromophenyl] -propane (No. Ichi Kogyo Seiyaku Co., Ltd. product name: SR-130) 11.7 g, amine compound 0.018 g trioctylamine, foaming agent addition amount 48.6 g mixed pentane and 32.4 g mixed butane otherwise in the same manner as in example 1 to obtain a flame retardant-containing expandable styrene resin particles.
(実施例4)
(スチレン系樹脂粒子の製造)
内容積50Lの攪拌機付き密閉容器に純水17000gを入れ、懸濁剤として第三リン酸カルシウム(太平化学産業株式会社製)を60g、界面活性剤としてαオレフィンスルフォン酸ソーダ(ライオン株式会社製 商品名:リポランLB−440=固形分37%水溶液)を2.3g、懸濁助剤として過硫酸カリウムを0.17g添加して水性懸濁液を作製した後に、過酸化ベンゾイル(25%水分含有品)40g、t−ブチルパーオキシ−2−エチルヘキシルモノカーボネート20g、流動パラフィン(セーボルト粘度60SUS)120g、スチレン単量体15000gを攪拌しながら仕込んだ。攪拌回転数を230rpmにして90℃まで加温後、100℃まで5時間かけて昇温し、その後120℃で6時間重合を行った。得られたスチレン系樹脂粒子懸濁液から遠心分離器で脱水し乾燥させた後に篩によって0.5mm〜1.4mmの範囲以外を取り除き、スチレン系樹脂粒子Bを得た。
Example 4
(Manufacture of styrene resin particles)
17000 g of pure water is put into an airtight container with an internal volume of 50 L, 60 g of tribasic calcium phosphate (manufactured by Taihei Chemical Sangyo Co., Ltd.) as a suspending agent, and α-olefin sulfonic acid soda (manufactured by Lion Corporation) as a surfactant. Lipolane LB-440 = Solid content 37% aqueous solution) 2.3 g, 0.17 g of potassium persulfate as a suspension aid was added to prepare an aqueous suspension, and then benzoyl peroxide (product containing 25% water) 40 g, 20 g of t-butylperoxy-2-ethylhexyl monocarbonate, 120 g of liquid paraffin (Saebold viscosity 60 SUS), and 15000 g of styrene monomer were charged with stirring. The mixture was heated to 90 ° C. with a stirring speed of 230 rpm, then heated to 100 ° C. over 5 hours, and then polymerized at 120 ° C. for 6 hours. The obtained styrene-based resin particle suspension was dehydrated with a centrifuge and dried, and then a portion other than the range of 0.5 mm to 1.4 mm was removed with a sieve to obtain styrene-based resin particles B.
(難燃剤含有発泡性スチレン系樹脂粒子の製造)
製造した樹脂粒子Bを内容積3Lの攪拌機付き密閉容器に仕込み、攪拌回転数を400rpmにして100℃まで昇温し、ポンプにて発泡剤として混合ペンタン21.6gと混合ブタン50.4gを30分かけて添加したこと以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Production of flame retardant-containing expandable styrene resin particles)
The produced resin particles B are charged into a closed container with a stirrer having an internal volume of 3 L, heated to 100 ° C. with a stirring speed of 400 rpm, and 21.6 g of mixed pentane and 50.4 g of mixed butane are used as a blowing agent by a pump. except that the added amount over in the same manner as in example 1 to obtain a flame retardant-containing expandable styrene resin particles.
(実施例5)
(難燃剤含有発泡性スチレン系樹脂粒子の製造)
難燃剤2,2,−ビス[4−アリルオキシ−3,5−ジブロモフェニル]プロパン(帝人化成株式会社製 商品名:ファイヤーガード3200)の添加量を12.6gとし、発泡剤の添加量を混合ペンタン16.2g、混合ブタン37.8gにしたこと以外は実施例4と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Example 5)
(Production of flame retardant-containing expandable styrene resin particles)
The addition amount of the flame retardant 2,2, -bis [4-allyloxy-3,5-dibromophenyl] propane (trade name: Fireguard 3200, manufactured by Teijin Chemicals Ltd.) is 12.6 g, and the addition amount of the foaming agent is mixed. pentane 16.2 g, except for the mixed butanes 37.8g in the same manner as in example 4 to obtain a flame retardant-containing expandable styrene resin particles.
(比較例1)
アミン系化合物を添加しなかったこと以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Comparative Example 1)
Flame retardant-containing expandable styrene resin particles were obtained in the same manner as in Example 1 except that no amine compound was added.
(比較例2)
電解質を添加しなかったこと以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Comparative Example 2)
Flame retardant-containing expandable styrene resin particles were obtained in the same manner as in Example 1 except that no electrolyte was added.
(比較例3)
実施例1において用いた発泡剤(混合ペンタン32.4gと混合ブタン48.6g)を、混合ペンタン81gのみに代えた以外は実施例1と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Comparative Example 3)
In the same manner as in Example 1 except that the foaming agent used in Example 1 (32.4 g of mixed pentane and 48.6 g of mixed butane) was replaced by 81 g of mixed pentane, the flame retardant-containing expandable styrene resin particles were obtained. Obtained.
(比較例4)
(重合一段での難燃剤含有発泡性スチレン系樹脂粒子の製造)
内容積50Lの攪拌機付き密閉容器に純水17000gを入れ、懸濁剤として第三リン酸カルシウム(太平化学産業株式会社製)を60g、界面活性剤としてαオレフィンスルフォン酸ソーダ(ライオン株式会社社製 商品名:リポランLB−440=固形分37%水溶液)を2.3g添加して水性懸濁液を作製した後に、過酸化ベンゾイル(25%水分含有品)34g、t−ブチルパーオキシ−2−エチルヘキシルモノカーボネート25g、スチレン単量体15000g、難燃剤として2,2−ビス[4’(2’’,3’’−ジブロモアルコキシ)−3’,5’−ジブロモフェニル]−プロパン(第一工業製薬株式会社製 商品名:SR−130)を165gを攪拌しながら仕込んだ。攪拌回転数を230rpmにして90℃まで加温後、100℃まで8時間かけて昇温する段階において、90℃から6時間経過した時点でポンプにて混合ペンタン375gと混合ブタン1125gを60分かけて添加した。添加終了から1時間後100℃に到達したら最終の重合温度である115℃まで昇温し8時間保持したのち、4時間かけて30℃まで冷却した。その後、遠心分離器にて脱水、流動乾燥装置にて表面水分を除去し、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Comparative Example 4)
(Production of flame retardant-containing expandable styrene resin particles in one stage of polymerization)
17000 g of pure water is put into a sealed container with a stirrer having an internal volume of 50 L, 60 g of tribasic calcium phosphate (made by Taihei Chemical Sangyo Co., Ltd.) is used as a suspending agent, and α-olefin sulfonic acid soda (manufactured by Lion Corporation) is used as a surfactant. : Lipolane LB-440 = Solid content 37% aqueous solution) 2.3 g was added to prepare an aqueous suspension, and then benzoyl peroxide (25% water-containing product) 34 g, t-butylperoxy-2-ethylhexyl mono 25 g of carbonate, 15000 g of styrene monomer, 2,2-bis [4 ′ (2 ″, 3 ″ -dibromoalkoxy) -3 ′, 5′-dibromophenyl] -propane as a flame retardant (Daiichi Kogyo Seiyaku Co., Ltd.) 165 g of company-made product name: SR-130) was charged with stirring. At the stage of heating to 90 ° C. with a stirring speed of 230 rpm and then raising the temperature to 100 ° C. over 8 hours, when 6 hours have passed from 90 ° C., 375 g of mixed pentane and 1125 g of mixed butane are applied over 60 minutes. Added. One hour after the end of the addition, when the temperature reached 100 ° C., the temperature was raised to 115 ° C. which was the final polymerization temperature, maintained for 8 hours, and then cooled to 30 ° C. over 4 hours. Thereafter, dehydration was performed with a centrifugal separator, and surface moisture was removed with a fluid drying device, to obtain flame retardant-containing expandable styrene resin particles.
(比較例5)
(重合一段での残存スチレン単量体の低減)
t−ブチルパーオキシ−2−エチルヘキシルモノカーボネートの量を50gとし、最終の重合温度を120℃とした以外は比較例4と同様にして、難燃剤含有発泡性スチレン系樹脂粒子を得た。
(Comparative Example 5)
(Reduction of residual styrene monomer in one stage of polymerization)
Flame retardant-containing expandable styrene resin particles were obtained in the same manner as in Comparative Example 4 except that the amount of t-butylperoxy-2-ethylhexyl monocarbonate was 50 g and the final polymerization temperature was 120 ° C.
(見掛け密度25kg/m3の発泡粒子成形体の製造)
攪拌羽根を備えた内容積30Lの発泡機に、発泡性樹脂粒子750gを投入し、攪拌しながらスチームを導入して加熱を行った。発泡粒子の体積が30Lレベルに到達したところで加熱をやめてエアーを導入し流動性が得られるまで乾燥を行い発泡機から取り出し、嵩密度25kg/m3の予備発泡粒子を得た。
300mm×200mm×25mmの金型を備えた発泡ポリスチレン用成形機(ダイセン社製VS−300)を使用し、金型内に予備発泡粒子を充填し、予備発泡粒子を0.07MPa(ゲージ圧)のスチームで20秒加熱して型内成形し、冷却後離型して、外形寸法300mm×200mm×25mm、見掛け密度25kg/m3の発泡粒子成形体を得た。
(Production of foamed particle molded body having an apparent density of 25 kg / m 3 )
750 g of expandable resin particles were introduced into a 30 L internal foaming machine equipped with stirring blades, and steam was introduced and heated while stirring. When the volume of the foamed particles reached the 30 L level, heating was stopped, air was introduced and drying was performed until fluidity was obtained, and the foamed particles were taken out from the foaming machine to obtain pre-foamed particles having a bulk density of 25 kg / m 3 .
Using an expanded polystyrene molding machine (Daisen VS-300) equipped with a 300 mm × 200 mm × 25 mm mold, the mold was filled with pre-expanded particles, and the pre-expanded particles were 0.07 MPa (gauge pressure). After heating for 20 seconds with this steam, molding was performed after cooling, and mold release was performed to obtain a foamed particle molded body having outer dimensions of 300 mm × 200 mm × 25 mm and an apparent density of 25 kg / m 3 .
なお、比較例3の予備発泡粒子は以下のようにして製造した。内部を加圧可能な攪拌羽根を備えた内容積50Lの発泡機を用い、発泡機に発泡性樹脂粒子を750g投入し、攪拌しながらスチームを導入し内部圧力を0.01MPa(ゲージ圧)に設定して加熱を行った。発泡粒子の体積が30Lレベルに到達したところで加熱をやめてエアーを導入し乾燥を行い発泡機から取り出し、嵩密度25kg/m3の予備発泡粒子を得た。 In addition, the pre-expanded particles of Comparative Example 3 were produced as follows. Using a 50 L internal volume foaming machine equipped with a stirring blade capable of pressurizing the inside, 750 g of foamable resin particles were introduced into the foaming machine, and steam was introduced while stirring to bring the internal pressure to 0.01 MPa (gauge pressure). Set and heated. When the volume of the foamed particles reached the 30 L level, heating was stopped, air was introduced, drying was performed, and the foamed particles were taken out from the foaming machine to obtain pre-foamed particles having a bulk density of 25 kg / m 3 .
(見掛け密度50kg/m3の発泡粒子成形体の製造)
攪拌羽根を備えた容積30Lの円筒状の小型発泡機に、発泡性樹脂粒子1500gを投入し、攪拌しながらスチームを導入して加熱を行った。発泡粒子の体積が30Lレベルに到達したところで加熱をやめてエアーを導入し流動性が得られるまで乾燥を行い発泡機から取り出し、嵩密度50kg/m3の予備発泡粒子を得た。
300mm×200mm×25mmの金型を備えた発泡ポリスチレン用成形機(ダイセン社製VS−300)を使用し、金型内に予備発泡粒子を充填し、予備発泡粒子を0.07MPa(ゲージ圧)のスチームで20秒加熱して型内成形し、冷却後離型して、外形寸法300mm×200mm×25mm、見掛け密度50kg/m3の発泡粒子成形体を得た。
(Production of foamed particle molded body having an apparent density of 50 kg / m 3 )
1500 g of expandable resin particles were put into a cylindrical small-sized foaming machine having a volume of 30 L equipped with stirring blades, and steam was introduced and heated while stirring. When the volume of the expanded particles reached the 30 L level, heating was stopped, air was introduced and drying was performed until fluidity was obtained, and the foamed particles were taken out of the expansion machine to obtain pre-expanded particles having a bulk density of 50 kg / m 3 .
Using an expanded polystyrene molding machine (Daisen VS-300) equipped with a 300 mm × 200 mm × 25 mm mold, the mold was filled with pre-expanded particles, and the pre-expanded particles were 0.07 MPa (gauge pressure). After heating for 20 seconds with this steam, the molded product was molded in the mold, and after mold release, the molded product was molded into a foamed particle having an outer dimension of 300 mm × 200 mm × 25 mm and an apparent density of 50 kg / m 3 .
実施例1〜5、比較例1〜3における発泡性樹脂粒子の製造時の配合を表1に示す。また、得られた発泡性樹脂粒子の組成、発泡性樹脂粒子を発泡させたときの気泡構造、発泡粒子成形体の物性を表2に示す。
また、実施例1、比較例1、比較例2で得られた発泡粒子の断面顕微鏡写真を図1〜4に示す。
Table 1 shows the blending of the expandable resin particles in Examples 1 to 5 and Comparative Examples 1 to 3. In addition, Table 2 shows the composition of the obtained expandable resin particles, the cell structure when the expandable resin particles are expanded, and the physical properties of the expanded particle molded body.
Moreover, the cross-sectional microscope picture of the expanded particle obtained in Example 1, the comparative example 1, and the comparative example 2 is shown to FIGS.
表1における、樹脂粒子の残存スチレン系単量体の含有量、重量平均分子量は、前記方法で測定した。 In Table 1, the content of the residual styrene monomer and the weight average molecular weight of the resin particles were measured by the above methods.
表2における各項目の測定、評価は次のように行った。
発泡性樹脂粒子の残存スチレン系単量体含有量、重量平均分子量、難燃剤の含有量は、前記方法で測定した。
Measurement and evaluation of each item in Table 2 were performed as follows.
Residual styrene monomer content, weight average molecular weight, and flame retardant content of the expandable resin particles were measured by the above methods.
発泡性樹脂粒子中の発泡剤(炭素数5の飽和炭化水素)の含有量
100mlのメスフラスコにエタノール約3gを小数点以下第3位まで精秤し、DMFを加えて全体を100mlとして内部標準溶液を調整した。容器内の約18mLのDMFに、小数点以下第3位まで精秤した約1gの測定用試料(発泡性樹脂粒子)を加え、さらに、作製した内部標準溶液をホールピペットにて正確に2mL加え、容器を密栓して試料を良く溶解させた。この溶液をマイクロシリンジにて1μL採集し、ガスクロマトグラフに導入し、前記測定条件に従ってクロマトグラムを得て、発泡性樹脂粒子中の発泡剤(炭素数5の飽和炭化水素)の含有量を測定した。
Content of foaming agent (saturated hydrocarbon having 5 carbon atoms) in the foamable resin particles About 3 g of ethanol is precisely weighed to the third decimal place in a 100 ml volumetric flask, and DMF is added to make the whole 100 ml. Adjusted. About 1 g of measurement sample (expandable resin particles) precisely weighed to the third decimal place is added to about 18 mL of DMF in the container, and 2 mL of the prepared internal standard solution is accurately added with a whole pipette, The container was sealed to dissolve the sample well. 1 μL of this solution was collected with a microsyringe, introduced into a gas chromatograph, a chromatogram was obtained according to the measurement conditions, and the content of the foaming agent (saturated hydrocarbon having 5 carbon atoms) in the foamable resin particles was measured. .
発泡性は次のように評価した。
底に金網が張ってある金属製の箱に約30gの発泡性樹脂粒子を入れ、次いで該箱を箱型バッチ式予備発泡機に入れ、吹込圧力0.08MPaのスチームを導入し270秒間加熱した。得られた発泡粒子を室温で1日風乾した後、1Lのメスシリンダーに発泡粒子を入れ、発泡粒子の体積1L当たりの重量を測定し、嵩密度(kg/m3)を測定した。
The foamability was evaluated as follows.
About 30 g of expandable resin particles are placed in a metal box with a wire mesh on the bottom, and then the box is placed in a box-type batch pre-foaming machine, steam with a blowing pressure of 0.08 MPa is introduced and heated for 270 seconds. . The obtained foamed particles were air-dried at room temperature for 1 day, and then the foamed particles were put into a 1 L graduated cylinder, the weight per volume of the foamed particles was measured, and the bulk density (kg / m 3 ) was measured.
嵩密度25kg/m3に発泡した場合及び嵩密度50kg/m3に発泡した場合の発泡粒子の平均気泡径、表層部の平均気泡径は、前記測定方法により測定した。なお、実施例5の発泡性粒子は前記方法により嵩密度25kg/m3まで発泡させることができなかったので、嵩密度50kg/m3に発泡した場合のみを評価した。
また、気泡の均一性の評価方法は、成形して得られた発泡粒子成形体をスライサーで約1mmに薄くカットし、断面の表層部を除く部分の気泡の状態を次の基準により目視で評価した。
○・・・均一
△・・・一部、粗い気泡や微細気泡がみられる
×・・・不均一
When foamed to a bulk density of 25 kg / m 3 and when foamed to a bulk density of 50 kg / m 3 , the average cell diameter of the foamed particles and the average cell diameter of the surface layer were measured by the measurement method. In addition, since the expandable particle of Example 5 was not able to be foamed to a bulk density of 25 kg / m 3 by the above method, only the case where the foam density was expanded to a bulk density of 50 kg / m 3 was evaluated.
In addition, the method for evaluating the uniformity of the bubbles is that the foamed particle molded body obtained by molding is thinly cut to about 1 mm with a slicer, and the state of bubbles in the portion excluding the surface layer portion of the cross section is visually evaluated according to the following criteria. did.
○ ・ ・ ・ Uniform △ ・ ・ ・ Partial, coarse and fine bubbles are observed × ・ ・ ・ Non-uniform
融着性
発泡成形体を割り、観察される破断面の面積のうち、粒子内部で破断している面積の割合(百分率)を目視にて判定した。
Fusing property The foamed molded product was divided, and the ratio (percentage) of the area fractured inside the particles out of the observed fractured surface area was visually determined.
外観
発泡粒子成形体の表面外観を目視にて下記基準にて評価した。
○・・・溶融した粒子はなく、見栄えがよい。
×・・・溶融した粒子がみられ、成形体面よりも陥没しており、見栄えが悪い。
Appearance The surface appearance of the foamed particle compact was visually evaluated according to the following criteria.
○ ... There are no molten particles and it looks good.
X: Molten particles are seen, and are depressed more than the surface of the molded body, and the appearance is poor.
難燃性評価
JIS A9511(2006R)の5.13.1の燃焼試験(測定方法A)に準拠して燃焼試験を行い、下記基準により発泡粒子成形体の難燃性を評価した。なお、この燃焼試験は建築物に使用されるプラスチック保温材に適用される難燃性の規格である。
○・・・平均消火時間が3秒以内で残塵がなく燃焼限界指示線を越えて燃焼が継続しなかった。
×・・・3秒を超えて燃焼が継続した場合あるいは燃焼限界指示線を越えて燃焼した。
また、FMVSS302に記載の燃焼性試験により燃焼速度を測定し、下記基準により発泡粒子成形体の自己消火性を評価した。なお、FMVSS302とは車両用の材料に対して実施される米国の試験規格のひとつで燃焼性能(燃焼速度)を試験する規格であり、得られた数値が小さいほど燃え難い性質を有している。
◎・・・着火せず、または炎がA標線に達する前に消火した。
○・・・A標線を越えてB標線に達した際の燃焼速度が100mm/分以下であった。
×・・・A標線を越えてB標線に達した際の燃焼速度が100mm/分を越えた。
Flame Retardancy Evaluation A flame test was performed in accordance with 5.13.1 combustion test (Measurement Method A) of JIS A9511 (2006R), and the flame retardancy of the foamed particle molded body was evaluated according to the following criteria. This combustion test is a flame retardance standard applied to plastic heat insulating materials used in buildings.
○ ... The average fire extinguishing time was within 3 seconds, there was no residual dust, and combustion did not continue beyond the combustion limit indicator line.
X: When combustion continued for more than 3 seconds, or burned beyond the combustion limit indicating line.
Moreover, the burning rate was measured by the flammability test described in FMVSS302, and the self-extinguishing property of the foamed particle molded body was evaluated according to the following criteria. Note that FMVSS 302 is one of US test standards for vehicle materials, and is a standard for testing combustion performance (combustion speed). The smaller the obtained numerical value, the more difficult it is to burn. .
◎ ・ ・ ・ Do not ignite or extinguish before flame reaches A mark.
B: The combustion speed when reaching the B mark beyond the A mark was 100 mm / min or less.
X: The burning speed when the mark B reached the mark B and exceeded the mark B exceeded 100 mm / min.
機械的物性
圧縮試験
発泡粒子成形体を切断して、50mm×50mm×25mmの試験片を5個作成し、JIS K 7220(1999)に準拠して、試験速度10mm/minの条件にて圧縮試験を行い、各試験片の変形10%時の圧縮応力(MPa)を算出し、5個の平均値を求めた。表中には「10%圧縮応力」と表記する。
Mechanical property compression test Five expanded specimens of 50 mm x 50 mm x 25 mm were cut from the foamed particle compact, and compression test was performed at a test speed of 10 mm / min in accordance with JIS K 7220 (1999). The compressive stress (MPa) at the time of 10% deformation of each test piece was calculated, and the average value of 5 pieces was obtained. In the table, it is expressed as “10% compressive stress”.
曲げ試験
発泡粒子成形体を切断して、縦300mm×横75mm×厚さ25mmの試験片(全面スキン付き)を5個作成し、JIS K 7221−2(1999)および附属書1に準拠して、試験速度10mm/minの条件にて3点曲げ試験を行い、各試験片の最大荷重を測定し曲げ強さ(MPa)を算出し、5個の平均値を求めた。
Bending test The foamed particle molded body was cut to prepare five test pieces (with full skin) of length 300 mm x width 75 mm x thickness 25 mm, in accordance with JIS K 7221-2 (1999) and Annex 1. Then, a three-point bending test was performed at a test speed of 10 mm / min, the maximum load of each test piece was measured, the bending strength (MPa) was calculated, and the average value of five pieces was obtained.
Claims (4)
前記難燃剤がハロゲン系難燃剤であり、
該発泡性スチレン系樹脂粒子中に、下記一般式(3)式で表されるアミン系化合物が含浸されており、
該発泡性スチレン系樹脂粒子中のスチレン単量体の含有量が50ppm未満(0ppmを含む。)であると共に、該発泡性スチレン系樹脂粒子を構成するスチレン系樹脂の重量平均分子量が20万超であり、
該発泡性スチレン系樹脂粒子は炭素数5の飽和炭化水素を含む発泡剤を含有し、該発泡性スチレン系樹脂粒子に対する炭素数5の飽和炭化水素の含有量が1〜8重量%であり、
下記(1)及び(2)の条件のうち少なくとも一方の条件を満足することを特徴とする発泡性スチレン系樹脂粒子。
(1)該発泡性スチレン系樹脂粒子を嵩密度25kg/m3に発泡させた場合に、発泡粒子の平均気泡径が20〜150μmとなると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が20μm以上となる。
(2)該発泡性スチレン系樹脂粒子を嵩密度50kg/m3に発泡させた場合に、発泡粒子の平均気泡径が15〜120μmとなると共に、発泡粒子断面における表面から半径方向50μm以内の表層部の平均気泡径が15μm以上となる。
NR 1 R 2 R 3 (3)
(但し、一般式(3)において、Nは窒素原子、R 1 、R 2 、R 3 は炭素数1〜22のアルキル基又はシクロアルキル基である。) In expandable styrene resin particles containing a flame retardant,
The flame retardant is a halogen flame retardant,
The foamable styrene resin particles are impregnated with an amine compound represented by the following general formula (3):
The content of the styrene monomer in the expandable styrene resin particles is less than 50 ppm (including 0 ppm), and the weight average molecular weight of the styrene resin constituting the expandable styrene resin particles exceeds 200,000. And
The expandable styrenic resin particles contain a foaming agent containing a saturated hydrocarbon having 5 carbon atoms, and the content of the saturated hydrocarbon having 5 carbon atoms with respect to the expandable styrene resin particles is 1 to 8% by weight,
Expandable styrenic resin particles satisfying at least one of the following conditions (1) and (2):
(1) When the expandable styrene-based resin particles are expanded to a bulk density of 25 kg / m 3 , the average cell diameter of the expanded particles is 20 to 150 μm, and the surface layer is within 50 μm in the radial direction from the surface of the expanded particle cross section. The average bubble diameter of the part is 20 μm or more.
(2) When the expandable styrene-based resin particles are expanded to a bulk density of 50 kg / m 3 , the average cell diameter of the expanded particles is 15 to 120 μm, and the surface layer is within 50 μm in the radial direction from the surface of the expanded particle cross section. The average bubble diameter of the part is 15 μm or more.
NR 1 R 2 R 3 (3)
(However, in the general formula (3), N is a nitrogen atom, R 1, R 2, R 3 is an alkyl group or a cycloalkyl group having from 1 to 22 carbon atoms.)
前記難燃剤がハロゲン系難燃剤であり、
前記電解質の濃度は水性媒体1Lに対して0.02〜5モルであり、
前記炭素数5の飽和炭化水素の添加量がスチレン系樹脂粒子100重量部に対して1〜15重量部、前記難燃剤の添加量がスチレン系樹脂粒子100重量部に対して0.3〜5重量部、前記アミン系化合物の添加量がスチレン系樹脂粒子100重量部に対して0.001〜0.1重量部であることを特徴とする発泡性スチレン系樹脂粒子の製造方法。
NR1R2R3 (3)
(但し、一般式(3)において、Nは窒素原子、R1、R2、R3は炭素数1〜22のアルキル基又はシクロアルキル基である。)
A styrene resin particle having a styrene monomer content of less than 50 ppm (including 0 ppm) and a weight average molecular weight of more than 200,000 is dispersed in an aqueous medium containing an electrolyte, and a flame retardant is contained in the aqueous medium. , blowing agent comprising saturated hydrocarbons having 5 carbon atoms, and the following general formula (3) by adding an amine compound represented by the formula, is impregnated with a flame retardant with a blowing agent to the styrene-based resins particles child, A method for producing expandable styrenic resin particles, comprising:
The flame retardant is a halogen flame retardant,
The concentration of the electrolyte is 0.02 to 5 mol with respect to 1 L of the aqueous medium,
The addition amount of the saturated hydrocarbon having 5 carbon atoms is 1 to 15 parts by weight with respect to 100 parts by weight of the styrene resin particles, and the addition amount of the flame retardant is 0.3 to 5 with respect to 100 parts by weight of the styrene resin particles. A method for producing expandable styrene resin particles, characterized in that the addition amount of said amine compound is 0.001 to 0.1 parts by weight with respect to 100 parts by weight of styrene resin particles.
NR 1 R 2 R 3 (3)
(However, in the general formula (3), N is a nitrogen atom, R 1, R 2, R 3 is an alkyl group or a cycloalkyl group having from 1 to 22 carbon atoms.)
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JP2020164582A (en) * | 2019-03-28 | 2020-10-08 | 積水化成品工業株式会社 | Flame-retardant composite resin foam particle, method for producing the same, and foam molding |
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