JP2005028796A - Transparent flame-retardant vinyl chloride-based resin laminate having hot water whitening resistance - Google Patents
Transparent flame-retardant vinyl chloride-based resin laminate having hot water whitening resistance Download PDFInfo
- Publication number
- JP2005028796A JP2005028796A JP2003271900A JP2003271900A JP2005028796A JP 2005028796 A JP2005028796 A JP 2005028796A JP 2003271900 A JP2003271900 A JP 2003271900A JP 2003271900 A JP2003271900 A JP 2003271900A JP 2005028796 A JP2005028796 A JP 2005028796A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- less
- flame
- transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、透明で難燃性があり、且つ耐温水白化性の優れた塩化ビニル系樹脂積層体に関する。 The present invention relates to a vinyl chloride resin laminate that is transparent, flame retardant, and has excellent hot water whitening resistance.
塩化ビニル系樹脂は分子中に塩素を含有するため、難燃性に優れている。また、各種の添加剤を広い含有量で添加できるため、広範囲の機械的特性、耐熱性、成形性、耐候性を実現することができる。 Since vinyl chloride resin contains chlorine in the molecule, it is excellent in flame retardancy. Moreover, since various additives can be added in a wide content, a wide range of mechanical properties, heat resistance, moldability, and weather resistance can be realized.
以上の様な特性を塩化ビニル系樹脂は有しているため、特に硬質塩化ビニル系樹脂組成物の成形品は、航空機、船舶、車両等の輸送機内外装材;建築物内外装材;家具、事務用具等の日用物品;家電機器、電子機器等のハウジング材;半導体装置の部品等として使用されてきた。 Since the vinyl chloride resin has the characteristics as described above, the molded product of the hard vinyl chloride resin composition is particularly suitable for interior / exterior materials for transport aircraft such as aircraft, ships, vehicles, etc .; It has been used as daily goods such as office tools; housing materials for home appliances, electronic devices, etc .; parts for semiconductor devices.
特に、本願発明の積層材は、温水が接触する部材、例えば半導体製造装置用工業部材として使用するのに適している。半導体洗浄装置等では温水を使用する場合があるので、のぞき窓、仕切板、液回収槽の部材等に温水がかかると従来の塩素化塩化ビニル樹脂の単層品では白化する場合がある。温水白化を防ぐ配合処方にすると透明性や難燃性が悪化する傾向がありその改良が望まれていた。 In particular, the laminated material of the present invention is suitable for use as a member in contact with hot water, for example, an industrial member for semiconductor manufacturing equipment. In some cases, warm water is used in a semiconductor cleaning device or the like. If warm water is applied to the inspection window, the partition plate, the member of the liquid recovery tank, etc., the conventional single layer product of chlorinated vinyl chloride resin may be whitened. When blended prescriptions that prevent warm water whitening tend to deteriorate transparency and flame retardancy, improvements have been desired.
また、塩化ビニル系樹脂は、火災等の理由により耐熱温度以上の高温に晒されると、分子内の塩素に起因して、多量に発煙すると共に、塩素ガスや塩化水素ガス等の有毒ガスを発生する。このため、添加剤の種類および配合量を検討することにより、有毒ガスの発生を抑制することが試みられてきた。 In addition, when vinyl chloride resin is exposed to high temperatures above the heat-resistant temperature due to fire or other reasons, it emits a large amount of smoke due to chlorine in the molecule and generates toxic gases such as chlorine gas and hydrogen chloride gas. To do. For this reason, attempts have been made to suppress the generation of toxic gases by examining the types and amounts of additives.
例えば、特許文献1では、FM規格を満足する透明塩化ビニル系樹脂を目的として、基層の少なくとも片面に表面層を積層した成形体であって表面層が塩素化度(樹脂の塩素含有率を質量%として表した数値を示す)が56.8%のストレート塩化ビニル樹脂とこれより塩素化度の高い塩素化塩化ビニル樹脂との平均塩素化度が58〜60%の混合樹脂に錫系安定剤を配合した層であり、基層は表面層の混合樹脂の平均塩素化度より高い塩素化度(60〜66%)を有する塩素化塩化ビニル樹脂に錫系安定剤を有する層より構成される透明難燃性塩化ビニル系樹脂成形体が開示されている。 For example, Patent Document 1 discloses a molded body in which a surface layer is laminated on at least one surface of a base layer for the purpose of a transparent vinyl chloride resin that satisfies the FM standard, and the surface layer has a chlorination degree (the chlorine content of the resin is expressed by mass). The tin-based stabilizer is a mixed resin having an average chlorination degree of 58 to 60% between a straight vinyl chloride resin of 56.8% and a chlorinated vinyl chloride resin having a higher chlorination degree. A transparent layer composed of a layer containing a tin-based stabilizer in a chlorinated vinyl chloride resin having a chlorination degree (60 to 66%) higher than the average chlorination degree of the mixed resin of the surface layer. A flame retardant vinyl chloride resin molded article is disclosed.
しかしながら、これには温水浸漬後の白化試験については一切記載されていないので、透明性、難燃性に加えて、温水の浸漬に耐える性質を兼ね備えることが必要な用途、例えば温水を用いる半導体製造装置等に使用できるかどうかを推定することはできない。 However, since this does not describe any whitening test after immersion in warm water, in addition to transparency and flame retardancy, it is necessary to combine the properties to withstand immersion in warm water, for example, semiconductor manufacturing using warm water It cannot be estimated whether the device can be used.
本願発明者等は上記特許文献1記載の成形体について検討を行ったが、この成形体は難燃性は満足するものの、温水の浸漬に耐える性質は備えていないため、前記半導体製造装置等の用途に使用することができないことが分かりこの改良が重要な課題であることが明らかとなった。 The inventors of the present application have examined the molded body described in Patent Document 1, but this molded body satisfies the flame retardancy, but does not have the property to withstand immersion in hot water. It became clear that this improvement was an important subject when it was found that it could not be used for applications.
また、特許文献−2では、FM規格を満足する透明塩化ビニル系樹脂を目的として、基層の少なくとも片面に表面層を積層した成形体であって表面層およびまたは基層のストレート塩化ビニル樹脂に発泡剤、分解促進剤、ラジカル発生剤、架橋剤の少なくともいずれか1種を添加し錫マレート、ラウレート系安定剤を用いた層より構成される透明難燃性塩化ビニル系樹脂成形体が開示されている。 Moreover, in patent document 2, it is the molded object which laminated | stacked the surface layer on the at least single side | surface of the base layer for the purpose of the transparent vinyl chloride resin which satisfy | fills FM specification, Comprising: A foaming agent is added to the surface layer and / or the straight vinyl chloride resin of a base layer. , A transparent flame-retardant vinyl chloride resin molded article comprising a layer using tin malate or a laurate stabilizer by adding at least one of a decomposition accelerator, a radical generator, and a crosslinking agent is disclosed. .
しかしながら、水を使用する環境、特に温水(60℃以上)が接触する環境で成形体を使用すると透明度が低下する(以下温水白化性と表記)問題があった。また、屈折率の異なる塩化ビニル樹脂(屈折率:1.540)と塩素化塩化ビニル樹脂(屈折率:1.550<塩素化度65%>)を混合しているので十分な透明性、特に表面/基層界面でのムラが改善しにくい問題を抱えていた。 However, when the molded body is used in an environment where water is used, particularly in an environment where warm water (60 ° C. or higher) contacts, there is a problem that the transparency is lowered (hereinafter referred to as hot water whitening). In addition, since vinyl chloride resins having different refractive indexes (refractive index: 1.540) and chlorinated vinyl chloride resins (refractive index: 1.550 <chlorination degree 65%>) are mixed, sufficient transparency, especially There was a problem that unevenness at the surface / base layer interface was difficult to improve.
よって、以上に記載した様な透明難燃性塩化ビニル系樹脂成形体においては、透明で難燃性があるものの耐温水白化性を満足したものではなかった。
本発明においては、十分な難燃性、耐温水白化性、成形加工における熱安定性および成形された時の外観に優れた難燃性塩化ビニル系樹脂組成物およびそれを用いた積層体を提供することを目的とする。 In the present invention, there are provided a flame retardant vinyl chloride resin composition excellent in flame retardancy, hot water whitening resistance, thermal stability in molding process and appearance when molded, and a laminate using the same. The purpose is to do.
本発明は以下の発明を包含する。 The present invention includes the following inventions.
[1]塩化ビニル系樹脂組成物よりなり、少なくとも基層と表面層を有する難燃性積層体であって、該基層が透明性を有しかつ難燃性を備えた樹脂組成物よりなり、該表面層が80℃24時間の温水浸漬後の全光線透過率が50%以上、且つヘイズ値が20%以下である耐温水白化性を有する樹脂組成物よりなることを特徴とする透明でかつ難燃性である塩化ビニル系樹脂積層体。 [1] A flame-retardant laminate comprising a vinyl chloride resin composition and having at least a base layer and a surface layer, the base layer comprising a resin composition having transparency and flame retardancy, Transparent and difficult, characterized in that the surface layer is made of a resin composition having a resistance to whitening with warm water having a total light transmittance of 50% or more after being immersed in warm water at 80 ° C. for 24 hours and a haze value of 20% or less. Flammable vinyl chloride resin laminate.
[2] 該基層の厚さが少なくとも1mm以上であり、該表面層の厚みが0.05mm、以上2mm以下であることを特徴とする[1]記載の透明でかつ難燃性である塩化ビニル系樹脂積層体。 [2] The transparent and flame-retardant vinyl chloride according to [1], wherein the thickness of the base layer is at least 1 mm or more, and the thickness of the surface layer is 0.05 mm or more and 2 mm or less -Based resin laminate.
[3] 該基層が塩素化度57.0%以上71.0%未満の塩素化塩化ビニル樹脂1種以上からなり、その平均塩素化度62.0%以上68.0%以下であることを特徴とする[1]または[2]に記載の透明でかつ難燃性である塩化ビニル系樹脂積層体。 [3] The base layer is composed of one or more chlorinated vinyl chloride resins having a chlorination degree of 57.0% or more and less than 71.0%, and has an average chlorination degree of 62.0% or more and 68.0% or less. The transparent and flame-retardant vinyl chloride resin laminate as described in [1] or [2].
[4] 該表層が塩素化度57.0%以上60.0%未満の塩素化塩化ビニル樹脂と、塩素化度60.0%以上71.0%未満の塩素化塩化ビニル樹脂を混合して、平均塩素化度58.0%以上62.0%未満とした塩素化塩化ビニル系樹脂組成物を用いることを特徴とする[1]乃至[3]のいずれかに記載の透明で難燃性である塩化ビニル系樹脂積層体。 [4] Mixing a chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 60.0% with a chlorinated vinyl chloride resin having a chlorination degree of 60.0% or more and less than 71.0%. The transparent and flame-retardant material according to any one of [1] to [3], wherein a chlorinated vinyl chloride resin composition having an average chlorination degree of 58.0% or more and less than 62.0% is used. A vinyl chloride resin laminate.
[5] ASTM E1354に準じて測定される平均発熱量(AHRR)と平均減光体積(ASEA)が、それぞれ65kW/m2以下、800m2/g以下である[1]乃至[4]の何れかに記載の透明で難燃性を有する塩化ビニル系樹脂積層体。 [5] Any of [1] to [4], wherein the average calorific value (AHRR) and average dimming volume (ASEA) measured in accordance with ASTM E1354 are 65 kW / m 2 or less and 800 m 2 / g or less, respectively. A transparent and flame retardant vinyl chloride resin laminate according to claim 1.
本発明によって、透明性、難燃性、加工性及び温水浸漬に耐える成型体を提供することが可能となった。 According to the present invention, it is possible to provide a molded body that can withstand transparency, flame retardancy, processability, and hot water immersion.
以下、本発明の好適な実施の形態について説明する。 Hereinafter, preferred embodiments of the present invention will be described.
本発明において塩化ビニル系樹脂としては、塩素化塩化ビニル樹脂、塩素化した塩化ビニル−エチレン共重合体、塩素化した塩化ビニル−酢酸ビニル共重合体または塩素化した塩化ビニル−アクリル共重合体等を使用することができる。 As the vinyl chloride resin in the present invention, chlorinated vinyl chloride resin, chlorinated vinyl chloride-ethylene copolymer, chlorinated vinyl chloride-vinyl acetate copolymer, chlorinated vinyl chloride-acrylic copolymer, etc. Can be used.
塩化ビニル系樹脂としては、ストレート塩化ビニル樹脂(塩素化度略56.8%)もあるが、それらを混合すると軟化温度が低下し高い温水白化性(たとえば温水温度が80℃)を確保しにくい。 There are straight vinyl chloride resins (chlorination degree of about 56.8%) as vinyl chloride resins, but when they are mixed, the softening temperature decreases and it is difficult to ensure high warm water whitening (for example, hot water temperature is 80 ° C). .
ストレート塩化ビニル樹脂と塩素化塩化ビニル樹脂との混合系はJIS K 7198準拠にて測定した損失正接(Tanδ)のピークが二山分布になることからミクロな不均一混合系になりやすく、しかもそれらの屈折率が異なるため屈折率差発生によって高い透明性を発現させにくい。また通常のストレート塩化ビニル樹脂と、塩素化塩化ビニル樹脂との混合では、そのミクロな不均一混合界面より温水が浸透し高い温水白化性を確保しにくいため塩素化塩化ビニル樹脂同士の混合が有効である。 The mixed system of straight vinyl chloride resin and chlorinated vinyl chloride resin tends to be a micro-inhomogeneous mixed system because the peak of loss tangent (Tanδ) measured according to JIS K 7198 has a two-peak distribution. Therefore, it is difficult to achieve high transparency due to the difference in refractive index. Also, when mixing ordinary straight vinyl chloride resin and chlorinated vinyl chloride resin, it is difficult to ensure high warm water whitening property because warm water penetrates from the micro uneven mixing interface, so mixing of chlorinated vinyl chloride resins is effective. It is.
ここでいう損失正接の二山分布とは混合体の損失正接曲線が塩化ビニル樹脂のみの損失正接曲線のピーク位置と塩素化塩化ビニル樹脂のみの損失正接曲線のピーク位置との2つの位置でピークを有し各ピークの合成としてなるもので各ピークの損失正接曲線値付近で変曲点をもつような状態をいう。そして混合体の損失正接曲線が二山分布になっていれば上記2種の樹脂により非相溶系ポリマーアロイが形成されていると判断されている。なお非相溶となる状態とは完全に相分離していることを意味するものではなく塩素化塩化ビニル樹脂とストレート塩化ビニル樹脂が実質的に相分離している状態を言い、一部に相溶する部分が存在している状態をも含むものである。この非相溶系ポリマーアロイの状態をミクロな不均一混合状態と記載する。また非相溶系ポリマーアロイには一般的に複数のガラス転移温度を有するため急激に軟化が進行する温度が2点以上存在する点でも同様の議論ができる。 The distribution of loss tangents here means that the loss tangent curve of the mixture peaks at two positions, the peak position of the loss tangent curve of the vinyl chloride resin only and the peak position of the loss tangent curve of the chlorinated vinyl chloride resin only. Is a composition of each peak, and has a point of inflection near the loss tangent curve value of each peak. If the loss tangent curve of the mixture has a bimodal distribution, it is determined that an incompatible polymer alloy is formed by the two types of resins. The state of incompatibility does not mean that the phases are completely separated, but the state in which the chlorinated vinyl chloride resin and the straight vinyl chloride resin are substantially phase-separated. It also includes a state in which a melted portion exists. The state of this incompatible polymer alloy is described as a micro-heterogeneous mixed state. Further, since the incompatible polymer alloy generally has a plurality of glass transition temperatures, the same argument can be made in that there are two or more temperatures at which softening proceeds rapidly.
塩素化塩化ビニルは重合して得られたストレート塩化ビニル樹脂を粒子構造で形成した後、スラリー状態で光を当てるか、加熱するかあるいは光を当てながら加熱して塩素を付加させるので、塩素化塩化ビニル樹脂は塩化ビニル樹脂に比べ塩素存在分布が広いため単に塩素化度の違いだけではなく塩素分布が異なる樹脂である。(参考文献 日刊工業新聞社 ポリ塩化ビニル−その基礎と応用 p168〜182)
塩素化塩化ビニル樹脂同士を見た場合はそのなかでも樹脂粒子中に存在する塩素を均一にする技術が検討されており、光塩素化法より熱塩素化法で塩素化された塩素化塩化ビニル樹脂が塩素分布が均一であるので使用するには好ましい。ストレート塩化ビニル樹脂と塩素化塩化ビニル樹脂混合では、不均一となり、透明性と温水白化に悪影響が生じやすく、塩素化塩化ビニル樹脂同士の混合では均一となるからと思われる。これがさまざまな現象の差を生じる原因と思われる。
Chlorinated vinyl chloride forms a straight vinyl chloride resin obtained by polymerization with a particle structure, and then applies light in a slurry state or heats it or heats it while applying light to add chlorine. Since vinyl chloride resin has a wider distribution of chlorine than vinyl chloride resin, it is not only a difference in chlorination degree but also a different chlorine distribution. (Reference: Nikkan Kogyo Shimbun, Polyvinyl Chloride-Fundamentals and Applications, p168-182)
Among the chlorinated vinyl chloride resins, a technology to make the chlorine present in the resin particles uniform is being studied. Chlorinated vinyl chloride chlorinated by thermal chlorination rather than photochlorination. The resin is preferred for use because of its uniform chlorine distribution. It seems that the mixture of straight vinyl chloride resin and chlorinated vinyl chloride resin becomes non-uniform, which tends to have an adverse effect on transparency and whitening of hot water, and the mixture of chlorinated vinyl chloride resins becomes uniform. This seems to be the cause of the difference between various phenomena.
安定剤は鉛系安定剤では透明性を確保できないので錫系安定剤が使用される。一般的に塩化ビニル系樹脂において錫系安定剤のなかでも透明性や温水白化性はメルカプト系が有利であるが軟化温度を低下させたり燃焼性が阻害しやすい。またマレート系、ラウレート系は透明性や温水白化性におとるが軟化温度や燃焼性を阻害しにくい。しかし燃焼性は塩素化塩化ビニル樹脂自体が支配的であるので、塩素化塩化ビニル樹脂においては透明性や温水白化性はメルカプト系が有利であるが軟化温度を低下させやすい。またマレート系、ラウレート系は透明性や温水白化性に劣るが軟化温度を阻害しにくい。よってこれらの特長を勘案し1種以上組み合わされて使用できる。たとえば本発明のような塩素化塩化ビニル系樹脂においては表層が錫メルカプト系で基層が錫メルカプト、錫マレート、錫ラウレートのいずれか1種の使用が有利である。 As the stabilizer, a tin-based stabilizer is used because transparency cannot be ensured with a lead-based stabilizer. In general, among the tin stabilizers in the vinyl chloride resin, the mercapto type is advantageous for transparency and warm water whitening, but the softening temperature is lowered and the flammability tends to be hindered. Malate and laurate systems have transparency and warm water whitening properties, but are less likely to hinder softening temperature and flammability. However, since flammability is dominated by the chlorinated vinyl chloride resin itself, in the chlorinated vinyl chloride resin, mercapto is advantageous for transparency and warm water whitening, but the softening temperature tends to be lowered. In addition, malate and laurate are inferior in transparency and warm water whitening, but hardly inhibit the softening temperature. Therefore, one or more types can be combined and used in consideration of these features. For example, in the chlorinated vinyl chloride resin as in the present invention, it is advantageous to use any one of tin mercapto based on the surface layer and tin mercapto, tin malate and tin laurate on the base layer.
なお、ここで言う透明性とは、厚さ5mmのとき全光線透過率が40%以上でヘイズ値が60%以上、好ましくは、全光線透過率が60%以上でヘイズ値が30%以下である。 The transparency mentioned here means that when the thickness is 5 mm, the total light transmittance is 40% or more and the haze value is 60% or more, preferably, the total light transmittance is 60% or more and the haze value is 30% or less. is there.
よって表層には塩素化塩化ビニル樹脂同士の混合樹脂に錫メルカプト系を用い、好ましくはビカット軟化温度が76℃以上であれば高い耐温水白化性を得ることができる。 Therefore, a tin-mercapto resin is used for the surface layer of a mixed resin of chlorinated vinyl chloride resins, and high hot water whitening resistance can be obtained if the Vicat softening temperature is preferably 76 ° C. or higher.
該基層は塩素化度57.0%以上71.0%未満、好ましくは61.0%以上、69.0%以下の塩素化塩化ビニル樹脂が1種以上からなり、平均塩素化度62.0%以上68.0%以下、好ましくは66.0%以上、66.0%以下である。 The base layer comprises at least one chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 71.0%, preferably 61.0% or more and 69.0% or less, and has an average chlorination degree of 62.0%. % Or more and 68.0% or less, preferably 66.0% or more and 66.0% or less.
表層は塩素化度57.0%以上、60%未満、好ましくは58.0%以上、59.0以下の塩素化塩化ビニル樹脂と、塩素化度60.0%以上71.0%未満、好ましくは63.0%以上、68.0%未満の塩素化塩化ビニル樹脂を混合した平均塩素化度58.0%以上62.0%未満、好ましくは60.0%以上、61.0%以下である。 The surface layer is a chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 60%, preferably 58.0% or more and 59.0 or less, and a chlorination degree of 60.0% or more and less than 71.0%, preferably Is an average chlorination degree of 58.0% or more and less than 62.0%, preferably 60.0% or more and 61.0% or less by mixing 63.0% or more and less than 68.0% chlorinated vinyl chloride resin. is there.
特に好ましくは、表層の塩素化度約58.0%の後塩素化塩化ビニル樹脂と塩素化度約65.0%の後塩素化塩化ビニル樹脂を75:25〜70:30混合し平均塩素化度59.8〜61.1%にし、基層の塩素化度は約65.0%の塩素化塩化ビニル樹脂を用いる。 Particularly preferably, 75:25 to 70:30 of a post-chlorinated vinyl chloride resin having a surface layer chlorination degree of about 58.0% and a post-chlorination vinyl chloride resin having a chlorination degree of about 65.0% are mixed in an average chlorination. A chlorinated vinyl chloride resin having a degree of chlorination of 59.8 to 61.1% and a chlorination degree of the base layer of about 65.0% is used.
塩素化度と難燃性は正の相関なので塩素化度が高いほど難燃性がよい。しかし塩素化度と成形加工性(変色や分解)、耐薬品性は負の相関なのでできるだけ塩素度が低いほど成形性、色調および耐薬品性がよい。よって平均塩素化度が低すぎると難燃性が得られない。また平均塩素化度が高すぎると初期着色や耐薬品性、成形加工性が悪化する。 Since the degree of chlorination and flame retardancy are positively correlated, the higher the degree of chlorination, the better the flame retardancy. However, since the degree of chlorination, moldability (discoloration and decomposition), and chemical resistance are negatively correlated, the lower the degree of chlorine, the better the moldability, color tone, and chemical resistance. Therefore, if the average chlorination degree is too low, flame retardancy cannot be obtained. On the other hand, if the average chlorination degree is too high, the initial coloring, chemical resistance and molding processability deteriorate.
表面および基層の全平均塩素化率は難燃性が確保できる範囲高くし、表層は耐薬品性に直接関係するので塩素化率を低く、基層は耐薬品性に直接関係ないので表面層より塩素化率を高くしたほうが有利である。 The total average chlorination rate of the surface and the base layer is set high in a range where flame retardancy can be secured, the surface layer is directly related to chemical resistance, so the chlorination rate is low, and the base layer is not directly related to chemical resistance, so It is advantageous to increase the conversion rate.
そのように基層より低い塩素化率を有する表層において1種の塩素化塩化ビニル樹脂であれば表層/基層の界面で急激な塩素化率の変化による屈折率変化によって透明性が低下したり界面ムラを生じる不具合点がある。よって表層は2種類以上の異なる塩素化塩化ビニル系樹脂を混合するほうが良好な透明性が得られる。その場合ストレート塩化ビニル樹脂とともに混合するとストレート塩化ビニル樹脂と塩素化塩化ビニル樹脂とのミクロな不均一混合系により表層自体の屈折率差が生じ、透明性が低下したり、表層/基層界面でムラが生じることがある。また十分な軟化温度上昇効果が得られにくく耐温水白化性や耐薬品性等が改善しにくくなる。よって表層は塩素化塩化ビニル樹脂系のなかで2種類以上の異なる塩素化塩化ビニル樹脂を混合するほうが良好な透明性、耐温水白化性が得られる。 If the surface layer having a lower chlorination rate than the base layer is one kind of chlorinated vinyl chloride resin, the transparency may decrease due to a change in the refractive index due to a sudden change in the chlorination rate at the interface between the surface layer and the base layer. There is a defect that causes Therefore, better transparency can be obtained by mixing two or more different chlorinated vinyl chloride resins on the surface layer. In that case, when mixed with straight vinyl chloride resin, the refractive index difference of the surface layer itself occurs due to the micro non-uniform mixing system of straight vinyl chloride resin and chlorinated vinyl chloride resin, resulting in lower transparency or unevenness at the surface layer / base layer interface. May occur. Further, it is difficult to obtain a sufficient softening temperature increasing effect, and it is difficult to improve warm water whitening resistance and chemical resistance. Therefore, better transparency and warm water whitening resistance can be obtained by mixing two or more different types of chlorinated vinyl chloride resins in the chlorinated vinyl chloride resin system.
次に、所定量の塩化ビニル系樹脂、錫系安定剤、滑剤、衝撃改良剤、加工助剤、顔料等をブレンダーやヘンシェルミキサー等を用いて混合する。 Next, a predetermined amount of vinyl chloride resin, tin stabilizer, lubricant, impact modifier, processing aid, pigment and the like are mixed using a blender, a Henschel mixer or the like.
以上の様にして得られた組成物は、押出成形、カレンダー成形、プレス成形法等により、フィルム、シート、板材、パイプ、異型品等の難燃性塩化ビニル系樹脂積層体に加工される。 The composition obtained as described above is processed into a flame retardant vinyl chloride resin laminate such as a film, a sheet, a plate material, a pipe, and an odd-shaped article by extrusion molding, calender molding, press molding method or the like.
以上の様にして製造された難燃性塩化ビニル系樹脂成形品の難燃性は、ASTM E1354に準じ、コーンカロリメータを用いて評価することができる。コーンカロリメータを用いた燃焼試験により評価される難燃特性としては、単位面積および単位時間当たりの燃焼による発熱量の最大値(最大発熱量、PHRRとも記載する;単位:kW/m2)、単位面積および単位時間当たりの燃焼による発熱量の平均値(平均発熱量、AHRRとも記載する;単位:kW/m2)、燃焼による総発熱量(総発熱量、THRとも記載する;単位:MJ/m2)、単位面積および単位時間当たりの燃焼による質量減少率の平均値(質量減少率、AMLRとも記載する;単位:g/sec・m2)、単位面積および単位時間当たりの燃焼による減光体積の最大値(最大減光体積、PSEAとも記載する;単位:m2/g)、単位面積および単位時間当たりの燃焼による減光体積の平均値(平均減光体積、ASEAとも記載する;単位:m2/g)等を挙げることができる。 The flame retardancy of the flame retardant vinyl chloride resin molded product produced as described above can be evaluated using a cone calorimeter according to ASTM E1354. The flame retardant properties evaluated by the combustion test using a corn calorimeter include the maximum value of calorific value due to combustion per unit area and unit time (maximum calorific value, also referred to as PHRR; unit: kW / m 2), unit area And the average value of calorific value by combustion per unit time (average calorific value, also described as AHRR; unit: kW / m2), total calorific value by combustion (also described as total calorific value, THR; unit: MJ / m2) Average value of mass reduction rate due to combustion per unit area and unit time (also referred to as mass reduction rate, AMLR; unit: g / sec · m 2), maximum value of light reduction volume due to combustion per unit area and unit time (Maximum dimming volume, also described as PSEA; unit: m2 / g), average value of dimming volume due to combustion per unit area and unit time (average dimming volume, ASEA and Described; Unit: m2 / g), and the like.
従来、難燃性の指標の一つとしては、産業相互保険組織(Factory Mutual System)が定める評価基準が有効に利用されてきた。 Conventionally, as one of the flame retardant indicators, evaluation standards defined by the Factory Mutual Insurance System have been used effectively.
この評価基準は、Class Number 4910として挙げられているクリーンルーム材料の難燃性テスト(FMRC、Clean Room Materials Flammability Test Protocol)に基づいて測定され、難燃性を示す延焼指数FPI、発煙性を示す発煙指数SDI、腐食性ガス発生を示す腐食指数CDI等が指標(FM規格とも記載する)とされる。 This evaluation standard was measured based on the flame retardant test (FMRC, Clean Room Materials Flammability Test Protocol) of clean room materials listed as Class Number 4910, and the flame spread index FPI indicating flame retardancy and fuming indicating smoke. An index SDI, a corrosion index CDI indicating the generation of corrosive gas, and the like are used as indexes (also referred to as FM standards).
本発明においては、FM規格に代えて、コーンカロリメータを用いた燃焼試験により評価される値を難燃性の指標とした。FM規格は、産業相互保険組織に試験片を提出し、産業相互保険組織が評価して得られる規格であるため、評価結果が得られるまでに時間を要し、非効率的であるのに対し、コーンカロリメータを用いた燃焼試験は、発明者らによって行うことができるため、効率的である。 In the present invention, instead of the FM standard, a value evaluated by a combustion test using a cone calorimeter is used as an index of flame retardancy. The FM standard is a standard that is obtained by submitting test specimens to an industry mutual insurance organization and evaluating the industry mutual insurance organization, so it takes time to obtain an evaluation result and is inefficient. The combustion test using a corn calorimeter is efficient because it can be performed by the inventors.
特に、FPIは、コーンカロリメータによって測定されるPHRR、AHRRおよびTHR等の発熱量に関する指標と強い相関を有する。また、SDIは、PSEAおよびASEA等の減光体積に関する指標と強い相関を有する。更に、CDIは、AMLR等の質量減少に関する指標と強い相関を有する。 In particular, FPI has a strong correlation with indices related to calorific values such as PHRR, AHRR and THR measured by a corn calorimeter. In addition, SDI has a strong correlation with indicators relating to dimming volume such as PSEA and ASEA. Furthermore, CDI has a strong correlation with an index related to mass loss such as AMLR.
従って、コーンカロリメータを用いて難燃性を評価することにより、FM規格の凡その値を、効率的に得ることができる。 Therefore, by evaluating the flame retardancy using a corn calorimeter, the approximate value of the FM standard can be obtained efficiently.
FM規格においては、FPIが6以下、SDIが0.4以下と要求されているが、本発明においては、この規格と同等以上として、PHRRが130kW/m2以下、AHRRが82kW/m2以下、THRが100MJ/m2以下、AMLRが13g/sec・m2以下、PSEAが1500m2/g以下、ASEAが1000m2/g以下であることが好ましい。そのなかで特にAHRR、ASEA特性が支配的で重要となる。 In the FM standard, FPI is 6 or less and SDI is 0.4 or less. In the present invention, PHRR is 130 kW / m 2 or less, AHRR is 82 kW / m 2 or less, THR Are 100 MJ / m 2 or less, AMLR is 13 g / sec · m 2 or less, PSEA is 1500 m 2 / g or less, and ASEA is 1000 m 2 / g or less. Among them, the AHRR and ASEA characteristics are particularly dominant and important.
以上の様にして製造された難燃性塩化ビニル系樹脂成形品の耐温水白化性は熱変形しない上限付近の温度領域で使用させた場合の透明性悪化度を示す指標であり、その温水白化性が良好なほど過酷な条件でも使用に耐えうる透明性を有することを示す。その温度は樹脂のガラス状領域を発現しうる上限付近での温度(JISK7207荷重たわみ温度が目安となる)が最も厳しい条件である。その温度になると樹脂そのものが軟化、変形してしまい成形体そのものの価値がない。またその温度よりも非常に低い温度ではたとえば常温(23℃)での評価であれば過酷な条件での状況を反映していない。よって好適には平均塩素化度65%の硬質塩素化塩化ビニル樹脂であれば85℃付近であるので80℃で評価される。 Warm water whitening resistance of flame retardant vinyl chloride resin molded products produced as described above is an index indicating the degree of transparency deterioration when used in the temperature range near the upper limit where heat deformation does not occur. It shows that it has the transparency which can endure use even in severe conditions, so that property is favorable. The temperature is the severest condition in the vicinity of the upper limit at which the glassy region of the resin can be manifested (the JISK 7207 load deflection temperature is a guide). At that temperature, the resin itself is softened and deformed, and the molded body itself is not valuable. Further, at a temperature much lower than that temperature, for example, evaluation at normal temperature (23 ° C.) does not reflect the situation under severe conditions. Accordingly, a hard chlorinated vinyl chloride resin having an average chlorination degree of 65% is evaluated at 80 ° C. because it is around 85 ° C.
本発明における難燃性塩化ビニル系樹脂組成物は、透明性が高く、難燃性に優れ発煙量も少なく、温水白化性の良好である特徴を有するものである。 The flame retardant vinyl chloride resin composition according to the present invention is characterized by high transparency, excellent flame retardancy, low smoke generation, and good warm water whitening properties.
従って、特に、硬質塩化ビニル系樹脂組成物の成形体は、航空機、船舶、車両等の内外装材;建築物内外装材;家具、事務用具等の日用物品;家電機器、電子機器等のハウジング材;半導体装置の部品等として、好適に使用することができる。 Therefore, in particular, the molded body of the hard vinyl chloride resin composition is used for interior / exterior materials for aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; daily goods such as furniture, office tools; home appliances, electronic devices, etc. Housing material; can be suitably used as a component of a semiconductor device.
以下に実施例によって本発明を更に詳細に説明するが、これらは、本発明を何ら限定するものではない。実施例において、使用原料と評価方法を以下に示す。
錫系安定剤:ジブチル錫メルカプトチオグリコール酸エステル
STNN JF−10B (三共有機合成(株)製)
加工助剤:メチルメタクリレート・ブチルアクリレート共重合体
カネエース PA−20(鐘淵化学工業(株)製)
滑剤:グリセリンモノステアリン酸エステル/ペンタエリスリトールアジピン酸ステアリン酸エステル 3/1混合物
(リケスターEW200、理研ビタミン(株)製)
衝撃改良剤:コア・シェル型改質剤
コアがブタジエン−スチレン共重合体、シェルがスチレン・メチルメタクリレート共重合体
(カネエース B−11A 鐘淵化学工業(株)製)
The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention. In the examples, raw materials used and evaluation methods are shown below.
Tin stabilizer: Dibutyltin mercaptothioglycolate
STNN JF-10B (manufactured by Sansha Co., Ltd.)
Processing aid: Methyl methacrylate / butyl acrylate copolymer Kaneace PA-20 (manufactured by Kaneka Chemical Co., Ltd.)
Lubricant: Glycerol monostearate / pentaerythritol adipate stearate 3/1 mixture (Ricester EW200, manufactured by Riken Vitamin Co., Ltd.)
Impact modifier: Core / shell modifier
The core is butadiene-styrene copolymer and the shell is styrene / methyl methacrylate copolymer
(Kane Ace B-11A Kaneka Chemical Co., Ltd.)
(評価方法)
(ア)難燃性の評価:アトラス社製コーンカロリメータを用いて、ASTM E1354に準じ、AHRR(kW/m2)、ASEA(m2/g)を測定した。
(イ)透明性:5mm板での全光線透過率、ヘーズ
積層界面の目視(ムラの有無)
(ウ)温水白化性の評価:80℃24時間浸漬後の全光線透過率、ヘーズ
(エ)耐薬品性の評価:60℃14日35%硫酸浸漬後の外観(割れの有無)
(オ)成形加工性の評価:プラストミルでの動的熱安定性評価法によって、200℃における分解時間を測定した。分解時間はトルクが10%以上増加し始めた時間。
(Evaluation methods)
(A) Evaluation of flame retardancy: AHRR (kW / m 2) and ASEA (m 2 / g) were measured according to ASTM E1354 using a cone calorimeter manufactured by Atlas.
(A) Transparency: total light transmittance and haze on a 5 mm plate
Visual observation of laminated interface (existence of unevenness)
(C) Evaluation of warm water whitening property: total light transmittance after immersion for 24 hours at 80 ° C., haze (e) Evaluation of chemical resistance: appearance after immersion in 35% sulfuric acid at 60 ° C. for 14 days (presence of cracks)
(E) Evaluation of molding processability: The decomposition time at 200 ° C. was measured by a dynamic thermal stability evaluation method using a plastmill. Decomposition time is the time when the torque starts to increase by more than 10%.
実験結果を表1に示す。 The experimental results are shown in Table 1.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003271900A JP4209735B2 (en) | 2003-07-08 | 2003-07-08 | Transparent and flame retardant vinyl chloride resin laminate with whitening resistance to hot water |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003271900A JP4209735B2 (en) | 2003-07-08 | 2003-07-08 | Transparent and flame retardant vinyl chloride resin laminate with whitening resistance to hot water |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005028796A true JP2005028796A (en) | 2005-02-03 |
JP4209735B2 JP4209735B2 (en) | 2009-01-14 |
Family
ID=34209616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003271900A Expired - Fee Related JP4209735B2 (en) | 2003-07-08 | 2003-07-08 | Transparent and flame retardant vinyl chloride resin laminate with whitening resistance to hot water |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4209735B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017031639A (en) * | 2015-07-31 | 2017-02-09 | 東リ株式会社 | Interior sheet for bathroom |
JP2019056045A (en) * | 2017-09-20 | 2019-04-11 | バンドー化学株式会社 | Polyvinyl chloride film, marking film, decorative molded article, and method for producing polyvinyl chloride film |
-
2003
- 2003-07-08 JP JP2003271900A patent/JP4209735B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017031639A (en) * | 2015-07-31 | 2017-02-09 | 東リ株式会社 | Interior sheet for bathroom |
JP2019056045A (en) * | 2017-09-20 | 2019-04-11 | バンドー化学株式会社 | Polyvinyl chloride film, marking film, decorative molded article, and method for producing polyvinyl chloride film |
JP7148231B2 (en) | 2017-09-20 | 2022-10-05 | バンドー化学株式会社 | Polyvinyl chloride film, marking film, decorative molding, and method for producing polyvinyl chloride film |
Also Published As
Publication number | Publication date |
---|---|
JP4209735B2 (en) | 2009-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5017637A (en) | Low toxicity fire retardant thermoplastic material | |
JP7382756B2 (en) | Fire-resistant hard vinyl chloride resin molding | |
JP2006291145A (en) | Vinyl chloride-based resin composition and cable covered therewith | |
WO2006071031A1 (en) | Flame-retardant, glycol-modified polyethylene terephthalate film | |
TWI334428B (en) | Flame resistant vinyl chloride type resin composition and its molded products | |
JP4402936B2 (en) | Extruded body | |
WO2008018521A1 (en) | Transparent flame-retardant vinyl chloride resin composition and molded body | |
JP4209735B2 (en) | Transparent and flame retardant vinyl chloride resin laminate with whitening resistance to hot water | |
JPH11140263A (en) | Vinyl chloride-based resin composition and coated electric wire using the same | |
JP4488578B2 (en) | Flame retardant vinyl chloride resin molding | |
CN101142271B (en) | Heat-recoverable article and composition therefor | |
JP2008208250A (en) | Vinyl chloride-based resin molded form | |
EP2093249A1 (en) | Unplasticized PVC composition | |
US6316118B1 (en) | Fire-retardant vinyl chloride resin molding | |
JP2000313748A (en) | Flame retardant vinyl chloride-based resin molded product | |
JP4490724B2 (en) | Flame-retardant vinyl chloride resin composition and molded article | |
JP5270116B2 (en) | Vinyl chloride resin molding | |
JPS6241248B2 (en) | ||
JP4490706B2 (en) | Flame-retardant vinyl chloride resin composition and molded article thereof | |
JP4164382B2 (en) | Flame retardant vinyl chloride resin composition molded product | |
JP2004107520A (en) | Molded plate of vinyl chloride-based resin | |
JP2005028805A (en) | Transparent vinyl chloride-based resin laminate having flame retardancy | |
JP3777449B2 (en) | Flame retardant transparent vinyl chloride resin molding | |
JPS62285940A (en) | Flexible flame-retarding resin composition | |
JP4149840B2 (en) | Flame retardant vinyl chloride resin composition and molded article thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060418 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080709 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080905 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081008 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081023 |
|
R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111031 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111031 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121031 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131031 Year of fee payment: 5 |
|
LAPS | Cancellation because of no payment of annual fees |