JP2014173003A - Vinyl chloride resin molded body having tmah resistance - Google Patents
Vinyl chloride resin molded body having tmah resistance Download PDFInfo
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本発明は、耐ＴＭＡＨ性（耐テトラメチルアンモニウムハイドロオキサイド性）を有する塩化ビニル系樹脂成形体に関し、更に詳しくは、耐ＴＭＡＨ性に加えて難燃性にも優れた塩化ビニル系樹脂成形体に関する。 The present invention relates to a vinyl chloride resin molded article having TMAH resistance (tetramethylammonium hydroxide resistance), and more particularly to a vinyl chloride resin molded article excellent in flame retardancy in addition to TMAH resistance. .
従来より、半導体洗浄容器には塩化ビニル樹脂製の容器が多用されている。
しかしながら、半導体の洗浄溶液にはＴＭＡＨ（テトラメチルアンモニウムハイドロオキサイド）が含まれており、塩化ビニル樹脂製の容器はこのＴＭＡＨの耐性が乏しいことから、ＴＭＡＨによって劣化し、クラックが発生するという問題があった。
Conventionally, containers made of vinyl chloride resin have been frequently used as semiconductor cleaning containers.
However, since the semiconductor cleaning solution contains TMAH (tetramethylammonium hydroxide) and the container made of vinyl chloride resin has poor resistance to TMAH, there is a problem that it is deteriorated by TMAH and cracks are generated. there were.
ところで、耐アルカリ性を有する塩化ビニル成形品を得ることができる塩化ビニル系樹脂組成物として、塩素化塩化ビニル系樹脂１００質量部に対して改質剤成分を４〜３０質量部を添加した組成物（塩化ビニル系樹脂成分が添加されている場合には塩化ビニル系樹脂成分と改質剤成分との合計が１０質量％以上で且つ改質剤成分が３０重量部未満であるもの）であって、その引張試験片を表面最大発生応力が１８．６〜１９．６ＭＰａとなるように円弧に曲げた状態で、濃度１４ｗｔ％のＫＯＨ水溶液中に５０℃で７２時間浸漬した後の破断伸び（Ｅａ）と、浸漬する前の破断伸び（Ｅｂ）から、次式（１）により計算される破断伸び保持率が３０％以上であることを特徴とする塩化ビニル系樹脂組成物が提案されている（特許文献１）。
破断伸び保持率（％）＝Ｅａ／Ｅｂ×１００ …（１）
By the way, the composition which added 4-30 mass parts of modifier components with respect to 100 mass parts of chlorinated vinyl chloride resin as a vinyl chloride resin composition which can obtain the vinyl chloride molded article which has alkali resistance. (When a vinyl chloride resin component is added, the total of the vinyl chloride resin component and the modifier component is 10% by mass or more and the modifier component is less than 30 parts by weight) Elongation at break after immersing the tensile test piece in a circular arc so that the maximum surface stress is 18.6 to 19.6 MPa in a 14 wt% KOH aqueous solution at 50 ° C. for 72 hours (Ea ) And the breaking elongation (Eb) before dipping, a breaking elongation retention calculated by the following formula (1) is 30% or more, and a vinyl chloride resin composition is proposed ( Patent Document 1).
Elongation at break (%) = Ea / Eb × 100 (1)
また、電子部品、その製造中間体、またはその製造工程の処理液と接触する器材であって、その接触面が熱可塑性飽和ノルボルネン樹脂で形成されていることを特徴とする電子部品処理用部材も提案されている（特許文献２）。 There is also provided an electronic component processing member characterized in that it is an electronic component, a manufacturing intermediate thereof, or an equipment that comes into contact with a processing liquid of the manufacturing process, and the contact surface is formed of a thermoplastic saturated norbornene resin. It has been proposed (Patent Document 2).
しかしながら、前記特許文献１の塩化ビニル系樹脂組成物は、ＫＯＨなどのアルカリに対する耐性を有するけれども、ＴＭＡＨに対する耐性までは確認されていない。
また、前記特許文献２の電子部品処理用部材は、耐熱性、耐薬品性、有機物低溶出性などに優れると記載されているが、ＴＭＡＨに対する耐性については不明である。
However, although the vinyl chloride resin composition of Patent Document 1 has resistance to alkalis such as KOH, resistance to TMAH has not been confirmed.
Moreover, although the electronic component processing member of Patent Document 2 is described as being excellent in heat resistance, chemical resistance, low organic matter elution, etc., resistance to TMAH is unclear.
本発明は上記事情の下になされたもので、その解決しようとする課題は、ＴＭＡＨを含んだ半導体洗浄溶液と長時間接触しても強度劣化が生じ難く、ストレスクラックも生じ難い、耐ＴＭＡＨ性に優れた塩化ビニル系樹脂成形体を提供することにある。 The present invention has been made under the circumstances described above, and the problem to be solved is that TMAH resistance is not likely to occur even if it is in contact with a semiconductor cleaning solution containing TMAH for a long time, stress cracks are difficult to occur, and resistance to TMAH. An object of the present invention is to provide a vinyl chloride resin molded article excellent in the above.
上記課題を解決するため、本発明の耐ＴＭＡＨ性を有する塩化ビニル系樹脂成形体は、重合度８００〜４０００の塩化ビニル樹脂又は共重合塩化ビニル樹脂を主成分とし、錫系安定剤及び脂肪酸系滑剤を含有させた塩化ビニル系樹脂成形体であって、濃度２５質量％のＴＭＡＨ水溶液中に３０℃で４８時間浸漬した後のＪＩＳ Ｋ７１６２−１Ｂ／５０による引張強度が、浸漬前の引張強度に対して９０％以上であることを特徴とするものである。 In order to solve the above-mentioned problems, a vinyl chloride resin molded article having TMAH resistance according to the present invention is mainly composed of a vinyl chloride resin or copolymerized vinyl chloride resin having a polymerization degree of 800 to 4000, a tin stabilizer and a fatty acid series. A vinyl chloride-based resin molded article containing a lubricant, and the tensile strength according to JIS K7162-1B / 50 after being immersed in a TMAH aqueous solution having a concentration of 25% by mass at 30 ° C. for 48 hours is the tensile strength before immersion. On the other hand, it is 90% or more.
本発明の塩化ビニル系樹脂成形体においては、上記主成分の樹脂にアクリル系加工助剤を更に含有させることが好ましく、また、上記主成分の樹脂に補強材として塩素化ポリエチレンを更に含有させることも好ましい。上記主成分の樹脂としては共重合塩化ビニル樹脂の方がより好ましく使用される。 In the vinyl chloride resin molded article of the present invention, it is preferable that the main component resin further contains an acrylic processing aid, and the main component resin further contains chlorinated polyethylene as a reinforcing material. Is also preferable. As the main component resin, a copolymerized vinyl chloride resin is more preferably used.
本発明の塩化ビニル系樹脂成形体は、主成分樹脂として耐薬性、特に耐ＴＭＡＨ性の向上に有効な重合度８００〜４０００の塩化ビニル樹脂又は共重合塩化ビニル樹脂を使用し、且つ、安定剤及び滑剤として耐ＴＭＡＨ性や難燃性の向上に有効な錫系安定剤及び脂肪酸系滑剤を含有させたものであるため、耐ＴＭＡＨ性や難燃性が向上し、後述の実施例のデータに示されるように、濃度２５質量％のＴＭＡＨ水溶液中に３０℃で４８時間浸漬した後のＪＩＳ Ｋ７１６２−１Ｂ／５０による引張強度が、浸漬前の引張強度に対して９０％以上となり、耐ストレスクラック性試験や難燃性試験の成績も良好である。 The vinyl chloride resin molded article of the present invention uses a vinyl chloride resin or copolymerized vinyl chloride resin having a polymerization degree of 800 to 4000 effective for improving chemical resistance, particularly TMAH resistance as a main component resin, and a stabilizer. In addition, since the tin stabilizer and the fatty acid lubricant are effective for improving the TMAH resistance and flame retardancy as the lubricant, the TMAH resistance and flame retardancy are improved. As shown, the tensile strength according to JIS K7162-1B / 50 after being immersed in a TMAH aqueous solution with a concentration of 25% by mass at 30 ° C. for 48 hours is 90% or more with respect to the tensile strength before immersion, and is resistant to stress cracking. The results of the property test and flame retardancy test are also good.
また、上記主成分樹脂にアクリル系加工助剤を更に含有させた塩化ビニル系樹脂成形体は、アクリル系加工助剤により加工安定性が向上することに加えて、アクリル系加工助剤が耐ＴＭＡＨ性に寄与するため、成形体の耐ＴＭＡＨ性が一層向上する。 In addition, the vinyl chloride resin molded article in which the main component resin further contains an acrylic processing aid is improved in processing stability by the acrylic processing aid, and the acrylic processing aid is resistant to TMAH. Since it contributes to the property, the TMAH resistance of the molded body is further improved.
また、上記主成分樹脂に補強材として塩素化ポリエチレンを更に含有させた塩化ビニル系樹脂成形体は、塩素化ポリエチレンが靭性の向上と耐ＴＭＡＨ性に寄与するため、強靱な成形体となり、耐ＴＭＡＨ性も一層向上する。 In addition, the vinyl chloride resin molded body in which chlorinated polyethylene is further added to the main component resin as a reinforcing material is a tough molded body because chlorinated polyethylene contributes to improved toughness and TMAH resistance. The characteristics are further improved.
また、主成分の樹脂として共重合塩化ビニル樹脂を用いた成形体は、共重合塩化ビニル樹脂が靭性の向上と耐ＴＭＡＨ性に大きく寄与するため、一層強靱な成形体となり、耐ＴＭＡＨ性もより一層向上する。 In addition, the molded body using the copolymerized vinyl chloride resin as the main component resin becomes a tougher molded body because the copolymerized vinyl chloride resin greatly contributes to the improvement of toughness and TMAH resistance. Further improvement.
以下、本発明に係る塩化ビニル系樹脂成形体の具体的な実施形態について説明する。 Hereinafter, specific embodiments of the vinyl chloride resin molded body according to the present invention will be described.
本発明の塩化ビニル系樹脂成形体は、重合度８００〜４０００の塩化ビニル樹脂又は共重合塩化ビニル樹脂を主成分とし、必須の添加剤として錫系安定剤と脂肪酸系滑剤が含有されたものである。そして、好ましくは、任意の添加剤として、アクリル系加工助剤や補強材なども含有される。 The vinyl chloride resin molded article of the present invention comprises a vinyl chloride resin or copolymerized vinyl chloride resin having a polymerization degree of 800 to 4000 as a main component, and contains a tin stabilizer and a fatty acid lubricant as essential additives. is there. Preferably, acrylic processing aids and reinforcing materials are also included as optional additives.
主成分樹脂である塩化ビニル樹脂としては、塩素化度５６．８％の塩化ビニル単独重合体であって、重合度（平均重合度）が８００〜４０００であるものが使用される。塩素化度の高い塩素化塩化ビニル樹脂は、耐ＴＭＡＨ性その他の耐薬性に劣るため不適当である。
また、主成分樹脂である共重合塩化ビニル樹脂としては、塩化ビニルを主成分とし、塩化ビニルモノマーと共重合可能な、例えばエチレン、酢酸ビニル、メチル（メタ）アクリレート等のモノマーとの共重合体であって、重合度（平均重合度）が８００〜４０００であるものが使用される。
重合度が８００よりも低い塩化ビニル樹脂や共重合塩化ビニル樹脂は、機械的強度や耐ＴＭＡＨ性が不充分であり、重合度が４０００よりも高い塩化ビニル樹脂や共重合塩化ビニル樹脂は、熱流動性が不充分で成形性に劣るので、いずれも不適当である。
As the vinyl chloride resin as the main component resin, a vinyl chloride homopolymer having a chlorination degree of 56.8% and a polymerization degree (average polymerization degree) of 800 to 4000 is used. A chlorinated vinyl chloride resin having a high degree of chlorination is unsuitable because it has poor TMAH resistance and other chemical resistance.
The copolymer vinyl chloride resin, which is the main component resin, is a copolymer with monomers such as ethylene, vinyl acetate, methyl (meth) acrylate, etc., which are mainly composed of vinyl chloride and can be copolymerized with vinyl chloride monomers. And what has a polymerization degree (average polymerization degree) of 800-4000 is used.
Vinyl chloride resins and copolymerized vinyl chloride resins having a polymerization degree lower than 800 have insufficient mechanical strength and TMAH resistance, and vinyl chloride resins and copolymerized vinyl chloride resins having a polymerization degree higher than 4000 are Since the fluidity is insufficient and the moldability is inferior, both are inappropriate.
必須添加剤である錫系安定剤としては、耐ＴＭＡＨ性や難燃性の向上に有効なメチル錫メルカプタイト、オクチル錫メルカプタイト、ジブチル錫マレートなどが好ましく、これらは単独で或いは２種以上混合して前記の主成分樹脂に添加される。特に、メチル錫メルカプタイトやオクチル錫メルカプタイトなどのメルカプタイト系安定剤は、ジブチル錫マレートなどのマレート系安定剤よりも有効であるので、より好ましく使用される。なお、鉛系安定剤は、成形体の透明性を損なうので不適当である。
錫系安定剤の添加量は限定されないが、前記の主成分樹脂１００質量部に対し２〜５質量部程度とすることが好ましい。
The tin-based stabilizer that is an essential additive is preferably methyltin mercaptite, octyltin mercaptite, dibutyltin malate, etc. effective for improving TMAH resistance and flame retardancy, and these may be used alone or in combination of two or more. It is added to the main component resin. In particular, mercaptite stabilizers such as methyltin mercaptite and octyltin mercaptite are more preferably used because they are more effective than malate stabilizers such as dibutyltin malate. Lead stabilizers are unsuitable because they impair the transparency of the molded body.
Although the addition amount of the tin stabilizer is not limited, it is preferably about 2 to 5 parts by mass with respect to 100 parts by mass of the main component resin.
また、必須添加剤である脂肪酸系滑剤としては、耐ＴＭＡＨ性や難燃性の向上に有効な、例えば脂肪酸、脂肪酸アルコールなどが好ましく、これらは単独で或いは２種以上混合して前記の主成分樹脂に添加される。
脂肪酸系滑剤以外のアクリル系滑剤、炭化水素系滑剤、脂肪酸アミド系滑剤などは、耐ＴＭＡＨ性や難燃性の向上に有効でないので、好ましくない。
脂肪酸系滑剤の添加量は限定されないが、前記の主成分樹脂１００質量部に対し０．２〜２質量部程度とするのが適当である。
In addition, as the fatty acid-based lubricant that is an essential additive, effective for improving TMAH resistance and flame retardancy, for example, fatty acid, fatty acid alcohol, and the like are preferable. Added to the resin.
Acrylic lubricants, hydrocarbon lubricants, fatty acid amide lubricants and the like other than fatty acid lubricants are not preferable because they are not effective in improving TMAH resistance and flame retardancy.
The addition amount of the fatty acid-based lubricant is not limited, but is suitably about 0.2 to 2 parts by mass with respect to 100 parts by mass of the main component resin.
任意の添加剤であるアクリル系加工助剤としては、加工安定性や耐ＴＭＡＨ性の向上に寄与する、例えばアクリル酸エステル、メタクリル酸エステル等が使用され、これらは単独で或いは２種以上混合して前記の主成分樹脂に添加される。特に、分子量が３００万以上のアクリル系加工助剤は、ＴＭＡＨなどの薬液によって分子が切断された場合でも、成形体の物性に与える影響が少なく、また、樹脂組成物の粘度が高くなって成形性が良くなる利点があるので好ましい。
アクリル系加工助剤の添加量は限定されないが、前記の主成分樹脂１００質量部に対し０．１〜１質量部程度とするのが適当である。
As an acrylic processing aid which is an optional additive, for example, an acrylic ester, a methacrylic ester or the like that contributes to an improvement in processing stability and TMAH resistance is used. These may be used alone or in combination of two or more. And added to the main component resin. In particular, an acrylic processing aid having a molecular weight of 3 million or more has little influence on the physical properties of the molded product even when the molecule is cut by a chemical solution such as TMAH, and the viscosity of the resin composition increases. This is preferable because there is an advantage of improving the property.
The amount of the acrylic processing aid added is not limited, but is suitably about 0.1 to 1 part by mass with respect to 100 parts by mass of the main component resin.
任意の添加剤である補強材としては、塩素化ポリエチレン、ＭＢＳ共重合体などが使用され、特に、塩素化度２０〜４５％程度の塩素化ポリエチレンは、成形体の靭性及び耐ＴＭＡＨ性の向上に大きく寄与するので、好ましく使用される。
補強材の添加量は特に限定されないが、前記の主成分樹脂１００質量部に対し３〜１０質量部程度とするのが適当である。
As a reinforcing material which is an optional additive, chlorinated polyethylene, MBS copolymer, etc. are used. In particular, chlorinated polyethylene having a chlorination degree of about 20 to 45% improves the toughness and TMAH resistance of the molded product. It is preferably used because it greatly contributes to
The addition amount of the reinforcing material is not particularly limited, but is suitably about 3 to 10 parts by mass with respect to 100 parts by mass of the main component resin.
上記のように、重合度８００〜４０００の塩化ビニル樹脂又は共重合塩化ビニル樹脂を主成分とし、これに錫系安定剤、脂肪酸系滑剤、アクリル系加工助剤、補強材などの添加剤を添加した樹脂組成物を用いて、押出成形、カレンダープレス成形、射出成形などの公知の成形手段により成形された、板状、異形状その他の所望形状の塩化ビニル樹脂成形体は、耐ＴＭＡＨ性や難燃性が向上し、下記の実施例のデータに示されるように、濃度２５質量％のＴＭＡＨ水溶液中に３０℃で４８時間浸漬した後のＪＩＳ Ｋ７１６２−１Ｂ／５０による引張強度が、浸漬前の引張強度に対して９０％以上となり、耐ストレスクラック性試験や難燃性試験の成績も良好である。従って、この塩化ビニル樹脂成形体は、洗浄液としてＴＭＡＨ水溶液を用いる半導体洗浄装置などの材料用成形体として、極めて有用である。 As described above, vinyl chloride resin or copolymerized vinyl chloride resin with a polymerization degree of 800 to 4000 is the main component, and additives such as tin stabilizers, fatty acid lubricants, acrylic processing aids, and reinforcing materials are added thereto. The molded PVC resin sheet having a plate shape, irregular shape, or other desired shape molded by a known molding means such as extrusion molding, calender press molding, injection molding, etc. As shown in the data of the following examples, the flammability is improved, and the tensile strength according to JIS K7162-1B / 50 after dipping in a TMAH aqueous solution having a concentration of 25% by mass at 30 ° C. for 48 hours is It is 90% or more with respect to the tensile strength, and the results of the stress crack resistance test and flame retardancy test are also good. Therefore, this vinyl chloride resin molded body is extremely useful as a molded body for a material such as a semiconductor cleaning apparatus using a TMAH aqueous solution as a cleaning liquid.
次に、本発明の更に具体的な実施例と比較例について説明する。 Next, more specific examples and comparative examples of the present invention will be described.
［実施例１〜１２］
下記の表１、表２に示す塩化ビニル系樹脂組成物を調製し、押出成形法で厚さ５ｍｍの塩化ビニル系樹脂板を作製した後、これを５ｍｍ×２０ｍｍ×１５０ｍｍの大きさに切断して、実施例１〜１２の塩化ビニル系樹脂試験片を得た。
これらの塩化ビニル系樹脂試験片を、濃度２５質量％のＴＭＡＨ水溶液中に３０℃で１５日間浸漬し、浸漬前、１日後、２日後、３日後、４日後、７日後、８日後、１０日後、１４日後、１５日後の各試験片についてＪＩＳ Ｋ７１６２−１Ｂ／５０による引張試験を行い、それぞれの引張強度を測定した。その結果を下記表１、表２に示す。
[Examples 1 to 12]
The vinyl chloride resin compositions shown in Table 1 and Table 2 below were prepared, and a vinyl chloride resin plate having a thickness of 5 mm was prepared by an extrusion molding method, and then cut into a size of 5 mm × 20 mm × 150 mm. Thus, vinyl chloride resin test pieces of Examples 1 to 12 were obtained.
These vinyl chloride resin test pieces are immersed in an aqueous TMAH solution having a concentration of 25% by mass at 30 ° C. for 15 days, before immersion, 1 day, 2 days, 3 days, 4 days, 7 days, 8 days, 10 days later. After 14 days and 15 days, the tensile test according to JIS K7162-1B / 50 was performed on each test piece, and the respective tensile strengths were measured. The results are shown in Tables 1 and 2 below.
また、実施例１〜１２のそれぞれの塩化ビニル系樹脂組成物を板状に押出成形した後、切断してストレスクラック試験用の試験片（５ｍｍ×２０ｍｍ×１００ｍｍ）を得た。
これらの試験片を３０ＭＰａの負荷応力で曲げストレスを加え、１日後、２日後、３日後、４日後、７日後、８日後、１０日後、１４日後、１５日後の各試験片の表面状態を肉眼で観察して、耐ストレスクラック性を評価した。その結果を下記表１、表２に示す。
更に、実施例４，９，１０，１１，１２のそれぞれの塩化ビニル系樹脂組成物で燃焼試験用の試験片（６ｍｍ×１００ｍｍ×１００ｍｍ）を作製し、ＩＳＯ５６６０−１の試験方法に基づいて最大発熱速度（ｋｗ／ｍ２）と最大発煙濃度（／ｍ）を測定した。その結果を下記表１、表２に示す。
Moreover, after extruding each vinyl chloride-type resin composition of Examples 1-12 in plate shape, it cut | disconnected and obtained the test piece (5 mm x 20 mm x 100 mm) for a stress crack test.
Bending stress was applied to these specimens with a load stress of 30 MPa, and the surface condition of each specimen after 1 day, 2 days, 3 days, 4 days, 7 days, 8 days, 10 days, 14 days, and 15 days was visually observed. Was observed to evaluate the stress crack resistance. The results are shown in Tables 1 and 2 below.
Further, test pieces (6 mm × 100 mm × 100 mm) for combustion test were prepared from the vinyl chloride resin compositions of Examples 4, 9, 10, 11, and 12, and the maximum was obtained based on the test method of ISO5660-1. The heat generation rate (kw / m 2 ) and the maximum smoke generation concentration (/ m) were measured. The results are shown in Tables 1 and 2 below.
［比較例１〜６］
比較のために、下記表３に示す塩化ビニル系樹脂組成物を調製し、実施例１〜１２と同様に試験片を作製して、実施例１〜１２と同様に引張試験とストレスクラック試験と燃焼試験を行った。その結果を下記表３に示す。
[Comparative Examples 1-6]
For comparison, a vinyl chloride resin composition shown in Table 3 below was prepared, and test pieces were prepared in the same manner as in Examples 1 to 12. A combustion test was conducted. The results are shown in Table 3 below.
なお、上記表１〜表３において、「〇」はクラック、メラツキ無し、「〇△」はメラツキ発生（クレーズに至らない表面光沢の低下等）、「△」は微小クレーズ発生、「△×」はクレーズ発生（微細な線状の表面割れ）、「×」はクラック発生、「折」は試験片折損、を表す。 In Tables 1 to 3, “◯” indicates cracks and no glazing, “◯ △” indicates glazing (decrease in surface gloss that does not lead to craze, etc.), “△” indicates microcrazing, and “△ ×”. Indicates craze generation (fine linear surface cracks), “x” indicates crack generation, and “fold” indicates test piece breakage.
上記表１、表２から、重合度８００〜３０００の塩化ビニル樹脂（塩化ビニル単独重合体）、ＥＶＡ共重合塩化ビニル樹脂、アクリルグラフト共重合塩化ビニル樹脂などを主成分とし、安定剤としてメチル錫メルカプタイト、オクチル錫メルカプタイト、ジブチル錫マレートなどの錫系安定剤を含み、滑剤として脂肪酸系滑剤（ステアリン酸、ステアリンアルコール）を含み、加工助剤としてアクリル系加工助剤（アクリル酸エステル、メタクリル酸エステル）を含んだ、実施例１〜１２の塩化ビニル系樹脂試験片は、引張試験の成績が最も悪いもの（実施例７）でも、ＴＭＡＨ水溶液中に３日浸漬した後の引張強度が、浸漬前の引張強度に対して９０％以上（９５％）であり、優れた耐ＴＭＡＨ性を有することが判る。さらに、実施例１〜１２では、ＴＭＡＨ水溶液中に４８時間浸漬後の引張試験における引張強度が全て６０ＭＰａ以上であり、耐ＴＭＡＨ溶液の浸漬後の引張強度も優れていることがわかる。そして、ストレスクラック試験の成績が最も悪いもの（実施例７）でも、２日後まではクラックもメラツキも発生することがなく、良好な耐ストレスクラック性を有しており、また、燃焼試験についても、最大発熱速度が９７．４〜１６８．７（ｋｗ／ｍ２）、最大発煙濃度が５．０〜７．３（／ｍ）であって、良好な難燃性を有することが判る。 From Tables 1 and 2 above, vinyl chloride resin (vinyl chloride homopolymer) having a polymerization degree of 800 to 3000, EVA copolymerized vinyl chloride resin, acrylic graft copolymerized vinyl chloride resin and the like as a main component, and methyl tin as a stabilizer Contains tin stabilizers such as mercaptites, octyl tin mercaptites, dibutyltin malates, fatty acid lubricants (stearic acid, stearic alcohol) as lubricants, acrylic processing aids (acrylic esters, methacrylic esters) as processing aids ), The vinyl chloride resin test pieces of Examples 1 to 12 having the worst tensile test results (Example 7) had a tensile strength after immersion in an aqueous TMAH solution of 3 days before immersion. It is 90% or more (95%) with respect to the tensile strength, and it can be seen that it has excellent TMAH resistance. Furthermore, in Examples 1-12, it turns out that all the tensile strengths in the tensile test after 48-hour immersion in TMAH aqueous solution are 60 Mpa or more, and the tensile strength after immersion of a TMAH-resistant solution is also excellent. And even if the result of the stress crack test is the worst (Example 7), there is no crack or unevenness until 2 days later, it has good stress crack resistance, and the combustion test also The maximum heat generation rate is 97.4 to 168.7 (kw / m 2 ), the maximum smoke concentration is 5.0 to 7.3 (/ m), and it can be seen that it has good flame retardancy.
特に、ＥＶＡ共重合塩化ビニル樹脂を主成分とし、錫系安定剤、滑剤、加工助剤に加えて、更に塩素化ポリエチレンを補強材として含有させた実施例１１、実施例１２の塩化ビニル系樹脂試験片は、ＴＭＡＨ水溶液に１５日浸漬した後の引張強度と浸漬前の引張強度が同じで１００％を維持しており、また、耐ストレスクラック性については、１５日経過した後でもクラックやメラツキが見られなかった。このことから、ＥＶＡ共重合塩化ビニル樹脂や補強材の塩素化ポリエチレンは、耐ＴＭＡＨ性、耐ストレスクラック性の向上に極めて有効であることが判る。 In particular, the vinyl chloride resins of Examples 11 and 12 which are mainly composed of EVA copolymerized vinyl chloride resin and contain chlorinated polyethylene as a reinforcing material in addition to tin stabilizer, lubricant and processing aid. The test piece has the same tensile strength after dipping in a TMAH aqueous solution for 15 days and the tensile strength before dipping, and is maintained at 100%. Was not seen. From this, it can be seen that EVA copolymerized vinyl chloride resin and chlorinated polyethylene as a reinforcing material are extremely effective in improving TMAH resistance and stress crack resistance.
これに対し、比較例３，５の塩化ビニル系樹脂試験片のように、重合度７００の塩化ビニル樹脂を主成分とし、アクリル系滑剤（またはアクリル系滑剤と脂肪酸アミド系滑剤と少量の脂肪酸系滑剤との混合物）と、補強材としてアクリル系補強材又はＭＢＳと塩素化ポリエチレンの混合物を含有させたものは、錫系安定剤を含んでいても、ＴＭＡＨ水溶液に２日浸漬した後の引張強度が浸漬前の引張強度の９０％以下となり、耐ストレスクラック性も１日後から微小クレーズ又はクレーズが発生した。このことから、重合度が８００よりも低い７００である塩化ビニル樹脂（塩化ビニル単独重合体）は、耐ＴＭＡＨ性及び耐ストレスクラック性の向上に寄与しないことが判る。 On the other hand, like a vinyl chloride resin test piece of Comparative Examples 3 and 5, the main component is a vinyl chloride resin having a polymerization degree of 700, and an acrylic lubricant (or an acrylic lubricant and a fatty acid amide lubricant and a small amount of a fatty acid resin are used. A mixture of a lubricant and an acrylic reinforcing material or a mixture of MBS and chlorinated polyethylene as a reinforcing material, even if it contains a tin stabilizer, the tensile strength after being immersed in an aqueous TMAH solution for 2 days Was 90% or less of the tensile strength before dipping, and the stress crack resistance was also microcrazed or crazed after one day. From this, it can be seen that the vinyl chloride resin (vinyl chloride homopolymer) having a polymerization degree of 700 lower than 800 does not contribute to the improvement of TMAH resistance and stress crack resistance.
また、比較例４，６の塩化ビニル系樹脂試験片のように、重合度８００の塩化ビニル樹脂（塩化ビニル単独重合体）を主成分とし、錫系安定剤と少量のアクリル系加工助剤を含有させていても、補強材として塩素化ポリエチレンを含有させてなく、脂肪酸系滑剤以外のアクリル系滑剤や炭化水素系滑剤を含有させたものは、ＴＭＡＨ水溶液に１日浸漬するだけで引張強度が浸漬前の引張強度の９０％を下回り、また、耐ストレスクラック性も１日後から微小クレーズ又はクレーズが発生した。このことから、補強材としての塩素化ポリエチレンや脂肪酸系滑剤は、耐ＴＭＡＨ性及び耐ストレスクラック性の向上に有効であることが判る。 Further, as in the vinyl chloride resin test pieces of Comparative Examples 4 and 6, the main component is a vinyl chloride resin having a polymerization degree of 800 (vinyl chloride homopolymer), a tin stabilizer and a small amount of acrylic processing aid. Even if it is contained, the chlorinated polyethylene is not contained as a reinforcing material, and those containing an acrylic lubricant or hydrocarbon lubricant other than the fatty acid lubricant have a tensile strength just by immersing in a TMAH aqueous solution for one day. Less than 90% of the tensile strength before dipping, and the microcraze or craze was generated from the stress crack resistance after 1 day. From this, it can be seen that chlorinated polyethylene and fatty acid-based lubricant as a reinforcing material are effective in improving TMAH resistance and stress crack resistance.
また、比較例１の塩化ビニル系樹脂試験片のように、重合度１０００の塩化ビニル樹脂（塩化ビニル単独重合体）を主成分とし、安定剤としてジブチル錫マレート、滑剤としてアクリル系滑剤を含有させたものは、補強材として塩素化ポリエチレンを含み、アクリル系加工助剤を含んでいても、ＴＭＡＨ水溶液に２日浸漬すれば引張強度が浸漬前の９０％以下となり、耐ストレスクラック性も３日後には微小クレーズが発生した。このことから、錫系安定剤であってもマレート系安定剤はメルカプタイト系安定剤ほど有効でなく、また、アクリル系滑剤は耐ＴＭＡＨ性及び耐ストレスクラック性の向上に殆ど寄与しないことが判る。 Further, like the vinyl chloride resin test piece of Comparative Example 1, a vinyl chloride resin having a polymerization degree of 1000 (vinyl chloride homopolymer) is the main component, dibutyltin maleate is included as a stabilizer, and an acrylic lubricant is included as a lubricant. Even if it contains chlorinated polyethylene as a reinforcing material and acrylic processing aid, if it is immersed in an aqueous TMAH solution for 2 days, the tensile strength will be 90% or less before immersion, and the stress crack resistance will also be 3 days. Later, fine crazing occurred. This shows that even if it is a tin stabilizer, the malate stabilizer is not as effective as the mercaptite stabilizer, and the acrylic lubricant hardly contributes to the improvement of TMAH resistance and stress crack resistance.
更に、比較例２の塩化ビニル系樹脂試験片のように、重合度１０００の塩化ビニル樹脂（塩化ビニル単独重合体）を主成分とし、鉛系安定剤やＭＢＳ補強材を含有させたものは、ＴＭＡＨ水溶液に４日浸漬すれば引張強度が浸漬前の９０％未満となり、耐ストレスクラック性も７日後には微小クレーズが発生した。このことから、鉛系安定剤やＭＢＳ補強材も、耐ＴＭＡＨ性及び耐ストレスクラック性の向上には、錫系安定剤や塩素化ポリエチレンほど有効でないことが判る。 Further, as in the vinyl chloride resin test piece of Comparative Example 2, a vinyl chloride resin having a polymerization degree of 1000 (vinyl chloride homopolymer) as a main component and containing a lead stabilizer and an MBS reinforcing material is as follows: When immersed in a TMAH aqueous solution for 4 days, the tensile strength became less than 90% before immersion, and the stress crack resistance also developed microcraze after 7 days. From this, it can be seen that lead-based stabilizers and MBS reinforcing materials are not as effective as tin-based stabilizers and chlorinated polyethylene in improving TMAH resistance and stress crack resistance.
Claims (4)
濃度２５質量％のテトラメチルアンモニウムハイドロオキサイド（以下、ＴＭＡＨと記す）水溶液中に３０℃で４８時間浸漬した後のＪＩＳ Ｋ７１６２−１Ｂ／５０による引張強度が、浸漬前の引張強度に対して９０％以上であることを特徴とする、耐ＴＭＡＨ性を有する塩化ビニル系樹脂成形体。 A vinyl chloride resin molded article comprising a vinyl chloride resin or a copolymerized vinyl chloride resin having a polymerization degree of 800 to 4000 as a main component and containing a tin stabilizer and a fatty acid lubricant,
The tensile strength according to JIS K7162-1B / 50 after being immersed in an aqueous solution of 25% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) at 30 ° C. for 48 hours is 90% of the tensile strength before immersion. A vinyl chloride resin molded article having TMAH resistance, which is as described above.
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| JP2002037972A (en) * | 2000-07-28 | 2002-02-06 | Sekisui Chem Co Ltd | High-polymerization degree vinyl chloride-based resin composition and molded form thereof |
| JP2002226659A (en) * | 2001-02-01 | 2002-08-14 | Takiron Co Ltd | Flame retardant polyvinyl chloride resin molded article |
| JP2006265373A (en) * | 2005-03-24 | 2006-10-05 | Denki Kagaku Kogyo Kk | Vinyl chloride resin composition comprising maleimide copolymer and vinyl chloride polymer |
| JP2008013632A (en) * | 2006-07-04 | 2008-01-24 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition for restored pipe and vinyl chloride-based resin restored pipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002037972A (en) * | 2000-07-28 | 2002-02-06 | Sekisui Chem Co Ltd | High-polymerization degree vinyl chloride-based resin composition and molded form thereof |
| JP2002226659A (en) * | 2001-02-01 | 2002-08-14 | Takiron Co Ltd | Flame retardant polyvinyl chloride resin molded article |
| JP2006265373A (en) * | 2005-03-24 | 2006-10-05 | Denki Kagaku Kogyo Kk | Vinyl chloride resin composition comprising maleimide copolymer and vinyl chloride polymer |
| JP2008013632A (en) * | 2006-07-04 | 2008-01-24 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition for restored pipe and vinyl chloride-based resin restored pipe |
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