【考案の詳細な説明】[Detailed explanation of the idea]
産業上の利用分野
本考案は、加温された種々の薬液を入れる貯槽
や容器等を製造するような場合に原料板として好
適に使用される樹脂積層板に関する。
従来の技術とその問題点
半導体等の製造に用いるエツチング液その他の
薬液は、その中に不純物が含まれると不良品発生
の原因となるため、耐薬品性の良好な塩化ビニル
樹脂板を加工して造つた貯槽や容器に入れて使用
する場合が多い。このような貯槽や容器は、その
原料板として用いられる塩化ビニル樹脂板の加工
性が良いので容易に製作できるが、その反面、該
樹脂板の熱変形温度は約76℃（荷重18.6Kg／cm2）
程度であり、あまり高い温度の薬液を入れること
はできない。けれども、エツチング液等の薬液
は、一般に温度が高いほど反応性が増すので、処
理効率の向上を図る観点から耐熱温度の高い貯槽
や容器を製作することが望ましく、そのため原料
板として少なくとも80℃以上の熱変形温度を有す
る塩化ビニル系の樹脂板が要望されるようになつ
てきた。
このような熱変形温度の高い塩化ビニル系の樹
脂板としては、塩素含量の多い塩素化塩化ビニル
樹脂板が従来より知られている。しかしながら、
塩素化塩化ビニル樹脂板は、塩化ビニル樹脂板に
比べると加工性が悪いため貯槽や容器の製作が容
易でなく、しかも塩素含量が多いため耐薬品性に
劣るという問題があり、薬液等の貯槽や容器の原
料板としては不向きである。
考案の目的
本考案は上記事情に鑑みてなされたもので、そ
の目的とするところは、加工性、耐薬品性が良好
で熱変形温度（荷重18.6Kg／cm2で測定、以下同
じ）が80℃以上と高く、加温した薬液を入れる貯
槽や容器等の原料板として好適に用いられる塩化
ビニル系の樹脂積層板を提供することにある。
目的を達成するための手段
かかる目的を達成するため、本考案の樹脂積層
板は、芯層が塩化ビニル樹脂と塩素化塩化ビニル
樹脂の混合物又は交互積層物からなり、この芯層
の上下の表面層が塩化ビニル樹脂からなる積層板
であつて、積層板中の塩化ビニル樹脂と塩素化塩
化ビニル樹脂の割合が重量比で３：１〜１：２で
あることを特徴としている。
考案の作用
本考案の樹脂積層板のように、芯層中に塩化ビ
ニル樹脂より耐熱性の良い塩素化塩化ビニル樹脂
が含まれ、積層板中の塩化ビニル樹脂と塩素化塩
化ビニル樹脂の割合が重量比で３：１〜１：２、
つまり塩素化塩化ビニル樹脂が樹脂全体の1/4〜
２／３を占めていると、塩化ビニル樹脂単独の板に
比べて熱変形温度が!?かに高くなり、後述の実験
データに示すように80℃以上となる。
しかも、本考案の樹脂積層板は、貯槽や容器を
製作した場合に薬液と接する表面層が耐薬品性の
良好な塩化ビニル樹脂より成るので、該表面層が
薬液に侵され不純物が混り込む心配もない。
また、本考案のように表面層が加工性の良い塩
化ビニル樹脂からなり、芯層にも塩化ビニル樹脂
が含まれて、塩化ビニル樹脂が樹脂全体の1/3〜
３／４を占めていると、塩素化塩化ビニル樹脂単独
の板に比べて加熱曲げ加工性等が遥かに向上し、
従来の塩化ビニル樹脂単独の板とあまり変わらな
い程度の容易さで貯槽や容器を製作することがで
きる。
塩化ビニル樹脂と塩素化塩化ビニル樹脂の割合
が上記の重量比の範囲を逸脱し、塩素化塩化ビニ
ル樹脂が全体の1/4より少なくなると、加工性は
向上するけれども耐熱性が低下して80℃以上の熱
変形温度が得難くなり、逆に、2/3より多くなる
と、耐熱性は向上するけれども加工性が大幅に低
下するので、いずれの場合も本考案の目的を充分
に達成できない。
実施例
以下、実施例を挙げて本考案を詳述する。
第１図は本考案の一実施例を示す端部拡大断面
図である。この実施例の樹脂積層板Ｂは、塩素化
塩化ビニル樹脂と塩化ビニル樹脂の混合物よりな
る芯層２ｂの上下両面に、塩化ビニル樹脂よりな
る表面層１ｂ，１ｂを設けたもので、具体的には
塩化ビニル樹脂のカレンダーシート１０（以下、
塩ビシートと記す）を複数枚（図では２枚）積層
し、その上に塩化ビニル樹脂と塩素化塩化ビニル
樹脂との混合樹脂のカレンダーシート３０（以
下、ミツクスシートと記す）を複数枚（図では14
枚）積層し、更にその上に塩ビシート１０を複数
枚（図では２枚）積層して、プレス機で熱圧一体
化したものである。
塩ビシート１０としては塩素含有率が56〜57％
程度、重合度が600〜1500程度の塩化ビニル樹脂
にPb系安定剤、安定化助剤、滑剤、加工助剤等
を添加し、カレンダーロールで混練して厚さ0.5
mmのシートにしたものが使用される。
また、ミツクスシート３０としては、塩素含有
率が60〜70％程度、重合度が300〜1500程度の塩
素化塩化ビニル樹脂と上記の塩化ビニル樹脂を
２：１〜１：２の割合でミツクスした混合樹脂
に、上記の各種添加剤を添加して厚さ0.5mm程度
のシートにしたものが使用される。
これらのシート１０，３０の積層枚数は、用途
や強度その他の諸条件を考慮して決定すればよい
が、得られる積層樹脂板Ｂ中の塩化ビニル樹脂と
塩素化塩化ビニル樹脂の割合が重量比で３：１〜
１：２の範囲内となるように、両シートの枚数の
比率を決定する必要がある。塩化ビニル樹脂と塩
素化塩化ビニル樹脂の割合が上記範囲を逸脱し、
塩素化塩化ビニル樹脂が樹脂全体の1/4より少な
くなると、耐熱性が低下して80℃以上の熱変形温
度が得難くなり、逆に、2/3より多くなると加工
性、特に加熱曲げ加工性の低下が顕著となるから
である。
また、芯層２ａの上下に積層する塩ビシート１
０の枚数は同数とするのが望ましい。枚数が異な
ると、塩ビシート１０とミツクスシート３０との
熱伸縮の差によつて樹脂積層板Ｂに反りを生じる
恐れが出てくるからである。
第２図は本考案の他の実施例を示す端部拡大断
面図である。この実施例の樹脂積層板Ｃは、塩化
ビニル樹脂と塩素化塩化ビニル樹脂の交互積層物
よりなる芯層２ｃの上下両面に、塩化ビニル樹脂
よりなる表面層１ｃ，１c1枚を設けたもので、具
体的には既述の塩ビシート１０の上に、塩素化塩
化ビニル樹脂のカレンダーシート２０（以下、塩
素化塩ビシートと記す）と塩ビシート１０を交互
に複数枚（図では合計17枚）積層し、更にその上
に塩ビシート１０を一枚積層して、プレス機で熱
圧一体化したものである。
塩素化塩ビシート２０としては、塩素含有率が
60〜70％程度、重合度が300〜1500程度の塩素化
塩化ビニル樹脂に既述の添加剤を添加し、カレン
ダーロールで混練して厚さ0.5mmのシートにした
ものが使用される。
この実施例の樹脂積層板Ｃについても、塩化ビ
ニル樹脂と塩素化塩化ビニル樹脂の割合が重量比
で３：１〜１：２の範囲内となるように、塩ビシ
ート１０と塩素化塩ビシート２０の枚数比率を決
定する必要があり、また、上下の表面層を形成す
る塩ビシート１０の枚数は同数とすることが望ま
しい。
以上のような樹脂積層板Ｂ，Ｃはいずれも、芯
層中に耐熱性の良い塩素化塩化ビニル樹脂が含ま
れ、塩化ビニル樹脂と塩素化塩化ビニル樹脂の割
合が重量比で３：１〜１：２の範囲内とされてい
るので、塩化ビニル樹脂単独の板に比べると熱変
形温度が!?かに高くなり、後述の実験データに示
すように80℃以上となる。しかも、貯槽や容器を
製作した場合に薬液と接する表面層が耐薬品性の
良好な塩化ビニル樹脂より成るので、該表面層が
薬液に侵され不純物が混り込む心配もない。ま
た、このように上下の表面層が加工性の良い塩化
ビニル樹脂からなり、芯層にも塩化ビニル樹脂が
含まれていると、塩素化塩化ビニル樹脂単独の板
に比べて加熱曲げ加工性等が遥かに向上するの
で、従来の塩化ビニル樹脂単独の板とあまり変わ
らない程度の容易さで貯槽や容器を製作すること
ができる。
次に、本考案の樹脂積層板について行つた物性
試験を説明する。
下記第１表に揚げる４種類の樹脂積層板の試験
片Ａ，Ｂ，Ｃ，Ｄと、比較例としての塩ビシート
単層板Ｅ及び塩素化塩ビシート単層板Ｆを、プレ
ス機で190℃、11Kg／cm2の条件下に作製し、各試
験片について熱変形温度（荷重18.6Kg／cm2）を測
定した。その結果を同表に示す。更に、25mmφの
棒ヒータを用いて、160℃で３分間、各試験片の
両面接触加熱を行つてから、180度折り曲げて曲
げ加工性を調べた。その結果を同表に示す。尚、
試験片Ａ，Ｄで用いたミツクスシートは塩化ビニ
ル樹脂と塩素化塩化ビニル樹脂を１：１の重量比
で混練したシートであり、また、表中の曲げ加工
性の評価記号の○は曲げ加工性が極めて良好で表
面層に亀裂等が全く発生しなかつたことを、△は
曲げ加工性が普通で表面層に僅かの亀裂等が発生
したことを、×は曲げ加工できなかつたことを意
味している。
INDUSTRIAL APPLICATION FIELD The present invention relates to a resin laminate plate that is suitably used as a raw material plate when manufacturing storage tanks, containers, etc. that contain various heated chemical solutions. Conventional technology and its problems Etching liquids and other chemical solutions used in the manufacture of semiconductors, etc., can cause defective products if they contain impurities. It is often used in a storage tank or container made by hand. Such storage tanks and containers can be easily manufactured because the PVC resin plate used as the raw material plate has good workability. 2 )
It is not possible to put in a chemical solution with a very high temperature. However, the reactivity of chemical solutions such as etching solutions generally increases as the temperature increases, so from the perspective of improving processing efficiency, it is desirable to manufacture storage tanks and containers with a high heat-resistant temperature. There has been a growing demand for vinyl chloride resin plates having a heat distortion temperature of . As such a vinyl chloride resin plate having a high heat distortion temperature, a chlorinated vinyl chloride resin plate with a high chlorine content has been known. however,
Compared to vinyl chloride resin plates, chlorinated vinyl chloride resin plates have poor processability, making it difficult to manufacture storage tanks and containers.Furthermore, due to their high chlorine content, they have poor chemical resistance. It is unsuitable as a raw material board for containers. Purpose of the invention This invention was made in view of the above circumstances, and its purpose is to have good workability and chemical resistance, and a heat distortion temperature (measured at a load of 18.6 kg/cm 2 , the same applies hereinafter) of 80. The object of the present invention is to provide a vinyl chloride-based resin laminate suitable for use as a raw material plate for storage tanks, containers, etc. for storing heated chemical solutions at temperatures as high as 0.degree. C. or higher. Means for Achieving the Object In order to achieve the object, the resin laminate of the present invention has a core layer consisting of a mixture or alternate laminate of vinyl chloride resin and chlorinated vinyl chloride resin, and the upper and lower surfaces of this core layer. It is a laminate in which the layers are made of vinyl chloride resin, and is characterized in that the weight ratio of vinyl chloride resin and chlorinated vinyl chloride resin in the laminate is 3:1 to 1:2. Effect of the invention Like the resin laminate of the invention, the core layer contains chlorinated vinyl chloride resin, which has better heat resistance than vinyl chloride resin, and the ratio of vinyl chloride resin and chlorinated vinyl chloride resin in the laminate is Weight ratio of 3:1 to 1:2,
In other words, chlorinated vinyl chloride resin accounts for 1/4 of the total resin.
If it occupies 2/3, the heat deformation temperature becomes much higher than that of a board made of vinyl chloride resin alone, reaching 80°C or more as shown in the experimental data described below. Moreover, in the resin laminate of the present invention, when a storage tank or container is manufactured, the surface layer that comes into contact with the chemical solution is made of vinyl chloride resin, which has good chemical resistance, so the surface layer is eroded by the chemical solution and impurities are mixed in. No worries. In addition, as in the present invention, the surface layer is made of vinyl chloride resin with good processability, and the core layer also contains vinyl chloride resin.
If it accounts for 3/4, heat bending workability etc. will be much improved compared to a board made of chlorinated vinyl chloride resin alone,
Storage tanks and containers can be manufactured with ease that is not much different from conventional boards made of vinyl chloride resin alone. If the proportion of vinyl chloride resin and chlorinated vinyl chloride resin deviates from the above weight ratio range, and the chlorinated vinyl chloride resin becomes less than 1/4 of the total, processability will improve, but heat resistance will decrease. It becomes difficult to obtain a heat deformation temperature of ℃ or higher, and conversely, if the temperature exceeds 2/3, the heat resistance improves but the workability decreases significantly, so the purpose of the present invention cannot be fully achieved in either case. Examples Hereinafter, the present invention will be described in detail with reference to examples. FIG. 1 is an enlarged end sectional view showing an embodiment of the present invention. The resin laminate B of this example has surface layers 1b, 1b made of vinyl chloride resin on both upper and lower surfaces of a core layer 2b made of a mixture of chlorinated vinyl chloride resin and vinyl chloride resin. is a vinyl chloride resin calendar sheet 10 (hereinafter referred to as
A plurality of sheets (hereinafter referred to as PVC sheets) (two sheets in the figure) are laminated, and a plurality of calender sheets 30 (hereinafter referred to as mix sheets) made of a mixed resin of vinyl chloride resin and chlorinated vinyl chloride resin are laminated on top of the sheets (hereinafter referred to as mix sheets). 14
PVC sheets 10) are laminated, and a plurality of PVC sheets 10 (two sheets in the figure) are laminated on top of the PVC sheets 10, which are then integrated under heat and pressure using a press machine. As PVC sheet 10, the chlorine content is 56-57%
Pb stabilizer, stabilizing aid, lubricant, processing aid, etc. are added to vinyl chloride resin with a degree of polymerization of about 600 to 1500, and the mixture is kneaded with a calendar roll to a thickness of 0.5
mm sheets are used. The mix sheet 30 is a mixture of chlorinated vinyl chloride resin with a chlorine content of about 60 to 70% and a degree of polymerization of about 300 to 1500 and the above vinyl chloride resin in a ratio of 2:1 to 1:2. A sheet of approximately 0.5 mm thick is used by adding the various additives mentioned above to the resin. The number of laminated sheets 10 and 30 may be determined by taking into consideration the use, strength, and other conditions, but the proportion of vinyl chloride resin and chlorinated vinyl chloride resin in the resulting laminated resin board B is determined by the weight ratio. So 3:1~
It is necessary to determine the ratio of the numbers of both sheets so that it is within the range of 1:2. If the ratio of vinyl chloride resin and chlorinated vinyl chloride resin deviates from the above range,
If the amount of chlorinated vinyl chloride resin is less than 1/4 of the total resin, heat resistance will decrease and it will be difficult to obtain a heat distortion temperature of 80℃ or higher.On the other hand, if it is more than 2/3, the processability, especially heat bending This is because the decline in sexual performance becomes noticeable. In addition, PVC sheets 1 are laminated above and below the core layer 2a.
It is desirable that the number of 0s be the same. This is because if the numbers are different, there is a risk that the resin laminate B will warp due to the difference in thermal expansion and contraction between the PVC sheet 10 and the mixed sheet 30. FIG. 2 is an enlarged end sectional view showing another embodiment of the present invention. The resin laminate C of this example has one surface layer 1c, 1c made of vinyl chloride resin on both upper and lower surfaces of a core layer 2c made of an alternate laminate of vinyl chloride resin and chlorinated vinyl chloride resin, Specifically, a plurality of calendar sheets 20 (hereinafter referred to as chlorinated PVC sheets) made of chlorinated vinyl chloride resin and a plurality of PVC sheets 10 (a total of 17 sheets in the figure) are laminated on top of the already described PVC sheet 10. Then, a single PVC sheet 10 was further laminated on top of the PVC sheet 10, and they were integrated under heat and pressure using a press. The chlorinated PVC sheet 20 has a chlorine content of
A chlorinated vinyl chloride resin having a polymerization degree of about 60 to 70% and a polymerization degree of about 300 to 1500 is added with the above-mentioned additives and kneaded with a calender roll to form a sheet with a thickness of 0.5 mm. Regarding the resin laminate C of this example, the PVC sheet 10 and the chlorinated PVC sheet 20 were made so that the ratio of vinyl chloride resin and chlorinated vinyl chloride resin was within the range of 3:1 to 1:2 by weight. It is necessary to determine the ratio of the number of PVC sheets 10, and it is desirable that the number of PVC sheets 10 forming the upper and lower surface layers be the same. Both of the above-mentioned resin laminates B and C contain chlorinated vinyl chloride resin with good heat resistance in the core layer, and the weight ratio of vinyl chloride resin and chlorinated vinyl chloride resin is 3:1 to 3:1. Since the ratio is within the range of 1:2, the heat distortion temperature is much higher than that of a board made of vinyl chloride resin alone, reaching 80°C or higher as shown in the experimental data described below. Furthermore, when the storage tank or container is manufactured, the surface layer that comes into contact with the chemical solution is made of vinyl chloride resin with good chemical resistance, so there is no fear that the surface layer will be eroded by the chemical solution and impurities will be mixed in. In addition, if the upper and lower surface layers are made of vinyl chloride resin with good workability, and the core layer also contains vinyl chloride resin, it will have better heat bending workability than a board made of chlorinated vinyl chloride resin alone. Since the properties are much improved, storage tanks and containers can be manufactured with the same ease as conventional plates made of vinyl chloride resin alone. Next, physical property tests conducted on the resin laminate of the present invention will be explained. Test pieces A, B, C, and D of the four types of resin laminates listed in Table 1 below, as well as a single-layer PVC sheet E and a single-layer chlorinated PVC sheet F as comparative examples, were heated at 190°C in a press. , 11Kg/cm 2 , and the heat distortion temperature (load 18.6Kg/cm 2 ) of each test piece was measured. The results are shown in the same table. Furthermore, using a rod heater with a diameter of 25 mm, contact heating was performed on both sides of each test piece at 160° C. for 3 minutes, and then the test piece was bent 180 degrees to examine bending workability. The results are shown in the same table. still,
The mix sheet used in test specimens A and D is a sheet made by kneading vinyl chloride resin and chlorinated vinyl chloride resin at a weight ratio of 1:1, and the evaluation symbol ○ for bending workability in the table indicates bending workability. △ means that the bending workability was normal and only a few cracks occurred on the surface layer, and × means that bending workability was not possible. ing.
【表】
考案の効果
以上の説明及び試験結果から明らかなように、
本考案は、芯層が塩化ビニル樹脂と塩素化塩化ビ
ニル樹脂の混合物又は交互積層物からなり、この
芯層の上下の表面層が塩化ビニル樹脂からなる積
層板であつて、塩化ビニル樹脂と塩素化塩化ビニ
ル樹脂の割合が重量比で３：１〜１：２である構
成としたため、従来の塩化ビニル樹脂板が有する
優れた耐薬品性と良好な加工性を留保したまま、
熱変形温度を80℃以上に高めることが可能とな
り、従つて、従来より温度の高い薬液等を入れる
貯槽や容器等の原料板として頗る好適に使用する
ことができる。[Table] Effect of the device As is clear from the above explanation and test results,
In the present invention, the core layer is made of a mixture or alternate laminate of vinyl chloride resin and chlorinated vinyl chloride resin, and the upper and lower surface layers of this core layer are laminates made of vinyl chloride resin, and the core layer is a laminate made of vinyl chloride resin and chlorinated vinyl chloride resin. Since the ratio of vinyl chloride resin is 3:1 to 1:2 by weight, it retains the excellent chemical resistance and good processability of conventional vinyl chloride resin plates.
It is possible to increase the heat deformation temperature to 80° C. or higher, and therefore, it can be used very suitably as a raw material plate for storage tanks, containers, etc. that contain chemical solutions, etc., which have a higher temperature than conventional ones.
【図面の簡単な説明】[Brief explanation of drawings]
第１図は本考案の一実施例を示す端部拡大断面
図、第２図は本考案の他の実施例を示す端部拡大
断面図である。
Ｂ，Ｃ……樹脂積層板、１ｂ，１ｃ……表面
層、２ｂ，２ｃ……芯層。
FIG. 1 is an enlarged end sectional view showing one embodiment of the present invention, and FIG. 2 is an enlarged end sectional view showing another embodiment of the invention. B, C... Resin laminate, 1b, 1c... Surface layer, 2b, 2c... Core layer.