JP3475076B2 - Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin composition - Google Patents
Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin compositionInfo
- Publication number
- JP3475076B2 JP3475076B2 JP12116798A JP12116798A JP3475076B2 JP 3475076 B2 JP3475076 B2 JP 3475076B2 JP 12116798 A JP12116798 A JP 12116798A JP 12116798 A JP12116798 A JP 12116798A JP 3475076 B2 JP3475076 B2 JP 3475076B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- inorganic filler
- hydroxysodalite
- resin
- 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.)
- Expired - Fee Related
Links
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- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、塩化ビニル系樹脂
を主成分とする樹脂成形物、塩化ビニル系樹脂組成物、
及びそれに使用する充填剤組成物に関する。特に耐熱性
に悪影響を与えず、耐候性、耐チョーキング性を向上さ
せる特定の無機充填剤を含有する塩化ビニル系樹脂を主
成分とする樹脂成形物、塩化ビニル系樹脂組成物、及び
それに使用する無機充填剤組成物に関する。TECHNICAL FIELD The present invention relates to a resin molded product containing a vinyl chloride resin as a main component, a vinyl chloride resin composition,
And a filler composition used therein. In particular, a resin molded product containing a vinyl chloride-based resin as a main component, which contains a specific inorganic filler that improves weather resistance and choking resistance without adversely affecting heat resistance, and a vinyl chloride-based resin composition, and used therein It relates to an inorganic filler composition.
【0002】[0002]
【従来の技術】塩化ビニル系樹脂は日常の生活におい
て、各種成形物として広く使用されている。特に硬質塩
化ビニル樹脂成形物としては雨樋、パイプ、窓枠、デッ
キ材、ベンチ材等、屋外で使用されるものが多い。一般
に塩化ビニル系樹脂は熱や光に対して不安定で、脱塩酸
反応を起こし易い。又、耐熱性が劣ることから、成形加
工する際に成形物が着色したり、機械的強度が低下した
りする。更に耐候性が劣ることから、成形物を屋外で使
用した場合に劣化を起こし易い等の欠点がある。これら
の欠点を改良するため、通常、塩化ビニル系樹脂には金
属石鹸、鉛系安定剤、スズ系安定剤、紫外線吸収剤、酸
化防止剤、滑剤、充填剤、着色剤等を添加した塩化ビニ
ル系樹脂組成物を使用して塩化ビニル系樹脂成形物を作
っている。2. Description of the Related Art Vinyl chloride resins are widely used as various molded products in daily life. In particular, many hard vinyl chloride resin moldings are used outdoors such as rain gutters, pipes, window frames, deck materials, and bench materials. Generally, vinyl chloride resins are unstable to heat and light and are liable to cause a dehydrochlorination reaction. Further, since the heat resistance is poor, the molded product is colored during the molding process and the mechanical strength is lowered. Further, since the weather resistance is inferior, there is a drawback that the molded product is apt to deteriorate when it is used outdoors. In order to improve these drawbacks, vinyl chloride resin is usually added with vinyl soap containing metal soap, lead stabilizer, tin stabilizer, ultraviolet absorber, antioxidant, lubricant, filler, colorant, etc. A vinyl chloride resin molded product is produced using the resin composition.
【0003】[0003]
【発明が解決しようとする課題】これらの塩化ビニル系
樹脂成形物では剛性、寸法安定性、難燃性の向上等の目
的で、充填剤として炭酸カルシウムを樹脂コンパウンド
に添加している。しかしながら、炭酸カルシウムを添加
し、加工した塩化ビニル系樹脂成形物は耐候性が劣り、
チョーキングと呼ばれる白化現象を引き起こすという欠
点を有している。BRIEF Problems to be Solved stiffness in these vinyl chloride-based resin molded product, the dimensional stability, in a countercurrent Choice purpose of flame retardancy, it is added to the resin compound for calcium carbonate as a filler. However, the vinyl chloride resin molded product obtained by adding and processing calcium carbonate has poor weather resistance,
It has the drawback of causing a whitening phenomenon called choking.
【0004】即ち、炭酸カルシウムを添加し、加工した
塩化ビニル系樹脂成形物を屋外暴露した場合、炭酸カル
シウムを添加しなかった場合に比べて、塩化ビニル系樹
脂の分解により発生した塩酸と化学反応して水溶性の塩
化物となって溶出し、溶出箇所が空洞化してしまい、外
観上成形物表面の炭酸カルシウムが存在していた部分が
凹凸になり、樹脂の劣化と相まってチョーキング現象が
起こるものと考えられる。従って本発明の目的は、耐熱
性、耐候性、耐チョーキング性等が向上した塩化ビニル
系樹脂を主成分とする成形物を提供することである。That is, when a vinyl chloride resin molded product processed by adding calcium carbonate is exposed outdoors, it reacts chemically with hydrochloric acid generated by the decomposition of the vinyl chloride resin, as compared with the case where calcium carbonate is not added. Then, it becomes a water-soluble chloride and elutes, and the elution part becomes hollow, and the part where calcium carbonate was present on the surface of the molded product on the appearance becomes uneven, and the chalking phenomenon occurs together with the deterioration of the resin. it is conceivable that. Therefore, an object of the present invention is to provide a molded product containing a vinyl chloride resin as a main component, which has improved heat resistance, weather resistance, choking resistance, and the like.
【0005】[0005]
【課題を解決するための手段】本発明者らは、前記よう
な従来技術の課題を克服するために鋭意研究を行った結
果、塩化ビニル系樹脂に添加する添加剤として、熱や光
の作用によって発生する塩酸を化学的に中和し、且つ樹
脂成形物に外観形状的な変化を与えにくい性質を有する
特定の無機充填剤を使用することによって、チョーキン
グ現象が起こりにくい塩化ビニル系樹脂成形物が得られ
るという知見を得て本発明を完成した。Means for Solving the Problems As a result of intensive studies to overcome the above-mentioned problems of the prior art, the present inventors have found that the action of heat or light as an additive to be added to a vinyl chloride resin. A vinyl chloride resin molded product that is unlikely to cause the choking phenomenon by using a specific inorganic filler that chemically neutralizes the hydrochloric acid generated by it and that does not easily change the appearance of the resin molded product. The present invention has been completed based on the finding that
【0006】即ち、本発明は、塩化ビニル系樹脂を主成
分とする樹脂に無機充填剤を配合及び成形してなる樹脂
成形物において、該無機充填剤が下記の組成式[I]を
有するヒドロキシソーダライトを主成分とする無機充填
剤であることを特徴とする耐チョーキング性塩化ビニル
系樹脂成形物、耐チョーキング性塩化ビニル系樹脂組成
物及びそれに使用する耐チョーキング性の無機充填剤組
成物を提供する。
Na4Al3Si3O12(OH) [I]That is, the present invention provides a resin molded product obtained by mixing and molding an inorganic filler in a resin containing a vinyl chloride resin as a main component, wherein the inorganic filler has a hydroxy group having the following composition formula [I]. A choking-resistant vinyl chloride resin molded article, a choking-resistant vinyl chloride resin composition, and a choking-resistant inorganic filler composition used for the same, which are inorganic fillers containing sodalite as a main component. provide. Na 4 Al 3 Si 3 O 12 (OH) [I]
【0007】[0007]
【発明の実施の形態】次に好ましい実施の形態を挙げて
本発明を更に詳しく説明する。本発明で使用する塩化ビ
ニル系樹脂を主成分とする樹脂とは、従来公知の塩化ビ
ニルを単量体とする単独の重合体若しくは共重合体を指
す。具体的に挙げると、ポリ塩化ビニル樹脂、塩化ビニ
ル共重合樹脂、例えば、塩化ビニル−酢酸ビニル共重合
樹脂、塩化ビニル−アクリルエステル共重合樹脂、エチ
レン−塩化ビニル共重合樹脂、プロピレン−塩化ビニル
共重合樹脂、アクリロニトリル−塩化ビニル共重合樹脂
等、ポリ塩化ビニリデン樹脂、塩化ビニリデン共重合樹
脂、塩素化ポリオレフィン樹脂等である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The resin containing a vinyl chloride resin as a main component used in the present invention refers to a conventionally known homopolymer or copolymer containing vinyl chloride as a monomer. Specifically, polyvinyl chloride resin, vinyl chloride copolymer resin, for example, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic ester copolymer resin, ethylene-vinyl chloride copolymer resin, propylene-vinyl chloride copolymer resin. Polymerization resins, acrylonitrile-vinyl chloride copolymer resins, polyvinylidene chloride resins, vinylidene chloride copolymer resins, chlorinated polyolefin resins and the like.
【0008】又、これら重合体に従来使用されている公
知の金属石鹸、鉛系安定剤、スズ系安定剤、紫外線吸収
剤、酸化防止剤、滑剤、無機充填剤、着色剤等を1種又
は2種以上添加しても差し支えない。又、添加の方法は
特に限定されず、公知の方法を用いることができる。Further, one of known metal soaps, lead-based stabilizers, tin-based stabilizers, ultraviolet absorbers, antioxidants, lubricants, inorganic fillers, colorants, etc., which have been conventionally used for these polymers, or It is possible to add two or more kinds. The addition method is not particularly limited, and a known method can be used.
【0009】本発明で使用する無機充填剤であるヒドロ
キシソーダライト(塩基性ナトリウムアルミニウムシリ
ケート)について説明する。ヒドロキシソーダライトは
下記の化学式[I]で示される化合物であって、安全性
の高い無害な無機物である。
Na4Al3Si3O12(OH) [I]
このヒドロキシソーダライトは、下記の化学式[II]で
示される含水けい酸アルミニウムを主成分とするカオリ
ン、白陶土或いはチャイナクレーと呼称される鉱物等を
アルカリ処理することで得られる。
Al2Si2O5(OH)4 [II]Hydroxysodalite (basic sodium aluminum silicate) which is an inorganic filler used in the present invention will be described. Hydroxysodalite is a compound represented by the following chemical formula [I] and is a safe and harmless inorganic substance. Na 4 Al 3 Si 3 O 12 (OH) [I] This hydroxysodalite is a mineral called kaolin, white clay or china clay whose main component is hydrous aluminum silicate represented by the following chemical formula [II]. And the like are treated with an alkali. Al 2 Si 2 O 5 (OH) 4 [II]
【0010】例えば、カオリン3モルを10モルの水酸
化ナトリウム水溶液(理論量の25モル%過剰に使用し
て)に添加して、充分に混合し、100℃〜130℃で
加熱する方法、或はカオリンと炭酸ナトリウムを粉末混
合したものを700℃で1時間仮焼し、それを水酸化ナ
トリウム水溶液に添加し、混合したものをオートクレー
ブで150℃で24時間水熱処理する方法等により得ら
れる。但し、上記した原料及び製造方法はその1例であ
り、本発明はこれらに限定されるものではない。For example, a method in which 3 mol of kaolin is added to 10 mol of an aqueous sodium hydroxide solution (used in a 25 mol% excess of the theoretical amount), mixed sufficiently, and heated at 100 ° C to 130 ° C, or Is obtained by, for example, calcining a powder mixture of kaolin and sodium carbonate at 700 ° C. for 1 hour, adding it to an aqueous sodium hydroxide solution, and hydrothermally treating the mixture in an autoclave at 150 ° C. for 24 hours. However, the above-mentioned raw materials and manufacturing method are only examples, and the present invention is not limited to these.
【0011】ヒドロキシソーダライト(塩基性ナトリウ
ムアルミニウムシリケート)と水中における塩酸との常
温における相互作用については、後述するように、塩素
イオンはヒドロキシソーダライト中のナトリウムイオン
により中和され、生成した塩化ナトリウムはヒドロキシ
ソーダライトの結晶外に溶出するが、ヒドロキシソーダ
ライトの結晶構造はその反応後も変わっていないことが
以下の実験から判明した。Regarding the interaction between hydroxysodalite (basic sodium aluminum silicate ) and hydrochloric acid in water at room temperature, as will be described later, chlorine ion is neutralized by sodium ion in hydroxysodalite, and sodium chloride is formed. Was eluted outside the crystals of hydroxysodalite, but it was found from the following experiment that the crystal structure of hydroxysodalite did not change after the reaction.
【0012】ヒドロキシソーダライトを主成分とする白
色粉末(以下単にヒドロキシソーダライトという場合が
ある)0.5グラム(0.448モルに相当する)をビ
ーカーに採り、純水30ミリリットルを加え、スターラ
ーで攪拌する。pHメーターで初めのpHを測定する。
1/10規定の塩酸水溶液5ミリリットルを加え、pH
を測定する。pHの変化が小さくなったところで、更に
1/10規定の塩酸水溶液5ミリリットルを加え、pH
を測定し、1/10規定の塩酸水溶液が合計20ミリリ
ットル(塩酸:2ミリ当量)になるまでこの操作を繰り
返した。その後、反応混合物を濾別し、濾液を1/10
規定の水酸化ナトリウム水溶液で滴定し、上記の反応に
使用されなかった過剰の塩酸を定量する。以上の結果は
下記表1に示した。更に濾過残渣を乾燥機で乾燥した
後、蛍光X線法及びX線回折法(図1及び図2)による
測定を行い、ヒドロキシソーダライトの塩酸による処理
前後を比較した。0.5 g (corresponding to 0.448 mol) of white powder containing hydroxysodalite as a main component (hereinafter sometimes simply referred to as hydroxysodalite) was placed in a beaker, 30 ml of pure water was added, and a stirrer was added. Stir with. Measure the initial pH with a pH meter.
Add 5 ml of 1/10 N hydrochloric acid aqueous solution to adjust pH
To measure. When the change in pH became small, 5 ml of 1/10 N hydrochloric acid aqueous solution was added to adjust the pH.
Was measured, and this operation was repeated until the total amount of the 1/10 N hydrochloric acid aqueous solution became 20 ml (hydrochloric acid: 2 meq). Then, the reaction mixture was filtered off, and the filtrate was 1/10.
Titrate with a defined aqueous sodium hydroxide solution to quantify excess hydrochloric acid not used in the above reaction. The above results are shown in Table 1 below. Further, the filtration residue was dried with a drier and then measured by a fluorescent X-ray method and an X-ray diffraction method (FIGS. 1 and 2) to compare before and after treatment of hydroxysodalite with hydrochloric acid.
【0013】[0013]
【表1】表1:ヒドロキシソーダライトと塩酸の反応 [Table 1] Table 1: Reaction of hydroxysodalite with hydrochloric acid
【0014】上記の結果では、ヒドロキシソーダライト
は更に塩酸を中和する能力を有していることが推察され
るが、0.448モルのヒドロキシソーダライトが1.
27当量の塩酸を中和していることから、1モルのヒド
ロキシソーダライトは2.83当量の塩酸を中和する能
力を有していることが分かった。この2.83当量はヒ
ドロキシソーダライトの水酸基の数2より多い当量であ
る。From the above results, it is inferred that hydroxysodalite has the ability to further neutralize hydrochloric acid, but 0.448 mol of hydroxysodalite is 1.
Since it neutralized 27 equivalents of hydrochloric acid, it was found that 1 mol of hydroxysodalite has the ability to neutralize 2.83 equivalents of hydrochloric acid. This 2.83 equivalent is equivalent to more than two hydroxyl groups of hydroxysodalite.
【0015】上記の処理前のヒドロキシソーダライト及
びその塩酸処理をした濾過残渣の乾燥物について蛍光X
線法で元素分析を行った。Regarding the dried product of hydroxysodalite before the above-mentioned treatment and its hydrochloric acid-treated filtration residue, fluorescence X
Elemental analysis was performed by the line method.
【表2】表2:蛍光X線法による塩酸処理前及び処理後
のヒドロキシソーダライトの元素分析(%は重量%であ
る)
Table 2: Elemental analysis of hydroxysodalite before and after hydrochloric acid treatment by fluorescent X-ray method (% is% by weight)
【0016】ヒドロキシソーダライトと塩酸との反応を
酸性サイドで終了させ、濾別したにもかかわらず、処理
生成物であるヒドロキシソーダライト中に塩素が検出さ
れていないことから、水中におけるヒドロキシソーダラ
イトと塩酸との反応には、高温時にヒドロキシソーダラ
イトと塩化水素ガスとの反応で起きたような水酸基が塩
素と置換してソーダライト(ナトリウムアルミニウムク
ロライドシリケート)を生成するような反応は起こって
いない。塩酸処理前と処理後におけるヒドロキシソーダ
ライト中の酸化物の含有量を比較すると酸化ナトリウム
が約半分強に減少している。このことから水溶液中での
ヒドロキシソーダライトと塩酸との反応は塩酸によるヒ
ドロキシソーダライトからのナトリウムイオンの溶出で
あると考えられる。Despite the fact that the reaction between hydroxysodalite and hydrochloric acid was terminated on the acidic side and filtered off, no chlorine was detected in the treated product, hydroxysodalite. There is no reaction in which the hydroxyl group replaces chlorine to form sodalite (sodium aluminum chloride silicate) as in the reaction between hydroxysodalite and hydrogen chloride gas at high temperature. . Comparing the content of oxides in the hydroxysodalite before and after the treatment with hydrochloric acid, the content of sodium oxide was reduced to about half or more. From this, it is considered that the reaction between hydroxysodalite and hydrochloric acid in the aqueous solution is elution of sodium ions from hydroxysodalite with hydrochloric acid.
【0017】又、処理前のヒドロキシソーダライト及び
その塩酸処理物についてX線回折法で結晶の比較を行っ
たが、ヒドロキシソーダライト(図1)及びその塩酸処
理物のデータ(図2)から両者が結晶的には変化してい
ないことが伺える。以上の結果から、ヒドロキシソーダ
ライトは熱又は光の作用で発生する塩酸を中和処理をし
て無害化し得る機能を有し、塩化ビニル系樹脂に対する
耐チョーキング性添加剤として優れた効果を有する。Crystals of hydroxysodalite before treatment and its hydrochloric acid-treated product were compared by X-ray diffraction. From the data of hydroxysodalite (FIG. 1) and its hydrochloric acid-treated product (FIG. 2), both were compared. It can be seen that has not changed crystallinely. These results, hydroxy sodalite has a function that can be detoxified by a neutralizing treatment with hydrochloric acid generated by the action of heat or light, for vinyl chloride-based resin
It has an excellent effect as a choking resistance additive.
【0018】本発明の耐チョーキング性塩化ビニル系樹
脂成形物は、塩化ビニル系樹脂を主成分とする樹脂に上
記の耐チョーキング性を有するヒドロキシソーダライト
を主成分とする無機充填剤を公知の方法に準じて、必要
に応じて他の添加剤と共に配合及び混合し、成形機に供
して所定の形状に成形して得られる。The choking-resistant vinyl chloride resin molded product of the present invention comprises a resin containing vinyl chloride-based resin as a main component and an inorganic filler containing hydroxysodalite as the main component having the above-mentioned choking resistance as a main component by a known method. According to the above, it is obtained by blending and mixing it with other additives as required, and using a molding machine to mold it into a predetermined shape.
【0019】ヒドロキシソーダライトの塩化ビニル系樹
脂を主成分とする樹脂に対する使用量は、樹脂100重
量部に対し、該ヒドロキシソーダライトを主成分をする
無機充填剤が0.05〜100重量部である。ヒドロキ
シソーダライトの量が前記範囲を上回ると、得られる組
成物の成形加工性の低下及び成形物の強度の低下を引き
起こすおそれがあり、一方、ヒドロキシソーダライトの
量が前記範囲を下回った場合には、得られる成形物にお
いて耐候性や耐チョーキング性等の向上が認められない
おそれがある。ヒドロキシソーダライトの樹脂への添加
方法は特に限定されず、従来公知の方法でよい。例え
ば、塩化ビニル系樹脂を主成分とする樹脂にヒドロキシ
ソーダライトを直接配合し、混練及び成形加工する方法
の他、成形に使用する樹脂成分、可塑剤或いは滑剤等に
予めヒドロキシソーダライトを高濃度で分散しておいた
無機充填剤組成物(所謂マスターバッチ)を使用する方
法が挙げられる。The amount of hydroxysodalite used with respect to the resin containing vinyl chloride as a main component is 0.05 to 100 parts by weight of the inorganic filler containing hydroxysodalite as a main component with respect to 100 parts by weight of the resin. is there. If the amount of hydroxysodalite exceeds the above range, it may cause deterioration of the molding processability of the obtained composition and the strength of the molded product, while if the amount of hydroxysodalite is below the above range. May not improve the weather resistance or the chalking resistance of the obtained molded product. The method of adding hydroxysodalite to the resin is not particularly limited and may be a conventionally known method. For example, in addition to the method of directly mixing hydroxysodalite with a resin containing vinyl chloride resin as a main component, kneading and molding, a high concentration of hydroxysodalite is previously added to a resin component, a plasticizer or a lubricant used for molding. The method of using the inorganic filler composition (so-called masterbatch) which has been dispersed in 1.
【0020】上記無機充填剤組成物中のヒドロキシソー
ダライトを主成分とする無機充填剤の含有率は凡そ5〜
95重量%である。この組成物に使用する樹脂成分、可
塑剤或いは滑剤等としては、従来同様の目的に使用され
ているもの、例えば、塩化ビニル系樹脂、ポリスチレ
ン、ポリエチレン系樹脂、ポリプロピレン系樹脂、(メ
タ)アクリル酸エステル系樹脂、ポリエステル系樹脂等
の樹脂、フタル酸エステル系、ヘキサハイドロフタル酸
エステル系、セバシン酸エステル系、アジピン酸エステ
ル系、リン酸エステル系、高沸点炭化水素系等の可塑
剤、パルミチン酸マグネシウム、オレイン酸カルシウ
ム、オレイン酸コバルト、ステアリン酸リチウム、ステ
アリン酸マグネシウム、ステアリン酸亜鉛、ステアリン
酸カルシウム、12−ヒドロキシステアリン酸カルシウ
ム等の金属石けん、ステアリン酸アミド、パルミチン酸
アミド、12−ヒドロキシステアリン酸アミド等の高級
脂肪酸アミド等の滑剤が挙げられる。The content of the inorganic filler containing hydroxysodalite as a main component in the above-mentioned inorganic filler composition is approximately 5 to 5.
It is 95% by weight. The resin component, plasticizer, lubricant, etc. used in this composition are those used for the same purpose as before, such as vinyl chloride resin, polystyrene, polyethylene resin, polypropylene resin, (meth) acrylic acid. Ester-based resins, polyester-based resins, phthalate-based, hexahydrophthalate-based, sebacate-based, adipate-based, phosphate-based, high-boiling hydrocarbon-based plasticizers, palmitic acid Metal soaps such as magnesium, calcium oleate, cobalt oleate, lithium stearate, magnesium stearate, zinc stearate, calcium stearate, and 12-hydroxy calcium stearate, stearic acid amide, palmitic acid amide, 12-hydroxystearic acid amide. Include lubricants such as higher fatty acid amides and the like.
【0021】上記無機充填剤組成物を調製する1例とし
ては、例えば、マスターバッチ用樹脂にヒドロキシソー
ダライトを主成分とする無機充填剤と分散剤とを配合
し、更に必要に応じて上記したその他の添加剤を添加し
てヘンシェルミキサー等の混合機にて配合物を混合し、
得られた混合物を更に加熱した二本ロールミルで混練
し、冷却後粉砕機で粉砕するか、或いは押出機により押
出成形してビーズ状、ペレット状或いは柱形状に成形す
る方法が挙げられる。As an example of preparing the above-mentioned inorganic filler composition, for example, a master batch resin is mixed with an inorganic filler containing hydroxysodalite as a main component and a dispersant, and if necessary, the above-mentioned components are added. Add other additives and mix the mixture with a mixer such as a Henschel mixer.
Examples of the method include kneading the obtained mixture with a heated two-roll mill, cooling and pulverizing with a pulverizer, or extrusion molding with an extruder to form beads, pellets, or columns.
【0022】本発明において、着色した塩化ビニル系樹
脂成形物を得る場合には、従来公知の有機顔料及び無機
顔料を着色剤として使用する。顔料としては、例えば、
フタロシアニンブルー顔料、フタロシアニングリーン顔
料等のフタロシアニン系顔料、溶性アゾ系顔料、不溶性
アゾ系顔料、ポリ縮合アゾ系顔料等のアゾ系顔料、アゾ
メチンアゾ系顔料等、アゾメチン系顔料、イソインドリ
ノン系顔料、キナクリドン系顔料、アンスラキノン系顔
料、ジオキサジン系顔料及びペリレン系顔料等の有機顔
料、カーボンブラック、酸化チタン系白色顔料、酸化チ
タン系黄色顔料、酸化チタン系黒色顔料、複合酸化物系
顔料、群青、ベンガラ等の無機充填剤顔料が挙げられ
る。In the present invention, when a colored vinyl chloride resin molded product is obtained, conventionally known organic pigments and inorganic pigments are used as colorants. As the pigment, for example,
Phthalocyanine pigments such as phthalocyanine blue pigment and phthalocyanine green pigment, soluble azo pigments, insoluble azo pigments, azo pigments such as polycondensed azo pigments, azomethine azo pigments, azomethine pigments, isoindolinone pigments, quinacridone Pigments, anthraquinone pigments, organic pigments such as dioxazine pigments and perylene pigments, carbon black, titanium oxide white pigments, titanium oxide yellow pigments, titanium oxide black pigments, complex oxide pigments, ultramarine blue, red iron oxide Inorganic filler pigments such as
【0023】本発明において使用するヒドロキシソーダ
ライトの塩化ビニル系樹脂に対する作用について述べ
る。一般に塩化ビニル系樹脂は、熱や光に対して不安定
で、加熱成形加工の際に成形物が着色したり、機械的強
度が低下したり、又、耐候性が劣り、成形物を屋外で使
用した場合に劣化を起こし易い。その原因は、塩化ビニ
ル系樹脂が熱や光によって脱塩酸反応を起こし、又、そ
れが更に脱塩酸を誘発し、樹脂の劣化を促進している。
本発明においては前記ヒドロキシソーダライトのナトリ
ウムイオンが上記の発生した塩酸を中和する。しかも、
ヒドロキシソーダライトの結晶からナトリウムイオンが
溶出した後もヒドロキシソーダライトは水に不溶性であ
り、充填剤粒子としての形状や体積も殆ど変化せず、無
機充填剤としての機能を維持する。従ってヒドロキシソ
ーダライトは塩化ビニル系樹脂を主成分とする樹脂の耐
チョーキング性の無機充填剤として優れた効果を有す
る。The action of hydroxysodalite used in the present invention on a vinyl chloride resin will be described. Generally, vinyl chloride resin is unstable to heat and light, and the molded product is colored during heat molding, its mechanical strength is reduced, and its weather resistance is poor. Deteriorates easily when used. The cause is that the vinyl chloride resin causes a dehydrochlorination reaction due to heat and light, and it further induces dehydrochlorination, which accelerates the deterioration of the resin.
In the present invention, the sodium ion of the hydroxy sodalite neutralizes the generated hydrochloric acid. Moreover,
Even after sodium ions are eluted from the crystals of hydroxysodalite, the hydroxysodalite is insoluble in water, its shape and volume as filler particles hardly change, and the function as an inorganic filler is maintained. Therefore, hydroxysodalite is resistant to vinyl chloride resin-based resins.
It has an excellent effect as an inorganic filler having a chalking property .
【0024】[0024]
【実施例】次に合成例、実施例及び比較例を挙げて本発
明を更に具体的に説明するが、本発明は下記の合成例及
び実施例に限定されるものではない。尚、文中、部又は
%とあるのは特に断りのない限り重量基準である。EXAMPLES Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Synthesis Examples and Examples. In the text, parts and% are based on weight unless otherwise specified.
【0025】合成例1
カオリン(純カオリン成分の含有率:98%)100.
0部を10%水酸化ナトリウム水溶液507.2部に加
え、充分混合し、得られた分散液を陶器製の容器に入
れ、乾燥機中で100℃〜125℃で120時間加熱し
た。得られた白色の板状物を粗砕し、1,000部の水
中に投入し、デカンテーションでアルカリ分を洗浄及び
除去した。洗浄した粒状物を更に磨砕し、1,000部
の水中に投入し、撹拌及び濾過をした。濾液が中性にな
るまで水洗し、乾燥及び粉砕することによって白色粉末
を得た。得られた白色粉末をX線回折法で分析した結果
(図1)、ヒドロキシソーダライトであることが確認さ
れた。更に蛍光X線分析法により成分を分析した結果、
ヒドロキシソーダライト成分の含有率がほぼ100%で
あることが確認された。以下、上記で得られたヒドロキ
シソーダライトを無機充填剤HSL−1と称する。Synthesis Example 1 Kaolin (content of pure kaolin component: 98%) 100.
0 part was added to 507.2 parts of a 10% sodium hydroxide aqueous solution, mixed well, and the obtained dispersion was put in a pottery container and heated in a dryer at 100 ° C. to 125 ° C. for 120 hours. The obtained white plate-like material was roughly crushed, put into 1,000 parts of water, and the alkali content was washed and removed by decantation. The washed granular material was further ground, put into 1,000 parts of water, stirred and filtered. The filtrate was washed with water until it became neutral, dried and pulverized to obtain a white powder. The white powder obtained was analyzed by X-ray diffractometry (FIG. 1), and it was confirmed to be hydroxysodalite. As a result of further analyzing the components by X-ray fluorescence analysis,
It was confirmed that the content of the hydroxy sodalite component was almost 100%. Hereinafter, the hydroxysodalite obtained above will be referred to as an inorganic filler HSL-1.
【0026】合成例2
合成例1と同様にして白陶土(純カオリン成分の含有
率:46%)21.51部を111.1部の10%水酸
化ナトリウム水溶液に加え、充分混合し、得られた分散
液を陶器製の容器に入れ、乾燥機中で100℃〜125
℃で120時間加熱した。得られた白色の板状物を粗砕
し、デカンテーションでアルカリ分を洗浄及び除去し、
得られた粒状物を更に磨砕し、水中で撹拌及び濾過をし
た。濾液が中性になるまで水洗し、乾燥及び粉砕して白
色粉末を得た。Synthesis Example 2 21.51 parts of white porcelain clay (content of pure kaolin component: 46%) were added to 111.1 parts of 10% sodium hydroxide aqueous solution in the same manner as in Synthesis Example 1 and mixed thoroughly to obtain Put the resulting dispersion in a pottery container and dry in a dryer at 100 ° C to 125 ° C.
Heat at 120 ° C. for 120 hours. The obtained white plate-like material is roughly crushed, the alkali content is washed and removed by decantation,
The granules obtained were further ground, stirred and filtered in water. The filtrate was washed with water until neutral, dried and pulverized to obtain a white powder.
【0027】得られた白色粉末をX線回折法で分析した
結果、この白色粉末はヒドロキシソーダライトを主成分
とし、又、酸化けい素も含有していることが確認され
た。更に蛍光X線分析法により分析した結果、ヒドロキ
シソーダライト成分の含有率は84%で、酸化けい素成
分は16%であった。原料白陶土中の酸化けい素成分は
前記の水酸化ナトリウムとの反応でかなりの部分が水溶
性に変わり、水洗浄により除去されている。以下、上記
で得られたヒドロキシソーダライトを主成分とする無機
物を無機充填剤HSL−2と称する。As a result of an X-ray diffraction analysis of the obtained white powder, it was confirmed that this white powder contains hydroxysodalite as a main component and also contains silicon oxide. As a result of further analysis by a fluorescent X-ray analysis method, the content of the hydroxysodalite component was 84% and the content of silicon oxide component was 16%. A large part of the silicon oxide component in the raw white clay changes into water-soluble due to the reaction with the above-mentioned sodium hydroxide, and is removed by washing with water. Hereinafter, the inorganic substance containing hydroxysodalite as a main component obtained above is referred to as an inorganic filler HSL-2.
【0028】実施例1
塩化ビニル樹脂粉末(平均重合度:800)100部、
三塩基性硫酸鉛1.0部、ステアリン酸鉛1.5部、合
成例1で得られた無機充填剤HSL−1を10部及びグ
レー色の着色剤を1.0部を配合し、高速混合機で3分
間混合し、二本ロールにより170℃で5分間混練し、
グレー色の塩化ビニル樹脂組成物を得た。次いで、上記
の組成物を170℃でプレス成形して1mm厚のシート
を作成した。尚、上記で使用したグレー色の着色剤は、
酸化チタン白色顔料80%、カーボンブラック顔料10
%及びステアリン酸カルシウム10%の組成で予め調製
したものである。Example 1 100 parts of vinyl chloride resin powder (average degree of polymerization: 800),
Add 1.0 part of tribasic lead sulfate, 1.5 parts of lead stearate, 10 parts of the inorganic filler HSL-1 obtained in Synthesis Example 1 and 1.0 part of a gray colorant, and mix at high speed. Mix for 3 minutes with a mixer, knead with a two-roll mill at 170 ° C for 5 minutes,
A gray-colored vinyl chloride resin composition was obtained. Then, the above composition was press-molded at 170 ° C. to form a sheet having a thickness of 1 mm. The gray colorant used above is
Titanium oxide white pigment 80%, carbon black pigment 10
% And calcium stearate 10%.
【0029】上記で得たグレー色の塩化ビニル樹脂シー
トを190℃のオ−ブンに入れ、熱安定性試験を実施し
た。その結果、シートの色調は変化せず、良好な耐熱性
を示した。又、上記のグレー色の塩化ビニル樹脂シート
を6ケ月間屋外暴露した後、表面状態を観察したが、表
面は殆ど変化せず、優れた耐候性を示した。又、上記で
使用した無機充填剤HSL−1に代えて合成例2で得ら
れた無機充填剤HSL−2を使用して上記と同様にして
グレー色の塩化ビニル樹脂シートを作り、同様にして熱
安定性試験及び耐候性試験を行った。その結果、熱安定
性についてはシートの色調は変化せず、良好な耐熱性を
示し、又、耐候性についても、表面状態は殆ど変化せ
ず、優れた耐候性を示した。The gray-colored vinyl chloride resin sheet obtained above was placed in an oven at 190 ° C. and subjected to a thermal stability test. As a result, the color tone of the sheet did not change, and good heat resistance was exhibited. The surface condition was observed after exposing the above-mentioned gray-colored vinyl chloride resin sheet to the outdoors for 6 months, but the surface showed almost no change and showed excellent weather resistance. A gray vinyl chloride resin sheet was prepared in the same manner as above using the inorganic filler HSL-2 obtained in Synthesis Example 2 in place of the inorganic filler HSL-1 used above. A thermal stability test and a weather resistance test were performed. As a result, regarding heat stability, the color tone of the sheet did not change, and good heat resistance was exhibited. Also, regarding weather resistance, the surface state hardly changed, and excellent weather resistance was exhibited.
【0030】実施例2〜3
実施例1の無機充填剤HSL−1の配合量を下記の表3
に示す量にした以外は実施例1と同様にしてグレー色の
塩化ビニル樹脂シートを調製し、実施例1と同様にして
オ−ブンで190℃で熱安定性試験、及び6ケ月間の屋
外暴露による耐候性試験を行った。試験結果は、下記の
表3に示すように、無機充填剤HSL−1の配合量が3
部のシートでは耐熱性は良好であったが、6ケ月間の屋
外暴露では少し白化現象が見られ、耐候性はやや良い程
度であった。無機充填剤HSL−1を30部配合したシ
ートでは、実施例1の無機充填剤HSL−1を10部配
合したシートと同様に耐熱性は良好であり、又、6ケ月
間の屋外暴露でも殆ど表面の変化はなく、優れた耐候性
を示した。Examples 2 to 3 The blending amount of the inorganic filler HSL-1 of Example 1 is shown in Table 3 below.
A gray-colored vinyl chloride resin sheet was prepared in the same manner as in Example 1 except that the amount was changed to the amount shown in 1., and in the same manner as in Example 1, a thermal stability test was carried out at 190 ° C. in an oven, and the outdoor for 6 months. A weather resistance test by exposure was performed. As shown in Table 3 below, the test results show that the inorganic filler HSL-1 content was 3
Although the heat resistance of the sheet of the part was good, the whitening phenomenon was slightly observed in the outdoor exposure for 6 months, and the weather resistance was slightly good. The sheet containing 30 parts of the inorganic filler HSL-1 has good heat resistance as in the case of the sheet containing 10 parts of the inorganic filler HSL-1 of Example 1, and is almost free from the outdoor exposure for 6 months. There was no change on the surface and it showed excellent weather resistance.
【0031】[0031]
【表3】表3 [Table 3] Table 3
【0032】比較例1〜4
上記の実施例の結果と比較するために、無機充填剤HS
L−1を使用しない以外は実施例1と同様にして塩化ビ
ニル樹脂、三塩基性硫酸鉛、ステアリン酸鉛及びグレー
色の着色剤を配合し、無機充填剤として何も使用しない
もの、及び炭酸カルシウムを無機充填剤として表4に示
す量で配合し、実施例1と同様の方法でシートを作成
し、実施例1と同様に熱安定性試験及び屋外暴露試験を
行った。Comparative Examples 1-4 In order to compare the results of the above examples, the inorganic filler HS
Vinyl chloride resin, tribasic lead sulfate, lead stearate and a gray colorant were blended in the same manner as in Example 1 except that L-1 was not used, and nothing was used as an inorganic filler, and carbonic acid. Calcium was blended as an inorganic filler in the amount shown in Table 4, a sheet was prepared in the same manner as in Example 1, and a thermal stability test and an outdoor exposure test were performed in the same manner as in Example 1.
【0033】上記試験結果は下記の表4に示すように、
無機充填剤として何も使用しないものも熱安定性試験に
おいては他の安定剤の効果で褐色化せずに良好であった
が、屋外暴露試験において褐色に変化し、耐候性は不十
分であった。炭酸カルシウムを使用したシートはいずれ
も同様に耐熱性は良好であったが、6ケ月間の屋外暴露
試験において、炭酸カルシウムの配合量が3部のシート
では白化現象が見られ、耐候性は不良であった。更に、
10部及び30部と炭酸カルシウムを増加して配合した
シートでは著しい白化現象が見られ、耐候性としては全
く不良の結果を示した。The above test results are shown in Table 4 below.
The one without any inorganic filler was also good in the thermal stability test without browning due to the effect of other stabilizers, but it turned brown in the outdoor exposure test and the weather resistance was insufficient. It was The sheets using calcium carbonate also had good heat resistance, but in an outdoor exposure test for 6 months, a whitening phenomenon was observed in the sheet containing 3 parts of calcium carbonate and the weather resistance was poor. Met. Furthermore,
A sheet containing 10 parts and 30 parts of calcium carbonate with an increased amount of calcium carbonate showed a remarkable whitening phenomenon and showed a completely poor weather resistance.
【0034】[0034]
【表4】表4 [Table 4] Table 4
【0035】尚、上記実施例及び比較例における熱安定
性試験、耐候性試験及びそれらの評価は次の通り行っ
た。耐熱性は190℃のオーブンで30分間熱安定性試
験を行い評価した。上記表3及び表4において、耐熱性
の○の表示は上記熱安定性試験において試料の黒変又は
褐色化が認められないことを示す。又、耐候性は6ヶ月
の屋外暴露試験で評価した。暴露地として大阪府東大阪
市、暴露条件として南面及び傾斜角45度で行なった。
評価は、屋外暴露6ヶ月後の試料と未照射品とを比較し
て表面状態の変化を観察し、評価した。The thermal stability test, weather resistance test and their evaluation in the above-mentioned examples and comparative examples were carried out as follows. The heat resistance was evaluated by conducting a thermal stability test for 30 minutes in an oven at 190 ° C. In Tables 3 and 4 above, the symbol "o" for heat resistance indicates that no blackening or browning of the sample was observed in the above thermal stability test. The weather resistance was evaluated by a 6-month outdoor exposure test. The exposure was performed in Higashi-Osaka City, Osaka Prefecture, and the exposure conditions were the south plane and a tilt angle of 45 degrees.
The evaluation was performed by comparing the sample after 6 months of outdoor exposure with the unirradiated product and observing the change in the surface condition.
【0036】[0036]
【発明の効果】本発明の塩化ビニル系樹脂用組成物は、
塩化ビニル系樹脂から熱或は光の作用で分解して発生す
る塩酸を中和し得る機能を有するヒドロキシソーダライ
トを主成分とする無機充填剤を配合することを特徴とし
ており、該組成物を用いて製造された塩化ビニル系樹脂
成形物は成形加工時に安定であり、又、得られた成形物
は長期間の屋外使用に際しても耐候性や耐チョーキング
性等の諸堅牢性に優れている。The vinyl chloride resin composition of the present invention comprises:
And characterized by blending an inorganic filler mainly composed of hydroxy sodalite having a function capable of neutralizing the hydrochloric acid generated by decomposition by the action of the vinyl chloride resin heat or light, the composition The vinyl chloride resin molded product produced by using is stable during molding processing, and the obtained molded product has excellent durability such as weather resistance and chalking resistance even when used outdoors for a long period of time. .
【図1】 ヒドロキシソーダライトを主成分とする白色
粉末のX線回折チャートFIG. 1 is an X-ray diffraction chart of a white powder containing hydroxysodalite as a main component.
【図2】 上記白色粉末の塩酸処理物のX線回折チャー
トFIG. 2 is an X-ray diffraction chart of the above-mentioned white powder treated with hydrochloric acid.
フロントページの続き (72)発明者 芝田 正之 東京都中央区日本橋馬喰町一丁目7番6 号 大日精化工業株式会社内 (72)発明者 阪本 守久 東京都中央区日本橋馬喰町一丁目7番6 号 大日精化工業株式会社内 (72)発明者 中村 道衞 東京都中央区日本橋馬喰町一丁目7番6 号 大日精化 工業株式会社内 (56)参考文献 特開 平10−101874(JP,A) 特開 平4−254409(JP,A) 特開 平4−50250(JP,A) 特開 昭54−34356(JP,A) 特開 平7−315830(JP,A) 特開 昭51−36251(JP,A) 特開 平9−118774(JP,A) 特開 平11−49513(JP,A) 特開 平9−241458(JP,A) 特開 平9−272769(JP,A) 特公 昭44−22612(JP,B1) (58)調査した分野(Int.Cl.7,DB名) C08L 27/06 Front page continued (72) Inventor Masayuki Shibata 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Within Dainichi Seika Kogyo Co., Ltd. (72) Morikuh Sakamoto 1-7-6 Nihonbashi-Bakuro-cho, Chuo-ku, Tokyo NISSEI KASEI KOGYO CO., LTD. (72) Inventor Michisuke Nakamura 1-7-6 Nihonbashi-Bakuro-cho, Chuo-ku, Tokyo DAI NISSEI KASEI KOGYO CO., LTD. (56) Reference Japanese Unexamined Patent Publication No. 10-101874 (JP, A) Kaihei 4-254409 (JP, A) JP 4-50250 (JP, A) JP 54-34356 (JP, A) JP 7-315830 (JP, A) JP 51-36251 ( JP, A) JP 9-118774 (JP, A) JP 11-49513 (JP, A) JP 9-241458 (JP, A) JP 9-272769 (JP, A) JP Sho 44-22612 (JP, B1) (58) Fields investigated (Int.Cl. 7 , DB name) C08L 27/06
Claims (7)
無機充填剤を配合及び成形してなる樹脂成形物におい
て、該無機充填剤が下記の組成式[I]を有するヒドロ
キシソーダライトを主成分とする無機充填剤であること
を特徴とする耐チョーキング性塩化ビニル系樹脂成形
物。 Na4Al3Si3O12(OH) [I]1. A resin molded product obtained by blending and molding an inorganic filler to a resin containing a vinyl chloride resin as a main component, wherein the inorganic filler is mainly hydroxysodalite having the following composition formula [I]. A chalking-resistant vinyl chloride resin molded product, which is an inorganic filler as a component. Na 4 Al 3 Si 3 O 12 (OH) [I]
00重量部に対し、ヒドロキシソーダライトを主成分と
する無機充填剤が0.05〜100重量部である請求項
1に記載の耐チョーキング性塩化ビニル系樹脂成形物。2. A resin 1 containing a vinyl chloride resin as a main component.
The choking-resistant vinyl chloride resin molded product according to claim 1, wherein the inorganic filler containing hydroxysodalite as a main component is contained in an amount of 0.05 to 100 parts by weight based on 100 parts by weight.
に、ヒドロキシソーダライトを主成分とする無機充填剤
を5〜95重量%含有する組成物を添加し、成形加工し
てなる請求項1に記載の耐チョーキング性塩化ビニル系
樹脂成形物。3. A composition containing 5 to 95% by weight of an inorganic filler containing hydroxysodalite as a main component, added to a resin containing a vinyl chloride resin as a main component, and molded. A vinyl chloride-based resin molded product having a choking resistance as described in 1.
請求項1〜3のいずれか1項に記載の耐チョーキング性
塩化ビニル系樹脂成形物。4. The choking-resistant vinyl chloride resin molded product according to claim 1, which contains an organic pigment and / or an inorganic pigment.
無機充填剤を配合してなる樹脂組成物において、該無機
充填剤が下記の組成式[I]を有するヒドロキシソーダ
ライトを主成分とする無機充填剤であることを特徴とす
る耐チョーキング性塩化ビニル系樹脂組成物。 Na4Al3Si3O12(OH) [I]5. A resin composition comprising a vinyl chloride resin-based resin and an inorganic filler, wherein the inorganic filler contains hydroxysodalite having the following composition formula [I] as a main component. A choking-resistant vinyl chloride resin composition, characterized by being an inorganic filler. Na 4 Al 3 Si 3 O 12 (OH) [I]
請求項5に記載の耐チョーキング性塩化ビニル系樹脂組
成物。6. The choking-resistant vinyl chloride resin composition according to claim 5, which contains an organic pigment and / or an inorganic pigment.
無機充填剤を5〜95重量%含有する耐チョーキング性
塩化ビニル系樹脂用無機充填剤組成物。7. A mineral filler the resistance to chalking resistance <br/> vinyl chloride resin inorganic filler composition containing 5 to 95 wt% of a main component hydroxy sodalite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12116798A JP3475076B2 (en) | 1998-04-30 | 1998-04-30 | Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12116798A JP3475076B2 (en) | 1998-04-30 | 1998-04-30 | Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11310675A JPH11310675A (en) | 1999-11-09 |
JP3475076B2 true JP3475076B2 (en) | 2003-12-08 |
Family
ID=14804512
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12116798A Expired - Fee Related JP3475076B2 (en) | 1998-04-30 | 1998-04-30 | Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3475076B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6777974B2 (en) * | 2015-04-01 | 2020-10-28 | デンカ株式会社 | Rain gutter |
JP6586250B1 (en) * | 2018-06-01 | 2019-10-02 | 積水化学工業株式会社 | Rigid vinyl chloride resin tube |
-
1998
- 1998-04-30 JP JP12116798A patent/JP3475076B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH11310675A (en) | 1999-11-09 |
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