JP6340611B2 - Anti-blocking effect durable flexible sheet and method for producing the same - Google Patents
Anti-blocking effect durable flexible sheet and method for producing the same Download PDFInfo
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Description
本発明は繊維織物を基材として、織物基材に軟質塩化ビニル樹脂層を被覆して得られる、間仕切り、シートシャッター、日除け・雨除け、防水エプロン、防水バッグなどに用いる産業用フレキシブルシートで、フレキシブルシートの表面タックが小さく、これら用途の製品の熱融着縫製工程におけるハンドリング性の良いフレキシブルシート関する。 The present invention is an industrial flexible sheet used as a partition, a sheet shutter, an awning / rain shield, a waterproof apron, a waterproof bag, etc. obtained by coating a textile fabric with a soft vinyl chloride resin layer as a base material, The present invention relates to a flexible sheet having a small surface tack and a good handleability in the heat fusion sewing process of products for these applications.
ジオクチルフタレート（ＤＯＰ）、ジイソノニルフタレート（ＤＩＮＰ）、ジヘプチルフタレート（ＤＨＰ）などのフタル酸ジエステル系可塑剤が多量に配合された軟質塩化ビニル樹脂成形物では表面にタック（ベタつき感）を残し、それによって製品同士がくっ付き、特に薄いフィルムではくっ付いて絡んだフィルムの引き剥がしを困難としている。また、シート製品では経時的に可塑剤が表面に移行（ブリード）して、シートをロール巻きで保管した場合や、重ね置きした状態でブロッキング（癒着）を生じ易く、しかも長期間放置するとシートの引剥しを困難とし、剥がすとブロッキング痕生じて製品の外観を損なう問題があった。またブリードした可塑剤は成型物表面をベトつかせ、これに煤塵や埃が付着することで汚れ易く、しかも汚れが除去し難いものとしていた。これら問題を解決する手段の１つとして特許文献１では、ロール剥離性、耐ブロッキング性などに優れた塩化ビニル系樹脂フィルムとして、１，２−シクロヘキサンジカルボン酸ジイソノニルエステルを可塑剤に使用することが提案されている。しかしブロッキング現象は環境温度、使用状態などで変化し、特に長期に亘る表面タックの改質効果の持続は困難で、可塑剤のブリード（移行）により、表面タックやブロッキングが酷くなるという現状の解決が必ずしもなされていなかった。 Soft vinyl chloride resin moldings containing a large amount of phthalic acid diester plasticizers such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), diheptyl phthalate (DHP) leave a tack (sticky feeling) on the surface. The products stick to each other, especially with thin films, making it difficult to peel off the entangled film. In sheet products, the plasticizer migrates to the surface over time (bleeds), and when the sheets are stored in rolls or when they are stacked, they tend to cause blocking (adhesion). There was a problem that peeling was difficult, and when it was peeled off, blocking marks were generated and the appearance of the product was impaired. In addition, the bleed plasticizer makes the surface of the molded product sticky, and dust and dirt adhere to it, making it easy to get dirty and difficult to remove. As one means for solving these problems, Patent Document 1 discloses that 1,2-cyclohexanedicarboxylic acid diisononyl ester is used as a plasticizer as a vinyl chloride resin film having excellent roll peelability and blocking resistance. Proposed. However, the blocking phenomenon changes depending on the environmental temperature, usage conditions, etc., and it is difficult to maintain the surface tack modification effect over a long period of time, and the current solution is that surface tack and blocking become severe due to plasticizer bleeding. Was not necessarily made.
また、耐ブリード性及び耐ブロッキング性の優れた塩化ビニル樹脂系エラストマー組成物として特許文献２には、塩化ビニル系樹脂及び塩素化ポリエチレンの合計１００重量部に対してＮＢＲ２０〜４００重量部並びに可塑剤１０〜３００重量部を配合した組成物が提案されている。しかしジオクチルフタレート（ＤＯＰ）のみ効果が示され、しかも塩化ビニル樹脂よりも多量のＮＢＲを必要とすることで、可塑剤の耐ブリード性には優れても、ＮＢＲ過多によるタック（ゴム性）が増すことで、これらをシート化したときのシート同士の滑り性を悪くする欠点は避けられないものであった。特に軟質塩化ビニル樹脂製のフレキシブルシートで表面がフラットかつ鏡面の透明間仕切りシートでは、重ね置きや巻き取りの状態で互いに密着し易く、温度環境や時間経過によってシート引き剥がしを困難とするブロッキング問題を有していた。このため製造会社は、製品全面にパウダー付着処理した状態でシートをロール巻きするような粉振りを施しているが、ユーザー側には付着パウダーの清拭除去の手間を掛け、しかも使用環境を粉塵汚染するなどの不満を残していた。特にフレキシブルシートによる産業資材の製造・縫製の現場では、フレキシブルシート同士の滑りが悪いと高周波ウエルダー機の作業台での取り扱い性が悪く、作業性に影響を及ぼすことがあった。また自走式熱風融着機による長尺のラップ縫製を行う場合に、フレキシブルシート端部の重ね合わせ部の所々に浮きや位置ズレを生じると問題部分ごとに修正の手間をかける必要があった。従って産業資材シート製品の大小に係わらず、タックが小さく、可塑剤ブリードが長期間に亘り極少量に抑止されることで、耐ブロッキング性が持続するような縫製作業の取り扱い性に優れたフレキシブルシートが望まれていた。 In addition, as a vinyl chloride resin elastomer composition having excellent bleed resistance and blocking resistance, Patent Document 2 discloses 20 to 400 parts by weight of NBR and a plasticizer based on 100 parts by weight of vinyl chloride resin and chlorinated polyethylene. A composition containing 10 to 300 parts by weight has been proposed. However, only dioctyl phthalate (DOP) has been shown to be effective, and a larger amount of NBR than vinyl chloride resin is required, so that even if the plasticizer is excellent in bleed resistance, tack (rubber property) due to excessive NBR is increased. Thus, the disadvantage of worsening the slipperiness between the sheets when they are formed into sheets is inevitable. In particular, flexible partition sheets made of soft vinyl chloride resin with a flat surface and a mirror-like transparent partition sheet tend to adhere to each other in a stacked or wound state, and have a blocking problem that makes it difficult to peel off the sheet due to the temperature environment and the passage of time. Had. For this reason, the manufacturing company gives powder dusting to roll the sheet in a state where the powder adheres to the entire surface of the product. He was dissatisfied with contamination. Particularly in the field of manufacturing and sewing industrial materials using flexible sheets, if the sliding between the flexible sheets is poor, the handling property on the work table of the high-frequency welder machine is poor, which may affect the workability. In addition, when performing long lap sewing with a self-propelled hot-air fusion machine, if there are floating or misaligned parts in the overlapping part of the end of the flexible sheet, it is necessary to take troublesome correction for each problem part. . Therefore, regardless of the size of the industrial material sheet product, a flexible sheet with excellent tackability in sewing work that has a small tack and suppresses plasticizer bleed to an extremely small amount over a long period of time, thus maintaining blocking resistance. Was desired.
本発明は繊維織物を基材として、織物基材に軟質塩化ビニル樹脂層を被覆して得られる、間仕切り、シートシャッター、日除け・雨除け、防水エプロン、防水バッグなどに用いる産業用フレキシブルシートで、タックが小さく、耐ブロッキング効果の持続性に優れ、特に上記産業資材製品などの製造工程における縫製作業時の取り扱い性に優れ、透視性、採光性など透明性にも優れるフレキシブルシートを提供しようとするものである。 The present invention is an industrial flexible sheet used as a partition, a sheet shutter, an awning / rain shield, a waterproof apron, a waterproof bag, etc. obtained by coating a textile fabric with a soft vinyl chloride resin layer as a base material, An attempt to provide a flexible sheet with a small tack, excellent blocking resistance, excellent handleability during sewing operations, especially in the manufacturing process of the above industrial material products, and excellent transparency such as transparency and daylighting Is.
本発明者は、産業用フレキシブルシートについて上記の現状に鑑みて研究、検討を行った結果、繊維織物を基材として、その少なくとも１面上に軟質塩化ビニル樹脂層が設けられた光透過性膜材において、繊維織物と軟質塩化ビニル樹脂層との質量比を特定範囲内とすること、及び軟質塩化ビニル樹脂層が塩化ビニル系樹脂、及びシクロヘキサンジカルボン酸ジアルキルエステル化合物とを主体に含み、さらに塩素化ポリエチレンを含有することによって、透視性、採光性など透明性に優れ、しかもタックが小さく、可塑剤ブリードが長期間に亘り極少量に抑止されることで、耐ブロッキング効果の持続を可能とするフレキシブルシートが得られることを見出して本発明を完成させるに至った。 As a result of studying and examining the industrial flexible sheet in view of the above-mentioned present situation, the present inventor has found that a light permeable film having a fiber woven fabric as a base material and a soft vinyl chloride resin layer provided on at least one surface thereof In the material, the mass ratio of the fiber fabric and the soft vinyl chloride resin layer is within a specific range, and the soft vinyl chloride resin layer mainly contains a vinyl chloride resin and a cyclohexanedicarboxylic acid dialkyl ester compound, and further contains chlorine. By containing chlorinated polyethylene, it is excellent in transparency such as transparency and daylighting, has a small tack, and a plasticizer bleed is suppressed to a very small amount over a long period of time, thereby enabling the anti-blocking effect to be maintained. The inventors have found that a flexible sheet can be obtained and have completed the present invention.
すなわち本発明の耐ブロッキング効果持続性フレキシブルシートは、繊維織物を基材として、その少なくとも１面上に軟質塩化ビニル樹脂層が設けられた光透過性膜材であって、前記繊維織物と前記軟質塩化ビニル樹脂層との質量比を１：５〜１：３０とし、かつ、前記軟質塩化ビニル樹脂層が塩化ビニル系樹脂１００質量部、及びシクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）１５〜６５質量部とを主体に含み、さらに塩素化ポリエチレンを１〜３０質量部含有することが好ましい。これによって得られるフレキシブルシートでは、透視性、採光性など透明性に優れ、タックが小さく、可塑剤ブリードを長期間に亘り極少量に抑止することで、耐ブロッキング効果の持続を可能とする。
That is, the anti-blocking effect durable flexible sheet of the present invention is a light-transmitting membrane material in which a fiber woven fabric is used as a base material and a soft vinyl chloride resin layer is provided on at least one surface thereof. The mass ratio with respect to the vinyl chloride resin layer was 1: 5 to 1:30, and the soft vinyl chloride resin layer was 100 parts by mass of vinyl chloride resin and cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) 15 It is preferable to contain ˜65 parts by mass and further contain 1 to 30 parts by mass of chlorinated polyethylene. The flexible sheet thus obtained has excellent transparency such as transparency and daylighting, has a small tack, and suppresses the plasticizer bleed to an extremely small amount over a long period of time, thereby enabling the blocking resistance to be maintained.
本発明の耐ブロッキング効果持続性フレキシブルシートは、前記軟質塩化ビニル樹脂層がさらに、低分子ポリエステル、芳香族リン酸エステルから選ばれた１種以上の化合物を含み、その併用量が１〜５０質量部であることが好ましい。低分子ポリエステル化合物の併用によって得られるフレキシブルシートではタックがより小さく、可塑剤ブリードを長期間に亘り極少量に抑止することで、耐ブロッキング効果の持続を可能とする。また芳香族リン酸エステル化合物の併用によって特に透明な軟質塩化ビニル樹脂層に防炎性を付与し、これによって透明性と透視性を有するフレキシブルシートを得ることができ、このフレキシブルシートは消防法の防炎規格に適合する間仕切りシートとして屋内外で使用することができる。 In the blocking resistant durable flexible sheet of the present invention, the soft vinyl chloride resin layer further contains one or more compounds selected from low molecular polyesters and aromatic phosphates, and the combined amount thereof is 1 to 50 mass. Part. The flexible sheet obtained by the combined use of the low molecular weight polyester compound has a smaller tack, and the anti-blocking effect can be maintained by suppressing the plasticizer bleed to a very small amount over a long period of time. In addition, the combined use of an aromatic phosphate ester compound imparts flame resistance to a particularly transparent soft vinyl chloride resin layer, and thereby a flexible sheet having transparency and transparency can be obtained. Can be used indoors and outdoors as a partition sheet that meets flameproof standards.
本発明の耐ブロッキング効果持続性フレキシブルシートは、前記繊維織物が、２軸織編物、３軸織編物、及び４軸織編物から選ばれた何れか１種の粗目織物であることが好ましい。これによって得られるフレキシブルシートは透視性、採光性など透明性に優れ、しかも良好な寸法安定性、物性バランス、及び外観意匠性を有する間仕切りシートとして使用することができる。 In the blocking resistant durable flexible sheet of the present invention, it is preferable that the fiber woven fabric is any one kind of coarse woven fabric selected from a biaxial knitted fabric, a triaxial woven knitted fabric, and a tetraaxial woven knitted fabric. The flexible sheet thus obtained can be used as a partition sheet having excellent transparency such as transparency and daylighting, and having good dimensional stability, physical property balance, and appearance design.
本発明の耐ブロッキング効果持続性フレキシブルシートの製造方法は、塩化ビニル系樹脂１００質量部、及びシクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）１５〜６０質量部を主体に含む第一軟質塩化ビニル樹脂熱混練物を準備し、次に前記塩化ビニル系樹脂１００質量部に対し１〜３０質量部の塩素化ポリエチレンを前記第一軟質塩化ビニル樹脂熱混練物に追加配合して得た第二軟質塩化ビニル樹脂熱混練物を用い、この第二軟質塩化ビニル樹脂熱混練物より圧延成型したフィルムを繊維織物の１面以上に積層することで、前記フィルムを軟質塩化ビニル樹脂層とし、前記繊維織物を基材としてなる光透過性膜材を得ることが好ましい。これによって軟質塩化ビニル樹脂層の可塑化を十分かつ均一なものとし、これに塩素化ポリエチレンを後分散させることで、可塑化軟質塩化ビニル樹脂分子鎖に対する塩素化ポリエチレン分子鎖の絡み拘束の状態を効果的とすることで、よりタックが小さく、可塑剤ブリードをより極少量に抑止することで、耐ブロッキング効果、及びその持続をさらに優れたものとする。
The method for producing a blocking resistant durable flexible sheet according to the present invention is a first soft chloride mainly comprising 100 parts by mass of a vinyl chloride resin and 15-60 parts by mass of a cycloalkyldicarboxylic acid dialkyl ester (group of [Chemical Formula 1]). A vinyl resin heat kneaded material was prepared, and then 1 to 30 parts by mass of chlorinated polyethylene was added to the first soft vinyl chloride resin heat kneaded material based on 100 parts by mass of the vinyl chloride resin. A soft vinyl chloride resin heat kneaded material is used, and a film formed by rolling from the second soft vinyl chloride resin heat kneaded material is laminated on one or more surfaces of the fiber fabric, so that the film becomes a soft vinyl chloride resin layer, and the fiber It is preferable to obtain a light-transmitting film material having a woven fabric as a base material. As a result, the plasticization of the soft vinyl chloride resin layer is made sufficiently and uniform, and the chlorinated polyethylene is post-dispersed in this, so that the entanglement constraint state of the chlorinated polyethylene molecular chain with respect to the plasticized soft vinyl chloride resin molecular chain can be reduced. By making it effective, the tack is smaller, and the plasticizer bleed is suppressed to a very small amount, thereby further improving the anti-blocking effect and its sustainability.
本発明の耐ブロッキング効果持続性フレキシブルシートは、透視性、採光性など透明性に優れ、しかもタックが小さく、可塑剤ブリードが長期間に亘り極少量に抑止されることで、耐ブロッキング性の持続を可能とするので、特に、間仕切り、シートシャッター、日除け・雨除け、防水エプロン、防水バッグ、などの産業資材製品などの製造工程における縫製作業時の取り扱い性に優れたフレキシブルシートとして極めて有用である。 The flexible sheet having a long blocking resistance according to the present invention is excellent in transparency such as transparency and daylighting, and has a small tack, and the plasticizer bleed is suppressed to a very small amount over a long period of time, thereby maintaining the blocking resistance. In particular, it is extremely useful as a flexible sheet with excellent handleability during sewing operations in the manufacturing process of industrial material products such as partitions, sheet shutters, sun and rain protection, waterproof apron, waterproof bags, etc. .
本発明の耐ブロッキング効果持続性フレキシブルシートの要件は、繊維織物を基材として、その少なくとも１面上に軟質塩化ビニル樹脂層が設けられた光透過性膜材において、軟質塩化ビニル樹脂層が塩化ビニル系樹脂、及びシクロヘキサンジカルボン酸ジアルキルエステル類とを主体に含み、さらに塩素化ポリエチレンを含有すること、及び透視性、採光性など透明性に優れるための要件として、繊維織物と前記軟質塩化ビニル樹脂層との質量比を１：５〜１：３０とすることを必須とする。 The requirement of the flexible sheet having a blocking-resistant effect according to the present invention is that, in a light-transmitting film material having a fiber woven fabric as a base material and a soft vinyl chloride resin layer provided on at least one surface thereof, the soft vinyl chloride resin layer is chlorinated. As a requirement for including a vinyl resin and cyclohexanedicarboxylic acid dialkyl ester as a main component, and further containing chlorinated polyethylene, and excellent transparency such as transparency and daylighting properties, a textile fabric and the soft vinyl chloride resin are used. It is essential that the mass ratio with the layer is 1: 5 to 1:30.
本発明の耐ブロッキング効果持続性フレキシブルシートに用いる基材としての繊維織物は、合成繊維、天然繊維、半合成繊維、無機繊維またはこれらの２種類以上から成る混用繊維から製織された質量５〜１００ｇ／ｍ２の織物及び編物である。合成繊維としては、ナイロン繊維、ビニロン繊維、ポリプロピレン繊維、ポリエスエル繊維、超高分子量ポリエチレン繊維、アラミド繊維、及びヘテロ環ポリマー繊維が挙げられる。天然繊維としては木綿、麻、ケナフが挙げられ、半合成繊維にはレーヨン、アセテートが挙げられる。無機繊維としては、ガラス繊維、シリカ繊維、アルミナ繊維、炭素繊維などが挙げられる。特に本発明においては合成繊維によるフィラメントヤーンまたはスパンヤーンによる粗目平織物またはネットが特に好ましいが、粗目ラッセル織物、粗目綾織物、粗目朱子織物、粗目模紗織物などであってもよい。これら粗目状の繊維織物は必要に応じて撥水処理、吸水防止処理、接着処理、難燃処理などが施されても良い。本発明に用いる繊維織物はポリエスエル繊維、ビニロン繊維、ナイロン繊維、ガラス繊維などから成る平織物が好ましい。 The fiber woven fabric as a base material used for the blocking resistant long-lasting flexible sheet of the present invention has a mass of 5 to 100 g woven from synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these. / M 2 woven fabric and knitted fabric. Synthetic fibers include nylon fibers, vinylon fibers, polypropylene fibers, polyester fibers, ultrahigh molecular weight polyethylene fibers, aramid fibers, and heterocyclic polymer fibers. Examples of natural fibers include cotton, hemp and kenaf, and examples of semisynthetic fibers include rayon and acetate. Examples of the inorganic fiber include glass fiber, silica fiber, alumina fiber, and carbon fiber. In the present invention, a coarse plain fabric or net made of synthetic yarn filament yarn or spun yarn is particularly preferred, but may be a coarse Russell fabric, a coarse twill fabric, a coarse satin fabric, a coarse patterned fabric, or the like. These coarse fiber fabrics may be subjected to a water repellent treatment, a water absorption prevention treatment, an adhesion treatment, a flame retardant treatment, and the like as necessary. The fiber fabric used in the present invention is preferably a plain fabric made of polyester fiber, vinylon fiber, nylon fiber, glass fiber or the like.
本発明のフレキシブルシートに適する繊維織物は、２７８〜３３３３dtex、好ましくは５５５〜２２２２dtexのマルチフィラメントヤーン（無撚ヤーン、右撚または左撚の撚糸・合撚糸）を用いた目合空隙率５０〜９６％の粗目織編物で、２軸織物、または３軸織物、または４軸織物が好ましい。これら織物の経糸及び緯糸の打込み密度は、上記ヤーンを経糸及び緯糸として１インチ間１〜１５本打込んで得られる２軸織物、３軸織物、４軸織物が寸法安定性、物性バランス、及び外観意匠的に好ましい。特に１インチ間１〜３本打込んで得られる超粗目織物（２軸織物、または３軸織物、または４軸織物）は、熱可塑性樹脂を含浸被覆（糊付）したマルチフィラメントヤーンを経糸及び緯糸として配置し、熱プレスで経糸と緯糸との交点を熱接着させて製造したネットが加工時の形状安定性に優れ好ましい。このような粗目織物を用い、特に可視光透過率７０％以上の軟質塩化ビニル樹脂層を、この粗目織物の両面に積層したときに、透視性や採光性に優れた間仕切りシート用、及びシートシャッター用に適したフレキシブルシートを得る。 The fiber fabric suitable for the flexible sheet of the present invention is 278-3333 dtex, preferably 555-2222 dtex multifilament yarn (untwisted yarn, right-handed or left-handed twisted yarn / twisted yarn), 50-96 mesh porosity % Coarse knitted fabric, preferably a biaxial woven fabric, a triaxial woven fabric, or a 4-axial woven fabric. The weaving density of the warp and weft of these woven fabrics is the dimensional stability, balance of physical properties, and biaxial woven fabric, triaxial woven fabric, and 4-axial woven fabric obtained by driving 1 to 15 yarns per inch using the yarn as warp and weft. It is preferable in appearance design. In particular, an ultra-coarse woven fabric (biaxial woven fabric, triaxial woven fabric, or 4-axial woven fabric) obtained by driving 1 to 3 yarns per inch is obtained by using a multifilament yarn impregnated with a thermoplastic resin (glued) as warp and A net that is arranged as a weft and is manufactured by heat-bonding the intersection of a warp and a weft with a heat press is preferable because of its excellent shape stability during processing. Using such a coarse woven fabric, particularly when a soft vinyl chloride resin layer having a visible light transmittance of 70% or more is laminated on both sides of the coarse woven fabric, the partition sheet is excellent in transparency and daylighting, and a sheet shutter. A flexible sheet suitable for use is obtained.
本発明のフレキシブルシートにおける軟質塩化ビニル樹脂層には、塩化ビニル系樹脂１００質量部、及びシクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）１５〜６５質量部とを主体に含み、さらに塩素化ポリエチレンを１〜３０質量部含有することが好ましい。シクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）は、１，２−シクロヘキサンジカルボン酸ジアルキルエステル群、１，３−シクロヘキサンジカルボン酸ジアルキルエステル群、及び１，４−シクロヘキサンジカルボン酸ジアルキルエステル群から選ばれた１種以上の化合物を含む。〔化１〕に示すジアルキルエステルの群において式中、Ｒは個々に同一又は異なって、炭素（Ｃ）数４〜１３の脂肪族一価の基、例えば直鎖状アルキル基、分岐鎖状のアルキル基、脂環族基などを表している。
The soft vinyl chloride resin layer in the flexible sheet of the present invention mainly contains 100 parts by mass of a vinyl chloride resin and 15 to 65 parts by mass of a dialkyl ester of cyclohexanedicarboxylic acid ([Chemical Group 1]), and further chlorinated. It is preferable to contain 1-30 mass parts of polyethylene. Cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) is selected from 1,2-cyclohexanedicarboxylic acid dialkylester group, 1,3-cyclohexanedicarboxylic acid dialkylester group, and 1,4-cyclohexanedicarboxylic acid dialkylester group One or more selected compounds. In the group of dialkyl esters represented by [Chemical Formula 1], in the formula, each R is the same or different and is an aliphatic monovalent group having 4 to 13 carbon atoms (C), such as a linear alkyl group or a branched chain. It represents an alkyl group, an alicyclic group, and the like.
シクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）の可塑剤は例えば、シクロヘキサンジカルボン酸ジ−２−エチルヘキシル（別名シクロヘキサンジカルボン酸ジオクチル）（Ｃ８：ＭＷ３９３）、シクロヘキサンジカルボン酸ジイソノニル（Ｃ９：ＭＷ４２１）が特に好ましく、その他シクロヘキサンジカルボン酸ジブチル（Ｃ４：ＭＷ２８１）、シクロヘキサンジカルボン酸ジイソブチル（Ｃ４：ＭＷ２８１）、シクロヘキサンジカルボン酸ジヘキシル（Ｃ６：ＭＷ３３７）、シクロヘキサンジカルボン酸ジヘプチル（Ｃ７：ＭＷ３６２）、シクロヘキサンジカルボン酸ジノニル（Ｃ９：ＭＷ４２１）、シクロヘキサンジカルボン酸ジイソデシル（Ｃ１０：ＭＷ４５０）、シクロヘキサンジカルボン酸ジデシル（Ｃ１０：ＭＷ４５０）、シクロヘキサンジカルボン酸ブチルベンジル（Ｃ４，Ｃ７：ＭＷ３１５）などが例示され、これらはすべてシクロヘキサン環に対するジカルボン酸ジアルキルエステルの結合位置が、オルト位（すなわち１．２−位置）、メタ位（すなわち１．３−位置）、パラ位（すなわち１．４−位置）の３態様を全て包含するものである。 Examples of the plasticizer of the dialkyl ester of cyclohexanedicarboxylic acid (the group of [Chemical Formula 1]) include di-2-ethylhexyl cyclohexanedicarboxylate (also known as dioctyl cyclohexanedicarboxylate) (C8: MW393) and diisononyl cyclohexanedicarboxylate (C9: MW421). Particularly preferred are dibutyl cyclohexanedicarboxylate (C4: MW281), diisobutylcyclohexanedicarboxylate (C4: MW281), dihexyl cyclohexanedicarboxylate (C6: MW337), diheptylcyclohexanedicarboxylate (C7: MW362), dinonyl cyclohexanedicarboxylate (C9). : MW421), cycloisodicarboxylate diisodecyl (C10: MW450), cyclohexanedicarboxylate didecyl (C10: W450), butylbenzyl cyclohexanedicarboxylate (C4, C7: MW315) and the like, all of which have a dicarboxylic acid dialkyl ester bonded to the cyclohexane ring in the ortho position (ie, 1.2-position), meta position (ie, 1.3-position) and para-position (that is, 1.4-position) are all included.
これらシクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）の可塑剤に併用するに好ましい他の可塑剤成分としては、低分子ポリエステル及び／または芳香族リン酸エステルを含み、好ましい併用量は１〜５０質量部である。低分子ポリエステルは、アジピン酸、アゼライン酸、セバシン酸、フタル酸などのジカルボン酸と、エチレングリコール、１，２−ブタンジオール、１，６−ヘキサンジオールなどから任意に合成されたオリゴマーまたはトリマーの液状化合物が好ましく、このような低分子ポリエステルの併用によってタックがより小さく、可塑剤ブリードを長期間に亘り極少量に抑止することで、耐ブロッキング効果の持続を可能とする。芳香族リン酸エステルは、具体的にリン酸トリクレジル（別名ＴＣＰ：トリクレジルフォスフェート）、リン酸トリフェニル（別名ＴＰＰ：トリフェニルフォスフェート）、リン酸トリキシレニル（別名ＴＸＰ：トリキシレニルフォスフェート）、リン酸クレジルジフェニル（別名ＣＤＰ：クレジルジフェニルフォスフェート）が挙げられ、特に透明な軟質塩化ビニル樹脂層に防炎性を付与し、これによって透明性と透視性を有するフレキシブルシートを得ることができ、このフレキシブルシートは消防法の防炎規格に適合する間仕切りシートとして屋内外で使用することができる。必要に応じてさらなる可塑剤の併用には、アセチルクエン酸トリブチル、アジピン酸ジ−２−エチルヘキシル、トリメリット酸トリ−２−エチルヘキシル、分子末端または側鎖に（メタ）アクリロイル基を２個以上有する反応性アクリル系化合物、及びアリル基を２個以上有するアリルフタレート系化合物などを１〜１５質量部程度使用してもよい。 Other preferable plasticizer components for use in combination with the plasticizer of these cyclohexanedicarboxylic acid dialkyl esters (the group of [Chemical Formula 1]) include low molecular weight polyesters and / or aromatic phosphate esters, and the preferred combined amount is 1 to 50 parts by mass. Low molecular weight polyester is a liquid oligomer or trimer arbitrarily synthesized from dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, phthalic acid, and ethylene glycol, 1,2-butanediol, 1,6-hexanediol, etc. A compound is preferable, and the tack is smaller by the combined use of such a low molecular weight polyester, and the anti-blocking effect can be maintained by suppressing the plasticizer bleed to an extremely small amount over a long period of time. Aromatic phosphates specifically include tricresyl phosphate (also known as TCP: tricresyl phosphate), triphenyl phosphate (also known as TPP: triphenyl phosphate), and trixylenyl phosphate (also known as TXP: trixylenyl phosphate). ), Cresyl diphenyl phosphate (also known as CDP: cresyl diphenyl phosphate), which gives flame resistance to a particularly transparent soft vinyl chloride resin layer, thereby obtaining a flexible sheet having transparency and transparency. This flexible sheet can be used indoors and outdoors as a partition sheet that complies with the fire prevention standards of the Fire Service Act. If necessary, for further use of a plasticizer, tributyl acetyl citrate, di-2-ethylhexyl adipate, tri-2-ethylhexyl trimellitic acid, two or more (meth) acryloyl groups at the molecular ends or side chains About 1 to 15 parts by mass of a reactive acrylic compound and an allyl phthalate compound having two or more allyl groups may be used.
本発明において軟質塩化ビニル樹脂層には、塩化ビニル系樹脂を主体に含み、シクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）の可塑剤を１種以上含み、さらに軟質塩化ビニル樹脂層（必要に応じて、安定剤、難燃剤、充填剤、顔料など公知の塩化ビニル樹脂用配合剤を含む）が塩素化ポリエチレンを１〜３０質量部含有することで軟質塩化ビニル樹脂層のタックが改善されて、表面の滑り性を向上すると同時に、可塑剤との相溶性にも優れ、それによって塩素化ポリエチレン中に可塑剤が安定保持されることで、これら可塑剤のブリードを長期間に亘り微量に抑止することを可能とする。本発明に用いる塩素化ポリエチレンは、高密度ポリエチレン、低密度ポリエチレンなどのエチレン単独重合体またはエチレンとα−オレフィンとの共重合体を塩素ガスで塩素化したものなどで、塩素化度（塩素含有率）が２０〜４５％の塩素化ポリエチレンが使用でき、これら塩素化ポリエチレンは（半）結晶性でも、非結晶性であってもよいが、間仕切りなどの透明フレキシブルシートにおいては特に（半）結晶性塩素化ポリエチレンの使用が透明性維持の観点において好ましい。塩素化ポリエチレンは具体的に、昭和電工株式会社製の商品名「エラスレン」シリーズ、ダイソー株式会社製の商品名「ダイソラック」シリーズなどが使用できる。塩素化ポリエチレンの結晶性、非結晶性は原料のポリエチレンの種類、共重合成分の種類と比率、およびこれらの重合度と塩素化度との関係によって左右される。塩素化ポリエチレンにはカレンダー加工性改良目的に、アクリル系共重合体ゴム（三菱レイヨン株式会社製の商品名「メタブレン」シリーズ、株式会社カネカ製の商品名「カネエース」シリーズ）、クロロプレンゴム、クロロスルホン化ポリエチレンゴムなどを１〜５質量部程度含んでいてもよい。 In the present invention, the soft vinyl chloride resin layer mainly contains a vinyl chloride resin, contains at least one plasticizer of cyclohexanedicarboxylic acid dialkyl ester ([Chemical Group 1]), and further contains a soft vinyl chloride resin layer (necessary) Depending on the type, the known vinyl chloride resin compounding agents such as stabilizers, flame retardants, fillers, and pigments) contain 1 to 30 parts by mass of chlorinated polyethylene to improve the tackiness of the soft vinyl chloride resin layer. In addition to improving the surface slipperiness, it also has excellent compatibility with plasticizers, which stabilizes the plasticizers in the chlorinated polyethylene, thereby reducing the bleed of these plasticizers over a long period of time. It can be deterred. The chlorinated polyethylene used in the present invention is an ethylene homopolymer such as high-density polyethylene or low-density polyethylene or a copolymer of ethylene and α-olefin chlorinated with chlorine gas. 20% to 45% of chlorinated polyethylene can be used, and these chlorinated polyethylenes may be (semi) crystalline or non-crystalline, but are particularly (semi) crystalline in transparent flexible sheets such as partitions. From the viewpoint of maintaining transparency, it is preferable to use basic chlorinated polyethylene. Specific examples of the chlorinated polyethylene include “Eraslen” series manufactured by Showa Denko KK, and “Disolac” series manufactured by Daiso Corporation. The crystallinity and non-crystallinity of chlorinated polyethylene depend on the type of raw polyethylene, the type and ratio of copolymer components, and the relationship between the degree of polymerization and the degree of chlorination. For chlorinated polyethylene, acrylic copolymer rubber (trade name “Metablene” series manufactured by Mitsubishi Rayon Co., Ltd., trade name “Kane Ace” series manufactured by Kaneka Co., Ltd.), chloroprene rubber, chlorosulfone, for the purpose of improving calendar processability About 1 to 5 parts by mass of a modified polyethylene rubber or the like may be included.
塩化ビニル系樹脂とは塩化ビニルモノマーの単独重合体（乳化重合タイプ、懸濁重合タイプで重合度が７００〜３８００のもの）の他、塩化ビニルモノマーと共重合し得る他のモノマー類との共重合体やグラフト重合体を含むものであるが、このような共重合体の場合、塩化ビニル含有成分が６０質量％を越える比率の共重合体を本発明要件における塩化ビニル樹脂として扱う。共重合成分としては、炭素数２〜３０のα−オレフィン類、アクリル酸及びそのエステル類、メタクリル酸及びそのエステル類、マレイン酸及びそのエステル類、酢酸ビニル、プロピオン酸ビニル、アルキルビニルエーテルなどのビニル化合物などが挙げられる。また軟質塩化ビニル樹脂層には、軟質塩化ビニル樹脂用の公知の添加剤を種々任意量配合することができ、軟質塩化ビニル樹脂用安定剤として、カルシウム亜鉛複合系、バリウム亜鉛複合系、有機錫ラウレート、有機錫メルカプタイト、エポキシ系などの安定剤を単独あるいは複数種併用できる。必要に応じて、耐光安定剤、紫外線吸収剤、酸化防止剤、抗菌剤、防黴剤、着色剤（顔料）、蛍光増白剤、帯電防止剤、ワックスなどを含んでもよい。 Vinyl chloride resin is a copolymer of vinyl chloride monomer homopolymer (emulsion polymerization type, suspension polymerization type with a polymerization degree of 700-3800) and other monomers that can be copolymerized with vinyl chloride monomer. In the case of such a copolymer, a copolymer having a vinyl chloride-containing component exceeding 60% by mass is treated as a vinyl chloride resin in the requirements of the present invention. Examples of copolymer components include α-olefins having 2 to 30 carbon atoms, acrylic acid and esters thereof, methacrylic acid and esters thereof, maleic acid and esters thereof, vinyl acetate, vinyl propionate, and alkyl vinyl ether. Compound etc. are mentioned. The soft vinyl chloride resin layer may contain various arbitrary amounts of known additives for soft vinyl chloride resin. As stabilizers for soft vinyl chloride resin, calcium zinc composite, barium zinc composite, organic tin Stabilizers such as laurate, organotin mercaptite, and epoxy can be used alone or in combination. If necessary, it may contain a light-resistant stabilizer, an ultraviolet absorber, an antioxidant, an antibacterial agent, an antifungal agent, a colorant (pigment), a fluorescent whitening agent, an antistatic agent, a wax and the like.
繊維織物に軟質塩化ビニル樹脂層を形成する方法として、例えば、塩化ビニル樹脂（１００質量部）に、シクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）１５〜６５質量部、及び塩素化ポリエチレンを１〜３０質量部含有するコンパウンド組成物を用い、これをカレンダー法で０．０５ｍｍ〜１．０ｍｍ厚に成型したフィルム（シート）、またはＴダイス法で０．０５ｍｍ〜１．０ｍｍ厚に押出成型したフィルム（シート）を繊維織物の両面に熱ラミネート法によってブリッジ積層、または接着剤で積層して繊維織物と軟質塩化ビニル樹脂層との質量比を１：５〜１：３０の範囲とするフレキシブルシートを得る。また好ましくは、塩化ビニル系樹脂１００質量部に、シクロヘキサンジカルボン酸ジアルキルエステル（〔化１〕の群）１５〜６５質量部を主体に含む第一軟質塩化ビニル樹脂熱混練物を準備し、次に塩化ビニル系樹脂１００質量部に対し１〜３０質量部の塩素化ポリエチレンを配合して第二軟質塩化ビニル樹脂熱混練物を準備し、この第二軟質塩化ビニル樹脂熱混練物をカレンダー法で０．０５ｍｍ〜１．０ｍｍ厚に成型したフィルム（シート）、またはＴダイス法で０．０５ｍｍ〜１．０ｍｍ厚に押出成型したフィルム（シート）を繊維織物の両面に熱ラミネート法によってブリッジ積層、または接着剤で積層することで繊維織物と軟質塩化ビニル樹脂層との質量比を１：５〜１：３０の範囲とするフレキシブルシートを得る。上記の２つの製造方法において接着剤は公知のエマルジョン系接着剤（例えば塩化ビニル樹脂系、ウレタン系、酢酸ビニル系）、公知の溶剤系接着剤（例えばイソシアネート系硬化剤を併用するウレタン系）の他、ペースト状の軟質塩化ビニル樹脂組成物が使用できる。 As a method of forming a soft vinyl chloride resin layer on a textile fabric, for example, vinyl chloride resin (100 parts by mass), cyclohexanedicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) 15 to 65 parts by mass, and chlorinated polyethylene are added. Using a compound composition containing 1 to 30 parts by mass, this is a film (sheet) molded to a thickness of 0.05 mm to 1.0 mm by a calender method, or extruded to a thickness of 0.05 mm to 1.0 mm by a T-die method Flexible film (sheet) is laminated on both sides of a fiber fabric by a thermal lamination method, or laminated with an adhesive so that the mass ratio of the fiber fabric to the soft vinyl chloride resin layer is in the range of 1: 5 to 1:30. Get a sheet. Also preferably, a first soft vinyl chloride resin heat-kneaded product mainly containing 15 to 65 parts by mass of cycloalkyldicarboxylic acid dialkyl ester (group of [Chemical Formula 1]) is prepared in 100 parts by mass of vinyl chloride resin, A second soft vinyl chloride resin thermal kneaded material is prepared by blending 1 to 30 parts by mass of chlorinated polyethylene with respect to 100 parts by mass of the vinyl chloride resin. A film (sheet) molded to a thickness of 0.05 mm to 1.0 mm, or a film (sheet) extruded to a thickness of 0.05 mm to 1.0 mm by the T-die method is bridge laminated on both sides of the fiber fabric by a thermal lamination method, or By laminating with an adhesive, a flexible sheet having a mass ratio of the fiber fabric and the soft vinyl chloride resin layer in the range of 1: 5 to 1:30 is obtained. In the above two production methods, the adhesive is a known emulsion-based adhesive (for example, vinyl chloride resin-based, urethane-based, vinyl acetate-based) or a known solvent-based adhesive (for example, urethane-based in combination with an isocyanate-based curing agent). In addition, a paste-like soft vinyl chloride resin composition can be used.
軟質塩化ビニル樹脂層上にはフッ素樹脂層が形成されることにより、得られるフレキシブルシートは、フッ素樹脂層がバリヤー層となって可塑剤のブリードが長期間に亘り防止される効果の発現と同時に、優れた防汚性、及び優れた汚れ除去性を付与する。また、軟質塩化ビニル樹脂層上には、無機コロイド物質が、シランカップリング剤の加水分解縮合物を含むバインダー成分に担持されてなる防汚層が設けられることにより、得られるフレキシブルシートは、防汚層がバリヤー層となって可塑剤のブリードが長期間に亘り防止される効果の発現と同時に、優れた防汚性、及び優れた汚れ除去性の発現を可能とし、さらには優れた帯電防止性を付与する。使用する無機コロイド物質は、光触媒性酸化チタンゾル、光触媒性酸化亜鉛ゾル、光触媒性酸化錫ゾル、酸化チタンゾル、酸化亜鉛ゾル、酸化錫ゾル、シリカゾル、酸化アルミニウムゾル、酸化ジルコニウムゾル、酸化セリウムゾル、及び複合酸化物（酸化亜鉛−五酸化アンチモン複合または酸化スズ−五酸化アンチモン複合）ゾルなどが使用できる。バインダー成分は公知のシランカップリング剤が使用できる。バインダー成分は必要に応じて、アクリル系樹脂、フッ素系共重合樹脂、アクリル−シリコン共重合樹脂、アクリルーフッ素共重合樹脂、アクリル−ウレタン共重合樹脂、アクリル系樹脂とフッ素系共重合樹脂とのブレンドなどを併用することもできる。 By forming a fluororesin layer on the soft vinyl chloride resin layer, the resulting flexible sheet has a manifestation of the effect that the fluororesin layer becomes a barrier layer and prevents plasticizer bleeding over a long period of time. , Imparts excellent antifouling properties and excellent soil removability. In addition, an antifouling layer in which an inorganic colloid substance is supported on a binder component containing a hydrolysis condensate of a silane coupling agent is provided on the soft vinyl chloride resin layer, whereby the obtained flexible sheet The soil layer becomes a barrier layer, and the effect of preventing bleeding of the plasticizer over a long period of time is achieved, and at the same time, it is possible to exhibit excellent antifouling properties and excellent soil removability, as well as excellent antistatic properties. Gives sex. The inorganic colloid materials used are photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and composite An oxide (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol can be used. A known silane coupling agent can be used as the binder component. As necessary, the binder component is an acrylic resin, a fluorine copolymer resin, an acrylic-silicon copolymer resin, an acrylic-fluorine copolymer resin, an acrylic-urethane copolymer resin, an acrylic resin and a fluorine copolymer resin. Blends can also be used in combination.
以下、本発明について実施例を挙げて具体的に説明するが、本発明はこれらに限定されるものではない。以下に実施例及び比較例のシートの評価方法を説明する。
〈１−１：可塑剤ブリードの抑止効果：濡れ性評価〉
１０ｃｍ×１０ｃｍサイズの試料２枚を重ね、２枚のガラス板（１０ｃｍ×１０ｃｍサイズ×５ｍｍ厚）で挟み、これを２３℃で平置した状態で２４００時間静置し、取り出し直後のガラス板面の曇り（フォギング）や濡れ（ブリード）の有無の目視及び指触判断を以って可塑剤のブリードの抑止性（防止性）を判断した。
１（良好）：ガラス板面に曇りを認めないレベル
２（やや不良）：ガラス板面に曇りを認め、触ると滑るレベル
３（不良）：ガラス板面に顕著な濡れを認め、試料表面にも濡れを認めるレベル
〈１−２：可塑剤ブリードの抑止効果:揮発減量評価〉
質量の明らかな１０ｃｍ×１０ｃｍサイズの試料２枚を重ね、８５℃に設定したギアーオーブン中に吊した状態で７２時間静置し、取り出し後の試料の質量より可塑剤の揮発量を求め、この揮発減量の「多い」「少ない」を以って可塑剤のブリードの抑止性（防止性）を判断した。
１：（ブリード防止効果を認める）：１０ｍｇ未満
２：（ややブリード抑止効果を認める）：１０〜２０ｍｇ未満
３：（ブリード防止効果が認められない）：２０ｍｇを越える
〈１−３：ブロッキング防止効果〉
１０ｃｍ×１０ｃｍサイズの試料２枚を重ね、２枚のガラス板（１０ｃｍ×１０ｃｍサイズ×５ｍｍ厚）で挟み、２０ｋｇの荷重を掛けた状態、３５℃で平置した状態で２４時間静置し、取り出した２枚積重試料を万能引張試験機で５０ｍｍ／ｍｉｎの速度で１８０°ピーリング分離し、得られた剥離応力からブロッキング防止性を判断した。
１（良好）：２００ｇｆ/１０ｃｍ未満
２（やや不良）：２００ｇｆ〜５００ｇｆ/１０ｃｍ未満
３（不良）：５００ｇｆ/１０ｃｍを超える
〈１−４：可塑剤ブリードの抑止効果:防汚性評価〉
南向き傾斜角３０度に設置し屋外曝露６０日（６月〜７月）の試料について、試料の色差ΔＥ値（ブランクとの対比）を測定し防汚性を下記基準で判定した。（埼玉県草加市内にて曝露）
１：６０日の防汚性として良好 ：ΔＥ＝ ５未満
２：６０日の防汚性としてやや劣る：ΔＥ＝５ 〜８未満
３：６０日の防汚性として劣る ：ΔＥ＝８以上
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. Below, the evaluation method of the sheet | seat of an Example and a comparative example is demonstrated.
<1-1: Plasticizer Bleed Deterrence Effect: Wettability Evaluation>
Two 10cm x 10cm size samples were stacked and sandwiched between two glass plates (10cm x 10cm size x 5mm thickness), which were left flat for 2400 hours at 23 ° C. The plasticizer bleed deterrence (prevention) was judged by visual inspection and finger touching for the presence or absence of fogging (fogging) or wetting (bleeding).
1 (Good): Level at which no fogging is observed on the glass plate surface 2 (Slightly bad): Level at which the glass plate surface is fogged and slips when touched 3 (Bad): Remarkable wetting is observed on the glass plate surface, and on the sample surface Level where wetting is recognized <1-2: Detergent effect of plasticizer bleed: Evaluation of volatile loss>
Two samples of 10 cm x 10 cm with a clear mass are stacked and left in a state of being hung in a gear oven set at 85 ° C for 72 hours, and the volatilization amount of the plasticizer is obtained from the mass of the sample after removal. The plasticizer bleed deterrence (preventiveness) was judged based on “large” and “small” volatilization loss.
1: (Bleed prevention effect is recognized): Less than 10 mg 2: (Slight bleed inhibiting effect is recognized): Less than 10-20 mg 3: (Bleed prevention effect is not recognized): Over 20 mg <1-3: Blocking prevention effect >
Two 10cm x 10cm size samples were stacked and sandwiched between two glass plates (10cm x 10cm size x 5mm thickness), left under a load of 20kg, and placed flat at 35 ° C for 24 hours, The two stacked samples taken out were separated by 180 ° peeling at a speed of 50 mm / min with a universal tensile tester, and the anti-blocking property was judged from the obtained peeling stress.
1 (good): less than 200 gf / 10 cm 2 (slightly bad): 200 gf to less than 500 gf / 10 cm 3 (bad): over 500 gf / 10 cm <1-4: Plasticizer bleed suppression effect: antifouling evaluation>
About the sample of 60 days (June-July) outdoor exposure which was installed in the south inclination | tilt angle of 30 degree | times, the color difference (DELTA) E value (contrast with a blank) of a sample was measured and antifouling property was determined on the following reference | standard. (Exposed in Soka City, Saitama Prefecture)
1: Good as antifouling property for 60 days: ΔE = less than 5 2: Slightly inferior as antifouling property for 60 days: ΔE = less than 5 to 8 3: Inferior as antifouling property for 60 days: ΔE = 8 or more
[実施例１]
〈繊維織物：基布１〉
５００ｄ（５５５dtex）のポリエステル（ＰＥＴ）マルチフィラメント糸条（アクリル系樹脂被覆：被覆率５質量％）を経緯糸条として、経糸条５本／１０ｃｍ、緯糸条５本／１０ｃｍの打ち込みで織配置し、これを熱接着した粗目平織物（質量１５ｇ/ｍ２：空隙率９２％）を基布１とした。まず〔配合１〕による第一軟質塩化ビニル樹脂コンパウンド（１７０℃熱混練物）を用意し、これをカレンダー成型機に掛け〔配合１〕による厚さ０．１３ｍｍのフィルムを得た。次いでこのフィルムを、ラミネーターにより基布１の両面に１７０℃の熱ロール条件でフィルムを軟化させた状態で積層し、空隙部のブリッヂ接着により厚さ０．２５ｍｍ、質量３３０ｇ/ｍ２の透明、透視性フレキシブルシートを得た。繊維織物と軟質塩化ビニル樹脂層との質量比は、１５：３１５（＝１：２１）であった。
〔配合１〕軟質塩化ビニル樹脂コンパウンド組成物
懸濁重合ポリ塩化ビニル樹脂（重合度１３００） １００質量部
１，２−シクロヘキサンジカルボン酸ジイソノニル（可塑剤） ２０質量部
※商品名：ヘキサモールＤＩＮＣＨ（ＢＡＳＦ社製）
リン酸クレジルジフェニル（防炎可塑剤） ２０質量部
（別名ＣＤＰ：クレジルジフェニルフォスフェート）
塩素化ポリエチレン（塩素化度３０％：半結晶性：ＭＦＲ２５） １０質量部
エポキシ化大豆油（可塑剤） ５質量部
バリウム／亜鉛複合安定剤 ２質量部
ベンゾトリアゾール化合物（紫外線吸収剤） ０．３質量部
[Example 1]
<Textile fabric: Base fabric 1>
A 500d (555 dtex) polyester (PET) multifilament yarn (acrylic resin coating: coverage 5% by mass) is used as a warp yarn and woven and arranged by driving 5 warps / 10 cm and 5 wefts / 10 cm. The base fabric 1 was a coarse plain fabric (mass 15 g / m 2 : porosity 92%) to which this was thermally bonded. First, a first soft vinyl chloride resin compound (mixed at 170 ° C.) according to [Blend 1] was prepared, and this was applied to a calendering machine to obtain a film having a thickness of 0.13 mm according to [Blend 1]. Next, this film was laminated on both sides of the base fabric 1 with a laminator in a state where the film was softened under a hot roll condition of 170 ° C., and a transparent film having a thickness of 0.25 mm and a mass of 330 g / m 2 by bridging the gap. A transparent flexible sheet was obtained. The mass ratio of the fiber fabric to the soft vinyl chloride resin layer was 15: 315 (= 1: 21).
[Formulation 1] Soft polyvinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 20 parts by mass * Product name: Hexamol DINCH (BASF (Made by company)
20 parts by mass of cresyl diphenyl phosphate (flameproof plasticizer) (also known as CDP: cresyl diphenyl phosphate)
Chlorinated polyethylene (degree of chlorination 30%: semi-crystalline: MFR25) 10 parts by mass Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 Parts by mass
[実施例２]
まず塩素化ポリエチレンを含まない〔配合２〕による第一軟質塩化ビニル樹脂コンパウンド（１７０℃熱混練物）を用意し、次いでこれに塩素化ポリエチレンを追加して１７０℃熱混練物とした第二軟質塩化ビニル樹脂コンパウンドを用い、これをカレンダー成型機に掛け〔配合１〕と同一の厚さ０．１６ｍｍのフィルムを得た。次にこのフィルムを、ラミネーターにより基布１の両面に１７０℃の熱ロール条件でフィルムを軟化させた状態で積層し、空隙部のブリッヂ接着により厚さ０．２５ｍｍ、質量３３０ｇ/ｍ２の透明、透視性フレキシブルシートを得た。繊維織物と軟質塩化ビニル樹脂層との質量比は、１５：３１５（＝１：２１）であった。
〔配合２〕軟質塩化ビニル樹脂コンパウンド組成物
懸濁重合ポリ塩化ビニル樹脂（重合度１３００） １００質量部
１，２−シクロヘキサンジカルボン酸ジイソノニル（可塑剤） ２０質量部
※商品名：ヘキサモールＤＩＮＣＨ（ＢＡＳＦ社製）
リン酸クレジルジフェニル（防炎可塑剤） ２０質量部
（別名ＣＤＰ：クレジルジフェニルフォスフェート）
エポキシ化大豆油（可塑剤） ５質量部
バリウム／亜鉛複合安定剤 ２質量部
ベンゾトリアゾール化合物（紫外線吸収剤） ０．３質量部
[Example 2]
First, prepare a first soft vinyl chloride resin compound (170 ° C. heat kneaded product) containing [chlorinated polyethylene] that does not contain chlorinated polyethylene, and then add chlorinated polyethylene to make a second soft kneaded material at 170 ° C. A vinyl chloride resin compound was used, and this was applied to a calender molding machine to obtain a film having a thickness of 0.16 mm which was the same as [Composition 1]. Next, this film was laminated on both sides of the base fabric 1 with a laminator in a state where the film was softened under a hot roll condition of 170 ° C., and transparent with a thickness of 0.25 mm and a mass of 330 g / m 2 by bridging the gap. A transparent flexible sheet was obtained. The mass ratio of the fiber fabric to the soft vinyl chloride resin layer was 15: 315 (= 1: 21).
[Formulation 2] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl (plasticizer) 20 parts by mass * Product name: Hexamol DINCH (BASF) (Made by company)
20 parts by mass of cresyl diphenyl phosphate (flameproof plasticizer) (also known as CDP: cresyl diphenyl phosphate)
Epoxidized soybean oil (plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Benzotriazole compound (ultraviolet absorber) 0.3 parts by mass
[実施例３]
実施例１で得たフレキシブルシートの表面に下記〔配合３〕による接着層を形成し、接着層を介在して厚さ５０μｍのポリビニリデンフルオライド（ＰＶｄＦ）透明フィルムを１８０℃で熱ラミネートして、フッ素樹脂層が設けられた厚さが０．３ｍｍ、質量が４００ｇ/ｍ２のフレキシブルシートを得た。
〈接着層〉
実施例１を基材として８０メッシュグラビアロール塗工条件の塗工機に掛け、軟質塩化ビニル樹脂層上に〔配合３〕の接着組成物による塗工を行い、１２０℃の熱風炉で３分間乾燥した。
〔配合３〕接着組成物
ポリエチレンイミンが反応性基としてグラフトされたアクリル樹脂
（固形分濃度３０質量％、アミン当量:１４００ｇ/eq） １００質量部
ビスフェノールＡ型エポキシ樹脂（エポキシ当量:２００ｇ/eq） ７重量部
ベンゾトリアゾール化合物（紫外線吸収剤） ０．５質量部
メチルエチルケトン １００質量部
[Example 3]
An adhesive layer according to the following [Formulation 3] was formed on the surface of the flexible sheet obtained in Example 1, and a polyvinylidene fluoride (PVdF) transparent film having a thickness of 50 μm was thermally laminated at 180 ° C. with the adhesive layer interposed. A flexible sheet having a thickness of 0.3 mm and a mass of 400 g / m 2 provided with a fluororesin layer was obtained.
<Adhesive layer>
Using Example 1 as a base material, it was applied to a coating machine under 80 mesh gravure roll coating conditions, coated with the adhesive composition of [Formulation 3] on the soft vinyl chloride resin layer, and heated in a 120 ° C. hot air oven for 3 minutes. Dried.
[Formulation 3] Adhesive composition Acrylic resin grafted with polyethyleneimine as a reactive group (solid content concentration 30% by mass, amine equivalent: 1400 g / eq) 100 parts by mass Bisphenol A type epoxy resin (epoxy equivalent: 200 g / eq) 7 parts by weight Benzotriazole compound (ultraviolet absorber) 0.5 parts by weight Methyl ethyl ketone 100 parts by weight
[実施例４]
実施例１で得たフレキシブルシートの表面に下記〔配合４〕による防汚層を形成し、厚さが０．２６ｍｍ、質量が３３３ｇ／ｍ２のフレキシブルシートを得た。
〈防汚層〉
実施例１を基材として８０メッシュグラビアロール塗工条件の塗工機に掛け、軟質塩化ビニル樹脂層上に〔配合４〕の防汚組成物による塗工を行い、１２０℃の熱風炉で３分間乾燥した。
〔配合４〕防汚組成物
シリカゾル（粒子径２０〜３０ｎｍ：固形分４８質量％） １００質量部
ビニルトリエトキシシラン（シランカップリング剤） ５０質量部
酸化亜鉛粒子（粒子径１５ｎｍ）（紫外線吸収剤） ０．５質量部
ポリエチレングリコール型非イオン活性剤（帯電防止剤） １質量部
希釈剤（水） １００質量部
[Example 4]
An antifouling layer according to the following [Composition 4] was formed on the surface of the flexible sheet obtained in Example 1, and a flexible sheet having a thickness of 0.26 mm and a mass of 333 g / m 2 was obtained.
<Anti-fouling layer>
Using Example 1 as a base material, it was applied to a coating machine under 80 mesh gravure roll coating conditions, coated on the soft vinyl chloride resin layer with the antifouling composition of [Composition 4], and heated in a 120 ° C. hot air oven. Dried for minutes.
[Formulation 4] Antifouling composition Silica sol (particle size 20-30 nm: solid content 48% by mass) 100 parts by mass Vinyltriethoxysilane (silane coupling agent) 50 parts by mass Zinc oxide particles (particle size 15 nm) (ultraviolet absorber) 0.5 parts by weight Polyethylene glycol type nonionic active agent (antistatic agent) 1 part by weight Diluent (water) 100 parts by weight
[比較例１]
実施例１の〔配合１〕に用いた塩素化ポリエチレン１０質量部を省略した以外は実施例１と同様として、厚さ０．２５ｍｍ、質量３３０ｇ/ｍ２の透明、透視性フレキシブルシートを得た。得られたフレキシブルシートは、軟質塩化ビニル樹脂層に塩素化ポリエチレンを含まないことで、耐ブロッキング性、及び可塑剤のブリード抑止性に劣り、煤塵付着などによって汚れ易いものであった。
[Comparative Example 1]
A transparent and transparent flexible sheet having a thickness of 0.25 mm and a mass of 330 g / m 2 was obtained in the same manner as in Example 1 except that 10 parts by mass of the chlorinated polyethylene used in [Composition 1] of Example 1 was omitted. . Since the obtained flexible sheet does not contain chlorinated polyethylene in the soft vinyl chloride resin layer, it is inferior in blocking resistance and bleed deterrence of the plasticizer, and easily becomes dirty due to dust adhesion.
[比較例２]
実施例１の〔配合１〕に用いた塩素化ポリエチレン１０質量部を４０質量部に増量したところ、カレンダー加工時のロール滑性が悪く、１７５℃熱条件のロール全面に粘着してことで軟質塩化ビニル樹脂層を得ることができなかった。
[Comparative Example 2]
When 10 parts by mass of the chlorinated polyethylene used in [Composition 1] of Example 1 was increased to 40 parts by mass, the roll lubricity at the time of calendering was poor, and it was soft by sticking to the entire roll at 175 ° C. under heat conditions. A vinyl chloride resin layer could not be obtained.
[比較例３]
実施例１の〔配合１〕に用いた１，２−シクロヘキサンジカルボン酸ジイソノニル２０質量部を、ジ−２−エチルヘキシル−フタレート（別名：フタル酸ジオクチル：ＤＯＰ）２０質量部に置換した以外は実施例１と同様として、厚さ０．２５ｍｍ、質量３３０ｇ/ｍ２の透明、透視性フレキシブルシートを得た。得られたフレキシブルシートでは耐ブロッキング性の効果が実施例１のフレキシブルシートに比較して不十分であった。
[Comparative Example 3]
Example except that 20 parts by mass of diisononyl 1,2-cyclohexanedicarboxylate used in [Formulation 1] of Example 1 was replaced with 20 parts by mass of di-2-ethylhexyl phthalate (also known as dioctyl phthalate: DOP). As in Example 1, a transparent, transparent flexible sheet having a thickness of 0.25 mm and a mass of 330 g / m 2 was obtained. In the obtained flexible sheet, the effect of blocking resistance was insufficient as compared with the flexible sheet of Example 1.
本発明によれば、タックが小さく、可塑剤ブリードが長期間に亘り極少量に抑止されることで、耐ブロッキング性の持続を可能とするので、特に、間仕切り、シートシャッター、日除け・雨除け、防水エプロン、防水バッグなどの産業資材の製造工程における縫製作業時の取り扱い性、透視性、採光性など透明性に優れたフレキシブルシートとして極めて有用である。 According to the present invention, the tack is small, and the plasticizer bleed is suppressed to a very small amount over a long period of time, so that the blocking resistance can be maintained, and in particular, the partition, the sheet shutter, the awning and the rain protection, It is extremely useful as a flexible sheet excellent in transparency, such as handleability, transparency, and daylighting during sewing operations in the manufacturing process of industrial materials such as waterproof apron and waterproof bag.
Claims (4)
A light-transmitting membrane material comprising a fiber fabric as a base material and a soft vinyl chloride resin layer provided on at least one surface thereof, wherein the mass ratio of the fiber fabric to the soft vinyl chloride resin layer is 1: 5 to 5 1:30, and the soft vinyl chloride resin layer mainly contains 100 parts by mass of vinyl chloride resin and 15 to 65 parts by mass of cycloalkyldicarboxylic acid dialkyl ester (group of [Chemical Formula 1]), and further chlorinated 1 to 30 parts by mass of polyethylene.
A first soft vinyl chloride resin thermal kneaded product mainly comprising 100 parts by mass of a vinyl chloride resin and 15 to 65 parts by mass of a dialkyl ester of cyclohexanedicarboxylic acid (group of [Chemical Formula 1]) is prepared, and then the vinyl chloride type Using the second soft vinyl chloride resin thermal kneaded material obtained by additionally blending 1 to 30 parts by mass of chlorinated polyethylene with 100 mass parts of the resin into the first soft vinyl chloride resin thermal kneaded material, A film formed by rolling from a vinyl resin heat-kneaded product is laminated on one or more sides of a fiber fabric, thereby obtaining a light-transmitting film material having the film as a soft vinyl chloride resin layer and the fiber fabric as a base material. A method for producing a blocking-effect-persistent flexible sheet.
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| JPH0625495A (en) * | 1992-04-14 | 1994-02-01 | Mitsubishi Kasei Vinyl Co | Vinyl chloride resin elastomer composition |
| JP4314711B2 (en) * | 2000-01-27 | 2009-08-19 | 新日本理化株式会社 | Cyclohexanedicarboxylic acid diester plasticizer, vinyl chloride resin composition, and vinyl chloride resin molded article using the same |
| JP2002060574A (en) * | 2000-08-21 | 2002-02-26 | Showa Denko Kk | Vinyl chloride-based desin composition |
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