JP4849954B2 - Flame retardant coated paper for printing - Google Patents
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- JP4849954B2 JP4849954B2 JP2006134359A JP2006134359A JP4849954B2 JP 4849954 B2 JP4849954 B2 JP 4849954B2 JP 2006134359 A JP2006134359 A JP 2006134359A JP 2006134359 A JP2006134359 A JP 2006134359A JP 4849954 B2 JP4849954 B2 JP 4849954B2
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本発明は、美術出版、図鑑、絵本、パンフレット、カタログ、ポスター、カレンダー、書籍、地図、ラベル、各種宣伝広告媒体、各種カード、壁紙スクリーン等に使用することのできる印刷適性を持った印刷対応用の難燃塗工紙に関する。 The present invention is for printing compatible with printability that can be used for art publications, picture books, picture books, brochures, catalogs, posters, calendars, books, maps, labels, various advertising media, various cards, wallpaper screens, etc. Related to flame retardant coated paper.
難燃剤により難燃処理された基紙の片面若しくは両面に無機顔料及びバインダーを主とする塗布層が、片面につき５ｇ／ｍ2以上３０ｇ／ｍ2未満の範囲の量で設けられてなるビニル壁紙裏打ち用難燃紙に関する技術がある（特許文献１参照）。無機顔料とセルロース繊維を配合した基紙の片面若しくは両面に、無機顔料を主体とする塗工層が設けられ無機質分として全体の８０質量％以上である不燃紙に関する技術がある（特許文献２参照。）。平均粒子径の異なる水酸化アルミニウムの少なくとも２種以上を混合して湿式抄紙した水酸化アルミニウム含有率４０〜６０質量％の原紙に、難燃性組成物を原紙当たり５〜１０質量％塗布したことを特徴とするビニル壁紙裏打ち用難燃紙に関する技術がある（特許文献３参照）。壁紙用基材と、少なくとも一方の面に無機充填剤を主体とする塗工層が設けられた塗工紙とを積層した化粧シートにおいて、前記塗工紙に少なくとも凹凸模様が形成されていることを特徴とする化粧シートに関する技術がある（特許文献４参照）。ノンハロゲン含窒素有機リン化合物、及びこの化合物が配合されてなる難燃性樹脂組成物に関し、優れた難燃性を示すものの発煙性や燃焼時の有毒ガスの発生などの原因となるハロゲンを含有しないノンハロゲン含窒素有機リン化合物及びこの化合物が配合されてなる難燃性樹脂組成物に関する技術がある（特許文献５参照）。 Vinyl wallpaper in which a coating layer mainly composed of an inorganic pigment and a binder is provided on one side or both sides of a base paper flame-retardant treated with a flame retardant in an amount in the range of 5 g / m 2 or more and less than 30 g / m 2 There is a technology related to flame retardant paper for backing (see Patent Document 1). There is a technique relating to non-combustible paper in which a coating layer mainly composed of an inorganic pigment is provided on one or both sides of a base paper containing an inorganic pigment and cellulose fiber, and the inorganic content is 80% by mass or more of the whole (see Patent Document 2) .) The flame retardant composition was applied to 5 to 10% by mass of the base paper with 40 to 60% by mass of the aluminum hydroxide content obtained by wet papermaking by mixing at least two kinds of aluminum hydroxides having different average particle sizes. There is a technology related to flame retardant paper for vinyl wallpaper lining (see Patent Document 3). In a decorative sheet in which a base material for wallpaper and a coated paper provided with a coating layer mainly composed of an inorganic filler are laminated on at least one surface, at least an uneven pattern is formed on the coated paper. There is a technology related to a decorative sheet characterized by the above (see Patent Document 4). Non-halogen nitrogen-containing organophosphorus compound and flame retardant resin composition containing this compound, which exhibits excellent flame retardancy, but does not contain halogens that cause smoke generation or generation of toxic gas during combustion There is a technique relating to a halogen-free nitrogen-containing organophosphorus compound and a flame retardant resin composition containing this compound (see Patent Document 5).
以上に述べた従来の難燃塗工紙等は壁紙用途が主体であり、印刷適性および難燃性に優れ、壁紙分野以外の用途に用いられるものではなかた。 The conventional flame retardant coated paper and the like described above are mainly used for wallpaper, are excellent in printability and flame retardancy, and have not been used for applications other than the wallpaper field.
本発明の課題は、加工の容易な紙を主体とした難燃塗工紙を対象とし、燃焼時の有毒ガスの発生がなく、優れた難燃効果を持ちながら、優れた印刷適性を有した印刷対応用の難燃塗工紙を提供することを目的とする。 An object of the present invention is to target flame-retardant coated paper mainly composed of easy-to-process paper, has no generation of toxic gas during combustion, has excellent flame retardancy, and has excellent printability. An object is to provide a flame-retardant coated paper for printing .
本発明は、上記課題に着目し、難燃剤を含浸した原紙の片面又は両面に印刷適性のある塗工層を塗布するという検討を重ね、上記課題を解決しようとするものである。 The present invention pays attention to the above-mentioned problems and intends to solve the above-mentioned problems by repeatedly investigating applying a printable coating layer on one or both sides of a base paper impregnated with a flame retardant.
すなわち本発明は、填料含有量が対パルプ当たり０〜１０質量％である、単層で又は多層で抄造された坪量４０〜２５０ｇ／ｍ２原紙に、無機系化合物およびリンおよび／または窒素含有の有機系化合物からなるノンハロゲン系難燃剤を用いて、原紙への含浸量が６〜３０ｇ／ｍ２（乾燥質量）となるように含浸処理を行い、その含浸処理した紙基材の片面又は両面に無機顔料及びバインダーを主体とした塗布層を片面当り５ｇ／ｍ２以上３０ｇ／ｍ２（乾燥質量）未満設けた塗工紙であり、かつ、該塗工紙がＵＬ規格においてＵＬ９４Ｖ−０及び／又はＵＬ９４ＶＴＭ−０とした印刷対応用の難燃塗工紙である。 That is, according to the present invention, an inorganic compound and phosphorus and / or nitrogen are contained in a base paper having a basis weight of 40 to 250 g / m 2 which is made of a single layer or multiple layers and has a filler content of 0 to 10% by mass per pulp. A non-halogen flame retardant composed of an organic compound is used to impregnate the base paper so that the impregnation amount is 6 to 30 g / m 2 (dry mass), and one or both sides of the impregnated paper base material The coated paper is provided with a coating layer mainly composed of an inorganic pigment and a binder at 5 g / m 2 or more and less than 30 g / m 2 (dry mass) per side, and the coated paper is UL94V-0 and It is a flame retardant coated paper for printing corresponding to UL94VTM-0.
また、本発明の有利な一つの実施態様は、無機顔料及びバインダーを主体とした前記塗布層中において、バインダー１００質量部（乾燥質量）に対し、５〜５０質量部（乾燥質量）のノンハロゲン系難燃剤を配合したものである。 In addition, in one advantageous embodiment of the present invention, in the coating layer mainly composed of an inorganic pigment and a binder, 5 to 50 parts by mass (dry mass) of a non-halogen system with respect to 100 parts by mass (dry mass) of the binder. It contains a flame retardant.
本発明のもう一つの有利な実施態様は、前記原紙中に、ポリオレフィン系合成パルプ、ポリエステル繊維、アクリル繊維、レーヨン繊維、ビニロン繊維の群からなる有機合成繊維及びガラス繊維、炭素繊維の群からなる無機繊維のいずれかの繊維を少なくとも１種類配合したものである。 In another advantageous embodiment of the present invention, the base paper is composed of a group of organic synthetic fibers and glass fibers and carbon fibers composed of polyolefin synthetic pulp, polyester fibers, acrylic fibers, rayon fibers and vinylon fibers. At least one kind of inorganic fiber is blended.
原紙へのノンハロゲン系難燃剤の含浸量が６〜３０ｇ／ｍ2（乾燥質量）であることによって塗工紙に難燃性が付与され、紙基材の片面又は両面に無機顔料及びバインダーを主体とした塗布層を片面当り５ｇ／ｍ2 以上３０ｇ／ｍ 2 （乾燥質量）未満設けることによって塗工紙に優れた印刷適性がもたらされる。更に難燃剤としてノンハロゲン系難燃剤が使用されているために、ハロゲン系難燃剤を使用する場合に燃焼時に問題となるダイオキシン等の有害物質の発生がない。 When the impregnation amount of the non-halogen flame retardant into the base paper is 6 to 30 g / m 2 (dry mass ) , flame resistance is imparted to the coated paper, and an inorganic pigment and a binder are added to one or both sides of the paper substrate. printability with excellent coated paper is effected by kicking set less per side 5 g / m 2 or more 30 g / m 2 (dry weight) of the coating layer containing mainly. Furthermore, since non-halogen flame retardants are used as flame retardants, no harmful substances such as dioxins, which are problematic during combustion, are generated when halogen flame retardants are used.
また、前記塗布層中において、バインダー１００質量部（乾燥質量）に対し、５〜５０質量部（乾燥質量）のノンハロゲン系難燃剤を配合することによって、塗工紙の難燃性が更に高められる。 Moreover, in the said coating layer, the flame retardance of a coated paper is further improved by mix | blending 5-50 mass parts (dry mass) non-halogen flame retardant with respect to 100 mass parts (dry mass) of binders. .
さらに、原紙中に、ポリオレフィン系合成パルプ、ポリエステル繊維、アクリル繊維、レーヨン繊維、ビニロン繊維の群からなる有機合成繊維及びガラス繊維、炭素繊維の群からなる無機繊維のいずれかの繊維を少なくとも１種類配合することによって、難燃性塗工紙の紙力および／または寸法安定性が増強される。 Furthermore, at least one fiber selected from the group consisting of synthetic synthetic pulp, polyester fiber, acrylic fiber, rayon fiber, vinylon fiber, and inorganic fiber composed of glass fiber and carbon fiber is used in the base paper. By blending, the paper strength and / or dimensional stability of the flame-retardant coated paper is enhanced.
上述したように、本発明の難燃塗工紙は、無機系化合物およびリンおよび／または窒素含有の有機系化合物からなるノンハロゲン系難燃剤を用いて難燃処理された原紙の片面又は両面に無機顔料及びバインダーを主体とした塗料を塗布することによって、従来の一般的な難燃塗工紙に比べて、燃焼によるダイオキシン等の有害物を発生することなく、優れた難燃性と優れた印刷適性を兼ね備えている。 As described above, the flame-retardant coated paper of the present invention is inorganic on one side or both sides of a base paper that has been flame-treated using an inorganic compound and a non-halogen flame retardant comprising phosphorus and / or a nitrogen-containing organic compound. By applying paints mainly composed of pigments and binders, superior flame retardancy and excellent printing can be achieved without generating harmful substances such as dioxins due to combustion compared to conventional general flame retardant coated paper. Combines aptitude.
以下、本発明について説明するが、本発明はこれらの実施形態に限定して解釈されない。 Hereinafter, the present invention will be described, but the present invention is not construed as being limited to these embodiments.
本発明は、無機系化合物およびリンおよび／または窒素含有の有機系化合物からなるノンハロゲン系難燃剤により難燃処理された原紙の片面又は両面に無機顔料及びバインダーを主体とした塗布層を設けた難燃塗工紙である。 In the present invention, it is difficult to provide a coating layer mainly composed of an inorganic pigment and a binder on one side or both sides of a base paper flame-treated with an inorganic compound and a halogen-free flame retardant comprising a phosphorus and / or nitrogen-containing organic compound. It is a flame-coated paper.
本発明の難燃塗工紙を構成する材料、該難燃塗工紙の構成要素及びその製法について項分けして説明する。 The material constituting the flame-retardant coated paper of the present invention, the constituent elements of the flame-retardant coated paper, and the production method thereof will be described separately.
本発明で、難燃塗工紙に用いる含浸用原紙を抄造するために使用する製紙用パルプは、特に制限はなく、通常の製紙で使用されるものは、どれでも使用することができる。例えば針葉樹未晒クラフトパルプ(Ｎ−ＵＫＰ)、針葉樹晒クラフトパルプ(Ｎ−ＢＫＰ)、広葉樹晒クラフトパルプ(Ｌ−ＢＫＰ)、針葉樹晒サルファイトパルプ(Ｎ−ＢＳＰ)等の木材パルプを主材とし、麻、木綿、藁パルプ、ケナフ等の非木材パルプも使用できる。木材パルプについては、均一な含浸性を得る点で広葉樹パルプよりも針葉樹パルプを使用する方が有利である。 In the present invention, the papermaking pulp used for making the base paper for impregnation used for the flame-retardant coated paper is not particularly limited, and any of those used in ordinary papermaking can be used. For example, wood pulp such as softwood unbleached kraft pulp (N-UKP), softwood bleached kraft pulp (N-BKP), hardwood bleached kraft pulp (L-BKP), softwood bleached sulfite pulp (N-BSP) Non-wood pulp such as hemp, cotton, straw pulp and kenaf can also be used. For wood pulp, it is more advantageous to use softwood pulp than hardwood pulp in terms of obtaining uniform impregnation.
上記パルプの他にも、紙力増強および／または寸法安定性のために、ポリオレフィン系合成パルプ、ポリエステル繊維、アクリル繊維、レーヨン繊維、ビニロン繊維の群からなる有機合成繊維及びガラス繊維、炭素繊維の群からなる無機繊維の中から各種の繊維を少なくとも１種類併用することも可能である。 In addition to the above-mentioned pulp, organic synthetic fiber and glass fiber, carbon fiber made of polyolefin synthetic pulp, polyester fiber, acrylic fiber, rayon fiber, vinylon fiber are used for enhancing paper strength and / or dimensional stability. It is also possible to use at least one kind of various kinds of fibers among inorganic fibers made of a group.
紙料中には内添サイズ剤、紙力剤、填料、硫酸バンド(硫酸アルミニウム)、歩留り向上剤、染料、蛍光染料等が適宜用いられる。 In the paper material, an internal sizing agent, a paper strength agent, a filler, a sulfate band (aluminum sulfate), a yield improver, a dye, a fluorescent dye, and the like are appropriately used.
内添サイズ剤としては、アルキルケテンダイマー(ＡＫＤ)、アルケニル無水琥珀酸(ＡＳＡ)、中性ロジン、酸性ロジン等が適宜用いられる。 As the internal sizing agent, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), neutral rosin, acidic rosin and the like are appropriately used.
紙力剤としては、澱粉、変性澱粉、ポリアクリルアミド等が適宜用いられる。 As the paper strength agent, starch, modified starch, polyacrylamide and the like are appropriately used.
填料としては、炭酸カルシウム、タルク、クレー、二酸化チタン等が適宜用いられる。 As the filler, calcium carbonate, talc, clay, titanium dioxide or the like is appropriately used.
歩留り向上剤としては、コロイダルシリカ、ポリアクリルアミド、ポリエチレンイミン等が適宜用いられる。 As the yield improver, colloidal silica, polyacrylamide, polyethyleneimine, or the like is appropriately used.
本発明で前記原紙の含浸に用いる難燃剤としては、臭素、塩素などのハロゲン化合物からなる難燃剤は、燃焼条件によってはダイオキシン等の有害物を発生する可能性がある為、ノンハロゲン系難燃剤が使用される。ノンハロゲン系難燃剤としては、無機系化合物およびリンおよび／または窒素含有の有機系化合物である一般に市販されているものであり、例えば水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、三酸化アンチモン、酸化ジルコニウム、亜リン酸アルミニウム等の金属酸化物、ホウ酸、ホウ酸亜鉛などのホウ素系化合物等の無機化合物、ポリリン酸、ポリリン酸アンモニウム、アミノ基変性リン酸エステル、又は水酸基含有リン酸エステル等のリン系化合物、メラミン又はメラミンシアヌレート化合物、メラミンリン酸塩、メラミンボレート等のメラミン系誘導体、グアニジン若しくはスルファミン酸グアニジン、リン酸グアニジン等のグアニジン系誘導体などのリンおよび／または窒素含有の有機系化合物 が挙げられるがこれら例示化合物に限定されるものではない。これらのノンハロゲン系難燃性化合物は、単独又は２種以上組み合わせて用いられる。 As a flame retardant used for impregnation of the base paper in the present invention, a flame retardant composed of halogen compounds such as bromine and chlorine may generate harmful substances such as dioxins depending on combustion conditions. used. Non-halogen flame retardants are generally commercially available inorganic compounds and organic compounds containing phosphorus and / or nitrogen, such as metal hydroxides such as magnesium hydroxide and aluminum hydroxide, antimony trioxide, and the like. , Metal oxides such as zirconium oxide and aluminum phosphite, inorganic compounds such as boron compounds such as boric acid and zinc borate, polyphosphoric acid, ammonium polyphosphate, amino group-modified phosphate ester, or hydroxyl group-containing phosphate ester Phosphorus compounds such as melamine or melamine cyanurate compounds, melamine phosphates, melamine derivatives such as melamine borate, guanidine or guanidine derivatives such as guanidine sulfamate, guanidine phosphates and the like and / or nitrogen-containing organics -Based compounds It is not limited to al exemplified compounds. These non-halogen flame retardant compounds are used alone or in combination of two or more.
本発明で塗布層用の塗料に添加してもよい難燃剤は、臭素、塩素などのハロゲン化合物からなる難燃剤では燃焼条件によってはダイオキシン等の有害物を発生する可能性があるので、ノンハロゲン系難燃剤であるのが好ましい。この場合に使用されるノンハロゲン系難燃剤も、原紙の含浸に用いる難燃剤として例示した種類のものである。 In the present invention, the flame retardant that may be added to the coating layer coating is a halogen-free flame retardant composed of halogen compounds such as bromine and chlorine, which may generate harmful substances such as dioxins depending on the combustion conditions. A flame retardant is preferred. The non-halogen flame retardant used in this case is also of the type exemplified as the flame retardant used for impregnation of the base paper.
本発明で使用する塗料用顔料としては、軽質炭酸カルシウムの他、白色顔料として従来公知の顔料が用いられる。例えば、重質炭酸カルシウム、カオリン、クレー、デラミネーテッドクレー、タルク、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、珪酸マグネシウム、合成シリカ、水酸化アルミニウム、アルミナ、ゼオライト、炭酸マグネシウム、水酸化マグネシウム、コロイダルシリカのような白色無機顔料、及びスチレン系プラスチックピグメント、アクリル系プラスチックピグメント、ポリエチレン、マイクロカプセル、尿素樹脂、メラミン樹脂のような有機顔料などが挙げられる。これらの顔料は、必要に応じて1種以上を適宜選択して使用することができる。 As the pigment for paint used in the present invention, a conventionally known pigment is used as a white pigment in addition to light calcium carbonate. For example, heavy calcium carbonate, kaolin, clay, delaminated clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate White inorganic pigments such as synthetic silica, aluminum hydroxide, alumina, zeolite, magnesium carbonate, magnesium hydroxide, colloidal silica, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, melamine resin Such organic pigments can be mentioned. One or more of these pigments can be appropriately selected and used as necessary.
本発明で使用する塗料用接着剤としては、塗工紙用に従来から用いられている、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体とポリビニルアルコール、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等の合成接着剤、及びカゼイン、大豆蛋白、合成蛋白等の蛋白質類、並びに酸化澱粉、カチオン化澱粉、尿素リン酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉等のエーテル化澱粉、デキストリン等の澱粉類、更にカルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシメチルセルロース等のセルロース誘導体等の接着剤１種類以上を適宜選択して使用される。これらの接着剤は、通常、顔料１００質量部当たり５〜１００質量部、好ましくは５〜５０質量部、より好ましくは５〜２５質量部（乾燥質量）程度の範囲で使用される。 As coating adhesives used in the present invention, styrene / butadiene, styrene / acrylic, ethylene / vinyl acetate, butadiene / methyl methacrylate, vinyl acetate / butyl, which are conventionally used for coated paper, are used. Synthetic adhesives such as acrylate-based copolymers and polyvinyl alcohol, maleic anhydride copolymers, acrylic acid / methyl methacrylate copolymers, and proteins such as casein, soy protein, synthetic proteins, and oxidized starch One or more adhesives such as cationized starch, urea phosphated starch, etherified starch such as hydroxyethyl etherified starch, starch such as dextrin, and cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, etc. It is appropriately selected and used. These adhesives are usually used in a range of about 5 to 100 parts by mass, preferably 5 to 50 parts by mass, more preferably about 5 to 25 parts by mass (dry mass) per 100 parts by mass of the pigment.
本発明で使用する塗料用助剤としては、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、着色剤等、通常の塗工紙用顔料に配合される各種助剤が適宜使用される。 As a coating aid used in the present invention, it is blended in a normal pigment for coated paper such as a dispersant, a thickener, a water retention agent, an antifoaming agent, a water resistance agent, a colorant, etc. Various auxiliaries are appropriately used.
難燃塗工紙に用いる含浸用原紙の製法は、特に限定されるものでなく、公知の抄紙機、すなわち長網、丸網、ハイブリッドフォーマー、ギャップフォーマー等を用いて単層で又は多層で抄造し、プレス工程、乾燥工程を経て通常４０〜２５０ｇ／ｍ2程度の該原紙を作成する。抄紙方法は、特に限定されず酸性紙、中性紙又はアルカリ性紙のいずれであってもよい。 The production method of the base paper for impregnation used for the flame-retardant coated paper is not particularly limited, and is a single layer or a multilayer using a known paper machine, that is, a long net, a round net, a hybrid former, a gap former, or the like. The base paper is usually made at a rate of about 40 to 250 g / m 2 through a pressing step and a drying step. The papermaking method is not particularly limited, and any of acid paper, neutral paper, or alkaline paper may be used.
前記原紙への難燃剤の含浸はオンマシンサイズプレス装置又は含浸コーターで行われるがこれらに限定されるものではない。これらの含浸量は、６〜３０g／ｍ2 （乾燥質量）、好ましくは１０〜２０g／ｍ2 （乾燥質量）である。含浸量が６g／ｍ2未満であると難燃化効果が不十分となり、３０g／ｍ2を超えると使用量にみあうそれ以上の効果が期待できず、経済的に不利である。 The impregnation of the flame retardant into the base paper is performed by an on-machine size press apparatus or an impregnation coater, but is not limited thereto. These impregnation amounts are 6 to 30 g / m 2 (dry mass) , preferably 10 to 20 g / m 2 (dry mass) . If the impregnation amount is less than 6 g / m 2 , the flame retarding effect is insufficient, and if it exceeds 30 g / m 2 , no further effect corresponding to the amount used can be expected, which is economically disadvantageous.
本発明では、前記のような塗工組成物の塗料を紙基材上へ塗布するには公知のコーター、例えばパイプコーター、ブレードコーター、エアーナイフコーター、ロールコーター、リバースロールコーター、バーコーター、ロッドブレードコーター、ショートドウェルコーター、カーテンコーター、ダイコーター、グラビアコーター、チャンプレックスコーター等から選ばれたコーターを用いて、オフマシンコーター又はオンマシンコーターで、単層若しくは多層に分けて塗布される。塗料の液性からはエアーナイフコーター、カーテンコーター、ロッドコーター等が好ましく、更に好ましくはエアーナイフコーターである。 In the present invention, a known coater such as a pipe coater, a blade coater, an air knife coater, a roll coater, a reverse roll coater, a bar coater, and a rod is used to apply the coating composition of the coating composition as described above onto a paper substrate. Using a coater selected from a blade coater, a short dwell coater, a curtain coater, a die coater, a gravure coater, a chamber coater, and the like, the coating is performed in an off-machine coater or an on-machine coater in a single layer or multiple layers. An air knife coater, a curtain coater, a rod coater or the like is preferable from the liquid property of the paint, and an air knife coater is more preferable.
本発明の含浸用原紙に難燃剤を含浸させた紙基材上に設ける塗布層は、該紙基材の片面又は両面に、単層若しくは二層以上設けることも可能である。塗布層の塗布量は、片面当たり５ｇ／ｍ2以上３０ｇ／ｍ2（乾燥質量）未満が好ましく、より好ましくは８ｇ／ｍ2〜２５ｇ／ｍ2（乾燥質量）、特に好ましくは１０〜２０g／ｍ2（乾燥質量）である。塗布量が５ｇ／ｍ2未満だと絶対量が少ないので塗布層が紙表面の全面を均一に覆うことができないため、一般印刷においてインキ受理均一性を悪化 させる。３０ｇ／ｍ2以上では、生産性、コスト的に好ましくない。 The coating layer provided on the paper base material in which the base paper for impregnation of the present invention is impregnated with the flame retardant can be provided as a single layer or two or more layers on one side or both sides of the paper base material. The coating amount of the coating layer is preferably 5 g / m 2 or more and less than 30 g / m 2 (dry mass) per side, more preferably 8 g / m 2 to 25 g / m 2 (dry mass), particularly preferably 10 to 20 g / m 2. m 2 (dry mass). If the coating amount is less than 5 g / m 2 , since the absolute amount is small, the coating layer cannot uniformly cover the entire surface of the paper, which deteriorates the ink acceptance uniformity in general printing. If it is 30 g / m 2 or more, it is not preferable in terms of productivity and cost.
ここで、顔料塗布層中には難燃剤を適宜配合することもできる。塗布層中の難燃剤配合量は、塗布層中のバインダー１００質量部（乾燥質量）に対し、５〜５０質量部の（乾燥質量）が好ましく、より好ましくは８〜５０質量部（乾燥質量）である。難燃剤配合が１００質量部を超えると、印刷適性が阻害され、また５質量部未満であると難燃効果が十分に発揮されない。 Here, a flame retardant can also be mix | blended suitably in a pigment application layer. The blending amount of the flame retardant in the coating layer is preferably 5 to 50 parts by mass (dry mass), more preferably 8 to 50 parts by mass (dry mass) with respect to 100 parts by mass (dry mass) of the binder in the coating layer. It is. When the amount of the flame retardant exceeds 100 parts by mass , the printability is impaired, and when the amount is less than 5 parts by mass , the flame retardant effect is not sufficiently exhibited.
塗布後の乾燥方式は特に限定されるものではなく、以下の乾燥方式、すなわち熱風乾燥、赤外乾燥、常温乾燥、凍結乾燥等が挙げられるが、その乾燥効率から赤外乾燥、熱風乾燥が好ましい。 The drying method after coating is not particularly limited, and examples include the following drying methods, namely hot air drying, infrared drying, room temperature drying, freeze drying, etc., but infrared drying and hot air drying are preferable because of the drying efficiency. .
また、平滑性向上、及び印刷品質向上等のため、上述の手法で得られた塗工紙を、表面処理することができる。表面処理方法としては、スーパーカレンダー、マシンカレンダー、ソフトニップカレンダー等、公知の表面処理装置を用いることができる。 Moreover, the coated paper obtained by the above-mentioned method can be surface-treated in order to improve smoothness and print quality. As the surface treatment method, a known surface treatment apparatus such as a super calender, a machine calender, or a soft nip calender can be used.
［実施例］
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。また、例中の「部」及び「％」は特に断らない限り「質量部」及び「質量％」を示す。
[Example]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples. Further, “parts” and “%” in the examples indicate “parts by mass” and “% by mass” unless otherwise specified.
＜原紙の作成＞
原料は、Ｎ−ＢＫＰ ７１部、Ｌ−ＢＫＰ ２９部とからなるカナダ標準濾水度（以下、「ＣＳＦ」と略す。） ４００mlのパルプスラリーに、タルク（商品名：太平高白タルク、太平タルク社製）を対パルプ９％、二酸化チタン（商品名：Ｂ−１０１、日本タルク社製）を対パルプ１％、硫酸バンド（テクノ北越社製）を対パルプ２％添加し、９０．７ｇ／ｍ2の原紙を抄造し、本発明の含浸用原紙を得た。
<Creation of base paper>
The raw material is Canadian standard freeness (hereinafter abbreviated as “CSF”) consisting of 71 parts of N-BKP and 29 parts of L-BKP. To 400 ml of pulp slurry, talc (trade name: Taihei Kakuhaku Talc, Taihei Talc) 9% for pulp, 9% titanium dioxide (trade name: B-101, manufactured by Nippon Talc Co., Ltd.) for 1% pulp, and 2% sulfate band (Techno Hokuetsu Co., Ltd.) for pulp. An m 2 base paper was made to obtain an impregnating base paper of the present invention.
上記原紙（坪量９０．７ｇ／ｍ2、厚さ０．１６１ｍｍ、密度０．５６ｇ／ｃｍ３）を用いて、水で３０％濃度に希釈したピロガード Ｆ−４００N（無機及び有機リン系・窒素系化合物のノンハロゲン系難燃剤含浸液：５０％濃度品、第一工業製薬社製）を含浸コーターにて含浸量（乾燥質量）が１２．９ｇ／ｍ2になるように含浸後、エアドライヤーで熱風乾燥し、難燃剤を含浸させた紙基材を得た。その後、該紙基材に下記組成の顔料塗布層用塗料をエアーナイフコーターにて塗布量が１０ｇ／ｍ2（乾燥質量）になるように片面塗布後、エアドライヤーにて熱風乾燥し、本発明の難燃塗工紙を得た。 Pyroguard F-400N (inorganic and organic phosphorus-based nitrogen) diluted to 30% concentration with water using the above base paper ( basis weight 90.7 g / m 2 , thickness 0.161 mm, density 0.56 g / cm 3 ) Non-halogen flame retardant impregnating solution of a compound based on a 50% concentration product, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. with an impregnation coater so that the impregnation amount (dry mass) is 12.9 g / m 2 , and then with an air dryer It was dried with hot air to obtain a paper base material impregnated with a flame retardant. After that, the paper base material is coated with a coating material for a pigment coating layer having the following composition with an air knife coater so that the coating amount becomes 10 g / m 2 (dry mass), and then dried with hot air with an air dryer. Of flame retardant coated paper.
<顔料塗布層用塗料の調製>
カオリン（商品名：ＵＷ−９０、エンゲルハード社製）２０部、炭酸カルシウム（商品名：Ｂｒｉｌｌｉａｎｔ−１５、白石工業社製）８０部を使用、そこに分散剤として、ポリカルボン酸ナトリウム塩（商品名：ＳＤＡ−４０Ｎ、４０％濃度品、ソマール社製）０．１部、水７２．３部を添加し、カウレス分散機で５８.0％の顔料スラリーを調製した。この顔料スラリーにアクリル系ラテックス（商品名：ポリトロンＦ２２１２、４８％濃度品、旭化成社製）３０部、澱粉（商品名：ＭＳ４６００、１０％濃度品、日本食品加工社製）３部、耐水化剤（商品名：ＳＰＩ−１０２Ａ、４５％濃度品、住友化学社製）０．００５部、消泡剤（商品名：ＡＦ−１、２５％濃度品、日信化学工業社製）０．００１部を添加、攪拌・分散し、さらに水を添加し、固形分濃度が４５％の塗料を得た。
<Preparation of paint for pigment coating layer>
20 parts of kaolin (trade name: UW-90, manufactured by Engelhard) and 80 parts of calcium carbonate (trade name: Brilliant-15, manufactured by Shiraishi Kogyo Co., Ltd.) are used as a dispersant, polycarboxylic acid sodium salt (product) (Name: SDA-40N, 40% concentration product, manufactured by Somar) 0.1 part and 72.3 parts of water were added, and a 58.0% pigment slurry was prepared with a cowless disperser. To this pigment slurry, 30 parts of acrylic latex (trade name: Polytron F2212, 48% concentration product, manufactured by Asahi Kasei Co., Ltd.), 3 parts of starch (trade name: MS4600, 10% concentration product, manufactured by Nippon Food Processing Co., Ltd.), water resistance agent (Trade name: SPI-102A, 45% concentration product, manufactured by Sumitomo Chemical Co., Ltd.) 0.005 part, antifoaming agent (trade name: AF-1, 25% concentration product, manufactured by Nissin Chemical Industry Co., Ltd.) 0.001 part Was added, stirred and dispersed, and water was further added to obtain a paint having a solid content concentration of 45%.
実施例１において含浸量が６．９ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例１と同様にして本発明の難燃塗工紙を得た。 A flame-retardant coated paper of the present invention was obtained in the same manner as in Example 1 except that the impregnation amount was 6.9 g / m 2 (dry mass) in Example 1.
実施例１において含浸量が１５．９ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例１と同様にして本発明の難燃塗工紙を得た。 A flame-retardant coated paper of the present invention was obtained in the same manner as in Example 1 except that the impregnation amount was 15.9 g / m 2 (dry mass) in Example 1.
実施例１において含浸量が１９．５ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例１と同様にして本発明の難燃塗工紙を得た。 A flame-retardant coated paper of the present invention was obtained in the same manner as in Example 1 except that the impregnation amount was 19.5 g / m 2 (dry mass) in Example 1.
＜原紙の作成＞
原料は、Ｎ−ＢＫＰ ３８部、Ｌ−ＢＫＰ ５４部、ポリエステル繊維 ８部とからなるＣＳＦ ５６０mlのパルプスラリーに、紙力増強剤（商品名：ＷＳ４０２０、星光ＰＭＣ社製）を対パルプ １．１％、硫酸バンド（テクノ北越社製）を対パルプ０．４３％添加し、１００ｇ／ｍ2の原紙を抄造し、本発明の含浸用原紙を得た以外は実施例１と同様にして本発明の難燃塗工紙を得た。
<Creation of base paper>
The raw material is a CSF 560 ml pulp slurry composed of 38 parts of N-BKP, 54 parts of L-BKP, and 8 parts of polyester fiber, and a paper strength enhancer (trade name: WS4020, manufactured by Seiko PMC). %, A sulfuric acid band (manufactured by Techno Hokuetsu Co., Ltd.) was added in an amount of 0.43% to pulp, and a base paper of 100 g / m 2 was made to obtain the base paper for impregnation of the present invention. Of flame retardant coated paper.
実施例１において顔料塗布層用塗料をエアーナイフコーターにて片面当たりの塗布量が１０ｇ／ｍ2（乾燥質量）になるように両面塗布した以外は実施例１と同様にして本発明の難燃塗工紙を得た。 The flame retardant of the present invention was carried out in the same manner as in Example 1 except that the coating for the pigment coating layer in Example 1 was applied on both sides with an air knife coater so that the coating amount per side became 10 g / m 2 (dry mass). Coated paper was obtained.
実施例５において塗布層中のバインダー１００部に対してＡＰＡ−１００（亜リン酸アルミ二ウムのノンハロゲン系難燃剤：１００％粉体品、太平化学産業社製）を５０部（乾燥質量）配合した以外は実施例５と同様にして本発明の難燃塗工紙を得た。 In Example 5, 50 parts (dry mass) of APA-100 (non-halogen flame retardant of aluminum phosphite: 100% powder product, manufactured by Taihei Chemical Industry Co., Ltd.) is added to 100 parts of binder in the coating layer. A flame-retardant coated paper of the present invention was obtained in the same manner as in Example 5 except that.
実施例５において塗布層中のバインダー１００部に対してＫＤ−４２５（ポリリン酸系化合物のノンハロゲン系難燃剤：２５％濃度品、高松油脂社製）を１０部（乾燥質量）配合し、含浸量が１９．５ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例５と同様にして本発明の難燃塗工紙を得た。 In Example 5, 10 parts (dry mass) of KD-425 (non-halogen flame retardant of polyphosphoric acid compound: 25% concentration product, manufactured by Takamatsu Yushi Co., Ltd.) is blended with 100 parts of the binder in the coating layer, and the impregnation amount The flame-retardant coated paper of the present invention was obtained in the same manner as in Example 5 except that the impregnation was 19.5 g / m 2 (dry mass).
（比較例１）
実施例１において含浸用原紙（坪量 ９０．７ｇ／ｍ2、厚さ ０．１６１ｍｍ、密度 ０．５６ｇ／ｃｍ３）に難燃剤を含浸させずに顔料塗布層用難燃剤不含塗料を塗布した以外は実施例１と同様にして塗工紙を得た。
(Comparative Example 1)
In Example 1, the base paper for impregnation (basis weight 90.7 g / m 2 , thickness 0.161 mm, density 0.56 g / cm 3 ) was applied with the flame retardant-free paint for the pigment coating layer without impregnating the flame retardant. A coated paper was obtained in the same manner as in Example 1 except that.
（比較例２）
実施例１において含浸量が４ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例１と同様
にして塗工紙を得た。
(Comparative Example 2)
A coated paper was obtained in the same manner as in Example 1 except that the impregnation amount was 4 g / m 2 (dry mass) in Example 1.
（比較例３）
実施例１において顔料塗布層用塗料を塗布しない以外は実施例１と同様にして難燃紙を得た。
(Comparative Example 3)
Flame retardant paper was obtained in the same manner as in Example 1, except that the pigment coating layer coating was not applied in Example 1.
（比較例４）
実施例１において顔料塗布層用塗料を塗布量が３ｇ／ｍ2（乾燥質量）になるように塗布した以外は実施例１と同様にして塗工紙を得た。
(Comparative Example 4)
A coated paper was obtained in the same manner as in Example 1 except that the pigment coating layer paint was applied in Example 1 so that the coating amount was 3 g / m 2 (dry mass).
（比較例５）
実施例７において含浸用原紙に難燃剤を含浸せずに塗布層中のバインダー１００部に対してＫＤ−４２５（ポリリン酸系化合物のノンハロゲン系難燃剤：２５％濃度品、高松油脂社製）を１０部（乾燥質量）配合した顔料塗布層用塗料を１０ｇ/ｍ2（乾燥質量）塗布した以外は実施例７と同様にして塗工紙を得た。
(Comparative Example 5)
In Example 7, KD-425 (non-halogen flame retardant of polyphosphoric acid compound: 25% concentration product, manufactured by Takamatsu Yushi Co., Ltd.) is used with respect to 100 parts of binder in the coating layer without impregnating the base paper for impregnation with the flame retardant. A coated paper was obtained in the same manner as in Example 7 except that 10 g / m 2 (dry mass) of the pigment coating layer paint blended with 10 parts (dry mass) was applied.
（比較例６）
比較例５において顔料塗布層用塗料を両面に、片面１０ｇ／ｍ2（乾燥質量）ずつ塗布した以外は比較例５と同様にして塗工紙を得た。
(Comparative Example 6)
In Comparative Example 5, a coated paper was obtained in the same manner as in Comparative Example 5, except that the pigment coating layer coating was applied on both sides by 10 g / m 2 (dry mass) on one side.
（比較例７）
実施例１においてＴ−ＸＰ１５２（ノンハロゲン系難燃剤：３０％濃度品、星光PMC（株）社製、スチレン系ポリマー）を含浸コーターにて含浸量が６．９ｇ／ｍ2（乾燥質量）になるように含浸した以外は実施例１と同様にして塗工紙を得た。
(Comparative Example 7)
In Example 1, T-XP152 (non-halogen flame retardant: 30% concentration product, manufactured by Seiko PMC Co., Ltd., styrene polymer) is impregnated to 6.9 g / m 2 (dry mass) with an impregnation coater. A coated paper was obtained in the same manner as in Example 1 except that it was impregnated.
［難燃塗工紙の物性評価］
このようにして得られた難燃紙も含めた難燃塗工紙において、難燃性を含めた物性の評価は、２３℃、５０％RH調湿後、以下の方法に準拠して行い、評価結果を表１に示した。
坪量：JIS P ８１２４：1998「紙及び板紙−坪量測定方法」。
厚さ、密度：JIS P ８１１８：1998「紙及び板紙−厚さ及び密度の試験方法」。
難燃性試験：安全規格 ＵＬ（Underwriters Laboratories Inc.）９４「Tests for Flammability of Plastic Materials for Parts in Devices and Appliances, fifth edition, (Edition Date October 29, 1996)」垂直燃焼試験（Ｖ-０〜Ｖ-２）、薄手材料垂直燃焼試験（VTM-０〜VTM-２）。
印刷強度：RI印刷試験機（（株）明製作所）を用い、特殊インキ（ＳＭＸタックグレード１０；東洋インキ社製）を用い塗工面及び難燃紙の非塗工面に印刷し、印刷面のピック状態を目視で評価した。○：ピック無し、ピック極めて少ない、△：ピックが散見し実用に絶えず、×：ピックが非常に多く実用に耐えない。
インキ受理ムラ：RI印刷試験機を用い、塗工紙及び難燃紙の表（Ｆ（フェルト））面についてプロセスインキ（ジオスＧ：大日本インキ化学工業社製）黄を印刷後、紅を印刷し、トラッピングの均一性を目視で評価した。○：均一、△：ややムラがあり実用に絶えず、×：ムラが顕著で実用に耐えない。
[Evaluation of physical properties of flame-retardant coated paper]
In the flame-retardant coated paper including the flame-retardant paper obtained in this way, the evaluation of physical properties including flame retardancy is performed in accordance with the following method after conditioning at 23 ° C. and 50% RH, The evaluation results are shown in Table 1.
Basis weight : JIS P 8124: 1998 "Paper and paperboard-Basis weight measuring method".
Thickness and density : JIS P 8118: 1998 “Paper and paperboard—Test method for thickness and density”.
Flame Retardancy Test : Safety Standard UL (Underwriters Laboratories Inc.) 94 "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances, fifth edition, (Edition Date October 29, 1996)" Vertical Combustion Test (V-0 to V -2) Thin material vertical combustion test (VTM-0 to VTM-2).
Printing strength : Using RI printing tester (Ming Seisakusho Co., Ltd.), printing on the coated surface and non-coated surface of flame retardant paper using special ink (SMX tack grade 10; manufactured by Toyo Ink Co., Ltd.) The state was evaluated visually. ○: No pick, very few picks, △: Picks are scattered and constantly in practical use, ×: Picks are very many and cannot be used practically.
Ink acceptance unevenness : Using a RI printing tester, print the process ink (Gios G: manufactured by Dainippon Ink & Chemicals) yellow on the surface (F (felt)) of coated paper and flame retardant paper, then print red Then, the trapping uniformity was visually evaluated. ○: Uniformity, Δ: Slightly uneven and constant for practical use, ×: Unevenness is remarkable and unusable for practical use.
表１の結果及び実施例から明らかなように、本発明の実施形態によれば、単層で又は多層で抄造された坪量４０〜２５０ｇ／ｍ2含浸用原紙に、無機系化合物およびリンおよび／または窒素含有の有機系化合物からなるノンハロゲン系難燃剤を６ｇ／ｍ2以上含浸処理した紙基材の片面又は両面に、無機顔料及びバインダーを主体とした塗布層を５ｇ／ｍ2以上設けることによって、燃焼によるダイオキシン等の有害物を発生することなく、優れた難燃性と優れた印刷適性を兼ね備えた効果が得られることがわかる。 As is clear from the results and examples of Table 1, according to the embodiment of the present invention, the base paper impregnated with a basis weight of 40 to 250 g / m 2 made of a single layer or multiple layers is coated with an inorganic compound and phosphorus and A coating layer mainly composed of an inorganic pigment and a binder is provided at 5 g / m 2 or more on one or both sides of a paper substrate impregnated with 6 g / m 2 or more of a non-halogen flame retardant comprising a nitrogen-containing organic compound. Thus, it can be seen that the effect of combining excellent flame retardancy and excellent printability can be obtained without generating harmful substances such as dioxin due to combustion.
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| EP2477814A4 (en) * | 2009-09-10 | 2013-04-03 | Brady Worldwide Inc | Flame retardant multi-layer label |
| JP5503262B2 (en) * | 2009-11-21 | 2014-05-28 | 大王製紙株式会社 | Sheet material |
| JP6074445B2 (en) * | 2014-02-18 | 2017-02-01 | 有限会社デジタルプランニングワークコア | Flameproof corrugated cardboard and manufacturing method thereof |
| JP2017145527A (en) * | 2016-02-17 | 2017-08-24 | 日本製紙株式会社 | Wall paper |
| CN116219800A (en) * | 2023-03-11 | 2023-06-06 | 武义蓝波科技有限公司 | Production method of flame-retardant wallpaper |
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| JPS62276077A (en) * | 1986-05-21 | 1987-11-30 | ユニチカ株式会社 | Flameproof processing of cellulosic fiber product |
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