JP4849954B2 - Flame retardant coated paper for printing - Google Patents

Description

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.

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).

Japanese Examined Patent Publication No. 6-41680 JP-A-3-260196 JP-A-4-50400 JP 2002-86659 A JP 2001-354684 A

  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.

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 .

  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.

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.

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.

  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.

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.

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. .

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.

  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.

  Hereinafter, the present invention will be described, but the present invention is not construed as being limited to these embodiments.

  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.

  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.

  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.

  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.

  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.

  As the internal sizing agent, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), neutral rosin, acidic rosin and the like are appropriately used.

  As the paper strength agent, starch, modified starch, polyacrylamide and the like are appropriately used.

  As the filler, calcium carbonate, talc, clay, titanium dioxide or the like is appropriately used.

  As the yield improver, colloidal silica, polyacrylamide, polyethyleneimine, or the like is appropriately used.

  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.

  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.

  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.

  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.

  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.

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.

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.

  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.

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.

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.

  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. .

  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.

[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.

<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.

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.

<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%.

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.

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.

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.

<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.

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.

  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.

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).

(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.

(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.

(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.

(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).

(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.

(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.

(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.

[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.

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.

Claims (3)

From inorganic compounds and phosphorus and / or nitrogen-containing organic compounds to a basis weight of 40 to 250 g / m ² base paper made in a single layer or multiple layers, with a filler content of 0 to 10% by weight per pulp The non-halogen flame retardant is impregnated so that the impregnation amount of the base paper is 6 to 30 g / m ² (dry mass), and an inorganic pigment and a binder are applied to one or both sides of the impregnated paper base. Is a coated paper provided with a coating layer mainly composed of 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 / or UL94VTM-0 in the UL standard. A flame-retardant coated paper for printing .   In the coating layer mainly composed of the inorganic pigment and the binder, 5 to 50 parts by mass (dry mass) of a non-halogen flame retardant is blended with respect to 100 parts by mass (dry mass) of the binder. Item 1. A flame retardant coated paper according to item 1.   In the base paper, at least one fiber selected from the group consisting of polyolefin synthetic pulp, polyester fiber, acrylic fiber, rayon fiber, vinylon fiber, organic synthetic fiber and glass fiber, and inorganic fiber consisting of carbon fiber is blended. The flame-retardant coated paper according to claim 1, wherein the flame-retardant coated paper is provided.