JPH0684600B2 - Method for producing flame-retardant paper for backing vinyl wallpaper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant paper used for backing vinyl wallpaper, and particularly to a method for producing a flame-retardant paper for backing vinyl wallpaper in which black spots are less likely to be generated by glue during its construction. It is about.

[Conventional technology]

Flame-retardant paper is widely used as a base paper for various wallpapers, and is particularly often used as a backing for vinyl wallpapers.

Vinyl chloride wallpaper, which is a typical vinyl wallpaper, is commercialized by applying vinyl chloride paste on the surface of flame-retardant paper for backing, gelating the vinyl paste by heating, and printing, embossing, foaming, etc. ing.

Currently, flame-retardant paper for backing vinyl wallpaper is generally wood pulp,
And titanium dioxide as a filler, a combination of titanium dioxide and talc or clay, or a paper sheet obtained by making a slurry made of aluminum hydroxide or the like with a paper machine, impregnated with a flame retardant and other chemicals, and produced by drying. However, especially when titanium dioxide is used, the pH of the slurry supplied to the paper machine is adjusted to 4 to 6 by adding a sulfuric acid band.
It is customary to make the acidic side of the front and back to promote fixing of papermaking chemicals such as a wet strength agent to pulp and to improve the yield and dehydration property in the wire part of the papermaking machine.

[Problems to be Solved by the Invention]

The present inventors have discovered that vinyl wallpaper, which uses flame-retardant paper as a backing paper, which is paper-made on these acidic sides and contains high-yield pulp, has a serious drawback. That is, if foreign substances containing iron are mixed in or adhered to the surface of the backing paper during the papermaking process or the subsequent PVC processing step, the diameter of the backing paper will be reduced when glue is applied to the backing paper and left in the construction of wallpaper products. 1 to 10 mm of black to gray conspicuous spotted spots (hereinafter abbreviated as black spots).

By the way, in the recent construction of wallpaper, the gluing and pasting work has been divided into labor, and it is not uncommon for the wallpaper to be left for several hours or one day or more after gluing, and the troubles due to the occurrence of these black spots have become apparent. It is coming.

When such black spots occur, they may be identified as stains on the surface (PVC surface) of the wallpaper after construction, or may be mistaken for mold, which significantly impairs their commercial value.

An object of the present invention is to prevent the occurrence of black spots as much as possible.

[Means for Solving the Problems]

As a result of various investigations by the present inventors to solve this problem, a high-yield pulp was blended, and in a vinyl wallpaper using a flame-retardant paper that was made on the acidic side by adding a sulfuric acid band as a backing paper, The present invention has been accomplished by finding that the problem can be solved by using a specific filler together with the pulp slurry.

As high-yield pulp, groundwood pulp (GP), thermomechanical pulp (TMP), refining ground pulp (R-GP), chemiground pulp (C-GP), chemithermomechanical pulp (C-TMP) Used,
This is because these compounds are extremely effective for imparting the functions such as hiding property, thickness and rigidity required for the flame-retardant paper for backing vinyl wallpaper.

Hereinafter, the present invention will be described in detail.

(A) When using a mixture of aluminum hydroxide and a small amount of calcium carbonate as a filler; aluminum hydroxide exhibits a flame-retardant effect by releasing water of crystallization at the time of flame-retardant. It is suitable as a paper filler.

In this case, by adding a small amount of calcium carbonate to aluminum hydroxide used as a filler, the slurry pH after addition to the pulp shifts from acidic to alkaline side, and the adhered iron is converted to a compound such as water-insoluble iron hydroxide. Can be converted.

Further, by adding calcium carbonate, it is possible to capture sulfate ions that promote the formation of a water-soluble iron compound as sparingly water-soluble calcium sulfate.

If the amount of calcium carbonate used is 1% by weight or more based on the pulp, the effect is sufficiently exhibited.

As the calcium carbonate used in the present invention, light or heavy calcium carbonate of various processed forms can be used, but spindle-shaped light calcium carbonate is particularly preferable.

(B) Titanium dioxide or a system in which talc or clay is used in combination with a small amount of calcium carbonate as a filler; titanium dioxide, or titanium dioxide and talc or clay is used as the flame-retardant paper for backing vinyl wallpaper. The flame-retardant paper of acidic papermaking used together is widely used. The reason why titanium dioxide is used is that the hiding property required for flame-retardant paper for backing vinyl wallpaper is significantly improved by its use.

(C) When using a combination of titanium dioxide, talc and aluminum hydroxide in which a small amount of calcium carbonate is added as a filler; aluminum hydroxide is further added to the system shown in (B) for the purpose of imparting flame retardancy. It can also be used.

The same method for preventing the generation of black spots by blending calcium carbonate as shown in the case of the filler (A) can be applied to this system.

(D) When titanium dioxide is used as a filler and a small amount of calcium hydroxide is used in combination with it; in the case of titanium dioxide compounded paper by acidic papermaking, pulp, filler and other mixed slurries introduced to a paper machine are changed from near neutral to weakly alkaline. By adjusting the pH, it is possible to prevent the generation of black spots. Sodium hydroxide, calcium hydroxide and the like are suitable as the alkali for pH adjustment.

One-pass yield of pulp and filler in the wire part of the paper machine is slightly reduced by adjusting pH, but there is no problem if cationic polyacrylamide, polyamide epichlorohydrin resin, etc., or polyacrylamide polymer yield improver is used. .

The flame retardancy-imparting method in the present invention is achieved by impregnating a paper web with a mixed aqueous solution mainly composed of a flame retardant, a binder, a surface sizing agent, etc., and drying.

As the flame retardant, guanidine sulfamate, a methylolated modification thereof, ammonium sulfamate, guanidine phosphate and the like are used, and they may be used alone or in combination of two or more kinds.

As the binder, polyvinyl alcohol, starch or a modified product thereof, carboxymethyl cellulose, synthetic resin emulsion may be used alone or in combination of two or more kinds.

In addition, surface sizing agents, dicyandiamide as a discoloration preventing agent, methylolated melamine, dyes, defoaming agents, paper strength improvers and the like may be used in combination.

The applied amount of these mixed solutions is 10 to 50, preferably 10 to 30% by weight, as solid content, based on the flame-retardant paper product, and the target applied amount can be obtained depending on the concentration of the liquid.

If the applied amount is less than the proper amount, the flame-retardant paper cannot have the basic property of self-extinguishing property, and if the applied amount is excessive, it causes deterioration of quality such as strength and rigidity and is not economical.

[Action]

This phenomenon occurs when the backing paper surface is coated with a glue using water such as starch, and sulfate ions generated from flame retardants such as the sulfuric acid band and guanidine sulfamate used in the manufacture of flame-retardant paper. , Reacts with foreign substances containing iron attached to the base paper to form water-soluble iron compounds such as ferrous sulfate, and mainly reacts with lignin or extracted components present in the high-yield pulp of the backing paper to form black spots. It is considered to generate. For example, it is well known that the phenol component present in lignin easily reacts with iron ion to form a black complex compound.

The inventors of the present invention focused on the point that the generation of black spots was caused by the reaction of the water-soluble iron compound and lignin or the extracted component, and the black spots that the conventional backing paper had by converting the attached iron content into the water-insoluble compound. It has succeeded in removing the cause of the.

〔Example〕

Hereinafter, the content of the present invention will be described in more detail with reference to Examples. The test method was according to the following method.

1. Basis weight Measured according to JIS P-8124 2. Content of filler in paper After burning the web at 900 ° C, weigh the remaining ash and correct the caustic loss of the filler to the weight before burning. Expressed as a percentage.

3. Evaluation of black spots Starch-based A-Yayoi Chemical Co., Ltd. A glue was diluted 3 times with water, brushed on the surface of flame-retardant paper, and scraped off from general carbon steel sheets and other materials. Sprinkle iron powder. Then, after covering with a polyethylene sheet or the like and leaving it wet for one day and night, the presence or absence of black spots around the iron powder is observed and confirmed.

Example 1 Pulp consisting of 50 parts by weight of N-BKP, 20 parts by weight of L-BKP, and 30 parts by weight of GP, 1.0 part by weight of sulfuric acid band, polyamide epichlorohydrin-based resin (trade name: Kaymen 557H, manufactured by Daikuku Chikyures). 0.4 part by weight was added.

Aluminum hydroxide (C-301 manufactured by Sumitomo Chemical Co., Ltd.) having a central particle diameter of 1.0 μm was added to this slurry as a filler.
1 part by weight of light calcium carbonate (Okutama Kogyo Co., Ltd., Tamapearl 121), and finally a high molecular weight polyacrylamide resin (Hakuto Chemical Co., Ltd.) as a yield improver.
(Manufactured by trade name Polymaster R-623) was added at 50 ppm and papermaking was carried out by a Fourdrinier paper machine to obtain 59 g / m ² of web.

Then, a 22 wt% aqueous solution of 100 parts by weight of guanidine sulfamate, 5 parts by weight of polyvinyl alcohol, 5 parts by weight of surface sizing agent, and 5 parts by weight of methylolmelamine manufactured by Sanwa Chemical Co., Ltd. It was impregnated in and dried to obtain 70 g / m ² flame-retardant paper.

Example 2 N-BKP 50 parts by weight, L-BKP 20 parts by weight, and TMP 30
8 parts by weight of titanium dioxide as a filler and 1 part by weight of calcium carbonate were added to a slurry prepared by adding the same papermaking chemicals as in Example 1 and a retention aid to 1 part by weight of pulp, and papermaking was carried out with a Fourdrinier paper machine to produce 57 g / m ² I got a paper.

Then, the paper web was impregnated with an aqueous solution having the same liquid composition as in Example 1 and having a concentration of 28% by a size press method, and then dried.
A flame-retardant paper of g / m ² was obtained.

Example 3 8 parts by weight of titanium dioxide as a filler and then sodium hydroxide as an alkali were added to a slurry obtained by adding the same paper-making chemicals to the same pulp as in Example 2 to adjust the pH to 7.5 and papermaking with a Fourdrinier paper machine. , 57 g / m ² was obtained.

Then, the paper web was impregnated with a 28% aqueous solution having the same liquid composition as in Examples 1 and 2 by a size press method, and then dried.
70 g / m ² flame-retardant paper was obtained.

Comparative Example 1 The same pulp and papermaking chemicals as in Example 1 were used, but as the filler, 20 parts by weight of aluminum hydroxide alone was added to produce paper and 59 g / m ² of paper was obtained.

Then, the paper web was impregnated with a 22% aqueous solution having the same liquid composition as in the example by a size press method, and then dried to 70 g /
A flame-retardant paper of m ² was obtained.

Comparative Example 2 The same pulp and papermaking chemicals as in Example 2 were used, but as the filler, 8 parts by weight of titanium dioxide alone was added for papermaking.
57 g / m ² of paper was obtained.

Then, the paper web was impregnated with a 28% aqueous solution having the same liquid composition as in the example by a size press method, and then dried to 70 g /
A flame-retardant paper of m ² was obtained.

Comparative Example 3 A pulp comprising 60 parts by weight of N-BKP and 40 parts by weight of L-BKP was mixed with 10 parts by weight of titanium dioxide alone to prepare paper by adding the same paper-making chemical as in the example, and a paper sheet of 57 g / m ² was produced. Got

Then, the paper web was impregnated with a 28% aqueous solution having the same liquid composition as in the example by a size press method, and then dried to 70 g /
A flame-retardant paper of m ² was obtained.

The following table shows the slurry compositions and characteristics of the flame-retardant papers of these Examples and Comparative Examples.

[Effects of the Invention] In the conventional flame-retardant paper manufacturing method shown in Comparative Examples 1 and 2 of the table, both aluminum hydroxide compounded paper and titanium dioxide compounded paper are black due to the adhesion of iron in the check at the stage of the base paper before PVC processing. All the spots are generated, which indicates that there is a high risk that black spots will be generated at the time of construction due to the adhesion of foreign matters containing iron such as PVC processing.

In Comparative Example 3 in which the high-yield pulp was not used, black spots did not occur, but the thickness and the concealing property required for the flame-retardant paper for backing vinyl wallpaper were insufficient, and it was unsuitable as a backing paper. Atsuta

On the other hand, in Examples 1, 2 and 3, no black spots were observed due to the adhesion of iron, and the effect of the present invention is certain.

Regarding the flame-retardant performance of the flame-retardant paper, quality such as strength and hiding power, and PVC suitability, Example 1, Comparative Example 1 and Example 2,
Almost no difference was observed between 3 and Comparative Example 2.

As described above, with respect to the problem of the generation of black spots that have come to the surface with the change in the construction work of the wallpaper, we have found a serious drawback that the conventional flame-retardant paper for backing vinyl wallpaper has, and according to the present invention the problem The significance of establishing a method for producing a backing paper that prevents such occurrences is extremely great.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location D21H 21/34 7199-3B D21H 1/34 A 7199-3B 3/78 (72) Inventor Yamashina Naoshi 505-1 Pulp-cho, Asahikawa-shi, Hokkaido Sanyo Kokusaku Pulp Co., Ltd. (56) Reference JP-A-58-60096 (JP, A) JP-A-59-100798 (JP, A)

Claims (1)

[Claims] 1. A flame retardant-treated slurry obtained by adding one of the following fillers to a slurry obtained by adding a sulfuric acid band to a wood pulp containing 5 to 50% by weight of a high-yield pulp and making it under neutral conditions. A method for producing a flame-retardant paper for backing a vinyl wallpaper, characterized in that (A) aluminum hydroxide mixed with a small amount of calcium carbonate, (B) titanium dioxide or a system in which talc or clay is used in combination A mixture of a small amount of calcium carbonate, (C) a combination system of titanium dioxide, talc and aluminum hydroxide, and a mixture of a small amount of calcium carbonate, (D) a combination of titanium dioxide and a trace amount of calcium hydroxide .