JP5531860B2 - Antibacterial / deodorant decorative paper and method for producing the same - Google Patents
Antibacterial / deodorant decorative paper and method for producing the same Download PDFInfo
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- JP5531860B2 JP5531860B2 JP2010188945A JP2010188945A JP5531860B2 JP 5531860 B2 JP5531860 B2 JP 5531860B2 JP 2010188945 A JP2010188945 A JP 2010188945A JP 2010188945 A JP2010188945 A JP 2010188945A JP 5531860 B2 JP5531860 B2 JP 5531860B2
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- 230000000844 anti-bacterial effect Effects 0.000 title claims description 36
- 239000002781 deodorant agent Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 amine compound Chemical class 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000007646 gravure printing Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 19
- 230000001877 deodorizing effect Effects 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000976 ink Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は住宅内装全般に用いる化粧紙に関し、特には洗面所や下駄箱などの菌の発生や臭いが問題となりやすい箇所に用いられ、国土交通省が定める室内空気規制物質の１つであるホルムアルデヒドが発生した際のホルムアルデヒドの分解に寄与する抗菌・消臭化粧紙およびその製造方法に関する。 TECHNICAL FIELD The present invention relates to decorative paper used in general interiors of houses, and in particular, formaldehyde, which is used in places where germs and odors such as toilets and clogs are prone to problems and is one of indoor air-regulated substances set by the Ministry of Land, Infrastructure, Transport and Tourism. The present invention relates to an antibacterial / deodorant decorative paper that contributes to the decomposition of formaldehyde when a rash occurs and a method for producing the same.
壁材、床材、天井材等の住宅内装全般に用いる、抗菌・消臭機能を有する化粧材としては、紙またはフィルム基材に適宜絵柄印刷を設け、その上から各種機能性を付与させるための添加剤を配合した樹脂をコーティングしたものが用いられてきた。 As a decorative material with antibacterial and deodorant functions used for general interiors of houses such as wall materials, floor materials, ceiling materials, etc., in order to provide various functions from above by providing appropriate printing on paper or film base materials. A resin coated with the above additive has been used.
また、最近、光触媒粒子を熱可塑性樹脂フィルムに練り込むか、あるいは熱可塑性樹脂液などに添加し、塗布にて光触媒機能層を設けたものがある、しかしながら光触媒粒子表面が樹脂で被覆されており、外気に直接、接していないために、抗菌性、脱臭性を充分に発揮することができないばかりか、更に、光触媒粒子が光照射を受けた際に、光触媒粒子表面を被覆している熱可塑性樹脂が光触媒粒子によって分解、破壊されてしまうため、熱可塑性樹脂層又は熱可塑性樹脂フィルムの脆化や光触媒粒子の脱落を招いてしまう問題を抱えている。 Recently, some photocatalyst particles are kneaded into a thermoplastic resin film or added to a thermoplastic resin liquid and provided with a photocatalyst functional layer by coating. However, the surface of the photocatalyst particles is coated with a resin. Because it is not in direct contact with the outside air, it cannot fully exhibit antibacterial and deodorizing properties. Furthermore, when the photocatalyst particles are irradiated with light, the thermoplastic coating the surface of the photocatalyst particles Since the resin is decomposed and destroyed by the photocatalyst particles, there is a problem in that the thermoplastic resin layer or the thermoplastic resin film becomes brittle or the photocatalyst particles fall off.
そこで、光触媒機能を用いないで抗菌・消臭機能を発現する添加剤を使用することが考えられた。しかしながらこれら添加剤は樹脂層中にある程度の割合で配合しないと優れた抗菌・消臭機能を発現しない。ただしあまり多く配合すると、コーティングの形成が困難になるばかりか形勢した塗膜の各種表面耐性、耐候性に劣るものとなってしまう。抗菌機能のみあるいは消臭機能のみであれば、ある程度の機能の発現が可能であるが、抗菌機能と消臭機能の両方を十分に発現させるのは困難であった。 Therefore, it has been considered to use an additive that exhibits an antibacterial / deodorizing function without using a photocatalytic function. However, these additives do not exhibit an excellent antibacterial / deodorant function unless blended in a certain proportion in the resin layer. However, when too much is blended, not only the formation of the coating becomes difficult, but also the various surface resistance and weather resistance of the formed coating film become inferior. If only the antibacterial function or only the deodorizing function is present, a certain level of function can be expressed, but it has been difficult to sufficiently develop both the antibacterial function and the deodorizing function.
本発明はこの問題点を解決しようとするものであり、すなわちその課題とするところは、優れた抗菌・消臭機能を発現しかつ各種表面耐性、耐候性に優れた抗菌・消臭化粧紙およびその製造方法を提供することにある。 The present invention is intended to solve this problem, that is, the problem is that antibacterial / deodorant decorative paper that exhibits excellent antibacterial / deodorant functions and has various surface resistance and weather resistance and It is in providing the manufacturing method.
本発明はこの課題を解決したものであり、すなわちその請求項１記載の発明は紙基材上に少なくとも絵柄模様層、抗菌機能と消臭機能を有するトップコート層を設けてなる抗菌・消臭化粧紙において、前記トップコート層が多層からなり、前記多層の少なくとも１層は固形分比で４５〜５５％のアミン系化合物を配合してなり、少なくとも１層は固形分比で０．５〜１．５％のリン酸チタニウム系化合物を配合してなることを特徴とする抗菌・消臭化粧紙である。 The present invention solves this problem, that is, the invention according to claim 1 is an antibacterial / deodorant comprising at least a pattern layer and a topcoat layer having antibacterial and deodorant functions on a paper substrate. In the decorative paper, the top coat layer is composed of a multilayer, at least one layer of the multilayer is blended with an amine compound of 45 to 55% in a solid content ratio, and at least one layer is 0.5 to 0.5 in a solid content ratio. 1. An antibacterial / deodorant decorative paper comprising 1.5% titanium phosphate compound.
またその請求項２記載の発明は、紙基材上に絵柄模様をグラビア印刷にて印刷し、乾燥後、ウレタン系樹脂にアミン系化合物を固形分比で４５〜５５％配合した樹脂をグラビアコーティングして５０〜７０℃の熱乾燥を行い、さらにその上からウレタン系樹脂にリン酸チタニウム系化合物を固形分比で０．５〜１．５％配合した樹脂をグラビアコーティングして５０〜７０℃の熱乾燥を行ってなることを特徴とする抗菌・消臭化粧紙の製造方法である。
Further, the invention according to
本願発明はその請求項１記載の発明により、優れた抗菌・消臭機能を発現する化粧紙を提供することが可能となるという効果を奏する。 The invention according to the present invention has an effect that it is possible to provide a decorative paper exhibiting an excellent antibacterial and deodorizing function by the invention described in claim 1.
またその請求項２記載の発明により、各種表面耐性、耐候性にすぐれたコーティング層の形成された抗菌・消臭機能を発現する化粧紙を提供することが可能となるという効果を奏する。
According to the invention described in
以下、本発明を図面に基づき詳細に説明する。図１に発明の消臭・抗菌化粧紙の一実施例の断面の構造を示す。
紙基材１の上に絵柄模様層２、消臭機能を有する第一トップコート層３、抗菌機能を有する第二トップコート層４を設けてなる。
Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the deodorant / antibacterial decorative paper of the invention.
On the paper substrate 1, a
本発明における紙基材１としては、難燃紙、不燃紙、紙間強化紙、樹脂含浸紙等を用いることができる、壁紙用としては、不燃紙、難燃紙が好ましく使用できる。 As the paper substrate 1 in the present invention, flame retardant paper, non-flammable paper, inter-paper reinforced paper, resin-impregnated paper, and the like can be used.
本発明における絵柄模様層２としては、着色用の顔料等を適宜のバインダー樹脂中に分散してなる従来公知の各種の印刷インキ又は塗料等を使用して、例えばグラビア印刷法、オフセット印刷法、グラビアオフセット印刷法、スクリーン印刷法、ロータリースクリーン印刷法、フレキソ印刷法、ドライオフセット印刷法、凸版印刷法、凹版印刷法、パッド印刷法、静電印刷法、電子写真法、感熱転写印刷法、インクジェット印刷法等の従来公知の任意の印刷方法や、例えばグラビアコート法、ロールコート法、ナイフコート法、エアーナイフコート法、リップコート法、コンマコート法、ダイコート法、キスコート法、ロッドコート法、スプレーコート法、フローコート法、ディップコート法等の従来公知の任意の塗布方法から選択した１種又は２種以上の組合せにより形成することができる
As the
本発明における消臭機能を有する第一トップコート層３としては、固形分比で４５〜５５％のアミン系化合物を配合してなるものを用いる。アミン系化合物としてはモノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどが好適である。具体的には１級アミノ基を末端に複数持つアミン系化合物と多孔質の無機化合物を複合化した化学吸着型の消臭剤である東亞合成（株）製「ケスモンＮＳ−２３１」などがあげられる。アミン系化合物の配合量が４５％より少ないと十分な消臭機能を発現できない。また配合量が５５％より多いと塗膜形成が悪くなり、表面の耐汚染性が落ちる。 As the 1st topcoat layer 3 which has a deodorizing function in this invention, the thing formed by mix | blending 45-55% of an amine compound by solid content ratio is used. As the amine compound, monoethanolamine, diethanolamine, triethanolamine and the like are suitable. Specific examples include “Kesmon NS-231” manufactured by Toagosei Co., Ltd., which is a chemisorption deodorant that is a composite of an amine compound having a plurality of primary amino groups at its terminal and a porous inorganic compound. It is done. When the compounding amount of the amine compound is less than 45%, a sufficient deodorizing function cannot be expressed. On the other hand, if the blending amount is more than 55%, the formation of the coating film is deteriorated and the surface stain resistance is lowered.
本発明における抗菌機能を有する第二トップコート層４としては、固形分比で０．５〜１．５％のリン酸チタニウム系化合物を配合してなるものを用いる。リン酸チタニウム系化合物は、一般式がＴｉ（ＯＨ）ｘ（ＰＯ４）ｙ（ＨＰＯ４）ｚ（Ｈ２ＰＯ４）ｍ（ＯＲ）ｎ（但し、Ｒは炭素数１〜４のアルキル基、ｘは０〜４の整数、ｙは０又は１、ｚは０〜２の整数、ｍは０〜４の整数、ｎは０〜４の整数であり、ｘ＋３ｙ＋２ｚ＋ｍ＋ｎ＝４を満たす。）で表されるものであり、例えば、Ｔｉ（ＯＨ）（Ｈ２ＰＯ４）２（ＯＲ）、Ｔｉ（ＯＨ）（ＰＯ４）、Ｔｉ（ＯＨ）２（Ｈ２ＰＯ４）（ＯＲ）、Ｔｉ（ＯＨ）（ＨＰＯ４）（ＯＲ）、Ｔｉ（ＯＨ）（ＨＰＯ４）、Ｔｉ（ＯＨ）２（Ｈ２ＰＯ４）２、Ｔｉ（ＯＨ）３（Ｈ２ＰＯ４）、Ｔｉ（ＯＨ）３（ＯＲ）等が用いられる。
リン酸チタニウム系化合物又はその縮合体は、例えば、以下の製造方法によって得られる。即ち、初めに、四塩化チタンを水若しくはアルコール、又はそれらの混合溶液と反応させる。アルコールとしては炭素数１〜４のメタノール，エタノール，イソプロピルアルコール等を用いることができる。次に、得られた反応溶液をリン酸と反応させることにより、リン酸チタニウム系化合物を得ることができる。得られた反応生成物は、水やアルコール、アルコールと水の混合溶媒で希釈して、溶液の状態又は分散液の状態のリン酸チタニウム液を得ることができる。リン酸チタニウム系化合物の配合量が０．５％より少ないと十分な抗菌機能が発現できない。配合量が１．５％より多いと塗膜形成が悪くなり、表面の耐汚染性が落ちる。
As the 2nd topcoat layer 4 which has an antibacterial function in this invention, what mix | blends a 0.5-1.5% titanium phosphate type compound by solid content ratio is used. Titanium phosphate compound, general formula Ti (OH) x (PO 4 ) y (HPO 4) z (
A titanium phosphate compound or a condensate thereof can be obtained, for example, by the following production method. That is, first, titanium tetrachloride is reacted with water or alcohol, or a mixed solution thereof. As alcohol, C1-C4 methanol, ethanol, isopropyl alcohol, etc. can be used. Next, a titanium phosphate compound can be obtained by reacting the obtained reaction solution with phosphoric acid. The obtained reaction product can be diluted with water, alcohol, or a mixed solvent of alcohol and water to obtain a titanium phosphate solution in a solution state or a dispersion state. If the amount of the titanium phosphate compound is less than 0.5%, sufficient antibacterial function cannot be exhibited. When the blending amount is more than 1.5%, the formation of the coating film is deteriorated and the contamination resistance of the surface is lowered.
本発明の第一トップコート層と第二トップコート層を設ける方法としてはトップコート樹脂をコーティングする際に６０℃程度の熱乾燥により揮発分を乾燥させる事によりアミン系化合物及びリン酸チタニウム化合物がそれぞれのトップコート樹脂中の上部付近に集まる事により抗菌・消臭性能が効率よく発現するようになる。又、このような条件で作成した抗菌・消臭シートはトップコート樹脂中への配合比率がバランスよく配合されている為、住宅用内装材全般に使用するのに十分な性能を有する。 As a method of providing the first topcoat layer and the second topcoat layer of the present invention, when coating the topcoat resin, the volatile matter is dried by thermal drying at about 60 ° C., whereby the amine compound and the titanium phosphate compound are obtained. The antibacterial and deodorant performance is efficiently exhibited by gathering near the upper part of each top coat resin. In addition, the antibacterial / deodorant sheet prepared under such conditions has sufficient performance for use in general interior materials for houses because the blending ratio in the top coat resin is well balanced.
紙基材１として３０ｇ紙間強化紙を用い、これに絵柄模様層２として木目の絵柄を昇華綿系インキにて印刷した。
乾燥後、絵柄模様層２の上面に第一トップコート層３としてウレタン系樹脂を用いた樹脂中にアミン系化合物（東亞合成（株）製「ケスモンＮＳ−２３１」）をトップコート樹脂固形分比率で５０％の割合で配合した樹脂を４ｇ／ｍ２ドライの塗布量でグラビアコーティングした。なお、揮発分の乾燥は６０℃加熱により行った。
更に第一トップコート層の上面に第二トップコート層としてウレタン系樹脂を用いた樹脂中に四塩化チタンと水とリン酸とを反応させて得たリン酸チタニウム化合物をトップコート樹脂固形分比率０．５％の割合で配合した樹脂を４ｇ／ｍ２ドライの塗布量でグラビアコーティングし、化粧紙を得た。なお、揮発分の乾燥は６０℃加熱により行った。
A 30 g inter-paper reinforced paper was used as the paper base material 1, and a wood grain pattern was printed on the
After drying, an amine compound (“Kesmon NS-231” manufactured by Toagosei Co., Ltd.) in a resin using a urethane resin as the first top coat layer 3 on the upper surface of the
Furthermore, a titanium phosphate compound obtained by reacting titanium tetrachloride, water, and phosphoric acid in a resin using a urethane-based resin as the second topcoat layer on the top surface of the first topcoat layer is a solid content ratio of the topcoat resin. The resin blended at a ratio of 0.5% was gravure coated at a coating amount of 4 g / m 2 dry to obtain a decorative paper. The volatile matter was dried by heating at 60 ° C.
＜比較例１＞
アミン系化合物をトップコート樹脂固形分比率で６０％の割合で配合した以外は実施例１と同様にして化粧紙を得た。このように作成した化粧紙は第一トップコート樹脂中のウレタン樹脂成分が低くなりすぎたことで塗膜形成が悪くなり、２時間後の耐汚染性（赤クレヨン、青インキ、黒マジック）のエタノール拭きによる色残りが発生し、不十分な性能となってしまった。
<Comparative Example 1>
A decorative paper was obtained in the same manner as in Example 1 except that the amine-based compound was blended at a top coat resin solid content ratio of 60%. The decorative paper made in this way has a poor coating formation due to the urethane resin component in the first topcoat resin being too low, and the stain resistance after 2 hours (red crayon, blue ink, black magic) Color residue caused by wiping with ethanol occurred, resulting in insufficient performance.
＜比較例２＞
リン酸チタニウム化合物をトップコート樹脂固形分比率５％の割合で配合した以外は実施例１と同様にして化粧紙を得ようとしたが、リン酸チタニウム化合物を安定的に分散させられる固形分濃度は０．２％程度なため、ウレタン系樹脂とのウエット配合比率がウレタン主剤に対してリン酸チタニウム化合物を配合した固形分比率が２％程度となってしまい、４ｇ／ｍ２ドライの塗布量で塗布することが出来なくなり、化粧紙の耐久力が不十分なものとなってしまった。このように作成した化粧紙はトップコートの塗膜形成が悪くなり、２時間後の耐汚染性（赤クレヨン、青インキ、黒マジック）のエタノール拭きによる色残りが発生し、不十分な性能となってしまった。
<Comparative example 2>
An attempt was made to obtain a decorative paper in the same manner as in Example 1 except that the titanium phosphate compound was blended at a top coat resin solid content ratio of 5%, but the solid content concentration at which the titanium phosphate compound was stably dispersed was obtained. Is about 0.2%, so the wet blending ratio with the urethane resin is about 2%, and the solid content ratio of the titanium phosphate compound blended with the urethane base is 4g / m2 dry. It became impossible to apply, and the durability of the decorative paper was insufficient. The decorative paper produced in this way has a poor topcoat film formation, resulting in poor color performance due to stain resistance (red crayon, blue ink, black magic) and ethanol remaining after 2 hours. It is had.
＜比較例３＞
第一トップコート層を８ｇ／ｍ２ドライの塗布量で塗布し、第二トップコート層を設けなかった以外は実施例１と同様にして化粧紙を得た。この場合、第一トップコート層が表層となるため、塗膜形成が悪くなり２時間後の耐汚染性（赤クレヨン、青インキ、黒マジック）のエタノール拭きによる色残りが発生し、不十分な性能となってしまった。
さらに抗菌性を付与する為に一般的にしようされる抗菌剤を添加してもアミン系添加剤の添加量が多い影響により、通常使用される２％程度の添加量では抗菌性が発現しなかった。
<Comparative Example 3>
A decorative paper was obtained in the same manner as in Example 1 except that the first topcoat layer was applied at an application amount of 8 g / m 2 dry and the second topcoat layer was not provided. In this case, since the first topcoat layer becomes the surface layer, the coating film formation is poor, and color residue due to stain resistance (red crayon, blue ink, black magic) after 2 hours is generated, which is insufficient. It became performance.
Furthermore, even if an antibacterial agent that is generally used to impart antibacterial properties is added, the antibacterial property does not appear at the addition amount of about 2% that is normally used due to the large amount of amine-based additive added. It was.
＜比較例４＞
第一トップコート層を設けずに、絵柄模様層の上に第２トップコート層を８ｇ／ｍ２ドライの塗布量で塗布した以外は実施例１とどうようにして化粧紙を得た。この場合、抗菌性は認められたものの、消臭性能には効果にばらつきがあり、安定した消臭性能は得られなかった。
<Comparative Example 4>
A decorative paper was obtained in the same manner as in Example 1 except that the second top coat layer was applied at a coating amount of 8 g / m 2 dry on the pattern layer without providing the first top coat layer. In this case, although antibacterial properties were recognized, the deodorization performance varied in effect, and stable deodorization performance could not be obtained.
＜抗菌性試験＞
（財）日本紡績検査協会の抗菌性能基準試験により測定した。抗菌性能基準は２．０以上とされるところ、実施例１では大腸菌で４．１、黄色ブドウ球菌で５．０の抗菌活性値を示し、十分な抗菌性能の発現を確認した。
<Antimicrobial test>
It was measured by the antibacterial performance standard test of Japan Spinning Inspection Association. When the antibacterial performance standard is 2.0 or more, Example 1 showed an antibacterial activity value of 4.1 for Escherichia coli and 5.0 for Staphylococcus aureus, confirming the expression of sufficient antibacterial performance.
＜消臭性試験＞
実施例１の化粧紙を６３０ｃｍ２に切り出し、化粧面以外はアルミ箔で覆い、１０リットルのテドラーバッグに入れて空気１０リットルを注入、ホルムアルデヒドを１０ｐｐｍ注入した２時間後と２４時間後の残存ガス濃度を測定した。ブランクの紙基材では２時間後に９．５ｐｐｍ、２４時間後に７．０ｐｐｍとなり減少率３０％であったが、実施例１では２時間後に６．０ｐｐｍ、２４時間後４．０ｐｐｍとなり減少率６０％となり、十分な消臭性能の発現を確認した。
<Deodorization test>
Cut out the decorative paper of Example 1 to 630 cm 2 , cover it with aluminum foil except the decorative surface, put it in a 10 liter Tedlar bag, inject 10 liters of air, and inject 10 ppm of
＜表面物性＞
実施例１の化粧紙を１２ｍｍパーチクルボード基材に貼り合わせた化粧板での表面物性を試験した。試験項目と結果を表１に示す。
<Surface properties>
The surface physical properties of a decorative board in which the decorative paper of Example 1 was bonded to a 12 mm particle board substrate were tested. Table 1 shows the test items and results.
本発明は住宅内装全般に用いる化粧紙に関し、特には洗面所や下駄箱などの菌の発生や臭いが問題となりやすい箇所に用いられ、国土交通省が定める室内空気規制物質の１つであるホルムアルデヒドが発生した際のホルムアルデヒドの分解に寄与する抗菌・消臭化粧紙として利用可能である。 TECHNICAL FIELD The present invention relates to decorative paper used in general interiors of houses, and in particular, formaldehyde, which is used in places where germs and odors such as toilets and clogs are prone to problems and is one of indoor air-regulated substances set by the Ministry of Land, Infrastructure, Transport and Tourism. It can be used as an antibacterial and deodorant decorative paper that contributes to the decomposition of formaldehyde when it occurs.
１…紙基材
２…絵柄模様層
３…消臭機能を有する第一トップコート層
４…抗菌機能を有する第二トップコート層
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