JP2005199532A - Decorative sheet - Google Patents

Decorative sheet Download PDF

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JP2005199532A
JP2005199532A JP2004007405A JP2004007405A JP2005199532A JP 2005199532 A JP2005199532 A JP 2005199532A JP 2004007405 A JP2004007405 A JP 2004007405A JP 2004007405 A JP2004007405 A JP 2004007405A JP 2005199532 A JP2005199532 A JP 2005199532A
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resin
decorative
layer
impregnated
paper
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JP3844135B2 (en
Inventor
Toshihiro Yamamoto
智弘 山本
Mitsuo Ando
三津雄 安藤
Keisuke Shitan
慶介 士反
Katsumi Honma
勝己 本間
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Aica Kogyo Co Ltd
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Aica Kogyo Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a decorative sheet excellent in impact resistance and strength, having flexibility and adaptable to a curved surface used at the normal temperature without applying special treatment such as watering, thermal processing or the like. <P>SOLUTION: A decorative layer-reinforcing layer is provided between a decorative layer and a core layer. The decorative layer is constituted by using an amino-formaldehyde resin impregnated decorative paper and the decorative layer-reinforcing layer is constituted of resin-impregnated paper obtained by impregnating a fiber base material with a thermosetting resin. As the core layer, resin-impregnated core paper obtained by impregnating a fiber base material with a slurry comprising a thermoplastic resin and an inorganic filler is used. The compounding ratio of the thermoplastic resin and the inorganic filler is set to 1:3-1:10 on a solid content basis. The impregnation ratio of the slurry is set to 700-2,000% by a calculation method represented by formula (1). The thermoplastic resin to be used has a glass transition temperature (Tg) of 0°C or below. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は化粧板に関する。   The present invention relates to a decorative board.

これまでより熱硬化性樹脂化粧板が知られており、中でもメラミン樹脂化粧板は各種物性に優れる面から、住宅機器、内装材などに幅広く使用されている。とりわけ近年においては、従来の１．０〜１．６ｍｍの厚みに代わり、耐衝撃性、強度をより向上させ、下地の影響を受けて貼り跡の目立たない厚み２．４〜３．６ｍｍの物、いわゆる厚物化粧板と称せられるものが知られている。   Thermosetting resin decorative boards have been known for a long time, and melamine resin decorative boards have been widely used for housing equipment, interior materials and the like because of their excellent physical properties. In particular, in recent years, in place of the conventional thickness of 1.0 to 1.6 mm, the impact resistance and strength are further improved, and the thickness of 2.4 to 3.6 mm is not noticeable due to the influence of the base. A so-called thick decorative board is known.

特開平５−３４５３８９JP-A-5-345389 特開平９−１１４０７JP-A-9-11407 特開２０００−２０２９７８JP 2000-202978 A 特開２００２−３７０３１３JP 2002-370313 特開２００１−９６７０２JP 2001-96702 A

しかしながら、耐衝撃性、強度には優れるもののフレキシビリティに欠け、曲面用途には不向きで、敢えて曲面に施工しようとすると、コア層の部分に溝を設けるなどの加工が必要とされていた。   However, although it is excellent in impact resistance and strength, it lacks flexibility and is unsuitable for curved surface applications. When it is intended to construct on a curved surface, processing such as providing a groove in the core layer portion is required.

本発明は、かかる状況に鑑み検討されたもので、化粧層とコア層の間に曲げ時の応力を分散できる層（以下、化粧層強化層という）が設けられた化粧板であって、該化粧層強化層は、繊維基材に熱硬化性樹脂が含浸された樹脂含浸紙からなり、コア層は、繊維基材に熱可塑性樹脂が含浸された樹脂含浸コア紙からなることを特徴とする化粧板である。   The present invention has been studied in view of such a situation, and is a decorative board provided with a layer capable of dispersing stress during bending (hereinafter referred to as a decorative layer reinforcing layer) between the decorative layer and the core layer, The decorative layer reinforcing layer is made of a resin-impregnated paper in which a fiber base material is impregnated with a thermosetting resin, and the core layer is made of a resin-impregnated core paper in which a fiber base material is impregnated with a thermoplastic resin. It is a decorative board.

本発明は、耐衝撃性、強度に優れる上、フレキシビリティであり、水打ちや熱加工等の特殊な処理無しでかつ常温において曲面用途に用いることができ、裏面側に溝を形成する必要がない。
以下、本発明について詳細に説明する。 The present invention is excellent in impact resistance and strength, is flexible, can be used for curved surfaces at room temperature without special treatment such as water hammering and heat processing, and it is necessary to form a groove on the back side. Absent.
Hereinafter, the present invention will be described in detail.

（化粧層の説明）
化粧層は、化粧性を有するものであれば特に支障はなく、コート紙、突板、樹脂含浸化粧紙など公知のものが挙げられる。樹脂含浸化粧紙は、化粧板用の化粧紙に熱硬化性樹脂を含浸したものであり、熱硬化性樹脂としては、ジアリルフタレート樹脂、不飽和ポリエステル樹脂、アミノ−ホルムアルデヒド樹脂、或いはこれらの混合物などが適用できるが、耐熱性、耐汚染性、耐摩耗性など各種の表面物性に優れるアミノ−ホルムアルデヒド樹脂がとりわけ好ましく、アミノ−ホルムアルデヒド樹脂としてはアミノ化合物、例えばメラミン、尿素、ベンゾグアナミン、アセトグアナミンなどとホルムアルデヒドを反応させた初期縮合物のほか、メチルアルコール、ブチルアルコールなどの低級アルコ−ルによるエ−テル化、パラトルエンスルホンアミドなどの可塑化を促す反応性変性剤で変性されたものが適用でき、特に耐光性に優れるメラミン−ホルムアルデヒド樹脂が好ましい。 (Description of makeup layer)
The decorative layer is not particularly limited as long as it has cosmetic properties, and examples thereof include known paper such as coated paper, veneer, and resin-impregnated decorative paper. The resin-impregnated decorative paper is obtained by impregnating a decorative paper for a decorative board with a thermosetting resin. Examples of the thermosetting resin include diallyl phthalate resin, unsaturated polyester resin, amino-formaldehyde resin, and a mixture thereof. However, amino-formaldehyde resins excellent in various surface properties such as heat resistance, stain resistance, and abrasion resistance are particularly preferable. Examples of amino-formaldehyde resins include amino compounds such as melamine, urea, benzoguanamine, and acetoguanamine. In addition to the initial condensate reacted with formaldehyde, those modified with reactive modifiers that promote etherification with lower alcohols such as methyl alcohol and butyl alcohol and plasticization such as paratoluenesulfonamide can be applied. Melamine-formaldehyde especially excellent in light resistance Resin.

（化粧層強化層の説明）
化粧層強化層は、曲げ加工した際化粧層に応力が集中してヒビが入り割れやすくなることを防ぐためのもので、繊維基材に熱硬化性樹脂を含浸したもので、熱硬化性樹脂としては、前述記載の樹脂の他、フェノール樹脂或いはこれらの混合物などが適用できる。フェノール樹脂は、フェノール類とアルデヒド類とをフェノール性水酸基１モルに対してアルデヒド類を１〜３モルの割合で塩基性触媒下或いは酸性触媒下にて反応させて得られるもので、フェノール類としては、フェノール、クレゾール、キシレノール、オクチルフェノール、フェニルフェノール、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＦなどが挙げられ、アルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、グリオキザール、トリオキザールなどが挙げられる。
また、必要に応じてパラトルエンスルフォンアミド、桐油、燐酸エステル類、グリコール類などの可塑化を促す変性剤で変性されたものも適用でき、塩基性触媒としては、ナトリウム、カリウムなどのアルカリ金属、及びマグネシウム、カルシウムなどのアルカリ土類金属の酸化物や水酸化物、及びトリエチルアミン、トリエタノールアミンなどのアミン類、アンモニアが挙げられ、酸性触媒としては、パラトルエンスルフォン酸、塩酸などが挙げられる。 (Explanation of makeup layer reinforcement layer)
The decorative layer reinforcing layer is intended to prevent stress from concentrating on the decorative layer and causing cracks to easily break when bent, and is a fiber base material impregnated with a thermosetting resin. For example, a phenol resin or a mixture thereof can be applied in addition to the above-described resins. Phenol resins are obtained by reacting phenols and aldehydes at a ratio of 1 to 3 moles of aldehydes with 1 mole of phenolic hydroxyl group under a basic catalyst or an acidic catalyst. Phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal, trioxal and the like.
In addition, those modified with a modifying agent that promotes plasticization such as paratoluene sulfonamide, tung oil, phosphoric esters, glycols, etc. can be applied as necessary, and basic catalysts include alkali metals such as sodium and potassium, And oxides and hydroxides of alkaline earth metals such as magnesium and calcium, amines such as triethylamine and triethanolamine, and ammonia. Examples of acidic catalysts include paratoluenesulfonic acid and hydrochloric acid.

繊維基材としては、クラフト紙や、ガラス繊維、ロックウール、炭素繊維などの無機繊維や有機繊維からなる不織布、織布など挙げられ、繊維基材の坪量は、５０〜２００ｇ／ｍ２の範囲であればよい。例えば嵩比重０．６相当のクラフト紙の場合には１００ｇ／ｍ２のものが好ましく、更に嵩比重の低い基材であれば坪量も低いものが好ましい。
含浸率（％）は数１で示される算出方法で、３０〜１５０％が好ましい。
Examples of the fiber base material include kraft paper, non-woven fabric and woven fabric made of inorganic fibers and organic fibers such as glass fiber, rock wool, and carbon fiber. The basis weight of the fiber base material is 50 to 200 g / m 2 . Any range is acceptable. For example, in the case of kraft paper corresponding to a bulk specific gravity of 0.6, one having a weight of 100 g / m 2 is preferable.
The impregnation rate (%) is a calculation method represented by Equation 1, and is preferably 30 to 150%.

（コア層の説明）
コア層をなす樹脂含浸コア紙は、酢酸ビニル樹脂、ＳＢＲ、アクリル樹脂、スチレンアクリル樹脂などの熱可塑性樹脂と無機充填剤などからなるスラリーを、前記の繊維基材や有機繊維基材に含浸したもので、有機繊維としては、例えばポリエチレン、ポリプロピレン、ビニロン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリアミド、ポリエステル、ポリウレタン等やこれらの変成物およびエチレン−酢酸ビニル共重合体などに代表される各種共重合体からなる繊維およびこれらの混合物か、さらにはこれらの重合体からなる複合繊維などが挙げられる。
熱可塑性樹脂の中でも曲げ性、密着性、成形性に優れるガラス転移温度が０℃以下のアクリル樹脂又はＳＢＲラテックスが好ましく、有機繊維の中では引っ張り強度の優れるポリエステルが好ましい。 (Description of core layer)
The resin-impregnated core paper forming the core layer is obtained by impregnating the fiber base or the organic fiber base with a slurry made of a thermoplastic resin such as vinyl acetate resin, SBR, acrylic resin, styrene acrylic resin and an inorganic filler. Examples of organic fibers include polyethylene, polypropylene, vinylon, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, polyester, polyurethane and the like, modified products thereof, and ethylene-vinyl acetate copolymer. Examples thereof include fibers made of various copolymers and mixtures thereof, and composite fibers made of these polymers.
Among thermoplastic resins, an acrylic resin or SBR latex having a glass transition temperature of 0 ° C. or less that is excellent in bendability, adhesion, and moldability is preferable, and polyester having excellent tensile strength is preferable among organic fibers.

（無機充填剤の説明）
スラリー中に含まれる無機充填剤は成形性の安定化、強度の向上、及び難燃効果を目的とするものであり、具体的には、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、シリカなどが挙げられ、平均粒子径が０．５〜２００μｍの範囲のものが繊維基材への含浸が可能であり、中でも、水酸化アルミニウムや水酸化マグネシウムなど結晶水を含むものは耐水性、耐熱性に優れる。 (Description of inorganic filler)
The inorganic filler contained in the slurry is for the purpose of stabilizing moldability, improving strength, and flame retardancy, and specifically includes aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica and the like. Those having an average particle diameter in the range of 0.5 to 200 μm can be impregnated into the fiber base material. Among them, those containing crystal water such as aluminum hydroxide and magnesium hydroxide are water resistant and heat resistant. Excellent.

（配合割合の説明）
該スラリー中の熱可塑性樹脂分と無機充填剤との配合割合は固形分比で１：３〜１：１０の範囲とするのが望ましく、熱可塑性樹脂分に対して無機充填剤が多いと密着性が低下し、また、無機充填剤が少くなると熱圧成形時に樹脂が染み出したりする。 (Explanation of blending ratio)
The blending ratio of the thermoplastic resin component and the inorganic filler in the slurry is preferably in the range of 1: 3 to 1:10 in terms of solid content, and if the inorganic filler is more than the thermoplastic resin component, the slurry is in close contact. If the inorganic filler is reduced, the resin may ooze out during hot pressing.

機繊維基材へのスラリー固形分含有率（％）は、数１で示される算出方法で、７００〜２０００％の範囲が好ましい。上限を超えると固形分の脱落が多くなり取り扱いにくく、また下限に満たないと層間剥離しやすくなる。   The slurry solid content (%) in the machine fiber substrate is a calculation method represented by Equation 1, and is preferably in the range of 700 to 2000%. If the upper limit is exceeded, the solid content will drop off, making it difficult to handle, and if the lower limit is not reached, delamination will easily occur.

以下、実施例を挙げてより詳細に説明するが、本発明をより具体的に示すものであって、特に限定するものではない。
実施例１（樹脂含浸化粧紙を用いた場合）
化粧層
坪量１００ｇ／ｍ２の無地柄の化粧紙に，メラミン−ホルムアルデヒド樹脂を数１で示す含浸率が１００％となるように含浸してメラミン樹脂含浸化粧紙を得た。
化粧層強化層
１８５ｇ／ｍ２のクラフト紙に，フェノール樹脂を数１で示す含浸率が１００％となるように含浸してフェノール樹脂含浸紙を得た。
コア層
５０ｇ／ｍ２のポリエステル繊維不織布に、Ｔｇが−５０℃のアクリル樹脂１０部に対して、水酸化アルミニウムを９０部配合したスラリーを、数２に示すスラリー固形分定着率が１６００％となるように含浸して樹脂含浸コア紙を得た。
化粧板
下から順に、樹脂含浸コア紙を６枚、フェノール樹脂含浸紙を１枚、メラミン樹脂含浸化粧紙を１枚積層して、フラット仕上げプレートを用いて１３０℃，１００ｋｇ／ｃｍ２、９０分間の条件で熱圧成形して、厚み３ｍｍの実施例１の化粧板を得た。 EXAMPLES Hereinafter, although an Example is given and demonstrated in detail, this invention is shown more concretely and is not specifically limited.
Example 1 (When resin impregnated decorative paper is used)
Decorative layer A plain paper decorative paper having a basis weight of 100 g / m 2 was impregnated with a melamine-formaldehyde resin so that the impregnation ratio represented by Equation 1 was 100% to obtain a melamine resin-impregnated decorative paper.
A decorative layer reinforcing layer 185 g / m 2 of kraft paper was impregnated with a phenol resin so that the impregnation ratio represented by Formula 1 was 100% to obtain a phenol resin-impregnated paper.
A slurry in which 90 parts of aluminum hydroxide is blended with 10 parts of an acrylic resin having a Tg of −50 ° C. in a polyester fiber nonwoven fabric having a core layer of 50 g / m 2 has a slurry solid content fixing ratio of 1600% shown in Equation 2. The resin-impregnated core paper was obtained by impregnation.
Decorative plate In order from the bottom, 6 sheets of resin-impregnated core paper, 1 sheet of phenol resin-impregnated paper, and 1 sheet of melamine resin-impregnated decorative paper are laminated at 130 ° C., 100 kg / cm 2 for 90 minutes using a flat finish plate. The decorative board of Example 1 having a thickness of 3 mm was obtained by hot-press molding under the following conditions.

実施例２（ガラス繊維不織布を用いた場合）
実施例１において、ポリエステル繊維不織布の代わりにガラス繊維不織布を用いた以外は同様に実施して、実施例２の化粧板を得た。 Example 2 (when glass fiber nonwoven fabric is used)
The decorative plate of Example 2 was obtained in the same manner as in Example 1 except that a glass fiber nonwoven fabric was used instead of the polyester fiber nonwoven fabric.

実施例３（アクルル樹脂以外の樹脂を用いた場合）
実施例１において、アクリル樹脂の代わりにＳＢＲラテックスを用いた以外は同様に実施して、実施例３の化粧板を得た。 Example 3 (When a resin other than an acrulule resin is used)
The decorative plate of Example 3 was obtained in the same manner as in Example 1 except that SBR latex was used instead of the acrylic resin.

比較例１（フェノール樹脂含浸紙を用いない場合）
実施例１において、フェノール樹脂含浸紙を用いなかった以外は同様に実施して比較例１の化粧シートを得た。 Comparative Example 1 (when no phenol resin impregnated paper is used)
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that no phenol resin-impregnated paper was used.

比較例２（樹脂成分に対して無機充填剤が少ない場合）
実施例１において、アクリル樹脂１０部に対して、水酸化アルミニウムを２０部配合したスラリーを用いた以外は同様に実施したが、熱圧成形時にアクリル樹脂が流れ出し、化粧シートが得られなかった。 Comparative example 2 (when there are few inorganic fillers with respect to the resin component)
In Example 1, it carried out similarly except having used the slurry which mix | blended 20 parts of aluminum hydroxide with respect to 10 parts of acrylic resins, However, Acrylic resin flowed out at the time of hot press molding, and the decorative sheet was not obtained.

比較例３（樹脂成分に対して無機充填剤が多い場合）
実施例１において、アクリル樹脂１０部に対して、水酸化アルミニウムを１５０部配合したスラリーを用いた以外は同様に実施したが、密着性が悪く化粧シートが得られなかった。 Comparative example 3 (when there are many inorganic fillers with respect to the resin component)
In Example 1, it carried out similarly except having used the slurry which mix | blended 150 parts of aluminum hydroxide with respect to 10 parts of acrylic resins, but adhesiveness was bad and the decorative sheet was not obtained.

比較例４（スラリーの定着率が下限未満の場合）
実施例１において、スラリー固形分定着率が５００％とした以外は同様に実施したが、密着性がやや劣り、得られた化粧シートはカッターナイフで層間剥離を起こした。 Comparative example 4 (when the fixing rate of the slurry is less than the lower limit)
In Example 1, the same procedure was performed except that the slurry solid content fixing ratio was 500%, but the adhesion was slightly inferior, and the resulting decorative sheet was delaminated with a cutter knife.

比較例５（スラリーの定着率が上限を超える場合）
実施例１において、スラリー固形分定着率が２２００％とした以外は同様に実施したが、熱圧成形時にアクリル樹脂が流れ出し、化粧シートが得られなかった。 Comparative Example 5 (When the slurry fixing rate exceeds the upper limit)
In Example 1, the same procedure was carried out except that the slurry solid content fixing rate was 2200%, but the acrylic resin flowed out during hot press molding, and a decorative sheet could not be obtained.

比較例６（熱可塑性樹脂のＴｇが０℃を超える場合）
実施例１において、Ｔｇが２０℃のアクリル樹脂を用いた以外は同様に実施して比較例６の化粧シートを得たが曲げ性に劣っていた。 Comparative Example 6 (when Tg of thermoplastic resin exceeds 0 ° C.)
In Example 1, the decorative sheet of Comparative Example 6 was obtained in the same manner except that an acrylic resin having a Tg of 20 ° C. was used, but the bendability was poor.

比較例７（通常の化粧板の場合）
実施例１において、フェノール樹脂含浸紙を７枚、メラミン樹脂含浸化粧紙を１枚積層した以外は同様に実施して、比較例７の化粧シートを得た。
Comparative Example 7 (in the case of a normal decorative board)
A decorative sheet of Comparative Example 7 was obtained in the same manner as in Example 1, except that seven phenol resin-impregnated papers and one melamine resin-impregnated decorative paper were laminated.

評価結果を表１に示す。
The evaluation results are shown in Table 1.

（試験方法）
試験方法は以下の通りとした。
曲げ性：規定のＲに沿う半円の曲げ合板に手力で貼り合わせた際の破断現象が起こらないレベル
弾性率：ＪＩＳ Ｋ ６９０２「熱硬化性樹脂化粧板」の弾性率試験方法による。
成形性：層間剥離しないものを○、カッターナイフで層間剥離するものを△とした。 (Test method)
The test method was as follows.
Bendability: Level elastic modulus that does not cause breakage when manually bonded to a semi-circular bent plywood along the prescribed R: According to the elastic modulus test method of JIS K 6902 “Thermosetting resin decorative board”.
Formability: A case where the delamination was not performed was evaluated as ◯, and a case where the delamination was performed with a cutter knife was evaluated as a Δ.

実施例１の化粧板の構成断面図。1 is a configuration cross-sectional view of a decorative board of Example 1. FIG.

符号の説明Explanation of symbols

１ 化粧層
２ 化粧層強化層
３ コア層
６ 化粧板 1 decorative layer 2 decorative layer reinforcing layer 3 core layer 6 decorative plate

Claims (5)

化粧層とコア層の間に化粧層強化層が設けられた化粧板であって、該化粧層強化層は、繊維基材に熱硬化性樹脂が含浸された樹脂含浸紙からなり、コア層は、繊維基材に熱可塑性樹脂と無機充填剤とからなるスラリーが含浸された樹脂含浸コア紙からなることを特徴とする化粧板。 A decorative board in which a decorative layer reinforcing layer is provided between a decorative layer and a core layer, the decorative layer reinforcing layer is made of resin-impregnated paper in which a fiber base material is impregnated with a thermosetting resin, and the core layer is A decorative board comprising a resin-impregnated core paper in which a fiber base material is impregnated with a slurry comprising a thermoplastic resin and an inorganic filler. 該熱可塑性樹脂と該無機充填剤の配合割合が固形分比で１：３〜１：１０であることを特徴とする請求項１記載の化粧板。 The decorative board according to claim 1, wherein a blending ratio of the thermoplastic resin and the inorganic filler is 1: 3 to 1:10 in terms of solid content. 該スラリーの含浸率が次式で示される算出方法で７００〜２０００％であることを特徴とする請求項１又は２記載の化粧板。 The decorative board according to claim 1 or 2, wherein the impregnation ratio of the slurry is 700 to 2000% by a calculation method represented by the following formula. 該熱可塑性樹脂のガラス転移温度（Ｔｇ）が０℃以下であることを特徴とする請求項１、２又は３記載の化粧板。 4. The decorative board according to claim 1, wherein the thermoplastic resin has a glass transition temperature (Tg) of 0 ° C. or lower. 該熱可塑性樹脂がアクリル樹脂又はＳＢＲラテックスであることを特徴とする請求項１、２、３又は４記載の化粧板。 5. The decorative board according to claim 1, wherein the thermoplastic resin is an acrylic resin or SBR latex.
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