JP2006219656A - High-glossy decorative sheet having good surface smoothness - Google Patents
High-glossy decorative sheet having good surface smoothness Download PDFInfo
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Abstract
Description
本発明はジアリルフタレート系化粧板の製造分野に関する。 The present invention relates to the field of manufacturing diallyl phthalate decorative boards.
従来、ジアリルフタレート系樹脂化粧板は、耐候性、自然な風合い、耐熱性、耐薬品性、寸法安定性を有する熱硬化性樹脂化粧板として知られている。これまでジアリルフタレート系樹脂化粧板は、ジアリルフタレートプレポリマー９０〜９３重量％、ジアリルフタレートモノマー７〜１０重量％に硬化剤、離型剤、重合調整剤、充填剤、紫外線吸収剤を含む樹脂溶解液あるいは、ジアリルフタレートプレポリマー３０〜９０重量％、不飽和ポリエステル１０〜７０重量％に硬化剤、離型剤、重合調整剤、充填剤、紫外線吸収剤を含む樹脂溶解液に印刷化粧紙を浸漬あるいは塗布乾燥した含浸塗布化粧紙を基材と熱圧成型して化粧板を得ている。 Conventionally, diallyl phthalate-based resin decorative boards are known as thermosetting resin decorative boards having weather resistance, natural texture, heat resistance, chemical resistance, and dimensional stability. Up to now, diallyl phthalate-based resin decorative boards have 90-93% by weight of diallyl phthalate prepolymer and 7-10% by weight of diallyl phthalate monomer. Printed decorative paper is immersed in a solution or a resin solution containing 30 to 90% by weight of diallyl phthalate prepolymer and 10 to 70% by weight of unsaturated polyester in a curing agent, mold release agent, polymerization regulator, filler, and UV absorber. Alternatively, a decorative board is obtained by hot-pressing a coated impregnated coated decorative paper with a base material.
ところで、かかる化粧板に関してはパーティクルボードや中密度繊維板（ＭＤＦ）等の化粧板基材の表層の凹凸が化粧板表面にそのまま現れるため、表面平滑性が十分ではなかった。
本発明は、従来のジアリルフタレート系化粧板では未解決であった、化粧板基材表層の凹凸が化粧板表面にそのまま現れることによる表面平滑性が損なわれるという問題を解決しようとするものである。 The present invention is intended to solve the problem that surface smoothness due to the appearance of irregularities on the surface of the decorative board substrate, which is unsolved in the conventional diallyl phthalate decorative board, is impaired on the surface of the decorative board. .
本発明は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４）表面処理剤で表面処理された水酸化アルミニウム５〜５０重量部を添加してなる化粧板用樹脂組成物である。 The present invention relates to a total of 100 parts by weight of (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50% by weight, 4) A resin composition for a decorative board, which is obtained by adding 5 to 50 parts by weight of aluminum hydroxide surface-treated with a surface treating agent.
また、本発明は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４Ａ）水酸化アルミニウム５〜５０重量部、および（４Ｂ）表面処理剤０．００５〜１．５重量部を添加してなる化粧板用樹脂組成物である。 Further, the present invention relates to a total of 100 parts by weight of (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50% by weight. , (4A) 5-50 parts by weight of aluminum hydroxide, and (4B) a resin composition for decorative plates, to which 0.005 to 1.5 parts by weight of a surface treatment agent are added.
本発明によれば、ジアリルフタレート系化粧板の従来特性である優れた耐水性、耐候性、耐薬品性等を損なうことなく、表面平滑性の良好な高光沢化粧板が得られる。
更に、本発明の樹脂組成物に対しては酸化チタンまたは酸化アルミニウムを比較的多量に添加することができ、酸化チタンを添加した場合には化粧板の隠蔽性が、また酸化アルミニウムを添加した場合には表面硬度がそれぞれ著しく改善される。
According to the present invention, a high-gloss decorative board having good surface smoothness can be obtained without impairing the excellent water resistance, weather resistance, chemical resistance, etc., which are conventional characteristics of diallyl phthalate decorative boards.
Furthermore, a relatively large amount of titanium oxide or aluminum oxide can be added to the resin composition of the present invention. When titanium oxide is added, the concealability of the decorative board is improved, and when aluminum oxide is added. The surface hardness is remarkably improved.
本発明の組成物は上述の通りであるが、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４）表面処理剤で表面処理された水酸化アルミニウム５〜５０重量部、および、更に（５）多官能（メタ）アクリルエステル０．１〜１０．０重量部を添加してなる化粧板用樹脂組成物が好ましい。 The composition of the present invention is as described above, but (1) diallyl phthalate prepolymer 50-90% by weight, (2) diallyl phthalate monomer 0-20% by weight, and (3) unsaturated polyester 0-50% by weight. (4) 5 to 50 parts by weight of aluminum hydroxide surface-treated with a surface treatment agent, and (5) 0.1 to 10.0 parts by weight of a polyfunctional (meth) acrylic ester. A resin composition for decorative plates, to which is added, is preferred.
また、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４Ａ）水酸化アルミニウム５〜５０重量部、および（４Ｂ）表面処理剤０．００５〜１．５重量部、および、更に（５）多官能（メタ）アクリルエステル０．１〜１０．０重量部を添加してなる化粧板用樹脂組成物が好ましい。 Further, (4A) with respect to a total of 100 parts by weight of (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50% by weight. 5 to 50 parts by weight of aluminum hydroxide and (4B) 0.005 to 1.5 parts by weight of a surface treatment agent and (5) 0.1 to 10.0 parts by weight of a polyfunctional (meth) acrylic ester are added. A resin composition for decorative plates is preferred.
はじめに、本発明の化粧板用樹脂組成物の各構成成分について説明する。
（１）ジアリルフタレートプレポリマーとは、ジアリルオルソフタレートプレポリマー、ジアリルイソフタレートプレポリマー、ジアリルテレフタレートプレポリマーの単独またはそれらの混合物である。また、下記ジアリルフタレートモノマー２種または３種の共重合体であってもよい。ジアリルフタレートプレポリマーの分子量は１００００〜５００００が適当である。
First, each component of the resin composition for decorative plates of the present invention will be described.
(1) A diallyl phthalate prepolymer is a diallyl orthophthalate prepolymer, a diallyl isophthalate prepolymer, or a diallyl terephthalate prepolymer alone or a mixture thereof. Moreover, the following diallyl phthalate monomer 2 type or 3 types of copolymers may be sufficient. The molecular weight of the diallyl phthalate prepolymer is suitably 10,000 to 50,000.
一方、（２）ジアリルフタレートモノマーとは、ジアリルオルソフタレート、ジアリルイソフタレート、ジアリルテレフタレートの単独またはこれら２種または３種の混合物である。 On the other hand, (2) diallyl phthalate monomer is diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate alone or a mixture of two or three of them.
（３）不飽和ポリエステルとしては、通常の液体状もしくは固体状の不飽和ポリエステル樹脂を使用することができる。不飽和ポリエステルは多塩基性の不飽和酸と多価アルコールから脱水重縮合して得ることができる。この場合、不飽和酸の一部が飽和酸で置き替わっていてもよい。数平均分子量が３０００〜５００００の不飽和ポリエステルが好ましい。
例えば、酸成分としてマレイン酸、フマル酸、イタコン酸、フタル酸、アジピン酸が挙げられる。一方、多価アルコール成分としてはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、ジエチレングリコール、水素化ビスフェノールＡ等が挙げられる。
(3) As the unsaturated polyester, a normal liquid or solid unsaturated polyester resin can be used. The unsaturated polyester can be obtained by dehydration polycondensation from a polybasic unsaturated acid and a polyhydric alcohol. In this case, a part of the unsaturated acid may be replaced with a saturated acid. An unsaturated polyester having a number average molecular weight of 3000 to 50000 is preferred.
Examples of the acid component include maleic acid, fumaric acid, itaconic acid, phthalic acid, and adipic acid. On the other hand, examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, hydrogenated bisphenol A, and the like.
また、（３）不飽和ポリエステルとして空気硬化型不飽和ポリエステル樹脂を用いてもよい。例えば、上記酸成分に他の酸成分としてテトラヒドロフタル酸、３，６−エンドメチレンテトラフタル酸、メチル−３，６−エンドメチレンテトラフタル酸等の脂肪族環状不飽和酸を、上記アルコール成分に他のアルコール成分としてアリルグリシジルエーテルをそれぞれさらに共存させた混合物から脱水重縮合して製造されたポリエステル樹脂が挙げられる。 Further, (3) an air-curable unsaturated polyester resin may be used as the unsaturated polyester. For example, an aliphatic cyclic unsaturated acid such as tetrahydrophthalic acid, 3,6-endomethylenetetraphthalic acid, methyl-3,6-endomethylenetetraphthalic acid or the like as the above acid component, Examples of other alcohol components include polyester resins produced by dehydration polycondensation from a mixture in which allyl glycidyl ether further coexists.
（４）表面処理剤で表面処理された水酸化アルミニウムは、分散性を高める等の目的で水酸化アルミニウム表面に表面処理剤が固定化された平均粒子径が０．５〜１０．０μｍ（＋４４μｍ、０．０５〜１．０％）の工業製品を好ましく使用することができる。 (4) The aluminum hydroxide surface-treated with the surface treatment agent has an average particle diameter of 0.5 to 10.0 μm (+44 μm) in which the surface treatment agent is immobilized on the surface of the aluminum hydroxide for the purpose of enhancing dispersibility. 0.05-1.0%) industrial products can be preferably used.
表面処理されるべき水酸化アルミニウムの形態は特に限定されず、円柱状、針状、球状等、種々のものを使用することができる。 The form of the aluminum hydroxide to be surface-treated is not particularly limited, and various forms such as a columnar shape, a needle shape, and a spherical shape can be used.
また、表面処理剤についても例えばシランカップリング剤やチタンカップリング剤等、特に限定はされないが、シランカップリング剤が好ましい。
シランカップリング剤としては、分子内に２個または３個のアルコキシ基を有する有機珪素化合物が好ましい。例えば、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（βメトキシエトキシ）シラン等のビニルシラン類、β−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン等のエポキシシラン類、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン等のアミノシラン類、その他γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン等が挙げられる。
The surface treatment agent is not particularly limited, for example, a silane coupling agent or a titanium coupling agent, but a silane coupling agent is preferable.
As the silane coupling agent, an organosilicon compound having 2 or 3 alkoxy groups in the molecule is preferable. For example, vinyl silanes such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (βmethoxyethoxy) silane, and epoxy such as β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Examples include silanes, γ-aminopropyltriethoxysilane, aminosilanes such as N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and other γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like. .
水酸化アルミニウムの表面処理の具体的方法の一例としては、水酸化アルミニウムを表面処理剤の原液または溶液中でスラリー状として表面処理を行う湿式法や、撹拌中の水酸化アルミニウムに表面処理剤の原液または溶液を振りかけて均一に分散、混合して表面処理を行う乾式法がある。この場合、水酸化アルミニウム１００重量部に対し、表面処理剤を０．１〜３．０重量部の割合で共存するよう混合するのが好ましい。 Examples of a specific method of surface treatment of aluminum hydroxide include a wet method in which aluminum hydroxide is slurried in a stock solution or solution of a surface treatment agent, or a surface treatment agent applied to aluminum hydroxide being stirred. There is a dry method in which a surface treatment is carried out by uniformly dispersing and mixing the stock solution or solution. In this case, it is preferable to mix so that a surface treating agent may coexist in the ratio of 0.1-3.0 weight part with respect to 100 weight part of aluminum hydroxide.
例えば具体的には、昭和電工（株）製のハイジライトＨ−３２ＳＴ（平均粒子径 約３μｍ）やハイジライトＨ−４２ＳＴＶ（平均粒子径 約１μｍ）、日本軽金属（株）製のＢ７０３ＳＴ（平均粒子径 約２μｍ）等が好ましく挙げられる。 For example, specifically, Hijilite H-32ST (average particle size of about 3 μm) or Heidilite H-42STV (average particle size of about 1 μm) manufactured by Showa Denko KK, B703ST (average particle of Nippon Light Metal Co., Ltd.) Preferably, the diameter is about 2 μm).
（４）表面処理された水酸化アルミニウムの添加量は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、５から５０重量部であるが、好ましくは１０〜３０重量部が望ましい。 (4) The amount of surface-treated aluminum hydroxide added is (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50%. The amount is 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight in total.
ところで、水酸化アルミニウムの表面処理は、上述のように独立した前処理として行う以外に、いわゆるインテグラルブレンド法、即ち、化粧板用樹脂組成物を混合する際、（４Ａ）水酸化アルミニウムと、（４Ｂ）表面処理剤を同時に共存させる手段でも行い得るが、この場合、（４Ａ）水酸化アルミニウム１００重量部に対し、（４Ｂ）表面処理剤を０．１〜３．０重量部の割合で添加するのが好ましい。 By the way, the surface treatment of aluminum hydroxide is performed as an independent pretreatment as described above, but when the so-called integral blend method, that is, when the resin composition for decorative plates is mixed, (4A) aluminum hydroxide, (4B) Although it can also be performed by means of coexisting the surface treatment agent, in this case, (4B) the surface treatment agent is used in a ratio of 0.1 to 3.0 parts by weight with respect to 100 parts by weight of aluminum hydroxide. It is preferable to add.
本発明においては、任意成分として、（５）多官能（メタ）アクリルエステルを更に添加することができる。
（５）多官能（メタ）アクリルエステルとしては、分子内にアクリロイル基又はメタクリロイル基（以下両者を総称して（メタ）アクリロイル基という）を３個以上有するペンタエリスリトールのポリアクリレート又はポリメタクリレート（以下両者を総称してポリ（メタ）アクリレートという）あるいは分子内に（メタ）アクリロイル基を４個以上有するジペンタエリスリトールのポリ（メタ）アクリレートが好ましく用いられる。
In the present invention, (5) polyfunctional (meth) acrylic ester can be further added as an optional component.
(5) As polyfunctional (meth) acrylic ester, pentaerythritol polyacrylate or polymethacrylate (hereinafter referred to as “methacryloyl group” or “methacryloyl group” in the molecule). A poly (meth) acrylate of dipentaerythritol having 4 or more (meth) acryloyl groups in the molecule is preferably used.
（５）多官能（メタ）アクリルエステルの添加量は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、０．１〜１０．０重量部であるが、好ましくは０．５〜５．０重量部の範囲がより望ましい。 (5) The addition amount of the polyfunctional (meth) acrylic ester is (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50%. Although it is 0.1-10.0 weight part with respect to a total of 100 weight part of weight%, Preferably the range of 0.5-5.0 weight part is more desirable.
ところで、本発明の樹脂組成物に、さらに（６ａ）酸化チタンを添加することで化粧板表面の隠蔽性を向上させることができ、また、本発明の樹脂組成物に、さらに（６ｂ）酸化アルミニウムを添加することで化粧板表面のスクラッチ特性を向上させることができる。これらを並存させて使用してもよい。 By the way, (6a) titanium oxide can be further added to the resin composition of the present invention to improve the concealability of the decorative plate surface, and (6b) aluminum oxide can be further added to the resin composition of the present invention. It is possible to improve the scratch characteristics of the decorative board surface. These may be used side by side.
例えば、含浸基材（例えば印刷紙）の坪量が低い場合（例えば坪量６０ｇ／ｍ２）、隠蔽性が悪く下地の色を拾いやすいため、化粧板にした後の表面の色が本来の印刷紙の色と比較して黒ずんで見えてしまう。このような場合に酸化チタンを添加すると、その顔料としての効果により化粧板にした後でも印刷紙本来の色が現れやすくなる。 For example, when the basis weight of the impregnated base material (for example, printing paper) is low (for example, basis weight 60 g / m 2 ), the surface color after making the decorative board is the original color because the concealability is poor and it is easy to pick up the base color It looks darker than the color of the printed paper. When titanium oxide is added in such a case, the original color of the printing paper is likely to appear even after the decorative board is made due to the effect of the pigment.
また、酸化アルミニウムはそれ自体硬度が非常に高い（モース硬度９）ため、適当量添加することにより飛躍的に化粧板表面の表面硬度が向上する。 In addition, since aluminum oxide itself has a very high hardness (Mohs hardness 9), the surface hardness of the decorative board surface is dramatically improved by adding an appropriate amount.
このような、樹脂組成物へ酸化チタンや酸化アルミニウムを添加すれば当該効果が発現することは当業者に公知である。しかし、従来のジアリルフタレート系樹脂組成物では酸化チタン等を多量に入れると分散不良（無機フィラー同士が凝集し、均一系にならない）を起こすため、添加量にみあう効果が得られない欠点があった。ところが、本発明の樹脂組成物においては酸化チタン等を比較的多量に入れてもそのような問題が生じない。 It is known to those skilled in the art that such effects are manifested by adding titanium oxide or aluminum oxide to such a resin composition. However, the conventional diallyl phthalate resin composition has a disadvantage that when adding a large amount of titanium oxide or the like, dispersion failure (inorganic filler aggregates and does not become a uniform system), so the effect of matching the added amount cannot be obtained. there were. However, in the resin composition of the present invention, such a problem does not occur even if a relatively large amount of titanium oxide or the like is added.
使用することのできる酸化チタンに制限はない。結晶タイプはルチル型、アナターゼ型のどちらでもよいが、安価なルチル型の方が望ましい。粒径も特に限定されないが、０．０１〜１．０μｍが好ましい。表面処理も行ってよいが特に必要はない。
好ましい市販品としては石原産業（株）製、タイペークシリーズなどが例示される。
There is no limitation on the titanium oxide that can be used. The crystal type may be either a rutile type or an anatase type, but an inexpensive rutile type is desirable. The particle size is not particularly limited, but is preferably 0.01 to 1.0 μm. Although surface treatment may be performed, it is not particularly necessary.
Preferable commercially available products include Ishihara Sangyo Co., Ltd., and Taipei series.
使用することのできる酸化アルミニウムに制限はない。研磨材として一般的に用いられている白色結晶で特に限定されないが、粒径が１〜１００μｍのものが望ましい。
好ましい市販品としてはキイライト研磨材（株）製、ホワイトアランダム（ＷＡ）シリーズが例示される。
There is no restriction on the aluminum oxide that can be used. Although it is not specifically limited by the white crystal generally used as an abrasive | polishing material, a thing with a particle size of 1-100 micrometers is desirable.
As a preferable commercially available product, White Alundum (WA) series manufactured by Keylite Abrasives Co., Ltd. is exemplified.
これら酸化チタンまたは酸化アルミニウムの好ましい添加量は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４）表面処理剤で表面処理された水酸化アルミニウム５〜５０重量部の共存下、５〜１００重量部であり、更に好ましくは（６ａ）酸化チタンについては５〜４０重量部、（６ｂ）酸化アルミニウムについては１０〜６０重量部がそれぞれ望ましい。
または、これら酸化チタンまたは酸化アルミニウムの好ましい添加量は、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、（４Ａ）水酸化アルミニウム５〜５０重量部、および（４Ｂ）表面処理剤０．００５〜１．５重量部の共存下、５〜１００重量部であり、更に好ましくは（６ａ）酸化チタンについては５〜４０重量部、（６ｂ）酸化アルミニウムについては１０〜６０重量部がそれぞれ望ましい。
この場合、更に（５）多官能（メタ）アクリルエステル０．１〜１０．０重量部が共存してもよい。
The preferred addition amounts of these titanium oxides or aluminum oxides are: (1) diallyl phthalate prepolymer 50-90% by weight, (2) diallyl phthalate monomer 0-20% by weight, and (3) unsaturated polyester 0-50% by weight. (4) 5 to 100 parts by weight in the presence of 5 to 50 parts by weight of aluminum hydroxide surface-treated with a surface treatment agent, and more preferably (6a) about 5 to 5 parts of titanium oxide. About 40 parts by weight and (6b) aluminum oxide, 10 to 60 parts by weight are preferable.
Alternatively, the preferred addition amount of these titanium oxide or aluminum oxide is (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50% by weight. % In total in the presence of 5 to 50 parts by weight of (4A) aluminum hydroxide, and (4B) 0.005 to 1.5 parts by weight of a surface treating agent, Preferably, (6a) titanium oxide is 5 to 40 parts by weight, and (6b) aluminum oxide is 10 to 60 parts by weight.
In this case, (5) 0.1 to 10.0 parts by weight of a polyfunctional (meth) acrylic ester may coexist.
次に、本発明による化粧板用樹脂組成物を含浸基材に含浸させたプリプレグについて説明する。
ここで、含浸基材としては印刷紙（印刷パターン紙）、クラフト紙、不織布、織布等が好ましく例示される。
Next, the prepreg obtained by impregnating the impregnated base material with the resin composition for decorative plates according to the present invention will be described.
Here, preferred examples of the impregnated substrate include printing paper (printing pattern paper), kraft paper, non-woven fabric, and woven fabric.
本発明の化粧板用樹脂組成物を用いてプリプレグを製造するには、当該樹脂組成物が低粘度の液体である場合は当該含浸基材を当該樹脂組成物中へ浸せばよい。一方、当該樹脂組成物が高粘度液体や固体である場合は、適当な溶剤、例えばアセトン、トルエン、メチルエチルケトン等の有機溶剤に本発明樹脂組成物を溶解させ樹脂液とし、そこへ前記含浸基材を浸した後、乾燥して溶媒を飛ばせばよい。含浸樹脂付着量は８０〜２５０ｇ／ｍ２が好ましい。
なお、後処理として、プリプレグを必要に応じてプレキュアすることで樹脂の硬化を進め、プリプレグ表面のタックを抑えることができる。
In order to produce a prepreg using the resin composition for decorative plates of the present invention, when the resin composition is a low-viscosity liquid, the impregnated substrate may be immersed in the resin composition. On the other hand, when the resin composition is a high-viscosity liquid or solid, the resin composition of the present invention is dissolved in an appropriate solvent, for example, an organic solvent such as acetone, toluene, or methyl ethyl ketone, to obtain a resin liquid, and the impregnated base material is dissolved therein. After soaking, the solvent may be removed by drying. The impregnated resin adhesion amount is preferably 80 to 250 g / m 2 .
In addition, as a post-treatment, the prepreg can be pre-cured as necessary, so that the resin can be cured and tackiness on the prepreg surface can be suppressed.
また、プリプレグの製造の際、含浸基材の表面には光沢度や硬度を重視する成分からなる樹脂組成物を、裏面には平滑性や隠蔽性を重視する成分からなる樹脂組成物を配置することで、表裏で成分の異なるプリプレグを作成することも可能である。具体的には、表面用樹脂に含浸基材全体を浸した後、裏面樹脂を敢えて掻きとり、さらに裏面用樹脂を裏面にコーティングする手法により通常のプリプレグに比べてもほとんど生産コストを上げずによりニーズにあったプリプレグを製造できる。 Further, when manufacturing the prepreg, a resin composition composed of components that place importance on glossiness and hardness is arranged on the surface of the impregnated base material, and a resin composition made up of components that places importance on smoothness and concealment properties on the back surface. Thus, it is possible to create prepregs having different components on the front and back sides. Specifically, after immersing the entire impregnated base material in the surface resin, the back surface resin is dared to scrape and further coated with the back surface resin on the back surface, almost without increasing the production cost compared to ordinary prepregs. A prepreg that meets your needs can be manufactured.
ところで、本発明の樹脂組成物は一般に硬化速度が遅く、それ単独では短時間に十分な硬化度が得られないため、通常、硬化剤が使用される。硬化剤としては、組成物中に存在する不飽和二重結合を重合させ得る化合物であれば特に限定されないが、例えばベンゾイルパーオキサイド、ターシャリーブチルパーベンゾエイト、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド等の有機過酸化物系硬化剤を好ましく挙げることができる。 By the way, the resin composition of the present invention generally has a slow curing rate, and a curing agent is usually used because it cannot obtain a sufficient degree of curing in a short time. The curing agent is not particularly limited as long as it is a compound capable of polymerizing an unsaturated double bond present in the composition. For example, benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, etc. The organic peroxide curing agent can be preferably mentioned.
硬化剤の添加のタイミングは、本発明の樹脂組成物の十分なポットライフを維持するためには、プリプレグ製造直前に当該本発明の樹脂組成物に対して添加するのが好ましい。
添加量としては、（１）ジアリルフタレートプレポリマー５０〜９０重量％、（２）ジアリルフタレートモノマー０〜２０重量％、および（３）不飽和ポリエステル０〜５０重量％の合計１００重量部に対し、１．０〜１０．０重量部、例えば３．０〜５．０重量部であってよい。
In order to maintain the sufficient pot life of the resin composition of the present invention, it is preferable to add the curing agent to the resin composition of the present invention immediately before the production of the prepreg.
The amount added is 100 parts by weight in total of (1) diallyl phthalate prepolymer 50 to 90% by weight, (2) diallyl phthalate monomer 0 to 20% by weight, and (3) unsaturated polyester 0 to 50% by weight. It may be 1.0 to 10.0 parts by weight, for example 3.0 to 5.0 parts by weight.
また、本発明の趣旨を逸脱しない限りにおいて、硬化剤以外にも必要に応じて多種の反応性モノマーや当該技術分野に通常用いられる添加剤、例えば、充填剤（微粉末シリカ等）、内部離型剤、難燃剤、重合調整剤、紫外線吸収剤、顔料等を添加することができる。 In addition to the curing agent, various reactive monomers and additives usually used in the technical field, for example, fillers (fine powder silica etc.), internal separations, etc. may be used as long as they do not depart from the spirit of the present invention. Molding agents, flame retardants, polymerization regulators, ultraviolet absorbers, pigments and the like can be added.
次に、本発明に係るプリプレグと化粧板基材とを一体成型してなるジアリルフタレート系化粧板について説明する。
ここで、化粧板基材としては、合板、パーティクルボード、中密度繊維板（ＭＤＦ）、無機質板及び樹脂が含浸され硬化されたクラフト紙等が好ましく例示される。
Next, a diallyl phthalate decorative board formed by integrally molding the prepreg according to the present invention and a decorative board substrate will be described.
Here, preferable examples of the decorative board substrate include plywood, particle board, medium density fiber board (MDF), inorganic board, and kraft paper impregnated with resin and cured.
プリプレグと化粧板基材とを一体成型する方法としては積層熱圧成型法、すなわち、プリプレグと、化粧板基材とを重ね合わせ、加熱加圧硬化するのが適当である。成型は例えばプレス成型機を用いて、時間１分〜１５分、圧力１０〜２５ｋｇ／ｃｍ２、温度１２０〜１９０℃で好ましく行うことができ、これにより樹脂組成物が硬化した化粧板が得られる。なお、ここでいう化粧板には多重に積層したいわゆる積層化粧板も含まれる。 As a method of integrally molding the prepreg and the decorative board base material, it is appropriate to laminate and heat-press molding, that is, to superimpose the prepreg and the decorative board base material and to heat and cure. Molding can be preferably performed, for example, using a press molding machine at a time of 1 to 15 minutes, a pressure of 10 to 25 kg / cm 2 , and a temperature of 120 to 190 ° C., thereby obtaining a decorative board in which the resin composition is cured. . Note that the decorative board referred to here includes so-called laminated decorative boards laminated in multiple layers.
次に実施例、比較例によって本発明を詳細に説明する。ここで、実施例、比較例の「部」は重量部を示す。また、各実施例・比較例において具体的記載のない構成成分については実施例１記載の成分と同一品を使用した。 Next, the present invention will be described in detail by way of examples and comparative examples. Here, “parts” in Examples and Comparative Examples represent parts by weight. In addition, the same components as those described in Example 1 were used for the components not specifically described in each Example and Comparative Example.
なお、「平滑性」については、蛍光灯から１メートル離した位置に化粧板を置き、表面に映る蛍光灯の直線部分の変形の状態を目視により観察することにより評価した。評価は、表面に映る蛍光灯の直線部分がシャープな直線に見える場合に◎、少し波状に見えるが依然として良好な直線を維持している場合は○、波状が強い場合は△、そして、あばた強く境界線が不鮮明な場合は×とした。
また、「分散性」については、樹脂液が均一な場合は○、凝集等の分散不良がある場合は×とした。なお、ここでいう「分散性」とは、酸化チタンまたは酸化アルミニウム添加後の樹脂組成物の状態を評価対象とする。「隠蔽性」については、印刷紙と同等の色合いであれば◎、やや暗くなるが大きな差がなければ○、黒ずみが目立つ場合は△、黒ずみで印刷紙の柄がはっきりしない場合は×とした。「鉛筆硬度」についてはＪＩＳ Ｋ５４００鉛筆引っかき値に準じて行った。
The “smoothness” was evaluated by placing a decorative plate at a position 1 meter away from the fluorescent lamp and visually observing the deformation state of the linear portion of the fluorescent lamp reflected on the surface. Evaluation is ◎ when the straight line portion of the fluorescent lamp reflected on the surface looks sharp straight line, ◯ when it looks a little wavy but still maintaining a good straight line, △ when the wave shape is strong, △ When the boundary line was unclear, it was set as x.
As for “dispersibility”, “◯” was given when the resin liquid was uniform, and “X” was given when there was poor dispersion such as agglomeration. The “dispersibility” here refers to the state of the resin composition after addition of titanium oxide or aluminum oxide. Concerning the “concealment”, ◎ if it is the same color as the printed paper, ◎ if it is slightly dark but there is no significant difference, △ if the darkness is noticeable, △, if the pattern of the printed paper is not clear, × . The “pencil hardness” was measured according to JIS K5400 pencil scratch value.
[製造例１]
無水マレイン酸１０モル、エチレングリコール３モル、プロピレングリコール６モル、水素化ビスフェノール１モルを反応容器に仕込み、ハイドロキノン０．５ｇの存在下、常圧下、窒素気流中にて反応温度１８０〜２１０℃の範囲を維持しつつ、目的物の数平均分子量が１００００〜１２０００の範囲になるよう３時間程度反応させ、その結果、数平均分子量が約１１０００、かつ酸価が１５ｍｇＫＯＨ／ｇの不飽和ポリエステルを得た。
以下の実施例、比較例ではかようにして作製された当該不飽和ポリエステルを使用した。
[Production Example 1]
10 mol of maleic anhydride, 3 mol of ethylene glycol, 6 mol of propylene glycol and 1 mol of hydrogenated bisphenol were charged into a reaction vessel, and the reaction temperature was 180 to 210 ° C. in the presence of 0.5 g of hydroquinone in a nitrogen stream under normal pressure. While maintaining the range, the reaction was carried out for about 3 hours so that the number average molecular weight of the target product was in the range of 10000 to 12000. As a result, an unsaturated polyester having a number average molecular weight of about 11000 and an acid value of 15 mgKOH / g was obtained.
In the following Examples and Comparative Examples, the unsaturated polyester thus produced was used.
[実施例１]
ジアリルオルソフタレートプレポリマー（メチルエチルケトン５０重量％溶液粘度（３０℃）９６．５ｃｐ、ヨウ素価５６．７、ダイソー（株）製）８０部、上記製造例１記載の不飽和ポリエステル２０部、ジペンタエリスリトールヘキサアクリレート１部、平均粒子径約３μｍで、表面処理された水酸化アルミニウム３０部（ハイジライトＨ−３２ＳＴ、昭和電工（株）製）、ベンゾイルパーオキサイド４部、内部離型剤（ゼレックＵＮ、デュポン社製）０．４部、ハイドロキノン（重合調整剤）０．０３部、微粉末シリカ（カープレックス、塩野義製薬（株）製）４部をアセトンに溶解して樹脂液を調整し、８０ｇ／ｍ２の印刷パターン紙に含浸して１８０ｇ／ｍ２の含浸紙を得た。
[Example 1]
80 parts of diallyl orthophthalate prepolymer (methyl ethyl ketone 50% by weight solution viscosity (30 ° C.) 96.5 cp, iodine value 56.7, manufactured by Daiso Co., Ltd.), 20 parts of unsaturated polyester described in Production Example 1, dipentaerythritol Hexaacrylate 1 part, average particle diameter of about 3 μm, surface-treated aluminum hydroxide 30 parts (Hijilite H-32ST, Showa Denko Co., Ltd.), benzoyl peroxide 4 parts, internal mold release agent (Zelec UN, A resin solution was prepared by dissolving 0.4 part of DuPont), 0.03 part of hydroquinone (polymerization regulator) and 4 parts of fine powder silica (Carplex, manufactured by Shionogi & Co., Ltd.) in acetone, and preparing 80 g impregnates / m 2 of the printed pattern paper to give the impregnated paper of 180 g / m 2.
３ｍｍの無機質不燃板、ダイライト（大建工業（株）製）上に該含浸紙を載せ、１３０℃、１２ｋｇ／ｃｍ２、１０分の熱圧成型で化粧板を得た。得られた化粧板はＪＩＳ
Ｋ６９０２、同Ｋ５４００及びＪＡＳに規定されている耐水性、耐候性、耐薬品性等に合格し、ＪＩＳ Ｚ８７４１の鏡面光沢度測定方法に規定された入射角２０度における光沢度（以下略して「光沢度」という）が９２〜９３と高い値を示し、なおかつ表面に映した蛍光灯の線もすっきりしており平滑性が良好であった。
The impregnated paper was placed on a 3 mm inorganic noncombustible plate and die light (manufactured by Daiken Kogyo Co., Ltd.), and a decorative plate was obtained by hot pressing at 130 ° C., 12 kg / cm 2 for 10 minutes. The obtained decorative board is JIS
It has passed the water resistance, weather resistance, chemical resistance, etc. stipulated in K6902, K5400, and JAS, and has a glossiness at an incident angle of 20 degrees stipulated in the specular gloss measurement method of JIS Z8741 (hereinafter referred to as “gloss”). "Degree") was a high value of 92 to 93, and the lines of fluorescent lamps reflected on the surface were clear and smoothness was good.
[実施例２]
ジアリルオルソフタレートプレポリマー５０部、不飽和ポリエステル５０部、ジペンタエリスリトールヘキサアクリレート１部、水酸化アルミニウム（Ｈ−３２ＳＴ）３０部、ベンゾイルパーオキサイド４部、内部離型剤０．４部、ハイドロキノン０．０３部、微粉末シリカ４部をアセトンに溶解して樹脂液を調整した以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９０〜９１と十分であり、平滑性も良好であった。
[Example 2]
50 parts of diallyl orthophthalate prepolymer, 50 parts of unsaturated polyester, 1 part of dipentaerythritol hexaacrylate, 30 parts of aluminum hydroxide (H-32ST), 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, hydroquinone 0 A decorative board was obtained in the same manner as in Example 1 except that 0.03 part and 4 parts of fine powdered silica were dissolved in acetone to prepare a resin solution. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., glossiness was sufficient as 90 to 91, and smoothness was also good.
[実施例３]
ジアリルオルソフタレートプレポリマー９０部、ジアリルオルソフタレートモノマー１０部、ジペンタエリスリトールヘキサアクリレート１部、水酸化アルミニウム（Ｈ−３２ＳＴ）３０部、ベンゾイルパーオキサイド４部、内部離型剤０．４部、ハイドロキノン０．０３部、微粉末シリカ４部をアセトンに溶解して樹脂液を調整した以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９１〜９２と高く、平滑性も良好であった。
[Example 3]
90 parts of diallyl orthophthalate prepolymer, 10 parts of diallyl orthophthalate monomer, 1 part of dipentaerythritol hexaacrylate, 30 parts of aluminum hydroxide (H-32ST), 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, hydroquinone A decorative board was obtained in the same manner as in Example 1 except that 0.03 part and 4 parts of fine powdered silica were dissolved in acetone to prepare a resin solution. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had a high glossiness of 91 to 92, and good smoothness.
[実施例４]
実施例１において、ジアリルオルソフタレートプレポリマーの代わりにジアリルイソフタレートプレポリマーを用いた以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９３〜９４と高く、平滑性も良好であった。
[Example 4]
A decorative board was obtained in the same manner as in Example 1 except that diallyl isophthalate prepolymer was used instead of diallyl orthophthalate prepolymer. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had a high glossiness of 93 to 94, and good smoothness.
[実施例５］
実施例１において、水酸化アルミニウム、Ｈ−３２ＳＴの代わりに平均粒子径約１μｍで、表面処理された水酸化アルミニウム３０部（ハイジライトＨ−４２ＳＴＶ、昭和電工（株）製）を用いた以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９３〜９４と高く、平滑性も良好であった。
[Example 5]
In Example 1, instead of aluminum hydroxide and H-32ST, 30 parts of surface-treated aluminum hydroxide having an average particle diameter of about 1 μm (Hydelite H-42STV, Showa Denko Co., Ltd.) was used. A decorative board was obtained in the same manner as in Example 1. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had a high glossiness of 93 to 94, and good smoothness.
[実施例６]
実施例１において、ジペンタエリスリトールヘキサアクリレートを添加しなかった以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９０〜９１と十分であり、平滑性も良好であった。
[Example 6]
A decorative board was obtained in the same manner as in Example 1 except that dipentaerythritol hexaacrylate was not added. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., glossiness was sufficient as 90 to 91, and smoothness was also good.
[実施例７]
実施例１において、表面処理された水酸化アルミニウム、Ｈ−３２ＳＴの添加量を３０部から１０部に減らした以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９４〜９５と高く、平滑性も良好であった。
[Example 7]
In Example 1, a decorative board was obtained in the same manner as in Example 1 except that the addition amount of the surface-treated aluminum hydroxide and H-32ST was reduced from 30 parts to 10 parts. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance and the like, and the glossiness was as high as 94 to 95, and the smoothness was also good.
[実施例８]
実施例１において、表面処理された水酸化アルミニウム、Ｈ−３２ＳＴの添加量を３０部から１０部に減らし、かつ、ジペンタエリスリトールヘキサアクリレートの添加量を５部に増やした以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９５〜９６と高く、平滑性も良好であった。
[Example 8]
In Example 1, the addition amount of the surface-treated aluminum hydroxide, H-32ST was reduced from 30 parts to 10 parts, and the addition amount of dipentaerythritol hexaacrylate was increased to 5 parts. A decorative board was obtained in the same manner. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had a high glossiness of 95 to 96 and good smoothness.
[実施例９]
実施例１において、水酸化アルミニウム、Ｈ−３２ＳＴ３０部の代わりに平均粒子径約３μｍで、表面処理されていない水酸化アルミニウム３０部（ハイジライトＨ−３２、昭和電工（株）製）とビニルトリエトキシシラン０．５重量部を混合したものを用いた以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も９１〜９２と高く、平滑性も良好であった。
[Example 9]
In Example 1, in place of 30 parts of aluminum hydroxide, H-32ST, 30 parts of aluminum hydroxide having an average particle diameter of about 3 μm and not surface-treated (Hijilite H-32, Showa Denko KK) and vinyl tri A decorative board was obtained in the same manner as in Example 1 except that 0.5 part by weight of ethoxysilane was used. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had a high glossiness of 91 to 92, and good smoothness.
[実施例１０]
ジアリルオルソフタレートプレポリマー（メチルエチルケトン５０重量％溶液粘度（３０℃）９６．５ｃｐ、ヨウ素価５６．７、ダイソー（株）製）８０部、上記製造例１記載の不飽和ポリエステル２０部、ジペンタエリスリトールヘキサアクリレート１部、平均粒子径約１μｍで、表面処理された水酸化アルミニウム３０部（ハイジライトＨ−４２ＳＴＶ、昭和電工（株）製）、平均粒子径約０．２６μｍのルチル型酸化チタン１０部（タイペークＲ−８２０、石原産業（株）製）、ベンゾイルパーオキサイド４部、内部離型剤（ゼレックＵＮ、デュポン社製）０．４部、ハイドロキノン（重合調製剤）０．０３部、微粉末シリカ（カープレックス、塩野義製薬（株）製）４部をアセトンに溶解して樹脂液を調整し、６０ｇ／ｍ２の印刷パターン紙に含浸して１４０ｇ／ｍ２の含浸紙を得た。
[Example 10]
80 parts of diallyl orthophthalate prepolymer (methyl ethyl ketone 50% by weight solution viscosity (30 ° C.) 96.5 cp, iodine value 56.7, manufactured by Daiso Co., Ltd.), 20 parts of unsaturated polyester described in Production Example 1, dipentaerythritol 1 part of hexaacrylate, 30 parts of surface-treated aluminum hydroxide (Heidilite H-42STV, Showa Denko KK) with an average particle diameter of about 1 μm, 10 parts of rutile titanium oxide with an average particle diameter of about 0.26 μm (Taipeke R-820, manufactured by Ishihara Sangyo Co., Ltd.), 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent (Zelek UN, manufactured by DuPont), 0.03 part of hydroquinone (polymerization preparation agent), fine powder silica dissolved (Carplex, Shionogi Co. Ltd.) 4 parts acetone to adjust the resin solution, the printing path of 60 g / m 2 Was obtained impregnated paper 140 g / m 2 was impregnated in over down paper.
３ｍｍの無機質不燃板、ダイライト（大建工業（株）製）上に該含浸紙を載せ、１３０℃、１２ｋｇ／ｃｍ２、１０分の熱圧成型で化粧板を得た。得られた化粧板はＪＩＳ
Ｋ６９０２、同Ｋ５４００及びＪＡＳに規定されている耐水性、耐候性、耐薬品性等に合格し、ＪＩＳ Ｚ８７４１の鏡面光沢度測定方法に規定された入射角２０度における光沢度や平滑性も良好であるとともに、表面の隠蔽性も高いものであった。
The impregnated paper was placed on a 3 mm inorganic noncombustible plate and die light (manufactured by Daiken Kogyo Co., Ltd.), and a decorative plate was obtained by hot pressing at 130 ° C., 12 kg / cm 2 for 10 minutes. The obtained decorative board is JIS
Passes the water resistance, weather resistance, chemical resistance, etc. specified in K6902, K5400 and JAS, and the glossiness and smoothness at an incident angle of 20 degrees specified in the specular gloss measurement method of JIS Z8741 are also good. In addition, the surface concealability was also high.
[実施例１１]
酸化チタンの添加量を３０部に変更した以外は実施例１０と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も平滑性も良好であり、表面の隠蔽性も非常に高いものであった。
[Example 11]
A decorative board was obtained in the same manner as in Example 10 except that the amount of titanium oxide added was changed to 30 parts. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had good glossiness and smoothness, and had very high surface concealability.
[実施例１２]
酸化チタンを平均粒子径約０．２１μｍのルチル型酸化チタン（タイペークＲ−６７０、石原産業（株）製）に代え、また、その添加量を３０部に変更した以外は実施例１０と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も平滑性も良好であり、表面の隠蔽性も非常に高いものであった。
[Example 12]
Titanium oxide was replaced with rutile titanium oxide (Typaque R-670, manufactured by Ishihara Sangyo Co., Ltd.) having an average particle size of about 0.21 μm, and the addition amount was changed to 30 parts in the same manner as in Example 10. I got a decorative board. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had good glossiness and smoothness, and had very high surface concealability.
[実施例１３]
酸化チタンを平均粒子径約３５μｍの酸化アルミニウム（キイライトＷＡ ＃５００、キイライト研磨材（株）製）に代え、また、その添加量を２０部に変更した以外は実施例１０と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も平滑性も良好であり、表面の鉛筆硬度も５Ｈと非常に高いものであった。
[Example 13]
Decorative plate in the same manner as in Example 10 except that titanium oxide was replaced with aluminum oxide having an average particle size of about 35 μm (Kylite WA # 500, manufactured by Kylite Abrasive Co., Ltd.) and the addition amount was changed to 20 parts. Got. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had good gloss and smoothness, and had a very high pencil hardness of 5H.
[実施例１４]
酸化アルミニウム（キイライトＷＡ ＃５００、キイライト研磨材（株）製）の添加量を５０部に変更した以外は実施例１３と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も平滑性も良好であり、表面の鉛筆硬度も７Ｈと非常に高いものであった。
[Example 14]
A decorative board was obtained in the same manner as in Example 13 except that the addition amount of aluminum oxide (Kylite WA # 500, manufactured by Kylite Abrasive Co., Ltd.) was changed to 50 parts. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had good glossiness and smoothness, and had a very high surface pencil hardness of 7H.
[実施例１５]
酸化アルミニウム（キイライトＷＡ ＃５００）を平均粒子径約２０μｍの酸化アルミニウム（キイライトＷＡ ＃８００）に変更した以外は実施例１３と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験にも合格し、光沢度も平滑性も良好であり、表面の鉛筆硬度も７Ｈと非常に高いものであった
[Example 15]
A decorative board was obtained in the same manner as in Example 13 except that the aluminum oxide (Kylite WA # 500) was changed to aluminum oxide (Kylite WA # 800) having an average particle size of about 20 μm. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., had good glossiness and smoothness, and had a very high surface pencil hardness of 7H.
[比較例１]
実施例１において、水酸化アルミニウムを添加しなかった以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験に合格し、光沢度も９４〜９５と高い値を示したが、基材の凹凸がそのまま表層に現れており、表面に映した蛍光灯の線が激しく波状に見えるほど平滑性は著しく低いものであった。
[Comparative Example 1]
A decorative board was obtained in the same manner as in Example 1 except that aluminum hydroxide was not added. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance and the like, and the glossiness was as high as 94 to 95, but the unevenness of the base material appeared on the surface layer as it was, and the surface The smoothness was so low that the line of the fluorescent lamp projected on the screen appeared intensely wavy.
[比較例２]
実施例１において、水酸化アルミニウム、Ｈ−３２ＳＴの代わりに平均粒子径約３μｍで、表面処理されていない水酸化アルミニウム３０部（ハイジライトＨ−３２、昭和電工（株）製）を用いた以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験には合格したが、樹脂液中の分散性が悪いためか光沢度は８５〜８８、平滑度も著しく悪く、鮮映性の低いものであった。
[Comparative Example 2]
In Example 1, instead of aluminum hydroxide and H-32ST, 30 parts of an average particle diameter of about 3 μm and non-surface-treated aluminum hydroxide (Hijilite H-32, manufactured by Showa Denko KK) was used. Obtained a decorative board in the same manner as in Example 1. The resulting decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., but the glossiness was 85 to 88 and the smoothness was remarkably poor due to poor dispersibility in the resin liquid. It was low in nature.
[比較例３]
実施例１において、水酸化アルミニウムの添加量を３部に減らした以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験に合格し、光沢度も９４〜９５と高い値を示したが、水酸化アルミニウムの添加効果がほとんど見られず、表面に映した蛍光灯の線が波状に見えるほど平滑性は低いものであった。
[Comparative Example 3]
A decorative board was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide added was reduced to 3 parts in Example 1. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance and the like, and the glossiness was as high as 94 to 95, but the addition effect of aluminum hydroxide was hardly seen, the surface The smoothness was so low that the line of the fluorescent lamp projected on the screen appeared wavy.
[比較例４]
実施例１において、水酸化アルミニウムの添加量を６０部に増やした以外は実施例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験に合格し、表面に映した蛍光灯の線もすっきりしており平滑性が良好であったが、光沢度が８０〜８５と著しく低下した。
[Comparative Example 4]
In Example 1, a decorative board was obtained in the same manner as Example 1 except that the amount of aluminum hydroxide added was increased to 60 parts. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., and the line of the fluorescent lamp reflected on the surface was clean and smooth, but the glossiness was 80- It was significantly reduced to 85.
[比較例５]
比較例１において６０ｇ／ｍ２の印刷パターン紙を用いた以外は比較例１と同様にして化粧板を得た。得られた化粧板は耐水性、耐候性、耐薬品性等、各種試験に合格し、光沢度も高い値を示したが、表面の平滑性が悪いばかりか、表面の印刷柄が黒ずみ隠蔽性も悪いものとなった。表面の鉛筆硬度は２Ｈであった。
[Comparative Example 5]
A decorative board was obtained in the same manner as in Comparative Example 1 except that the printed pattern paper of 60 g / m 2 was used in Comparative Example 1. The obtained decorative board passed various tests such as water resistance, weather resistance, chemical resistance, etc., and showed a high gloss value, but the surface smoothness was not good, and the printed pattern on the surface was darkened. Was also bad. The surface pencil hardness was 2H.
[比較例６]
比較例５において、更に酸化チタン（タイペークＲ−８２０）を５部添加した以外は比較例５と同様にして化粧板を得た。その結果、樹脂液の分散性はそこそこであったが、隠蔽性が向上するには至らなかった。
[Comparative Example 6]
In Comparative Example 5, a decorative board was obtained in the same manner as Comparative Example 5 except that 5 parts of titanium oxide (Typaque R-820) was further added. As a result, the dispersibility of the resin liquid was moderate, but the concealability was not improved.
[比較例７]
比較例５において、更に酸化チタン（タイペークＲ−８２０）を３０部添加した以外は比較例５と同様にして化粧板を得た。その結果、酸化チタンの凝集のため樹脂液の分散性が悪く、なおかつ隠蔽性が向上するには至らなかった。
[Comparative Example 7]
A decorative board was obtained in the same manner as in Comparative Example 5 except that 30 parts of titanium oxide (Typaque R-820) was further added. As a result, the dispersibility of the resin liquid was poor due to the aggregation of titanium oxide, and the concealability was not improved.
[比較例８]
比較例５において、更に酸化アルミニウム（キイライトＷＡ ＃５００）を５部添加した以外は比較例５と同様にして化粧板を得た。その結果、樹脂液の分散性はそこそこであったが、鉛筆硬度は２Ｈとほとんど向上することはなかった。
[Comparative Example 8]
In Comparative Example 5, a decorative board was obtained in the same manner as Comparative Example 5 except that 5 parts of aluminum oxide (Kylite WA # 500) was further added. As a result, the dispersibility of the resin liquid was moderate, but the pencil hardness was hardly improved to 2H.
[比較例９]
比較例５において、更に酸化アルミニウム（キイライトＷＡ ＃５００）を３０部添加した以外は比較例５と同様にして化粧板を得た。その結果、酸化チタンの凝集のため樹脂液の分散性が悪く、なおかつ鉛筆硬度は３Ｈとほとんど向上することはなかった。
[Comparative Example 9]
In Comparative Example 5, a decorative board was obtained in the same manner as Comparative Example 5 except that 30 parts of aluminum oxide (Kylite WA # 500) was further added. As a result, the dispersibility of the resin liquid was poor due to the aggregation of titanium oxide, and the pencil hardness was hardly improved to 3H.
[参考例１]
印刷紙の坪量を８０ｇ／ｍ２から６０ｇ／ｍ２に変更した以外は実施例５と同様にして得られた化粧板について、隠蔽性、および鉛筆硬度を測定したところ、十分ではなかった。
[Reference Example 1]
The decorative board obtained in the same manner as in Example 5 except that the basis weight of the printing paper was changed from 80 g / m 2 to 60 g / m 2 , and the concealability and the pencil hardness were measured, were not sufficient.
上記実施例、比較例の組成物の配合および各測定結果を次に表１および表２にまとめる。なお、表２中、実施例９〜１４、および参考例１においては、試験に供される化粧板はいずれも十分な光沢度（90前後）と優れた平滑性（◎）を示す事実を前提とする。
本発明は、ジアリルフタレート系高光沢化粧板の製造業界において有効に利用することができる。 The present invention can be effectively used in the manufacturing industry of diallyl phthalate-based high gloss decorative boards.
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| CN100391846C (en) * | 2006-08-29 | 2008-06-04 | 惠州学院 | Method for prepring and modifying high heat-resistant aluminium hydroxide |
| JP2008155501A (en) * | 2006-12-25 | 2008-07-10 | Daiso Co Ltd | Manufacturing method of diallyl phthalate based decorative sheet |
| JP2009234200A (en) * | 2008-03-28 | 2009-10-15 | Daiso Co Ltd | Decorative board with high sharpness |
| WO2011065115A1 (en) * | 2009-11-26 | 2011-06-03 | 株式会社タムラ製作所 | Thermosetting white ink composition with excellent color fastness, and thermoset product thereof |
| JP2011201960A (en) * | 2010-03-24 | 2011-10-13 | Taiyo Holdings Co Ltd | Active energy ray-curable white resin composition and printed wiring board having insulating layer composed of cured product thereof |
| KR101245716B1 (en) * | 2007-04-26 | 2013-03-25 | 아이카고교 가부시키가이샤 | Decorative board |
| JP2016150959A (en) * | 2015-02-16 | 2016-08-22 | 利昌工業株式会社 | Thermosetting resin composition, prepreg, and laminated plate |
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| WO2011065115A1 (en) * | 2009-11-26 | 2011-06-03 | 株式会社タムラ製作所 | Thermosetting white ink composition with excellent color fastness, and thermoset product thereof |
| JP5802133B2 (en) * | 2009-11-26 | 2015-10-28 | 株式会社タムラ製作所 | Thermosetting white ink composition excellent in color fastness and cured product thereof |
| JP2011201960A (en) * | 2010-03-24 | 2011-10-13 | Taiyo Holdings Co Ltd | Active energy ray-curable white resin composition and printed wiring board having insulating layer composed of cured product thereof |
| JP2016150959A (en) * | 2015-02-16 | 2016-08-22 | 利昌工業株式会社 | Thermosetting resin composition, prepreg, and laminated plate |
| WO2016132564A1 (en) * | 2015-02-16 | 2016-08-25 | 利昌工業株式会社 | Heat-curable resin composition, prepreg, and laminated sheet |
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