JP2019151033A - Decorative sheet and decorative member - Google Patents
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Abstract
Description
本発明は、住宅などの建築材に用いられる化粧シートおよびその化粧シートを使用した化粧部材に関する。 The present invention relates to a decorative sheet used for a building material such as a house and a decorative member using the decorative sheet.
化粧シートの最表面には、耐候性、耐傷性、耐汚染性および表面の艶の調整、などのため表面保護層が形成されている。
近年、住宅の長期保証が求められてきており、化粧シートの耐候性向上は大きな課題となっている。化粧シートの表面保護層としてはアクリル系樹脂を用いる事が多く、その耐候性を更に上げるため、紫外線吸収剤やラジカル捕捉剤などの耐候剤が添加されるのが一般的である（例えば、特許文献１〜４）。
A surface protective layer is formed on the outermost surface of the decorative sheet for weather resistance, scratch resistance, contamination resistance, and surface gloss adjustment.
In recent years, long-term guarantees for houses have been demanded, and improvement of the weather resistance of decorative sheets has become a major issue. As the surface protective layer of the decorative sheet, an acrylic resin is often used, and a weathering agent such as an ultraviolet absorber or a radical scavenger is generally added to further improve the weather resistance (for example, patents) Literatures 1-4).
しかしながら、耐候剤の添加量を増加させることで耐候性を向上させることができるが、耐候剤は高価であるため、コストアップする問題がある。また添加量の増加によりブリードアウトの虞もあるため、添加量を増やすことには限界があった。また、それらの問題を回避できたとしても、耐候剤の劣化を避けることは困難である。また、折り曲げなどの後加工があると、その部分にクラックが発生し、そのクラックから劣化が進む虞があった。その対策として、表面保護層に柔軟性を持たせる方法が検討されたが、化粧シートの製造工程において、ブロッキングが発生し易くなり、生産性が低下する。 However, although the weather resistance can be improved by increasing the amount of the weathering agent added, there is a problem that the cost increases because the weathering agent is expensive. Moreover, since there is a possibility of bleeding out due to an increase in the addition amount, there is a limit to increasing the addition amount. Moreover, even if those problems can be avoided, it is difficult to avoid deterioration of the weathering agent. Further, when post-processing such as bending is performed, a crack is generated in the portion, and there is a possibility that deterioration proceeds from the crack. As a countermeasure, a method of giving the surface protective layer flexibility has been studied. However, in the manufacturing process of the decorative sheet, blocking tends to occur, and productivity is lowered.
上記の事情に鑑み、本発明は、化粧シートを折り曲げ加工してもクラックを生じる事がない柔軟性を備え、且つ化粧シートをロール状に巻回してもブロッキングを起こすことがない、化粧シートの表面保護層を提供することを課題とする。 In view of the above circumstances, the present invention provides a flexibility that does not cause cracking even when the decorative sheet is bent, and does not cause blocking even when the decorative sheet is wound into a roll. It is an object to provide a surface protective layer.
上記の課題を解決する手段として、本発明の請求項１に記載の発明は、基材上に表面保護層を積層した化粧シートにおいて、
表面保護層は、アクリル系樹脂組成物を主剤とし、ポリイソシアネートを硬化剤としたイソシアネート硬化型アクリル系樹脂組成物からなり、
ポリイソシアネートのプレポリマーは、ヘキサメチレンジイソシアネート（以下、ＨＤＩと記す。）にキシリレンジイソシアネート（以下、ＸＤＩと記す。）を１〜２０重量％の範囲で重合させた硬化剤Ａと、側鎖にウレタン結合を含むＨＤＩの３量体である硬化剤Ｂと、を硬化剤Ａ：硬化剤Ｂ＝１０〜４０重量％：９０〜６０重量％の範囲で配合させた硬化剤であることを特徴とする化粧シートである。
As means for solving the above problems, the invention according to claim 1 of the present invention is a decorative sheet in which a surface protective layer is laminated on a base material.
The surface protective layer is composed of an isocyanate curable acrylic resin composition having an acrylic resin composition as a main component and a polyisocyanate as a curing agent,
The polyisocyanate prepolymer comprises a curing agent A obtained by polymerizing xylylene diisocyanate (hereinafter referred to as XDI) in a range of 1 to 20% by weight to hexamethylene diisocyanate (hereinafter referred to as HDI), and a side chain. Curing agent B, which is a trimer of HDI containing a urethane bond, and curing agent A: curing agent B = 10 to 40% by weight: 90 to 60% by weight It is a decorative sheet.
また、請求項２に記載の発明は、前記表面保護層が、フィラーを含有していることを特徴とする請求項１に記載の化粧シートである。 The invention according to claim 2 is the decorative sheet according to claim 1, wherein the surface protective layer contains a filler.
また、請求項３に記載の発明は、前記表面保護層の厚みが２〜２０μｍであり、且つ化粧シートの総厚が４０〜３００μｍであることを特徴とする請求項１または２に記載の化粧シートである。 The invention described in claim 3 is characterized in that the thickness of the surface protective layer is 2 to 20 μm and the total thickness of the decorative sheet is 40 to 300 μm. It is a sheet.
また、請求項４に記載の発明は、前記表面保護層の表面に凹凸が形成されていることを特徴とする請求項１〜３のいずれかに記載の化粧シートである。 The invention according to claim 4 is the decorative sheet according to any one of claims 1 to 3, wherein irregularities are formed on the surface of the surface protective layer.
また、請求項５に記載の発明は、請求項１〜４のいずれかに記載の化粧シートの前記基材側に木質系または金属系基板を積層してなることを特徴とする化粧部材である。 The invention according to claim 5 is a decorative member comprising a woody or metal substrate laminated on the base side of the decorative sheet according to any one of claims 1 to 4. .
また、請求項６に記載の発明は、前記化粧部材が折り曲げ加工、または前記化粧シート面がラッピング加工、を施されていることを特徴とする請求項５に記載の化粧部材である。 The invention according to claim 6 is the decorative member according to claim 5, wherein the decorative member is subjected to a bending process, or the decorative sheet surface is subjected to a wrapping process.
本発明の化粧シートの表面保護層は、アクリル系樹脂組成物を主剤とし、ポリイソシアネートを硬化剤としたイソシアネート硬化型アクリル系樹脂組成物からなり、ポリイソシアネートのプレポリマーは、ヘキサメチレンジイソシアネート（以下、ＨＤＩと記す。）にキシリレンジイソシアネート（以下、ＸＤＩと記す。）を１〜２０重量％の範囲で重合させた硬化剤Ａと、側鎖にウレタン結合を含むＨＤＩの３量体である硬化剤Ｂと、を硬化剤Ａ：硬化剤Ｂ＝１０〜４０重量％：９０〜６０重量％の範囲で配合させた硬化剤であるため、化粧シートを折り曲げ加工してもクラックを生じる事がない柔軟性を備え、且つ化粧シートをロール状に巻回してもブロッキングを起こすことがない。 The surface protective layer of the decorative sheet of the present invention comprises an isocyanate curable acrylic resin composition containing an acrylic resin composition as a main component and a polyisocyanate as a curing agent, and the polyisocyanate prepolymer is hexamethylene diisocyanate (hereinafter referred to as hexamethylene diisocyanate). , HDI)), a curing agent A obtained by polymerizing xylylene diisocyanate (hereinafter referred to as XDI) in the range of 1 to 20% by weight, and a HDI trimer containing urethane bonds in the side chains. Since it is a curing agent in which the agent B is blended in the range of curing agent A: curing agent B = 10 to 40% by weight: 90 to 60% by weight, no crack is generated even if the decorative sheet is bent. It has flexibility and does not cause blocking even when the decorative sheet is wound into a roll.
＜化粧シート＞
本発明の化粧シートについて説明する。
本発明の化粧シートは、図１に例示した様に、基材２上に表面保護層１を積層した化粧シート１０−１である。
<Coating sheet>
The decorative sheet of the present invention will be described.
As illustrated in FIG. 1, the decorative sheet of the present invention is a decorative sheet 10-1 in which a surface protective layer 1 is laminated on a substrate 2.
本発明の化粧シート１０−１の表面保護層１は、アクリル系樹脂組成物を主剤とし、ポリイソシアネートを硬化剤としたイソシアネート硬化型アクリル系樹脂組成物からなり、ポリイソシアネートのプレポリマーは、ヘキサメチレンジイソシアネート（以下、ＨＤＩと記す。）にキシリレンジイソシアネート（以下、ＸＤＩと記す。）を１〜２０重量％の範囲で重合させた硬化剤Ａと、側鎖にウレタン結合を含むＨＤＩの３量体である硬化剤Ｂと、を硬化剤Ａ：硬化剤Ｂ＝１０〜４０重量％：９０〜６０重量％の範囲で配合させた硬化剤であることを特徴とする化粧シートである。 The surface protective layer 1 of the decorative sheet 10-1 of the present invention comprises an isocyanate curable acrylic resin composition containing an acrylic resin composition as a main component and a polyisocyanate as a curing agent. 3 amounts of a curing agent A obtained by polymerizing xylylene diisocyanate (hereinafter referred to as XDI) to methylene diisocyanate (hereinafter referred to as HDI) in the range of 1 to 20% by weight and HDI containing a urethane bond in the side chain. It is a decorative sheet characterized in that it is a curing agent in which curing agent B as a body is blended in the range of curing agent A: curing agent B = 10 to 40% by weight: 90 to 60% by weight.
硬化剤Ａを、ＨＤＩにＸＤＩを１重量％未満配合したものとすることにより、耐ブロッキング性能が低下する。また、２０重量％を超えて配合したものとすることにより、柔軟性及び耐候性が低下する。 The anti-blocking performance is reduced by adding less than 1% by weight of XDI to HDI. Moreover, a softness | flexibility and a weather resistance fall by setting it as a mixture exceeding 20 weight%.
また、硬化剤Ａ：硬化剤Ｂが１０重量％未満：９０重量％超としたものとすることにより、耐ブロッキング性能が十分ではなくなる。また、硬化剤Ａ：硬化剤Ｂが４０重量％超：６０重量％未満としたものとすることにより、柔軟性が十分ではなくなる。 Further, when the curing agent A: the curing agent B is less than 10% by weight and more than 90% by weight, the anti-blocking performance is not sufficient. Further, when the curing agent A: the curing agent B is more than 40% by weight and less than 60% by weight, the flexibility is not sufficient.
また、表面保護層１には、フィラーを含有していても良い。フィラーを含有することにより、表面に凹凸が形成されるため、ブロッキングを起こし難くなる。 The surface protective layer 1 may contain a filler. By containing a filler, since unevenness is formed on the surface, blocking becomes difficult to occur.
また、表面保護層１の厚みが２〜２０μｍであり、且つ化粧シート１０−１の総厚が４０〜３００μｍであることが好適である。表面保護層１の厚みが２μｍ未満では耐候性が不十分となり、２０μｍを超えるとコート時の乾燥性が悪くなり、且つ耐ブロッキング性が低下する。また、化粧シート１０−１の総厚が４０μｍ未満ではとなり、３００μｍを超えるとシートの柔軟性が低下し、曲げ加工が適さなくなる。 Moreover, it is suitable that the thickness of the surface protective layer 1 is 2-20 micrometers, and the total thickness of the decorative sheet 10-1 is 40-300 micrometers. When the thickness of the surface protective layer 1 is less than 2 μm, the weather resistance is insufficient, and when it exceeds 20 μm, the drying property at the time of coating is deteriorated and the blocking resistance is lowered. Further, the total thickness of the decorative sheet 10-1 is less than 40 μm, and if it exceeds 300 μm, the flexibility of the sheet is lowered and bending is not suitable.
また、図２に例示するように、本発明の化粧シート１０−２の基材２´は、オレフィン系樹脂からなる着色熱可塑性樹脂層３の一方の面に、印刷したインキ層などからなる絵柄層４と、ウレタン系接着剤などからなる接着性樹脂層５と、透明熱可塑性樹脂層６と、表面保護層７と、がこの順に備えられており、もう一方の面に、金属基板との密着性を向上させるプライマー層８が備えられている基材２´であっても良い。接着性樹脂層５と透明熱可塑性樹脂層６の間に、透明接着性樹脂層が備えられていても構わない。 In addition, as illustrated in FIG. 2, the base material 2 ′ of the decorative sheet 10-2 of the present invention is a pattern made of a printed ink layer or the like on one surface of a colored thermoplastic resin layer 3 made of an olefin resin. The layer 4, the adhesive resin layer 5 made of a urethane-based adhesive, the transparent thermoplastic resin layer 6, and the surface protective layer 7 are provided in this order, and the other surface is provided with a metal substrate. The base material 2 'provided with the primer layer 8 for improving the adhesion may be used. A transparent adhesive resin layer may be provided between the adhesive resin layer 5 and the transparent thermoplastic resin layer 6.
また、図２に例示するように、表面保護層１の表面に凹凸部９が形成されていても良い。表面に凹凸が形成されていることによりブロッキングを起こし難くなる。 In addition, as illustrated in FIG. 2, uneven portions 9 may be formed on the surface of the surface protective layer 1. It is difficult to cause blocking due to the formation of irregularities on the surface.
＜化粧部材＞
次に、本発明の化粧部材について説明する。
本発明の化粧部材は、本発明の化粧シート１０−１、１０−２の基材２、２´側に木質系または金属系基板を積層した構成を備えている。
<Decorative material>
Next, the decorative member of the present invention will be described.
The decorative member of the present invention has a configuration in which a wooden or metal substrate is laminated on the base material 2, 2 'side of the decorative sheets 10-1 and 10-2 of the present invention.
本発明の化粧部材は、折り曲げ加工、または化粧部材の化粧シート面がラッピング加工を施されていても構わない。折り曲げ加工されても、化粧部材の最表面にある表面保護層にはクラックが生じないため、表面保護層の保護機能が劣化する事は無い。また、化粧シート面がラッピング加工されて、図２に例示した様に、表面保護層７に凹凸部９が形成されていても、表面保護層７の保護機能が劣化する事は無く、且つラッピング加工により形成された表面保護層７の凹凸部９により、ブロッキングが発生し難くなる。 The decorative member of the present invention may be bent, or the decorative sheet surface of the decorative member may be lapped. Even if it is bent, since the surface protective layer on the outermost surface of the decorative member does not crack, the protective function of the surface protective layer does not deteriorate. Further, even if the decorative sheet surface is lapped and the surface protective layer 7 has uneven portions 9 as illustrated in FIG. 2, the protective function of the surface protective layer 7 is not deteriorated, and the lapping is performed. Blocking is unlikely to occur due to the uneven portions 9 of the surface protective layer 7 formed by processing.
次に、本発明の実施例について説明する。 Next, examples of the present invention will be described.
＜実施例１＞
着色ポリエチレン樹脂からなる基材（厚さ：５５μｍ）の一方の面を、コロナ放電処理を施した後、ウレタン系印刷インキを使用して絵柄層を印刷した後、ウレタン系接着剤層と、透明接着性樹脂層と、透明熱可塑性樹脂層（厚さ：７０μｍ）と、アクリル系樹脂組成物を主成分とした表面保護層と、をこの順に塗布・乾燥することにより形成した。絵柄層の印刷にはグラビア印刷装置を、絵柄層以外のウレタン系接着剤層などの塗布にはグラビアコータを使用した。
<Example 1>
After one side of the base material (thickness: 55 μm) made of colored polyethylene resin is subjected to corona discharge treatment, a pattern layer is printed using urethane printing ink, and then a urethane adhesive layer and transparent An adhesive resin layer, a transparent thermoplastic resin layer (thickness: 70 μm), and a surface protective layer mainly composed of an acrylic resin composition were applied and dried in this order. A gravure printing apparatus was used for printing the pattern layer, and a gravure coater was used for applying a urethane adhesive layer other than the pattern layer.
また、基材のもう一方の面には、コロナ放電処理を施した後、プライマー層を、グラビアコータを用いて、乾燥後の膜厚１μｍとなる様に形成した。 Further, after the corona discharge treatment was performed on the other surface of the substrate, a primer layer was formed using a gravure coater so as to have a film thickness after drying of 1 μm.
なお、各層の塗液組成は下記のものを使用した。 The coating composition of each layer was as follows.
（ウレタン系接着剤層）
ウレタン変性ポリエステルポリオール ８０重量部、ヘキサメチレンジイソシアネート
１０重量部、イソホロンジイソシアネート １０重量部、で混合してなる２液硬化型のアンカーコート剤。
(Urethane adhesive layer)
Urethane-modified polyester polyol 80 parts by weight, hexamethylene diisocyanate 10 parts by weight, isophorone diisocyanate 10 parts by weight, a two-component curable anchor coating agent.
（透明接着性樹脂層）
マレイン酸変性ランダムポリプロピレン樹脂６９．５重量部に対してエチレン−プロピレン共重合樹脂２９．５重量部、トリアジン系紫外線吸収剤「ＴＩＮＵＶＩＮ１６００」（ＢＡＳＦジャパン（株）製）０．５重量％と、ヒンダードアミン系ラジカル捕捉剤「ＴＩＮＵＶＩＮＸＴ８５０」（ＢＡＳＦジャパン（株）製）０．５重量％とを添加。
(Transparent adhesive resin layer)
29.5 parts by weight of ethylene-propylene copolymer resin with respect to 69.5 parts by weight of maleic acid-modified random polypropylene resin, 0.5% by weight of triazine UV absorber “TINUVIN 1600” (manufactured by BASF Japan Ltd.), hindered amine -Based radical scavenger "TINUVINXT850" (manufactured by BASF Japan Ltd.) 0.5 wt% was added.
（透明熱可塑性樹脂層）
立体規則性の低いホモポリプロピレン「ＴＰＯ」（（株）プライムポリマー製、ＭＦＲ４．５ｇ／１０ｍｉｎ）を用い、これにトリアジン系紫外線吸収剤「ＴＩＮＵＶＩＮ１６００」（ＢＡＳＦジャパン（株）製）０．５重量％と、ヒンダードアミン系ラジカル捕捉剤「ＴＩＮＵＶＩＮＸＴ８５０」（ＢＡＳＦジャパン（株）製）０．５重量％とを添加。
(Transparent thermoplastic resin layer)
Homopolypropylene “TPO” with low stereoregularity (manufactured by Prime Polymer Co., Ltd., MFR 4.5 g / 10 min) was used, and triazine-based ultraviolet absorber “TINUVIN 1600” (manufactured by BASF Japan Ltd.) 0.5% by weight And 0.5% by weight of a hindered amine radical scavenger “TINUVINXT850” (manufactured by BASF Japan Ltd.).
（表面保護層）
硬化剤Ａ：硬化剤Ｂ＝２０重量％：８０重量％で配合した硬化剤を、アクリル系樹脂１００重量部に対して１０重量部（ＮＣＯ基／ＯＨ基のモル比＝１．０）添加したものを塗液とした。なお、硬化剤Ａは、ポリイソシアネートのプレポリマーとして、ＨＤＩにＸＤＩを１０重量％配合し重合させた硬化剤である。また硬化剤Ｂは、側鎖にウレタン結合を含むＨＤＩの３量体である。
(Surface protective layer)
Curing agent A: Curing agent B = 20 wt%: Curing agent blended at 80 wt% was added 10 parts by weight (NCO group / OH group molar ratio = 1.0) with respect to 100 parts by weight of acrylic resin. The thing was used as the coating liquid. In addition, the hardening | curing agent A is a hardening | curing agent which mix | blended and polymerized 10 weight% of XDI in HDI as a polyisocyanate prepolymer. Curing agent B is a trimer of HDI containing a urethane bond in the side chain.
（プライマー層）
ポリエステルウレタン系８０重量％と塩化ビニル−酢酸ビニル共重合系（塩酢ビ系）樹脂２０重量％に対してにシリカ１．５重量％を添加したものに、硬化剤３重量％添加。
(Primer layer)
Addition of 3% by weight of curing agent to 80% by weight of polyester urethane and 20% by weight of vinyl chloride-vinyl acetate copolymer (vinyl chloride) resin with addition of 1.5% by weight of silica.
なお、化粧シートとしての総厚を１３５μｍとして化粧シートを作製した。総厚は、基材（５５μｍ）と透明熱可塑性樹脂層（７０μｍ）の他に、絵柄層とウレタン系接着剤層と透明接着性樹脂層および表面保護層の厚さの合計値（１０μｍ）を含む化粧シートとしての厚さである。
本実施例においては、絵柄層１μｍ、ウレタン系接着剤層１μｍ、透明接着性樹脂層１μｍ、表面保護層７μｍとした。
A decorative sheet was prepared with a total thickness of 135 μm as the decorative sheet. The total thickness is the total thickness (10 μm) of the pattern layer, urethane adhesive layer, transparent adhesive resin layer and surface protective layer, in addition to the substrate (55 μm) and the transparent thermoplastic resin layer (70 μm). It is the thickness as a decorative sheet including.
In this example, the pattern layer was 1 μm, the urethane adhesive layer was 1 μm, the transparent adhesive resin layer was 1 μm, and the surface protective layer was 7 μm.
＜比較例１＞
硬化剤として柔軟性を付与しない硬化剤Ａのみを使用した事以外は実施例１と同様とした。
<Comparative Example 1>
Example 1 was the same as Example 1 except that only the curing agent A that did not impart flexibility was used as the curing agent.
＜比較例２＞
硬化剤として硬化剤Ｂのみ（硬化剤Ａを含まない。）とした事以外は実施例１と同様とした。
<Comparative example 2>
Example 1 was the same as Example 1 except that only curing agent B (not including curing agent A) was used as the curing agent.
＜比較例３＞
硬化剤Ａ：硬化剤Ｂ＝５５重量％：４５重量％とした事意外は実施例１と同様とした。
<Comparative Example 3>
Curing agent A: Curing agent B = 55 wt%: 45 wt%
＜評価＞
実施例１と比較例１〜３で作製した化粧シートのサンプルに対して、ラッピング試験と耐候性試験とブロッキングの評価を行った。
<Evaluation>
The decorative sheet samples prepared in Example 1 and Comparative Examples 1 to 3 were evaluated for lapping test, weather resistance test and blocking.
（ラッピング試験）
ラッピング試験は、アルミ角材の角部のＲ面取り加工（角部を丸く面取りする加工）をしていない角材に化粧シートをラッピングした際に、表面保護層にクラックが生じたかどうかを、アルミ角材の角部を３０倍の実体顕微鏡で観察する試験である。観察の結果、クラックを見出す事が無かった場合を◎、表面保護層のクラックが表面層だけに形成されている場合を○、表面保護層のクラックが下地まで至っていないが深い場合を△、表面保護層のクラックが下地まで至っている場合を×とした。
(Lapping test)
In the lapping test, when a decorative sheet is wrapped on a square material that has not been subjected to R chamfering processing (round chamfering of the corner portion) of the aluminum square material, This is a test in which the corner is observed with a 30-fold stereomicroscope. As a result of observation, ◎ indicates that no crack was found, ◯ indicates that the surface protective layer crack was formed only on the surface layer, △ indicates that the surface protective layer crack did not reach the ground but was deep, △ The case where the crack of the protective layer reached the ground was marked as x.
（耐候性試験）
耐候性試験は、耐候性試験機であるメタルウェザー（ダイプラ・ウィンテス株式会社の登録商標）ＫＷ−Ｒ７ＴＰを使用して、ランプ出力６５ｍＷ／ｃｍ２、１３００時間の処
理後、目視による外観の変化の有無を評価した。変化が無い場合を○、僅かに変化が認められる場合を△、明らかな変化が認められる場合を×とした。
(Weather resistance test)
The weather resistance test was performed using a metal weather (registered trademark of Daipura Wintes Co., Ltd.) KW-R7TP, which is a weather resistance tester, with a lamp output of 65 mW / cm 2 and a treatment for 1300 hours. The presence or absence was evaluated. The case where there was no change was indicated by ◯, the case where a slight change was observed was indicated by Δ, and the case where an obvious change was observed was indicated by ×.
（ブロッキング性評価）
作製した化粧シートサンプルを三つ折りにすることで、面々と面裏が重なる様にして、その三つ折りにしたサンプルの上に２Ｋｇ／ｃｍ２の重石を乗せ、４０℃、３日間放置した後の面々と面裏の密着の状態を確認した。ここで面は表面、裏はプライマー面とした。評価基準として、全く密着が認められなかった場合を◎、密着は認められず生産上の問題は無いが◎より劣る場合を○、軽微な密着が認められるが生産上は問題が無いレベルを△、密着が認められ、生産上の問題が発生する場合を×、とした。以上の評価結果をまとめて表１に示す。
(Blocking evaluation)
The prepared decorative sheet sample was folded in three, so that the back and back of each face overlapped, and a 2 kg / cm 2 weight stone was placed on the trifolded sample and left at 40 ° C. for 3 days. The state of close contact between the faces was confirmed. Here, the surface was the front surface and the back surface was the primer surface. As evaluation criteria, ◎ when no adhesion was found at all, no adhesion was found and there was no problem in production, but ◎ inferior to ◎, a slight adhesion was recognized but there was no problem in production △ The case where adhesion was recognized and a problem in production occurred was marked as x. The above evaluation results are summarized in Table 1.
表１に示した様に、実施例１で作製した化粧シートは、ラッピング試験、耐候性試験、ブロッキング性の全ての評価で○となり、良好な結果が得られた。 As shown in Table 1, the decorative sheet produced in Example 1 was good in all evaluations of the lapping test, weather resistance test, and blocking property, and good results were obtained.
比較例１では、硬化剤として硬化剤Ａのみを使用した。硬化剤Ａは柔軟性を付与しない材料であるため、ブロッキング性が非常に良い（◎）結果となったが、ラッピング試験ではクラックが発生する結果（×となった。また耐候性試験においても、僅かに変化が見られ、良好とは言えない評価（△）となった。 In Comparative Example 1, only curing agent A was used as the curing agent. Since the curing agent A is a material that does not impart flexibility, the blocking property was very good (◎), but in the wrapping test, a crack was generated (x). Also in the weather resistance test, A slight change was observed, and the evaluation (Δ) was not good.
比較例２では、硬化剤Ａを使用せず、硬化剤Ｂのみを使用したため、表面保護層の硬化が十分ではなく、ブロッキングが発生した（×）。一方、硬化が不十分であったため、柔軟性が高くなったことにより、ラッピング試験ではクラックの発生が無く、非常に良好な結果（◎）となった。 In Comparative Example 2, since the curing agent A was not used and only the curing agent B was used, the surface protective layer was not sufficiently cured, and blocking occurred (x). On the other hand, since the curing was inadequate and the flexibility was high, no crack was generated in the lapping test, and a very good result (◎) was obtained.
比較例３では、硬化剤Ａと硬化剤Ｂの配合比率を５５重量％：４５重量％としたことにより、耐ブロッキング性は良い結果（○）となったが、ラッピング試験、耐候性試験で良好な結果とは言えない結果（△）となった。 In Comparative Example 3, the blending ratio of the curing agent A and the curing agent B was 55% by weight: 45% by weight, so that the blocking resistance was a good result (◯), but it was good in the lapping test and the weather resistance test. The result was not good (△).
１・・・表面保護層
２、２´・・・基材
３・・・着色熱可塑性樹脂層
４・・・絵柄層
５・・・接着性樹脂層
６・・・透明熱可塑性樹脂層
７・・・表面保護層
８・・・プライマー層
９・・・凹凸部
１０−１、１０−２・・・化粧シート
DESCRIPTION OF SYMBOLS 1 ... Surface protective layer 2, 2 '... Base material 3 ... Colored thermoplastic resin layer 4 ... Picture layer 5 ... Adhesive resin layer 6 ... Transparent thermoplastic resin layer 7 ..Surface protective layer 8 ... Primer layer 9 ... Uneven portions 10-1, 10-2 ... decorative sheet
Claims (6)
表面保護層は、アクリル系樹脂組成物を主剤とし、ポリイソシアネートを硬化剤としたイソシアネート硬化型アクリル系樹脂組成物からなり、
ポリイソシアネートのプレポリマーは、ヘキサメチレンジイソシアネート（以下、ＨＤＩと記す。）にキシリレンジイソシアネート（以下、ＸＤＩと記す。）を１〜２０重量％の範囲で重合させた硬化剤Ａと、側鎖にウレタン結合を含むＨＤＩの３量体である硬化剤Ｂと、を硬化剤Ａ：硬化剤Ｂ＝１０〜４０重量％：９０〜６０重量％の範囲で配合させた硬化剤であることを特徴とする化粧シート。 In a decorative sheet in which a surface protective layer is laminated on a substrate,
The surface protective layer is composed of an isocyanate curable acrylic resin composition having an acrylic resin composition as a main component and a polyisocyanate as a curing agent,
The polyisocyanate prepolymer comprises a curing agent A obtained by polymerizing xylylene diisocyanate (hereinafter referred to as XDI) in a range of 1 to 20% by weight to hexamethylene diisocyanate (hereinafter referred to as HDI), and a side chain. Curing agent B, which is a trimer of HDI containing a urethane bond, and curing agent A: curing agent B = 10 to 40% by weight: 90 to 60% by weight Makeup sheet.
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|---|---|---|---|---|
| JPH07330858A (en) * | 1994-06-02 | 1995-12-19 | Nippon Kayaku Co Ltd | Polyurethane (meth)acrylate, ultraviolet-setting resin composition containing the same and its cured material |
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