JPH05170941A - Acrylic resin film having improved weather resistance - Google Patents
Acrylic resin film having improved weather resistanceInfo
- Publication number
- JPH05170941A JPH05170941A JP2267091A JP2267091A JPH05170941A JP H05170941 A JPH05170941 A JP H05170941A JP 2267091 A JP2267091 A JP 2267091A JP 2267091 A JP2267091 A JP 2267091A JP H05170941 A JPH05170941 A JP H05170941A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet absorber
- film
- acrylic resin
- hydroxy
- ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、温室、サンル−フ、看
板、ド−ム、標識、防音壁あるいは太陽温水器等の被覆
材として有効な耐侯性が改良されたアクリル樹脂フィル
ム及び該フィルムを積層したフィルム又はシ−トに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin film having improved weather resistance, which is effective as a covering material for greenhouses, sunroofs, signboards, domes, signs, soundproof walls, solar water heaters, etc. The present invention relates to a laminated film or sheet.
【０００２】[0002]
【従来の技術】アクリル樹脂はプラスチック材料の中で
最も耐侯性の優れる材料として知られており、メチルメ
タクリレ−トを主成分とする重合体のフィルムはその特
徴を活かして各種プラスチック材料の上に積層して該プ
ラスチック材料の耐侯性劣化を抑える目的で使用されて
いる。2. Description of the Related Art Acrylic resin is known as the most weather resistant material among plastic materials, and a polymer film containing methyl methacrylate as a main component is utilized on various plastic materials by utilizing its characteristics. Used for the purpose of suppressing deterioration of weather resistance of the plastic material.
【０００３】ところで、耐侯性を向上させるために各種
のプラスチック材料に紫外線吸収剤が添加されている
が、紫外線吸収剤はプラスチック材料に比べると分子量
が低いため、このプラスチック材料を長時間屋外で使用
していると紫外線吸収剤が徐々にブリ−ドアウトしてく
る。また、紫外線吸収剤の融点はプラスチック材料に比
べて低いので、フィルム製造時にフィルムが接するキャ
スティングロ−ルや引き取りロ−ル表面だけでなくフィ
ルム表面自体も汚れてしまう。しかも結果として紫外線
吸収剤の含有濃度も減少するという問題点もある。更
に、同様のことは、紫外線吸収剤を混入させたプラスチ
ックフィルムを基材樹脂に熱ラミネ−トする際にも起こ
り、紫外線吸収剤がブリ−ドアウトして、紫外線吸収剤
の含有濃度が減少してしまう。By the way, an ultraviolet absorber is added to various plastic materials in order to improve weather resistance, but since the ultraviolet absorber has a lower molecular weight than the plastic material, this plastic material is used outdoors for a long time. As it does, the UV absorber gradually bleeds out. Further, since the melting point of the ultraviolet absorber is lower than that of the plastic material, not only the casting roll and the take-up roll surface which the film comes into contact with during the film production but also the film surface itself is contaminated. In addition, as a result, there is a problem that the content concentration of the ultraviolet absorber is also reduced. Further, the same thing occurs when heat laminating a plastic film mixed with an ultraviolet absorber to a base resin, the ultraviolet absorber is bleed out, and the content concentration of the ultraviolet absorber decreases. Will end up.
【０００４】これを改善するためにプラスチック材料の
ポリマ−鎖中に紫外線吸収性モノマ−を共重合させた
り、グラフトさせる方法が考えられるが、プラスチック
の物性を低下させやすく、また紫外線吸収性成分の動き
が束縛されて十分な耐候性効果が得られないことが多
い。In order to improve this, a method of copolymerizing or grafting a UV-absorbing monomer in the polymer chain of the plastic material can be considered, but the physical properties of the plastic are easily deteriorated and the UV-absorbing component Movement is often constrained to provide sufficient weather resistance.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前記の種々
の問題点を解消した、耐候性の良いアクリル樹脂フィル
ムを提供することを目的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide an acrylic resin film having good weather resistance, which has solved the above-mentioned various problems.
【０００６】[0006]
【課題を解決する為の手段】すなわち本発明は、紫外線
吸収剤を共重合させたポリマ−と紫外線吸収剤とを含有
する耐侯性アクリル樹脂フィルムである。That is, the present invention is a weather resistant acrylic resin film containing a polymer obtained by copolymerizing an ultraviolet absorber and the ultraviolet absorber.
【０００７】紫外線吸収性モノマ−を重合させたり共重
合させて得た紫外線吸収性ポリマ−をプラスチック材料
に添加することは、前述の如くよく知られている。しか
し、これらを単独で用いる場合には紫外線吸収性能を持
たせるためにどうしても添加量を増やさざるを得ない。
特にフィルムの場合には、添加量を増やすと物性の低下
が著しくなってしまう。また相溶性の問題を考えなくて
はならない。本願発明は、紫外線吸収性ポリマ−と紫外
線吸収剤とを併用することにより、紫外線吸収性ポリマ
−の添加量を少なくして優れた紫外線吸収性能を持たせ
たものである。このように紫外線吸収性ポリマ−と紫外
線吸収剤とを併用すると、紫外線吸収剤の使用量も少な
くてすむので前述の紫外線吸収剤のブリ−ドアウト、フ
ィルム製造時やラミネ−ト加工時のフィルム汚染の問題
点も解消することができ、フィルムの透明性も改善でき
る。As described above, it is well known to add an ultraviolet absorbing polymer obtained by polymerizing or copolymerizing an ultraviolet absorbing monomer to a plastic material. However, when these are used alone, the addition amount must be increased in order to have the ultraviolet absorbing performance.
In particular, in the case of a film, if the addition amount is increased, the physical properties are significantly deteriorated. Also, the issue of compatibility must be considered. In the present invention, the ultraviolet absorbing polymer and the ultraviolet absorbing agent are used in combination to reduce the added amount of the ultraviolet absorbing polymer and provide excellent ultraviolet absorbing performance. When the UV absorbing polymer and the UV absorbing agent are used together in this way, the amount of the UV absorbing agent used can be small. Therefore, the UV absorbing agent is bleed out, and the film is contaminated during the film production or the laminating process. The problem of can be solved and the transparency of the film can be improved.
【０００８】本発明で用いる紫外線吸収剤を共重合させ
た紫外線吸収性ポリマ−としては、ビニル単量体と共重
合可能な官能基を有するベンゾフェノンやベンゾトリア
ゾ−ルとメタクリル酸メチルなどの単量体との共重合体
が用いられるが、２−ヒドロキシ−４−（メタクリロイ
ルオキシエトキシ）ベンゾフェノンとメタクリル酸メチ
ルの共重合体が特に好ましい。この共重合体はアクリル
樹脂との相溶性も良く、良好な紫外線吸収剤であること
を見い出した。The UV absorbing polymer copolymerized with the UV absorbing agent used in the present invention is a monomer such as benzophenone or benzotriazole having a functional group copolymerizable with a vinyl monomer and methyl methacrylate. A copolymer of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and methyl methacrylate is particularly preferable. It was found that this copolymer has a good compatibility with an acrylic resin and is a good ultraviolet absorber.
【０００９】また、この紫外線吸収性コポリマ−の平均
重量分子量は、１０万以下であることが望ましい。分子
量が数１０万のオ−ダ−になるとアクリル樹脂との相溶
性が悪くなり、フィルム表面に凹凸が発生したり、透明
性が低下するので好ましくない。また、あまり分子量が
低いとコポリマ−の耐熱性が低下し、成形時に分解しや
すくなる。従って望ましくは１万〜１０万の範囲に分子
量を設定すべきである。The average weight molecular weight of this ultraviolet absorbing copolymer is preferably 100,000 or less. If the molecular weight is on the order of several hundreds of thousands, the compatibility with the acrylic resin is deteriorated, unevenness is generated on the film surface, and the transparency is lowered, which is not preferable. On the other hand, if the molecular weight is too low, the heat resistance of the copolymer decreases, and it tends to decompose during molding. Therefore, the molecular weight should preferably be set in the range of 10,000 to 100,000.
【００１０】更に上記のコポリマ−においては、２−ヒ
ドロキシ−４−（メタクリロイルオキシエトキシ）ベン
ゾフェノンとメタクリル酸メチルの組成比は、１０／９
０〜６０／４０の間に設定しておくことが必要である。
２−ヒドロキシ−４−（メタクリロイルオキシエトキ
シ）ベンゾフェノン自体はアクリル樹脂との相溶性があ
まり良くないため、２−ヒドロキシ−４−（メタクリロ
イルオキシエトキシ）ベンゾフェノンの割合をあまり増
やすと、紫外線吸収性能は良くなるが、フィルムの透明
性を損なうことになる。但し２−ヒドロキシ−４−（メ
タクリロイルオキシエトキシ）ベンゾフェノンの割合が
少ないと、紫外線吸収性能を出すためには、フィルム中
への濃度を増やさなくてはならない。Further, in the above copolymer, the composition ratio of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and methyl methacrylate is 10/9.
It is necessary to set it between 0 and 60/40.
2-Hydroxy-4- (methacryloyloxyethoxy) benzophenone itself does not have a good compatibility with the acrylic resin, so if the proportion of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone is increased too much, the ultraviolet absorption performance is good. However, this will impair the transparency of the film. However, if the proportion of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone is low, the concentration in the film must be increased in order to obtain the ultraviolet absorbing performance.
【００１１】紫外線吸収性コポリマ−のアクリル樹脂フ
ィルムへの添加量は、５０μｍ厚に対し１〜５％位にと
どめるべきである。紫外線カット性を維持させるために
はできるだけ添加量を多くする方が良いが、あまり添加
量を高くするとフィルム物性への悪影響が生じ、またフ
ィルムの製膜性が低下する。The addition amount of the ultraviolet absorbing copolymer to the acrylic resin film should be about 1 to 5% with respect to the thickness of 50 μm. It is better to increase the addition amount as much as possible in order to maintain the ultraviolet ray blocking property, but if the addition amount is too high, the physical properties of the film are adversely affected and the film forming property of the film is deteriorated.
【００１２】本発明で用いられる紫外線吸収剤は、一般
に用いられている紫外線吸収剤から選択することができ
る。紫外線吸収剤としてはフェニルサリシレ−ト、ｐ−
ｔｅｒｔ−ブチルフェニルサリシレ−トなどのサリシル
酸系、２−４ジヒドロキシベンゾフェノン、２−ヒドロ
キシ−４−メトキシベンゾフェノン、２−ヒドロキシ−
４−オクトキシベンゾフェノン、２−ヒドロキシ−４−
ドデシルオキシベンゾフェノンなどのベンゾフェノン
系、２−（２’−ヒドロキシ５’−ｔｅｒｔ−ブチルフ
ェニル）ベンゾトリアゾ−ル、２−（２’ヒドロキシ−
３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾト
リアゾ−ル、２−（２’−ヒドロキシ−３’−ｔｅｒｔ
−ブチル−５’−メチルフェニル）−５−クロロベンゾ
トリアゾ−ル、２−（２’ヒドロキシ−３’，５’−ジ
−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリ
アゾ−ルなどのベンゾトリアゾ−ル系、２−エチルヘキ
シル−２−シアノ−３，３’−ジフェニルアクリレ−
ト、エチル−２−シアノ−３，３’−ジフェニルアクリ
レ−トなどのシアノアクリレ−ト系がある。また、これ
らの他にニッケルビス（オクチルフェニル）サルファイ
ド、（２，２’−チオビス（４−ｔｅｒｔ−オクチルフ
ェノラ−ト）−ｎ−ブチルアミンニッケルなどの紫外線
吸収剤やビス（２，２，６，６−テトラメチル−４−ピ
ペリジル）セバケ−トのようなヒンダ−ドアミン系光安
定剤などから選択しても良い。これらの紫外線吸収剤は
単独で用いることもあるいは２種以上を混合して用いる
ことも可能である。The ultraviolet absorber used in the present invention can be selected from the commonly used ultraviolet absorbers. As an ultraviolet absorber, phenyl salicylate, p-
Salicylate such as tert-butylphenyl salicylate, 2-4 dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
4-octoxybenzophenone, 2-hydroxy-4-
Benzophenone series such as dodecyloxybenzophenone, 2- (2'-hydroxy 5'-tert-butylphenyl) benzotriazole, 2- (2'hydroxy-
3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert
-Butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and the like. Benzotriazole type, 2-ethylhexyl-2-cyano-3,3′-diphenylacryle
And ethyl-2-cyano-3,3'-diphenyl acrylate. In addition to these, UV absorbers such as nickel bis (octylphenyl) sulfide and (2,2'-thiobis (4-tert-octylphenolato) -n-butylamine nickel) and bis (2,2,6) , 6-Tetramethyl-4-piperidyl) sebacate, etc. These UV absorbers may be used alone or in admixture of two or more. It is also possible to use.
【００１３】一般の紫外線吸収剤の添加量はフィルム厚
が５０μｍとした場合紫外線吸収剤の種類によって異な
るが１〜３％程度が適当であり、これ以上の添加量では
ブリ−ドアウトが激しくなったり、フィルムの物性に悪
影響が出てくる。従って性能を満足させるための最低限
の添加量に抑えることが望ましい。When the film thickness is 50 μm, the addition amount of a general ultraviolet absorber varies depending on the kind of the ultraviolet absorber, but about 1 to 3% is appropriate, and if it is more than this amount, the bleed-out becomes severe. , The physical properties of the film will be adversely affected. Therefore, it is desirable to control the addition amount to the minimum amount to satisfy the performance.
【００１４】本発明はコポリマ−型紫外線吸収剤と一般
の紫外線吸収剤の併用によるものであるが、その両者の
合計の添加量も望ましくは５％以下に抑えるべきであ
り、あまり添加量が大きいと、フィルム物性への悪影響
が大きくなり好ましくない。本発明で用いるアクリル樹
脂は、特公昭４９−４６１５８号公報、特公昭５９−３
６６４５号公報、特開昭５７−１４０１６１号公報、特
開昭５８−６２０４６号公報、特開昭６３−７７９６３
号公報などに記載されているようなアクリル系多層構造
重合体が好ましい。また、厚みが厚く強度保持ができる
場合にはメチルメタクリレ−トを主成分とするアクリル
樹脂を用いても良い。The present invention is based on the combined use of a copolymer type ultraviolet absorber and a general ultraviolet absorber, and the total addition amount of both is preferably suppressed to 5% or less, and the addition amount is too large. If so, the physical properties of the film are adversely affected, which is not preferable. The acrylic resin used in the present invention is disclosed in JP-B-49-46158 and JP-B-59-3.
6645, JP-A-57-140161, JP-A-58-62046, and JP-A-63-77963.
Acrylic-based multi-layer structure polymers as described in Japanese Patent Laid-Open Publication No. 1993-242242 are preferable. Further, when the thickness is large and strength can be maintained, an acrylic resin containing methyl methacrylate as a main component may be used.
【００１５】本発明のアクリル樹脂フィルムは適当な基
材樹脂に熱ラミネ−トすることができる。このような基
材樹脂としてはアルリル樹脂、ポリカ−ボネ−ト樹脂、
塩化ビニル樹脂、ポリスチロ−ル樹脂などのフィルムま
たはシ−トが挙げられる。これらの基材樹脂に熱ラミネ
−トすることによって、基材樹脂の耐侯性を大きく改善
でき、更にこれを熱加工して、サンル−フ、看板、ド−
ムなどを製造することもできる。The acrylic resin film of the present invention can be heat-laminated on a suitable base resin. Examples of such base resin include allyl resin, polycarbonate resin,
Examples of the film or sheet include vinyl chloride resin and polystyrene resin. By heat laminating these base resins, the weather resistance of the base resins can be greatly improved, and the base resins can be heat-processed to produce sunroofs, signboards, and drapes.
It is also possible to manufacture such products.
【００１６】本発明の好ましい実施態様は次のとおりで
ある。 １．メチルメタクリレ−トと２−ヒドロキシ−４−（メ
タクリロイルオキシエトキシ）ベンゾフェノンの組成比
が重量部で９０／１０〜６０／４０である請求項２記載
の耐侯性アクリル樹脂フィルム。A preferred embodiment of the present invention is as follows. 1. The weather resistant acrylic resin film according to claim 2, wherein the composition ratio of methyl methacrylate and 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone is 90/10 to 60/40 in parts by weight.
【００１７】２．紫外線吸収剤を共重合させたポリマ−
と紫外線吸収剤の合計量の濃度がアクリル樹脂１００重
量部に対し１〜５重量部である請求項１記載の耐侯性ア
クリル樹脂フィルム。2. Polymer copolymerized with UV absorber
The weather resistant acrylic resin film according to claim 1, wherein the total concentration of the ultraviolet absorber and the ultraviolet absorber is 1 to 5 parts by weight based on 100 parts by weight of the acrylic resin.
【００１８】３．紫外線吸収剤を共重合させたポリマ−
の重量平均分子量が１０万以下である請求項１記載の耐
侯性アクリル樹脂フィルム。3. Polymer copolymerized with UV absorber
The weather-resistant acrylic resin film according to claim 1, having a weight average molecular weight of 100,000 or less.
【００１９】[0019]
実施例１〜６及び比較例１〜３ コポリマ−型紫外線吸収剤Ａとして２−ヒドロキシ−４
−（メタクリロイルオキシエトキシ）ベンゾフェノン３
０重量部とメタクリル酸メチル７０重量部からなる分子
量３５０００の共重合体、コポリマ−型紫外線吸収剤Ｂ
として２−ヒドロキシ−４−（メタクリロイルオキシエ
トキシ）ベンゾフェノン５０重量部とメタクリル酸メチ
ル５０重量部とからなる分子量３５０００の共重合体及
び紫外線吸収剤としてチヌビンＰ［商標名、チバガイギ
−社製：２−（５−メチル−２−ヒドロキシフェニル）
ベンゾトリアゾ−ル］を用意した。アクリル樹脂として
ハイペットＨＢＳ０００（商標名、三菱レイヨン株式会
社製）を用いて、表１の組成でそれぞれ５０μｍ、７５
μｍ、１００μｍのフィルムを作成した。Examples 1 to 6 and Comparative Examples 1 to 2 2-Hydroxy-4 as copolymer type ultraviolet absorber A
-(Methacryloyloxyethoxy) benzophenone 3
Copolymer of 05,000 parts by weight and 70 parts by weight of methyl methacrylate and having a molecular weight of 35,000, copolymer type ultraviolet absorber B
As a copolymer of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and 50 parts by weight of methyl methacrylate having a molecular weight of 35,000 and as an ultraviolet absorber, TINUVIN P [trade name, manufactured by Ciba-Geigy: 2- (5-methyl-2-hydroxyphenyl)
Benzotriazole] was prepared. Hypet HBS000 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the acrylic resin, and the composition of Table 1 was 50 μm and 75 μm, respectively.
Films of μm and 100 μm were prepared.
【００２０】[0020]
【表１】 [Table 1]
【００２１】これらのフィルムについて透過光分布、全
光透過性及びブリ−ドアウト性を調べた。The transmitted light distribution, total light transmittance and bleed-out property of these films were examined.
【００２２】（透過光分布）各フィルムについて透過光
分布を測定した。その結果を順に図１〜図９に示す。比
較例１は、コポリマ−型紫外線吸収剤Ａを３％添加した
ものであるが、図７に示すごとく、透過曲線を見ると１
００μｍまで厚くしても、３５０mmまでしか紫外線をカ
ットできず、しかも透過のカ−ブの立上りがゆるやか
で、シャ−プにカットできていない。ちなみに厚さ１０
０μｍのこの濃度を５０μｍに換算すると６％に相当す
る。フィルムの物性が低下するのみならず、コストの上
昇にもつながってしまう。(Transmitted light distribution) The transmitted light distribution was measured for each film. The results are shown in order in FIGS. Comparative Example 1 was prepared by adding 3% of the copolymer type ultraviolet absorber A, and the transmission curve was 1 as shown in FIG.
Even if the thickness is increased to 00 μm, ultraviolet rays can be cut only up to 350 mm, and the rising curve of the transmission curve is gentle, so that it cannot be cut sharply. By the way, thickness 10
Converting this concentration of 0 μm to 50 μm corresponds to 6%. Not only will the physical properties of the film deteriorate, but it will also lead to higher costs.
【００２３】この傾向は、コポリマ−型紫外線吸収剤Ｂ
を３％添加した比較例２の場合も同様である。この場合
はメタクリル酸メチルの割合が少ないので、１００μｍ
のように厚くなると透過率も下がってくることがわか
る。比較例３はチヌビンＰを３％添加したフィルムであ
る。この場合は紫外線カット性能はかなり良好ではある
ものの、フィルム製膜時に、ロ−ル汚れがひどく、製造
上に問題が生じた。This tendency is due to the copolymer type ultraviolet absorber B.
The same applies to Comparative Example 2 in which 3% is added. In this case, the proportion of methyl methacrylate is low, so 100 μm
It can be seen that as the thickness increases, the transmittance also decreases. Comparative Example 3 is a film containing 3% of tinuvin P added. In this case, although the ultraviolet ray cutting performance was quite good, roll contamination was severe during the film formation, which caused a problem in production.
【００２４】しかし実施例１〜６では、図１〜図６にみ
るように、紫外線カット性もシャ−プカット性も良好で
あり、かつチヌビンＰが１％という低濃度であるために
フィルム製膜時のロ−ル汚れも極めて少なかった。However, in Examples 1 to 6, as shown in FIGS. 1 to 6, both the ultraviolet ray cut property and the sharp cut property were good, and the tinuvin P had a low concentration of 1%, so that the film formation was performed. There was also very little roll fouling.
【００２５】（全光透過性）表２は、フィルムの全光透
過性とヘ−ズの値を示したものである。実施例１〜３の
ようにメタクリル酸メチルの割合の多いコポリマ−型紫
外線吸収剤Ａを添加した場合は透明性が良く、ヘ−ズの
値も小さい。メタクリル酸メチルの割合が少ないコポリ
マ−型紫外線吸収剤Ｂを添加した場合は、実施例６のよ
うにややヘ−ズの値が高くなってくる傾向を示したが、
この程度では実用上問題ない。(Total Light Transmittance) Table 2 shows the total light transmittance and haze value of the film. When the copolymer type ultraviolet absorber A having a large proportion of methyl methacrylate is added as in Examples 1 to 3, the transparency is good and the haze value is small. When the copolymer-type ultraviolet absorber B having a small proportion of methyl methacrylate was added, the haze value tended to be slightly higher as in Example 6, but
At this level, there is no practical problem.
【００２６】[0026]
【表２】 [Table 2]
【００２７】（ブリ−ドアウト性）図１０及び図１１
は、実施例１の５０μｍのフィルムと比較例３の５０μ
ｍフィルムを８０℃２４時間炉加熱した後の透過光分布
をそれぞれ示したものである。比較例３のチヌビンＰ単
独ではブリ−ドアウトにより、紫外線カット能力が低下
しているが、実施例１のコポリマ−型紫外線吸収剤を併
用したものはブリ−ドアウト性が改善されることがわ
る。(Bleed-out property) FIGS. 10 and 11
Is 50 μm of the film of Example 1 and 50 μm of Comparative Example 3.
The distributions of transmitted light after heating the m-film in a furnace at 80 ° C. for 24 hours are shown respectively. The UV-cutting ability of Tinuvin P alone in Comparative Example 3 was reduced due to bleed-out, but the combination of the copolymer type UV-absorbing agent of Example 1 improved the bleed-out property.
【００２８】[0028]
【発明の効果】本発明のアクリル樹脂フィルムは、紫外
線吸収剤を共重合させたポリマーと紫外線吸収剤とを併
用して含有させたので、屋外での長期使用において紫外
線吸収剤のブリードアウトを生じることがなく、またフ
ィルムの製造時や他の基材樹脂への熱ラミネート時にお
いても紫外線吸収剤のブリードアウトを生じることがな
い。そして、耐候性が極めて優れているので、工業上優
れた効果を奏する。The acrylic resin film of the present invention contains a polymer obtained by copolymerizing an ultraviolet absorber and the ultraviolet absorber in combination, so that the bleed-out of the ultraviolet absorber occurs during long-term outdoor use. In addition, bleed-out of the ultraviolet absorber does not occur during the production of the film or thermal lamination to other base resin. And since it has extremely excellent weather resistance, it has an excellent industrial effect.
【図１】本発明の実施例１の積層フィルムの透過光分布
図である。FIG. 1 is a transmitted light distribution diagram of a laminated film of Example 1 of the present invention.
【図２】本発明の実施例２の積層フィルムの透過光分布
図である。FIG. 2 is a transmitted light distribution diagram of a laminated film of Example 2 of the present invention.
【図３】本発明の実施例３の積層フィルムの透過光分布
図である。FIG. 3 is a transmitted light distribution diagram of a laminated film of Example 3 of the present invention.
【図４】本発明の実施例４の積層フィルムの透過光分布
図である。FIG. 4 is a transmitted light distribution diagram of a laminated film of Example 4 of the present invention.
【図５】本発明の実施例５の積層フィルムの透過光分布
図である。FIG. 5 is a transmitted light distribution diagram of the laminated film of Example 5 of the present invention.
【図６】本発明の実施例６の積層フィルムの透過光分布
図である。FIG. 6 is a transmitted light distribution diagram of a laminated film of Example 6 of the present invention.
【図７】本発明の比較例１の積層フィルムの透過光分布
図である。FIG. 7 is a transmitted light distribution diagram of the laminated film of Comparative Example 1 of the present invention.
【図８】本発明の比較例２の積層フィルムの透過光分布
図である。FIG. 8 is a transmitted light distribution diagram of a laminated film of Comparative Example 2 of the present invention.
【図９】本発明の比較例３の積層フィルムの透過光分布
図である。FIG. 9 is a transmitted light distribution diagram of a laminated film of Comparative Example 3 of the present invention.
【図１０】本発明の比較例３の積層フィルムのブリード
アウト性を示す図である。FIG. 10 is a diagram showing the bleed-out property of the laminated film of Comparative Example 3 of the present invention.
【図１１】本発明の実施例１の積層フィルムのブリード
アウト性を示す図である。FIG. 11 is a diagram showing the bleed-out property of the laminated film of Example 1 of the present invention.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年５月２０日[Submission date] May 20, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Name of item to be amended] Title of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の名称】 耐候性が改良されたアクリル樹脂フィ
ルムTitle: Acrylic resin film with improved weather resistance
Claims (2)
外線吸収剤とを含有する耐侯性アクリル樹脂フィルム。1. A weather-resistant acrylic resin film containing a polymer obtained by copolymerizing an ultraviolet absorber and an ultraviolet absorber.
メチルメタクリレ−トと２−ヒドロキシ−４−（メタク
リロイルオキシエトキシ）ベンゾフェノンの共重合体で
ある請求項１記載の耐侯性アクリル樹脂フィルム。2. A polymer obtained by copolymerizing an ultraviolet absorber,
The weather-resistant acrylic resin film according to claim 1, which is a copolymer of methyl methacrylate and 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267091A JPH05170941A (en) | 1991-01-24 | 1991-01-24 | Acrylic resin film having improved weather resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267091A JPH05170941A (en) | 1991-01-24 | 1991-01-24 | Acrylic resin film having improved weather resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05170941A true JPH05170941A (en) | 1993-07-09 |
Family
ID=12089285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2267091A Pending JPH05170941A (en) | 1991-01-24 | 1991-01-24 | Acrylic resin film having improved weather resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05170941A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0659829A1 (en) * | 1993-12-14 | 1995-06-28 | Röhm Gmbh | Weather-resistant sheet and articles coated therewith |
| JPH07276831A (en) * | 1994-02-21 | 1995-10-24 | Dainippon Printing Co Ltd | Protective layer transfer film and printed matter |
| JPH082192A (en) * | 1994-06-22 | 1996-01-09 | C I Kasei Co Ltd | Transfer foil and sheet material using the same |
| JPH09123693A (en) * | 1995-08-31 | 1997-05-13 | Nissha Printing Co Ltd | Transfer material and transfer matter |
| WO2007040182A1 (en) | 2005-10-03 | 2007-04-12 | Nippon Shokubai Co., Ltd. | Amorphous thermoplastic resin and extruded film or sheet |
| WO2008047836A1 (en) * | 2006-10-18 | 2008-04-24 | Nippon Shokubai Co., Ltd. | Thermoplastic resin composition |
| JP2008138044A (en) * | 2006-11-30 | 2008-06-19 | Nippon Shokubai Co Ltd | Thermoplastic resin composition |
| US7716872B2 (en) * | 1997-11-03 | 2010-05-18 | Rsb Laboratorium B.V. | Removable protective coating |
| KR20120001733A (en) * | 2009-03-24 | 2012-01-04 | 에보니크 룀 게엠베하 | Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition |
| JP2016164222A (en) * | 2015-03-06 | 2016-09-08 | スリーエム イノベイティブ プロパティズ カンパニー | Ultraviolet crosslinkable composition |
| JP2020132850A (en) * | 2019-02-20 | 2020-08-31 | 東洋インキＳｃホールディングス株式会社 | Resin composition for molding and molded body |
-
1991
- 1991-01-24 JP JP2267091A patent/JPH05170941A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0659829A1 (en) * | 1993-12-14 | 1995-06-28 | Röhm Gmbh | Weather-resistant sheet and articles coated therewith |
| JPH07276831A (en) * | 1994-02-21 | 1995-10-24 | Dainippon Printing Co Ltd | Protective layer transfer film and printed matter |
| JPH082192A (en) * | 1994-06-22 | 1996-01-09 | C I Kasei Co Ltd | Transfer foil and sheet material using the same |
| JPH09123693A (en) * | 1995-08-31 | 1997-05-13 | Nissha Printing Co Ltd | Transfer material and transfer matter |
| US7716872B2 (en) * | 1997-11-03 | 2010-05-18 | Rsb Laboratorium B.V. | Removable protective coating |
| WO2007040182A1 (en) | 2005-10-03 | 2007-04-12 | Nippon Shokubai Co., Ltd. | Amorphous thermoplastic resin and extruded film or sheet |
| WO2008047836A1 (en) * | 2006-10-18 | 2008-04-24 | Nippon Shokubai Co., Ltd. | Thermoplastic resin composition |
| JPWO2008047836A1 (en) * | 2006-10-18 | 2010-02-25 | 株式会社日本触媒 | Thermoplastic resin composition |
| JP2008138044A (en) * | 2006-11-30 | 2008-06-19 | Nippon Shokubai Co Ltd | Thermoplastic resin composition |
| KR20120001733A (en) * | 2009-03-24 | 2012-01-04 | 에보니크 룀 게엠베하 | Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition |
| JP2012521456A (en) * | 2009-03-24 | 2012-09-13 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Composition comprising, as aqueous dispersion, preferably a (meth) acrylate polymer containing benzophenone in a mixture with a (meth) acrylate polymer different from this polymer, as well as the use of said composition |
| US8669328B2 (en) | 2009-03-24 | 2014-03-11 | Evonik Roehm Gmbh | Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition |
| TWI482813B (en) * | 2009-03-24 | 2015-05-01 | Evonik Roehm Gmbh | Composition encompassing an aqueous dispersion of preferably benzophenone-containing (meth) acrylate polymers in a mixture with (meth) acrylate polymers which differ from these, and the use of the composition |
| JP2016164222A (en) * | 2015-03-06 | 2016-09-08 | スリーエム イノベイティブ プロパティズ カンパニー | Ultraviolet crosslinkable composition |
| JP2020132850A (en) * | 2019-02-20 | 2020-08-31 | 東洋インキＳｃホールディングス株式会社 | Resin composition for molding and molded body |
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