JPH03281220A - Oriented material - Google Patents
Oriented materialInfo
- Publication number
- JPH03281220A JPH03281220A JP8555690A JP8555690A JPH03281220A JP H03281220 A JPH03281220 A JP H03281220A JP 8555690 A JP8555690 A JP 8555690A JP 8555690 A JP8555690 A JP 8555690A JP H03281220 A JPH03281220 A JP H03281220A
- Authority
- JP
- Japan
- Prior art keywords
- film
- stretching
- less
- ors
- sheet
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title abstract description 7
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims abstract description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims abstract description 3
- 230000005606 hygroscopic expansion Effects 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 13
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 125000005641 methacryl group Chemical group 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000113 methacrylic resin Substances 0.000 description 16
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分計］
本発明は、吸湿寸法安定性に優れたメタクリル樹脂系延
伸フィルムまたはシートに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a methacrylic resin-based stretched film or sheet having excellent moisture absorption dimensional stability.
［従来の技術］
メタクリル酸メチルとアルキル基の炭素数が１〜４であ
るアクリル酸アルキルエステルの共重合体樹脂である一
般のメタクリル樹脂は、看板、照明用カバーあるいは自
動車部品などに多用されている。この樹脂は透明性、耐
候性（耐光性）、美匠性に優れ、光学分野の保護フィル
ムあるいはシートとしての用途、例えば光学式のコンパ
クトデスクあるいはレーザーデスクの保護フィルムとし
ての用途が期待される。[Prior Art] General methacrylic resin, which is a copolymer resin of methyl methacrylate and acrylic acid alkyl ester in which the alkyl group has 1 to 4 carbon atoms, is widely used in signboards, lighting covers, automobile parts, etc. There is. This resin has excellent transparency, weather resistance (light resistance), and aesthetic properties, and is expected to be used as a protective film or sheet in the optical field, for example, as a protective film for optical compact desks or laser desks.
光学式のコンパクトデスクあるいはレーザーデスクの保
護フィルムとしては、これも透明性の高いトリアセチル
セルロース樹脂のフィルムが検討されたがその吸湿性が
高く、貼着復吸）Ｗ膨張のためにしわが発生する欠点が
あり実用に至っていない。A highly transparent triacetyl cellulose resin film was considered as a protective film for optical compact desks or laser desks, but it has high hygroscopicity and wrinkles occur due to the expansion of W after adhesion. It has shortcomings and has not been put into practical use.
一般のメタクリル樹脂はトリアセチルセルロース樹脂よ
り吸湿性に優れ、押出成形によりフィルム化し保護フィ
ルムとしての特性を調べたが、吸 ２−
湿性の改良が十分てなくまた脆く、このような表面保護
用途には使用できないものであった。General methacrylic resin has better hygroscopicity than triacetylcellulose resin, and was made into a film by extrusion molding to examine its properties as a protective film, but its hygroscopicity was not sufficiently improved and it was brittle, making it difficult to use for such surface protection applications. was unusable.
［発明が解決しようとする課題］
本発明は、メタクリル樹脂の透明性等の特長を保持し、
かつ吸湿寸法安定性および脆性が改良された、上記のよ
うな表面保護用途に好適なメタクリル樹脂系のフィルム
またはシートの開発を目的とする。[Problems to be solved by the invention] The present invention maintains the characteristics of methacrylic resin such as transparency,
Another object of the present invention is to develop a methacrylic resin film or sheet that has improved moisture absorption dimensional stability and brittleness and is suitable for surface protection applications as described above.
［課題を解決するための手段］
本発明の目的は、メタクリル酸メチル単位９５〜４０重
量％およびメタクリル酸シクロヘキシル単位５〜６０重
量％からなり、メルトフローインデックスが１２ｇ／１
０分以下であるメタクリル系共重合体樹脂のフィルムま
たはシート状の二軸延伸物であって、二軸両方向のオリ
エンテーションリリースストレスが３〜３０ Ｋｇ／ｃ
ｍ２の範囲である延伸物により達成される。[Means for Solving the Problems] The object of the present invention is to achieve a composition comprising 95 to 40% by weight of methyl methacrylate units and 5 to 60% by weight of cyclohexyl methacrylate units, and having a melt flow index of 12 g/1.
A film or sheet-like biaxially stretched product of methacrylic copolymer resin that has an orientation release stress of 3 to 30 Kg/c in both biaxial directions.
This is achieved with a drawn product in the range of m2.
メタクリル酸メチル単位の量は９５〜４０重量％である
のが好ましく、９５％をこえた場合吸湿性の改良が不十
分となる。また４０％未満では透明性の低下や耐候性が
低下するなど、メタクリル樹脂の特長が損われたものと
なる。The amount of methyl methacrylate units is preferably 95 to 40% by weight; if it exceeds 95%, the improvement in hygroscopicity will be insufficient. If it is less than 40%, the characteristics of the methacrylic resin will be impaired, such as a decrease in transparency and weather resistance.
メタクリル酸シクロヘキシル単位の量は５〜６０重量％
であるのが好ましく、５％を未満では吸湿性の改良が不
十分となる。また６０％をこえた場合機械的強度や耐候
性が低下する。The amount of cyclohexyl methacrylate units is 5-60% by weight
If it is less than 5%, the improvement in hygroscopicity will be insufficient. Moreover, when it exceeds 60%, mechanical strength and weather resistance decrease.
一般のメタクリル樹脂のフィルムまたはシートの吸湿膨
張率（乾燥したフィルムまたはシートを２３℃、９５％
湿度の環境に４８時間おいたときの膨張率）は約０．４
％であるがメタクリル酸シクロヘキシル単位を含む本発
明の延伸物により０゜３％以下のものが達成される。特
に０．２％以下のものは、光学式のコンパクトデスクあ
るいはレーザーデスクの保護等に使用した場合、高湿度
下でもシワが生ぜず好適に使用される。Hygroscopic expansion coefficient of general methacrylic resin film or sheet (dry film or sheet at 23℃, 95%
The expansion rate (when left in a humid environment for 48 hours) is approximately 0.4.
%, but 0.3% or less can be achieved with the drawn product of the present invention containing cyclohexyl methacrylate units. Particularly, those having a content of 0.2% or less are suitable for use in protecting optical compact desks or laser desks because they do not wrinkle even under high humidity.
必須単量体以外に、これらと共重合性の単量体を、本発
明の効果を損わない範囲で共重合してもよい。In addition to the essential monomers, monomers copolymerizable with these monomers may be copolymerized within a range that does not impair the effects of the present invention.
このような単量体としては、例えばメタクリル酸メチル
およびメタクリル酸シクロヘキシル以外のメタクリル酸
エステル、アクリル酸エステル、Ｎ−アルキルマレイミ
ド、Ｎ−アリールマレイミド、スチレンなどが挙げられ
る。Examples of such monomers include methacrylic esters other than methyl methacrylate and cyclohexyl methacrylate, acrylic esters, N-alkylmaleimides, N-arylmaleimides, styrene, and the like.
共重合体樹脂のメル（・フローインデックス（ＡＳＴＭ
ＤＩ２３８−■条件、以下ＭＦ工と略記する）は１
２ｇ／１０分以下である必要がある。Copolymer resin mel (・flow index (ASTM)
DI238-■Condition (hereinafter abbreviated as MF engineering) is 1
It needs to be 2g/10 minutes or less.
大きすぎる、すなわち分子量が小さくなると、分子間の
絡み合いが弱くなり、延伸中に高分子間のすべりが生じ
やすくなる。延伸による脆性改良効果が低下し、安定し
ない。If the molecular weight is too large, that is, if the molecular weight is small, the entanglement between molecules becomes weak, and slippage between polymer molecules tends to occur during stretching. The brittleness improvement effect by stretching is reduced and it is not stable.
共重合体は必要に応じ、連鎖移動剤を添加した上記単量
体の混合物より通常のメタクリル樹脂の重合方法により
、例えばアゾビスイソブチロニトリルのようなラジカル
重合触媒により懸濁重合により製造できる。ＭＦＩ値が
０．５ｇ／分より小さいと、すなわち分子量が高くなる
と、加工性が劣り延伸用の原料フィルムまたはシートの
作製に押出し成形が適用できない。この場合には、例え
ばガラス板セル中で原料単量体混合物を重合するキャス
ト重合法が採用され、原料フィルムまたは ５
シートが作製される。The copolymer can be produced by suspension polymerization using a radical polymerization catalyst such as azobisisobutyronitrile, for example, from a mixture of the above-mentioned monomers to which a chain transfer agent is added, if necessary, according to a conventional methacrylic resin polymerization method. . When the MFI value is less than 0.5 g/min, that is, when the molecular weight is high, the processability is poor and extrusion molding cannot be applied to produce a raw material film or sheet for stretching. In this case, for example, a cast polymerization method is employed in which a raw material monomer mixture is polymerized in a glass plate cell, and a raw material film or 5 sheet is produced.
共重合体に、本発明の効果を損わない範囲で、可塑剤、
着色剤、紫外線吸収剤、酸化防止剤おＪ：び滑剤などの
樹脂改質剤を添加、あるいは他の樹脂をブレンドするこ
とができる。A plasticizer, a copolymer, to the extent that the effects of the present invention are not impaired,
Resin modifiers such as colorants, ultraviolet absorbers, antioxidants, and lubricants may be added, or other resins may be blended.
特に耐候性が要求される場合紫外線吸収剤の添加が有効
であり、ベンゾトリアゾール系、ベンゾフェノン系の紫
外線吸収剤を０．００５〜３重景％用いるのがよい。In particular, when weather resistance is required, it is effective to add an ultraviolet absorber, and it is preferable to use a benzotriazole-based or benzophenone-based ultraviolet absorber in an amount of 0.005 to 3%.
ブレンドする樹脂としてはポリフッ化ビニリデンなどが
挙げられる。Examples of the resin to be blended include polyvinylidene fluoride.
本発明のフィルムまたはシートは、両方向のオリエンテ
ーションリリースストレス（以下、ＯＲ８と略記する）
が３〜３０Ｋｇ／Ｃｌ１１２の範囲の二軸延伸物である
必要があり、特に５〜２０Ｋｇ／Ｃｌ１１２のものが好
ましい。これによって脆性が改良される。The film or sheet of the present invention has a bidirectional orientation release stress (hereinafter abbreviated as OR8).
It is necessary that the biaxially drawn product has a value of 3 to 30 Kg/Cl112, and particularly preferably 5 to 20 Kg/Cl112. This improves brittleness.
ＯＲ８は、延伸物の配向した分子が配向前の状態に戻ろ
うとする応力と定義され、延伸の程度を表すパラメータ
ーである。ＯＲ８が３ Ｋｇ／ｃｍ２未満では脆性の改
良が不十分で、実用的な機械的強度が −
不足し５、取扱中に容易に破断する。また３ ０ Ｋｇ
／ｃｍ・７をこえた場合、引裂き強度が弱いものとなる
。OR8 is defined as the stress by which the oriented molecules of the stretched product try to return to the state before orientation, and is a parameter representing the degree of stretching. If OR8 is less than 3 Kg/cm2, the improvement in brittleness is insufficient, practical mechanical strength is insufficient5, and the material is easily broken during handling. Also 30 kg
/cm·7, the tear strength becomes weak.
本発明のフィルムまたはシートは、未延伸フィＩＩｌ、
またはシートを、延伸可能な温度に加温し、同時二軸延
伸法、逐次二軸延伸法あるいはインフレーション法等に
にり延伸して製造される。The film or sheet of the present invention comprises an unstretched film,
Alternatively, the sheet can be produced by heating the sheet to a temperature at which it can be stretched, and stretching it by a simultaneous biaxial stretching method, a sequential biaxial stretching method, an inflation method, or the like.
未延伸フィルムまたはシートは、例えば懸濁重合によｌ
］製造された樹脂を押出成形することにより作製でき、
またＭ Ｆ Ｉが０．５ｇ／分Ｊ、り小さい場合、キャ
スト重合により作製できる。押出温度は樹脂の４１量体
絹成等により君干異なるが大体２３０〜２６０ ℃が使
用される。The unstretched film or sheet can be processed by, for example, suspension polymerization.
] Can be produced by extrusion molding the manufactured resin,
Further, when M F I is smaller than 0.5 g/min J, it can be produced by cast polymerization. The extrusion temperature varies depending on the 41-mer silk composition of the resin, etc., but is generally 230 to 260°C.
延伸温唯は、大体１３０−１７０°Ｃの範囲、づなわち
樹脂のガラス転移温度（’ｒ ｇ ）より１０〜４０゛
（”高い）ｎ度が好ましく使用される。延伸温度が低４
きると、大きな延伸荷重が必要でまた延伸物のＱ ｌ’
？、 Ｓが大きすぎたものとなり、更にｆｇいと破断り
、−Ｃ延伸できない。延伸温度が高ずぎた場合、延伸ｌ
、うが生じ、またＯＲ３が低く脆性改良の不十分なもの
となる。The stretching temperature is preferably in the range of 130-170°C, that is, 10-40° (higher) than the glass transition temperature ('r g ) of the resin.
When the stretched material is stretched, a large stretching load is required and the Q l'
? , S becomes too large, and furthermore, it breaks at fg and cannot be stretched by -C. If the stretching temperature is too high, the stretching l
, porosity occurs, and OR3 is low, resulting in insufficient brittleness improvement.
延伸倍率は一方向１．３〜３．０倍がよい。延伸倍率が
小さすきると延伸効果が発現ゼず、ＯＲ８が低く脆性の
劣るものしか得られない。また大きすぎると破断しやす
く、破断しない場合もＯＲ８の大きすきたものとなる。The stretching ratio is preferably 1.3 to 3.0 times in one direction. If the stretching ratio is too small, the stretching effect will not be exhibited, and only a material with a low OR8 and poor brittleness will be obtained. Also, if it is too large, it will easily break, and even if it does not break, it will have a large OR8.
延伸速度は１００〜５０００％／分がよい。遅ずきると
配向緩和によりＯＲ８が小さいものとなり、また速１き
た場合延伸中破断しやすい。The stretching speed is preferably 100 to 5000%/min. If the stretching is done too late, the OR8 will be small due to orientation relaxation, and if the stretching is done at a speed of 1, the stretching will be prone to breakage.
本発明に使用の樹脂は非品性であり、延伸終了復長時間
延伸温瓜■におくと配向緩和が無視てきす、５分以内に
は゛ｒｇ以下の温度に冷却すべきである。The resin used in the present invention is of poor quality, and if it is left in the stretching warmer for a long time to recover after stretching, the relaxation of orientation will be ignored, and it should be cooled to a temperature below ゛rg within 5 minutes.
本発明の延伸物を光学式のコンパクトデスクあるいはレ
ーザーデスクの保護に使用する場合には、光路差が大き
いと正常に再生されず、小さい必要がある。本発明の延
伸物は本質的に複屈折性が小さく好ましい。特に光路差
が１．５ｎｍ以下であることが好ましく、このにうなも
のは、例えば二軸両方向の延伸倍率が等しい同時二軸延
伸に代表されるバランス延伸により容易に作製できる。When the stretched product of the present invention is used to protect an optical compact disk or a laser disk, if the optical path difference is large, normal reproduction will not be possible, so the difference must be small. The stretched product of the present invention preferably has essentially low birefringence. In particular, it is preferable that the optical path difference is 1.5 nm or less, and such a film can be easily produced, for example, by balance stretching, typified by simultaneous biaxial stretching in which the stretching ratios in both directions are equal.
本発明の延伸物の厚みは本質的に制限されるものではな
いが、生産性から２５μ〜１ｍｍが作りやすい。Although the thickness of the stretched product of the present invention is not essentially limited, it is easy to make a thickness of 25 μm to 1 mm from the viewpoint of productivity.
２５μ未満ては延伸中破断しやずく、この場合的の樹脂
のフィルムを補強フィルムとして弱くラミネートし、−
緒に延伸し、たのち剥がす方法を用いるのがよい。If it is less than 25 μm, it will break during stretching, so in this case, a weakly laminated resin film is used as a reinforcing film.
It is preferable to use a method in which the film is stretched along with the film and then peeled off.
また１ｎ＋ｍをこえるシートの製造においては、原料シ
ー１−の厚みが厚くなり、オーブン中にセットしても原
料シートの内部まで延伸温度に到達するのに時間を要し
、生産性が低下する。例えば５ｍｉのシートを延伸する
場合、１５分以上加熱するのが望ましい。Further, in the production of sheets exceeding 1n+m, the thickness of the raw material sheet 1- increases, and even if it is set in an oven, it takes time for the interior of the raw material sheet to reach the drawing temperature, resulting in a decrease in productivity. For example, when stretching a 5 mm sheet, it is desirable to heat the sheet for 15 minutes or more.
尚、本発明においては２５４μ未満の厚みのものをフィ
ルム、２５４μ以」二のものをシートと区別した。In the present invention, those with a thickness of less than 254μ are classified as films, and those with a thickness of 254μ or more are classified as sheets.
以下に発明の説明において用いた物性値の測定方法を示
す。The method for measuring physical property values used in the description of the invention will be shown below.
・Ｏ）マＳ：ＡＳＴＭ Ｄ１５０４により測定した。・O) MaS: Measured according to ASTM D1504.
・ＭＦＩ：ＡＳＴＭ Ｄ１２３８（Ｉ条件）により測
定した。- MFI: Measured according to ASTM D1238 (I conditions).
・吸）Ｂ肢張率 ８０ ℃の温風循環式乾無機で２４時
間乾無した試料を、２３°Ｃ１９５％湿度の環境に４８
時間おいたときの膨張率を求めた。・耐折強度：被測定
物を］。５ｍＩＱ幅の短冊にして、ＭＩＴ型耐折疲労試
験機（東洋精機（株）製、折曲げ速度３０回／分）によ
り破断するまでの折曲げ回数を求めた。・B) Limb tensile modulus A sample that had been dried for 24 hours in a hot air circulating dry inorganic at 80°C was placed in an environment of 23°C and 195% humidity for 48 hours.
The expansion rate after a period of time was determined. - Folding strength: measured object]. A strip having a width of 5 mIQ was made, and the number of times it was bent until it broke was determined using an MIT type folding fatigue tester (manufactured by Toyo Seiki Co., Ltd., bending speed: 30 times/min).
光路差測定法：偏光顕微鏡（日本光学工業（株）製、Ｌ
Ａ口０ＰＨＯＴ−Ｐｏｔ）を使用し測定した。Optical path difference measurement method: Polarizing microscope (manufactured by Nippon Kogaku Kogyo Co., Ltd., L
Measurement was performed using A-port 0 PHOT-Pot).
［実施例］ 本発明を実施例にＪ：り具体的に説明する。[Example] The present invention will be specifically explained using Examples.
実施例１
メタクリル酸メチル６５重量％とメタクリル酸シクロヘ
キシル３５重量％の単量体混合物から共重合して得られ
たメタクリル系樹脂（λｆＦＩ：２゜５ ｇ ／ １０
分）を、シリンダー径２０ｍｍの押出成形機で成形し４
００〃の厚みのシートを作製した。Example 1 Methacrylic resin obtained by copolymerizing a monomer mixture of 65% by weight of methyl methacrylate and 35% by weight of cyclohexyl methacrylate (λfFI: 2°5 g/10
) was molded using an extrusion molding machine with a cylinder diameter of 20 mm.
A sheet having a thickness of 0.00 mm was produced.
パンタグラフ式延伸試験機（東洋精機（株）製）０
を用い、１４５°Ｃの延伸温度、一方向２倍の延伸倍率
で同時二軸延伸を行なった。延伸速度は１０００％／分
であり、延伸終了後２０秒以内に延伸物を冷風でＴｇ以
下の温度まで冷却した。Simultaneous biaxial stretching was performed at a stretching temperature of 145°C and a stretching ratio of 2 times in one direction using a pantograph type stretching tester (manufactured by Toyo Seiki Co., Ltd.). The stretching speed was 1000%/min, and the stretched product was cooled to a temperature below Tg with cold air within 20 seconds after the stretching was completed.
吸湿膨張率は０．１５％であった。またＯＲ３値は、縦
横１２ Ｋｇ／ｃｍ２であり、脆性改良の指標となる耐
折性も、未延伸フィルムが最初の折り曲げによって破損
するのに比べ、縦横とも約２５回以上と大きく改良され
た。The hygroscopic expansion rate was 0.15%. In addition, the OR3 value was 12 Kg/cm2 in the length and width, and the folding durability, which is an indicator of brittleness improvement, was significantly improved to about 25 times or more in both the length and width, compared to the unstretched film which breaks at the first bend.
このフィルムにコンパクトデスクの内周部と外周部のみ
貼着されるように部分的に糊をつけコンパクトデスクに
張りつけた。このものを２５°Ｃで４０％の湿度から９
０％の湿度まで変化させたがシワは発生しなかった。This film was partially coated with glue and attached to the compact desk so that only the inner and outer peripheries of the compact desk were attached. 9 from 40% humidity at 25°C.
Even when the humidity was changed to 0%, wrinkles did not occur.
一方１２０μのトリアセチルセルロース樹脂のフィルム
（フジタック（富士写真フィルム（株）製）を同様に張
りつけたものは上記の湿度変化でシワが生じた。このフ
ィルムの吸湿膨張率は０゜６％であった。On the other hand, when a 120 μm triacetyl cellulose resin film (Fujitac (manufactured by Fuji Photo Film Co., Ltd.) was pasted in the same way, wrinkles appeared due to the above humidity change. The hygroscopic expansion coefficient of this film was 0°6%. Ta.
実施例２
１
メタクリル酸メチル７０重量％とメタクリル酸シクロヘ
キシル３０重量％の単量体混合物から共重合して得られ
たメタクリル系樹脂（ＭＦ工二６゜５ｇ／１０分）から
実施例１と同様の条件で厚みが４００μの未延伸シート
を作製した。これから実施例１に使用した延伸試験機に
より、１４５°Ｃの延伸温度で、最初の方向を２倍に延
伸し次にその直角方向を２，２倍に延伸する逐次二軸延
伸法により延伸フィルムを作製した。延伸速度は１００
０％／分であり、延伸終了後２０秒以内に延伸物を冷風
でＴｇ以下の温度まで冷却した。Example 2 1 Same as Example 1 from a methacrylic resin obtained by copolymerizing a monomer mixture of 70% by weight of methyl methacrylate and 30% by weight of cyclohexyl methacrylate (MF Koji 6°5 g/10 minutes). An unstretched sheet with a thickness of 400 μm was produced under the following conditions. A stretched film was then produced using the stretching testing machine used in Example 1 at a stretching temperature of 145°C and a sequential biaxial stretching method in which the initial direction was stretched twice and then the perpendicular direction was stretched 2.2 times. was created. Stretching speed is 100
The stretched product was cooled to a temperature below Tg with cold air within 20 seconds after the stretching was completed.
吸湿膨張率が０．２％で、ＯＲ３値がｍ １０ Ｋｇ／
Ｃ１１］２、横１５ Ｋｇ／ｃｍ２であった。耐折強度
が縦２０回、横３５回であり、吸湿寸法安定性と機械的
強度に優れたフィルムであった。The hygroscopic expansion coefficient is 0.2% and the OR3 value is m 10 Kg/
C11]2 and 15 Kg/cm2 in width. The film had a folding strength of 20 times vertically and 35 times horizontally, and was excellent in moisture absorption dimensional stability and mechanical strength.
このフィルムをコンパクトデスクに張り付は実施例１と
同様のテストを行なったがシワの発生は認められなかっ
た。The same test as in Example 1 was conducted to apply this film to a compact desk, but no wrinkles were observed.
比較例１
メタクリル酸メチル９４重量％、アクリル酸メ２
チル６重量％の単量体混合物から共重合して得られたメ
タクリル系樹脂（ＭＦＩ ： １．５ｇ／ｌ ０分）か
ら実施例１と同様にして、厚さ４００μの未延伸シート
を作製した。実施例１と同様にして１３５°Ｃの延伸温
度、一方向２倍の延伸倍率で同時二軸延伸を行ない、縦
横のＯＲ８値が１３ Ｋｇ／ｃｌ！１２の延伸物を得た
。Comparative Example 1 Example 1 and methacrylic resin (MFI: 1.5 g/l 0 min) obtained by copolymerizing a monomer mixture of 94% by weight of methyl methacrylate and 6% by weight of methyl acrylate were prepared. In the same manner, an unstretched sheet with a thickness of 400 μm was produced. Simultaneous biaxial stretching was carried out in the same manner as in Example 1 at a stretching temperature of 135°C and a stretching ratio of 2 times in one direction, and the OR8 value in the longitudinal and lateral directions was 13 Kg/cl! 12 drawn products were obtained.
延伸物は、耐折強度が約４０回と機械的強度が良好であ
ったが、実施例１と同様にして求めた吸湿膨張率は０．
４％と劣っていた。The stretched product had good mechanical strength with a folding strength of approximately 40 times, but the hygroscopic expansion rate determined in the same manner as in Example 1 was 0.
It was inferior at 4%.
このフィルムをコンパクトデスクに張り付は実施例１と
同様のテストを行なったがシワが発生した。The same test as in Example 1 was carried out to apply this film to a compact desk, but wrinkles occurred.
比較例２
メタクリル酸メチル９４重量％、メタクリル酸シクロヘ
キシル３重量％、アクリル酸メチル３重量％の単量体混
合物から共重合して得られたメタクリル系樹脂（ＭＦ
Ｉ ： ２．０ ｇ／ｌ ０分）から、厚さ４００μの
未延伸シートを作製した。実施例１と同様にして１４０
°Ｃの延伸温度、一方向２倍の延伸倍率で同時二軸延伸
を行ない、縦横のＯＲ８値が１０ Ｋｇ／ｃｍ２の延伸
物を得た。Comparative Example 2 A methacrylic resin (MF
I: 2.0 g/l 0 minutes), an unstretched sheet with a thickness of 400 μm was prepared. 140 in the same manner as in Example 1
Simultaneous biaxial stretching was carried out at a stretching temperature of °C and a stretching ratio of 2 times in one direction to obtain a stretched product having an OR8 value of 10 Kg/cm2 in the longitudinal and lateral directions.
延伸物は、耐折強度が約３０回と機械的強度が良好であ
ったが、実施例１と同様にして求めた吸湿膨張率は０．
４％であり、改良が認められなかった。The stretched product had good mechanical strength with a folding strength of about 30 times, but the hygroscopic expansion rate determined in the same manner as in Example 1 was 0.
4%, and no improvement was observed.
このフィルムをコンパクトデスクに張り付は実施例１と
同様のテストを行なったがシワが発生した。The same test as in Example 1 was carried out to apply this film to a compact desk, but wrinkles occurred.
実施例３
実施例１に使用の樹脂から２００μの未延伸フィルムを
押出成形により作製した。これから延伸倍率のみ一方向
１，５倍に変えて実施例】の方法により延伸フィルムを
作製した。吸湿膨張率が０１５％で、ＯＲ３値が縦横５
Ｋｇ／ｃｍ２．耐折強度が約６回と、吸湿寸法安定性
と機械的強度が改良されたフィルムであった。Example 3 A 200μ unstretched film was produced from the resin used in Example 1 by extrusion molding. From this, a stretched film was produced by the method of Example except that the stretching ratio was changed to 1.5 times in one direction. The hygroscopic expansion rate is 0.15% and the OR3 value is 5 in the vertical and horizontal directions.
Kg/cm2. The film had a folding strength of about 6 times, and had improved moisture absorption dimensional stability and mechanical strength.
実施例４
実施例１において延伸倍率のみ一方向２．５倍に変えて
延伸フィルムを作製した。吸湿膨張率が４
０１５％で、ＯＲ８値が縦横２０ Ｋｇ／ｃｍ２、耐折
強度が約４０回と、吸）Ｊ寸法安定性と機械的強度が改
良されたフィルムであった。Example 4 A stretched film was produced in Example 1 except that the stretching ratio was changed to 2.5 times in one direction. The film had a hygroscopic expansion coefficient of 4015%, an OR8 value of 20 Kg/cm2 in the vertical and horizontal directions, and a folding strength of about 40 times, and had improved dimensional stability and mechanical strength.
比較例３
実施例１に使用の樹脂より実施例１の押出方法により、
厚みが１００μの未延伸シートを作製した。このものに
ＯＲ８は認められず（ＯＫｇ／ｃｍ２）１、耐折強度は
最初の折り曲げて破断（０回）し、取扱中容易に破断す
る脆いものであった。Comparative Example 3 From the resin used in Example 1, by the extrusion method of Example 1,
An unstretched sheet having a thickness of 100 μm was prepared. OR8 was not observed in this product (OKg/cm2) 1, and the folding strength was that it broke at the first bending (0 times) and was brittle and easily broke during handling.
比較例４
実施例３において延伸倍率のみ一方向１．２倍に変えて
延伸フィルムを作製した。このもののＯＲ８は２ Ｋｇ
／ｃｍ”であり、耐折強度は最初の折り曲げて破断く０
回）し、取扱中容易に破断した。Comparative Example 4 A stretched film was produced in Example 3 except that the stretching ratio was changed to 1.2 times in one direction. The OR8 of this item is 2 Kg.
/cm", and the bending strength is 0 when it breaks at the first bend.
times) and easily broke during handling.
実施例５
実施例１と組成の同じ単量体混合物より、キャスト重合
によりＭＦＩが０．１ｇ／１０分の１２００μの未延伸
シートを作製した。このシートを１６０ ”Ｑで１０分
間予熱復一方向２倍の延伸倍率で実施例１と同様にして
同時二軸延伸して３００５
μの延伸シーＩ・を作製した。吸湿膨張率は０８１５％
であり、縦横のＯＲ８値が１０ Ｋｇ／ｃｍ’≧で、吸
湿寸法安定性、機械的強度が良好な延伸物であった。Example 5 From a monomer mixture having the same composition as in Example 1, an unstretched sheet with an MFI of 0.1 g/10/1200 μ was produced by cast polymerization. This sheet was preheated for 10 minutes at 160"Q, and then biaxially stretched simultaneously at a stretching ratio of 2 times in one direction in the same manner as in Example 1 to produce a stretched sheet I of 3005 μm.The hygroscopic expansion rate was 0815%.
The OR8 value in the longitudinal and lateral directions was 10 Kg/cm'≧, and the stretched product had good moisture absorption dimensional stability and mechanical strength.
比較例５
実施例」の組成でＭＦＩが２５ｇ／１０分の樹脂から、
実施例１と同様の方法により、延伸フィルムを作製した
。耐折強度が、０〜２０回と場所による差が大きい、機
械的強度に再現性のない延伸物であった。Comparative Example 5 From the resin with the composition of “Example” and an MFI of 25 g/10 minutes,
A stretched film was produced in the same manner as in Example 1. The stretched product had a bending resistance of 0 to 20 times, which varied greatly depending on the location, and the mechanical strength was not reproducible.
実施例６
メタクリル酸メチル５０重量％、メタクリル酸シクロヘ
キシル４７重量％、アクリル酸メチル３重量％の単量体
混合物から共重合して得られたメタクリル系樹脂（ＭＦ
Ｉ ： ２．０ｇ７１０分）から、延伸温度のみ１５０
°Ｃに変えて実施例１と同様にして同時二軸延伸を行な
い延伸フィルムを作製した。吸湿膨張率が０．１％で、
ＯＲ３値が縦横１０ Ｋｇ／ｃｍ２、耐折強度が約１０
回と、吸湿寸法安定性と機械的強度が改良されたフィル
ムであ６
った。Example 6 A methacrylic resin (MF
I: 2.0g 710 minutes), stretching temperature only 150
A stretched film was produced by simultaneous biaxial stretching in the same manner as in Example 1 except that the temperature was changed to °C. The hygroscopic expansion rate is 0.1%,
OR3 value is 10 kg/cm2 in length and width, folding strength is approximately 10
It was a film with improved moisture absorption dimensional stability and mechanical strength.
実施例７
メタクリル酸メチル８５重量％、メタクリル酸シクロヘ
キシル１５重量％の単量体混合物から共重合して得られ
たメタクリル系樹脂（ＭＦＩ・２゜０ｇ／］、０分）か
ら、実施例］と同様にして同時二軸延伸を行ない延伸フ
ィルムを作製した。吸湿膨張率が０．３％で、ＯＲ６値
が縦横１２ Ｋｇ／ｃｍ２耐折強度が約３０回と、吸湿
寸法安定性と機械的強度が改良されたフィルムであった
。Example 7 From a methacrylic resin (MFI 2°0 g/], 0 minutes) obtained by copolymerizing a monomer mixture of 85% by weight of methyl methacrylate and 15% by weight of cyclohexyl methacrylate, Simultaneous biaxial stretching was performed in the same manner to produce a stretched film. The film had a hygroscopic expansion coefficient of 0.3%, an OR6 value of 12 Kg/cm2 in the vertical and horizontal directions, and a bending strength of about 30 times, indicating that the dimensional stability after hygroscopic absorption and the mechanical strength were improved.
実施例８
メタクリル酸メチル７５重量％、メタクリル酸シクロヘ
キシル１０重量％、メタクリル酸トリブロムフェニル１
０重量％、アクリル酸メチル５重量％の単量体混合物か
ら共重合して得られたメタクリル系樹脂（ＭＦＩ ：
３．５ｇ／１０分）から、延伸温度のみ１５０℃に変え
て実施例１と同様にして同時二軸延伸を行ない延伸フィ
ルムを作製した。吸湿膨張率が０．２％で、ＯＲ３値が
縦横１０Ｋｇ／Ｃｌ１１２、耐折弛度が約２０回と、吸
湿寸法安定性と機械的強度が改良されたフィルムであっ
た。Example 8 Methyl methacrylate 75% by weight, cyclohexyl methacrylate 10% by weight, tribromphenyl methacrylate 1
Methacrylic resin (MFI:
3.5 g/10 minutes), simultaneous biaxial stretching was performed in the same manner as in Example 1 except that only the stretching temperature was changed to 150° C. to produce a stretched film. The film had a hygroscopic expansion coefficient of 0.2%, an OR3 value of 10 Kg/Cl112 in the length and width, and a folding resistance of about 20 times, and thus had improved hygroscopic dimensional stability and mechanical strength.
実施例９
実施例１に使用の樹脂から４８０μの未延伸シートを作
製し、一方向２倍の倍率で同時二軸延伸し、１２０μの
厚みの延伸フィルムを作製した。Example 9 An unstretched sheet of 480 μm was prepared from the resin used in Example 1, and simultaneously biaxially stretched in one direction at a magnification of 2 times to produce a stretched film of 120 μm thick.
吸湿膨張率は縦横両方向とも０．１５％であった。The hygroscopic expansion coefficient was 0.15% in both the vertical and horizontal directions.
ＯＲ３が縦横１５ ｋｇ／ｃｍ”であり、耐折強度が１
５回以上と機械的強度に優れていた。また、光路差はな
く測定誤差範囲内（３％ｍ）であった。このフィルムに
コンパクトデスクの内周部と外周部のみ貼着されるよう
に部分的に糊をつけコンパクトデスクに張りつけた。こ
れをコンパクトデスクプレーヤーて再生したが特に異常
はな変かった。OR3 is 15 kg/cm” in length and width, and folding strength is 1
The mechanical strength was excellent as it was tested 5 times or more. Further, there was no optical path difference and it was within the measurement error range (3% m). This film was partially coated with glue and attached to the compact desk so that only the inner and outer peripheries of the compact desk were attached. I played this on a compact desk player and found nothing unusual.
一方縦１．５倍、横３倍の倍率で同時二軸延伸した光路
差が３０ｎｍのフィルムを同様に保護フィルムとして用
いたが再生できなかった。On the other hand, a film with an optical path difference of 30 nm that was simultaneously biaxially stretched at a magnification of 1.5 times in length and 3 times in width was similarly used as a protective film, but could not be reproduced.
以下余白
８
［発明の効果］
メタクリル酸シクロヘキシルを重合成分とするメタクリ
ル系樹脂の二軸延伸フィルムまたはシートにより、透明
性、吸湿寸法安定性、機械的強度に優れたフィルムまた
はシートが得られた。これらは吸湿寸法安定性が必要な
光学分野の保護フィルムあるいはシートとしての用途、
例えば光学式のコンパクトデスクあるいはレーザーデス
クの保護フィルムまたはシートとして一一一優れている
。Margin 8 below [Effects of the Invention] A biaxially stretched film or sheet of a methacrylic resin containing cyclohexyl methacrylate as a polymerization component provided a film or sheet with excellent transparency, moisture absorption dimensional stability, and mechanical strength. These are used as protective films or sheets in the optical field that require moisture absorption and dimensional stability.
For example, it is excellent as a protective film or sheet for optical compact desks or laser desks.
Claims (3)
メタクリル酸シクロヘキシル単位５〜６０重量％からな
り、メルトフローインデックスが１２ｇ／１０分以下で
あるメタクリル系共重合体樹脂のフィルムまたはシート
状の二軸延伸物であって、二軸両方向のオリエンテーシ
ョンリリースストレスが３〜３０Ｋｇ／ｃｍ＾２の範囲
にある延伸物。(1) Biaxial film or sheet of methacrylic copolymer resin consisting of 95 to 40% by weight of methyl methacrylate units and 5 to 60% by weight of cyclohexyl methacrylate units and having a melt flow index of 12 g/10 minutes or less A stretched product having orientation release stress in both directions of two axes in the range of 3 to 30 Kg/cm^2.
料を、２３℃、９５％湿度の環境に４８時間おいたとき
の吸湿膨張率が０．２％以内である請求項１に記載の延
伸物。(2) Claim 1, wherein the sample dried for 24 hours in a warm air circulation dryer at 80°C has a hygroscopic expansion coefficient of 0.2% or less when left in an environment of 23°C and 95% humidity for 48 hours. Stretched product as described.
の延伸物。(3) The stretched product according to claim 1 or 2, wherein the optical path difference is within 15 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8555690A JPH03281220A (en) | 1990-03-29 | 1990-03-29 | Oriented material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8555690A JPH03281220A (en) | 1990-03-29 | 1990-03-29 | Oriented material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03281220A true JPH03281220A (en) | 1991-12-11 |
Family
ID=13862097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8555690A Pending JPH03281220A (en) | 1990-03-29 | 1990-03-29 | Oriented material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03281220A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002331576A (en) * | 2001-05-11 | 2002-11-19 | Kanegafuchi Chem Ind Co Ltd | Optical film |
| US6716505B2 (en) | 2001-08-31 | 2004-04-06 | General Electric Company | Storage medium for data with improved dimensional stability |
-
1990
- 1990-03-29 JP JP8555690A patent/JPH03281220A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002331576A (en) * | 2001-05-11 | 2002-11-19 | Kanegafuchi Chem Ind Co Ltd | Optical film |
| US6716505B2 (en) | 2001-08-31 | 2004-04-06 | General Electric Company | Storage medium for data with improved dimensional stability |
| US6893700B2 (en) | 2001-08-31 | 2005-05-17 | General Electric Company | Storage medium for data with improved dimensional stability |
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