JP2000265136A - Film for protecting coated film on automotive car - Google Patents
Film for protecting coated film on automotive carInfo
- Publication number
- JP2000265136A JP2000265136A JP6734999A JP6734999A JP2000265136A JP 2000265136 A JP2000265136 A JP 2000265136A JP 6734999 A JP6734999 A JP 6734999A JP 6734999 A JP6734999 A JP 6734999A JP 2000265136 A JP2000265136 A JP 2000265136A
- Authority
- JP
- Japan
- Prior art keywords
- film
- weight
- polyisobutylene
- undercoat layer
- layer
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は自動車塗膜保護用フ
ィルムに係り、特に表面に塗膜が形成された自動車の曲
面に接着作業性に優れ、塗膜の表面保護に優れた自動車
塗膜保護用フィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for protecting a paint film of an automobile, and more particularly to a paint film having excellent workability for bonding to a curved surface of an automobile having a paint film formed on the surface thereof and excellent protection of the paint film surface. Related to film.
【０００２】[0002]
【従来の技術】表面に塗膜が形成された自動車をトラッ
クや船に積載して遠隔地や海外等に輸送する場合、ある
いは屋外に保管する場合、酸性雨、砂塵、ホコリ、鉄
粉、ガス等により塗膜が損傷する問題や太陽光線による
塗膜の光沢変化、変色などの外観劣化による商品価値の
低下が問題となっている。これらの弊害を防止するた
め、従来、自動車業界では塗装表面の保護に油性あるい
は水性ワックス系塗膜保護剤が用いられてきた。ところ
がこれら塗膜保護剤は鉄粉等の付着、鳥の糞や酸性雨に
よる塗膜汚染に十分な保護効果が得られない等の問題点
があり、さらにワックス自体の除去の際発生する排水に
よる公害や処理費用等の問題がある。これらの解決に最
近、自動車塗膜用保護フイルムが開発されている。しか
し、これらの自動車用保護フイルムを長期間使用の場合
には自動車の塗膜面に糊残りなどの問題が起こることが
ある。更に自動車の様な大面積に自動車用保護フイルム
を使用した場合、使用後の自動車用保護フイルムを剥が
す時にフイルムが引き裂けてしまい作業性が劣るという
問題がある。2. Description of the Related Art When an automobile having a coating film formed on its surface is loaded on a truck or ship and transported to a remote place or overseas, or stored outdoors, acid rain, sand, dust, dust, iron powder, gas, etc. Thus, there is a problem that the coating film is damaged due to the above-mentioned factors, and a reduction in commercial value due to deterioration in appearance such as a change in gloss and discoloration of the coating film due to sunlight. In order to prevent these adverse effects, oil-based or water-based wax-based coating film protective agents have been used in the automotive industry to protect painted surfaces. However, these coating film protective agents have problems such as adhesion of iron powder and the like, and insufficient effect of protecting the coating film from bird droppings and acid rain. There are problems such as pollution and disposal costs. To solve these problems, protective films for automotive coatings have recently been developed. However, when these automotive protective films are used for a long period of time, problems such as adhesive residue may occur on the coating surface of the automobile. Further, when the protective film for an automobile is used in a large area such as an automobile, there is a problem that the film is torn when the protective film for an automobile is peeled off after use, resulting in poor workability.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、支持フイル
ムとの接着性に優れ、支持基材および粘着剤の耐光性の
低下による粘着剤の被着体への糊残りがなく、また長期
間圧着しても被着体の塗膜面を汚染することがなく、ま
た再剥離時にフイルムが裂けるという不具合が無く、更
には小石等の落下による塗膜面の傷付きを防止すること
ができる自動車塗膜保護用フィルムを提供することを目
的とする。DISCLOSURE OF THE INVENTION The present invention has excellent adhesiveness to a support film, has no adhesive residue on an adherend due to a decrease in light resistance of the support base material and the adhesive, and has a long term An automobile that does not contaminate the coating surface of the adherend even when pressed, does not have the problem of tearing the film upon re-peeling, and can prevent the coating surface from being damaged by falling pebbles An object of the present invention is to provide a film for protecting a paint film.
【０００４】[0004]
【課題を解決するための手段】上記した目的は，エチレ
ン・αオレフィン共重合体を２．５〜４０重量％、ポリ
エチレンを５〜４０重量％含有するポリプロピレン系組
成物から形成される支持フィルム上に、ポリイソブチレ
ン、Ａ−Ｂ−Ａ型ブロックポリマ−、およびイソシアネ
−トを含む下塗層を設け、該下塗層面にポリイソブチレ
ンを主成分とする粘着剤層を設けたことを特徴とする自
動車塗膜保護用フィルムによって達成される。また、前
記支持フィルムの粘着剤層を設けた面と反対側の面に長
鎖アルキル型離型剤を含む離型層を設けることが望まし
い。さらに前記支持フィルムの全光線透過率が４０％以
下の白色であり、さらに耐光性安定剤の添加量が３重量
％以下である支持フィルムを用いることが望ましい。An object of the present invention is to provide a support film formed from a polypropylene-based composition containing 2.5 to 40% by weight of an ethylene / α-olefin copolymer and 5 to 40% by weight of polyethylene. An undercoat layer containing polyisobutylene, ABA type block polymer and isocyanate, and an adhesive layer containing polyisobutylene as a main component provided on the undercoat layer surface Achieved by a coating protection film. It is preferable that a release layer containing a long-chain alkyl release agent is provided on the surface of the support film opposite to the surface on which the pressure-sensitive adhesive layer is provided. Further, it is desirable to use a support film in which the total light transmittance of the support film is 40% or less in white and the amount of the light fastness stabilizer added is 3% by weight or less.
【０００５】[0005]
【発明の実施の形態】以下、本発明の好ましい実施の形
態について説明する。 ［支持フィルム］本発明において、支持フィルムはエチ
レン・αオレフィン共重合体を２．５〜４０重量％、ポ
リエチレンを５〜４０重量％含有するポリプロピレン系
組成物から形成される。ここで、エチレン・αオレフィ
ン共重合体の密度は０．８８以下が好ましく、より好ま
しくは、０．８７以下である。エチレン・αオレフィン
共重合体の密度が０．８８よりも大きいと、支持フィル
ムの引裂き等の強度向上が認められず好ましくない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. [Support Film] In the present invention, the support film is formed from a polypropylene composition containing 2.5 to 40% by weight of an ethylene / α-olefin copolymer and 5 to 40% by weight of polyethylene. Here, the density of the ethylene / α-olefin copolymer is preferably 0.88 or less, more preferably 0.87 or less. If the density of the ethylene / α-olefin copolymer is larger than 0.88, no improvement in strength such as tearing of the support film is observed, which is not preferable.
【０００６】エチレン・αオレフィン共重合体には、例
えば，市販品としてデュポン・ダウエラストマーズ社製
の「エンゲージ」、エクソンケミカル社製の「ＥＸＡＣ
Ｔ」シリーズ等を挙げることができるが、これらの中
で、特にフィルム物性改善効果の点からデュポン・ダウ
エラストマーズ社製の「エンゲージ」が望ましい。Examples of the ethylene / α-olefin copolymer include “Engage” manufactured by DuPont Dow Elastomers and “EXAC” manufactured by Exxon Chemical as commercial products.
T "series and the like. Among them," Engage "manufactured by DuPont Dow Elastomers is particularly desirable from the viewpoint of the effect of improving film physical properties.
【０００７】ポリエチレンには、低密度ポリエチレン、
高密度ポリエチレン、リニア低密度ポリエチレン等から
なるエチレン系ポリマー、エチレン・プロピレン共重合
体等が挙げられ、これらを１種または２種以上を用いる
ことができる。[0007] Polyethylene includes low density polyethylene,
Examples thereof include an ethylene-based polymer such as high-density polyethylene and linear low-density polyethylene, and an ethylene-propylene copolymer. One or more of these can be used.
【０００８】本発明において、ポリプロピレン系組成物
中には、エチレン・αオレフィン共重合体を２．５〜４
０重量％、好ましくは５〜３０重量％，より好ましくは
１０〜２０重量％含有する。ポリプロピレン系組成物中
のエチレン・αオレフィン共重合体の含有量が２．５重
量％未満であると、支持フィルムの引っ張り強度の改善
効果がなく、また、４０重量％を超えると、支持フィル
ムの強度低下と共に耐熱性が著しく低下してしまう。In the present invention, an ethylene / α-olefin copolymer contains 2.5 to 4
0 wt%, preferably 5 to 30 wt%, more preferably 10 to 20 wt%. When the content of the ethylene / α-olefin copolymer in the polypropylene-based composition is less than 2.5% by weight, there is no effect of improving the tensile strength of the support film. As the strength decreases, the heat resistance significantly decreases.
【０００９】さらにポリプロピレン系組成物中にポリエ
チレンを５〜４０重量％、好ましくは１０〜２５重量％
含有する。ポリプロピレンフィルム中のポリエチレンの
含有量が１０重量％未満であると耐寒性が低下し、低温
時作業性が乏しくなり、一方、４０重量％を超えると、
支持フィルムの耐熱性が低下してしまい好ましくない。Further, 5 to 40% by weight, preferably 10 to 25% by weight of polyethylene is contained in the polypropylene composition.
contains. When the content of polyethylene in the polypropylene film is less than 10% by weight, cold resistance is reduced, and workability at low temperature becomes poor. On the other hand, when the content exceeds 40% by weight,
The heat resistance of the support film is undesirably reduced.
【００１０】ポリプロピレン系組成物を構成するポリプ
ロピレンは、ポリプロピレンのホモポリマーやブロック
ポリマー、ランダムポリマー等が挙げられる。ポリプロ
ピレン系組成物には、上記したエチレン・αオレフィン
共重合体、ポリエチレン、ポリプロピレンの他に必要に
応じて性能向上のための耐候性向上剤、着色剤などの各
種添加剤を添加をしても良い。耐候性向上剤としては、
アミン系、キノリン系、ヒドロキノン系、フェノール
系、亜燐酸エステル系等の老化防止剤、酸化防止剤、又
はサリチル酸誘導体、ベンゾフェノン系、ベンゾトリア
ゾール系、ヒンダードアミン系等の紫外線吸収剤、光安
定剤等が挙げられ、特にヒンダードアミン系のものが相
溶性、耐候性の向上効果に優れることから好ましい。耐
候性向上剤の添加量は粘着剤への移行などの悪影響から
概ね５重量部以下が好ましい。The polypropylene constituting the polypropylene composition includes a homopolymer, a block polymer and a random polymer of polypropylene. To the polypropylene-based composition, in addition to the above-described ethylene / α-olefin copolymer, polyethylene, and polypropylene, if necessary, various additives such as a weather resistance improver for improving performance and a colorant may be added. good. As the weather resistance improver,
Amine-based, quinoline-based, hydroquinone-based, phenol-based, phosphite-based antioxidants, antioxidants, or salicylic acid derivatives, benzophenone-based, benzotriazole-based, hindered amine-based ultraviolet absorbers, light stabilizers, and the like. Hindered amine-based compounds are particularly preferred because they are excellent in improving the compatibility and weather resistance. The addition amount of the weather resistance improver is preferably about 5 parts by weight or less from adverse effects such as migration to the pressure-sensitive adhesive.
【００１１】支持フィルムは、該支持フィルムを介して
後述する下塗層、粘着剤層に到達する光の量を低減させ
ることが好ましく、かつ白色であることが望ましく、支
持フィルムを構成するポリプロピレン系形組成物中に配
合される着色剤としては、酸化チタン、炭酸カルシウ
ム、硫酸バリウム、酸化亜鉛等の隠蔽性の高い顔料が好
ましい。The support film preferably reduces the amount of light reaching the undercoat layer and the pressure-sensitive adhesive layer, which will be described later, via the support film, and is preferably white. As the coloring agent to be incorporated into the shaped composition, pigments having high concealing properties such as titanium oxide, calcium carbonate, barium sulfate, and zinc oxide are preferable.
【００１２】上記した全光線透過率とは、ＪＩＳ Ｋ６
７１８に基づく積方球式光線透過率測定器により測定し
た値を意味し、この全光線透過率の値が４０％以下が好
ましく、より好ましくは３５％以下である。全光線透過
率の値が４０％を超えると、下塗層、粘着剤層に到達す
る光の量が多くなり、 その分、下塗層および粘着剤層に
おける耐候性を配慮した組成が要求され、その他の特性
が損なわれるおそれがある。The above-mentioned total light transmittance refers to JIS K6
718 means a value measured by a square sphere light transmittance measuring instrument, and the value of the total light transmittance is preferably 40% or less, more preferably 35% or less. When the value of the total light transmittance exceeds 40%, the amount of light reaching the undercoat layer and the pressure-sensitive adhesive layer increases, and accordingly, a composition considering the weather resistance of the undercoat layer and the pressure-sensitive adhesive layer is required. And other characteristics may be impaired.
【００１３】支持フィルムの厚さは１０〜１５０μｍ、
好ましくは３０〜１００μｍ、より好ましくは４０〜５
０μｍである。支持フィルムの厚さが、１０μｍ未満で
は、塗装面のキズ付き防止効果が不充分となり、１５０
μｍを超えると、曲面への貼り付けがしずらい等作業性
が低下しやすい。The thickness of the supporting film is 10 to 150 μm,
Preferably from 30 to 100 μm, more preferably from 40 to 5
0 μm. If the thickness of the supporting film is less than 10 μm, the effect of preventing the painted surface from being scratched becomes insufficient,
If it exceeds μm, the workability tends to deteriorate, such as difficulty in sticking to a curved surface.
【００１４】［下塗層］次に支持フィルム上には下塗層
が設けられる。この下塗層はポリイソブチレン、Ａ−Ｂ
−Ａ型ブロックポリマ−、およびイソシアネ−トを含む
層である。下塗層におけるポリイソブチレンは，特に制
約はないが,粘着剤に使用している重量平均分子量で８
０万〜１２０万のものが好ましい。[Undercoat layer] Next, an undercoat layer is provided on the support film. This undercoat layer is made of polyisobutylene, AB
A layer containing an A-type block polymer and an isocyanate. Polyisobutylene in the undercoat layer is not particularly limited, but the weight average molecular weight used in the adhesive is 8%.
Those in the range of 100,000 to 1.2 million are preferable.
【００１５】下塗層においてポリイブチレンのみでは、
粘着剤と支持体フィルムとの投錨力が不充分なため粘着
剤と支持フィルム間の界面破壊や、長期間屋外で使用す
ると凝集力が低下し糊残りが発生する。本発明におい
て、Ａ−Ｂ−Ａ型ブロックポリマ−とは、少なくとも異
なる２種以上のビニルモノマーのポリマーにおいて、単
一種の重合体を１ブッロクとし、その末端に少なくと1
種以上の異種の重合体のブロックを連結したポリマーを
いう。これらのポリマーの中でも、下塗層にポリイソブ
チレンとの相溶性および支持フイルムとの接着性に優
れ、さらに耐光安定性の良い、Ａ−Ｂ−Ａ型ブロックポ
リマ−の水添タイプであるスチレン・エチレン・ブチレ
ン・スチレンブロックポリマ−（ＳＥＢＳ）、スチレン
・エチレン・プロピレン・スチレンブロックポリマ−
（ＳＥＰＳ）、カルボキシル化ＳＥＢＳブロックポリマ
−を用いることで前述した問題を解決できること、さら
にまたＡ−Ｂ−Ａ型ブロックポリマ−の水添タイプであ
るスチレン・エチレン・ブチレン・スチレンブロックポ
リマ−（ＳＥＢＳ）等に残存する反応基に注目し、イソ
シアネ−トを添加することで架橋が可能であり、支持フ
イルムとの接着性をより強固にすることができる事が判
った。In the undercoat layer, if only polybutylene is used,
Insufficient anchoring force between the pressure-sensitive adhesive and the support film causes interface destruction between the pressure-sensitive adhesive and the support film, and when used outdoors for a long period of time, reduces cohesion and generates adhesive residue. In the present invention, the ABA type block polymer is a polymer of at least two or more different types of vinyl monomers, a single type of polymer is defined as one block, and at least 1
A polymer in which two or more different kinds of polymer blocks are linked. Among these polymers, the undercoat layer has excellent compatibility with polyisobutylene and adhesion to a support film, and furthermore has excellent light stability, and is a styrene / hydrogenated ABA type block polymer. Ethylene / butylene / styrene block polymer (SEBS), styrene / ethylene / propylene / styrene block polymer
(SEPS) and the use of a carboxylated SEBS block polymer to solve the above-mentioned problems, and furthermore, a styrene / ethylene / butylene / styrene block polymer (SEBS) which is a hydrogenated type of ABA type block polymer. Attention was paid to the reactive groups remaining in (1) and the like, and it was found that crosslinking was possible by adding isocyanate, and the adhesion to the supporting film could be further enhanced.
【００１６】本発明において、イソシアネ−トとして
は、住友バイエルウレタン社製のデスモジュールＲ、デ
スモジュールＲＦ、デスモジュールＩＬ、デスモジュー
ルＲＦＥ等、住友化学工業社製のスミジュールＬ等が挙
げられる。In the present invention, examples of the isocyanate include Desmodule R, Desmodule RF, Desmodule IL and Desmodule RFE manufactured by Sumitomo Bayer Urethane Co., Ltd., and Sumidule L manufactured by Sumitomo Chemical Co., Ltd.
【００１７】ポリイソブチレンとＡ−Ｂ−Ａ型ブロック
ポリマ−の配合比率は、ポリイソブチレン１００重量部
に対してＡ−Ｂ−Ａ型ブロックポリマ−が１００重量部
〜４００重量部、より好ましくは２５０重量部〜３５０
重量部である。ポリイソブチレンに対するＡ−Ｂ−Ａ型
ブロックポリマ−の配合比率が１００重量部より少ない
場合、支持フィルムとの接着力が不充分となり、一方４
００重量部を超えると耐熱性の低下が大きくなり好まし
くない。さらにはＡ−Ｂ−Ａ型ブロックポリマ−に対す
るイソシアネートの添加量は、Ａ−Ｂ−Ａ型ブロックポ
リマ−１００重量部に対してイソシアネートが０．１重
量部〜１０重量部、好ましくは１．０重量部〜５．０重
量部である。Ａ−Ｂ−Ａ型ブロックポリマ−１００重量
部に対してイソシアネートが０．１重量部より少ない
と、下塗層と支持フィルムとの接着性が低下し、一方、
イソシアネートが１０重量部を超えると、未反応の成分
が塗装面に移行して汚染するおそれがある点で好ましく
ない。The mixing ratio of the polyisobutylene and the ABA type block polymer is such that the ABA type block polymer is 100 parts by weight to 400 parts by weight, more preferably 250 parts by weight, based on 100 parts by weight of the polyisobutylene. Parts by weight to 350
Parts by weight. When the mixing ratio of the ABA type block polymer to the polyisobutylene is less than 100 parts by weight, the adhesion to the support film becomes insufficient, and
If it exceeds 00 parts by weight, the heat resistance is greatly reduced, which is not preferable. Furthermore an A-B-A type block polymer - amount of isocyanate relative to the isocyanate 0.1 fold <br/> amount unit 10 parts by weight based on A-B-A type block polymer -100 parts by weight, Preferably it is 1.0 part by weight to 5.0 parts by weight. When the isocyanate is less than 0.1 part by weight based on 100 parts by weight of the ABA type block polymer, the adhesion between the undercoat layer and the support film is reduced,
If the amount of the isocyanate exceeds 10 parts by weight, unreacted components may migrate to the painted surface and become undesirably contaminated.
【００１８】下塗層には，上記した成分の他に下塗層の
長期安定性の点より、耐候性向上剤、老化防止剤、光安
定剤などを添加するのが好ましい。耐候性向上剤として
は、アミン系、キノリン系、ヒドロキノン系、フェノー
ル系、亜燐酸エステル等の老化防止剤、酸化防止剤、あ
るいはサリチル酸誘導体、ベンゾフェノン系、ベンゾト
リアゾール系、ヒンダードアミン系等の紫外線吸収剤、
光安定剤等が挙げられ、特にベンゾトリアゾール系の紫
外線吸収剤が相溶性、耐候性の向上効果に優れることか
ら好ましい。耐候性向上剤の添加量は０．５重量％〜５
重量％が好ましい。０．５重量％より少ないと性能が不
十分であり、５重量％を超えると吐出により塗装表面に
悪影響を及ぼす。It is preferable to add a weather resistance improver, an antioxidant, a light stabilizer and the like to the undercoat layer in addition to the above-mentioned components in view of the long-term stability of the undercoat layer. Examples of the weather resistance improver include amines, quinolines, hydroquinones, phenols, antioxidants such as phosphites, antioxidants, and ultraviolet absorbers such as salicylic acid derivatives, benzophenones, benzotriazoles, and hindered amines. ,
Light stabilizers and the like can be mentioned. In particular, a benzotriazole-based ultraviolet absorber is preferred because of its excellent effect of improving compatibility and weather resistance. The addition amount of the weather resistance improver is 0.5% by weight to 5%.
% By weight is preferred. When the amount is less than 0.5% by weight, the performance is insufficient. When the amount exceeds 5% by weight, the coating surface is adversely affected by discharge.
【００１９】下塗層は,上記の成分を適宜溶媒に溶解し
た溶液を支持フィルム上に塗布し、乾燥することによっ
て設けられる。下塗層は乾燥重量で０．１〜３μｍ、好
ましくは０．５〜２μｍ設けることができる。下塗層の
塗布量が乾燥重量で０．１μｍよりも少ないと、接着力
が不充分となり、一方、３μｍを超えても更なる接着力
の向上は期待できず、コストがかさむだけである。The undercoat layer is provided by applying a solution obtained by appropriately dissolving the above components in a solvent onto a support film and drying the solution. The undercoat layer can be provided in a dry weight of 0.1 to 3 μm, preferably 0.5 to 2 μm. If the applied amount of the undercoat layer is less than 0.1 μm in terms of dry weight, the adhesion becomes insufficient. On the other hand, if it exceeds 3 μm, further improvement in the adhesion cannot be expected, and only the cost increases.
【００２０】［粘着剤層］本発明において、粘着剤層
は、ポリイソブチレンを主成分とする層である。このポ
リイソブチレンは、重量平均分子量８０万〜１２０万が
好ましく、より好ましくは９０万〜１１０万である。ポ
リイソブチレンの重量平均分子量が８０万未満では老化
後の粘着力上昇が大きく、自動車塗装面からの再剥離性
が著しく低下し、場合によっては剥離出来なくなる恐れ
もある。また重量平均分子量が１２０万を超えると初期
粘着力が乏しく輸送時の剥がれ発生も起こりうる。分子
量の測定方法は、高速液体クロマトグラフ法が簡便であ
り、一般的な方法として広く用いられており、好ましい
測定法である。[Pressure-sensitive adhesive layer] In the present invention, the pressure-sensitive adhesive layer is a layer containing polyisobutylene as a main component. The polyisobutylene preferably has a weight average molecular weight of 800,000 to 1.2 million, more preferably 900,000 to 1.1 million. If the weight average molecular weight of the polyisobutylene is less than 800,000, the adhesive strength after aging increases greatly, and the removability from the painted surface of an automobile is significantly reduced, and in some cases, it may not be possible to remove the material. When the weight average molecular weight exceeds 1.2 million, the initial adhesive strength is poor, and peeling during transportation may occur. As a method for measuring the molecular weight, high-performance liquid chromatography is simple, widely used as a general method, and is a preferable measuring method.
【００２１】また、粘着剤層には，必要に応じて接着力
調整等を目的に粘着付与剤を配合してもよく、粘着付与
剤としては、ロジン、ロジン誘導体、テルペン樹脂、、
テルペンフェノール樹脂等の天然樹脂のものや、石油樹
脂系、アルキルフェノール系樹脂等が挙げられるが、ポ
リイソブチレンとの相溶性に優れるものが好ましい。ま
た、充填剤、顔料、老化防止剤、安定剤等の適宜な添加
剤を含有するものであってもよい。粘着剤層の厚みは，
乾燥厚みで５〜５０μｍ，好ましくは１０〜３０μｍで
ある。粘着剤層の厚みが５μｍ未満では、接着力が不充
分となり、５０μｍを超えると、剥離後の塗装面に糊残
りが発生しやすい。A tackifier may be added to the pressure-sensitive adhesive layer, if necessary, for the purpose of adjusting adhesive strength, and the tackifier may be rosin, rosin derivative, terpene resin,
Examples include natural resins such as terpene phenol resins, petroleum resin-based resins, and alkylphenol-based resins, but those having excellent compatibility with polyisobutylene are preferred. Further, it may contain appropriate additives such as a filler, a pigment, an antioxidant, and a stabilizer. The thickness of the adhesive layer is
The dry thickness is 5 to 50 μm, preferably 10 to 30 μm. If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the adhesive strength becomes insufficient, and if it exceeds 50 μm, adhesive residue is apt to be generated on the coated surface after peeling.
【００２２】［離型剤層］次に本発明においては、支持
フィルムの下塗層および粘着剤層を設けた面と反対側の
面に離型剤層を設けることができる。このような離型剤
層を設けることによって，自動車用保護フィルムを巻回
した後，開反する際、作業性を向上させることができ
る。離型剤層における離型剤としては制約なく、ポリジ
メチルシロキサン等のポリオルガノシロキサンを主成分
とするシリコーン系離型剤、長鎖アルキル型離型剤等を
使用することができるが、粘着剤層への移行防止の点か
らアルキルカルバメートのような長鎖アルキル基含有物
の離型剤が好ましい。これらの離型剤を用い自背面粘着
力を適度にすることが開反時の作業性から必要であり、
自背面粘着力は５Ｎ／２５ｍｍ以下、より好ましくは１
Ｎ／２５ｍｍ以下である。[Release Agent Layer] In the present invention, a release agent layer can be provided on the surface opposite to the surface on which the undercoat layer and the pressure-sensitive adhesive layer of the support film are provided. By providing such a release agent layer, workability can be improved when the protective film for an automobile is wound and then opened. The release agent in the release agent layer is not limited, and a silicone-based release agent containing a polyorganosiloxane such as polydimethylsiloxane as a main component, a long-chain alkyl-type release agent, or the like can be used. From the viewpoint of preventing transfer to a layer, a release agent containing a long-chain alkyl group such as an alkyl carbamate is preferable. It is necessary from the workability at the time of opening the back that it is necessary to make the self-back surface adhesive strength appropriate using these release agents,
The self-back surface adhesive strength is 5 N / 25 mm or less, and more preferably 1
N / 25 mm or less.
【００２３】[0023]
【実施例】以下実施例により具体的に説明するが、本発
明はこれに限定されるものではない。 実施例１ ポリプロピレン（チッソ石油化学（株）製、ＦＭ１２１
Ｂ）７５重量％にリニア低密度ポリエチレン（東ソ−
（株）製、Ｆ２０）１５重量％、エチレン・αオレフィ
ン共重合体（デュポン・ダウエラストマ−ズ社製、EG８
２００、密度０．８７）１０重量％の組成物１００重量
部に対して酸化チタン（石原産業（株）製、タイペーク
ＣＲ−９０）１０重量部、耐候性向上剤（ヒンダードア
ミン系、チバ・ガイギ−社製、チヌビン６２２ＬＤ）
０．５重量部を配合してなる樹脂組成物をＴダイ法にて
厚さ５０μｍのフィルムになるように製膜し、支持フィ
ルムとした。この支持フィルムの全光線透過率は３５％
であった。この支持フィルムに下塗層としてポリイソブ
チレン（ト−ネックス（株）製、ＭＭＬ−１００）２５
重量％、スチレン・エチレン・ブチレン・スチレンブロ
ックポリマー（シェルジャパン（株）製、クレイトンＧ
１６５７、略称ＳＥＢＳ）７５重量％、さらに当該組成
物１００重量部に対してデスモジュ−ルＲＦＥ（住友バ
イエルウレタン（株））１．５重量部を添加してなる組
成物の１０％トルエン溶液を支持フイルム上に１０ｇ／
ｍ2塗布して７０℃×１分乾燥して下塗層を設けた。さ
らにその上にポリイソブチレンＭＭＬ−１００（ト−ネ
ックス（株）製）８０重量％、低分子量ポリイソブチレ
ンＬＭＭＳ（ト−ネックス（株）製）２０重量％の組成
物（重量平均分子量９６万）をトルエンで溶解して２０
％トルエン溶液を作成し、粘着剤の厚さが乾燥後１０μ
ｍになる様に塗布して塗膜保護用フイルムを作成した。
支持フイルムの非当該面にはピ−ロイル＃１０１０（一
方社油脂工業（株）製、長鎖アルキル基含有物の離形
剤）を加熱してトルエンの１％濃度になる様に溶解し、
これを１２０メッシユグラビアにて付量１０ｇ／ｍ2で
離形処理をした。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Polypropylene (manufactured by Chisso Petrochemical Co., Ltd., FM121)
B) 75% by weight of linear low density polyethylene (Toso-
F20), 15% by weight, ethylene / α-olefin copolymer (manufactured by Dupont Dowelast Mars, EG8)
200, density 0.87) 10 parts by weight of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipaque CR-90), 10 parts by weight with respect to 100 parts by weight of a composition having 10% by weight, a weather resistance improver (hindered amine, Ciba Geigy) Manufactured by Tinuvin 622LD)
A resin composition containing 0.5 parts by weight was formed into a film having a thickness of 50 μm by a T-die method to obtain a support film. The total light transmittance of this support film is 35%
Met. Polyisobutylene (manufactured by Tonex Corporation, MML-100) 25 as an undercoat layer on this support film
% By weight, styrene-ethylene-butylene-styrene block polymer (Shell Japan Co., Ltd., Kraton G
1657, abbreviated SEBS), and a 10% toluene solution of a composition obtained by adding 1.5 parts by weight of Desmodur RFE (Sumitomo Bayer Urethane Co., Ltd.) to 100 parts by weight of the composition. 10g / on film
m 2 was applied and dried at 70 ° C. × 1 minute to form an undercoat layer. Furthermore, a composition (weight average molecular weight: 960,000) of 80% by weight of polyisobutylene MML-100 (manufactured by Tonex) and 20% by weight of low molecular weight polyisobutylene LMMS (manufactured by Tonex) was further added thereto. Dissolve in toluene and add 20
% Toluene solution, the thickness of the adhesive is 10μ
m to form a film for protecting the coating film.
Pyroyl # 1010 (on the other hand, a release agent for a long-chain alkyl group-containing substance, manufactured by Yushi Yushi Kogyo Co., Ltd.) was heated and dissolved to a concentration of 1% of toluene on the non-relevant surface of the supporting film.
This was subjected to a mold release treatment at a coating weight of 10 g / m 2 using a 120 mesh gravure.
【００２４】実施例２ ポリプロピレン（チッソ石油化学（株）製、ＦＭ１２１
Ｂ）８０重量％にリニア低密度ポリエチレン（東ソ−
（株）製、Ｆ２０）１５重量％、エチレン・αオレフィ
ン共重合体（デュポン・ダウエラストマ−ズ社製、EG８
２００、密度０．８７）５重量％の組成物１００重量部
に対して酸化チタン（石原産業（株）製、タイペークＣ
Ｒ−９０）１０重量部、耐候性向上剤（ヒンダードアミ
ン系、チバ・ガイギ−社製、チヌビン６２２ＬＤ）０．
５重量部を配合してなる樹脂組成物をＴダイ法にて厚さ
５０μｍのフィルムになるように製膜し、支持フィルム
とした。この支持フイルムの上に実施例１と同じ組成の
下塗層を設け、さらにその上にポリイソブチレンＭＭＬ
−１００（ト−ネックス（株）製）８５重量％、低分子
量ポリイソブチレンＬＭＭＨ（ト−ネックス（株）製）
１５重量％の組成物（重量平均分子量１０３万）の２０
％トルエン溶液を、粘着剤の厚さが乾燥後１５μｍにな
る様に塗布して塗膜保護用フイルムを作成した。支持フ
イルムの非当該面は実施例１と同様に離形処理をした。Example 2 Polypropylene (FM121, manufactured by Chisso Petrochemical Co., Ltd.)
B) 80% by weight of linear low density polyethylene (Toso-
F20), 15% by weight, ethylene / α-olefin copolymer (manufactured by Dupont Dowelast Mars, EG8)
200, density 0.87) 100 parts by weight of 5% by weight of a composition, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipaek C)
R-90) 10 parts by weight, weather resistance improver (hindered amine type, Ciba Geigy Co., Tinuvin 622LD)
A resin composition containing 5 parts by weight was formed into a film having a thickness of 50 μm by a T-die method to obtain a support film. An undercoat layer having the same composition as in Example 1 was provided on this support film, and further, a polyisobutylene MML was further formed thereon.
-100 (manufactured by Tonex) 85% by weight, low molecular weight polyisobutylene LMMH (manufactured by Tonex)
20% of a 15% by weight composition (weight average molecular weight 1,030,000)
% Toluene solution was applied so that the thickness of the adhesive became 15 μm after drying to prepare a film for protecting a coating film. The non-relevant surface of the supporting film was subjected to release treatment in the same manner as in Example 1.
【００２５】比較例 ポリプロピレン（チッソ石油化学（株）製、ＦＭ１２１
Ｂ）８５重量％にリニア低密度ポリエチレン（東ソ−
（株）製、Ｆ２０）１５重量％の組成物１００重量部に
対して酸化チタン（石原産業（株）製、タイペークＣＲ
−９０）１０重量部、耐候性向上剤（ヒンダードアミン
系、チバ・ガイギ−社製、チヌビン６２２ＬＤ）０．５
重量部を配合してなる樹脂組成物をＴダイ法にて厚さ５
０μｍのフィルムになるように製膜し、支持フィルムと
した。支持フイルムにポリイソブチレンＭＭＬ−１００
（ト−ネックス（株）製）８０重量％、低分子量ポリイ
ソブチレンＬＭＭＳ（ト−ネックス（株）製）２０重量
％の組成物（重量平均分子量９６万）をトルエンで溶解
して２０％トルエン溶液を作成し、粘着剤の厚さが乾燥
後１０μｍになる様に塗布して塗膜保護用フイルムを作
成した。Comparative Example Polypropylene (FM121 manufactured by Chisso Petrochemical Co., Ltd.)
B) 85% by weight of linear low density polyethylene (Toso-
T20 (manufactured by Ishihara Sangyo Co., Ltd.)
-90) 10 parts by weight, weather resistance improver (hindered amine, Ciba Geigy Co., Tinuvin 622LD) 0.5
5 parts by weight of the resin composition obtained by blending parts by weight
It was formed into a film having a thickness of 0 μm and used as a support film. Polyisobutylene MML-100 for supporting film
A composition (weight average molecular weight: 960,000) of 80% by weight (manufactured by Tonex) and 20% by weight of low molecular weight polyisobutylene LMMS (manufactured by Tonex) is dissolved in toluene to prepare a 20% toluene solution. Was prepared and applied so that the thickness of the adhesive became 10 μm after drying to prepare a film for protecting the coating film.
【００２６】上記の実施例および比較例で得られた各々
の塗膜保護用フイルムについてフイルム強度を測定し、
また２液硬化アクリル型自動車塗装板に所定の方法で張
り合わせ、初期粘着力、老化後の粘着力（促進試験およ
び屋外曝露試験）及び自背面粘着力を下記の評価方法で
評価した。結果は表１、表２、表３、および表４に示し
た。The film strength of each of the coating film protecting films obtained in the above Examples and Comparative Examples was measured.
In addition, the two-component cured acrylic type automobile coated plate was adhered by a predetermined method, and the initial adhesive strength, the adhesive strength after aging (acceleration test and outdoor exposure test), and the self-back surface adhesive strength were evaluated by the following evaluation methods. The results are shown in Table 1, Table 2, Table 3, and Table 4.
【００２７】測定方法は以下のとおりである。 フイルム強度測定：ＪＩＳ Ｋ６７８２、ＪＩＳ Ｚ
１７０７ 被着体：２液硬化アクリル型自動車塗装板 粘着力測定：ＪＩＳ Ｋ６８５４に準じ、剥離速度３
００ｍｍ／分、１８０度剥離にて測定した。 経時粘着力 促進耐熱試験：ギャオ−ブン８０℃、１６８時間 促進耐候試験：サンシャインウェザ−メ−タ−５００時
間照射 屋外曝露試験：沖縄宮古島暴露試験、一年間実施 促進試験後の評価方法は初期粘着力の評価と同様に１８
０度剥離強度及び剥離した際の再剥離性を評価した。再
剥離性の評価基準は次の通りである。 The measuring method is as follows. Film strength measurement: JIS K6782, JIS Z
1707 Adherend: Two-component cured acrylic type automobile coated plate Adhesive strength measurement: Peeling speed 3 according to JIS K6854
The measurement was performed at 180 mm peeling at 00 mm / min. Adhesive strength over time Accelerated heat resistance test: GAOVEN 80 ° C, 168 hours Accelerated weathering test: Sunshine weather meter 500 hours irradiation Outdoor exposure test: Okinawa Miyakojima exposure test, conducted for one year The evaluation method after the accelerated test is initial adhesion 18 as well as the power rating
The 0-degree peel strength and the re-peelability upon peeling were evaluated. The evaluation criteria for removability are as follows.
【００２８】表１： フイルム強度：ＭＤ方向のみ 単位（ヤング率、破断強度、破断伸度：ｋｇ／ｍｍ2、
引裂強度：ｋｇ／ｃｍ）Table 1: Film strength: MD direction only Units (Young's modulus, breaking strength, breaking elongation: kg / mm 2 ,
(Tear strength: kg / cm)
【表１】 [Table 1]
【００２９】表２： 粘着力 （単位： Ｎ／２５ｍ
ｍ）Table 2: Adhesive strength (unit: N / 25m)
m)
【表２】 [Table 2]
【００３０】表３：再剥離性Table 3: Removability
【表３】 [Table 3]
【００３１】表４：沖縄屋外曝露、再剥離性Table 4: Okinawa outdoor exposure, removability
【表４】 [Table 4]
【００３２】[0032]
【発明の効果】本発明によれば、支持フイルムとの接着
力が強く、貼り付け時の開反作業性が良好でまた使用後
の粘着力の増加が少なく、再剥離時にフイルムが引き裂
けることがなく、長期使用に耐えられる自動車塗膜保護
用フイルムが提供することが可能になる。According to the present invention, the film has a strong adhesive force with the supporting film, has good openability at the time of sticking, has a small increase in the adhesive force after use, and tears the film upon re-peeling. Therefore, it is possible to provide a film for protecting automotive coatings which can be used for a long time without any problem.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｊ 123/22 Ｃ０９Ｊ 123/22 Ｆターム(参考） 4F071 AA15X AA20X AA21 AA21X AA22X AA75 AC12 AH07 BA02 BB02 BC02 4J002 BB181 BP012 ER006 GH00 4J004 AA05 AA07 AA14 AB01 CA04 CC02 CE01 DA05 DB03 EA01 FA04 4J038 CB131 CQ002 DG262 JB18 NA10 PA07 PB03 PB07 PC08 4J040 DA141 EK032 JA09 JB09 LA06 NA16 PA10 PA13 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09J 123/22 C09J 123/22 F-term (Reference) 4F071 AA15X AA20X AA21 AA21X AA22X AA75 AC12 AH07 BA02 BB02 BC02 4J002 BB181 BP012 ER006 GH00 4J004 AA05 AA07 AA14 AB01 CA04 CC02 CE01 DA05 DB03 EA01 FA04 4J038 CB131 CQ002 DG262 JB18 NA10 PA07 PB03 PB07 PC08 4J040 DA141 EK032 JA09 JB09 LA06 NA16 PA10 PA13
Claims (3)
〜４０重量％、ポリエチレンを５〜４０重量％含有する
ポリプロピレン系組成物から形成される支持フィルム上
に、ポリイソブチレン、Ａ−Ｂ−Ａ型ブロックポリマ−
およびイソシアネ−トを含む下塗層を設け、該下塗層面
にポリイソブチレンを主成分とする粘着剤層を設けたこ
とを特徴とする自動車塗膜保護用フィルム。1. An ethylene / α-olefin copolymer having a content of 2.5
Polyisobutylene, ABA type block polymer on a support film formed from a polypropylene composition containing -40% by weight and 5-40% by weight of polyethylene.
An undercoat layer containing an isocyanate and an undercoat layer, and an adhesive layer containing polyisobutylene as a main component is provided on the undercoat layer surface.
反対側の面に長鎖アルキル型離型剤を含む離型層を設け
たことを特徴とする請求項１に記載の自動車塗膜保護用
フィルム。2. The automotive coating according to claim 1, wherein a release layer containing a long-chain alkyl release agent is provided on a surface of the support film opposite to the surface on which the pressure-sensitive adhesive layer is provided. Film for membrane protection.
白色であり、さらに耐光性安定剤の添加量が３重量％以
下である支持体を用いることを特徴とする請求項１また
は請求項２に記載の自動車塗膜保護用フィルム。3. The support according to claim 1, wherein the support is white in which the total light transmittance is 40% or less, and the addition amount of the light fastness stabilizer is 3% by weight or less. The film for protecting automotive coatings according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6734999A JP2000265136A (en) | 1999-03-12 | 1999-03-12 | Film for protecting coated film on automotive car |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6734999A JP2000265136A (en) | 1999-03-12 | 1999-03-12 | Film for protecting coated film on automotive car |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000265136A true JP2000265136A (en) | 2000-09-26 |
Family
ID=13342466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6734999A Pending JP2000265136A (en) | 1999-03-12 | 1999-03-12 | Film for protecting coated film on automotive car |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000265136A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004231694A (en) * | 2003-01-28 | 2004-08-19 | Panac Co Ltd | Pressure-sensitive adhesive film obtained by laminating flexible polymer |
| JP2006089654A (en) * | 2004-09-27 | 2006-04-06 | Panac Co Ltd | Double-sided adhesive sheet |
| JP2008030349A (en) * | 2006-07-31 | 2008-02-14 | Toray Advanced Film Co Ltd | Surface protective film |
| JP2009242762A (en) * | 2008-04-01 | 2009-10-22 | Nitto Denko Corp | Coating film protective sheet |
| JP2009242763A (en) * | 2008-04-01 | 2009-10-22 | Nitto Denko Corp | Coating film protective sheet |
| JP2010076287A (en) * | 2008-09-26 | 2010-04-08 | Hitachi Chem Co Ltd | Adhesive film for optical sheet protection and its manufacturing method |
| JP2010523342A (en) * | 2007-03-30 | 2010-07-15 | エアバス・オペレーションズ・ゲーエムベーハー | Metal cutting machining method and semi-finished product |
| WO2011046064A1 (en) * | 2009-10-15 | 2011-04-21 | 日東電工株式会社 | Protective sheet for coating film |
| JP2011102400A (en) * | 2011-01-27 | 2011-05-26 | Nitto Denko Corp | Surface protection sheet and method for producing the same |
-
1999
- 1999-03-12 JP JP6734999A patent/JP2000265136A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004231694A (en) * | 2003-01-28 | 2004-08-19 | Panac Co Ltd | Pressure-sensitive adhesive film obtained by laminating flexible polymer |
| JP2006089654A (en) * | 2004-09-27 | 2006-04-06 | Panac Co Ltd | Double-sided adhesive sheet |
| JP2008030349A (en) * | 2006-07-31 | 2008-02-14 | Toray Advanced Film Co Ltd | Surface protective film |
| JP2010523342A (en) * | 2007-03-30 | 2010-07-15 | エアバス・オペレーションズ・ゲーエムベーハー | Metal cutting machining method and semi-finished product |
| JP2009242762A (en) * | 2008-04-01 | 2009-10-22 | Nitto Denko Corp | Coating film protective sheet |
| JP2009242763A (en) * | 2008-04-01 | 2009-10-22 | Nitto Denko Corp | Coating film protective sheet |
| JP2010076287A (en) * | 2008-09-26 | 2010-04-08 | Hitachi Chem Co Ltd | Adhesive film for optical sheet protection and its manufacturing method |
| WO2011046064A1 (en) * | 2009-10-15 | 2011-04-21 | 日東電工株式会社 | Protective sheet for coating film |
| JP2011084655A (en) * | 2009-10-15 | 2011-04-28 | Nitto Denko Corp | Coating film protective sheet |
| CN102666762A (en) * | 2009-10-15 | 2012-09-12 | 日东电工株式会社 | Protective sheet for coating film |
| CN102666762B (en) * | 2009-10-15 | 2015-07-01 | 日东电工株式会社 | Protective sheet for coating film |
| JP2011102400A (en) * | 2011-01-27 | 2011-05-26 | Nitto Denko Corp | Surface protection sheet and method for producing the same |
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