JP2021014531A - Surface protective film - Google Patents
Surface protective film Download PDFInfo
- Publication number
- JP2021014531A JP2021014531A JP2019130217A JP2019130217A JP2021014531A JP 2021014531 A JP2021014531 A JP 2021014531A JP 2019130217 A JP2019130217 A JP 2019130217A JP 2019130217 A JP2019130217 A JP 2019130217A JP 2021014531 A JP2021014531 A JP 2021014531A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- mol
- pentene
- methyl
- less
- 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.)
- Granted
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、例えば被着体に貼り付けて使用する表面保護フィルムに関する。 The present invention relates to, for example, a surface protective film used by being attached to an adherend.
表面保護フィルムは、光学基材や建材材料等の樹脂製品、金属製品、ガラス製品、半導体ウエハなどの被着体に貼り付けて使用され、これらを輸送、保管、加工する際に、傷付き、破損、異物の混入を防ぐ等の役割や、所定の工程における支持体の役割を果たしている。これらの表面保護フィルムは、一般には粘着性を有しない離型性の高い背面層と、前記被着体と粘着させるための粘着層とを含む。背面層としては、通常、ポリエチレンやポリプロピレンなどのポリオレフィンや、ポリエチレンテレフタレートなどのポリエステル、ポリ塩化ビニルなどのビニル重合体から形成された層が使用されている。 The surface protective film is used by being attached to an adherend such as a resin product such as an optical base material or a building material, a metal product, a glass product, or a semiconductor wafer, and is damaged when transported, stored, or processed. It plays a role of preventing damage and mixing of foreign substances, and also plays a role of a support in a predetermined process. These surface protective films generally include a highly releasable back layer having no adhesiveness and an adhesive layer for adhering to the adherend. As the back layer, a layer formed of a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, or a vinyl polymer such as polyvinyl chloride is usually used.
このような表面保護フィルムに必要な特性は、被着体に対する適切な粘着力を発現すること、被着体から表面保護フィルムの浮きや剥がれがないこと、被着体に変形や欠けといった欠陥が生じないこと、表面保護フィルムを剥がして除去する場合には、被着体に粘着成分が残留しないことである。特に、表面保護フィルムを被着体に貼り付けて得られた構造物（以下、これを「積層体」ということがある。）が高温条件下におかれる場合には、被着体や、表面保護フィルムに収縮や軟化が生じやすい。例えば近年、スマートフォンやタブレット端末等に代表される携帯情報電子機器が普及しており、偏光板等の光学フィルムや透明導電膜（ＩＴＯ；スズドーブ酸化インジウム）が採用されている。当該部材を硬化型接着剤等で貼り合わせる熱処理工程、あるいは、透明電導膜の結晶化を促進するためのアニール処理等が行われることがある。したがって、表面保護フィルムとしては、一般的な粘着フィルムよりも、さらなる高度な性能が求められる。 The properties required for such a surface protective film are that it exhibits appropriate adhesive force to the adherend, that the surface protective film does not float or peel off from the adherend, and that the adherend has defects such as deformation or chipping. It does not occur, and when the surface protective film is peeled off and removed, the adhesive component does not remain on the adherend. In particular, when a structure obtained by attaching a surface protective film to an adherend (hereinafter, this may be referred to as a "laminated body") is placed under high temperature conditions, the adherend or the surface The protective film is prone to shrinkage and softening. For example, in recent years, portable information electronic devices such as smartphones and tablet terminals have become widespread, and optical films such as polarizing plates and transparent conductive films (ITO; indium tin oxide) have been adopted. A heat treatment step of bonding the members with a curable adhesive or the like, or an annealing treatment for promoting crystallization of the transparent conductive film may be performed. Therefore, the surface protective film is required to have higher performance than a general adhesive film.
特許文献１には、実質的にシンジオタクチック構造を有するポリプロピレンを基材層に含む、耐熱性に優れ、フィルムの引き伸ばし時にも白化を抑制し、特に保管・輸送時の温度変化においてもフィルムの浮きや剥がれを生じない、密着性を有した表面保護フィルムが開示されている。 Patent Document 1 contains polypropylene having a substantially syndiotactic structure in the base material layer, has excellent heat resistance, suppresses whitening even when the film is stretched, and particularly when the film is changed in temperature during storage and transportation. A surface protective film having adhesiveness that does not cause floating or peeling is disclosed.
特許文献２には、基材層にプロピレン系共重合体を用いることで保管等の際に温度変化が生じてもフィルムの浮や剥がれを抑制できる表面保護フィルムが開示されている。
特許文献３には、４−メチル−１−ペンテンに由来する構成単位及び炭素数２又は３のα−オレフィンに由来する構成単位を含む共重合体である熱可塑性樹脂（Ａ）と、エチレン系重合体、プロピレン系重合体、ブテン系重合体、及び４−メチル−１−ペンテン系重合体からなる群より選ばれる少なくとも１種の重合体である、前記熱可塑性樹脂（Ａ）以外の熱可塑性樹脂（Ｂ）を含む応力緩和層よりなる表面保護フィルムが開示されている。
Patent Document 2 discloses a surface protective film capable of suppressing floating and peeling of a film even if a temperature change occurs during storage or the like by using a propylene-based copolymer as a base material layer.
Patent Document 3 describes a thermoplastic resin (A) which is a copolymer containing a structural unit derived from 4-methyl-1-pentene and a structural unit derived from α-olefin having 2 or 3 carbon atoms, and an ethylene-based material. Thermoplastics other than the thermoplastic resin (A), which is at least one polymer selected from the group consisting of a polymer, a propylene-based polymer, a butene-based polymer, and a 4-methyl-1-pentene-based polymer. A surface protective film composed of a stress relaxation layer containing a resin (B) is disclosed.
近年、ブラウン管ディスプレイから、液晶ディスプレイやプラズマディスプレイ等のフラットパネルディスプレイへの移行や、多機能携帯電話、スマートフォンやタブレット端末等に代表される携帯情報電子機器の普及が進んでいる。これらに用いる部材において、高機能化、高性能化に伴い、凹凸の大きい表面形状を有する、または、表面が凹凸になるように表面処理された部材が増えており、これらの部材と、表面保護フィルムの粘着層との接触面積が必然的に小さくなることから、表面保護フィルムが部分的に変形した状態になりやすくなっている。このような状態で輸送、保管、加工等をする際に、高温下で曝されると、変形した部分は元の状態に回復しようとするため、表面保護フィルムと被着体との界面で浮き上がりが生じ、あるいは表面保護フィルムが剥がれ易くなるという問題がある。 In recent years, the shift from CRT displays to flat panel displays such as liquid crystal displays and plasma displays, and the spread of portable information electronic devices such as multifunctional mobile phones, smartphones and tablet terminals have been progressing. Among the members used for these, the number of members having a surface shape with large irregularities or surface treatment so that the surface becomes uneven is increasing along with higher functionality and higher performance, and these members and surface protection Since the contact area of the film with the adhesive layer is inevitably small, the surface protective film tends to be in a partially deformed state. When transporting, storing, processing, etc. in such a state, if exposed to high temperature, the deformed part will try to recover to the original state, so it will rise at the interface between the surface protection film and the adherend. There is a problem that the surface protective film is easily peeled off.
近年、偏光板等の光学フィルムや透明導電膜の採用が著しい。当該部材を硬化型接着剤等で貼り合わせる熱処理工程、あるいは、透明電導膜の結晶化を促進するためのアニール処理等が行われることがある。したがって、表面保護フィルムには、高温下においても被着体との界面で浮き上がりや剥がれが抑制される性能が求められている。 In recent years, the adoption of optical films such as polarizing plates and transparent conductive films has been remarkable. A heat treatment step of bonding the members with a curable adhesive or the like, or an annealing treatment for promoting crystallization of the transparent conductive film may be performed. Therefore, the surface protective film is required to have a performance of suppressing floating and peeling at the interface with the adherend even at a high temperature.
しかしながら、特許文献１では、６０℃に於ける収縮率のみ述べられており、より高温下での収縮率や被着体からの反りについては述べられていない。
特許文献２に記載の表面保護フィルムは、５０℃における被着体からの反りは抑制されるが、より高温条件下では被着体と表面保護フィルムとの界面で浮き上がりや剥離が生ずることがわかった。
However, Patent Document 1 describes only the shrinkage rate at 60 ° C., and does not describe the shrinkage rate at a higher temperature or the warpage from the adherend.
It was found that the surface protective film described in Patent Document 2 suppresses warpage from the adherend at 50 ° C., but floats or peels off at the interface between the adherend and the surface protective film under higher temperature conditions. It was.
さらに、特許文献３に記載の表面保護フィルムは、２３℃での剥離強度が述べられているのみであり、より高温下においては積層体の反りや表面保護フィルムの剥離が起こることがある。 Further, the surface protective film described in Patent Document 3 only describes the peel strength at 23 ° C., and the laminated body may warp or the surface protective film may peel off at a higher temperature.
本発明は、以上のことに鑑みてなされたものであり、被着体に対し高温下でも、被着体からの浮きや剥離が起こりにくい表面保護フィルムであり、かつ積層体の反りを抑制できる表面保護フィルムを提供することを課題とする。 The present invention has been made in view of the above, and is a surface protective film that is unlikely to float or peel off from the adherend even at a high temperature with respect to the adherend, and can suppress warpage of the laminate. An object of the present invention is to provide a surface protective film.
本発明者らは前記課題を解決するべく鋭意検討した結果、特定の表面保護フィルムによれば、前記課題を解決できることを見出し、本発明を完成するに至った。
本発明の構成例は、以下の通りである。
As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a specific surface protective film, and have completed the present invention.
A configuration example of the present invention is as follows.
本発明は、４−メチル−１−ペンテンから導かれる構成単位の含有率が９０モル％以上１００モル％以下であり、炭素原子数２〜２０のα−オレフィン（４−メチル−１−ペンテンを除く）から導かれる構成単位の含有率が１０モル％以下である（前記４−メチル−１−ペンテンから導かれる構成単位および前記α−オレフィンから導かれる構成単位の含有率の合計を１００モル％とする）共重合体である熱可塑性樹脂（Ｘ）と、
４−メチル−１−ペンテンから導かれる構成単位の含有率が７０モル％以上９０モル％未満であり、炭素原子数２〜１２のα−オレフィン（４−メチル−１−ペンテンを除く）から導かれる構成単位の含有率が１０モル％を超え３０モル％以下である（前記４−メチル−１−ペンテンから導かれる構成単位および前記α−オレフィンから導かれる構成単位の含有率の合計を１００モル％とする）の共重合体である熱可塑性樹脂（Ｙ）とを含み、
前記熱可塑性樹脂（Ｘ）の含有量が２０質量％以上８０質量％以下、前記熱可塑性樹脂（Ｙ）の含有量が２０質量％以上８０質量％以下であり（熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）の合計量を１００質量％とする。）、
ＪＩＳ Ｋ７１３３に準拠して測定した寸法変化率において、１５０℃で、３０分加熱した後の縦方向および横方向の寸法変化率の絶対値が０．２０％未満（ただし、前記寸法変化率において、プラスの数値は膨張したときの変化の比率を、マイナスの数値は収縮したときの変化の比率を示す。）の表面保護フィルムである。
In the present invention, an α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) having a content of a structural unit derived from 4-methyl-1-pentene of 90 mol% or more and 100 mol% or less. The content of the structural unit derived from (excluding) is 10 mol% or less (the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin is 100 mol%. The thermoplastic resin (X), which is a copolymer, and
Derived from α-olefins (excluding 4-methyl-1-pentene) having a content of constituent units derived from 4-methyl-1-pentene of 70 mol% or more and less than 90 mol% and having 2 to 12 carbon atoms. The content of the constituent units to be obtained is more than 10 mol% and 30 mol% or less (the total content of the constituent units derived from 4-methyl-1-pentene and the constituent units derived from the α-olefin is 100 mol. %) With the thermoplastic resin (Y) which is a copolymer of
The content of the thermoplastic resin (X) is 20% by mass or more and 80% by mass or less, and the content of the thermoplastic resin (Y) is 20% by mass or more and 80% by mass or less (thermoplastic resin (X) and heat). The total amount of the plastic resin (Y) is 100% by mass.),
In the dimensional change rate measured in accordance with JIS K7133, the absolute value of the dimensional change rate in the vertical and horizontal directions after heating at 150 ° C. for 30 minutes is less than 0.20% (however, in the dimensional change rate, A positive value indicates the rate of change when expanded, and a negative value indicates the rate of change when contracted.) The surface protective film.
前記表面保護フィルムは、前記熱可塑性樹脂（Ｙ）が下記の要件（ｉ）〜（ｉｖ）を満たすことが好ましい。
（ｉ）１３５℃デカリン中で測定した極限粘度〔η〕が０．１〜５．０ｄｌ／ｇである、
（ｉｉ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比である分子量分布（Ｍｗ／Ｍｎ）が１．０〜３．５である、
（ｉｉｉ）ＤＳＣで測定した融点（Ｔｍ）が２００℃未満であるか、またはＤＳＣで融点が観測されない、
（ｉｖ）密度が８３０〜８６０ｋｇ／ｍ3である。
In the surface protective film, it is preferable that the thermoplastic resin (Y) satisfies the following requirements (i) to (iv).
(I) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.1 to 5.0 dl / g.
(Ii) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) to the number average molecular weight (Mn), is 1.0 to 3.5. ,
(Iii) The melting point (Tm) measured by DSC is less than 200 ° C., or no melting point is observed by DSC.
(Iv) The density is 830-860 kg / m 3 .
前記表面保護フィルムの好適な態様として、前記熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）を含む基材層と、該基材層の少なくとも一方の面に設けられた粘着層とを有する表面保護フィルムを挙げることができる。 As a preferred embodiment of the surface protective film, a surface having a base material layer containing the thermoplastic resin (X) and the thermoplastic resin (Y) and an adhesive layer provided on at least one surface of the base material layer. A protective film can be mentioned.
本発明に係る表面保護フィルムは、被着体に対して適度な粘着力を発現し、高温下においても、被着体からの浮きや剥離が起こりにくい。被着体から剥離させる際には、容易に剥がすことができ、かつ、被着体へ粘着剤成分が残りにくい。また、本発明に係る表面保護フィルムを用いることで、高温下でも反りが起こり難い積層体を得ることができる。このため、本発明に係る表面保護フィルムは、光学基材、建材、自動車部品、半導体ウエハ等に使用される表面保護フィルムとして好適に用いることができ、産業上の利用価値は極めて高い。 The surface protective film according to the present invention exhibits an appropriate adhesive force to the adherend, and is unlikely to float or peel off from the adherend even at a high temperature. When peeling from the adherend, it can be easily peeled off, and the adhesive component does not easily remain on the adherend. Further, by using the surface protective film according to the present invention, it is possible to obtain a laminated body in which warpage is unlikely to occur even at a high temperature. Therefore, the surface protective film according to the present invention can be suitably used as a surface protective film used for optical substrates, building materials, automobile parts, semiconductor wafers, etc., and has extremely high industrial utility value.
また、本発明に係る表面保護フィルムは、凹凸の大きい表面形状を有する被着体を用いた場合であっても、前記の効果を十分に発揮する。 Further, the surface protective film according to the present invention sufficiently exerts the above-mentioned effect even when an adherend having a surface shape having large irregularities is used.
以下、本発明の具体的な実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。なお、本明細書において、「（共）重合体」なる語句は、単独重合体および共重合体を包含する意味で用いられる。
本発明の表面保護フィルム（以下「本フィルム」ということがある。）は、以下に述べる熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）を含有する。
Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and is carried out with appropriate modifications within the scope of the object of the present invention. be able to. In addition, in this specification, the term "(co) polymer" is used in the meaning which includes a homopolymer and a copolymer.
The surface protective film of the present invention (hereinafter sometimes referred to as "the present film") contains the thermoplastic resin (X) and the thermoplastic resin (Y) described below.
＜熱可塑性樹脂（Ｘ）＞
熱可塑性樹脂（Ｘ）としては、後述する熱可塑性樹脂（Ｙ）以外の４-メチル‐１‐ペンテンを主成分とする４-メチル‐１‐ペンテン（共）重合体を使用することができる。４-メチル‐１‐ペンテン（共）重合体は、従来公知のオレフィン重合用触媒、例えば、バナジウム系触媒、チタン系触媒、マグネシウム担持型チタン触媒、国際公開第０１／５３３６９号パンフレット、国際公開第０１／２７１２４号パンフレット、特開平３−１９３７９６号広報あるいは特開平０２−４１３０３号広報に記載のメタロセン触媒などを用いて、４−メチル−１−ペンテンと、必要に応じて炭素原子数２〜２０のα−オレフィン（４−メチル−１−ペンテンを除く）やその他の化合物を重合することにより得ることができる。
<Thermoplastic resin (X)>
As the thermoplastic resin (X), a 4-methyl-1-pentene (co) polymer containing 4-methyl-1-pentene as a main component other than the thermoplastic resin (Y) described later can be used. The 4-methyl-1-pentene (co) polymer is a conventionally known catalyst for olefin polymerization, for example, vanadium-based catalyst, titanium-based catalyst, magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. 01/53369. 4-Methyl-1-pentene and, if necessary, 2 to 20 carbon atoms, using the metallocene catalyst described in the pamphlet of 01/27124, the public relations of Japanese Patent Application Laid-Open No. 3-193996, or the public relations of JP-A-02-41303. It can be obtained by polymerizing α-olefin (excluding 4-methyl-1-pentene) and other compounds.
具体的には、４−メチル−１−ペンテンの単独重合体、および４−メチル−１−ペンテンから導かれる構成単位の含有率が９０モル％以上 、好ましくは９２モル％以上９９モル％以下 、炭素数２〜２０、 好ましくは６〜２０のα−オレフィンから導かれる構成単位の含有率が１０モル％以下 、好ましくは１モル％以上８モル％以下である４−メチル−１−ペンテン・α−オレフィンランダム共重合体が挙げられる。構成単位の含有率（モル％）の値は、13Ｃ−ＮＭＲにより測定され、具体的な測定方法については実施例に記載の通りである。 Specifically, the content of the homopolymer of 4-methyl-1-pentene and the structural unit derived from 4-methyl-1-pentene is 90 mol% or more, preferably 92 mol% or more and 99 mol% or less. 4-Methyl-1-pentene α having a content of 10 mol% or less, preferably 1 mol% or more and 8 mol% or less, of a structural unit derived from an α-olefin having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms. − Olefin random copolymers can be mentioned. The value of the content rate (mol%) of the structural unit is measured by 13 C-NMR, and the specific measurement method is as described in Examples.
４−メチル−１−ペンテン・α−オレフィンランダム共重合体の場合、４−メチル−１−ペンテンと共重合するα−オレフィンとしては、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンなどの炭素数２〜２０ 、好ましくは６〜２０のα−オレフィンが挙げられる。これらは、１種単独で、あるいは２種以上組み合せて用いることができる。４−メチル−１−ペンテン（共）重合体のメルトマスフローレイト（ＭＦＲ；ＪＩＳ Ｋ７２１０−１、温度２６０℃ 、荷重５．０ｋｇ）は、０．１〜２００ｇ／１０分であることが好ましく、１〜１００ｇ／１０分の範囲内にあることがより好ましい。 In the case of 4-methyl-1-pentene / α-olefin random copolymer, the α-olefins copolymerized with 4-methyl-1-pentene include 1-hexene, 1-octene, 1-decene, and 1-dodecene. , 1-Tetradecene, 1-Hexadecene, 1-Ocdecene, 1-Eicocene and the like, and α-olefins having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms are used. These can be used alone or in combination of two or more. The melt mass flow rate (MFR; JIS K7210-1, temperature 260 ° C., load 5.0 kg) of the 4-methyl-1-pentene (co) polymer is preferably 0.1 to 200 g / 10 minutes, 1 More preferably, it is in the range of ~ 100 g / 10 minutes.
また、熱可塑性樹脂（Ｘ）として使用される４−メチル−１−ペンテン（共）重合体としては、市販品を使用することもでき、例えば三井化学株式会社製ＴＰＸ（登録商標）が挙げられる。 Further, as the 4-methyl-1-pentene (co) polymer used as the thermoplastic resin (X), a commercially available product can also be used, and examples thereof include TPX (registered trademark) manufactured by Mitsui Chemicals, Inc. ..
＜熱可塑性樹脂（Ｙ）＞
熱可塑性樹脂（Ｙ）としては、４−メチル−１−ペンテンから導かれる構成単位を７０モル％以上９０モル％未満含有するオレフィン系共重合体が好ましく、周波数１．６Ｈｚでの動的粘弾性測定におけるｔａｎδ値（損失正接）のピーク温度が５℃以上で観測されるオレフィン系共重合体がより好ましい。
<Thermoplastic resin (Y)>
The thermoplastic resin (Y) is preferably an olefin-based copolymer containing 70 mol% or more and less than 90 mol% of a structural unit derived from 4-methyl-1-pentene, and has dynamic viscoelasticity at a frequency of 1.6 Hz. An olefin-based copolymer in which the peak temperature of the tan δ value (loss tangent) in the measurement is observed at 5 ° C. or higher is more preferable.
熱可塑性樹脂（Ｙ）としては、４−メチル−１−ペンテンと、少なくとも１種の炭素数２〜１２のα−オレフィンとのオレフィン共重合体がさらに好ましく、４−メチル−１−ペンテンから導かれる構成単位（Ｉ）、および炭素数２〜１２のオレフィン（４−メチル−１−ペンテンを除く）から導かれる構成単位（ＩＩ）の合計を１００モル％とした場合、構成単位（Ｉ）の含有率が７０モル％以上９０モル％未満、より好ましくは７０〜８８モル％であり、かつ、構成単位（ＩＩ）の含有率が１０モル％を超え３０モル％以下、より好ましくは１２〜３０モル％である共重合体であることが特に好ましい。 As the thermoplastic resin (Y), an olefin copolymer of 4-methyl-1-pentene and at least one α-olefin having 2 to 12 carbon atoms is more preferable, and it is derived from 4-methyl-1-pentene. When the total of the structural unit (I) to be obtained and the structural unit (II) derived from the olefin having 2 to 12 carbon atoms (excluding 4-methyl-1-pentene) is 100 mol%, the structural unit (I) The content is 70 mol% or more and less than 90 mol%, more preferably 70 to 88 mol%, and the content of the constituent unit (II) is more than 10 mol% and 30 mol% or less, more preferably 12 to 30. It is particularly preferable that the copolymer is in mol%.
構成単位の含有率（モル％）の値は、13Ｃ−ＮＭＲにより測定され、具体的な測定方法については実施例に記載の通りである。
前記炭素数２〜１２のオレフィンの具体例としては、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−デセン、１−ドデセンなどが挙げられ、このなかでも特にプロピレンが好ましい。
熱可塑性樹脂（Ｙ）は、下記の要件（ｉ）〜（ｉｖ）を満たすことが好ましい。
The value of the content rate (mol%) of the structural unit is measured by 13 C-NMR, and the specific measurement method is as described in Examples.
Specific examples of the olefin having 2 to 12 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-decene, 1-dodecene, and the like, and propylene is particularly preferable.
The thermoplastic resin (Y) preferably satisfies the following requirements (i) to (iv).
要件（ｉ）
前記熱可塑性樹脂（Ｙ）の、デカリン中１３５℃で測定した極限粘度〔η〕は、０．１〜５．０ｄｌ／ｇの範囲にある。前記極限粘度〔η〕は、好ましくは０．５〜４．０ｄｌ／ｇ、より好ましくは１．０〜４．０ｄｌ／ｇである。後述するように重合中に水素を併用すると分子量を制御でき、低分子量体から高分子量体まで自在に得ることができるので、極限粘度〔η〕を調整することができる。
前記極限粘度〔η〕が０．１ｄｌ／ｇよりも小さい、または５．０ｄｌ／ｇよりも大きいと、フィルムの成形性が損なわれることがある。
Requirements (i)
The ultimate viscosity [η] of the thermoplastic resin (Y) measured at 135 ° C. in decalin is in the range of 0.1 to 5.0 dl / g. The ultimate viscosity [η] is preferably 0.5 to 4.0 dl / g, more preferably 1.0 to 4.0 dl / g. As will be described later, when hydrogen is used in combination during polymerization, the molecular weight can be controlled, and a low molecular weight substance to a high molecular weight substance can be freely obtained, so that the ultimate viscosity [η] can be adjusted.
If the ultimate viscosity [η] is less than 0.1 dl / g or more than 5.0 dl / g, the moldability of the film may be impaired.
要件（ｉｉ）
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定されるポリスチレン換算での重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比である分子量分布（Ｍｗ／Ｍｎ）は、１．０〜３．５の範囲にある。なお、測定条件等の詳細は、後述する実施例の欄に記載のとおりである。前記分子量分布（Ｍｗ／Ｍｎ）は、好ましくは１．２〜３．０、さらに好ましくは１．５〜２．８である。前記分子量分布（Ｍｗ／Ｍｎ）が３．５よりも大きいと、組成分布に由来する低分子量、低立体規則性ポリマーの影響が現れて、成形性が悪くなる。
Requirements (ii)
The molecular weight distribution (Mw / Mn), which is the ratio of the polystyrene-equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5. Is in the range of. The details of the measurement conditions and the like are as described in the column of Examples described later. The molecular weight distribution (Mw / Mn) is preferably 1.2 to 3.0, more preferably 1.5 to 2.8. When the molecular weight distribution (Mw / Mn) is larger than 3.5, the influence of the low molecular weight and low stereoregular polymer derived from the composition distribution appears, and the moldability deteriorates.
また、熱可塑性樹脂（Ｙ）の、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される重量平均分子量（Ｍｗ）は、ポリスチレン換算で、好ましくは５００〜１０，０００，０００、より好ましくは１，０００〜５，０００，０００、さらに好ましくは１，０００〜２，５００，０００である。 The weight average molecular weight (Mw) of the thermoplastic resin (Y) measured by gel permeation chromatography (GPC) is preferably 500 to 10,000,000, more preferably 1,000 in terms of polystyrene. It is ~ 5,000,000, more preferably 1,000-2,500,000.
要件（ｉｉｉ）
前記熱可塑性樹脂（Ｙ）のＤＳＣ（示差走査熱量測定）で測定した融点（Ｔｍ）は、２００℃未満であるか、またはＤＳＣで融点が観測されない。融点を有する場合、その上限は好ましくは１８０℃、より好ましくは１６０℃、さらに好ましくは１４０℃である。なお、下限は特に限定されないが、通常１３０℃である。
Requirements (iii)
The melting point (Tm) of the thermoplastic resin (Y) measured by DSC (differential scanning calorimetry) is less than 200 ° C., or no melting point is observed by DSC. When it has a melting point, its upper limit is preferably 180 ° C., more preferably 160 ° C., and even more preferably 140 ° C. The lower limit is not particularly limited, but is usually 130 ° C.
上記融点の値は、重合体の立体規則性ならびに共に重合するα−オレフィン量に依存して変化する。後述するオレフィン重合用触媒を用いて所望の組成に制御して、融点を調整することが可能である。 The melting point value varies depending on the stereoregularity of the polymer and the amount of α-olefins polymerized together. It is possible to adjust the melting point by controlling the composition to a desired value using a catalyst for olefin polymerization described later.
前記熱可塑性樹脂（Ｘ）と前記熱可塑性樹脂（Ｙ）を組み合わせた場合、熱可塑性樹脂（Ｘ）の耐熱性が高く、また相容性が良いことから機械物性を損ねることなく、寸法安定性が良好な表面保護フィルムを得ることができる。 When the thermoplastic resin (X) and the thermoplastic resin (Y) are combined, the thermoplastic resin (X) has high heat resistance and good compatibility, so that dimensional stability is not impaired without impairing mechanical properties. A good surface protective film can be obtained.
要件（ｉｖ）
前記熱可塑性樹脂（Ｙ）の密度は、８３０〜８６０ｋｇ／ｍ3、好ましくは８３０〜８５０ｋｇ／ｍ3である。なお、測定条件等の詳細は、後述する実施例の欄に記載のとおりである。密度は、４−メチル−１−ペンテン・α−オレフィン共重合体のコモノマー組成比によって適宜変えることができる。密度が上記範囲内にある前記熱可塑性樹脂（Ｙ）は、表面保護フィルムの透明性や寸法安定性を高める上で有利である。
Requirements (iv)
The density of the thermoplastic resin (Y) is 830 to 860 kg / m 3 , preferably 830 to 850 kg / m 3 . The details of the measurement conditions and the like are as described in the column of Examples described later. The density can be appropriately changed depending on the comonomer composition ratio of the 4-methyl-1-pentene / α-olefin copolymer. The thermoplastic resin (Y) having a density within the above range is advantageous in enhancing the transparency and dimensional stability of the surface protective film.
＜表面保護フィルム＞
本発明に係る表面保護フィルムは、ＪＩＳ Ｋ７１３３に準拠して測定した寸法変化率において、１５０℃で、３０分加熱した後の縦方向（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ；以下、「ＭＤ方向」ということがある）および横方向（Ｔｒａｎｓｖｅｒｓｅ Ｄｉｒｅｃｔｉｏｎ；以下、「ＴＤ方向」ということがある）の寸法変化率の絶対値が０．２０％未満である。前記寸法変化率の測定方法は、実施例において詳説する。
<Surface protection film>
The surface protective film according to the present invention has a dimensional change rate measured in accordance with JIS K7133 in the vertical direction (Machine Direction; hereinafter, may be referred to as “MD direction”) after heating at 150 ° C. for 30 minutes. The absolute value of the dimensional change rate in the lateral direction (Transverse Direction; hereinafter, sometimes referred to as “TD direction”) is less than 0.20%. The method for measuring the dimensional change rate will be described in detail in Examples.
前記寸法変化率の測定において、表面保護フィルムである試験片が膨張したときには寸法変化率はプラスの数値をとり、収縮したときには寸法変化率はマイナスの数値をとり、膨張も収縮もしなかったときには寸法変化率は０となる。寸法変化率の絶対値が０．２０％未満であるということは、寸法変化率が０であるか、寸法変化率の数値が０を上回り、＋０．２０％に至らない範囲内であるか、または寸法変化率の数値が０を下回り、−０．２０％に至らない範囲内であることを意味する。なお、寸法変化率がプラスの数値であるときには、あえて「＋」は表記しない場合がある。 In the measurement of the dimensional change rate, the dimensional change rate takes a positive value when the test piece, which is the surface protective film, expands, the dimensional change rate takes a negative value when it contracts, and the dimension changes when neither expansion nor contraction occurs. The rate of change is 0. If the absolute value of the dimensional change rate is less than 0.20%, it means that the dimensional change rate is 0, or the value of the dimensional change rate exceeds 0 and does not reach + 0.20%. Alternatively, it means that the numerical value of the dimensional change rate is less than 0 and does not reach −0.20%. When the dimensional change rate is a positive value, "+" may not be indicated.
本発明の表面保護フィルムは、上記の性質を有することにより、被着体に対し高温下でも、被着体からの浮きや剥離が起こりにくく、積層体の反りを抑制することができる。
一般的に、キャストフィルム等の押出成形法で作製される樹脂フィルムは、ＭＤ方向に溶融樹脂が配向した状態で固化する。そこで、得られたフィルムをガラス転移温度（Ｔｇ）以上に加熱すれば、ＭＤ方向に収縮することが知られている。
Since the surface protective film of the present invention has the above-mentioned properties, it is difficult for the adherend to float or peel off from the adherend even at a high temperature, and the warp of the laminated body can be suppressed.
Generally, a resin film produced by an extrusion molding method such as a cast film is solidified in a state where the molten resin is oriented in the MD direction. Therefore, it is known that when the obtained film is heated to a glass transition temperature (Tg) or higher, it shrinks in the MD direction.
４−メチル−１−ペンテン系樹脂（前記熱可塑性樹脂（Ｘ）に相当する）により作製した樹脂フィルムも、ガラス転移温度（Ｔｇ）以上に加熱すれば、同様にＭＤ方向に収縮するので、高温下での寸法安定性に課題があった。 A resin film made of 4-methyl-1-pentene resin (corresponding to the thermoplastic resin (X)) also shrinks in the MD direction when heated above the glass transition temperature (Tg), so that the temperature is high. There was a problem with dimensional stability underneath.
一方で、前記熱可塑性樹脂（Ｙ）からなるフィルムは、ガラス転移温度（Ｔｇ）以上に加熱すると、一般的な樹脂フィルムとは挙動が異なり、膨張することがわかった。この性質は、前記熱可塑性樹脂（Ｙ）の高い応力吸収性に起因していると考えられる。したがって、前記熱可塑性樹脂（Ｙ）は、ＭＤ方向に溶融樹脂が配向しても、分子鎖の変形によって起こりうる熱エネルギーを吸収する作用が働き、配向した状態で熱的に安定化する。
つまり、ガラス転移温度（Ｔｇ）以上に加熱しても、配向を緩和することなく収縮が生じない。このことは、分子配向していない状態で、ガラス転移温度（Ｔｇ）以上に加熱することと同じような現象と考えられ、分子鎖の運動が活発になり、フィルムが膨張する傾向にある。
On the other hand, it was found that the film made of the thermoplastic resin (Y) behaves differently from a general resin film and expands when heated to a glass transition temperature (Tg) or higher. This property is considered to be due to the high stress absorption of the thermoplastic resin (Y). Therefore, even if the molten resin is oriented in the MD direction, the thermoplastic resin (Y) has an action of absorbing thermal energy that may occur due to deformation of the molecular chain, and is thermally stabilized in the oriented state.
That is, even if the glass is heated above the glass transition temperature (Tg), shrinkage does not occur without relaxing the orientation. This is considered to be a phenomenon similar to heating above the glass transition temperature (Tg) in a state where the molecules are not oriented, and the movement of the molecular chains becomes active, and the film tends to expand.
すなわち、前記熱可塑性樹脂（Ｘ）と前記熱可塑性樹脂（Ｙ）を配合してなる樹脂フィルムは、収縮と膨張が相殺される効果を発現し、結果として高温下においても、極めて寸法変化の小さいフィルムとなる。以上のような理由から、本フィルムは、ＪＩＳ Ｋ７１３３に準拠して測定した寸法変化率において、１５０℃で、３０分加熱した後の縦方向および横方向の寸法変化率の絶対値が０．２０％未満であるという性質を有すると考えられる。 That is, the resin film obtained by blending the thermoplastic resin (X) and the thermoplastic resin (Y) exhibits an effect of canceling shrinkage and expansion, and as a result, the dimensional change is extremely small even at a high temperature. It becomes a film. For the above reasons, the absolute value of the dimensional change rate in the vertical and horizontal directions after heating at 150 ° C. for 30 minutes is 0.20 at the dimensional change rate measured in accordance with JIS K7133. It is considered to have the property of less than%.
本フィルムにおいて、前記熱可塑性樹脂（Ｘ）および前記熱可塑性樹脂（Ｙ）の合計１００質量％に対する熱可塑性樹脂（Ｘ）の含有量は、前記効果がより発揮される等の点から、好ましくは２０質量％以上、より好ましくは２０〜８０質量％、さらに好ましくは３０〜７０質量％、特に好ましくは４０〜６０質量％である。 In this film, the content of the thermoplastic resin (X) with respect to a total of 100% by mass of the thermoplastic resin (X) and the thermoplastic resin (Y) is preferably from the viewpoint that the above effects are more exhibited. It is 20% by mass or more, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
本フィルムにおいて、前記熱可塑性樹脂（Ｘ）および前記熱可塑性樹脂（Ｙ）の合計１００質量％に対する前記前記熱可塑性樹脂（Ｙ）の含有量は、前記効果がより発揮される点から、好ましくは８０質量％以下、より好ましくは２０〜８０質量％、さらに好ましくは３０〜７０質量％、特に好ましくは４０〜６０質量％である。 In this film, the content of the thermoplastic resin (Y) with respect to a total of 100% by mass of the thermoplastic resin (X) and the thermoplastic resin (Y) is preferably from the viewpoint that the effect is more exhibited. It is 80% by mass or less, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
本フィルムの厚みとしては、例えば、４〜５００μｍ、好ましくは１０〜４００μｍ、さらに好ましくは２０〜３００μｍである。
本フィルムの用途としては特に制限されないが、本発明の効果がより発揮される等の点から、光学、建材、自動車部品、半導体ウエハ等に使用される表面保護フィルム等が挙げられる。また、本フィルムは、被着体を加工等する際の支持体としても用いることができる。
The thickness of this film is, for example, 4 to 500 μm, preferably 10 to 400 μm, and more preferably 20 to 300 μm.
The application of this film is not particularly limited, and examples thereof include surface protective films used for optics, building materials, automobile parts, semiconductor wafers, etc. from the viewpoint of more exerting the effects of the present invention. In addition, this film can also be used as a support when processing an adherend or the like.
本フィルムの好適な態様として、前記熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）を含む基材層と、該基材層の少なくとも一方の面に設けられた粘着層とを有する表面保護フィルムを挙げることができる。さらに、前記基材層の、粘着層が設けられた面とは反対側の面に背面層が設けられていてもよい。 As a preferred embodiment of the present film, a surface protective film having a base material layer containing the thermoplastic resin (X) and the thermoplastic resin (Y) and an adhesive layer provided on at least one surface of the base material layer. Can be mentioned. Further, the back surface layer may be provided on the surface of the base material layer opposite to the surface on which the adhesive layer is provided.
＜粘着層＞
前記粘着層を設ける方法としては、例えば、溶剤塗工法が挙げられる。溶剤塗工を行うにあたり、基材層を製膜した後に、粘着層を設けようとする基材層であるフィルムの一方の片面に、予め従来公知のコロナ放電処理、プラズマ処理、プライマー処理、アンカーコーティング処理の易接着処理が施されてもよい。
<Adhesive layer>
Examples of the method for providing the adhesive layer include a solvent coating method. In solvent coating, after the base material layer is formed, one side of the film, which is the base material layer to which the adhesive layer is to be provided, is previously known in advance for corona discharge treatment, plasma treatment, primer treatment, and anchor. The easy-adhesion treatment of the coating treatment may be applied.
なかでも、比較的高い接着力が短い処理時間で得られ、フィルム成形やラミネーションなどの工程との組み合わせることが容易であるコロナ放電処理が好ましい。コロナ放電処理は、フィルム表面のぬれ張力（ｍＮ／ｍ）を改質せしめて、粘着剤の塗工性を向上させることができる。一般的に、放電量（Ｗ・ｍｉｎ／ｍ2）とフィルム表面のぬれ張力は比例関係にあり、放電量を増加させるとフィルム表面のぬれ張力が高くなる傾向がある。 Among them, the corona discharge treatment is preferable because a relatively high adhesive force can be obtained in a short treatment time and it is easy to combine with processes such as film molding and lamination. The corona discharge treatment can modify the wetting tension (mN / m) of the film surface to improve the coatability of the adhesive. In general, the amount of discharge (W · min / m 2 ) and the wetting tension on the film surface are in a proportional relationship, and increasing the amount of discharging tends to increase the wetting tension on the film surface.
フィルム表面のぬれ張力は、ＪＩＳ Ｋ６７６８に準拠して測定することができる。本フィルムの粘着層を設ける溶剤塗工法に必要なフィルム表面のぬれ張力は特に制限されないが、３０〜５０ｍＮ／ｍが好ましく、より好ましくは３２〜４８ｍＮ／ｍ、さらに好ましくは３４〜４８ｍＮ／ｍである。 The wetting tension of the film surface can be measured according to JIS K6768. The wetting tension of the film surface required for the solvent coating method for providing the adhesive layer of the film is not particularly limited, but is preferably 30 to 50 mN / m, more preferably 32 to 48 mN / m, and further preferably 34 to 48 mN / m. is there.
前記溶剤塗工法によると、例えばコロナ放電照射によりぬれ張力が改質されたフィルム表面に、粘着剤を溶剤塗工し、乾燥することで本フィルムの粘着層を得ることができる。
前記溶剤塗工法は、粘着剤を含む溶液の粘度を調整して塗工を行うことが可能なため、粘着層の厚みを制御し易い利点がある。前記溶剤塗工としては、従来公知の塗工方法、例えば、ロールコーター法、グラビアロール法、バーコーター法、ダイコーター法、ナイフコート法、コンマコーター法などが挙げられる。溶剤塗工の乾燥条件には特に制限がないが、一般的には、６０〜２００℃の温度範囲において、１０秒〜１０分間乾燥することが好ましい。より好ましくは、８０℃〜１７０℃において、１５秒〜５分間乾燥する。
According to the solvent coating method, for example, the adhesive layer of the present film can be obtained by solvent coating an adhesive on the surface of the film whose wetting tension has been modified by corona discharge irradiation and drying.
The solvent coating method has an advantage that the thickness of the adhesive layer can be easily controlled because the coating can be performed by adjusting the viscosity of the solution containing the adhesive. Examples of the solvent coating include conventionally known coating methods such as a roll coater method, a gravure roll method, a bar coater method, a die coater method, a knife coating method, and a comma coater method. The drying conditions for solvent coating are not particularly limited, but in general, it is preferable to dry for 10 seconds to 10 minutes in a temperature range of 60 to 200 ° C. More preferably, it is dried at 80 ° C. to 170 ° C. for 15 seconds to 5 minutes.
溶剤塗工法に用いる粘着剤としては、例えば、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、オレフィン系粘着剤、スチレン系粘着剤などが挙げられる。なかでも、粘着力の制御が容易であり、かつ耐熱性の観点からアクリル系粘着剤が好ましい。 Examples of the pressure-sensitive adhesive used in the solvent coating method include an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, an olefin-based pressure-sensitive adhesive, and a styrene-based pressure-sensitive adhesive. Of these, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of easy control of adhesive strength and heat resistance.
アクリル系粘着剤に含まれるアクリル系重合体としては、例えば、（メタ）アクリル酸エステル化合物の単独重合体、（メタ）アクリル酸エステル化合物とコモノマーとの共重合体等が挙げられる。（メタ）アクリル酸エステル化合物としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ジメチルアミノエチルアクリレート等が挙げられる。これらの（メタ）アクリル酸エステル化合物は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the acrylic polymer contained in the acrylic pressure-sensitive adhesive include a homopolymer of a (meth) acrylic acid ester compound, a copolymer of a (meth) acrylic acid ester compound and a comonomer, and the like. Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and dimethylaminoethyl acrylate. Can be mentioned. These (meth) acrylic acid ester compounds may be used alone or in combination of two or more.
（メタ）アクリル系共重合体を構成するコモノマーとしては、例えば、酢酸ビニル、（メタ）アクリルニトリル、メチロール（メタ）アクリルアミド、無水マレイン酸等が挙げられる。これらのコモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the comonomer constituting the (meth) acrylic copolymer include vinyl acetate, (meth) acrylonitrile, methylol (meth) acrylamide, maleic anhydride and the like. These comonomer may be used alone or in combination of 2 or more types.
さらに、溶剤塗工法に用いる粘着剤に、必要に応じて架橋剤等を加えてもよい。架橋剤としては、例えば、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル等のエポキシ系化合物、Ｎ，Ｎ‘−ジフェニルメタン−４，４’−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ‘−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキシアミド）等のアジリジン化合物、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート等のイソシアネート系化合物が挙げられる。 Further, a cross-linking agent or the like may be added to the pressure-sensitive adhesive used in the solvent coating method, if necessary. Examples of the cross-linking agent include epoxy compounds such as sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether, N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxylamide), and N, N'-hexa. Examples thereof include aziridine compounds such as methylene-1,6-bis (1-aziridine carboxylamide) and isocyanate compounds such as tetramethylene diisocyanate and hexamethylene diisocyanate.
前記架橋剤の含有量は、フィルム表面との密着力や耐熱性の観点から、アクリル系重合体１００質量部に対して、０．１〜１０質量部であることが好ましい。
前記溶剤塗工法による粘着層の厚みは特に制限されず、所望の用途に応じて適宜選択すればよいが、例えば、１〜２０μｍ、好ましくは２〜１２μｍである。
The content of the cross-linking agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer from the viewpoint of adhesion to the film surface and heat resistance.
The thickness of the adhesive layer obtained by the solvent coating method is not particularly limited and may be appropriately selected depending on the desired application. For example, it is 1 to 20 μm, preferably 2 to 12 μm.
前記粘着層を設ける方法として、共押出製法も挙げられる。共押出製法は、基材層となる樹脂と粘着剤を溶融状態にして多層化して得られる。溶剤の使用が不要であり、基材層と粘着剤とを同時に製膜できる利点がある。 As a method of providing the adhesive layer, a coextrusion manufacturing method can also be mentioned. The coextrusion method is obtained by melting the resin and the pressure-sensitive adhesive, which are the base material layers, into multiple layers. There is no need to use a solvent, and there is an advantage that the base material layer and the adhesive can be formed at the same time.
共押出製法に適する粘着剤としては、公知の粘着力を有する単独重合体、または共重合体を用いることができる。共押出製法に用いられる粘着剤は、例えばスチレン系重合体、および、（メタ）アクリル系重合体から選ばれる１種類以上の重合体を含むことが好ましい。 As a pressure-sensitive adhesive suitable for the coextrusion production method, a homopolymer having a known adhesive strength or a copolymer can be used. The pressure-sensitive adhesive used in the coextrusion method preferably contains, for example, one or more polymers selected from, for example, a styrene-based polymer and a (meth) acrylic-based polymer.
共押出製法に用いられる粘着剤としては、例えば（メタ）アクリロイル基を有する重合体であれば特に制限されないが、例えば、エチレン性二重結合を有するモノマーと、反応性官能基を有する共重合性モノマーとを共重合して得られた共重合体と、前記反応性官能基と反応し得る基を有する重合性炭素−炭素二重結合を含むモノマーと、を反応させた重合体が挙げられる。 The pressure-sensitive adhesive used in the coextrusion method is not particularly limited as long as it is a polymer having a (meth) acryloyl group, but is, for example, a copolymer having an ethylenic double bond and a reactive functional group. Examples thereof include a polymer obtained by reacting a copolymer obtained by copolymerizing with a monomer and a monomer containing a polymerizable carbon-carbon double bond having a group capable of reacting with the reactive functional group.
さらに、前記共押出製法に用いられる粘着材として具体的には、スチレン・ブタジエン共重合体（ＳＢＲ）、スチレン・イソプレン・スチレン共重合体（ＳＩＳ）、スチレン・ブタジエン・スチレン共重合体（ＳＢＳ）、スチレン・エチレン・ブタジエン・スチレン共重合体（ＳＥＢＳ）、これらの水素化物、スチレン・イソブチレン・スチレントリブロック共重合体（ＳＩＢＳ）、スチレン・イソブチレンジブロック共重合体（ＳＩＢ）等が挙げられる。好ましくは、ＳＩＢＳ、ＳＩＢ、およびこれらの混合化合物である。 Further, as the pressure-sensitive adhesive material used in the coextrusion production method, specifically, a styrene-butadiene copolymer (SBR), a styrene-isoprene-styrene copolymer (SIS), and a styrene-butadiene-styrene copolymer (SBS). , Styrene-ethylene-butadiene-styrene copolymer (SEBS), hydrides thereof, styrene-isobutylene-styrene triblock copolymer (SIBS), styrene-isobutyrene block copolymer (SIB) and the like. Preferably, it is SIBS, SIB, and a mixed compound thereof.
前記エチレン性二重結合を有するモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル等の（メタ）アクリル酸アルキルエステル酢酸ビニル等のビニルエステル；アクリロニトリル；（メタ）アクリルアミド；スチレンが挙げられる。 Examples of the monomer having an ethylenic double bond include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Vinyl esters such as alkyl ester vinyl acetate; acrylonitrile; (meth) acrylamide; styrene.
これらは単独で用いてもよく、２種以上を併用してもよい。
前記反応性官能基を有する共重合性モノマーとしては、例えば、（メタ）アクリル酸、マレイン酸、２−ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミドが挙げられる。
These may be used alone or in combination of two or more.
Examples of the copolymerizable monomer having a reactive functional group include (meth) acrylic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and N-methylol (meth) acrylamide. ..
これらは単独で用いてもよく、２種以上を併用してもよい。
前記反応性官能基と反応し得る基を有する重合性炭素−炭素二重結合を含むモノマーとしては、特に限定されない。例えば、前記反応性官能基と、該反応性官能基と反応し得る基との組み合わせの例としては、カルボキシル基とエポキシ基、カルボキシル基とアジリジル基、水酸基とイソシアネート基が挙げられる。
These may be used alone or in combination of two or more.
The monomer containing a polymerizable carbon-carbon double bond having a group capable of reacting with the reactive functional group is not particularly limited. For example, examples of a combination of the reactive functional group and a group capable of reacting with the reactive functional group include a carboxyl group and an epoxy group, a carboxyl group and an aziridyl group, and a hydroxyl group and an isocyanate group.
これらは単独で用いてもよく、２種以上を併用してもよい。
また、前記共押出製法に用いる粘着材は、粘着力の調整を目的として、本発明の特性を損なわない範囲で、ポリエチレンおよびポリプロピレンに代表される公知のポリオレフィン、従来公知の添加剤として、例えば、ポリエステルエラストマー等の樹脂改質剤、石油樹脂、水添系石油樹脂、クロマン・インデン樹脂、ロジン誘導体、テルペン系樹脂等の粘着付与剤、ポリオレフィン系ワックス、シリコーン系ワックス、シリカやタルクに代表されるアンチブロッキング剤等公知の離型付与剤、帯電防止剤、導電剤、耐候剤、結晶核剤、酸化防止剤を含有してもよい。
前記共押出製法による粘着層の厚みは特に制限されず、所望の用途に応じて適宜選択すればよいが、例えば、１〜１００μｍ、好ましくは４〜８０μｍである。
These may be used alone or in combination of two or more.
Further, the pressure-sensitive adhesive used in the co-extrusion method is a known polyolefin represented by polyethylene and polypropylene, as a conventionally known additive, for example, as long as the characteristics of the present invention are not impaired for the purpose of adjusting the pressure-sensitive adhesive strength. Resin modifiers such as polyester elastomers, petroleum resins, hydrogenated petroleum resins, chroman-inden resins, rosin derivatives, tackifiers such as terpene resins, polyolefin waxes, silicone waxes, silica and talc. It may contain a known release-imparting agent such as an anti-blocking agent, an antioxidant, a conductive agent, a weather resistant agent, a crystal nucleating agent, and an antioxidant.
The thickness of the pressure-sensitive adhesive layer produced by the coextrusion method is not particularly limited and may be appropriately selected depending on the desired application. For example, it is 1 to 100 μm, preferably 4 to 80 μm.
＜背面層＞
本フィルムにおいては、離型性、剛性、寸法安定性、ハンドリング性等の扱い易さなどを考慮し、基材層の、粘着層が設けられた面とは反対側の面に、背面層を設けてもよい。
前記背面層としては、ポリオレフィン、ポリエステル、ポリアミド、ポリスチレン、シリコーン樹脂、フッ素樹脂、ポリ塩化ビニルなどのビニル重合体等の公知の樹脂を含む層が挙げられる。これらの中でも、取り扱い性に優れる、ポリオレフィンからなる層が好ましい。
<Back layer>
In this film, in consideration of ease of handling such as releasability, rigidity, dimensional stability, and handleability, the back layer is provided on the surface of the base material layer opposite to the surface on which the adhesive layer is provided. It may be provided.
Examples of the back layer include a layer containing a known resin such as a vinyl polymer such as polyolefin, polyester, polyamide, polystyrene, silicone resin, fluororesin, and polyvinyl chloride. Among these, a layer made of polyolefin, which is excellent in handleability, is preferable.
該ポリオレフィンとしては、具体的には、プロピレン単独重合体、プロピレンと少なくとも１種の炭素数３以外のα−オレフィンとからなる共重合体、高圧法低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、４−メチル−１−ペンテン共重合体等が挙げられるが、これらの中でも、フィッシュアイ（架橋ゲル）が生じにくい、プロピレン単独重合体、プロピレンと少なくとも１種の炭素数３以外のα−オレフィンとからなる共重合体等のプロピレン系重合体がより好ましく、離形性等の点から、プロピレンと少なくとも１種の炭素数３以外のα−オレフィンとからなるブロック共重合体がさらに好ましい。 Specific examples of the polyolefin include a propylene homopolymer, a copolymer composed of propylene and at least one α-olefin having a carbon number other than 3, high-pressure low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. Examples thereof include high-density polyethylene and 4-methyl-1-pentene copolymer. Among these, propylene homopolymer, which is less likely to cause fish eyes (crosslinked gel), propylene and at least one α other than α having 3 carbon atoms. A propylene-based polymer such as a copolymer composed of −olefin is more preferable, and a block copolymer composed of propylene and at least one α-olefin having a carbon number other than 3 is further preferable from the viewpoint of releasability and the like. ..
前記背面層は、１種の樹脂を含んでもよく、２種以上の樹脂を含んでもよく、また必要に応じて、本発明の特性を損なわない範囲で、従来公知の添加剤、例えば、ポリオレフィン系ワックス、液状シリコン樹脂、テトラフロロエチレン樹脂、メタクリル樹脂粉末、微粉末架橋樹脂、微粉末シリカ、微粉末酸化アルミニウム、タルクに代表されるアンチブロッキング剤等の公知の離型付与剤、帯電防止剤、染料、塩酸吸収剤、導電剤、耐候剤、結晶核剤、酸化防止剤、滑剤を含有してもよい。 The back layer may contain one kind of resin, two or more kinds of resins, and if necessary, a conventionally known additive, for example, a polyolefin-based one, as long as the characteristics of the present invention are not impaired. Known mold release agents such as wax, liquid silicon resin, tetrafluoroethylene resin, methacrylic resin powder, fine powder crosslinked resin, fine powder silica, fine powder aluminum oxide, antiblocking agent typified by talc, antistatic agent, It may contain a dye, a hydrochloric acid absorber, a conductive agent, a weather resistant agent, a crystal nucleating agent, an antioxidant, and a lubricant.
酸化防止剤としては、公知の酸化防止剤が使用可能である。具体的には、ヒンダードフェノール化合物、硫黄系酸化防止剤、ラクトーン系酸化防止剤、有機ホスファイト化合物、有機ホスフォナイト化合物、あるいはこれらを数種組み合わせたものが使用できる。 As the antioxidant, a known antioxidant can be used. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination thereof can be used.
滑剤としては、例えば、ラウリル酸、オレイン酸、パルミチン酸、ステアリン酸などの飽和または不飽和脂肪酸のナトリウム、カルシウム、マグネシウム塩などが挙げられ、これらは単独で、または２種以上を混合して用いることができる。滑剤の配合量は、重合体組成物１００質量部に対して、０．１〜３質量部、好ましくは０．１〜２質量部程度であることが望ましい。
前記背面層を設ける場合、背面層の厚みは特に制限されず、所望の用途に応じて適宜選択すればよいが、例えば、１〜１００μｍ、好ましくは２〜８０μｍである。
Examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, oleic acid, palmitic acid and stearic acid, which are used alone or in combination of two or more. be able to. The blending amount of the lubricant is preferably about 0.1 to 3 parts by mass, preferably about 0.1 to 2 parts by mass with respect to 100 parts by mass of the polymer composition.
When the back layer is provided, the thickness of the back layer is not particularly limited and may be appropriately selected depending on the desired application, but is, for example, 1 to 100 μm, preferably 2 to 80 μm.
＜表面保護フィルムの製造方法＞
本フィルムを製造する方法は特に制限されないが、各層を形成する重合体等を用い、共押出成形や押出ラミネートなどの公知の成形方法により製造することができる。また、予め、キャストフィルム成形、あるいはインフレーションフィルム成形等にて得られた層上に、押出コーティングする方法や各層となるフィルムをドライラミネーションなどにより積層する方法も挙げることができる。
<Manufacturing method of surface protective film>
The method for producing this film is not particularly limited, but it can be produced by a known molding method such as coextrusion molding or extrusion lamination using a polymer or the like forming each layer. In addition, a method of extrusion coating on a layer obtained by casting film molding, inflation film molding, or the like in advance, or a method of laminating a film to be each layer by dry lamination or the like can also be mentioned.
＜積層体＞
本発明では、表面保護フィルムと被着体とを貼り付けて得られた構造物を積層体という。
前記被着体としては特に制限されないが、ＪＩＳ Ｋ７１２７に準拠（ただし、幅１５ｍｍ、長さ１００ｍｍ、厚み５０μｍである試験片タイプ２を使用）して、２３℃、試験速度２００ｍｍ／分により測定される引張弾性率が１５００ＭＰａ以上、好ましくは１８００〜４５００ＭＰａであるものを好適に用いることができる。
<Laminated body>
In the present invention, a structure obtained by attaching a surface protective film and an adherend is referred to as a laminate.
The adherend is not particularly limited, but is measured at 23 ° C. and a test speed of 200 mm / min in accordance with JIS K7127 (however, using a test piece type 2 having a width of 15 mm, a length of 100 mm, and a thickness of 50 μm). A material having a tensile elastic modulus of 1500 MPa or more, preferably 1800 to 4500 MPa can be preferably used.
引張弾性率が前記範囲にある被着体は、室温下で硬く、収縮しにくい特徴がある。
前記被着体の具体例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリエチレンナフタレート（ＰＥＮ）、ポリイミド（ＰＩ）、ポリアミド（ＰＡ）、ポリカーボネート（ＰＣ）、シクロオレフィンポリマー（ＣＯＰ）、シクロオレフィンコポリマー（ＣＯＣ）、ポリ（メタ）アクリレート、シリコンウエハ、ガラスなどが挙げられる。
An adherend having a tensile elastic modulus in the above range is characterized by being hard at room temperature and less likely to shrink.
Specific examples of the adherend include polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), polycarbonate (PC), and cycloolefin polymer (PET). COP), cycloolefin copolymer (COC), poly (meth) acrylate, silicon wafer, glass and the like.
以下に本発明を実施例によって詳細な説明をするが、本発明はこれら実施例に限定されるものではない。
熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）の物性は、以下のように測定した。
＜構成単位の含有率＞
ポリマー中の４−メチル−１−ペンテンから導かれる構成単位の含有率（以下、４−メチル−１−ペンテン含量ともいう）、およびα−オレフィンから導かれる構成単位の含量率（以下、α−オレフィン含量ともいう）の測定は、以下の装置および条件により13Ｃ−ＮＭＲで測定した結果を基にして行った。ただし、本測定結果のα−オレフィン含量には、４−メチル−１−ペンテン含量は含まれない。
The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples.
The physical characteristics of the thermoplastic resin (X) and the thermoplastic resin (Y) were measured as follows.
<Content rate of constituent units>
The content of the structural unit derived from 4-methyl-1-pentene in the polymer (hereinafter, also referred to as 4-methyl-1-pentene content) and the content rate of the structural unit derived from α-olefin (hereinafter, α- The measurement of (also referred to as olefin content) was carried out based on the results of measurement by 13 C-NMR with the following equipment and conditions. However, the α-olefin content of this measurement result does not include the 4-methyl-1-pentene content.
日本電子社製ＥＣＰ５００型核磁気共鳴装置を用い、オルトジクロロベンゼン／重水素化ベンゼン（８０／２０容量％）混合溶媒、試料濃度５５ｍｇ／０．６ｍｌ、測定温度１２０℃において、観測核は13Ｃ（１２５ＭＨｚ）、シーケンスはシングルパルスプロトンデカップリング、パルス幅は４．７μ秒（４５°パルス）、繰り返し時間は５．５秒、積算回数は１万回以上とし、２７．５０ｐｐｍをケミカルシフトの基準値として測定した。得られた13Ｃ−ＮＭＲスペクトルにより、４−メチル−１−ペンテン含量、α−オレフィン含量を測定した。 Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., the observed nucleus is 13 C at a mixed solvent of orthodichlorobenzene / deuterated benzene (80/20% by volume), a sample concentration of 55 mg / 0.6 ml, and a measurement temperature of 120 ° C. (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μsec (45 ° pulse), repetition time is 5.5 seconds, integration frequency is 10,000 or more, and 27.50 ppm is the standard for chemical shift. Measured as a value. The 4-methyl-1-pentene content and the α-olefin content were measured from the obtained 13 C-NMR spectrum.
＜極限粘度〔η〕＞
極限粘度〔η〕は、デカリン溶媒を用いて、１３５℃で測定した。重合パウダー、ペレットまたは樹脂塊を約２０ｍｇ採取し、デカリン１５ｍｌに溶解して、１３５℃に加熱したオイルバス中で比粘度ηｓｐを測定した。このデカリン溶液にデカリン溶媒を５ｍｌ追加して希釈後、同じように比粘度ηｓｐを測定した。この希釈操作をさらに２回繰り返し、濃度（Ｃ）をゼロに外挿した時のηｓｐ／Ｃの値を極限粘度として算出した（下式参照）。
[η]＝ｌｉｍ（ηｓｐ／Ｃ）、ただしＣ＝０
<Ultimate viscosity [η]>
The ultimate viscosity [η] was measured at 135 ° C. using a decalin solvent. About 20 mg of the polymerized powder, pellets or resin mass was collected, dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath heated to 135 ° C. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to zero was calculated as the ultimate viscosity (see the formula below).
[η] = lim (ηsp / C), but C = 0
＜重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、分子量分布（Ｍｗ／Ｍｎ値）＞
各分子量は、ゲルパーミエーションクロマトグラフィーにより測定した。液体クロマトグラフとしてＷａｔｅｒｓ製ＡＬＣ／ＧＰＣ１５０−Ｃｐｌｕｓ型（示唆屈折計検出器一体型）を用い、分離カラムとして東ソー株式会社製ＧＭＨ６−ＨＴを２本、およびＧＭＨ６−ＨＴＬを２本直列接続して用い、移動相媒体としてｏ−ジクロロベンゼン、および酸化防止剤として０．０２５質量％のＢＨＴ（武田薬品工業社製）を用い、移動相媒体を１．０ｍｌ／分で移動させ、試料濃度は１５ｍｇ／１０ｍｌとし、試料注入量は５００マイクロリットルとし、検出器は示差屈折計を用いた。標準ポリスチレンとしては、重量平均分子量（Ｍｗ）が１，０００以上、４０００，０００以下において、東ソー社製の標準ポリスチレンを用いた。
<Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn value)>
Each molecular weight was measured by gel permeation chromatography. Waters ALC / GPC150-Cplus type (integrated differential refractometer detector) is used as the liquid chromatograph, and two GMH6-HT manufactured by Toso Co., Ltd. and two GMH6-HTL are connected in series as the separation column. Using o-dichlorobenzene as the mobile phase medium and 0.025% by mass BHT (manufactured by Takeda Yakuhin Kogyo Co., Ltd.) as the antioxidant, the mobile phase medium was moved at 1.0 ml / min, and the sample concentration was 15 mg / min. The sample injection volume was 10 ml, the sample injection volume was 500 microliters, and a differential refractometer was used as the detector. As the standard polystyrene, standard polystyrene manufactured by Tosoh Corporation was used when the weight average molecular weight (Mw) was 1,000 or more and 4,000,000 or less.
得られたクロマトグラムを、公知の方法によって、標準ポリスチレンサンプルを用いて検量線を作成して解析することで、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、および分子量分布（Ｍｗ／Ｍｎ値）を算出した。１サンプル当たりの測定時間は６０分であった。 The obtained chromatogram is analyzed by preparing a calibration curve using a standard polystyrene sample by a known method, whereby the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are analyzed. Value) was calculated. The measurement time per sample was 60 minutes.
＜メルトマスフローレイト（ＭＦＲ）＞
メルトマスフローレイトは、ＪＩＳ Ｋ７２１０−１に準拠して、前記熱可塑性樹脂（Ｘ）については、温度２６０℃、荷重５．０ｋｇで測定し、前記熱可塑性樹脂（Ｙ）については、温度２３０℃、荷重２．１６ｋｇで測定した。
<Melt Mass Flow Rate (MFR)>
The melt mass flow rate was measured at a temperature of 260 ° C. and a load of 5.0 kg for the thermoplastic resin (X) in accordance with JIS K7210-1, and the temperature of the thermoplastic resin (Y) was 230 ° C. It was measured with a load of 2.16 kg.
＜融点＞
ＪＩＳ Ｋ７１２１に準拠し、セイコーインスルメンツ社製示差走査熱量計ＤＳＣ２２０Ｃを用い、昇温速度１０℃／分で測定される融解ピーク頂点の最も高い温度を融点（Ｔｍ）とした。融解ピーク頂点が現れなかった場合は、融点が観測されないと評価した。
<Melting point>
The highest temperature of the melting peak peak measured at a heating rate of 10 ° C./min was defined as the melting point (Tm) by using a differential scanning calorimeter DSC220C manufactured by Seiko Instruments Co., Ltd. in accordance with JIS K7121. If the melting peak apex did not appear, it was evaluated that the melting point was not observed.
＜密度＞
密度は、ＪＩＳ Ｋ７１１２に準拠して、密度勾配管を用いて測定した。
<Density>
The density was measured using a density gradient tube according to JIS K7112.
＜ｔａｎδ（損失正接）の測定＞
各重合体から、厚さ２ｍｍのプレスシートを作製して試験片とした。
Ａｎｔｏｎ Ｐａａｒ社製レオメータＭＣＲ３０１を用いて、周波数１．６Ｈｚ、歪み設定０．１％、昇温速度２℃／分の条件にて、−２０〜１００℃における動的粘弾性の温度分散を測定し、ガラス転移温度に起因する損失正接（ｔａｎδ）が最大値となる温度（本発明において、「ｔａｎδピーク温度」ともいう。）、その際の損失正接（ｔａｎδ）の値（本発明において、「ｔａｎδピーク値」ともいう。）を測定した。
熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）を以下の方法により調製した。
<Measurement of tan δ (tangent loss)>
A press sheet having a thickness of 2 mm was prepared from each polymer and used as a test piece.
Using the Antonio Pear rheometer MCR301, the temperature dispersion of dynamic viscoelasticity at -20 to 100 ° C was measured under the conditions of a frequency of 1.6 Hz, a strain setting of 0.1%, and a temperature rise rate of 2 ° C / min. , The temperature at which the loss tangent (tan δ) due to the glass transition temperature becomes the maximum value (also referred to as “tan δ peak temperature” in the present invention), and the value of the loss tangent (tan δ) at that time (in the present invention, “tan δ”). It is also called "peak value").
The thermoplastic resin (X) and the thermoplastic resin (Y) were prepared by the following methods.
＜熱可塑性樹脂（Ｘ）＞
国際公開２００６／０５４６１３号パンフレットの方法に準じ、４−メチル−１−ペンテン、１−ヘキサデセン、１−オクタデセン、水素の割合を調整し、表１に示す各物性を有する熱可塑性樹脂（Ｘ）を得た。各物性の測定結果を表１に示す。
<Thermoplastic resin (X)>
Adjust the proportions of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene, and hydrogen according to the method of the International Publication No. 2006/054613 pamphlet, and obtain a thermoplastic resin (X) having each of the physical characteristics shown in Table 1. Obtained. Table 1 shows the measurement results of each physical property.
＜熱可塑性樹脂（Ｙ−１）＞
充分に窒素置換した容量１．５リットルの攪拌翼付ＳＵＳ製オートクレーブに、２３℃でノルマルヘキサン３００ｍｌ（乾燥窒素雰囲気下、活性アルミナ上で乾燥したもの）、４−メチル−１−ペンテンを４５０ｍｌ挿入した。このオートクレーブに、トリイソブチルアルミニウム（ＴＩＢＡＬ）の１．０ｍｍｏｌ／ｍｌトルエン溶液を０．７５ｍｌ挿入して攪拌機を回した。
<Thermoplastic resin (Y-1)>
Insert 300 ml of normal hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23 ° C into an autoclave made of SUS with a stirring blade having a capacity of 1.5 liters sufficiently replaced with nitrogen. did. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was inserted into this autoclave, and the stirrer was rotated.
次に、オートクレーブを内温６０℃まで加熱し、全圧が０．４０ＭＰａ（ゲージ圧）となるようにプロピレンで加圧した。続いて、予め調製しておいたメチルアルミノキサンをＡｌ換算で１ｍｍｏｌ、ジフェニルメチレン（１−エチル−３−ｔ−ブチル−シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−フルオレニル）ジルコニウムジクロリドを０．０１ｍｍｏｌを含むトルエン溶液０．３４ｍｌを窒素でオートクレーブに圧入し、重合を開始した。重合反応中、オートクレーブ内温が６０℃になるように温度を調整した。重合開始６０分後、オートクレーブにメタノール５ｍｌを窒素で圧入し重合を停止し、オートクレーブを大気圧まで脱圧した。反応溶液にアセトンを攪拌しながら注いだ。 Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure became 0.40 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride 0.34 ml of a toluene solution containing 0.01 mmol of the mixture was press-fitted into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the temperature inside the autoclave was 60 ° C. 60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.
得られた溶媒を含むパウダー状の重合体を１００℃、減圧下で１２時間乾燥した。得られた熱可塑性樹脂（Ｙ−１）は３６．９ｇで、樹脂中の４−メチル−１−ペンテン含量は７４ｍｏｌ％、プロピレン含量は２６ｍｏｌ％であった。ＤＳＣ測定を行ったところ、融点（Ｔｍ）は観測されなかった。各物性の測定結果を表１に示す。 The powdery polymer containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained thermoplastic resin (Y-1) weighed 36.9 g, and the 4-methyl-1-pentene content in the resin was 74 mol% and the propylene content was 26 mol%. When DSC measurement was performed, no melting point (Tm) was observed. Table 1 shows the measurement results of each physical property.
＜熱可塑性樹脂（Ｙ−２）＞
充分に窒素置換した容量１．５リットルの攪拌翼付ＳＵＳ製オートクレーブに、２３℃でノルマルヘキサン３００ｍｌ（乾燥窒素雰囲気下、活性アルミナ上で乾燥したもの）、４−メチル−１−ペンテンを４５０ｍｌ装入した。このオートクレーブに、トリイソブチルアルミニウム（ＴＩＢＡＬ）の１．０ｍｍｏｌ／ｍｌトルエン溶液を０．７５ｍｌ挿入して攪拌機を回した。
<Thermoplastic resin (Y-2)>
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently substituted with nitrogen was loaded with 300 ml of normal hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23 ° C. I entered. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was inserted into this autoclave, and the stirrer was rotated.
次に、オートクレーブを内温６０℃まで加熱し、全圧が０．１９ＭＰａ（ゲージ圧）となるようにプロピレンで加圧した。続いて、予め調製しておいたメチルアルミノキサンをＡｌ換算で１ｍｍｏｌ、ジフェニルメチレン（１−エチル−３−ｔ−ブチル−シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−フルオレニル）ジルコニウムジクロリドを０．０１ｍｍｏｌを含むトルエン溶液０．３４ｍｌを窒素でオートクレーブに圧入し、重合を開始した。重合反応中、オートクレーブ内温が６０℃になるように温度を調整した。重合開始６０分後、オートクレーブにメタノール５ｍｌを窒素で圧入し重合を停止し、オートクレーブを大気圧まで脱圧した。反応溶液にアセトンを攪拌しながら注いだ。 Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure became 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride 0.34 ml of a toluene solution containing 0.01 mmol of the mixture was press-fitted into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the temperature inside the autoclave was 60 ° C. 60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.
得られた溶媒を含むパウダー状の重合体を１００℃、減圧下で１２時間乾燥した。得られた熱可塑性樹脂（Ｙ−２）は４４．０ｇで、樹脂中の４−メチル−１−ペンテン含量は８４ｍｏｌ％、プロピレン含量は１６ｍｏｌ％であった。ＤＳＣ測定を行ったところ、融点（Ｔｍ）は１３１℃であった。各物性の測定結果を表１に示す。 The powdery polymer containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained thermoplastic resin (Y-2) weighed 44.0 g, and the 4-methyl-1-pentene content in the resin was 84 mol% and the propylene content was 16 mol%. When the DSC measurement was performed, the melting point (Tm) was 131 ° C. Table 1 shows the measurement results of each physical property.
［実施例１］
熱可塑性樹脂（Ｘ）８０質量％と、熱可塑性樹脂（Ｙ−１）２０質量％の割合でそれぞれペレットを混合配合し、スクリュー直径φ２５ｍｍ、Ｌ／Ｄ＝２６（スクリュー長さ：Ｌ、スクリュー直径：Ｄ）の単軸押出機に、Ｔダイ幅３５０ｍｍとエアーチャンバーをそれぞれ装備したキャストフィルム成形機を用いて、シリンダー温度２７０〜２８０℃、スクリュー回転数３０〜３５ｒｐｍ、冷却ロール温度３０℃、引取速度１．５〜２．０ｍ／分の条件範囲で調整し、厚み４０μｍの単層フィルムを得た。
[Example 1]
Pellets are mixed and blended at a ratio of 80% by mass of the thermoplastic resin (X) and 20% by mass of the thermoplastic resin (Y-1), and the screw diameter is φ25 mm, L / D = 26 (screw length: L, screw diameter). : Using a cast film forming machine equipped with a T-die width of 350 mm and an air chamber in the single-screw extruder of D), cylinder temperature 270 to 280 ° C, screw rotation speed 30 to 35 rpm, cooling roll temperature 30 ° C, pick-up. The speed was adjusted in the condition range of 1.5 to 2.0 m / min to obtain a single-layer film having a thickness of 40 μm.
次いで、単層フィルムの一方の片面にコロナ放電照射を行い、フィルム表面のぬれ張力が４０ｍＮ／ｍになるように放電量を調整し、紙管を用いて巻き取った。
さらに、巻き取った単層フィルムを繰り出し、前記のぬれ張力が調整されたフィルム面に対し、ロールコーターを用いてアクリル系粘着剤（綜研化学社製ＳＫダイン（登録商標）、銘柄名１９３９Ｕ）の塗工した後、温度１００℃で１分間の乾燥処理を経て、前記単層フィルムからなる基材層の表面に膜厚８μｍの粘着層を設けて形成された表面保護フィルムを作製した。この表面保護フィルムを用いて、後述の評価を行った。その結果を表２に示す。
Next, one side of the single-layer film was irradiated with corona discharge, the amount of discharge was adjusted so that the wetting tension on the film surface was 40 mN / m, and the film was wound up using a paper tube.
Further, the wound single-layer film is unwound, and an acrylic pressure-sensitive adhesive (SK Dyne (registered trademark) manufactured by Soken Kagaku Co., Ltd., brand name 1939U) is applied to the film surface on which the wetting tension is adjusted by using a roll coater. After coating, the film was dried at a temperature of 100 ° C. for 1 minute to prepare a surface protective film formed by providing an adhesive layer having a thickness of 8 μm on the surface of the base material layer made of the single-layer film. Using this surface protective film, the evaluation described later was performed. The results are shown in Table 2.
［実施例２〜１０］
使用する樹脂の種類、および配合量を表２に記載した通り変更した以外は、実施例１と同様にして、表面保護フィルムを作製した。前記で作製した表面保護フィルムを用いて、後述の評価を行った。その結果を表２に示す。
[Examples 2 to 10]
A surface protective film was produced in the same manner as in Example 1 except that the type of resin used and the blending amount were changed as shown in Table 2. The evaluation described later was carried out using the surface protective film prepared above. The results are shown in Table 2.
［比較例１〜５］
使用する樹脂の種類、および配合量を表３に記載した通り変更した以外は、実施例１と同様にして、表面保護フィルムを作製した。前記で作製した表面保護フィルムを用いて、後述の評価を行った。その結果を表３に示す。
[Comparative Examples 1 to 5]
A surface protective film was produced in the same manner as in Example 1 except that the type of resin used and the blending amount were changed as shown in Table 3. The evaluation described later was carried out using the surface protective film prepared above. The results are shown in Table 3.
＜寸法変化率＞
表面保護フィルムから、１２０ｍｍ×１２０ｍｍの寸法に裁断し、その内側に１００ｍｍ×１００ｍｍの標線を設けた試験片を作製し、オーブン中で１５０℃、３０分間保持した。その後、オーブンから表面保護フィルムを取り出して、室温まで自然放冷し、ＪＩＳ Ｋ７１３３に準拠して、ＭＤ方向およびＴＤ方向の寸法変化率を測定した。
<Dimensional change rate>
A test piece was cut from the surface protective film to a size of 120 mm × 120 mm, and a test piece provided with a 100 mm × 100 mm marked line inside thereof was prepared and held in an oven at 150 ° C. for 30 minutes. Then, the surface protective film was taken out from the oven, allowed to cool naturally to room temperature, and the dimensional change rate in the MD direction and the TD direction was measured according to JIS K7133.
＜積層体の反り評価＞
被着体として、厚み５０μｍの光学基材用ポリエチレンテレフタレートフィルム（東洋紡社製コスモシャイン（登録商標）、銘柄名Ａ４１００）を１００ｍｍ×１００ｍｍの寸法に裁断し、該被着体に積層するように、１００ｍｍ×１００ｍｍに裁断した表面保護フィルムを、ＭＤ方向およびＴＤ方向がそれぞれ一致するように貼り合わせた後、２本連結したニップロールを通過させて試験片を圧着し、積層体を作製した。
<Evaluation of warpage of laminated body>
As an adherend, a polyethylene terephthalate film for an optical substrate having a thickness of 50 μm (Cosmo Shine (registered trademark) manufactured by Toyobo Co., Ltd., brand name A4100) is cut into a size of 100 mm × 100 mm and laminated on the adherend. A surface protective film cut into 100 mm × 100 mm was laminated so that the MD direction and the TD direction coincided with each other, and then the test pieces were crimped by passing through two connected nip rolls to prepare a laminated body.
積層体を温度２３℃、湿度８０％ＲＨの条件で２４時間静置した後、１５０℃に設定したオーブン中で３０分間、無荷重の状態で静置した。
積層体をオーブンから取り出して室温まで自然放冷した後、鉄製の定盤に表面保護フィルムが上側となるように積層体を置いた。
The laminate was allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 80% RH, and then allowed to stand in an oven set at 150 ° C. for 30 minutes without a load.
The laminate was taken out of the oven and allowed to cool naturally to room temperature, and then the laminate was placed on an iron surface plate so that the surface protective film was on the upper side.
積層体の四隅の定盤からの高さ（定盤からの浮き上がり）をステンレス定規で測定し、これらの測定値から四隅の平均高さ（以下「反り量」ともいう。）を算出し、下記の基準で積層体の反りを評価した。また、積層体が１周以上に丸まってしまい、定盤からの高さが測定困難な場合はＣと判定した。
Ａ判定：反り量が１０ｍｍ未満であった。
Ｂ判定：反り量が１０ｍｍ以上、３０ｍｍ未満であった。
Ｃ判定：反り量が３０ｍｍ以上、または積層体が１周以上丸くカールして測定が困難であった。
The height of the laminated body from the surface plate (lifting from the surface plate) is measured with a stainless steel ruler, and the average height of the four corners (hereinafter also referred to as "warp amount") is calculated from these measured values. The warp of the laminated body was evaluated according to the criteria of. Further, when the height from the surface plate was difficult to measure because the laminated body was curled to one circumference or more, it was determined to be C.
Judgment A: The amount of warpage was less than 10 mm.
B judgment: The amount of warpage was 10 mm or more and less than 30 mm.
Judgment C: The amount of warpage was 30 mm or more, or the laminated body was curled round by one circumference or more, making measurement difficult.
高温下における表面保護フィルムと被着体を貼り合わせた積層体の反り量（定盤から四隅の高さ平均）は、３０ｍｍ未満が好ましく、より好ましくは１０ｍｍ未満、さらに好ましくは５ｍｍ以下である。 The amount of warpage (average height of the four corners from the surface plate) of the laminated body in which the surface protective film and the adherend are bonded under high temperature is preferably less than 30 mm, more preferably less than 10 mm, still more preferably 5 mm or less.
表２からわかるように、実施例で得られた表面保護フィルムは、高温下においても寸法変化が極めて少なく、反りを抑制できるものであった。 As can be seen from Table 2, the surface protective film obtained in the examples had very little dimensional change even at a high temperature and was able to suppress warpage.
Claims (3)
４−メチル−１−ペンテンから導かれる構成単位の含有率が７０モル％以上９０モル％未満であり、炭素原子数２〜１２のα−オレフィン（４−メチル−１−ペンテンを除く）から導かれる構成単位の含有率が１０モル％を超え３０モル％以下である（前記４−メチル−１−ペンテンから導かれる構成単位および前記α−オレフィンから導かれる構成単位の含有率の合計を１００モル％とする）共重合体である熱可塑性樹脂（Ｙ）とを含み、
前記熱可塑性樹脂（Ｘ）の含有量が２０質量％以上８０質量％以下、前記熱可塑性樹脂（Ｙ）の含有量が２０質量％以上８０質量％以下であり（熱可塑性樹脂（Ｘ）および熱可塑性樹脂（Ｙ）の合計量を１００質量％とする。）、
ＪＩＳ Ｋ７１３３に準拠して測定した寸法変化率において、１５０℃で、３０分加熱した後の縦方向および横方向の寸法変化率の絶対値が０．２０％未満（ただし、前記寸法変化率において、プラスの数値は膨張したときの変化率を、マイナスの数値は収縮したときの変化率を示す。）である表面保護フィルム。 The content of the structural unit derived from 4-methyl-1-pentene is 90 mol% or more and 100 mol% or less, and is derived from α-olefin (excluding 4-methyl-1-pentene) having 2 to 20 carbon atoms. The content of the constituent units to be obtained is 10 mol% or less (the total content of the constituent units derived from 4-methyl-1-pentene and the constituent units derived from the α-olefin is 100 mol%). The thermoplastic resin (X), which is a polymer, and
Derived from α-olefins (excluding 4-methyl-1-pentene) having a content of constituent units derived from 4-methyl-1-pentene of 70 mol% or more and less than 90 mol% and having 2 to 12 carbon atoms. The content of the constituent units to be obtained is more than 10 mol% and 30 mol% or less (the total content of the constituent units derived from 4-methyl-1-pentene and the constituent units derived from the α-olefin is 100 mol. %) With the thermoplastic resin (Y) which is a copolymer.
The content of the thermoplastic resin (X) is 20% by mass or more and 80% by mass or less, and the content of the thermoplastic resin (Y) is 20% by mass or more and 80% by mass or less (thermoplastic resin (X) and heat). The total amount of the plastic resin (Y) is 100% by mass.),
In the dimensional change rate measured in accordance with JIS K7133, the absolute value of the dimensional change rate in the vertical and horizontal directions after heating at 150 ° C. for 30 minutes is less than 0.20% (however, in the dimensional change rate, A positive value indicates the rate of change when expanded, and a negative value indicates the rate of change when contracted.) A surface protective film.
（ｉ）１３５℃デカリン中で測定した極限粘度〔η〕が０．１〜５．０ｄｌ／ｇである、
（ｉｉ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比である分子量分布（Ｍｗ／Ｍｎ）が１．０〜３．５である、
（ｉｉｉ）ＤＳＣで測定した融点（Ｔｍ）が２００℃未満であるか、またはＤＳＣで融点が観測されない、
（ｉｖ）密度が８３０〜８６０ｋｇ／ｍ3である。 The surface protective film according to claim 1, wherein the thermoplastic resin (Y) satisfies the following requirements (i) to (iv).
(I) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.1 to 5.0 dl / g.
(Ii) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) to the number average molecular weight (Mn), is 1.0 to 3.5. ,
(Iii) The melting point (Tm) measured by DSC is less than 200 ° C., or no melting point is observed by DSC.
(Iv) The density is 830-860 kg / m 3 .
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| WO2013099876A1 (en) * | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition |
| JP2014208797A (en) * | 2013-03-25 | 2014-11-06 | 三井化学株式会社 | 4-methyl-1-pentene copolymer composition |
| JP2015214658A (en) * | 2014-05-12 | 2015-12-03 | 三井化学株式会社 | Expandable substrate film, expandable adhesive film, dicing film, production method of expandable substrate film and production method of semiconductor device |
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| JP2014208797A (en) * | 2013-03-25 | 2014-11-06 | 三井化学株式会社 | 4-methyl-1-pentene copolymer composition |
| JP2015214658A (en) * | 2014-05-12 | 2015-12-03 | 三井化学株式会社 | Expandable substrate film, expandable adhesive film, dicing film, production method of expandable substrate film and production method of semiconductor device |
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