JP5880390B2 - Releasable composition for pressure-sensitive adhesive - Google Patents

Description

  The present invention relates to a releasable composition for pressure-sensitive adhesives that exhibits good releasability with respect to a silicone-based pressure-sensitive adhesive and is excellent in water and oil repellency, transparency and adhesion. More specifically, it includes a polyfluoroalkylvinyl monomer having a perfluoroalkyl group having 6 or less carbon atoms at the molecular chain terminal, which is said to have low bioaccumulation, and has a hydrolyzable group bonded to a silicon atom. The present invention relates to a releasable composition for pressure-sensitive adhesives containing a (co) polymer containing no monomer as an active ingredient.

  Conventionally, in order to exhibit surface modification functions such as mold release performance and water / oil repellency, for example, Japanese Patent Publication No. 1-42983 (Patent Document 1) and Japanese Patent Application Laid-Open No. 7-109317 (Patent Document 2). As shown in FIG. 2, a polymer of a fluorine-based acrylic or methacrylic monomer has been used.

  Further, it has been considered that a long-chain perfluoroalkyl group having 8 or more carbon atoms is indispensable for exerting surface modification functions such as high mold release performance and water / oil repellency. However, in recent years, the accumulation of perfluorooctanoic acid (hereinafter referred to as PFOA) having a perfluoroalkyl group having 8 or more carbon atoms has attracted attention. In March 2003, the US Environmental Protection Agency (USEPA) A preliminary risk study report on the safety of PFOA detected in various environments, including wild animals and human blood, has been released. Furthermore, in January 2006, PFOA and its related substances and their precursor substances were proposed to reduce emissions into the environment and to reduce their content in products, and the participation of eight fluoropolymer manufacturers was announced. ing.

  When the number of carbon atoms in the perfluoroalkyl group is 6 or less, the risk to living bodies and the environment is greatly reduced, but surface modification such as mold release performance and water / oil repellency performance caused by the perfluoroalkyl group in the polymer. Quality function is significantly reduced. This is because a perfluoroalkyl group having 8 or more carbon atoms has crystallinity, but a perfluoroalkyl group having 6 or less carbon atoms does not form a crystal structure and therefore does not exhibit a sufficient surface modification function. Because.

  WO2009 / 034773 (Patent Document 3) discloses a homopolymer or copolymer of a (meth) acrylic acid derivative containing a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation. Is described as a water- and oil-repellent agent and a surface modifier, but it is described as a water- and oil-repellent agent and a surface modifier. There is no description about.

Japanese Patent Publication No. 1-42983 JP-A-7-109317 International Publication No. 2009/034773

  The present invention has been made in view of the above circumstances, has low risk to living organisms and the environment, exhibits good releasability with respect to the silicone-based pressure-sensitive adhesive, and has excellent water and oil repellency, transparency, and adhesion. It aims at providing the mold release composition for adhesives.

（式中、Ｒは水素原子又はメチル基であり、ｎは１〜６の整数、ａは１〜４の整数、ｂは０〜３の整数、ｃは１〜３の整数である。）で表されるポリフルオロアルキルビニル単量体、分子中に少なくとも１個のケイ素原子に結合した加水分解可能な基を含有する有機ケイ素系ビニル単量体、及び必要により上記両成分と共重合可能で、かつケイ素原子に結合した加水分解可能な基を含まない非ケイ素系又は有機ケイ素系ビニル単量体の単量体混合物の共重合体が、生体及び環境へのリスクが低く、従来の含フッ素重合体と同等の離型性能を有し、該共重合体を有効成分としてなる組成物を、粘着剤用離型剤として使用した場合に、シリコーン系粘着剤に対して良好な離型性を示し、透明性、密着性に優れることを提案している（特開２０１２−４１３８８号公報）。該共重合体には、基材との密着性や被膜強度の向上を目的として重合体中に加水分解性基を組み込んでいたが、更なる検討を重ねた結果、加水分解性基を導入しない方が、剥離特性が良好であることを知見した。 The present inventor previously described the following general formula (I):

(In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3). The polyfluoroalkyl vinyl monomer represented, an organosilicon vinyl monomer containing a hydrolyzable group bonded to at least one silicon atom in the molecule, and, if necessary, copolymerizable with both of the above components And a copolymer of a monomer mixture of a non-silicon-based or organosilicon-based vinyl monomer that does not contain a hydrolyzable group bonded to a silicon atom has a low risk to living bodies and the environment, and is a conventional fluorine-containing copolymer. When a composition having a release performance equivalent to that of a polymer and using the copolymer as an active ingredient is used as a release agent for a pressure-sensitive adhesive, it has a good release property for a silicone-based pressure-sensitive adhesive. And has been proposed to be excellent in transparency and adhesion (Japanese Patent Laid-Open No. 2012) 41,388 JP). The copolymer incorporated a hydrolyzable group in the polymer for the purpose of improving adhesion to the base material and film strength, but as a result of further studies, no hydrolyzable group was introduced. It has been found that the peel properties are better.

  That is, it includes a polyfluoroalkylvinyl monomer represented by the above general formula (I) having a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, at the molecular chain end, (Co) polymers that do not contain monomers with bound hydrolyzable groups have low risk to living organisms and the environment, and release performance, water and oil repellency, etc. equivalent to conventional fluoropolymers When the composition having the surface modification function and comprising the (co) polymer as an active ingredient is used as a release agent for an adhesive, it exhibits good release properties with respect to a silicone-based adhesive. The present inventors have found that it is excellent in water and oil repellency, transparency and adhesion, and has better peeling properties than the above-mentioned copolymer.

（式中、Ｒは水素原子又はメチル基であり、ｎは１〜６の整数、ａは１〜４の整数、ｂは０〜３の整数、ｃは１〜３の整数である。）
で表されるポリフルオロアルキルビニル単量体： ５０〜１００質量％、
（２）（１）成分と共重合可能で、かつケイ素原子に結合した加水分解可能な基を含まない非ケイ素系又は有機ケイ素系ビニル単量体： ０〜５０質量％
からなる単量体又は単量体混合物の（共）重合体を有効成分としてなり、加水分解性基を含まないことを特徴とするシリコーン系粘着剤用離型性組成物。
〔２〕
（１）成分が５０〜９９．９質量％、（２）成分が０.１〜５０質量％からなる単量体混合物の共重合体を有効成分としてなる〔１〕記載の粘着剤用離型性組成物。
〔３〕
式（Ｉ）において、ｎが２〜４の整数、ａが１又は２、ｂが１〜３の整数、ｃが１又は２である〔１〕又は〔２〕記載の粘着剤用離型性組成物。 Therefore, this invention provides the following mold release composition for adhesives.
[1]
(1) The following general formula (I)

(In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3.)
A polyfluoroalkylvinyl monomer represented by: 50 to 100% by mass,
(2) Non-silicon-based or organosilicon-based vinyl monomer that is copolymerizable with component (1) and does not contain a hydrolyzable group bonded to a silicon atom: 0 to 50% by mass
A release agent composition for a silicone-based pressure - sensitive adhesive, comprising a monomer or a (co) polymer of a monomer mixture as an active ingredient and containing no hydrolyzable group.
[2]
[1] The release agent for pressure-sensitive adhesives according to [1], comprising as an active ingredient a copolymer of a monomer mixture comprising 50 to 99.9% by mass of component (1) and 0.1 to 50% by mass of component (2). Sex composition.
[3]
In the formula (I), n is an integer of 2 to 4, a is 1 or 2, b is an integer of 1 to 3, and c is 1 or 2. [1] or [2] Composition .

The releasable composition for pressure-sensitive adhesives of the present invention has a perfluoroalkyl group having 6 or less carbon atoms with low bioaccumulation at the molecular chain end, and is easily decomposed by ozonolysis in the middle of the molecular chain. A (co) polymer containing a polyfluoroalkylvinyl monomer having a derived —CH ₂ CF ₂ — group and not containing a hydrolyzable group bonded to a silicon atom is used as an active ingredient. Therefore, since the (co) polymer has the same performance as conventional fluoropolymers, it is effective for surface modifiers such as mold release agents and water / oil repellents. It can be suitably used as a component.

（式中、Ｒは水素原子又はメチル基であり、ｎは１〜６の整数、ａは１〜４の整数、ｂは０〜３の整数、ｃは１〜３の整数である。）
で表されるポリフルオロアルキルビニル単量体： ５０〜１００質量％、
（２）（１）成分と共重合可能で、かつケイ素原子に結合した加水分解可能な基を含まない非ケイ素系又は有機ケイ素系ビニル単量体： ０〜５０質量％。 The releasable composition for pressure-sensitive adhesives of the present invention comprises, as an active ingredient, a polymer of the following component (1) or a copolymer of monomer mixtures of the following components (1) and (2). .
(1) The following general formula (I)

(In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3.)
A polyfluoroalkylvinyl monomer represented by: 50 to 100% by mass,
(2) Non-silicon-based or organosilicon-based vinyl monomer that is copolymerizable with component (1) and does not contain a hydrolyzable group bonded to a silicon atom: 0 to 50% by mass.

（式中、Ｒは水素原子又はメチル基であり、ｎは１〜６の整数、ａは１〜４の整数、ｂは０〜３の整数、ｃは１〜３の整数である。）
で表される、一方の分子鎖末端に炭素数６以下のパーフルオロアルキル基を有し、もう一方の分子鎖末端にアクリロキシ基又はメタクリロキシ基を有するものである。 The (1) component polyfluoroalkylvinyl monomer constituting the (co) polymer of the present invention has the following general formula (I):

(In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3.)
Which has a perfluoroalkyl group having 6 or less carbon atoms at one molecular chain terminal and an acryloxy group or methacryloxy group at the other molecular chain terminal.

(1) The component polyfluoroalkylvinyl monomer is not only composed of a perfluoroalkyl group having a carbon number of 6 or less with low bioaccumulation, but also derived from vinylidene fluoride in the middle of the molecular chain. -CH ₂ CF ₂ -group, and the -CH ₂ CF ₂ -group is easily deHFed to form a double bond, which is easily decomposed by ozonolysis, and more easily by biodegradation. Since it is a compound having a small number of carbon atoms, the (co) polymer containing the monomer is less likely to inhibit the environment and has the same performance as a conventional fluoropolymer. It can be suitably used as an active ingredient of a surface modifier such as a water / oil repellent.

  In the general formula (I), n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3. From the viewpoints of solubility, polymerization rate and surface modification performance of the polymer, n is preferably an integer of 2 to 4, a is an integer of 1 or 2, b is an integer of 1 to 3, and c is 1 or 2. .

Examples of the vinyl monomer containing such a polyfluoroalkyl group include those represented by the following formula.

  This polyfluoroalkyl vinyl monomer may be one kind of the above-mentioned compounds or a mixture of two or more kinds.

  This polyfluoroalkyl vinyl monomer (1) monomer contained in the present composition (that is, the total amount of monomer of component (1) and component (2) described below) If the mass ratio of the monomer (1) is less than 50% by mass, the silicone-based adhesive of the releasable composition containing the (co) polymer of the monomer mixture as an active ingredient Since the release effect on the agent is not sufficient, it is necessary to set the range of 50 to 100% by mass, and a more preferable range is 80 to 100% by mass. In addition, when mix | blending (2) component mentioned later, (1) component is 99.9 mass% or less, It is preferable to set it as 99 mass% or less especially.

  Next, as a component (2) constituting the copolymer of the present invention, non-silicon-based (ie, containing no silicon atom in the molecule) or organosilicon-based (ie, silicon substituted with an organic group in the molecule) The vinyl monomer (containing an atom) is a vinyl monomer that can be copolymerized with the component (1) and does not contain a hydrolyzable group bonded to a silicon atom. It is an optional component added for the purpose of adjusting the strength, hardness, adhesion to the substrate, stain resistance, etc. of the coating.

  (2) Component non-silicon or organosilicon vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl Silicon group-containing acrylates such as (meth) acrylates, acrylates such as octadecyl (meth) acrylate, methacrylates, γ-tris (trimethylsiloxy) silylpropyl (meth) acrylate, and γ-bis (trimethylsiloxy) silylpropyl (meth) acrylate , Methacrylates, aromatic vinyl compounds such as styrene and vinyltoluene, diesters of unsaturated carboxylic acids such as maleic acid and fumaric acid and monohydric alcohols having 1 to 18 carbon atoms, maleic anhydride, n-butyl Vinyl ether, cyclohe Examples thereof include vinyl ethers such as xyl vinyl ether and β-hydroxyethyl (meth) acrylate.

  When the non-silicon-based or organosilicon-based vinyl monomer as the component (2) is used, it may be one kind of the above-mentioned compound or a mixture of two or more kinds.

  The mass ratio of the non-silicon-based or organosilicon-based vinyl monomer (2) in the monomer mixture contained in the present composition is such that the mass ratio of the monomer (2) is 50 in the copolymer. What is necessary is just to make it become a component ratio to mass%, and it is 0-50 mass%, Preferably it is 0-20 mass%. If the mass ratio of the monomer (2) exceeds 50% by mass, the release effect on the silicone-based pressure-sensitive adhesive of the release composition containing the copolymer of the monomer mixture as an active ingredient is not sufficient. End up. In addition, when mix | blending a monomer (2), it is preferable to set it as 0.1 mass% or more, especially 1 mass% or more.

  The (co) polymer, which is the main component of the composition of the present invention, comprises the above-mentioned monomer (1) or a mixture of the components (1) and (2) as a radical reaction initiator. And can be obtained by (co) polymerization by a known method such as solution polymerization.

  Here, as a radical reaction initiator, azobisisobutyl nitrile, di-t-butyl peroxide, dibenzoyl peroxide, t-butyl perbenzoate, t-butyl peroxy-2-ethyl hexanate, methyl ethyl ketone peroxide, etc. Examples of the azo compounds and organic peroxides.

  Moreover, since this reaction has much content of a fluorine-containing vinyl monomer, it is partially fluorinated solvent, such as NovecHFE-7200, 7300 (product name made by Sumitomo 3M), m-xylene hexafluoride, or ethyl acetate, It is preferable to carry out in an organic solvent such as acetates such as butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and in some cases, a lower monohydric alcohol such as methanol, ethanol, propanol or butanol and the solvent. You may implement in mixed solvent or presence of chain transfer agents, such as mercaptans.

  The weight average molecular weight (Mw) of the (co) polymer thus obtained is shown by a high performance liquid chromatography method, preferably about 2,000 to 2,000,000, more preferably 10, 000-500,000.

  The composition of the present invention is usually provided as an organic solvent solution of the (co) polymer described above. Here, the amount of the (co) polymer in the organic solvent solution is preferably 0.01 to 50% by mass, particularly 0.05 to 30% by mass.

  The composition of the present invention forms a cured film by easily and firmly adhering to a substrate such as glass, paper, plastic, or metal. This cured film has excellent water and oil repellency because it contains fluorine atoms in the (co) polymer, and is non-adhesive. Therefore, it can be used as fiber, paper, porous body, water / oil repellent for resin, antifouling coating material, protective agent for outer wall, release paper, mold release agent, etc., especially silicone adhesive The usefulness that it can be used effectively also as a separator of is shown. In this application, it may be used as it is as a clear coating agent or may be used after adding a pigment or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part in the following example shows a mass part.

The weight average molecular weight (Mw) of the (co) polymer is measured by high performance liquid chromatography analysis. The equipment used, measurement conditions, etc. are shown below.
[Equipment used] Liquid feed pump: Hitachi L-7100
Column oven: Hitachi L-7300
Detector: Eurosep Instruments DDL-31 [Evaporative light scattering detector]
[Column conditions] Column: Tosoh TSK-GEL MulutiporeHxL x 2
Solvent [moving layer]: Asahi Glass AK-225 for general industrial use
Column temperature: 35 ° C
Liquid feeding speed: 1.0 ml / min
[Detection conditions] Detection temperature: 45 ° C
PM Gain: 450
N ₂ gas pressure: 1.5 bar

で示されるポリフルオロアルキルビニル単量体Ａ９０部、部分フッ素化溶剤としてＮｏｖｅｃＨＦＥ−７３００（住友スリーエム社製商品名）２１０部及びラジカル反応開始剤としてパーブチルＯ（有機過酸化物重合触媒、日油社製商品名）０．５部を仕込み、窒素ガスを通気させながら６５〜７５℃で５時間反応させ、次いでそのままの温度で１５時間熟成させて、ポリフルオロアルキルビニル単量体Ａ１００質量％の重合体（重量平均分子量（Ｍｗ）：２１０，０００）の溶液（母液）を調製した。
次に、得られた母液を固形分が５質量％となるようＮｏｖｅｃＨＦＥ−７３００で希釈してから、これを基材としてのＰＥＴ（ポリエチレンテレフタレート）フィルム（５０μｍ）に乾燥後の膜厚が０．３μｍとなるように塗布し、１５０℃で３０秒間熱処理したのち、この面にシリコーン粘着テープ・ニトフロン９０３ＵＬテープ（日東電工社製商品名）を２０ｇ／ｃｍ²の圧力で圧着し、２５℃及び７０℃で１日間放置してから、これを剥離してその剥離力（Ｎ／１９ｍｍ）を測定（測定は引張試験機を用いて１８０°の角度で剥離速度３００ｍｍ／ｍｉｎで実施）すると共に、この剥離したニトフロン９０３ＵＬテープをＳＵＳ（ステンレススチール）板に貼付けてその接着力を測定したところ、表２に示したとおりの結果が得られた。
次に、母液を固形分が１質量％となるようＮｏｖｅｃＨＦＥ−７３００で希釈してから、これを基材としてのガラス板にＤｉｐ塗布（１０秒浸漬→１５０ｍｍ／ｍｉｎ、乾燥後の膜厚が０．０５μｍ）し、１５０℃で３０秒間熱処理したのち、このガラス板について接触角計（協和界面科学社製Ａ３型）を用いて、純水及びデカンに対する接触角を測定したところ、表２に示したとおりの結果が得られた。 [Example 1]
In a 300 ml four-necked flask equipped with a thermometer, inert gas inlet, reflux condenser, and stirrer, the following formula

90 parts of a polyfluoroalkyl vinyl monomer A shown in the above, 210 parts of Novec HFE-7300 (trade name, manufactured by Sumitomo 3M) as a partially fluorinated solvent and perbutyl O (an organic peroxide polymerization catalyst, NOF Corporation) as a radical reaction initiator Product name) 0.5 parts was charged, reacted for 5 hours at 65 to 75 ° C. while aeration of nitrogen gas, and then aged for 15 hours at the same temperature to give 100% by weight of polyfluoroalkylvinyl monomer A A solution (mother liquor) of a combination (weight average molecular weight (Mw): 210,000) was prepared.
Next, after diluting the obtained mother liquor with NovecHFE-7300 so that the solid content becomes 5% by mass, the film thickness after drying on PET (polyethylene terephthalate) film (50 μm) as a base material is 0.00. After applying to 3 μm and heat-treating at 150 ° C. for 30 seconds, a silicone adhesive tape / Nitoflon 903UL tape (trade name, manufactured by Nitto Denko Corporation) is pressure-bonded to this surface at a pressure of 20 g / cm ^2. This was left at 1 ° C. for 1 day, and then peeled off and the peel strength (N / 19 mm) was measured (measurement was performed at a peel angle of 300 mm / min at an angle of 180 ° using a tensile tester). When the peeled nitflon 903UL tape was attached to a SUS (stainless steel) plate and the adhesion was measured, the results shown in Table 2 were obtained.
Next, after diluting the mother liquor with NovecHFE-7300 so that the solid content becomes 1% by mass, this is applied to a glass plate as a base material by dip coating (10 seconds immersion → 150 mm / min, the film thickness after drying is 0 .05 μm), and after heat treatment at 150 ° C. for 30 seconds, the contact angle for pure water and decane was measured for this glass plate using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.). The exact result was obtained.

で示されるポリフルオロアルキルビニル単量体Ｂ〜Ｆ、及びケイ素原子に結合した加水分解可能な基を含まないビニル単量体として、下記式

で示されるビニル系単量体Ｉ〜IIIを、表１に示した量で使用したこと以外は実施例１と同様にして、それぞれの（共）重合体溶液を調製した。得られた（共）重合体の重量平均分子量（Ｍｗ）を表１に併記する。
これらをＮｏｖｅｃＨＦＥ−７３００で同様に希釈した組成物について、上記実施例１と同じ方法でその剥離力、接着力、接触角を調べたところ、表２に併記したとおりの結果が得られた。 [Examples 2-7, Comparative Examples 1-3]
In Example 1 above, the polyfluoroalkyl vinyl monomer A or the following formula

As the polyfluoroalkyl vinyl monomers B to F represented by the formula (1) and the vinyl monomer containing no hydrolyzable group bonded to the silicon atom,

Each (co) polymer solution was prepared in the same manner as in Example 1 except that the vinyl monomers I to III shown by the above were used in the amounts shown in Table 1. The weight average molecular weight (Mw) of the obtained (co) polymer is also shown in Table 1.
About the composition which diluted these similarly with NovecHFE-7300, when the peeling force, the adhesive force, and the contact angle were investigated by the same method as the said Example 1, the result as having written together in Table 2 was obtained.

Claims (3)

(1) The following general formula (I)

(In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3.)
A polyfluoroalkylvinyl monomer represented by: 50 to 100% by mass,
(2) Non-silicon-based or organosilicon-based vinyl monomer that is copolymerizable with component (1) and does not contain a hydrolyzable group bonded to a silicon atom: 0 to 50% by mass
A release agent composition for a silicone-based pressure - sensitive adhesive, comprising a monomer or a (co) polymer of a monomer mixture as an active ingredient and containing no hydrolyzable group.   The release agent for pressure-sensitive adhesives according to claim 1, wherein the active ingredient is a copolymer of a monomer mixture comprising (1) 50 to 99.9% by weight of component and (2) 0.1 to 50% by weight of component. Sex composition. In formula (I), n is an integer of 2-4, a is 1 or 2, b is an integer of 1-3, c is 1 or 2, The release composition for adhesives of Claim 1 or 2 .