JP7251607B2 - PSA COMPOSITION AND LAMINATED FILM USING THE SAME - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate film that can be suitably used as a surface protective film for protecting the surface of an adherend for a predetermined period, and a pressure-sensitive adhesive composition that is used to form an adhesive layer of the laminate film.

Conventionally, transparent substrates such as polyethylene, polyester, polypropylene, etc., have usually been applied to the surfaces of various displays, optical components such as polarizing plates and similar laminates, and electrical substrates, mainly for the purpose of protecting the surfaces. is laminated through.

Since the purpose is to protect the surface, it is necessary that the base material and the adhesive can be easily peeled off from the adherend after the purpose is achieved, but the adhesive will lose its adhesion over time. It is generally known that the force increases, which may cause problems such as the adhesive remaining when peeled off and the base film being cut.

As a method for preventing these inconveniences, for example, a method of mixing a release agent such as wax or a long-chain alkyl group-containing compound with the adhesive composition forming the adhesive layer has been provided (for example, Patent Document 1). reference).

In addition, as described above, when peeling after the purpose of the protective function is achieved, static electricity is generated due to friction, which may cause deterioration of the performance of the adherend. Antistatic property is also one of the important properties. In response to this, for example, a method of adding a compound that adjusts the charging property to the adhesive composition forming the adhesive layer (see, for example, Patent Document 2), or a method of using a resin having a special structure as the adhesive. (see, for example, Patent Document 3) has been proposed.

Although various improvements have been made in the functions of surface protective films according to Patent Documents 1 to 3, the method of peeling the surface protective film by machine has become the mainstream for displays and optical members that have become larger in recent years. Peeling speed often varies depending on the process, and there is a demand for a pressure-sensitive adhesive composition that is easier to adjust the peeling force (adhesive force) and has good antistatic properties, and a laminated film having this as an adhesive layer. .

JP 2017-019158 A JP-A-2005-146045 Japanese Patent Application Laid-Open No. 2007-002111

The problem to be solved by the present invention is a pressure-sensitive adhesive composition that facilitates adjustment of the adhesive strength of the pressure-sensitive adhesive and can suppress electrification at the time of peeling, and has this as an adhesive layer and is suitable as a surface protection film. To provide a laminated film that can be used for

The present inventors have made intensive studies to solve the above problems, and found that by using a fluorine-containing compound having a fluorinated alkyl group having 1 to 6 carbon atoms and a polyoxyalkylene chain in combination with an adhesive, the above-mentioned We have found that the problem can be solved, and have completed the present invention.

That is, the present invention provides a pressure-sensitive adhesive composition containing a fluorine-containing compound (A) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyalkylene chain (a2) and a pressure-sensitive adhesive (B). and a laminated film having this as an adhesive layer.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminated film which is easy to adjust the adhesive strength to various adhesives, has little change in adhesive strength even after storage, and has good releasability. In addition, the laminated film of the present invention has good antistatic properties at the time of peeling, and can be suitably used as a surface protective film for various optical members, electronic members, and the like.

The pressure-sensitive adhesive composition of the present invention is characterized by using a fluorine-containing compound (A) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyalkylene chain (a2).

In general, it is well known that the adhesive force can be reduced by using a compound having a fluorine atom or a silicon atom or a compound having a long-chain alkyl group in combination with the adhesive. be. However, in such generally known compounds, especially compounds known as mold release agents and surfactants, it is easy to adjust the adhesive strength even with a small addition amount, and the adhesive strength is maintained even after long-term storage. To date, there has not been found anything that has been thoroughly studied on the detailed structure of a compound that exhibits little enhancement, excellent peelability, and good antistatic properties when peeled off.

In the present invention, as a result of examining such problems, it is effective to use a fluorine-containing compound (A) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyalkylene chain (a2). It was found to be a solution.

The fluorinated alkyl group (a1) having 1 to 6 carbon atoms in the fluorine-containing compound (A) indicates that the number of carbon atoms to which the fluorine atom is directly bonded is in the range of 1 to 6, and the carbon atom A part of the atoms bonded to may be hydrogen atoms, and the alkyl group may be branched or linear. It may also have a structure in which a plurality of the fluorinated alkyl groups (a1) are linked by an ether bond, a thioether bond, or an alkylene chain having no fluorine atom.

Among these, the number of carbon atoms to which fluorine atoms are directly bonded is in the range of 3 to 6, from the viewpoint that it is easy to adjust the adhesive strength of the adhesive and can effectively suppress adhesive residue at the time of peeling. is preferred, and 4 or 6 is more preferred. From the same point of view, a perfluoroalkyl group containing no hydrogen atoms is more preferable. Further, the fluorine-containing compound (A) preferably contains two or more of the fluorinated alkyl groups (a1) in one molecule from the viewpoint of facilitating adjustment of the adhesive force.

The polyoxyalkylene chain (a2) in the fluorine-containing compound (A) is not particularly limited, and an alkylene chain having 1 to 6 carbon atoms such as polyoxyethylene, polyoxypropylene, and polyoxybutylene is an ether bond. The structure of the alkylene chain may be linear or branched. In particular, in the synthesis of the fluorine-containing compound (A) described later, from the viewpoint of easy raw material availability, and antistatic at the time of peeling when the pressure-sensitive adhesive composition using the obtained fluorine-containing compound (A) is used as an adhesive layer From the viewpoint of compatibility, it is preferably a polyoxyalkylene chain in which a plurality of alkylene chains having 2 to 3 carbon atoms are linked via an ether bond.

Furthermore, the number of repetitions of the polyoxyalkylene chain (a2) is preferably in the range of 5-50. In addition, when units with different carbon numbers are bonded by ether bonds, the format may be block or random, and the total number of repeating units is preferably within the above range. .

The content of fluorine atoms in the fluorine-containing compound (A) is not particularly limited, but it is compatible with the adhesive (B) described later, ease of adjustment of adhesive strength, and ease of production. Therefore, it is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass. Although the fluorine atom content can be calculated from the feed ratio of raw materials, it can also be measured by combustion ion chromatography of the fluorine-containing compound (A). In the present invention, the latter measured value is preferably within the above range.

In addition, the weight average molecular weight of the fluorine-containing compound (A) is not particularly limited, but compatibility with the adhesive (B) described later, ease of adjustment of adhesive strength, and antistatic properties at the time of peeling From the viewpoint of, etc., it is preferably in the range of 3,000 to 300,000, particularly preferably in the range of 3,000 to 200,000, and most preferably in the range of 5,000 to 100,000. It is most preferable from the viewpoint of the uniformity of the peeling force when used as a surface protection film for optical members and the like.

Incidentally, the weight average molecular weight in the present invention is a value measured by gel permulation chromatography (GPC) under the following conditions.

[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: guard column "HHR-H" manufactured by Tosoh Corporation (6.0 mm ID × 4 cm) + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8 mm ID × 30 cm) + Tosoh Corporation Made by "TSK-GEL GMHHR-N" (7.8mmID × 30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmID × 30cm) + Tosoh Corporation "TSK- GEL GMHHR-N" (7.8mm I.D. x 30cm)
Detector: ELSD ("ELSD2000" manufactured by Ortec Japan Co., Ltd.)
Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml/min Sample: A tetrahydrofuran solution of 1.0% by mass in terms of solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30".

(monodispersed polystyrene)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation
"F-550" manufactured by Tosoh Corporation

The fluorine-containing compound (A) used in the present invention has a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyalkylene chain (a2) as described above. From the viewpoint of good compatibility and easy adjustment of the adhesive strength of the adhesive, a compound (x1) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and an active hydrogen and a polyoxyalkylene chain (a2 ) and a compound (x2) having a (meth)acryloyl group (a3), a Michael adduct (A-1), or a fluorinated alkyl group-containing ethylenically unsaturated monomer (x3), and a polyoxyalkylene chain It is preferably a copolymer (A-3) containing an ethylenically unsaturated monomer (x4) as an essential raw material.

In particular, as the Michael adduct (A-1), the following general formula (5)

〔式中、Ｒｆはそれぞれ－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）であり、Ｙはそれぞれ酸素原子又は硫黄原子であり、Ｒ^３はそれぞれ－（ＣＨ_２）_ｔ－、又は－（ＣＨ_２）_ｕ－ＳＯ_２－ＮＲ－（ＣＨ_２）_ｔ－（式中、ｔは１又は２であり、ｕは０又は２であり、Ｒは水素原子又は炭素数１～２４の炭化水素基である。）であり、Ｒ’はポリオキシアルキレン鎖の末端が水素原子又はアルキル基であるポリオキシアルキレン基であり、複数あるＲｆ、Ｒ^３、Ｙは同一でも異なっていてもよい。〕
で表される化合物（Ａ－２）であることが好ましい。

[Wherein, each Rf is -C _n F _2n+1 (where n is an integer of 1 to 6), each Y is an oxygen atom or a sulfur atom, and each R ³ is -(CH ₂ ) _t -, or -(CH ₂ ) _u -SO ₂ -NR-(CH ₂ ) _t - (wherein t is 1 or 2, u is 0 or 2, and R is a hydrogen atom or a 24), R′ is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain, and a plurality of Rf, R ³ , and Y may be the same or different. good too. ]
Compound (A-2) represented by is preferred.

Furthermore, as the copolymer (A-3), the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) is represented by the following general formula (7)

〔式中、Ｒｆはそれぞれ－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）であり、Ｒ^５はそれぞれ独立して、炭素原子数１～３のアルキレン鎖又は直接結合であり、Ｙ^１はそれぞれ独立して、酸素原子、硫黄原子又は－ＳＯ_２－ＮＲ－（Ｒは水素原子又は炭素数１～２４の炭化水素基である。）であり、Ｒ^６は水素原子又はメチル基であり、ｗは１～３の整数であり、複数あるＲｆ、Ｒ^５、Ｙ^１は同一でも異なっていてもよい。〕
で表される含フッ素ウレタン（メタ）アクリレート（ｘ５）を用いたものであることが好ましい。

[In the formula, each Rf is -C _n F _2n+1 (where n is an integer of 1 to 6), and each R ⁵ is independently an alkylene chain having 1 to 3 carbon atoms or a direct bond; and each Y ¹ is independently an oxygen atom, a sulfur atom or —SO ₂ —NR— (R is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms), and R ⁶ is a hydrogen atom or is a methyl group, w is an integer of 1 to 3, and a plurality of Rf, R ⁵ and Y ¹ may be the same or different. ]
A fluorine-containing urethane (meth)acrylate (x5) represented by is preferably used.

First, a compound (x1) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and an active hydrogen, and a compound (x2) having a polyoxyalkylene chain (a2) and a (meth)acryloyl group (a3) Michael adducts with are described.

As the compound (x1) having the fluorinated alkyl group (a1) having 1 to 6 carbon atoms and an active hydrogen, for example, the following general formula (1)
Rf( _CH2 ) _mZH (1)
[Wherein, m is an integer of 0 to 20, Rf is -C _n F _2n+1 (where n is an integer of 1 to 6.), Z is an oxygen atom, a sulfur atom, -NR- or —SO ₂ —NR— (where R is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms). ] or the following general formula (2)

〔式中、Ｙは酸素原子または硫黄原子であり、ｐとｑはそれぞれ０～４の整数であり、Ｒｆはそれぞれ－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）であり、Ｌはそれぞれ直接結合、カルボニル基、カルボニル基を有する炭素原子数１～４の炭化水素基又は炭素原子数１～４の炭化水素基であり、複数あるＲｆ、Ｌは同一でも異なっていてもよい。〕
で表される化合物が挙げられる。

[In the formula, Y is an oxygen atom or a sulfur atom, p and q are each an integer of 0 to 4, and Rf is each -C _n F _2n+1 (where n is an integer of 1 to 6). and L each represents a direct bond, a carbonyl group, a hydrocarbon group having 1 to 4 carbon atoms having a carbonyl group, or a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of Rf and L may be the same or different. good too. ]
The compound represented by is mentioned.

Examples of the compound represented by the general formula (1) include the following compounds, which may be used alone or as a mixture of two or more.
_{C4F9SO2N ( CH3 )} H
_{C4F9SO2N ( C3H7 ) H
C4F9CH2CH2N ( C8H17 ) H _
C4F9CH2CH2SH _ _ _
C4F9CH2CH2OH _ _ _
C6F13CH2CH2SO2N ( C8H17 ) H _ _
C6F13CH2CH2SH _ _ _
C6F13CH2CH2N ( C4H9 ) H _}

Examples of the compound represented by the general formula (2) include the following compounds, which may be used alone or as a mixture of two or more.

As a method for producing the compound represented by the general formula (2), for example, 2-hydroxysuccinic acid (hereinafter referred to as malic acid), 2-mercaptosuccinic acid (hereinafter referred to as thiomalic acid), fluorine and a method of reacting a fluorinated alkyl group-containing alcohol or a fluorinated alkyl group-containing mercaptan to form a diester. Specifically, it can be synthesized according to the following reaction formula (see, for example, JP-A-2004-292658).

As the compound (x2) having the polyoxyalkylene chain (a2) and the (meth)acryloyl group (a3), for example, the following general formula (3)

〔式中、Ｒ’はポリオキシアルキレン鎖の末端が水素原子又はアルキル基であるポリオキシアルキレン基であり、Ｒ^１は（メタ）アクリロイル基であり、Ｒ^２は水素原子又は炭素原子数１～１８のアルキルカルボニル基であり、ｒは１～３の整数であり、ｓは０～２の整数であって、ｒ＋ｓ＝３である。〕
で表される化合物（ｘ２－１）、又は下記一般式（４）
Ｒ^１Ｏ－Ｒ’’－ＯＲ^１ （４）
〔式中、Ｒ^１は同一又は異なる（メタ）アクリロイル基であり、Ｒ’’はオキシアルキレン鎖である。〕
で表される化合物（ｘ２－２）が挙げられる。尚、本発明において（メタ）アクリロイル基はアクリロイル基とメタクリロイル基の一方あるいはその混合物の総称として用いる。

[Wherein, R′ is a polyoxyalkylene group having a polyoxyalkylene chain terminated with a hydrogen atom or an alkyl group, R ¹ is a (meth)acryloyl group, and R ² is a hydrogen atom or a C 1 to 18 alkylcarbonyl groups, r is an integer from 1 to 3, s is an integer from 0 to 2, and r+s=3. ]
Compound represented by (x2-1), or the following general formula (4)
R ¹ OR''-OR ¹ (4)
[In the formula, R ¹ is the same or different (meth)acryloyl group, and R'' is an oxyalkylene chain. ]
and the compound (x2-2) represented by In the present invention, the (meth)acryloyl group is used as a general term for either one of an acryloyl group and a methacryloyl group or a mixture thereof.

Examples of the compounds (x2-1) and (x2-2) include ethylene oxide (hereinafter abbreviated as EO)-modified 1,6-hexanediol di(meth)acrylate (for example, RCC13-361 manufactured by San Nopco Co., Ltd.), Diethylene glycol di(meth)acrylate (for example, BLEMMER ADE-100 manufactured by NOF Corporation), EO-modified neopentyl glycol di(meth)acrylate (for example, Photomer 4160 manufactured by San Nopco Co., Ltd.), propylene oxide (hereinafter abbreviated as PO) ) modified neopentyl glycol di (meth) acrylate (eg, SR-9003 manufactured by Kayaku Sartomer Co., Ltd.), polyethylene glycol di (meth) acrylate (eg, BLEMMER ADE-200 manufactured by NOF Corporation), polypropylene glycol di (Meth) acrylate (for example, BLEMMER ADP-200 manufactured by NOF Corporation), polyethylene glycol-propylene glycol-polyethylene glycol di(meth)acrylate (for example, BLEMMER ADC series manufactured by NOF Corporation), polytetramethylene di Glycol di(meth)acrylate (e.g., Kyoeisha Chemical Co., Ltd. Light acrylate PTMGA-250, etc.), polyethylene glycol di(meth)acrylate (e.g., Kyoeisha Chemical Co., Ltd. Light acrylate 3EG-A), EO-modified glycerol acrylate (e.g., , Daiichi Kogyo Seiyaku Co., Ltd. New Frontier GE3A, etc.), PO-modified glycerol triacrylate (e.g., Arakawa Chemical Co., Ltd. Beamset 720), EO-modified phosphate triacrylate (e.g., Osaka Organic Chemical Co., Ltd. Viscoat 3A) , (EO) or (PO)-modified trimethylolpropane triacrylate (eg, New Frontier TMP-3P manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

These may be used alone, or may be used by mixing a plurality of compounds having different numbers of (meth)acryloyl groups, or by mixing a plurality of compounds having different structures. In many cases, the commercially available compound is a mixture of compounds having a different number of (meth)acryloyl groups than the target compound, which is the main component. When used, the compound having the desired number of (meth)acryloyl groups may be taken out by various purification methods such as chromatography and extraction, or the mixture may be used as it is.

Furthermore, polyoxyalkylene chain-containing (meth)acrylates represented by the following general formula may be used.

〔式中、Ａは、酸素原子、置換基を有してもよい炭素数１～１２のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１２のアリール基、または置換基を有してもよい炭素数６～２４のアラルキル基であり、これらが単独で、あるいは複数組み合わさってなる二価の連結基であり、Ｒ^６は水素原子又はメチル基であり、Ｒ’はポリオキシアルキレン鎖の末端が水素原子又はアルキル基であるポリオキシアルキレン基である。〕

[Wherein, A is an oxygen atom, an optionally substituted C 1-12 alkyl group, an optionally substituted C 3-12 cycloalkyl group, a substituted an aryl group having 6 to 12 carbon atoms, which may be substituted, or an aralkyl group having 6 to 24 carbon atoms, which may have a substituent, which is a divalent linking group consisting of one or more of these , R ⁶ is a hydrogen atom or a methyl group, and R′ is a polyoxyalkylene group whose polyoxyalkylene chain ends with a hydrogen atom or an alkyl group. ]

Examples of the polyoxyalkylene chain-containing (meth)acrylate include, for example, polyoxyalkylene acrylate and polyoxyalkylene methacrylate, which are commercially available hydroxypoly(oxyalkylene) materials such as the product name "Pluronic" [Pluronic (Asahi Denka Kogyo Co., Ltd.) Co., Ltd.), Adeka Polyether (manufactured by Asahi Denka Kogyo Co., Ltd.) “Carbowax (Glico Products)”, “Triton” (Toriton (Rohm and Haas)), P.E. .G (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) is produced by reacting it with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride, acrylic anhydride or methacrylic anhydride, etc. by various methods. Also, polyoxyalkylene diacrylates obtained by various production methods can be used.

Commercially available (meth)acrylates include, for example, NOF Co., Ltd. hydroxyl-terminated polyalkylene glycol mono(meth)acrylates such as BLEMMER PE-90, BLEMMER PE-200, BLEMMER PE-350, BLEMMER AE-90, BLEMMER AE-200, BLEMMER AE-400, BLEMMER PP-1000, BLEMMER PP-500, BLEMMER PP-800, BLEMMER AP-150, BLEMMER AP-400, BLEMMER AP-550, BLEMMER AP-800, BLEMMER 50PEP-300, BLEMMER 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Blemmer 10PPB-500B , and Blemmer 10APB-500B. Similarly, as alkyl-terminated polyalkylene glycol mono (meth) acrylates manufactured by NOF Corporation, Blenmer PME-100, Blenmer PME-200, Blenmer PME-400, Blenmer PME-1000, Blenmer PME-4000, Blenmer AME-400, Blenmer 50POEP-800B, Blenmer 50AOEP-800B, Blenmer PLE-200, Blenmer ALE-200, Blenmer ALE-800, Blenmer PSE-400, Blenmer PSE-1300, Blenmer ASEP series, Blenmer PKEP series, Blenmer AKEP series, Blenmer ANE-300 , Blenmer ANE-1300, Blenmer PNEP series, Blenmer PNPE series, Blenmer 43ANEP-500, Blenmer 70ANEP-550, etc. Also manufactured by Kyoeisha Chemical Co., Ltd. Light Ester MC, Light Ester 130MA, Light Ester 041MA, Light Acrylate BO-A, Light Examples include acrylate EC-A, light acrylate MTG-A, light acrylate 130A, light acrylate DPM-A, light acrylate P-200A, light acrylate NP-4EA, and light acrylate NP-8EA. As these polyoxyalkylene chain-containing (meth)acrylates, only one type may be used, or two or more types may be used in combination.

The reaction between the compound (x1) and the compound (x2) can be carried out according to a normal Michael addition reaction method, and no particular consideration is required for having a fluorine atom. can be manufactured. When a solvent is used, it is appropriately selected in consideration of the solubility and boiling point of the compound (x1) and the compound (x2), the equipment to be used, etc. Specifically, for example, acetic acid esters such as ethyl and butyl acetate, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl Ketones such as isobutyl ketone (hereinafter abbreviated as MIBK), alcohols such as methanol, ethanol and isopropanol, aprotic polar compounds such as dimethylformamide, dimethylformacetamide and dimethylsulfoxide, ethers such as diethyl ether and tetrahydrofuran and aliphatic hydrocarbons such as hexane, heptane, etc., and may be used alone or in combination of two or more. Among these, esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformacetamide, dimethylsulfoxide, etc. are preferably used, and esters, ketones, alcohols, ethers are preferably used. Especially preferred.

This reaction can be carried out without a catalyst, but from the viewpoint of reaction efficiency, it is also possible to appropriately select and use a reaction aid such as a catalyst. Examples of the reaction aid include metal alcoholates such as sodium methoxide and sodium ethoxide; amines such as trimethylamine, triethylamine, 1,4-diazabicyclo-[2.2.2]-octane; sodium hydride, and hydrogen. metal hydrides such as lithium chloride; ammonium salts such as benzyltrimethylammonium hydroxide and tetraammonium fluoride; peroxides such as peracetic acid; and the like, preferably metal alcoholates, amines and ammonium salts. and particularly preferably amines. The amount of the reaction aid used is not particularly limited, but is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, relative to 1 mol of the compound (x1) used as a raw material. be.

Furthermore, depending on the compound (x1) and compound (x2) used, heat can also be used alone or in combination as a reaction activation energy source. The reaction temperature is generally 0°C to reflux temperature, preferably 20 to 100°C, particularly preferably 20 to 70°C. When a solvent or the like is used during the reaction, the solute concentration is usually 2 to 90% by mass, preferably 20 to 80% by mass. There are no particular restrictions on the order in which the reaction materials are added. The product thus obtained can be used after being washed by extraction or the like and purified by column chromatography or the like, or it can be used as it is. In particular, when the compound (x2) with a large number of (meth)acryloyl groups is used, it is usually difficult to control the site where the compound (x1) is added. A certain Michael adduct is obtained, but even in this case, it is not necessary to take out a single substance by isolation and purification, and it is possible to use it as a mixture of various compounds having different positions in the Michael addition reaction.

As described above, by going through the Michael addition reaction between the compound (x1) and the compound (x2), the present invention can be obtained under simpler and milder conditions without undergoing a condensation reaction that requires a strong acid catalyst or the like. The fluorine-containing compound (A-1) used in the invention can be produced. In addition, since it is possible to use various polyfunctional (meth)acrylates, which are currently readily available as commercial products or are easily synthesized, as starting materials, it is possible to select a structure or a single It can be said that it is a more effective production method because it is easy to make changes such as appropriately adjusting the fluorine atom content in the molecule.

〔式中、Ｒｆはそれぞれ－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）であり、Ｙはそれぞれ酸素原子又は硫黄原子であり、Ｒ^３はそれぞれ－（ＣＨ_２）_ｔ－、又は－（ＣＨ_２）_ｕ－ＳＯ_２－ＮＲ－（ＣＨ_２）_ｔ－（式中、ｔは１又は２であり、ｕは０又は２であり、Ｒは水素原子又は炭素数１～２４の炭化水素基である。）であり、Ｒ’はポリオキシアルキレン鎖の末端が水素原子又はアルキル基であるポリオキシアルキレン基であり、複数あるＲｆ、Ｒ^３、Ｙは同一でも異なっていてもよい。〕
で表される化合物（Ａ－２）であることが、後述する粘着剤との相溶性、粘着力の調整の容易性の観点から好ましい化合物である。 Among the Michael adducts synthesized above, the following general formula (5)

[Wherein, each Rf is -C _n F _2n+1 (where n is an integer of 1 to 6), each Y is an oxygen atom or a sulfur atom, and each R ³ is -(CH ₂ ) _t -, or -(CH ₂ ) _u -SO ₂ -NR-(CH ₂ ) _t - (wherein t is 1 or 2, u is 0 or 2, and R is a hydrogen atom or a 24), R′ is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain, and a plurality of Rf, R ³ , and Y may be the same or different. good too. ]
The compound (A-2) represented by is a preferable compound from the viewpoint of compatibility with the pressure-sensitive adhesive described later and ease of adjustment of the pressure-sensitive adhesive strength.

Examples of the compound represented by the compound (A-2) include compounds represented by the following structural formulas.

As the fluorine-containing compound (A) used in the present invention, as described above, a fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) and a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4) may be a copolymer (A-3) containing as an essential raw material.

As the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3), for example, even a vinyl ether type represented by the following formula (x3-1), the following formula (x3-2) It may be a fluorinated alkyl group-containing (meth)acrylate represented by.

〔式中、Ａ’は、置換基を有してもよい炭素数１～１２のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１２のアリール基、または置換基を有してもよい炭素数６～２４のアラルキル基であり、これらが単独で、あるいは複数組み合わさってなる二価の連結基であり、Ａは、酸素原子、置換基を有してもよい炭素数１～１２のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１２のアリール基、または置換基を有してもよい炭素数６～２４のアラルキル基であり、これらが単独で、あるいは複数組み合わさってなる二価の連結基であり、Ｒ^６は水素原子又はメチル基であり、Ｒｆは－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）である。〕

[Wherein, A′ is an optionally substituted C 1-12 alkyl group, an optionally substituted C 3-12 cycloalkyl group, a substituted an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 24 carbon atoms which may have a substituent; is an oxygen atom, an optionally substituted C 1-12 alkyl group, an optionally substituted C 3-12 cycloalkyl group, an optionally substituted carbon number an aryl group of 6 to 12, or an aralkyl group of 6 to 24 carbon atoms which may have a substituent, which is a divalent linking group consisting of one or more of these, and R ⁶ is hydrogen; an atom or a methyl group, and Rf is -C _n F _2n+1 (where n is an integer from 1 to 6). ]

Further, as the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4), even if it is a vinyl ether type represented by the following (x4-1), the polyoxyalkylene chain-containing (meth) It may be an acrylate.

〔式中、Ａ’は、置換基を有してもよい炭素数１～１２のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１２のアリール基、または置換基を有してもよい炭素数６～２４のアラルキル基であり、これらが単独で、あるいは複数組み合わさってなる二価の連結基であり、Ａは、酸素原子、置換基を有してもよい炭素数１～１２のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１２のアリール基、または置換基を有してもよい炭素数６～２４のアラルキル基であり、これらが単独で、あるいは複数組み合わさってなる二価の連結基であり、Ｒ^６は水素原子又はメチル基であり、Ｒ’はポリオキシアルキレン鎖の末端が水素原子又はアルキル基であるポリオキシアルキレン基である。〕

[Wherein, A′ is an optionally substituted C 1-12 alkyl group, an optionally substituted C 3-12 cycloalkyl group, a substituted an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 24 carbon atoms which may have a substituent; is an oxygen atom, an optionally substituted C 1-12 alkyl group, an optionally substituted C 3-12 cycloalkyl group, an optionally substituted carbon number an aryl group of 6 to 12, or an aralkyl group of 6 to 24 carbon atoms which may have a substituent, which is a divalent linking group consisting of one or more of these, and R ⁶ is hydrogen; is an atom or a methyl group, and R' is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain. ]

The method for copolymerizing the vinyl ether type monomer is not particularly limited, but a radical polymerization method using a radical polymerization reaction is preferred, and a free radical polymerization method is preferred.

The free radical polymerization method includes, for example, a method of polymerizing a mixture of vinyl ether type monomers in an organic solvent using an initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, and hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility and polymerizability.

Examples of the initiator include azo initiators, peroxide initiators, ionic initiators and redox initiators.

From the viewpoint of obtaining a compound suitable as the fluorine-containing compound (A) used in the present invention, the fluorine atom-containing vinyl ether and the oxyalkylene chain-containing vinyl ether are mixed at a molar ratio [former/latter] of from 10/90. Those obtained by reacting at a ratio of 60/40 are preferable, and those obtained by reacting at a ratio of 20/80 to 50/50 are more preferable.

〔式中、Ｒｆはそれぞれ－Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１～６の整数である。）であり、Ｒ^５はそれぞれ独立して、炭素原子数１～３のアルキレン鎖又は直接結合であり、Ｙ^１はそれぞれ独立して、酸素原子、硫黄原子又は－ＳＯ_２－ＮＲ－（Ｒは水素原子又は炭素数１～２４の炭化水素基である。）であり、Ｒ^６は水素原子又はメチル基であり、ｗは１～３の整数であり、複数あるＲｆ、Ｒ^５、Ｙ^１は同一でも異なっていてもよい。〕
で表される含フッ素ウレタン（メタ）アクリレート（ｘ５）であると、後述する粘着剤（Ｂ）、特にはアクリル系粘着剤（ｂ１）又はウレタン系粘着剤（ｂ２）との相溶性が良好であって、粘着層を形成したときの透明性も維持でき、また粘着力の調整も容易となる観点から好ましいものである。 Further, as the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3), the following general formula (7)

[In the formula, each Rf is -C _n F _2n+1 (where n is an integer of 1 to 6), and each R ⁵ is independently an alkylene chain having 1 to 3 carbon atoms or a direct bond; and each Y ¹ is independently an oxygen atom, a sulfur atom or —SO ₂ —NR— (R is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms), and R ⁶ is a hydrogen atom or is a methyl group, w is an integer of 1 to 3, and a plurality of Rf, R ⁵ and Y ¹ may be the same or different. ]
When the fluorine-containing urethane (meth)acrylate (x5) represented by is, the compatibility with the adhesive (B) described later, particularly the acrylic adhesive (b1) or the urethane adhesive (b2) is good. Therefore, it is preferable from the viewpoint that transparency can be maintained when the adhesive layer is formed and that the adhesive force can be easily adjusted.

The monomer represented by the general formula (7) is obtained, for example, by reacting a fluorine compound having a hydroxyl group represented by the following formula with a compound having an isocyanate group and a (meth)acryloyl group.

（式中のＲｆ、Ｒ^５、Ｙ^１は前記と同じである。）

(Rf, R ⁵ and Y ¹ in the formula are the same as above.)

Specific examples of the fluorine compound having a hydroxyl group represented by the above formula include the following.

Specific examples of Rf--R ⁵ --Y ¹ in the general formula (3) include CF ₃ CH ₂ O--, C ₂ F ₅ CH ₂ O--, C ₃ F ₇ CH ₂ O-- and C ₄ F _{9 CH2O- , C5F11CH2O- , C6F13CH2O- , C4F9CH2CH2O- , C6F13CH2CH2O- , C4F9CH _ _ _ _ _ _ 2CH2S- , C6F13CH2CH2S- , CF3SO2N ( CH3 ) - , CF3SO2N} ( _{C2H5 ) -} , _{C2F5SO2N (} C _3H7 )- _{, C3F7SO2N(C4H9 ) - , C3F7OCF ( CF3 ) CH2O- , C3F7OCF ( CF3} )CF2OCF _{( CF3} ) _{CH2O- , C3F7OCF} ( _CF3 )CF2OCF( _{CF3 ) CF2OCF} ( _{CF3 ) CH2O-} , _C3F7OCF ( _{CF3 ) CH2CH2O-} , _C3F7OCF ( _CF3 )CF2OCF ₍ CF3 _{) CH2CH2O- , C3F7OCF(CF3 ) CF2OCF ( CF3 ) CF2OCF ( CF3 ) CH2CH2} O- _{, C3F7OCF ( CF3 )} CH2CH2S- _{, C3F7OCF ( CF3 ) CF2OCF} ( _CF3 )CH2CH2S- _{, C3F7OCF} ( _CF3 ) CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CH ₂ CH ₂ S—, and more specific examples include compounds represented by the following formulae.

The method for producing a fluorine compound having a hydroxyl group represented by the above formula is not particularly limited. It can be manufactured by the method of

Examples of the (meth)acrylate having an isocyanate group include compounds represented by the following formulas.

（式中のＲ^６は、水素原子又はメチル基を表し、Ａ’’は、炭素原子数２～３のアルキレン基を表す。）

(R ⁶ in the formula represents a hydrogen atom or a methyl group, and A'' represents an alkylene group having 2 to 3 carbon atoms.)

A'' in the above formula represents an alkylene group having 2 to 3 carbon atoms, and specifically, an ethylene group (--CH ₂ CH ₂ --) and a propylene group (--CH ₂ CH ₂ CH ₂ --). , or a branched propylene group (--CH ₂ CH(CH ₃ )--, --CH(CH ₃ )CH ₂ --).

Specific examples of the compounds represented by the above formulas include compounds represented by the following formulas.

Among the above compounds, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate in which A'' in the above formula is an ethylene group are preferred.

When the fluorine compound having a hydroxyl group is reacted with the (meth)acrylate having an isocyanate group, 0.05 of the (meth)acrylate having the isocyanate group is added to 1 mol of the fluorine compound having a hydroxyl group. It is preferable to charge 80 to 1.20 mol, more preferably 0.98 to 1.00 mol.

Further, in this reaction (urethanization reaction), in order to promote the reaction between the secondary hydroxyl group of the fluorine compound having the hydroxyl group and the terminal isocyanate group of the (meth)acrylate having the isocyanate group, for example, triethylamine, benzyldimethyl Tertiary amines such as amines; dilaurates such as dibutyltin dilaurate and dioctyltin dilaurate can be used as catalysts. The amount of catalyst added is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.1% by mass, based on the total reaction mixture. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably 30-120°C, more preferably 30-100°C.

The reaction can be carried out without a solvent, or a solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene which are inert to isocyanate groups can be used as a reaction solvent.

Specific examples of the fluorine-containing compound obtained by the above synthesis include compounds represented by the following formulas.

The fluorine-containing compound (A) used in the present invention is a copolymer containing the aforementioned fluorine-containing urethane (meth)acrylate (x5) and an ethylenically unsaturated monomer having a polyoxyalkylene chain as essential components. is preferred, but any of the above-described ethylenically unsaturated monomers having a polyoxyalkylene chain can be suitably used.

In addition to these essential monomers, other monomers may be used in combination as starting materials for the copolymer within a range that does not impair the effects of the present invention. Moreover, as this monomer, you may use together 2 or more types.

Examples of the other monomer include acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

More specifically, acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, and furfuryl. Acrylate, tetrahydrofurfuryl acrylate and the like. Methacrylate esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate. etc. Examples of acrylamides include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, e.g., methyl group, ethyl group, propyl group), N,N-dialkylacrylamide (alkyl group having carbon atoms 1 to 3), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like. Examples of methacrylamides include methacrylamide, N-alkylmethacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl and propyl), N,N-dialkylmethacrylamide (alkyl group has 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide, and the like.

Allyl compounds include allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol etc. Vinyl ethers include alkyl vinyl ethers (e.g., hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl Vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Vinyl esters: vinyl bityrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl Diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, etc. Itaconic acid. Dialkyls include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc. Dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate, crotonic acid, itaconic acid, acrylonitrile, Also included are methacrylonitrile, maleionitrile, styrene, and the like.

When synthesizing the copolymer, the ratio of the monomers to be used is not particularly limited, but in a total of 100 parts by mass of the monomers, the fluorinated alkyl group-containing ethylenically unsaturated The content of the monomer (x3) is preferably 5 to 90 parts by mass, particularly preferably 10 to 80 parts by mass, most preferably 10 to 70 parts by mass. Further, it preferably contains 10 to 95 parts by mass, more preferably 15 to 80 parts by mass, of the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4).

The copolymer can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc., but the radical polymerization method is particularly convenient, Industrially preferred. For example, it can be produced by adding a general-purpose radical polymerization initiator to a monomer mixture in an organic solvent and polymerizing it. Depending on the polymerizability of the monomers used, a dropping polymerization method in which monomers and an initiator are dropped into a reaction vessel while polymerizing is also effective for obtaining a copolymer having a uniform composition.

Various polymerization initiators can be used, and examples include peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane, and the like. Examples include azo compounds, metal chelate compounds such as Mn(acac) ₃ and transition metal catalysts that cause living radical polymerization. Furthermore, if necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as a chain transfer agent. It can be used as an additive such as

Polymerization can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of solvents include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone; methyl acetate, ethyl acetate, acetic acid; butyl, methyl lactate, ethyl lactate, esters such as butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, Monocarboxylic acid esters such as ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, methyl cellosolve, cellosolve, butyl cellosolve, Ethers such as butyl carbitol and ethyl cellosolve acetate, propylene glycols and their esters such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, 1, Halogen solvents such as 1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and fluorinated inerts such as perfluorooctane and perfluorotri-n-butylamine. Examples include liquids. These can be used alone or in combination of two or more.

As the adhesive (B) used in the present invention, any adhesive can be used without any particular limitation. For example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, etc. can be used. (b2) is preferably used.

The (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) may use a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main monomer as a raw material monomer constituting the acrylic pressure-sensitive adhesive (b1). can. One or more of the (meth)acrylic monomers can be used as a main component. By using the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it becomes easy to control the adhesive force to the adherend (protected object) to be low, and easy peelability and removability A surface protective film with excellent properties can be obtained. The “main component” in the present invention means the component with the largest amount in the total amount of constituent components, preferably exceeding 40% by mass, more preferably exceeding 50% by mass, and still more preferably 60% by mass. It means exceeding.

Examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate , isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate and the like.

Among these, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (Meth)acrylic having an alkyl group of 6 to 14 carbon atoms such as (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate The system monomer is preferable from the viewpoint that the adhesive force to the adherend can be easily controlled to be low and the removability is excellent.

In particular, it is preferable to contain 50% by mass or more of a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms with respect to 100% by mass of the total amount of monomer components constituting the (meth)acrylic polymer. , more preferably 60% by mass or more, still more preferably 70 to 99% by mass, and most preferably 80 to 97% by mass.

Moreover, it is preferable that the (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth)acrylic monomer having a hydroxyl group, one or two or more can be used.

By using the (meth)acrylic monomer having a hydroxyl group, it becomes easier to control the cross-linking of the pressure-sensitive adhesive composition, and thus the balance between improvement in wettability due to flow and reduction in adhesive force in peeling is easily controlled. It is also preferable from the viewpoint of antistatic.

Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, acrylates, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, N-methylol (meth)acrylamide, etc. is given. In particular, it is preferable to use a (meth)acrylic monomer having a hydroxyl group in which the alkyl group has 4 or more carbon atoms because it facilitates easy peeling during high-speed peeling.

It is preferable to contain 15 parts by mass or less of the (meth)acrylic monomer having a hydroxyl group with respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, and more preferably. is 1 to 13 parts by weight, more preferably 2 to 10 parts by weight, and most preferably 3 to 8 parts by weight. Within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive strength of the resulting pressure-sensitive adhesive layer can be easily controlled, which is preferable.

In addition, as other polymerizable monomer components, since it is easy to balance adhesive performance, Tg is set to 0 ° C. or less (usually -100 ° C. or more), and the glass transition temperature and peeling of the (meth) acrylic polymer A polymerizable monomer or the like for adjusting the properties can be used.

Other polymerizable monomers other than the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the (meth)acrylic monomer having a hydroxyl group used in the (meth)acrylic polymer , a (meth)acrylic monomer having a carboxyl group can be used.

Examples of the (meth)acrylic monomer having a carboxyl group include (meth)acrylic acid, carboxylethyl (meth)acrylate, and carboxylpentyl (meth)acrylate.

The (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, and 3 parts by mass. Part or less is more preferable, less than 1 part by mass is more preferable, less than 0.2 part by mass is even more preferable, and 0.01 part by mass or more and less than 0.1 part by mass is most preferable. Within the above range, it is possible to prevent an increase in adhesive strength over time (adhesive strength increase prevention property), which is preferable.

In addition, in order to achieve both peel electrification properties and adhesion strength increase prevention properties, the hydroxyl group-containing (meth)acrylic monomer and the carboxyl group-containing (meth)acrylic monomer may be used in combination. be.

Furthermore, the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth)acrylic monomer having a hydroxyl group, and the (meth)acrylic monomer having a carboxyl group used in the (meth)acrylic polymer Polymerizable monomers other than acrylic monomers can be used without particular limitation. For example, cohesion and heat resistance improving components such as cyano group-containing monomers, vinyl ester monomers, and aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and N-acryloylmorpholine. , a component having a functional group acting as a base point for cross-linking or improving adhesive strength, such as a vinyl ether monomer, can be appropriately used. Among them, cyano group-containing monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, and nitrogen-containing monomers such as N-acryloylmorpholine are preferably used. The use of a nitrogen-containing monomer is useful because it is possible to secure an appropriate adhesive strength that does not cause lifting or peeling, and to obtain a surface protective film having excellent shear strength. These polymerizable monomers may be used alone or in combination of two or more.

Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, and the like.

Examples of the aromatic vinyl monomers include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene and other substituted styrenes.

Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethyl methacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetoneacrylamide and the like.

Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide and itaconimide.

Examples of the amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl glycidyl ether.

Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.

Other polymerizable monomers other than (meth)acrylic monomers having an alkyl group having 1 to 14 carbon atoms, (meth)acrylic monomers having a hydroxyl group, and (meth)acrylic monomers having a carboxyl group have the above carbon number. It is preferably 0 to 40 parts by mass, and preferably 0 to 30 parts by mass, with respect to 100 parts by mass of a (meth)acrylic monomer having an alkyl group of 1 to 14. It is preferable from the viewpoint that it can be adjusted.

The (meth)acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.

The average added mole number of oxyalkylene units in the alkylene oxide group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, and even more preferably 4 to 35. , 5 to 30 is particularly preferred. When the average number of added moles is 1 or more, there is a tendency that the effect of reducing contamination of the adherend (object to be protected) can be efficiently obtained. On the other hand, when the average added mole number is more than 40, the viscosity of the pressure-sensitive adhesive composition tends to increase, making coating difficult. The terminal of the oxyalkylene chain may be a hydroxyl group as it is or may be substituted with another functional group.

The alkylene oxide group-containing reactive monomer may be used alone, or two or more may be mixed and used, but the content as a whole is the total amount of the monomer components of the (meth)acrylic polymer It is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, further preferably 4% by mass or less, and 3% by mass or less. It is particularly preferable that the content is 1% by mass or less.

Examples of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer include those having an alkylene group having 1 to 6 carbon atoms, such as oxymethylene group, oxyethylene group, oxypropylene group and oxybutylene group. be done. The hydrocarbon group of the oxyalkylene chain may be linear or branched.

Further, it is more preferable that the alkylene oxide group-containing reactive monomer is a reactive monomer having an ethylene oxide group. By using a (meth)acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, the compatibility between the base polymer and the fluorine-containing compound is improved, bleeding to the adherend is suitably suppressed, and the A staining adhesive composition is likely to be obtained.

Examples of the alkylene oxide group-containing reactive monomer include (meth)acrylic acid alkylene oxide adducts, reactive surfactants having reactive substituents such as acryloyl groups, methacryloyl groups, and allyl groups in the molecule, and the like. can give.

Specific examples of the (meth)acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) ) acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, ethoxypolyethyleneglycol (meth)acrylate, butoxypolyethyleneglycol (meth)acrylate, octoxypolyethyleneglycol (meth)acrylate, lauroxypolyethylene Glycol (meth)acrylate, stearoxypolyethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, octoxypolyethyleneglycol-polypropyleneglycol (meth)acrylate and the like.

Further, specific examples of the reactive surfactant include, for example, an anionic reactive surfactant having a (meth)acryloyl group or an allyl group, a nonionic reactive surfactant, a cationic reactive surfactant, and the like. is given.

The (meth)acrylic polymer preferably has a weight average molecular weight (Mw) of 100,000 to 5,000,000, more preferably 200,000 to 2,000,000, and still more preferably 300,000 to 800,000. When the weight-average molecular weight is more than 100,000, the cohesive force of the pressure-sensitive adhesive layer becomes appropriate, and adhesive residue tends to be suppressed. On the other hand, when the weight-average molecular weight is 5,000,000 or less, the fluidity of the polymer is appropriate, the adherend is sufficiently wetted, and blistering occurs between the adherend and the pressure-sensitive adhesive layer of the surface protection film. can be suppressed. In addition, a weight average molecular weight means the thing obtained by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0° C. or lower, more preferably -10° C. or lower (usually -100° C. or higher). If the glass transition temperature is higher than 0° C., the polymer tends to be difficult to flow, resulting in insufficient wetting. In particular, by setting the glass transition temperature to −61° C. or lower, it becomes easier to obtain a pressure-sensitive adhesive layer excellent in wettability and easy peelability. Incidentally, the glass transition temperature of the (meth)acrylic polymer can be adjusted within the above range by appropriately changing the monomer components and the composition ratio to be used.

The method for polymerizing the (meth)acrylic polymer is not particularly limited, and can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. Solution polymerization is a more preferable mode from the viewpoint of properties such as low contamination to the adherend (object to be protected). Moreover, the polymer obtained may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.

When using a urethane-based pressure-sensitive adhesive (b2) as the pressure-sensitive adhesive, any appropriate urethane-based pressure-sensitive adhesive can be adopted. As such a urethane-based pressure-sensitive adhesive, preferably, one made of a urethane resin (urethane-based polymer) obtained by reacting a polyol and a polyisocyanate compound can be mentioned. Examples of polyols include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and the like. Examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.

When using a silicone-based pressure-sensitive adhesive for the pressure-sensitive adhesive layer, any appropriate silicone-based pressure-sensitive adhesive can be adopted. As such a silicone-based pressure-sensitive adhesive, one obtained by blending or aggregating a silicone resin (silicone-based polymer, silicone component) can be preferably employed.

Examples of the silicone-based pressure-sensitive adhesive include addition reaction-curable silicone-based pressure-sensitive adhesives and peroxide-curable silicone-based pressure-sensitive adhesives. Among these silicone-based pressure-sensitive adhesives, addition reaction-curable silicone-based pressure-sensitive adhesives are preferred because they do not use peroxides (such as benzoyl peroxide) and do not generate decomposition products.

As the curing reaction of the addition reaction-curable silicone-based pressure-sensitive adhesive, for example, when obtaining a polyalkylsilicone-based pressure-sensitive adhesive, a method of curing a polyalkylhydrogensiloxane composition with a platinum catalyst is generally used.

The pressure-sensitive adhesive composition in the present invention may essentially contain the fluorine-containing compound (A) and the pressure-sensitive adhesive (B) described above, and the blending ratio thereof can be appropriately set according to the desired adhesive strength. However, from the viewpoint that the function as a surface protective film is easily exhibited, the content of the fluorine-containing compound (A) is preferably 0.01 to 20% by mass in the solid content of the pressure-sensitive adhesive composition. , more preferably 0.1 to 5% by mass.

The pressure-sensitive adhesive composition in the present invention can optionally contain various additives and the like as long as the effects of the present invention are not impaired.

For example, an organopolysiloxane having an oxyalkylene chain lowers the surface free energy of the pressure-sensitive adhesive surface and can be used in combination as it can realize easy release. The polyoxyalkylene chain-containing compound improves the wettability of the adhesive or pressure-sensitive adhesive, particularly when another member is adhered to the optical member with an adhesive or pressure-sensitive adhesive after peeling the surface protective film from the optical member. can be preferably used.

Furthermore, it is preferable that the pressure-sensitive adhesive composition contains a cross-linking agent. For example, when the pressure-sensitive adhesive composition contains the (meth)acrylic polymer, crosslinking is performed by appropriately adjusting the constituent units of the (meth)acrylic polymer, the composition ratio, the selection and addition ratio of the crosslinking agent, and the like. Thereby, a pressure-sensitive adhesive layer having more excellent heat resistance can be easily obtained.

As the cross-linking agent, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like may be used, and the use of an isocyanate compound is particularly preferred. Moreover, these compounds may be used individually and may be used in mixture of 2 or more types.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI) and dimer acid diisocyanate; Aromatic isocyanates such as cyclic isocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), and the isocyanate compounds with allophanate bonds, biuret bonds, isocyanurate bonds, and uretdione bonds , urea bond, carbodiimide bond, uretonimine bond, oxadiazinetrione bond and the like. For example, commercially available products include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidule T80, Sumidule L, Desmodur N3400 (Sumika Bayer Urethane). (manufactured by Nippon Polyurethane Industry Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, and Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.). These isocyanate compounds may be used alone or in combination of two or more, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination. By using a cross-linking agent in combination, it becomes possible to achieve both adhesiveness and repulsion resistance (adhesion to curved surfaces), and a laminated film having more excellent adhesion reliability can be obtained.

Further, when a difunctional isocyanate compound and a trifunctional or higher isocyanate compound are used in combination as the isocyanate compound, the compounding ratio (mass ratio) of both compounds is [bifunctional isocyanate compound]/[3 Functional or higher isocyanate compound] (mass ratio) is preferably blended at 0.1/99.9 to 50/50, more preferably 0.1/99.9 to 20/80, 0.1/99 0.9 to 10/90 are more preferred, 0.1/99.9 to 5/95 are more preferred, and 0.1/99.9 to 1/99 are most preferred. By adjusting and blending within the above range, a pressure-sensitive adhesive layer having excellent adhesiveness and repulsion resistance is obtained, which is a preferred embodiment.

Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-m-xylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis(N,N-di glycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

Examples of the melamine-based resin include hexamethylolmelamine. Examples of aziridine derivatives include commercially available products under the trade names HDU, TAZM, and TAZO (manufactured by Sogo Pharmaceutical Co., Ltd.).

Examples of the metal chelate compound include metal components such as aluminum, iron, tin, titanium and nickel, and chelate components such as acetylene, methyl acetoacetate and ethyl lactate.

The content of the cross-linking agent is, for example, preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer used in the acrylic pressure-sensitive adhesive (b1). , more preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass. By using the cross-linking agent within this range, the cohesive force of the pressure-sensitive adhesive layer to be obtained is appropriate, sufficient heat resistance is easily obtained, and adhesive residue is suppressed. These cross-linking agents may be used alone or in combination of two or more.

Furthermore, the pressure-sensitive adhesive composition can contain a cross-linking catalyst for more effectively promoting any of the cross-linking reactions described above. Examples of such cross-linking catalysts include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonato)iron, tris(hexane-2,4-dionato)iron, and tris(heptane-2,4-dionato). iron, tris(heptane-3,5-dionato)iron, tris(5-methylhexane-2,4-dionato)iron, tris(octane-2,4-dionato)iron, tris(6-methylheptane-2, 4-dionato)iron, tris(2,6-dimethylheptane-3,5-dionato)iron, tris(nonane-2,4-dionato)iron, tris(nonane-4,6-dionato)iron, tris(2 ,2,6,6-tetramethylheptane-3,5-dionato)iron, tris(tridecane-6,8-dionato)iron, tris(1-phenylbutane-1,3-dionato)iron, tris(hexafluoro Acetylacetonato) iron, Tris(ethyl acetoacetate) iron, Tris(n-propyl) iron, Tris(isopropyl acetoacetate) iron, Tris(n-butyl acetoacetate) iron, Tris(acetoacetate-sec -butyl) iron, tris(tert-butyl acetoacetate) iron, tris(methyl propionyl acetate) iron, tris(ethyl propionyl acetate) iron, tris(propionyl acetate-n-propyl) iron, tris(isopropyl propionyl acetate) iron , tris(propionylacetate-n-butyl)iron, tris(propionylacetate-sec-butyl)iron, tris(propionylacetate-tert-butyl)iron, tris(benzylacetoacetate)iron, tris(dimethylmalonate)iron, Iron-based catalysts such as tris(diethylmalonate)iron, trimethoxyiron, triethoxyiron, triisopropoxyiron, and ferric chloride can be used. One of these crosslinking catalysts may be used, or two or more thereof may be used in combination.

The content of the crosslinking catalyst is not particularly limited, but for example, it is preferably about 0.0001 to 1 part by mass, and 0.001 to 0.5 parts by mass, relative to 100 parts by mass of the (meth)acrylic polymer. Parts by mass are more preferred. Within this range, the speed of the cross-linking reaction is high when the pressure-sensitive adhesive layer is formed, and the pot life of the pressure-sensitive adhesive composition is lengthened, which is a preferred embodiment.

The laminated film of the present invention is obtained by laminating an adhesive layer made of the adhesive composition on at least one side of a substrate layer. At that time, the cross-linking of the pressure-sensitive adhesive composition is generally carried out after the application of the pressure-sensitive adhesive composition, but it is also possible to transfer the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition after cross-linking to a substrate or the like. be.

In addition, the method of forming the pressure-sensitive adhesive layer on the substrate is not particularly limited. It is made by forming on. After that, curing may be carried out for the purpose of adjusting component migration of the pressure-sensitive adhesive layer and adjusting the cross-linking reaction. In addition, when the adhesive composition is coated on a substrate to prepare a laminated film, one or more solvents other than the polymerization solvent are newly added to the adhesive composition so that the substrate can be uniformly coated. may be added to

In addition, as a method for forming an adhesive layer when manufacturing the laminated film of the present invention, a known method used for manufacturing adhesive tapes is used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and extrusion coating using a die coater.

The laminated film of the present invention is usually produced so that the thickness of the pressure-sensitive adhesive layer is about 3 to 100 μm, preferably about 5 to 50 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, it is easy to obtain an appropriate balance between removability and adhesiveness, which is preferable.

The laminated film of the present invention preferably has a total thickness of 1 to 400 μm, more preferably 10 to 200 μm, and most preferably 20 to 100 μm. Within the above range, adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties are excellent, which is a preferred embodiment. In addition, the said total thickness means the total thickness including all layers, such as a base material, an adhesive layer, an antistatic layer, and an antistatic layer.

The substrate layer forming the laminated film of the present invention is not particularly limited, but examples include transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, flexibility, and dimensional stability. It is preferable to use those having excellent properties such as toughness. In particular, when the base material has flexibility, the pressure-sensitive adhesive composition can be applied with a roll coater or the like, and can be wound into a roll, which is useful.

Materials that can be used as the substrate include, for example, polyester-based polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose-based polymers such as diacetylcellulose and triacetylcellulose; polycarbonate-based polymers. ; acrylic polymer such as polymethyl methacrylate; can. Other examples of the resin material include styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers; olefin-based polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride-based polymer; amide-based polymer such as nylon 6, nylon 6,6, and aromatic polyamide; and the like are used as resin materials. Still other examples of the resin material include imide-based polymers, sulfone-based polymers, polyethersulfone-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, and vinyl butyral-based polymers. , arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, and the like. The substrate may be a blend of two or more of the above polymers.

As the substrate, a plastic film made of a transparent thermoplastic resin material can be preferably employed. Among the plastic films, it is more preferable to use a polyester film. Here, the polyester film is a film whose main resin component is a polymer material (polyester resin) having a main skeleton based on an ester bond such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, or the like. say. Such a polyester film has favorable properties as a substrate for a surface protection film, such as excellent optical properties and dimensional stability.

Various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, antiblocking agents, etc. may have been In addition, the surface of the film used as the base material may be subjected to a known or commonly used surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer, and the like.

Furthermore, the laminated film of the present invention may have an antistatic layer on the base material, and as the base material, it is also possible to use a plastic film that has undergone antistatic treatment. The use of the base material is preferable because it suppresses charging of the film itself when the film is peeled off. Further, by using a plastic film as the base material and subjecting the plastic film to an antistatic treatment, it is possible to reduce the static charge of the laminated film itself and to obtain an excellent antistatic ability to the adherend. The method for imparting the antistatic function is not particularly limited, and conventionally known methods can be used. Examples thereof include a method of applying a contained conductive resin, a method of depositing or plating a conductive substance, and a method of kneading an antistatic agent or the like. When using an antistatic agent, a lubricant can be used together.

The thickness of the substrate layer is usually 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the base material layer is within the above range, the workability of bonding to an adherend and the workability of peeling from the adherend are excellent, which is preferable.

In order to protect the adhesive surface of the laminate film of the present invention, a separator may be adhered to the surface of the adhesive layer, if necessary.

Materials constituting the separator include paper and plastic films, and plastic films are preferably used because of their excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer. Examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer Coalesced films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.

The thickness of the separator is usually about 5-200 μm, preferably about 10-100 μm. When it is within the above range, it is preferable because it is excellent in lamination workability to the pressure-sensitive adhesive layer and peeling workability from the pressure-sensitive adhesive layer. For the separator, if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as

The laminated film of the present invention can be suitably used as a surface protection film for optical members and the like. Since the laminated film of the present invention is excellent in antistatic properties and stability of the peeling electrification voltage over time, it can be used for surface protection purposes during processing, transportation, shipping, etc., and thus can be used to protect the surface of optical members such as polarizing plates. to be useful. Since it can be used for plastic products that are particularly prone to static electricity, it is also useful for antistatic applications in technical fields related to optical and electronic components where static electricity is a particularly serious problem.

Several examples related to the present invention are described below, but the present invention is not intended to be limited to those shown in such examples. "Parts" and "%" in the following explanations and tables are based on mass unless otherwise specified, and indicate solid content or active ingredients.

In addition, evaluation in the Example was performed according to the following.
<180° Peel Force Measurement>
The resulting laminated film was attached to a glass plate by crimping with one reciprocation of a 2 kgf roller. The peel force was measured. Measurement conditions are as follows.
・ Tensile speed: 0.3 m / min
・Peeling direction: 180°
・Sample size: 25mm x 70mm
・Measurement temperature and humidity environment: 23°C x 50% RH
JIS Z0237-2000 (adhesive tape/adhesive sheet test method) compliant

Synthesis example 1
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 30 g of a block copolymer of ethylene oxide and propylene oxide represented by the following formula (1-1-1), 2.8 g of acrylic acid, a solvent 64 g of toluene as a polymerization inhibitor, 0.03 g of phenothiazine as a polymerization inhibitor, and 0.6 g of methanesulfonic acid as a catalyst were charged. After confirming dehydration of 0.63 g, it was cooled to 65° C. and neutralized with triethylamine. After neutralization, the temperature was raised to 85° C., 2.3 g of ion-exchanged water was added, liquid separation was performed, and the lower layer was extracted. The pH of the lower layer was measured, and the washing operation was repeated until the pH reached 7 or higher. After cooling, it was diluted with toluene to obtain a toluene solution containing 55% by mass of a mixture (1-1) of three kinds represented by the following formulas (1-1-1) to (1-1-3).

190.0 g of toluene was added to a glass flask equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 105° C. while stirring in a nitrogen stream. Then, 27.1 g of 2-(perfluorohexyl)ethyl acrylate, 123.2 g of the mixture (1-1) obtained above, and 62.7 g of toluene were mixed dropwise, tert-butyl=2-ethylperoxyhexa A dropping liquid obtained by dissolving 71.2 g of Noat in 190.0 g of toluene was set in a dropping device, and both the dropping liquids were dropped over 4 hours while maintaining the inside of the flask at 105°C. After completion of dropping, the mixture was stirred at 105° C. for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain fluorine-containing compound (1). The weight average molecular weight (Mw, converted to standard polystyrene manufactured by Tosoh Corporation) was 6,700.

Synthesis example 2
2-(perfluorohexyl)-ethanol 80.1 g (0.22 mol), epichlorohydrin 9.3 g (0.10 mol), triethylbenzylammonium chloride 1.1 g (0.005 mol) and sodium hydroxide 6.0 g (0.15 mol) was reacted at 65° C. for 6 hours. After completion of the reaction, 100 ml of diisopropyl ether was added and insoluble matter was filtered. The filtrate was concentrated and the residue was distilled under reduced pressure to obtain 46.2 g (0.06 mol) of a colorless oily product (2-1).

46.2 g (0.06 mol) of the product (2-1) obtained above in 200 ml of methyl isobutyl ketone (MIBK), 2-isocyanatoethyl methacrylate (9.31 g, 0.06 mol, manufactured by Showa Denko KK, Karenz MOI), 0.05 g of methoquinone and 0.05 g of dibutyltin dilaurate were added and reacted at 70° C. for 4 hours. MIBK was distilled off under reduced pressure to obtain compound (2-2) represented by the following structural formula.

302.3 g of MIBK was added to a glass flask equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 90° C. while stirring in a nitrogen stream. 170.8 g of compound (2-2), 101.3 g of hydroxypoly(oxyethylene) monomethacrylate (“NK Ester M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd.) and dicyclopentanyl acrylate (Hitachi Chemical Co., Ltd. "Funkryl FA-513A") 30.2 g dissolved in MIBK 234.5 g dropping solution, polymerization initiator 2,2'-azobis (dimethyl isobutyrate)) (manufactured by Wako Pure Chemical Industries, Ltd. "MAIB") 15 A dropping solution prepared by dissolving .1 g of MIBK in 136.0 g of MIBK was set in a dropping device, and both of the dropping solutions were dropped over 4 hours while maintaining the inside of the flask at 90°C. After completion of dropping, the mixture was stirred at 90°C for 4 hours and then stirred at 110°C for 3 hours. After cooling to 30° C., the mixture was diluted with MIBK to obtain a solution containing 30% by mass of fluorine-containing compound (2). As a result of analyzing this copolymer by a gel permeation graph, it was found to have a weight average molecular weight Mw of 9,700.

Example 1
5.5 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) per 100 parts of the solid content of the urethane adhesive (APU-505: manufactured by DIC) 0.5 part of compound (1) was added, diluted with ethyl acetate to a solid content of 50%, and thoroughly mixed to obtain an adhesive composition. The pressure-sensitive adhesive composition was applied directly to the corona-treated surface of a 60-μm-thick polyester film as a substrate using an automatic coating device bar coater (PI-1210: manufactured by Tester Co., Ltd.) so that the adhesive layer had a thickness of 60 μm. coated. Then, after drying at 60° C. for 3 minutes and at 100° C. for 3 minutes to form an adhesive layer, the adhesive layer was covered with a 38 μm-thick silicone-coated polyester film separator to prepare a laminated film. Furthermore, the laminated film obtained above was cured at 40° C. for 3 days and used as a sample for an evaluation test. The adhesive strength based on the above-mentioned peel test was 0.04 N/25 mm, confirming easy peeling. When the surface of the glass plate after peeling was visually observed, no adhesive residue was observed, and no dust adhered.

Example 2
5.5 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) per 100 parts of the solid content of the urethane adhesive (APU-505: manufactured by DIC) 0.5 part of the compound (2) was added, diluted with ethyl acetate to a solid content of 50%, and thoroughly mixed to obtain an adhesive composition. A laminate film was produced in the same manner as in Example 1 using this adhesive composition. The adhesive strength based on the above-mentioned peel test was 0.02 N/25 mm, confirming easy peeling. When the surface of the glass plate after peeling was visually observed, no adhesive residue was observed, and no dust adhered.

Comparative example 1
5.5 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) is added to 100 parts of the solid content of a urethane type adhesive (APU-505: manufactured by DIC), and the solid content is adjusted with ethyl acetate. was diluted to 50% and thoroughly mixed to obtain an adhesive composition. A laminate film was produced in the same manner as in Example 1 using this adhesive composition. The adhesive strength based on the above peel test was 0.07 N/25 mm, which was higher than the peel strength in the examples, and it was confirmed that it was difficult to handle as a surface protection film. In addition, when the surface of the glass plate after peeling was visually observed, it was observed that there was some irregular reflection and there was adhesive residue. In addition, it was found that dust adhered to the surface and that the surface was electrified.

Comparative example 2
5.5 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) and an aqueous dispersion of a fluorine compound ( Octadecyl acrylate/perfluorohexylethyl methacrylate/vinyl chloride = 66/17/17: polymerized at a mass ratio) was added in 0.5 parts in terms of solid content, and ethyl acetate was added so that the solid content was 50%. It was diluted and thoroughly mixed to obtain an adhesive composition. A laminate film was produced in the same manner as in Example 1 using this adhesive composition. The adhesive strength based on the above peel test was 0.05 N/25 mm, which was higher than the peel strength in the examples, confirming that it is difficult to handle as a surface protection film. The surface of the glass plate after peeling was visually observed, and it was found that although there was no adhesive residue, dust had adhered and the surface was charged.

Claims (8)

A pressure-sensitive adhesive composition containing a fluorine-containing compound (A) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyalkylene chain (a2) and a pressure-sensitive adhesive (B),
The fluorine-containing compound (A) is a copolymerization of a fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) and a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4) as essential raw materials. In the coalescence (A-3), the proportion of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) used is 5 to 90 parts by mass in 100 parts by mass of the raw material, and the polyoxyalkylene chain-containing A fluorine-containing compound in which the ratio of the ethylenically unsaturated monomer (x4) used is 10 to 95 parts by mass in 100 parts by mass of the raw material and the fluorine atom content is 5 to 30% by mass,
A pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive (B) is an acrylic pressure-sensitive adhesive (b1) or a urethane-based pressure-sensitive adhesive (b2). 2. The pressure-sensitive adhesive composition according to claim 1, wherein the fluorine-containing compound (A) has at least two fluorinated alkyl groups (a1) in one molecule. The copolymer (A-3) is one or more selected from acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers and vinyl esters , a copolymer of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) and the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4), or the fluorinated alkyl group-containing ethylene 3. The pressure-sensitive adhesive composition according to claim 1, which is a copolymer of the ethylenically unsaturated monomer (x3) and the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x4). 4. The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the fluorine-containing compound (A) has a weight average molecular weight in the range of 3,000 to 300,000. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the content of the fluorine-containing compound (A) is 0.01 to 20% by mass based on the solid content of the pressure-sensitive adhesive composition. The fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) is represented by the following general formula (7)

[In the formula, each Rf is -C _n F _2n+1 (where n is an integer of 1 to 6), and each R ⁵ is independently an alkylene chain having 1 to 3 carbon atoms or a direct bond; and each Y ¹ is independently an oxygen atom, a sulfur atom or —SO ₂ —NR— (R is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms), and R ⁶ is a hydrogen atom or is a methyl group, w is an integer of 1 to 3, and a plurality of Rf, R ⁵ and Y ¹ may be the same or different. ]
The pressure-sensitive adhesive composition according to any one of claims 1 to 5, which is a fluorine-containing urethane (meth)acrylate (x5) represented by A laminated film comprising an adhesive layer of the adhesive composition according to any one of claims 1 to 6 and a substrate layer. 8. The laminated film according to claim 7, which is a surface protection film for an optical member.