TWI766166B - Adhesive composition and laminated film using the same - Google Patents

Abstract

The present invention provides an adhesive composition and a laminated film; the adhesive composition is easy to adjust the adhesive force of the adhesive, has good wettability during sticking, and can also prevent residual adhesive after peeling; the laminated film has the aforementioned The adhesive composition can be suitably used as an adhesive layer and as a surface protective film. Specifically, it is an adhesive composition and a laminated film, characterized in that the adhesive composition contains: a fluorinated alkyl group (a1) having a carbon number of 1 to 6, a polyoxyalkylene chain (a2 ) and the fluorine-containing compound (A) of the silicone chain (a3), and the adhesive (B); the laminated film has an adhesive layer composed of the above-mentioned adhesive composition, and a substrate layer. The fluorine-containing compound (A) is preferably a copolymer containing the following as essential raw materials: a fluorinated alkyl group-containing ethylenically unsaturated monomer (x1), a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1). x2), and an ethylenically unsaturated monomer containing a silicone chain (x3).

Description

Adhesive composition and laminated film using the same

The present invention relates to a laminated film and an adhesive composition for forming an adhesive layer of the laminated film; the laminated film can be suitably used as a surface protection film for protecting the surface of an adherend for a specified period of time.

Conventionally, on the surfaces of various displays, polarizing plates and optical components such as laminates suitable for them, electrical substrates, etc., it is usually mainly for the purpose of protecting the surface that polyethylene, polyester, polypropylene, etc. are laminated through adhesives. Transparent substrate.

For the purpose of surface protection, after the purpose is achieved, the substrate and the adhesive must be easily and integrally peeled from the adherend, but it is generally known that the adhesive force will change with time. If it is too large, it may cause inconvenience when peeling, residual adhesive, or disconnection of the substrate film.

As a method for preventing such inconvenience, for example, there is provided a method of mixing a release agent such as a wax and a long-chain alkyl group-containing compound into an adhesive composition for forming an adhesive layer (for example, refer to Patent Document 1).

On the other hand, when the surface protective film is attached by manual work, air bubbles may be entangled between the adherend and the surface protective film. Therefore, several techniques have been reported for improving the wettability of the surface protective film without involving air bubbles at the time of sticking. For example, there is known a surface protection film using a silicone resin having a rapid wetting speed for the adhesive layer. However, when silicone resin is used for the adhesive layer, the adhesive component tends to contaminate the adherend, and it is used as a surface protection film for protecting the surfaces of optical components and electronic components that are particularly required to have low contamination. There will be problems in use.

As a surface protection film with little contamination originating in an adhesive component, the surface protection film which used an acrylic resin for an adhesive layer is known. However, the surface protection film using acrylic resin for the adhesive layer has poor wettability. Therefore, when the surface protection film is attached by manual work, air bubbles may be drawn between the object to be adhered and the surface protection film. . In addition, when an acrylic resin is used for the adhesive layer, there is a problem that paste dregs easily occurs when peeling off; it is a surface for protecting the surface of members such as optical members and electronic members that are particularly averse to foreign matter mixing. There is a problem with the use of the protective film.

As means for solving these problems, for example, there is provided a method of using a urethane-based resin obtained by using a specific polyfunctional polyol as an adhesive (for example, refer to Patent Document 2), but it lacks both moisture and humidity. An adequacy of resistance, residue and adhesion.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2017-019158

Patent Document 2: Japanese Patent Laid-Open No. 2014-111701

The problem to be solved by the present invention is to provide an adhesive composition and a laminated film; the adhesive composition is easy to adjust the adhesive force of the adhesive, and has good wettability during sticking and can also prevent adhesive residue after peeling. ; The laminated film has the aforementioned adhesive composition as an adhesive layer, and can be suitably used as a surface protection film.

As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention have found that the above-mentioned The problems were solved, and the present invention was completed.

That is, the present invention provides an adhesive composition and a laminated film; the adhesive composition contains: a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyalkylene chain (a2) and a silicone chain (a3) The fluorine-containing compound (A), and the adhesive (B); the laminated film has the above-mentioned adhesive composition as an adhesive layer.

ADVANTAGE OF THE INVENTION According to this invention, it is easy to adjust the adhesive force with respect to various adhesive agents, and the change of adhesive force after preservation|save is little, and it can provide the laminated film with favorable peelability. In addition, the laminated film of the present invention is also excellent in wettability and adhesive residue resistance, and can be suitably used as a surface protection film for various optical members, electronic members, and the like.

[Form for carrying out the invention]

The adhesive composition of the present invention is characterized by using a fluorinated compound (A) having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyalkylene chain (a2), and a silicone chain (a3).

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, a compound having a long-chain alkyl group, or the like in combination with the adhesive. However, among such generally known compounds, especially among the compounds known as release agents and surfactants, there has not yet been found a detailed structure of a compound such as the following: it is easy to adjust the adhesion even with a small amount of addition. It is a compound that has less adhesion enhancement after long-term storage, excellent peeling properties, and excellent wettability and anti-residue properties.

As a result of examining such a subject in the present invention, it was found that the use of a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyalkylene chain (a2), and a silicone chain (a3) is used. The fluorine-containing compound (A) is an effective solution.

The fluorinated alkyl group (a1) having 1 to 6 carbon atoms in the aforementioned fluorine-containing compound (A) means that the number of carbon atoms directly bonded to the fluorine atom is in the range of 1 to 6, and the number of carbon atoms bonded to the carbon atom is in the range of 1 to 6. A part may be a hydrogen atom, and in the case of an alkyl group, it may be branched or linear. In addition, a plurality of the above-mentioned fluorinated alkyl groups (a1) may have a structure connected through an ether bond, a thioether bond, or an alkylene chain which does not have a fluorine atom.

Among these, the number of carbon atoms to which the fluorine atoms are directly bonded is preferably in the range of 3 to 6, from the viewpoints that the adhesive force of the adhesive can be easily adjusted and the adhesive residue at the time of peeling can be effectively suppressed. More preferably, it is 4 or 6. Moreover, from the same viewpoint, a perfluoroalkyl group containing no hydrogen atom is more preferable. Furthermore, from the viewpoint of making it easier to adjust the adhesive force, the fluorine-containing compound (A) preferably contains two or more of the aforementioned fluorinated alkyl groups (a1) in one molecule.

The polyoxyalkylene chain (a2) in the aforementioned fluorine-containing compound (A) is not particularly limited, and is a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and the like having 1 to 1 carbon atoms. The alkylene chain of 6 may be connected by a plurality of ether bonds, and the structure of the alkylene chain may be linear or branched. In particular, from the viewpoints of easy acquisition of raw materials and antistatic properties at the time of peeling when the adhesive composition using the obtained fluorine-containing compound (A) is used as an adhesive layer, the following fluorine-containing In the synthesis of the compound (A), a polyoxyalkylene chain in which a plurality of alkylene chains having 2 to 3 carbon atoms are linked through an ether bond is preferred.

Furthermore, the number of repetitions of the polyoxyalkylene chain (a2) is preferably in the range of 2 to 50. In addition, when units with different carbon numbers are bound by ether bonds, the form may be block or random, and the above-mentioned repeating number is preferably the above-mentioned range in the total of each unit.

The silicone chain (a3) in the above-mentioned fluorine-containing compound (A) is not particularly limited, and examples thereof include the silicone chain represented by the following formula.

(In the formula, R, R', R" and R'"' each independently represent an alkyl group or a phenyl group having 1 to 18 carbon atoms, and n is the number of repeating units, and represents an integer of 1 to 200.)

The weight-average molecular weight of the silicone chain (a3) is preferably in the range of 200 to 50,000, particularly preferably 200 to 30,000 range.

The content of fluorine atoms in the fluorine-containing compound (A) is not particularly limited, but is preferred from the viewpoints of compatibility with the adhesive (B) described later, ease of adjustment of the adhesive force, and ease of manufacture. It is the range of 1-50 mass %, More preferably, it is the range of 1-30 mass %. In addition, although the fluorine atom content rate can be calculated from the feed ratio of a raw material, it can also be measured by the combustion ion chromatography of a fluorine-containing compound (A). In the present invention, among the latter actual measured values, the aforementioned range is preferable.

The weight-average molecular weight of the fluorine-containing compound (A) is not particularly limited, but is compatible with the adhesive (B) described later, the ease of adjustment of the adhesive force, and the balance between wettability and adhesive residue. From the viewpoint of, etc., the range of 3,000 to 300,000 is preferable, and the range of 3,000 to 200,000 is particularly preferable. From the viewpoint of the uniformity of the peeling force when used as a surface protection film of a large-area optical member or the like, the most preferable range is Preferably, it is the range of 4,000-100,000.

In addition, the weight average molecular weight in this invention is the value measured by the gel permeation chromatography (GPC) of the following conditions.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,

Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0mmI.D.×4cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)+Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)+Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)+Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by Alltech Japan Co., Ltd.)

Data processing: "GPC-8020 Mode II Data Analysis Version 4.30" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40°C

Developing solvent Tetrahydrofuran (THF)

Flow rate 1.0ml/min

Sample: A 1.0 mass % tetrahydrofuran solution in terms of solid content was filtered through a microfilter (5 μl).

Standard sample: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of the aforementioned "GPC-8020 Model II Data Analysis Version 4.30".

(monodisperse polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

"F-288" manufactured by Tosoh Co., Ltd.

"F-550" manufactured by Tosoh Co., Ltd.

The fluorine-containing compound (A) used in the present invention is a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyalkylene chain (a2) and a silicone chain (a3) as described above, especially From the viewpoint of good compatibility with the adhesive and easy adjustment of the adhesive force of the adhesive, it is preferable to use the fluorinated alkyl group-containing ethylenically unsaturated monomer (x1), the polyoxyalkylene chain-containing ethylenically insoluble monomer. A copolymer of a saturated monomer (x2) and an ethylenically unsaturated monomer containing a silicone chain (x3) as an essential raw material. These monomers may be composed of a single substance, respectively, or may be obtained by copolymerizing a plurality of them in combination, and the copolymerization form may be block or random.

The ethylenically unsaturated group contained in the above-mentioned monomer is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and examples thereof include (meth)acryloyl group, vinyl group, and maleimide. Base et al. Among them, (meth)acryloyl group and vinyl group are preferred, and (meth)acryloyl group and vinyl group are particularly preferred because of the availability of raw materials, compatibility with the adhesive (B) described later, or good polymerization reactivity. group) acrylyl group.

Examples of the aforementioned fluorinated alkyl group-containing ethylenically unsaturated monomer (x1) include vinyl ethers represented by the following formula (x1-1), vinyl ethers represented by the following formula (x1-2) Typical fluorinated alkyl-containing (meth)acrylates.

[In the formula, A' is an alkyl group with 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group with 3 to 12 carbon atoms which may have a substituent, an aryl group with 6 to 12 carbon atoms which may have a substituent, Or an aralkyl group with a carbon number of 6 to 24 that may have a substituent, and these are either alone or in combination of a plurality of divalent linking groups; A is an oxygen atom, and the carbon number of the substituent group is 1 ~12 alkyl groups, optionally substituted cycloalkyl groups with 3 to 12 carbon atoms, optionally substituted aryl groups with 6 to 12 carbon atoms, or optionally substituted aralkanes with 6 to 24 carbon atoms R ⁶ is a hydrogen atom or a methyl group; R f is -C _n F _2n+1 (but n is an integer of 1~6. ). ]

In addition, in the case of the aforementioned fluorinated alkyl group-containing ethylenically unsaturated monomer (x1), if it is a fluorinated urethane (meth)acrylate represented by the following formula (x1-3), then It has good compatibility with the adhesive (B) described later, especially with the acrylic adhesive (b1) or the urethane adhesive (b2), and can also maintain the transparency when the adhesive layer is formed, In addition, it is preferable from the viewpoint that it is easy to adjust the adhesive force.

[In the formula, Rf is respectively -C _n F _2n+1 (but, n is an integer of 1 to 6.); R ⁵ is independently an alkylene chain with 1 to 3 carbon atoms or a direct bond; Y ¹ Respectively 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.); R ⁶ is a hydrogen atom or a methyl group; w is an integer of 1 to 3; Rf, R ⁵ , and Y ¹ of each may be the same or different. ].

The monomer represented by the aforementioned formula (x1-3) can be 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.

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

Specific examples of Rf-R ⁵ -Y ¹ in the above formula include CF ₃ CH ₂ O-, C ₂ F ₅ CH ₂ O-, C ₃ F ₇ CH ₂ O-, C ₄ F ₉ CH ₂ O-, C ₅ F ₁₁ CH ₂ O-, C ₆ F ₁₃ CH ₂ O-, C ₄ F ₉ CH ₂ CH ₂ O-, C ₆ F ₁₃ CH ₂ CH ₂ O-, C ₄ F ₉ CH ₂ CH ₂ S-, C ₆ F ₁₃ CH ₂ CH ₂ S-, CF ₃ SO ₂ N(CH ₃ )-, CF ₃ SO ₂ N(C ₂ H ₅ )-, C ₂ F ₅ SO ₂ N(C ₃ H ₇ )-, C ₃ F ₇ SO ₂ N(C ₄ H ₉ )-, C ₃ F ₇ OCF(CF ₃ )CH ₂ O-, C ₃ F ₇ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CH ₂ O-, C ₃ F ₇ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CH ₂ O-, C ₃ F ₇ OCF(CF ₃ )CH ₂ CH ₂ O-, _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-, etc.; more specific examples include compounds represented by the following formulae.

The production method of the fluorine compound having a hydroxyl group represented by the above formula is not particularly limited, but can be described in, for example, Japanese Patent Application Laid-Open No. 1-193236, Japanese Patent Application Laid-Open No. 9-67334, and Japanese Patent Application Laid-Open No. 9-67334. Manufactured according to the method of 2002-3428 Publication and the like.

As for the (meth)acrylate which has the said isocyanate group, the compound represented by the following formula is mentioned.

(R ⁶ in the formula represents a hydrogen atom or a methyl group; A" represents an alkylene group with 2 to 3 carbon atoms.)

"A" in the aforementioned formula represents an alkylene group having 2 to 3 carbon atoms, and specifically, ethylidene (-CH ₂ CH ₂ -), propylidene (-CH ₂ CH ₂ CH ₂ -) may be mentioned. , or branched propylidene (-CH2CH( _CH3 ) _- , -CH( _{CH3 )} CH2-).

As a specific example of the compound represented by the said formula, the compound represented by the following formula is mentioned, for example.

Among the above-mentioned compounds, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate in which A" in the aforementioned formula is ethylidene are preferred.

When the fluorine compound having a hydroxyl group and the (meth)acrylate having an isocyanate group are reacted, the fluorine compound having a hydroxyl group is preferably 0.80 to 1.20 mol with respect to 1 mol. The aforementioned (meth)acrylate having an isocyanate group is fed in in a manner of 0.98-1.00 moles.

In addition, in this reaction (urethane reaction), in order to promote the reaction of the secondary hydroxyl group of the fluorine compound having a hydroxyl group with the terminal isocyanate group of the (meth)acrylate having an isocyanate group, for example , can use: tertiary amines such as triethylamine and benzyl dimethylamine; dilaurate such as dibutyltin dilaurate and dioctyltin dilaurate as catalysts. The addition amount of the catalyst is preferably 0.001 to 5.0 mass %, more preferably 0.01 to 1.1 mass % with respect to the entire reaction mixture. The reaction time is preferably 1 to 10 hours. In addition, the reaction temperature is preferably 30 to 120°C, more preferably 30 to 100°C.

The aforementioned reaction is solvent-free, or solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene, which are inert to isocyanate groups, can be used as the reaction solvent.

As a specific example of the monomer which can be obtained by the said synthesis, the monomer represented by the following formula is mentioned, for example.

Examples of the aforementioned polyoxyalkylene chain-containing ethylenically unsaturated monomer (x2) include a compound (x2-1) represented by the following general formula (3), or a compound (x2-1) represented by the following general formula ( 4) Compound (x2-2) shown:

[In the formula, R' is a polyoxyalkylene group whose end of the polyoxyalkylene chain is a hydrogen atom or an alkyl group; R ¹ is a (meth)acryloyl group; R ² is a hydrogen atom or a carbon number of 1～1～ Alkylcarbonyl of 18; r is an integer from 1 to 3; s is an integer from 0 to 2; and r+s=3. ], R ¹ OR"-OR ¹ (4)

[In the formula, R ¹ is the same or different (meth)acryloyl group; R" is an oxyalkylene chain.].

In addition, in the present invention, the (meth)acryloyl group is used as a general term for one of an acryl group and a methacryloyl group, or a mixture thereof.

For the aforementioned compounds (x2-1) and (x2-2), for example, ethylene oxide (hereinafter abbreviated as EO) modified 1,6-hexanediol di(meth)acrylate (eg , RCC13-361 manufactured by Sannopco Co., Ltd., etc.), diethylene glycol di(meth)acrylate (for example, Blemmer ADE-100 manufactured by NOF Corporation), EO-modified neopentyl glycol di(methyl) Acrylates (for example, Photomer 4160 manufactured by Sannopco Co., Ltd.), propylene oxide (hereinafter abbreviated as PO) modified neopentyl glycol di(meth)acrylate (for example, SR-9003 manufactured by Kayaku Sartomer Co., Ltd.) etc.), polyethylene glycol di(meth)acrylate (for example, Blemmer ADE-200 manufactured by NOF Corporation, etc.), polypropylene glycol di(meth)acrylate (for example, Blemmer ADP manufactured by NOF Corporation) -200, etc.), polyethylene glycol-propylene glycol-polyethylene glycol di(meth)acrylate (for example, Blemmer ADC series manufactured by NOF Corporation, etc.), polytetramethylene glycol di(methyl) Acrylate (for example, Light acrylate PTMGA-250 manufactured by Kyōeisha Chemical Co., Ltd., etc.), polyethylene glycol di(meth)acrylate (for example, Light acrylate 3EG-A manufactured by Kyōeisha Chemical Co., Ltd.), EO-modified glycerol acrylate (eg, New frontier GE3A manufactured by Daiichi Kogyo Co., Ltd.), PO-modified glycerol triacrylate (eg, Beamset 720 manufactured by Arakawa Chemical Co., Ltd.), EO-modified phosphoric acid triacrylate (eg, Viscoat 3A manufactured by Osaka Organic Chemical Co., Ltd.), (EO) or (PO) modified trimethylolpropane triacrylate (eg, New frontier TMP-3P manufactured by Daiichi Kogyo Co., Ltd.), etc. .

These can be used alone or in combination with a plurality of compounds having different numbers of (meth)acryloyl groups, and further, a plurality of compounds with different structures can also be mixed and used. Moreover, in general, the said compound which can be obtained commercially is a mixture of the compound which differs in the number of (meth)acryloyl groups with respect to the target compound as a main component. At the time of use, the compound having the desired number of (meth)acryloyl groups may be extracted and used by various purification methods such as chromatography and extraction, or the mixture may be used as it is.

Furthermore, the polyoxyalkylene chain-containing (meth)acrylate represented by the following general formula can also be used.

[In the formula, A is an oxygen atom, an alkyl group with 1 to 12 carbon atoms that may have a substituent, a cycloalkyl group with 3 to 12 carbon atoms that may have a substituent, and an aryl group that may have a substituent group of 6 to 12 carbon atoms R ⁶ is a hydrogen atom or a methyl group; R ' is a hydrogen atom or a methyl group The terminal of the polyoxyalkylene chain is a hydrogen atom or a polyoxyalkylene group of an alkyl group. ]

For the aforementioned (meth)acrylate containing polyoxyalkylene chain, for example, polyoxyalkylene acrylate, or polyoxyalkylene methacrylate, a commercially available hydroxyl group can be obtained by using various methods. Poly(oxyalkylene) (hydroxypoly(oxyalkylene)) materials, for example, under the trade names "Pluronic" (manufactured by ADEKA Co., Ltd.), Adeka Polyether (manufactured by ADEKA Co., Ltd.), "Carbowax" (Glico Products), "Toriton" (manufactured by Rohm and Haas), P.E.G (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), react with acrylic acid, methacrylic acid, acryl chloride, methacryloyl chloride, acrylic anhydride or methacrylic anhydride, etc. Moreover, polyoxyalkylene diacrylate etc. obtained by various manufacturing methods can also be used for manufacture.

Commercially available (meth)acrylates include, for example, hydroxyl-terminated polyalkylene glycol mono(meth)acrylates manufactured by NOF Corporation: Blemmer PE-90 and 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, Blemmer 10APB-500B, etc. Similarly, examples of alkyl-terminated polyalkylene glycol mono(meth)acrylates manufactured by NOF Corporation include Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer AKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer 70ANEP-550, etc., or Light Ester MC, Light manufactured by Kyoeisha Chemical Co., Ltd. Ester 130MA, Light Ester 041MA, Light acrylate BO-A, Light acrylate EC-A, Light acrylate MTG-A, Light acrylate 130A, Light acrylate DPM-A, Light acrylate P-200A, Light acrylate NP-4EA, Light acrylate NP -8EA etc. Only one type may be used for these polyoxyalkylene chain-containing (meth)acrylates, or two or more types may be used in combination.

In addition, the above-mentioned polyoxyalkylene chain-containing ethylenically unsaturated monomer (x2) may be of the vinyl ether type shown below.

[In the formula, A' is an alkyl group with 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group with 3 to 12 carbon atoms which may have a substituent, an aryl group with 6 to 12 carbon atoms which may have a substituent, Or an aralkyl group with a carbon number of 6 to 24 that may have substituents, and these are divalent linking groups formed alone or in combination; R ⁶ is a hydrogen atom or a methyl group; R ' is a polyoxygen The end of the alkylene chain is a polyoxyalkylene group with a hydrogen atom or an alkyl group. ]

For the aforementioned ethylenically unsaturated monomer (x3) containing a silicone chain, it can be either a vinyl ether type or a (meth)acrylate type, and it is preferably the aforementioned fluorinated alkyl group that is copolymerized with The ethylenically unsaturated monomer (x1) and the ethylenically unsaturated monomer (x2) containing a polyoxyalkylene chain are the same system. It is preferable to use a (meth)acrylate from a viewpoint of the easiness of acquisition of a raw material.

As a specific example of the said monomer (x3), the monomer represented by the following general formula is mentioned.

(in the formula, R ¹ represents a hydrogen atom or a methyl group; R ³ ˜R ⁶ , R ¹⁰ ˜R ¹⁷ independently represent an alkyl group or a phenyl group with 1 to 18 carbon atoms; R ² , R ⁷ ˜R ⁹ and R ¹⁸ to R ²⁰ each independently represent an alkyl group or a phenyl group having 1 to 8 carbon atoms. In addition, m and l each independently represent an integer of 1 to 6; n represents an integer of 0 to 250; r, s, t , v, w, x, y, and z independently represent integers from 1 to 250.)

In addition, in the fluorine-containing compound (A) used in the present invention, the necessary monomers and other monomers may be used as raw materials of the copolymer in the range not impairing the effect of the present invention. Moreover, you may use 2 or more types together about this monomer.

Examples of the aforementioned other monomers include acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, and vinyl ethers. Classes, vinyl esters, etc.

More specifically, acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, and benzyl acrylate. ester, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc. Examples of methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, and trimethylolpropane. Monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc. Examples of acrylamides include acrylamides, N-alkyl acrylamides (for alkyl groups, those having 1 to 3 carbon atoms, for example, methyl, ethyl, and propyl), N,N-Dialkylacrylamide (one with 1 to 3 carbon atoms in the alkyl group), N-hydroxyethyl-N-methacrylamide, N-2-acetamideethyl- N-Acetyl acrylamide and the like. The methacrylamides include: methacrylamides, N-alkylmethacrylamides (for alkyl groups, those having 1 to 3 carbon atoms, such as methyl, ethyl, propyl group), N,N-dialkylmethacrylamide (for alkyl groups, those with 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N- 2-acetamidoethyl-N-acetamidomethacrylamide, etc.

Allyl compounds include allyl esters (for example, allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, ene stearate) propyl ester, allyl benzoate, allyl acetyl acetate, allyl lactate, etc.), allyloxyethanol, etc. Examples of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, etc.) ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl Ethyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetra Hydrofurfuryl vinyl ether, etc.; vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl hexanoate , Vinyl Chloroacetate, Vinyl Dichloroacetate, Vinyl Methoxyacetate, Vinyl Butoxyacetate, Vinyl Lactate, Vinyl-β-phenyl Butyrate, Vinyl Cyclohexyl Carboxylate, etc. Dialkyl itaconate includes dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc. Dialkylesters or monoalkyl itaconate of fumaric acid may be mentioned. Esters include dibutyl fumarate, etc., and others include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, and the like.

When synthesizing the aforementioned copolymer, the usage ratio of the monomers to be used is not particularly limited, but it is preferable to contain 5 to 90 parts by mass of the fluorinated alkyl group in the total of 100 parts by mass of the monomers The ethylenically unsaturated monomer (x1) is particularly preferably 5-80 parts by mass, and most preferably 5-70 parts by mass. Moreover, it is preferable to contain 5-95 mass parts of ethylenically unsaturated monomers (x2) containing a polyoxyalkylene chain, and it is especially preferable to contain 5-80 mass parts. Furthermore, it is preferable to contain 5-95 mass parts of ethylenically unsaturated monomers containing a silicone chain (x3), and it is especially preferable to contain 5-80 mass parts.

The aforementioned copolymers can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, or the like, but in particular, the free radical polymerization method is simple and industrial. above is better. For example, it can be produced by adding a general-purpose radical polymerization initiator to an organic solvent to polymerize a monomer mixture. Depending on the polymerizability of the monomers to be used, a dropwise polymerization method or the like in which the monomers and the initiator are added dropwise to the reaction vessel for polymerization is also effective for obtaining a copolymer having a uniform composition.

For the aforementioned polymerization initiator, various polymerization initiators can be used, for example, peroxides such as benzoyl peroxide, diacyl peroxide, azo, etc. can be used. Azo compounds such as bisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane, metal chelate compounds such as Mn(acac) ₃ , transition metal catalysts that cause living radical polymerization, etc. . Further according to needs, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, octylthioglycolic acid, etc. can also be used, or γ -Mercaptopropyltrimethoxysilane and other thiol compounds with coupling groups are used as additives such as chain transfer agents.

烷等醚類、苯、甲苯、二甲苯等芳香族類，進一步可舉：全氟辛烷、全氟三-正丁基胺等氟化惰性液體(inert liquid)類等。該等可單獨使用亦可併用2種以上。 The polymerization can be carried out in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include alcohols such as ethanol, isopropanol, n-butanol, isobutanol, and tertiary butanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. esters, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate and other esters, methyl 2-oxypropionate, 2-oxypropionate Ethyl, 2-Oxypropionate, 2-Oxypropionate, 2-Oxypropionate, 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropionate , Monocarboxylic acid esters such as butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, methyl cellosolve, cellosolve, Ethers such as butyl cellosolve, butyl carbitol, ethylcellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid Esters, propylene glycols such as propylene glycol monobutyl ether acetate, and their esters, 1,1,1-trichloroethane, halogen-based solvents such as chloroform, tetrahydrofuran, dichloromethane

Ethers, such as alkane, aromatics, such as benzene, toluene, and xylene, further include fluorinated inert liquids, such as perfluorooctane and perfluorotri-n-butylamine. These may be used alone or in combination of two or more.

The adhesive (B) used in the present invention can be used without any particular limitation as long as it has adhesiveness. For example, acrylic adhesives, urethane-based adhesives, synthetic rubber-based adhesives, natural rubber-based adhesives, silicone-based adhesives, etc. can also be used, and among them, it is preferable to use: acrylic-based adhesives (b1 ), urethane adhesive (b2).

The (meth)acrylic polymer constituting the aforementioned acrylic adhesive (b1) can be mainly composed of a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a raw material monomer constituting the (meth)acrylic polymer. monomer. As for the said (meth)acrylic-type monomer, 1 type or 2 or more types can be used as a main component. By using the aforementioned (meth)acrylic monomer having an alkyl group with a carbon number of 1 to 14, it becomes easy to control the adhesive force to the adherend (to be protected) to be low, and light peelability or releasability can be obtained. Surface protection film with excellent peelability. In the present invention, the "main component" means the component that constitutes the largest amount in the total amount of components, preferably more than 40% by mass, more preferably more than 50% by mass, and still more preferably more than 60% by mass.

As the (meth)acrylic monomer having the aforementioned alkyl group having 1 to 14 carbon atoms, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and n-(meth)acrylate can be mentioned. Butyl, tertiary butyl (meth)acrylate, tertiary butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate ) Isodecyl acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc.

Among these, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate ester, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, ( (Meth)acrylic monomers with alkyl groups of carbon number 6 to 14, such as n-tetradecyl meth)acrylate, can easily control the adhesive force to the adherend to be low, and it will be excellent in releasability. From the point of view of things, it is better.

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

Moreover, it is preferable that the said (meth)acrylic-type polymer which comprises the said acryl-type adhesive agent contains the (meth)acrylic-type monomer which has a hydroxyl group as a raw material monomer. As for the (meth)acrylic-type monomer which has the said hydroxyl group, 1 type or 2 or more types can be used.

By using the above-mentioned (meth)acrylic monomer having a hydroxyl group, it becomes easy to control the crosslinking of the adhesive composition, etc., and it becomes easy to control the balance between the improvement of the wettability due to the flow and the decrease of the adhesive force during peeling, Moreover, it is also preferable from the viewpoint of antistatic.

As a (meth)acrylic-type monomer which has the said hydroxyl group, (meth)acrylic-acid-2-hydroxyethyl, (meth)acrylic-acid-2-hydroxypropyl, (meth)acrylic acid are mentioned, for example: -4-Hydroxybutyl, (meth)acrylate-6-hydroxyhexyl, (meth)acrylate-8-hydroxyoctyl, (meth)acrylate-10-hydroxydecyl, (meth)acrylate-12 -Hydroxylauryl ester, (4-hydroxymethylcyclohexyl)methyl(meth)acrylate, N-methylol(meth)acrylamide, etc. In particular, by using a (meth)acrylic monomer having a hydroxyl group and having an alkyl group of 4 or more carbon atoms, it is preferable to facilitate light peeling during high-speed peeling.

It is preferable to contain 15 parts by mass or less of the aforementioned (meth)acrylic monomer having a hydroxyl group, more preferably 1 ~13 parts by mass, more preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass. Within the above-mentioned range, it becomes easy to control the wettability of the adhesive composition and the balance with the cohesive force of the obtained adhesive layer is preferable.

In addition, as another polymerizable monomer component, from the viewpoint of being easy to achieve a balance of adhesive properties, it can be used to adjust (a The glass transition temperature of the acrylic polymer or the polymerizable monomer of peeling property, etc.

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

As a (meth)acrylic-type monomer which has the said carboxyl group, (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, etc. are mentioned, for example.

The (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass, relative to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. The mass part or less is more preferably less than 1 mass part, still more preferably less than 0.2 mass part, and most preferably 0.01 mass part or more and less than 0.1 mass part. Within the aforementioned range, it is preferable to be able to prevent an increase in the adhesive force over time (adhesive force increase prevention property).

Moreover, in order to satisfy|fill the peeling electrification property and adhesive force rise prevention property especially, you may use together the (meth)acrylic-type monomer which has the said hydroxyl group, and the (meth)acrylic-type monomer which has the said carboxyl group.

啉、乙烯基醚單體等提升黏著力或具有作為交聯化基點作用之官能基的成分。其中，較佳為使用：含有氰基的單體、含有醯胺基的單體、含有醯亞胺基的單體、含有胺基的單體、及N-丙烯醯基

啉等含氮單體。透過使用含氮單體，能夠確保不會發生浮起或剝落等之適度的黏著力，進一步可獲得剪切力優良的表面保護薄膜，因此是有用的。該等聚合性單體可單獨使用，或亦可混合2種以上而使用。 Further, the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth)acrylic monomer having a hydroxyl group, and Other polymerizable monomers other than the (meth)acrylic monomer having a carboxyl group can be used without particular limitation. For example, cohesion/heat resistance improving components such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, etc., amide group-containing monomers, amide-imide group-containing monomers can be suitably used , monomer containing amine group, monomer containing epoxy group, N-acryloyl group

Phytoline, vinyl ether monomers, etc. to improve adhesion or to have functional groups that act as cross-linking bases. Among them, it is preferable to use: a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amine group-containing monomer, and an N-acryloyl group

Nitrogen-containing monomers such as phenoline. By using a nitrogen-containing monomer, it is possible to ensure an appropriate adhesive force such that no floating or peeling occurs, and to obtain a surface protection film excellent in shear force, which is useful. These polymerizable monomers may be used alone, or two or more of them may be mixed and used.

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

As said vinyl ester monomer, vinyl acetate, vinyl propionate, vinyl laurate, etc. are mentioned, for example.

As said aromatic vinyl monomer, styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrene etc. are mentioned, for example.

Examples of the aforementioned amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylpropene Amide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebispropene Amide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetone acrylamide, etc.

Examples of the above-mentioned monomer containing an imide group include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and iconimide Wait.

Examples of the aforementioned amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethacrylate Methylaminopropyl (meth)acrylate, etc.

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

As said vinyl ether monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. are mentioned, for example.

With respect to 100 parts by mass of the aforementioned (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a (meth)acrylic monomer having a hydroxyl group, ) acrylic monomers and other polymerizable monomers other than the (meth)acrylic monomers having a carboxyl group are preferably 0 to 40 parts by mass, from the viewpoint of being able to appropriately adjust good releasability. 0 to 30 parts by mass.

The aforementioned (meth)acrylic polymer may further contain a polyoxyalkylene chain-containing reactive monomer as a monomer component.

In addition, in terms of the average added molar number of the oxyalkylene unit of the aforementioned polyoxyalkylene-containing reactive monomer, it is preferably 1 to 40, more preferably 3 to 40, and still more preferably 4 ~35, the best is 5~30. When the above-mentioned average added molar number is 1 or more, there is a tendency that the effect of reducing contamination of the adherend (to-be-protected body) can be efficiently obtained. Moreover, when the said average added molar number exceeds 40, the viscosity of an adhesive composition will increase and there exists a tendency for coating to become difficult. Furthermore, the terminal of the oxyalkylene chain is maintained as a hydroxyl group, or can be substituted with other functional groups or the like.

The reactive monomer containing the polyoxyalkylene chain can be used alone or in combination of two or more, and the overall content is in the total amount of the monomer components of the (meth)acrylic polymer. , preferably 20 mass % or less, more preferably 10 mass % or less, more preferably 5 mass % or less, still more preferably 4 mass % or less, particularly preferably 3 mass % or less, still more preferably 1 mass % the following.

The oxyalkylene unit of the reactive monomer containing the polyoxyalkylene chain includes those having an alkylene group having 1 to 6 carbon atoms, for example, oxymethylene, oxyalkylene Ethyl, oxypropylene, oxybutylene, etc. The hydrocarbon group of the oxyalkylene chain may be straight or branched.

Furthermore, the reactive monomer containing the polyoxyalkylene chain is more preferably a reactive monomer having an oxirane group. By using a (meth)acrylic polymer having a reactive monomer having an ethylene oxide group as a matrix polymer, the compatibility between the matrix polymer and the fluorine-containing compound (A) is improved, and leakage is appropriately suppressed As for the adherend, it is easy to obtain an adhesive composition with low contamination.

Examples of the reactive monomer containing the polyoxyalkylene chain include (meth)acrylic acid alkylene oxide adducts, or those having an acryl group, a methacryloyl group, an alkene in the molecule Reactive surfactants of reactive substituents such as propyl group, etc.

Specific examples of the above-mentioned (meth)acrylic acid alkylene oxide adduct include, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polyethylene glycol Propylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylic acid ester, ethoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, octoxy polyethylene glycol (meth)acrylate, lauryloxy polyethylene glycol Alcohol (meth)acrylate, stearyloxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, octyl Oxypolyethylene glycol-polypropylene glycol (meth)acrylate, etc.

Moreover, as a specific example of the said reactive surfactant, for example, the anionic reactive surfactant which has a (meth)acryloyl group or an allyl group, and a nonionic reactive surfactant can be mentioned. , cationic reactive surfactants, etc.

The weight average molecular weight (Mw) of the aforementioned (meth)acrylic polymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 2,000,000, and further preferably 300,000 to 800,000. When the weight average molecular weight is larger than 100,000, the cohesive force of the adhesive layer becomes appropriate and the residual adhesive 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 wetting of the adherend becomes sufficient, and the occurrence of generation between the adherend and the adhesive layer of the surface protective film can be suppressed. The bulge occurs. In addition, the weight-average molecular weight refers to what was measured by GPC (gel permeation chromatography).

In addition, 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). When the glass transition temperature is higher than 0°C, the polymer does not flow easily, and there is a tendency that the wetting becomes insufficient. In particular, by setting the glass transition temperature to -61° C. or lower, it becomes easy to obtain an adhesive layer excellent in wettability and light peelability. In addition, the glass transition temperature of a (meth)acrylic-type polymer can be adjusted in the said range by suitably changing the monomer component or composition ratio used.

The polymerization method of the aforementioned (meth)acrylic polymer is not particularly limited, and can be polymerized by known methods such as solution polymerization, emulsion polymerization, block polymerization, and suspension polymerization, but in particular, from the viewpoint of workability, and from the In terms of properties such as low contamination properties of the adherend (protected body), solution polymerization is more preferable. Moreover, the polymer obtained may be any of random copolymers, block copolymers, alternating copolymers, graft copolymers, and the like.

When the urethane-based adhesive (b2) is used as the aforementioned adhesive, any appropriate urethane-based adhesive can be used. As such a urethane-based adhesive, a thing composed of a urethane resin (urethane-based polymer) obtained by reacting a polyol with a polyisocyanate compound is preferably mentioned. . As a polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, etc. are mentioned, for example. As a polyisocyanate compound, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned, for example.

When a silicone-based adhesive is used in the aforementioned adhesive layer, any appropriate silicone-based adhesive can be used. As such a silicone-based adhesive, one obtained by blending or agglomerating a silicone resin (silicon-based polymer, silicone component) is preferably used.

Moreover, as for the said silicone type adhesive agent, an addition reaction hardening type silicone type adhesive agent and a peroxide hardening type silicone type adhesive agent are mentioned. Among these silicone-based adhesives, since no peroxide (benzyl peroxide, etc.) is used, decomposition products do not occur, and addition reaction-curable silicone-based adhesives are preferred.

Regarding the hardening reaction of the above-mentioned addition reaction hardening type silicone adhesive, for example, when obtaining a polyalkyl silicone adhesive, in general, it is possible to use a platinum catalyst to make polyalkyl hydrogen A method of hardening a silicone composition.

The adhesive composition in the present invention only needs to be the aforementioned fluorine-containing compound (A) and the adhesive (B). The blending ratio can be appropriately set according to the desired adhesive force. However, the content of the fluorine-containing compound (A) in the solid content of the adhesive composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 20% by mass, in particular from the viewpoint of easiness to express the function as a surface protective film. 5% by mass.

The adhesive composition of the present invention can optionally contain various additives and the like within a range not impairing the effects of the present invention.

Furthermore, in an adhesive composition, it is preferable to contain a crosslinking agent. For example, when the above-mentioned adhesive composition contains the above-mentioned (meth)acrylic-based polymer, the above-mentioned (meth)acrylic-based polymer is appropriately adjusted by adjusting the structural unit, the structural ratio, the selection of the crosslinking agent, the addition ratio, and the like. By performing crosslinking, it is possible to easily obtain an adhesive layer with better heat resistance.

(aziridine)衍生物、及金屬螯合化合物等，特別是使用異氰酸酯化合物是為較佳的態樣。又，該等化合物可單獨使用，亦可混合2種以上而使用。 As the aforementioned crosslinking agent, there can be used: isocyanate compound, epoxy compound, melamine-based resin, acridine

(aziridine) derivatives, metal chelate compounds, and the like, especially isocyanate compounds are preferably used. In addition, these compounds may be used individually or in mixture of 2 or more types.

二

三酮鍵等將前述異氰酸酯化合物進行改性而得之聚異氰酸酯改性體。例如，作為市售品，可舉：商品名Takenate 300S、Takenate 500、Takenate 600、Takenate D165N、Takenate D178N(以上為武田藥品工業公司製)、sumidur T80、sumidur L、Desmodur N3400(以上為Sumika Bayer Urethane公司製)、Millionate MR、Millionate MT、Coronate L、Coronate HL、Coronate HX(以上為Nippon Polyurethane Industry Co.,Ltd.製)等。該等異氰酸酯化合物可單獨使用，亦可混合2種以上而使用，亦能夠併用2官能的異氰酸酯化合物與3官能以上的異氰酸酯化合物而使用。透過併用交聯劑而使用變得能夠兼顧黏著性與耐排斥性(對曲面的接著性)，且能夠獲得接著可靠性更優良的積層薄膜。 The aforementioned isocyanate compounds include, for example, aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; Cyclopentyl diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI) and other alicyclic isocyanates; 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzene diisocyanate Aromatic isocyanates such as xylylene diisocyanate (XDI); through allophanate bond, biuret bond, trimeric isocyanate bond, uretdione bond, urea bond, carbodiimide bond, urea bond Ketimine (uretone-imine) bond,

two

A modified polyisocyanate obtained by modifying the aforementioned isocyanate compound with a triketone bond or the like. For example, commercially available products include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (the above are manufactured by Takeda Pharmaceutical Co., Ltd.), sumidur T80, sumidur L, Desmodur N3400 (the above are Sumika Bayer Urethane) Company), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (the above are manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like. These isocyanate compounds may be used alone, two or more of them may be mixed and used, or a bifunctional isocyanate compound and a trifunctional or more functional isocyanate compound may be used in combination. By using a crosslinking agent in combination, it is possible to achieve both adhesion and repellency resistance (adhesion to curved surfaces), and to obtain a laminated film with more excellent adhesion reliability.

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-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

衍生物而言，例如，可舉：作為市售品之商品名HDU、TAZM、TAZO(以上為相互藥工公司製)等。 As said melamine-type resin, hexamethylol melamine etc. are mentioned. just acridine

Derivatives include, for example, commercially available trade names HDU, TAZM, and TAZO (the above are manufactured by Mutual Pharmaceutical Co., Ltd.).

The metal chelate compound includes aluminum, iron, tin, titanium, nickel, and the like as the metal component, and acetylene, methyl acetoacetate, ethyl lactate, and the like as the chelate component.

For example, the content of the crosslinking agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer used in the acrylic adhesive (b1). 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 crosslinking agent in this range, the cohesive force of the obtained adhesive layer is appropriate, sufficient heat resistance can be easily obtained, and adhesive residue is also suppressed. These crosslinking agents may be used alone or in combination of two or more.

Furthermore, in the adhesive composition, a crosslinking catalyst may be contained in order to make any one of the above-mentioned crosslinking reactions proceed more efficiently. As such a crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; Keto) iron, ginseng (heptane-2,4-dione) iron, ginseng (heptane-3,5-dione) iron, ginseng (5-methylhexyl-2,4-dione) iron, ginseng (heptane-2,4-dione) iron -2,4-dione)iron, ginseng (6-methylhept-2,4-dione)iron, ginseng (2,6-dimethylhept-3,5-dione)iron, ginseng (nonyl) -2,4-dione) iron, ginseng (nonan-4,6-dione) iron, ginseng (2,2,6,6-tetramethylhept-3,5-dione) iron, ginseng (ten Trioxane-6,8-dione)iron, ginseng (1-phenylbutan-1,3-dione)iron, ginseng (hexafluoroacetone)iron, ginseng (ethylacetate)iron, ginseng (n-propyl acetoacetate) iron, ginseng (isopropyl acetoacetate) iron, ginseng (n-butyl acetoacetate) iron, ginseng (secondary butyl acetate) iron, ginseng (triacetate triacetate) iron Butyl ester) iron, ginseng (methyl propyl acetate) iron, ginseng (acetate ethyl acetate) iron, ginseng (n-propyl acetate) iron, ginseng (isopropyl acetate) iron, ginseng ( N-butyl propionate acetate) iron, ginseng (tertiary butyl acetate propionate) iron, ginseng (tertiary butyl acetate propionate) iron, ginseng (benzyl acetate) iron, ginseng (dimethyl malonate) Ester) iron, ginseng (diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, iron chloride and other iron-based catalysts. These crosslinking catalysts may be used alone or in combination of two or more.

Although content of the said crosslinking catalyst is not specifically limited, For example, it is preferable to set it as about 0.0001-1 mass part with respect to 100 mass parts of said (meth)acrylic-type polymers, More preferably, it is 0.001-0.5 mass part. Within the above-mentioned range, the rate of the crosslinking reaction is rapid when the adhesive layer is formed, and the pot life of the adhesive composition becomes long, which is a preferable aspect.

The laminate film of the present invention is obtained by laminating an adhesive layer composed of the above-mentioned adhesive composition on at least one of the base material layers. In this case, the crosslinking of the adhesive composition is generally performed after applying the adhesive composition, but an adhesive layer composed of the crosslinked adhesive composition may be transferred to a substrate or the like.

Moreover, the method of forming the adhesive layer on the substrate is not particularly concerned. For example, the adhesive layer is formed on the substrate by applying the above-mentioned adhesive composition (solution) to the substrate and drying to remove the polymerization solvent or the like. make. After that, for the purpose of adjusting the component transfer of the adhesive layer and adjusting the cross-linking reaction, it is also possible to perform good curing. In addition, when the adhesive composition is applied on a substrate to produce a laminated film, in order to be able to uniformly coat the substrate on the substrate, one or more kinds of solvents other than the polymerization solvent may be newly added to the adhesive composition. solvent.

Moreover, the well-known method used for manufacture of an adhesive tape etc. can be used for the formation method of the adhesive bond layer at the time of manufacture of the laminated film of this invention. Specifically, for example, roll coating, gravure coating, reverse roll coating, roll coating, spray coating, air knife coating, extrusion coating by a die coater, etc. are mentioned.

The laminate film of the present invention is usually prepared so that the thickness of the adhesive layer is 3 to 100 μm, preferably about 5 to 50 μm. It is preferable that the thickness of an adhesive bond layer exists in the said range, since it becomes easy to obtain the balance of moderate re-peelability and adhesiveness.

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

The base material layer forming the laminated film of the present invention is not particularly limited, and for example, transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, flexibility, and dimensional stability are preferably used. Those with excellent characteristics such as sex. In particular, since the base material has flexibility, the adhesive composition can be applied by a roll coater or the like, and it can be wound into a roll shape, which is useful.

As the above-mentioned base material user, for example, a plastic film composed of a resin material having the following as the main resin component (the main component in the resin component, typically accounting for 50% by mass or more): Polyterephthalic acid Polyester-based polymers such as ethylene glycol (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; diacetyl cellulose, triacetyl cellulose Cellulose polymers such as triacetyl cellulose; polycarbonate polymers; acrylic polymers such as polymethyl methacrylate. Other examples of the aforementioned resin materials include the following as resin materials: styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer; polyethylene, polypropylene, cyclic or norbornene Structural polyolefins, ethylene-propylene copolymers and other olefin polymers; vinyl chloride polymers; nylon 6, nylon 6,6, amide polymers such as aromatic polyamides, etc. Further other examples of the aforementioned resin materials include imide-based polymers, ethylene-based polymers, polyether ethylene-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, and vinyl alcohol-based polymers , vinylidene chloride based polymers, vinyl butyral based polymers, aryl ester based polymers, polyoxymethylene based polymers, epoxy based polymers and the like. A base material composed of a blend of two or more of the above-mentioned polymers may also be used.

As the aforementioned base material, a plastic film made of a transparent thermoplastic resin material can be preferably used. Among the aforementioned plastic films, polyester film is also more preferable. Here, the so-called polyester film refers to the following as the main resin component: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, etc. A polymer material (polyester resin) having a main skeleton based on an ester bond. Such a polyester film is excellent in optical properties and dimensional stability, etc., and is preferable as a base material for a surface protection film.

For the resin material constituting the aforementioned base material, various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, anti-blocking agents, etc. can also be blended according to needs. . The surface of the film used as a substrate can also be subjected to known or conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and primer coating.

Further, the laminated film of the present invention may have an antistatic layer on the base material, and an antistatic treated plastic film may also be used as the aforementioned base material. By using the above-mentioned base material, the charging of the film itself at the time of peeling is suppressed, which is preferable. In addition, when the base material is a plastic film, and the plastic film is subjected to antistatic treatment, the charging of the laminated film itself can be reduced, and an excellent antistatic ability to the adherend can be obtained. Furthermore, the method for imparting antistatic function is not particularly limited, and conventionally known methods can be used, for example, coating an antistatic resin composed of an antistatic agent and a resin A method of conducting a conductive polymer, a conductive resin, and a method of vapor-depositing or plating a conductive material, and a method of kneading an antistatic agent or the like. When an antistatic agent is used, a slip agent may be used together.

The thickness of the said base material layer is 5-200 micrometers normally, Preferably it is about 10-100 micrometers. When the thickness of the said base material layer is in the said range, since the workability|operativity of sticking to an adherend and the workability|operativity of peeling from an adherend are excellent, it is preferable.

In the laminated film of the present invention, if necessary, for the purpose of protecting the adhesive surface, a separator can be attached to the surface of the adhesive layer.

As the material constituting the separator, there are paper and plastic film, but since the surface smoothness is excellent, a plastic film can be suitably used. The film is not particularly limited as long as it can protect the above-mentioned adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, and polymethylpentene. Film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc. .

The thickness of the aforementioned separator is usually 5 to 200 μm, preferably about 10 to 100 μm. Within the above-mentioned range, the workability of sticking to the adhesive layer and the workability of peeling from the adhesive layer are excellent, which is preferable. For the aforementioned separator, release and antifouling treatment due to silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silicon oxide powder, etc. can also be performed as needed, or Antistatic treatment such as coating type, kneading type, and vapor deposition type is performed.

The laminated film of the present invention can be suitably used as a surface protection film for optical members and the like. The laminated film of the present invention is also excellent in stability over time, and can be used for surface protection applications such as processing, transportation, and shipping, and is therefore useful for surface protection of optical members such as polarizing plates.

[Example]

Hereinafter, some examples concerning the present invention will be described, but the present invention is not intended to be limited to those shown in such examples. In addition, unless otherwise specified, "parts" and "%" in the following descriptions and tables are based on mass, and represent solid content or active ingredients.

In addition, the evaluation in an Example was performed as follows.

<Adhesion>

The obtained laminated film was attached to a glass plate by reciprocating crimping with a 2 kgf roll 1, and after 24 hours from the attachment, the measurement was performed using a texture analyzer TA.XT plus (manufactured by Stable Micro Systems). Adhesion. Measurement conditions are as follows.

‧Peeling speed: 300mm/min, 2400mm/min

‧Peeling direction: 180°

‧Sample size: 25mm×70mm

<humidity>

The obtained laminated film was cut out into 25 mm×120 mm, bent at the center, placed on a glass plate, and released. Measure the time from the center to the wetness of 50mm on both sides.

<residual glue>

The obtained laminated film was attached to a glass plate in the same manner as in the measurement of the adhesive force. After storing at 40°C for one week, the film was peeled off, and the adhesive residue was evaluated according to the following criteria.

○: There will be no glue residue on the glass plate

×: Residual glue is left on a part of the glass plate

Synthesis Example 1

及0.6g作為觸媒之甲烷磺酸饋入於備有攪拌裝置、溫度計、冷凝管、滴加裝置之玻璃燒瓶，並在空氣氣流下起始攪拌，加熱到120℃，並進行了回流脫水。確認0.63g之脫水後，冷卻到65℃，並利用三乙胺進行了中和。中和後，升溫到85℃，添加2.3g離子交換水，進行了分液、下層抽取。測定下層的pH，重覆實施洗淨操作至pH成為7以上。冷卻後，利用甲苯進行稀釋，獲得了包含55質量%下述式(1-1-1)~(1-1-3)所示之3種 混合物(1-1)的甲苯溶液。 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, 64 g of toluene as a solvent, and 0.03 g of phenothiae as a polymerization inhibitor

And 0.6g of methanesulfonic acid as a catalyst was fed into a glass flask equipped with a stirring device, a thermometer, a condenser tube, and a dripping device, and the stirring was initiated under the air flow, heated to 120 ° C, and refluxed for dehydration. 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, and liquid separation and lower layer extraction were performed. The pH of the lower layer was measured, and the washing operation was repeated until the pH became 7 or more. After cooling, it diluted with toluene, and obtained the toluene solution containing 55 mass % of 3 kinds of mixture (1-1) represented by following formula (1-1-1) - (1-1-3).

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

46.2 g (0.06 mol) of the product (2-1) obtained above, (9.31 g, 0.06 mol, manufactured by Showa Denko Co., Ltd., Karenz MOI) 2-isocyanatoethyl methacrylate, 0.05 g of 4-Methoxyphenol and 0.05 g of dibutyltin dilaurate were added to 200 ml of methyl isobutyl ketone (MIBK) and reacted at 70° C. for 4 hours. MIBK was distilled off under reduced pressure and diluted with MIBK to obtain a solution containing 60% by mass of the compound (2-2) represented by the following structural formula.

Synthesis Example 2

300.00 g of toluene was added to a glass flask, and it heated up to 105 degreeC, stirring in nitrogen flow. Subsequently, the following dropping liquids were placed in the dropping device respectively: 14.25 g of 2-(perfluorohexyl)ethyl acrylate, 194.73 g of mixture (1-1), 99.05 g of toluene, 11.25 g of starter Perbutyl O (manufactured by NOF Corporation) mixed with dropwise solution, and 28.65 g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., SILAPLANE FM-0721K) was dissolved in 30.00 g Two kinds of dropping liquids were added dropwise over 4 hours while maintaining the inside of the flask at 105°C. After completion of the dropwise addition, the mixture was stirred at 105°C for 10 hours. After completion of the reaction, the solvent was distilled off to obtain a fluorine-containing compound (1). The copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=16,200.

Synthesis Example 3

The synthesis of the fluorine-containing compound (1) was carried out in the same manner as the fluorine-containing compound (1), except that 42.90 g of 2-(perfluorohexyl)ethyl acrylate was used and SILAPLANE FM-0721K was not added. , the fluorine-containing compound (2) was obtained. The result of analyzing this copolymer by GPC was the weight average molecular weight Mw=12,700.

Synthesis Example 4

225.00 g of methyl ethyl ketone (MEK) was added to the glass flask, and the temperature was raised to 80°C while stirring in a nitrogen stream. Subsequently, the following dropping liquids were respectively placed in the dropping device: 22.50 g of 2-(perfluorohexyl)ethyl acrylate, 82.65 g of polyethylene glycol monoacrylate (manufactured by NOF Corporation, Blemmer AE) -400), 150.00g MEK, 7.50g starting agent 2,2'-azobis(isobutyric acid) dimethyl ester (manufactured by Wako Pure Chemical Industries, Ltd., MAIB) mixed dropwise solution, 44.85 g of a monomethacrylate compound having a polysiloxane bond (Silaplane FM-0721K, manufactured by JNC Co., Ltd.) was dissolved in 75.00 g of MEK, while maintaining the inside of the flask at 80° C., The two dripping solutions were added dropwise over 4 hours. After the dropwise addition, the mixture was stirred at 80°C for 2 hours. Then, while maintaining the inside of the flask at 80 degreeC, the mixed solution of 0.75g of MAIB and 7.50g of MEK was dripped over 15 minutes. After the dropwise addition, the mixture was stirred at 80°C for 9 hours. After cooling to 30 degreeC, it diluted with MEK, and obtained the solution containing 25 mass % of fluorine-containing compounds (3). This copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=9,100.

Synthesis Example 5

The synthesis of the fluorine-containing compound (3) was carried out in the same manner as the fluorine-containing compound (3), except that 67.35 g of 2-(perfluorohexyl)ethyl acrylate was used and SILAPLANE FM-0721K was not added. , a solution containing 25% by mass of the fluorine-containing compound (4) was obtained. This copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=9,600.

Synthesis Example 6

83.0 g of compound (2-2), 11.8 g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., SILAPLANE FM-0721K), 22.5 g of a mixture (1-1), 116.0 g of A mixed solution A was prepared by mixing the methyl methacrylate, 10.0 g of 2-hydroxyethyl methacrylate, and 298.3 g of MIBK. 25 mass % of the mixed solution A, 94.9 g of MIBK, and 5.0 g of a starter Perbutyl O (manufactured by NOF Corporation) were charged into a glass flask, and the temperature was raised to 80° C. over 30 minutes under a nitrogen atmosphere. After the temperature rise, 30.0 g of MIBK and 15.0 g of Perbutyl O were added to 75 mass % of the mixture A to prepare a dropwise solution, which was added dropwise at 80° C. over 3 hours. After completion of the dropwise addition, the mixture was stirred at 80°C for 3 hours, and then stirred at 110°C for 2.5 hours. Then, desolvation was performed to 65% of solid content, and the solution containing 50 mass % of fluorine-containing compounds (5) was obtained by diluting with MIBK. The copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=18,600.

Synthesis Example 7

Except that the compound (2-2) was substituted with 49.80 g of 2-(perfluorohexyl)ethyl methacrylate in the liquid mixture A during the synthesis of the fluorine-containing compound (5), and 331.52 g of MIBK was used , was synthesized in the same manner as the fluorine-containing compound (5) to obtain a solution containing 50% by mass of the fluorine-containing compound (6). This copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=16,300.

Synthesis Example 8

In addition to the mixed solution A during the synthesis of the fluorine-containing compound (5), SILAPLANE FM-0721K was substituted with 11.80 g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., SILAPLANE FM-0711) Other than that, it synthesize|combined similarly to fluorine-containing compound (5), and obtained the solution containing 50 mass % of fluorine-containing compounds (7). This copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=17,200.

Synthesis Example 9

Except that 102.67 g of compound (2-2) and 290.45 g of MIBK were used in the mixed solution A for synthesizing the fluorine-containing compound (5), and SILAPLANE FM-0721K was not added, it was the same as the fluorine-containing compound (5) Synthesis was carried out in the same manner to obtain a solution containing 50% by mass of the fluorine-containing compound (8). This copolymer was analyzed by GPC, and the result was that the weight average molecular weight was Mw=17,200.

Example 1

It was obtained by adding 2.9 parts of D-100K (manufactured by DIC Corporation) as a hardener (crosslinking agent) and 0.5 part of solid content to 100 parts of solid content of acrylic adhesive (CT-3088: manufactured by DIC Corporation). The fluorine-containing compound (1) was diluted with methyl ethyl ketone so that the solid content was 35%, and mixed sufficiently to obtain an adhesive composition. This adhesive composition was directly applied to a corona of a 50-μm-thick polyester film as a base material using an automatic coater bar coater (PI-1210: manufactured by Tester) so that the thickness of the adhesive layer was 20 μm. handle surface. Then, after drying at 85 degreeC for 3 minutes to form an adhesive layer, the 38-micrometer-thick polyester film separator coated with silicone was coated on this adhesive layer, and a laminated film was produced. Furthermore, the laminated film obtained by using the above was cured at 40° C. for 3 days as a sample for the evaluation test. The evaluation results are shown in Table 1.

Comparative Example 1

A sample for the evaluation test was prepared in the same manner as in Example 1 except that the fluorine-containing compound (1) was not used. The evaluation results are shown in Table 1.

Comparative Example 2

A sample for the evaluation test was prepared in the same manner as in Example 1, except that the fluorine-containing compound (1) was replaced by the fluorine-containing compound (2). The evaluation results are shown in Table 1.

Example 2

The content obtained by adding 2.9 parts of D-100K (manufactured by DIC Corporation) as a hardener (crosslinking agent) and 0.5 part of solid content to 100 parts of solid content of acrylic adhesive (CT-3088: manufactured by DIC Corporation) The fluorine compound (3) was diluted with methyl ethyl ketone so that the solid content was 35%, and it was sufficiently mixed to obtain an adhesive composition. The adhesive composition was directly applied to the corona of a 50-μm-thick polyester film serving as a substrate using an automatic coater bar coater (PI-1210: manufactured by Tester) so that the thickness of the adhesive layer would be 20 μm. handle surface. Then, after drying at 85 degreeC for 3 minutes to form an adhesive layer, a 38-micrometer-thick polyester film separator coated with silicone was coated on the adhesive layer, and a laminated film was produced. Furthermore, the laminated film obtained by using the above was cured at 40° C. for 3 days, and used as a sample for the evaluation test. The evaluation results are shown in Table 2.

Comparative Example 3

A sample for the evaluation test was produced in the same manner as in Example 2 except that the fluorine-containing compound (3) was not used. The evaluation results are shown in Table 2

Comparative Example 4

A sample for the evaluation test was prepared in the same manner as in Example 2, except that the fluorine-containing compound (3) was replaced by the fluorine-containing compound (4). The evaluation results are shown in Table 2.

Example 3

5.5 parts of D-100K (manufactured by DIC Corporation) as a curing agent (crosslinking agent) and 0.5 part of solid content were added to 100 parts of solid content of urethane-based adhesive (APU-505: manufactured by DIC Corporation). The obtained fluorine-containing compound (5) was diluted with ethyl acetate so that the solid content was 50%, and the mixture was sufficiently mixed to obtain an adhesive composition. The adhesive composition was directly applied to the corona of a polyester film having a thickness of 50 μm as a base material using an automatic coater bar coater (PI-1210: manufactured by Tester) so that the thickness of the adhesive layer was 60 μm. handle surface. Then, after drying at 60°C for 3 minutes and drying at 100°C for 3 minutes to form an adhesive layer, a silicone-coated polyester film separator with a thickness of 38 μm was coated on the adhesive layer to produce a Laminated films. Furthermore, the laminate film obtained above was cured at 40°C for 3 days, and used as a sample for the evaluation test. The evaluation results are shown in Table 3.

Example 4

A sample for the evaluation test was prepared in the same manner as in Example 3, except that the fluorine-containing compound (5) was replaced by the fluorine-containing compound (6). The evaluation results are shown in Table 3.

Example 5

A sample for the evaluation test was prepared in the same manner as in Example 3, except that the fluorine-containing compound (5) was replaced by the fluorine-containing compound (7). The evaluation results are shown in Table 3.

Comparative Example 5

A sample for the evaluation test was produced in the same manner as in Example 3 except that the fluorine-containing compound (5) was not used. The evaluation results are shown in Table 4.

Comparative Example 6

A sample for the evaluation test was prepared in the same manner as in Example 3, except that the fluorine-containing compound (5) was replaced by the fluorine-containing compound (8). The evaluation results are shown in Table 4.

Claims (9)

An adhesive composition comprising: a fluorinated compound (A) having a fluorinated alkyl group (a1) having a carbon number of 1 to 6, a polyoxyalkylene chain (a2) and a silicone chain (a3), and an adhesive Agent (B), wherein the content of the aforementioned fluorine-containing compound (A) is 0.01 to 20% by mass in the solid content of the adhesive composition. The adhesive composition according to claim 1, wherein the fluorine-containing compound (A) has a fluorine atom content in the range of 1 to 50% by mass. The adhesive composition according to claim 1 or 2, wherein the weight average molecular weight of the fluorine-containing compound (A) is in the range of 3,000 to 300,000. The adhesive composition of claim 1 or 2, wherein the above-mentioned polyoxyalkylene chain (a2) is a polyoxyethylene chain (a2-1) and/or a polyoxypropylidene chain (a2-2), And the average value of the number of repetitions is the range of 2-50. The adhesive composition of claim 1 or 2, wherein the silicone chain (a3) has a molecular weight in the range of 200 to 50,000. The adhesive composition of claim 1 or 2, wherein the adhesive (B) is an acrylic adhesive (b1) or a urethane adhesive (b2). The adhesive composition according to claim 1 or 2, wherein the fluorine-containing compound (A) is an ethylenically unsaturated monomer (x1) containing a fluorinated alkyl group, an ethylenically unsaturated monomer containing a polyoxyalkylene chain Monomer (x2), a copolymer with an ethylenically unsaturated monomer (x3) containing a silicone chain as an essential raw material. A laminated film characterized by having an adhesive layer of the adhesive composition according to any one of Claims 1 to 7, and a base material layer. The laminated film according to claim 8, which is a surface protection film of an optical member.