JPWO2020184161A1 - Adhesive composition and laminated film using it - Google Patents

Abstract

Provided are a pressure-sensitive adhesive composition having excellent performance stability capable of suppressing a change in the pressure-sensitive adhesive force of the pressure-sensitive adhesive over time, and a laminated film using the pressure-sensitive adhesive layer as a surface protective film. Specifically, it contains a polyoxyalkylene compound (A) having a polyoxyalkylene chain (a1) and a silicone chain (a2) and having a glass transition temperature of 0 ° C. or lower, and an adhesive (B). Adhesive composition.

Description

The present invention relates to a pressure-sensitive adhesive composition and a laminated film using the same.

In the field of the electronic industry, in the manufacture, transportation, use, etc. of electronic devices and electronic components, the surface is protected by attaching an adhesive protective film to the surfaces of the electronic devices and electronic components.
For the same reason, an adhesive protective film is also attached to the surface of optical members such as polarizing plates, retardation plates, optical compensation films, and transparent conductive films used in liquid crystal displays, organic EL displays, touch panels, etc. It is said.

For optical members used in displays that have become larger in recent years, the method of peeling the surface protective film by a machine has become the mainstream, and the peeling speed often differs depending on the process, so the peeling force (adhesive force) can be adjusted more. There is a demand for a pressure-sensitive adhesive composition that is easy to use and has a small amount of adhesive residue after peeling, and a laminated film having the pressure-sensitive adhesive layer.
In response to the above requirements, surface protective films have been developed that have both slightly adhesiveness that can be peeled off even with a small force and re-peelability that can be peeled off cleanly once attached (for example, patent documents). 1).

Japanese Unexamined Patent Publication No. 2019-026707

Demand for electronic devices and electronic components in the electronic industry field fluctuates sharply, and surface protective films used in this field are also required to have performance stability so that they can be used whenever demand arises. There is a problem that the adhesive strength of the agent composition rapidly increases with the passage of time, and the agent composition cannot be used as a surface protective film.
The problem to be solved by the present invention is an adhesive composition having excellent performance stability that can suppress a change in the adhesive force of the adhesive with time, and a laminate that can be suitably used as a surface protective film by using this as an adhesive layer. To provide a film.

As a result of diligent studies to solve the above problems, the present inventors have made a polyoxyalkylene compound having a polyoxyalkylene chain (a1) and a silicone chain (a2) and having a glass transition temperature of 0 ° C. or lower. The present invention has been completed by finding that a pressure-sensitive adhesive composition containing (A) and a pressure-sensitive adhesive (B) can solve the above-mentioned problems.

That is, the present invention contains a polyoxyalkylene compound (A) having a polyoxyalkylene chain (a1) and a silicone chain (a2) and having a glass transition temperature of 0 ° C. or lower, and an adhesive (B). It relates to a pressure-sensitive adhesive composition.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive composition having excellent performance stability capable of suppressing a change in the adhesive force of the adhesive with time, and a laminated film which can be suitably used as a surface protective film by using the adhesive layer.

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.
In the specification of the present application, "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid.

<Adhesive composition>
The pressure-sensitive adhesive composition of the present invention comprises a polyoxyalkylene compound (A) having a polyoxyalkylene chain (a1) and a silicone chain (a2) and having a glass transition temperature of 0 ° C. or lower, and a pressure-sensitive adhesive (B). And contains.
A pressure-sensitive adhesive composition containing a polyoxyalkylene compound having a polyoxyalkylene chain and a silicone chain and having a glass transition temperature of 0 ° C. or lower can suppress a rapid increase in adhesive strength over time.
Hereinafter, each component contained in the pressure-sensitive adhesive composition of the present invention will be described.

[Polyoxyalkylene compound (A)]
The polyoxyalkylene compound (A) is a compound having a polyoxyalkylene chain (a1) and a silicone chain (a2), and has a glass transition temperature of 0 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but is, for example, −100 ° C.
The glass transition temperature of the polyoxyalkylene compound (A) is preferably in the range of −20 ° C. to −50 ° C.
The glass transition temperature of the polyoxyalkylene compound (A) is measured by the method described in Examples.

The polyoxyalkylene chain (a1) contained in the polyoxyalkylene compound (A) is not particularly limited, and alkylene chains having 1 to 6 carbon atoms such as polyoxyethylene, polyoxypropylene, and polyoxybutylene are ether-bonded. The structure of the alkylene chain may be linear or branched.

The polyoxyalkylene chain (a1) contained in the polyoxyalkylene compound (A) is preferably a polyoxyethylene chain. Here, the polyoxyethylene chain means a structure in which two or more oxyethylene groups are linked, and the polyoxyethylene chain may be linear or branched.
The polyoxyalkylene compound (A) preferably has a polyoxyethylene chain, and may further have a polyoxyalkylene chain having 1 to 6 carbon atoms such as polyoxypropylene and polyoxybutylene excluding the polyoxyethylene chain. good. When the polyoxyalkylene compound (A) has a polyoxyalkylene chain having 1 to 6 carbon atoms excluding the polyoxyethylene chain, the polyoxyalkylene chain having 1 to 6 carbon atoms is preferably a polyoxypropylene chain.

The average value of the number of repetitions of the polyoxyalkylene chain (a1) is preferably in the range of 2 to 50.
The polyoxyalkylene compound (A) has a polyoxyethylene chain and a polyoxyalkylene chain having 1 to 6 carbon atoms other than the polyoxyethylene chain, and the ethylene unit and the alkylene unit are bonded by an ether bond. In the case, the form may be block or random, and the number of repetitions is preferably in the above range in the total of each unit.

The silicone chain (a2) contained in the polyoxyalkylene compound (A) is not particularly limited, and examples thereof include a silicone chain represented by the following formula.

（式中、Ｒ、Ｒ’、Ｒ’’およびＲ’’’は、それぞれ独立に炭素数１〜１８のアルキル基またはフェニル基を表す。複数あるＲ、Ｒ’、Ｒ’’およびＲ’’’は、それぞれ互いに同一でも異なっていてもよい。
ｎは繰り返し単位数であり、それぞれ独立に１〜２００の整数を表す。）

(In the formula, R, R', R'' and R'''independently represent an alkyl group or a phenyl group having 1 to 18 carbon atoms, respectively. A plurality of R, R', R'' and R'''Can be the same or different from each other.
n is the number of repeating units, and each independently represents an integer of 1 to 200. )

The weight average molecular weight of the silicone chain (a2) is preferably in the range of 200 to 50,000, and more preferably in the range of 200 to 30,000 from the viewpoint of peelability.

The polyoxyalkylene compound (A) preferably has a fluorinated alkyl group (a3) having 1 to 6 carbon atoms. The fluorinated alkyl group (a3) having 1 to 6 carbon atoms indicates that the number of carbon atoms to which the fluorine atom is directly bonded is in the range of 1 to 6, and a part of the atoms bonded to the carbon atom is hydrogen. It may be an atom. The alkyl group of the fluorinated alkyl group may be either branched or linear.
Further, the structure may be such that the plurality of the fluorinated alkyl groups (a3) are linked by an ether bond, a thioether bond or an alkylene chain having no fluorine atom.

The fluorinated alkyl group (a3) having 1 to 6 carbon atoms has a direct fluorine atom from the viewpoint that the adhesive strength of the pressure-sensitive adhesive (B) can be easily adjusted and the adhesive residue at the time of peeling can be effectively suppressed. The number of carbon atoms bonded is preferably in the range of 3 to 6, and more preferably 4 or 6. From the same viewpoint, the fluorinated alkyl group (a3) having 1 to 6 carbon atoms is more preferably a perfluoroalkyl group containing no hydrogen atom.
When the polyoxyalkylene compound (A) contains two or more fluorinated alkyl groups (a3) in one molecule, it is preferable from the viewpoint that the adhesive strength can be more easily adjusted.

The fluorine atom content in the polyoxyalkylene compound (A) is not particularly limited, but from the viewpoints of compatibility with the adhesive (B) described later, ease of adjusting the adhesive force, and ease of production. Therefore, it is preferably in the range of 1 to 50% by mass, and more preferably in the range of 1 to 30% by mass.
The fluorine atom content can be calculated from the charging ratio of the raw material of the polyoxyalkylene compound (A), but it can also be measured by combustion ion chromatography of the polyoxyalkylene compound (A). In the present invention, the latter measured value is preferably in the above range.

The polyoxyalkylene compound (A) preferably has one or more selected from the repeating unit represented by the following formula (a4) and the repeating unit represented by the following formula (a5).

（式中、
Ｒ_１は置換基を有してもよい炭化水素基である。
Ｒ_２は炭素数４以上のアルキル基である。
＊は結合手を表す。）

(During the ceremony,
R ₁ is a hydrocarbon group which may have a substituent.
R ₂ is an alkyl group having 4 or more carbon atoms.
* Represents a bond. )

The polyoxyalkylene compound (A) has one or more selected from the repeating unit represented by the formula (a4) and the repeating unit represented by the formula (a5). The glass transition temperature can be lowered and adjusted to 0 ° C. or lower.
When the polyoxyalkylene compound (A) has a repeating unit represented by the formula (a4), the repeating unit represented by the formula (a4) may be one kind or two or more kinds.
When the polyoxyalkylene compound (A) has a repeating unit represented by the formula (a5), the repeating unit represented by the formula (a5) may be one kind or two or more kinds.

In the formula (a4), R ₁ is a hydrocarbon group which may have a substituent, and the hydrocarbon group is a hydrocarbon group excluding the alicyclic hydrocarbon group. The _{hydrocarbon group which may have a substituent of R 1} is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms. It is a hydroxyalkyl group having 1 to 6 carbon atoms.
Specific examples of R ₁ include a methyl group, an ethyl group, an isopropyl group, an nbutyl group, a 2-ethylhexyl group, an isobutyl group, an nhexyl group, a 2-hydroxyethyl group, a hydroxypropyl group, a 4-hydroxybutyl group and the like. Can be mentioned.

In the formula (a5), R ₂ is an alkyl group having 4 or more carbon atoms, preferably an alkyl group having 6 or more carbon atoms.
Specific examples of R _2, n-butyl group, 2-ethylhexyl group, an isobutyl radical, n-hexyl group, lauryl group and the like.

The ratio of the repeating unit represented by the formula (a4) and the repeating unit represented by the formula (a5) in the polyoxyalkylene compound (A) is preferably in the range of 500,000 to 300,000 in weight average molecular weight. ..

The polyoxyalkylene compound (A) may have a polyoxyalkylene chain (a1) and a silicone chain (a2), and is further represented by a fluorinated alkyl group (a3) having 1 to 6 carbon atoms and a formula (a4). It may have one or more kinds selected from the repeating unit and the repeating unit represented by the formula (a5).
The polyoxyalkylene compound (A) is preferably selected from a fluorinated alkyl group (a3) having 1 to 6 carbon atoms, a repeating unit represented by the formula (a4) and a repeating unit represented by the formula (a5). It has one or more kinds, a polyoxyalkylene chain (a1), and a silicone chain (a2).
The polyoxyalkylene compound (A) is more preferably one or more selected from the repeating unit represented by the formula (a4) and the repeating unit represented by the formula (a5), and the polyoxyalkylene chain (a1). , A silicone chain (a2) and a fluorinated alkyl group (a3) having 1 to 6 carbon atoms.
The polyoxyalkylene compound (A) is more preferably one or more selected from the repeating unit represented by the formula (a4) and the repeating unit represented by the formula (a5), and the polyoxyalkylene chain (a1). , Only the silicone chain (a2) and the fluorinated alkyl group (a3) having 1 to 6 carbon atoms.

The weight average molecular weight of the polyoxyalkylene compound (A) is not particularly limited, but from the viewpoint of compatibility with the adhesive (B) described later, ease of adjusting the adhesive force, and reduction of adhesive residue, etc. Therefore, it is preferably in the range of 3,000 to 300,000, more preferably in the range of 3,000 to 200,000, and preferably in the range of 4,000 to 100,000 for large area optics. It is most preferable from the viewpoint of uniformity of peeling force when used as a surface protective film for a member or the like.

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

(GPC measurement conditions)
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-" GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: Evaporative light scattering detector ("ELSD2000" manufactured by Alltech 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 velocity 1.0 ml / min Sample: 1.0 mass% tetrahydrofuran solution in terms of solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30".

(Unidispersed 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

When a compound having a polyoxyalkylene chain (a1) and a silicone chain (a2) is used as the polyoxyalkylene compound (A), the compatibility with the pressure-sensitive adhesive is particularly good, and the adhesive strength of the pressure-sensitive adhesive can be easily adjusted. From a certain point of view, the polyoxyalkylene compound (A) uses a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) and a silicone chain-containing ethylene unsaturated monomer (x2) as essential raw materials. It is preferably a polymer.
The polyoxyalkylene compound (A) is selected from a fluorinated alkyl group (a3) having 1 to 6 carbon atoms, a repeating unit represented by the formula (a4), and a repeating unit represented by the formula (a5). When a compound having more than a seed and a polyoxyalkylene chain (a1) and a silicone chain (a2) is used, the compatibility with the pressure-sensitive adhesive is good and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive can be easily adjusted. The alkylene compound (A) is an ethylenic unsaturated monomer (x3) containing an alkyl fluorinated group, an acrylate monomer (x4) represented by the following formula, and a methacrylate monomer (x5) represented by the following formula. A copolymer containing one or more selected from the above, a polyoxyalkylene chain-containing ethylene unsaturated monomer (x1), and a silicone chain-containing ethylene unsaturated monomer (x2) as essential raw materials. Is preferable.
Each of these monomers may be a single one, or a plurality of types may be copolymerized in combination, and the copolymerization form may be a block. It may be random.

（式中、
Ｒ_１は置換基を有してもよい炭化水素基である。
Ｒ_２は炭素数４以上のアルキル基である。）

(During the ceremony,
R ₁ is a hydrocarbon group which may have a substituent.
R ₂ is an alkyl group having 4 or more carbon atoms. )

Ethylene unsaturated monomer containing polyoxyalkylene chain (x1), ethylene unsaturated monomer containing silicone chain (x2), and ethylenically unsaturated monomer containing fluorinated alkyl group (x3) As the saturated group, a carbon-carbon unsaturated double bond having radical polymerizable property is preferable, and examples thereof include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, (meth) acryloyl group and vinyl group are preferable, and (meth) acryloyl group is particularly preferable, because the raw material is easily available, the compatibility with the adhesive (B) described later, or the polymerization reactivity is good. preferable.

Examples of the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) include compounds represented by the following formula (x1-1).

〔式中、Ｒ’はポリオキシアルキレン鎖の末端が水素原子またはアルキル基であるポリオキシアルキレン基である。
Ｒ^１は（メタ）アクリロイル基である。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。
Ｒ^２は水素原子または炭素数１〜１８のアルキルカルボニル基である。
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。〕

[In the formula, R'is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain.
R ¹ is a (meth) acryloyl group. In the present invention, the (meth) acryloyl group is used as a general term for one of an acryloyl group and a methacryloyl group or a mixture thereof.
R ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
r is an integer of 1 to 3, s is an integer of 0 to 2, and r + s = 3. ]

Examples of the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) include compounds represented by the following formula (x1-2).
R ¹ OR''-OR ¹ (x1-2)
(Wherein two R ¹ are identical or different (meth) acryloyl groups. Here, the (meth) acryloyl group, is meant to include both acryloyl group and methacryloyl group.
R'' is a polyoxyalkylene chain. )

Examples of the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) include a compound represented by the following formula (x1-3) and a compound represented by the following formula (x1-4).

（式中、Ｒ^３は、水素原子またはメチル基である。複数のＲ^３は互いに同じでも異なってもよい。
Ｒ^４およびＲ^５は、それぞれ独立に炭素数１〜６の直鎖または分岐のアルキレン基である。
Ｒ^６は、水素原子又は炭素数１〜６のアルキル基である。
ｎは２以上の整数である。
ｍは０以上の整数である。
ｋは０以上の整数である。）

(In the formula, R ³ is a hydrogen atom or a methyl group. Multiple R ^3s may be the same or different from each other.
R ⁴ and R ⁵ are linear or branched alkylene groups having 1 to 6 carbon atoms, respectively.
R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n is an integer of 2 or more.
m is an integer greater than or equal to 0.
k is an integer greater than or equal to 0. )

In the formula (X1-3) and (x1-4), an alkylene group having 1 to 6 carbon atoms ^{R 4} and ^{R 5,} if it is an alkylene group having 2 or 3 carbon atoms preferably.

Examples of the compounds (x1-1), (x1-2), (x1-3), and (x1-4) include ethylene oxide (hereinafter abbreviated as EO) modified 1,6-hexanediol di (meth) acrylate (for example). , RCC13-361 manufactured by Sannopco Co., Ltd.), Diethylene glycol di (meth) acrylate (for example, Blemmer ADE-100 manufactured by Nippon Yushi Co., Ltd.), EO-modified neopentyl glycol di (meth) acrylate (for example, Photomer 4160 manufactured by Sannopco Co., Ltd.) Etc.), propylene oxide (hereinafter abbreviated as PO) modified neopentyl glycol di (meth) acrylate (for example, SR-9003 manufactured by Chemicals Sartmer Co., Ltd.), polyethylene glycol di (meth) acrylate (for example, Nippon Oil & Fats Co., Ltd.) Blemmer ADE-200, etc.), Polypropylene glycol di (meth) acrylate (for example, Blemmer ADP-200, etc. manufactured by Nippon Yushi Co., Ltd.), Polyethylene glycol-propylene glycol-Polyethylene glycol di (meth) acrylate (for example, Nippon Yushi Co., Ltd.) Blemmer ADC series, etc.), Polytetramethylene diglycol di (meth) acrylate (for example, light acrylate PTMGA-250 manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol di (meth) acrylate (for example, light acrylate manufactured by Kyoeisha Chemical Co., Ltd.) 3EG-A), EO-modified glycerol acrylate (for example, New Frontier GE3A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), PO-modified glycerol triacrylate (for example, Beamset 720 manufactured by Arakawa Chemical Co., Ltd.), EO-modified phosphate triacrylate (for example) For example, Osaka Organic Chemical Co., Ltd. Viscoat 3A), (EO) or (PO) modified trimethylol propantriacrylate (for example, New Frontier TMP-3P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), methoxypolyethylene glycol methacrylate (for example, new). Nakamura Chemical Industry Co., Ltd., M230G) and the like.

These compounds may be used alone, a plurality of compounds having different (meth) acryloyl groups may be mixed, or a plurality of compounds having different structures may be mixed and used.
In addition, the commercially available compound is often a mixture of compounds having a different number of (meth) acryloyl groups from the target compound as a main component. At the time of use, the compound having the desired (meth) acryloyl group number may be taken out and used by various purification methods such as chromatography and extraction, but the mixture may be used as it is.

As the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1), a polyoxyalkylene chain-containing (meth) acrylate 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る。
Ｒ^６は水素原子またはメチル基である。
Ｒ’はポリオキシアルキレン鎖の末端が水素原子またはアルキル基であるポリオキシアルキレン基である。）

(In the formula, A has an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, and a substituent. It is an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 24 carbon atoms which may have a substituent, and is a divalent linking group consisting of these alone or in combination of two or more. ..
R ⁶ is a hydrogen atom or a methyl group.
R'is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain. )

As the polyoxyalkylene chain-containing (meth) acrylate, for example, polyoxyalkylene acrylate or polyoxyalkylene methacrylate is a commercially available hydroxypoly (oxyalkylene) material, for example, trade name "Pluronic" [Pluronic (Asahi Denka Kogyo). (Manufactured by Co., Ltd.), Adecapolyether (manufactured by Asahi Denka Kogyo Co., Ltd.) "Carbowax [Carbowax (Glyco-Products)]," Triton "[Toriton (manufactured by Rohm and Haas)), PE . G (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is manufactured by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride, acrylic acid anhydride, methacrylic acid anhydride, etc. by various methods. Also, polyoxyalkylene diacrylates and the like obtained by various production methods can be used.

Examples of commercially available (meth) acrylates include Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, and Blemmer as hydroxyl group-terminated polyalkylene glycol mono (meth) acrylates manufactured by NOF CORPORATION. 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 , Bremmer 10APB-500B and the like. Similarly, as alkyl-terminated polyalkylene glycol mono (meth) acrylates manufactured by Nippon Oil & Fats Co., Ltd., 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 43 ANEP-500, Blemmer 70 ANEP-550, etc. Examples thereof 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.

As the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1), a compound containing a vinyl ether structure as represented by the following general formula may be used.

（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る。
Ｒ^６は水素原子またはメチル基である。
Ｒ’はポリオキシアルキレン鎖の末端が水素原子またはアルキル基であるポリオキシアルキレン基である。）

(In the formula, A'may have an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, and a substituent. It is a good aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 24 carbon atoms which may have a substituent, and is a divalent linking group consisting of these alone or in combination of two or more.
R ⁶ is a hydrogen atom or a methyl group.
R'is a polyoxyalkylene group having a hydrogen atom or an alkyl group at the end of the polyoxyalkylene chain. )

The silicone chain-containing ethylenically unsaturated monomer (x2) may be a monomer containing a vinyl ether structure or a monomer containing a (meth) acrylate structure.
The silicone chain-containing ethylenically unsaturated monomer (x2) is preferably in the same system as the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) to be copolymerized.
From the viewpoint of availability of raw materials, it is preferable to use a monomer containing a (meth) acrylate structure as the silicone chain-containing ethylenically unsaturated monomer (x2).

Specific examples of the silicone chain-containing ethylenically unsaturated monomer (x2) include a monomer represented by the following general formula.

（式中、Ｒ^１は水素原子またはメチル基を表す。
Ｒ^３〜Ｒ^６、Ｒ^１０〜Ｒ^１７は、それぞれ独立に炭素数１〜１８のアルキル基またはフェニル基を表す。
Ｒ^２、Ｒ^７〜Ｒ^９およびＲ¹⁸〜Ｒ²⁰はそれぞれ独立に炭素数１〜８のアルキル基またはフェニル基を表す。
ｍおよびｌはそれぞれ独立に１〜６の整数を表し、ｎは０〜２５０の整数を表し、ｒ、ｓ、ｔ、ｖ、ｗ、ｘ、ｙおよびｚは、それぞれ独立に１〜２５０の整数を表す。）

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

Commercially available products can be used as the silicone chain-containing ethylenically unsaturated monomer (x2), and the commercially available products include silaplane FM-0711 and silaplane FM-, which are ethylenically unsaturated group-containing polysiloxane monomers. Examples thereof include 0721K, silaplane FM-0725, and silaplane TM-0701T (all manufactured by JNC Co., Ltd.).

Examples of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) include vinyl ether represented by the following formula (x3-1) and fluorinated alkyl group-containing monomer (x3-2) represented by the following formula (x3-2). Meta) acrylate and the like can be mentioned.

〔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は水素原子またはメチル基である。
Ｒｆは−Ｃ_ｎＦ_２ｎ＋１（但し、ｎは１〜６の整数である。）である。〕

[In the formula, A'may have an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or a substituent. A good aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 24 carbon atoms which may have a substituent, and these are divalent linking groups consisting of a single group or a combination of a plurality of carbon groups.
A is an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, and a carbon which may have a substituent. An aryl group having a number of 6 to 12 or an aralkyl group having 6 to 24 carbon atoms which may have a substituent, and these are divalent linking groups consisting of a single group or a combination of a plurality of the groups.
R ⁶ is a hydrogen atom or a methyl group.
Rf is −C _n F _{2n + 1} (where n is an integer of 1 to 6). ]

Examples of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) include fluorinated urethane (meth) acrylate represented by the following formula (x3-3).

〔式中、Ｒｆは、それぞれ独立に、−（Ｃ_ｘＦ_２ｘ−Ｏ）_ｐ−（Ｃ_ｙＦ_２ｙ−Ｏ）_ｑ−Ｃ_ｎＦ_２ｎ＋１で表される基（ｐおよびｑはそれぞれ独立に０以上の整数であり、ｎ、ｘおよびｙはそれぞれ独立に１〜６の整数である）、炭素数１〜７のアルキル基、またはフェニル基であり、２つのＲｆの少なくとも一方は、−（Ｃ_ｘＦ_２ｘ−Ｏ）_ｐ−（Ｃ_ｙＦ_２ｙ−Ｏ）_ｑ−Ｃ_ｎＦ_２ｎ＋１で表される基である。
Ｒ^５はそれぞれ独立に、炭素数１〜３のアルキレン鎖または直接結合である。
Ｙ^１はそれぞれ独立に、酸素原子、硫黄原子または−ＳＯ_２−ＮＲ−（Ｒは水素原子または炭素数１〜２４の炭化水素基である。）である。
Ｒ^６は水素原子またはメチル基である。
Ｒ^７は炭素数１〜３の直鎖又は分岐のアルキレン基である。〕

[In the formula, Rf are independently _{groups represented by − (C x} F _2x −O) _p − (C _y F _2y −O) _q −C _n F _{2n + 1} (p and q are 0 independently, respectively). The above integers, n, x and y are each independently an integer of 1 to 6), an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and at least one of the two Rfs is-(C. _x F _2x −O) _p − (C _y F _2y −O) _q −C _n F _{2n + 1} .
Each of R ⁵ is independently an alkylene chain having 1 to 3 carbon atoms or a direct bond.
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).
R ⁶ is a hydrogen atom or a methyl group.
R ⁷ is a linear or branched alkylene group having 1 to 3 carbon atoms. ]

The fluorine-containing urethane (meth) acrylate represented by the formula (x3-3) has good compatibility with the adhesive (B) described later, particularly the acrylic adhesive (b1) or the urethane adhesive (b2). Therefore, it is preferable from the viewpoint that the transparency when the adhesive layer is formed can be maintained and the adhesive strength can be easily adjusted.

The fluorine-containing urethane (meth) acrylate represented by the formula (x3-3) is, for example, 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. Obtained by

（式中のＲｆ、Ｒ^５、Ｙ^１は前記式（ｘ３−３）と同じである。）

(Rf in the ^formula, R ^{5, Y 1} is the same as the formula (x3-3).)

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-, and 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-, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ CH ₂ O-, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ CH ₂ O-, C ₃ F ₇ OCF (CF ₃ ) CH ₂ CH ₂ S-, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ CH ₂ S-, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ CH ₂ S- and the like can be mentioned.

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

The method for producing the fluorine compound having a hydroxyl group represented by the above formula is not particularly limited, and is described in, for example, JP-A-1-193236, JP-A-9-67334, JP-A-2002-3428 and the like. It can be manufactured by the method of.

Examples of the compound having an isocyanate group and a (meth) acryloyl group ((meth) acrylate having an isocyanate group) include a compound represented by the following formula.

（式中のＲ^６は、水素原子またはメチル基を表す。
Ａ’’は、炭素数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.
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 −), a propylene group (−CH ₂ CH ₂ CH ₂ −), Alternatively, a branched propylene group (-CH ₂ CH (CH ₃ )-, -CH (CH ₃ ) CH _2- ) can be mentioned.

Specific examples of the compound represented by the above formula include a compound represented by the following formula.

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

When the fluorine compound having a hydroxyl group and the (meth) acrylate having an isocyanate group are reacted, the (meth) acrylate having the isocyanate group is added to 1 mol of the fluorine compound having a hydroxyl group. It is preferably charged to be 80 to 1.20 mol, and more preferably 0.98 to 1.00 mol.

In the reaction (urethaneization reaction) between the fluorine compound having a hydroxyl group and the (meth) acrylate having an isocyanate group, the terminal of the secondary hydroxyl group of the fluorine compound having a hydroxyl group and the (meth) acrylate having the isocyanate group. In order to promote the reaction of the isocyanate group, for example, tertiary amines such as triethylamine and benzyldimethylamine; dilaurylates such as dibutyltin dilaurylate and dioctyltin dilaurylate can be used as a catalyst.
The amount of the 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 to 120 ° C, more preferably 30 to 100 ° C.

In the reaction, a solvent-free solvent or a solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, or xylene which is inert to the isocyanate group can be used as the reaction solvent.

Specific examples of the monomer represented by the above formula (x3-3) obtained by the above reaction include a monomer represented by the following formula.

As a specific example of the acrylate monomer (x4), R ₁ in the formula (x4) is a methyl group, an ethyl group, an isopropyl group, an nbutyl group, a 2-ethylhexyl group, an isobutyl group, an nhexyl group, 2-. Examples thereof include compounds having a hydroxyethyl group, a hydroxypropyl group or a 4-hydroxybutyl group.
As the acrylate monomer (x4), a commercially available product can be used.

Specific examples of the methacrylate monomer (x5) include compounds in which R ₂ in the formula (x5) is an nbutyl group, a 2-ethylhexyl group, an isobutyl group, an nhexyl group, a lauryl group, and the like.
As the methacrylate monomer (x5), a commercially available product can be used.

The polyoxyalkylene compound (A) contains a fluorinated alkyl group using a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) and a silicone chain-containing ethylenically unsaturated monomer (x2) as essential reaction raw materials. When one or more selected from an ethylenically unsaturated monomer (x3), an acrylate monomer (x4) and a methacrylate monomer (x5) are copolymerized as an arbitrary reaction raw material, these simple compounds are used. In addition to the metric, other monomers may be used as raw materials for the copolymer as long as the effects of the present invention are not impaired.
The other monomers may be used alone or in combination of two or more.

Examples of the other monomer include acrylic acid, methacrylic acid, acrylic acid esters other than the acrylate monomer (x4), methacrylic acid esters other than the methacrylate monomer (x5), acrylamides, and methacrylicamide. , Allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, dialkyl esters of methacrylic acid, monoalkyl esters and the like.

Examples of the acrylic acid esters which are the other monomers include furfuryl acrylate and tetrahydrofurfuryl acrylate.

Examples of the other monomeric methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chlorethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylpropan monomethacrylate, benzyl methacrylate, and methoxybenzyl methacrylate. Examples thereof include furfuryl methacrylate and tetrahydrofurfuryl methacrylate.

Examples of the acrylamides as the other monomers include acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkylacrylamide. (Alkyl groups have 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamide ethyl-N-acetylacrylamide and the like can be mentioned.

Examples of the other monomeric methacrylamides include methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, and propyl group), N, N-. Examples thereof include dialkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamide ethyl-N-acetylmethacrylamide and the like.

Examples of the allyl compound which is the other monomer include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, etc. Allyl lactate, etc.), allyl oxyethanol, etc. can be mentioned.

Examples of the vinyl ethers as the other monomers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- Examples thereof include 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 and the like.

Examples of the vinyl esters which are the other monomers include vinyl bitylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, and vinyl methoxy. Examples thereof include acetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Examples of the other monomer dialkyl itaconic acid include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.
Examples of the dialkyl esters or monoalkyl esters of fumaric acid, which is the other monomer, include dibutyl fumarate and the like.
In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene and the like can also be mentioned.

The proportion of the monomers used in synthesizing the copolymer of the polyoxyalkylene compound (A) is not particularly limited, but polyoxy is used in a total of 100 parts by mass of the monomers. The alkylene chain-containing ethylenically unsaturated monomer (x1) is preferably contained in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass.
The silicone chain-containing ethylenically unsaturated monomer (x2) is preferably contained in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass, out of a total of 100 parts by mass of the monomers.
It is preferable that 5 to 90 parts by mass of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x3) is contained in the total of 100 parts by mass of the monomers, and 5 to 80 parts by mass is contained. Is more preferable, and it is further preferable that the content is 5 to 70 parts by mass.
The acrylate monomer (x4) is preferably contained in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass, and 10 to 80 parts by mass in the total of 100 parts by mass of the monomers. It is more preferable that the portion is contained.
The methacrylate monomer (x5) is preferably contained in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass, and 5 to 70 parts by mass in a total of 100 parts by mass of the monomers. It is more preferable that the portion is contained.

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

As the polymerization initiator, various compounds can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane and the like. Examples thereof include an azo compound, _{a metal chelate compound such as Mn (acac) 3} , and a transition metal catalyst that causes living radical polymerization.
If necessary, a chain transfer agent such as lauryl mercaptoethanol, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane can be used as a chain transfer agent. It may be used as an additive of.

The 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 the solvent used for the polymerization 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 and acetic acid. Ethers such as ethyl, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2-methoxypropion Monocarboxylic acid esters such as methyl acid, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, methylcellosolve, cellosolve , Ethers such as butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and their esters. , 1,1,1-Trichloroethane, halogen-based solvents such as chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and perfluorooctane, perfluorotri-n-butylamine and the like. Examples include fluorinated inert liquids.
These solvents may be used alone or in combination of two or more.
The solvent used for the polymerization of the polyoxyalkylene compound (A) may be the solvent of the pressure-sensitive adhesive composition of the present invention.

[Adhesive (B)]
The adhesive (B) can be used without particular limitation as long as it has adhesiveness. For example, an acrylic adhesive, a urethane adhesive, a synthetic rubber adhesive, a natural rubber adhesive, and a silicone adhesive. And so on. Among these pressure-sensitive adhesives, it is preferable to use an acrylic pressure-sensitive adhesive (b1) and / or a urethane-based pressure-sensitive adhesive (b2).

The (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) is obtained from a raw material monomer containing a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component monomer.
The (meth) acrylic monomer can be used as a main component of one kind or two or more kinds. 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 body) to be low, and it is easy to peel off and re-peelable. An excellent surface protective film can be obtained.
The "main component" in the present invention means the most abundant component in the total amount of the constituent components, and the "main component" preferably exceeds 40% by mass, more preferably exceeds 50% by mass, and is even more preferable. Means that it exceeds 60% by mass.

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

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

It is preferable that the (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) contains a (meth) acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth) acrylic monomer having a hydroxyl group, one kind or two or more kinds can be used.

By using the (meth) acrylic monomer having a hydroxyl group, it becomes easy to control the cross-linking of the pressure-sensitive adhesive composition, and by extension, it becomes easy to control the balance between the improvement of wettability due to flow and the reduction of adhesive force in peeling. Also, it is 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, and 6-hydroxyhexyl (meth). Acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, N-methylol (meth) acrylamide, etc. Can be mentioned. In particular, it is preferable to use a (meth) acrylic monomer having a hydroxyl group having 4 or more carbon atoms in the alkyl group, because light peeling at the time of high-speed peeling becomes easy.

It is preferable and more 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. Is 1 to 13 parts by mass, more preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass. When it is within the above range, it is easy to control the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the obtained pressure-sensitive adhesive layer, which is preferable.

As other polymerizable monomer components, the Tg is set to 0 ° C. or lower (usually -100 ° C. or higher) to reduce the glass transition temperature and peelability of the (meth) acrylic polymer because it is easy to balance the adhesive performance. A polymerizable monomer or the like for adjusting can be used.

Examples of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms used in the (meth) acrylic polymer and other polymerizable monomers other than the (meth) acrylic monomer having a hydroxyl group include , 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, preferably 3 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. It is more preferably less than parts, more preferably less than 1 part by mass, even more preferably less than 0.2 parts by mass, and most preferably 0.01 parts by mass or more and less than 0.1 parts by mass. If it is within the above range, it is possible to prevent the adhesive strength from increasing with time (adhesive strength increase preventing property), which is preferable.

It is also possible to use the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having a carboxyl group in combination for the purpose of achieving both the peeling charge property and the adhesive force increase preventing property.

Further, 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) having a carboxyl group used in the (meth) acrylic polymer. The polymerizable monomer other than the acrylic monomer can be used without particular limitation. For example, a cohesiveness / heat resistance improving component such as a cyano group-containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, and N-acryloylmorpholin. , Vinyl ether monomer and other components having a functional group that acts as an adhesive strength improving or cross-linking base point can be appropriately used. Among them, it is preferable to use a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and a nitrogen-containing monomer such as N-acryloylmorpholine. By using the nitrogen-containing monomer, it is possible to secure an appropriate adhesive force that does not cause floating or peeling, and it is possible to obtain a surface protective film having excellent shearing force, which is useful. 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 monomer 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-dimethylmethacrylicamide, N, N-diethylacrylamide, N, N-diethyl. Examples thereof include methacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropyl methacrylamide, diacetone acrylamide 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, methyl glycidyl (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.

The polymerizable monomer other than 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 has the above-mentioned carbon number. It is preferably 0 to 40 parts by mass, and 0 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer having an alkyl group of 1 to 14, as appropriate for good removability. It is preferable from the viewpoint that it can be adjusted.

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

The average c of the oxyalkylene units of the polyoxyalkylene group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, still more preferably 4 to 35, and 5 to 35. It is particularly preferably 30.
When the average number of added moles is 1 or more, the effect of reducing contamination of the adherend (protected body) tends to be efficiently obtained. On the other hand, when the average number of added moles is larger than 40, the viscosity of the pressure-sensitive adhesive composition tends to increase, making coating difficult. The terminal of the oxyalkylene chain may remain as a hydroxyl group or may be substituted with another functional group or the like.

The polyoxyalkylene chain-containing reactive monomer may be used alone or in combination of two or more, but the total content is the monomer component of the (meth) acrylic polymer. It is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, still more preferably 4% by mass or less, and 3% by mass or less. Is particularly preferable, and it is still more preferable that the content is 1% by mass or less.

Examples of the oxyalkylene unit of the polyoxyalkylene chain-containing reactive monomer include those having an alkylene group having 1 to 6 carbon atoms, and examples thereof include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. Can be mentioned. The hydrocarbon group of the oxyalkylene chain may be linear or branched.

It is more preferable that the polyoxyalkylene chain-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 polyoxyethylene compound (A) is improved, and bleeding to an adherend is preferable. It is easy to obtain a pressure-sensitive adhesive composition that is suppressed and has low contamination.

Examples of the polyoxyalkylene chain-containing reactive monomer include a (meth) acrylate alkylene oxide adduct, a reactive surfactant having a reactive substituent such as an acryloyl group, a methacryloyl group, and an allyl group in the molecule. Can be mentioned.

Specific examples of the (meth) acrylate alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, and polyethylene glycol-polybutylene glycol (meth). ) Acrylic, Polyethylene Glycol-Polybutylene Glycol (Meta) acrylate, methoxypolyethylene Glycol (Meta) acrylate, ethoxypolyethylene Glycol (Meta) acrylate, Butoxypolyethylene Glycol (Meta) acrylate, Octoxypolyethylene glycol (Meta) acrylate, Lauroxypolyethylene Glycol (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate and the like can be mentioned.

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. Can be mentioned.

The (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) preferably has a weight average molecular weight (Mw) of 100,000 to 5 million, more preferably 200,000 to 2 million, and further preferably 300,000 to 300,000. It is 800,000. When the weight average molecular weight is larger than 100,000, the cohesive force of the pressure-sensitive adhesive layer becomes appropriate and there is a tendency to suppress adhesive residue. On the other hand, when the weight average molecular weight is 5 million or less, the fluidity of the polymer is appropriate, the adherend is sufficiently wetted, and blisters generated between the adherend and the pressure-sensitive adhesive layer of the surface protective film are generated. Can be suppressed.
The weight average molecular weight is obtained by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) 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 tends to be difficult to flow and wetting tends to be insufficient. In particular, when the glass transition temperature is set to −61 ° C. or lower, an adhesive layer having excellent wettability and light peelability can be easily obtained.
The glass transition temperature of the (meth) acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio used.

The polymerization method of the (meth) acrylic polymer is not particularly limited and can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., but particularly from the viewpoint of workability and subject matter. Solution polymerization is a more preferable embodiment from the viewpoint of characteristics such as low contamination of the body (protected body). Further, the obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.

When a urethane-based pressure-sensitive adhesive (b2) is used as the pressure-sensitive adhesive (B), any suitable urethane-based pressure-sensitive adhesive may be used. The urethane-based pressure-sensitive adhesive (b2) preferably includes a urethane resin (urethane-based polymer) obtained by reacting a polyol with a polyisocyanate compound.
Examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like.
Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.

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

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 preferable because peroxides (benzoyl peroxide and the like) are not used and decomposition products are not generated.

Examples of the curing reaction of the addition reaction curing type silicone-based pressure-sensitive adhesive include, for example, a method of curing a polyalkyl hydrogen siloxane composition with a platinum catalyst in the case of obtaining a polyalkyl silicone-based pressure-sensitive adhesive.

In the pressure-sensitive adhesive composition of the present invention, the blending ratio of the polyoxyethylene compound (A) and the pressure-sensitive adhesive (B) may be appropriately set according to the desired adhesive strength. When the pressure-sensitive adhesive composition of the present invention is used for the pressure-sensitive adhesive layer of the surface protective film, the content of the polyoxyethylene compound (A) is 0.01 to 20% by mass in the solid content of the pressure-sensitive adhesive composition. It is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 5.0% by mass. Within this range, the polyoxyethylene compound (A) can sufficiently exert its function as an adhesive strength adjusting agent.
In the present invention, the "solid content" means a component obtained by removing the solvent from the pressure-sensitive adhesive composition.

[Other ingredients]
The pressure-sensitive adhesive composition of the present invention may contain the polyoxyalkylene compound (A) and the pressure-sensitive adhesive (B), and may optionally contain other components such as various additives as long as the effects of the present invention are not impaired. Can be done.

The pressure-sensitive adhesive composition of the present invention preferably contains a cross-linking agent as another component. For example, when the pressure-sensitive adhesive composition of the present invention contains the (meth) acrylic polymer as the pressure-sensitive adhesive (B), the constituent unit and the constituent ratio of the (meth) acrylic polymer are further contained by further containing a cross-linking agent. By appropriately adjusting the selection of the cross-linking agent, the addition ratio, and the like for cross-linking, 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-based resin, an aziridine derivative, a metal chelate compound and the like may be used, and the use of an isocyanate compound is particularly preferable. Further, these compounds may be used alone or in combination of two or more.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI) and dimerate diisocyanate, and fats such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate (IPDI). Aromatic isocyanates such as cyclic isocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), and these isocyanate compounds are allophanate bond, biuret bond, isocyanurate bond, uretdione bond. , Urea bond, carbodiimide bond, uretonimine bond, oxadiazine trione bond and the like modified polyisocyanate modified product.
Examples of commercially available products of the isocyanate compound include trade names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takeda D178N (all manufactured by Takeda Pharmaceutical Company Limited), Sumijour T80, Sumijuru L, and Death Module N3400 (or more). , Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (all manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like.
These isocyanate compounds may be used alone or in combination of two or more, or a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination. By using a mixture of two or more cross-linking agents, it is possible to achieve both adhesiveness and resilience resistance (adhesiveness to curved surfaces), and a laminated film having more excellent adhesive reliability can be obtained.

Examples of the epoxy compound include N, N, N', N'-tetraglycidyl-m-xylene diamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Inc.) and 1,3-bis (N, N-diamine). Glycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like can be mentioned.

Examples of the melamine-based resin include hexamethylol melamine and the like.
Examples of the aziridine derivative include commercially available commercial products such as HDU, TAZM, and TAZO (all manufactured by Mutual Pharmaceutical Co., Ltd.).

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

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

The pressure-sensitive adhesive composition can contain a cross-linking catalyst for more effectively advancing any of the above-mentioned cross-linking reactions.
Examples of the cross-linking catalyst include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron, tris (hexane-2,4-dionat) iron, and tris (heptane-2,4-dionat). Iron, Tris (Heptane-3,5-Zionato) Iron, Tris (5-Methylhexane-2,4-Zionato) Iron, Tris (Octane-2,4-Zionato) Iron, Tris (6-Methylheptane-2, 4-Zionato iron, Tris (2,6-dimethylheptane-3,5-Zionato) iron, Tris (Nonan-2,4-Zionato) iron, Tris (Nonan-4,6-Zionato) 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 (ethylacetate acetate) iron, tris (acetoacetate-n-propyl) iron, tris (isopropylacetate isopropyl) iron, tris (acetoacetate-n-butyl) iron, tris (acetoacetate-sec) -Butyl) iron, tris (acetoacetate-tert-butyl) iron, tris (propionylmethylacetate) iron, tris (propionylacetate ethyl) iron, tris (propionylacetate-n-propyl) iron, tris (propionylacetate isopropyl) iron , Tris (propionyl acetate-n-butyl) iron, tris (propionyl acetate-sec-butyl) iron, tris (propionyl acetate-tert-butyl) iron, tris (benzyl acetoacetate) iron, tris (dimethyl malonate) iron, Iron-based catalysts such as tris (diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, and ferric chloride can be used. These cross-linking catalysts may be used alone or in combination of two or more.

The content of the cross-linking catalyst is not particularly limited, but is preferably about 0.0001 to 1 part by mass, and 0.001 to 0.5 parts by mass, for example, with respect to 100 parts by mass of the (meth) acrylic polymer. Parts by mass are more preferred. When it is within the above range, the rate 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 long, which is a preferable embodiment.

<Laminated film>
The laminated film of the present invention has an adhesive layer and a base material layer, and the adhesive layer is a layer formed by using the adhesive composition of the present invention.
The laminated film of the present invention can be produced by applying and cross-linking the pressure-sensitive adhesive composition of the present invention on at least one surface of a base material layer. The laminated film of the present invention can also be produced by transferring a pressure-sensitive adhesive layer obtained by pre-crosslinking the pressure-sensitive adhesive composition of the present invention onto at least one surface of a base material layer.

The method for forming the pressure-sensitive adhesive layer on the base material layer is not particularly limited. For example, the pressure-sensitive adhesive composition (solution) of the present invention is applied to the base material, and the polymerization solvent or the like is dried and removed to base the pressure-sensitive adhesive layer. It is produced by forming it on a material. After that, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer, adjusting the cross-linking reaction, and the like.
When the pressure-sensitive adhesive composition is applied onto a base material to prepare a laminated film, one or more solvents other than the polymerization solvent are newly added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive composition can be uniformly applied on the base material layer. May be added.

As a method for forming the pressure-sensitive adhesive layer when manufacturing the laminated film of the present invention, a known method used for manufacturing pressure-sensitive adhesive tapes is used. Specific examples thereof include a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coat method, an extrusion coat method using a die coater and the like.

The laminated film of the present invention is usually produced so that the thickness of the pressure-sensitive adhesive layer is about 1 to 200 μm, preferably about 3 to 100 μm. When the thickness of the pressure-sensitive adhesive layer is within the 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 150 μm. When the total thickness of the laminated film is within the above range, the adhesive properties (removability, adhesiveness, etc.), workability, and appearance characteristics are excellent, which is a preferable embodiment.
The "total thickness" means the total thickness including all layers such as the base material layer, the adhesive layer, and the antistatic layer of the laminated film.

The base material layer constituting the laminated film of the present invention is not particularly limited, but for example, transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, flexibility, and dimensional stability. It is preferable to use a base material having excellent properties such as properties. In particular, since the base material has flexibility, the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll shape, which is useful.

Examples of the base material that can be used are polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; and polycarbonate polymers. An acrylic polymer such as polymethylmethacrylate; a plastic film composed of a resin material containing the main resin component (main component of the resin component, typically a component accounting for 50% by mass or more) can be mentioned. 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; Examples thereof include those using a vinyl chloride polymer; an amide polymer such as nylon 6, nylon 6, 6, and aromatic polyamide; and the like as a resin material.
Still other examples of the resin material include imide-based polymers, sulfone-based polymers, polyether sulfone-based polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, and vinyl butyral-based polymers. , Arilate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer and the like.
It may be a base material composed of a blend of two or more of the above-mentioned polymers.

As the base material, a plastic film made of a transparent thermoplastic resin material can be preferably adopted. Among the plastic films, it is more preferable to use a polyester film. Here, the polyester film is mainly composed of a polymer material (polyester resin) having a main skeleton based on an ester bond such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. say. Such a polyester film has preferable properties as a base material of a surface protective 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. are blended in the resin material constituting the base material, if necessary. It may have been done. Further, the surface of the film used as a base material may be subjected to known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent.

The laminated film of the present invention may have an antistatic layer on the base material layer, and it is also possible to use a plastic film which has been subjected to antistatic treatment as the base material. It is preferable to use such a base material because the charge of the film itself at the time of peeling can be suppressed.
Further, the base material is a plastic film, and by applying the antistatic treatment to the plastic film, it is possible to reduce the charge of the laminated film itself and obtain an excellent antistatic ability to the adherend. The method for imparting the antistatic function is not particularly limited, and a conventionally known method can be used. For example, an antistatic resin, a conductive polymer, or a conductive substance composed of an antistatic agent and a resin component can be used. Examples thereof include a method of applying the 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 also be used in combination.

The thickness of the base material layer is usually about 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the base material layer is within the above range, it is preferable because it is excellent in the workability of attaching to the adherend and the workability of peeling from the adherend.

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

Paper and a plastic film are examples of the material constituting the separator, and the plastic film is preferably used because of its excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and is, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-weight. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

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

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

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

Synthesis example 1
In a glass flask equipped with a stirrer, a thermometer, a cooling tube 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, and a solvent. As a result, 64 g of toluene, 0.03 g of phenothiazine as a polymerization inhibitor, and 0.6 g of methanesulfonic acid as a catalyst were charged, stirring was started under an air stream, and the mixture was heated to 120 ° C. and reflux dehydrated. After confirming dehydration of 0.63 g, the mixture 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 the liquid was separated 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).

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 diisopyropillar ether was added and the insoluble material 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).

Product (2-1) obtained in 200 ml of methyl isobutyl ketone (MIBK) 46.2 g (0.06 mol), 2-isocyanatoethyl methacrylate (9.31 g, 0.06 mol, manufactured by Showa Denko Co., Ltd., Karenz MOI ), 0.05 g of methquinone and 0.05 g of dibutyltin dilaurate were added, and the mixture was 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 formula.

Synthesis example 3
83.0 g of a solution containing 60% by mass of the compound (2-2) obtained in Synthesis Example 2, 11.8 g of a monomethacrylate compound having a polysiloxane bond (Cyraplane FM-0721K, manufactured by JNC Co., Ltd.), in Synthesis Example 1. Mixture A is prepared by mixing 22.5 g of a toluene solution containing 55% by mass of the obtained mixture (1-1), 116.0 g of ethyl acrylate, 10.0 g of 4-hydroxybutyl acrylate, and 298.3 g of MIBK as a solvent. bottom.
25% by mass of the mixed solution A, 94.9 g of MIBK, and 5.0 g of the initiator Perbutyl O (manufactured by NOF CORPORATION) were placed in a glass flask, and the temperature was raised to 80 ° C. over 30 minutes in a nitrogen atmosphere. After the temperature was raised, 30.0 g of MIBK and 15.0 g of perbutyl O were added to 75% by mass of the mixture A to prepare a dropping solution, which was added dropwise at 80 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 3 hours and then at 110 ° C. for 2.5 hours. Then, after removing the solvent to a solid content of 65%, it was diluted with MIBK to obtain a solution containing 50% by mass of the polyoxyalkylene compound (1).

As a result of analyzing the copolymer polyoxyalkylene compound (1) by GPC, the weight average molecular weight Mw was 20,600.
Moreover, when the glass transition temperature of the polyoxyalkylene compound (1) was measured by differential scanning calorimetry (DSC) under the following conditions, the glass transition temperature was −40 ° C.
Measuring machine: METTLER TOLEDO DSC3 +
Temperature rise temperature: 10 ° C / min
Measurement atmosphere: Nitrogen measurement weight: Approximately 5 mg

Synthesis example 4
100 g of butyl acetate was placed in a glass flask, and the temperature was raised to 95 ° C. over 30 minutes in a nitrogen atmosphere. 2- (Perfluorohexyl) ethyl acrylate 24.9 g, monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., Silaplane FM-0721K) 5.9 g, monoacrylate compound having an ethylene oxide chain (manufactured by Nichiyu Co., Ltd.) , Blemmer AE-400) 6.2 g, ethyl acrylate 50.4 g, 4-hydroxybutyl acrylate 12.6 g, butyl acetate 133.3 g as solvent, initiator Perbutyl O (manufactured by Nichiyu Co., Ltd.) 3.0 g. The mixture was mixed to prepare a mixed solution A.
The mixed solution A was added dropwise at 95 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 95 ° C. for 3 hours and then at 110 ° C. for 1.0 hour. Then, it cooled and obtained the solution containing 30% by mass of the polyoxyalkylene compound (2).
As a result of analyzing the copolymer polyoxyalkylene compound (2) by GPC, the weight average molecular weight Mw was 18,500. The glass transition temperature of the polyoxyalkylene compound (2) was −35 ° C.

Synthesis example 5
100 g of butyl acetate was placed in a glass flask, and the temperature was raised to 95 ° C. over 30 minutes in a nitrogen atmosphere. 2- (Perfluorohexyl) ethyl acrylate 24.9 g, monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., Silaplane FM-0721K) 5.9 g, monoacrylate compound having an ethylene oxide chain (manufactured by Nichiyu Co., Ltd.) , Blemmer AE-400) 6.2 g, ethyl acrylate 50.4 g, 4-hydroxybutyl acrylate 12.6 g, butyl acetate 50.0 g as solvent, initiator Perbutyl O (manufactured by Nichiyu Co., Ltd.) 3.0 g. The mixture was mixed to prepare a mixed solution A.
The mixed solution A was added dropwise at 95 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 95 ° C. for 3 hours and then at 110 ° C. for 1.0 hour. Then, it cooled and obtained the solution containing 40% by mass of the polyoxyalkylene compound (3).
As a result of analyzing the copolymer polyoxyalkylene compound (3) by GPC, the weight average molecular weight Mw was 26,500. The glass transition temperature of the polyoxyalkylene compound (3) was −33 ° C.

Synthesis example 6
83.0 g of a solution containing 60% by mass of the compound (2-2) obtained in Synthesis Example 2, 11.8 g of a monomethacrylate compound having a polysiloxane bond (Cyraplane FM-0721K, manufactured by JNC Co., Ltd.), in Synthesis Example 1. Mixture A is prepared by mixing 22.5 g of a toluene solution containing 55% by mass of the obtained mixture (1-1), 116.0 g of ethyl acrylate, 25.2 g of 2-hydroxyethyl acrylate, and 298.3 g of MIBK as a solvent. bottom.
25% by mass of the mixed solution A, 94.9 g of MIBK, and 5.0 g of the initiator Perbutyl O (manufactured by NOF CORPORATION) were placed in a glass flask, and the temperature was raised to 90 ° C. over 30 minutes in a nitrogen atmosphere. After the temperature was raised, 30.0 g of MIBK and 15.0 g of perbutyl O were added to 75% by mass of the mixed solution A to prepare a dropping solution, which was added dropwise at 90 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 90 ° C. for 3 hours and then at 110 ° C. for 2.5 hours. Then, the solvent was removed to a solid content of 65% and diluted with MIBK to obtain a solution containing 50% by mass of the polyoxyalkylene compound (4).
As a result of analyzing the copolymer polyoxyalkylene compound (4) by GPC, the weight average molecular weight Mw was 15,000. The glass transition temperature of the polyoxyalkylene compound (4) was −32 ° C.

Synthesis example 7
83.0 g of the compound (2-2) obtained in Synthesis Example 2, 11.8 g of a monomethacrylate compound having a polysiloxane bond (Cyraplane FM-0721K, manufactured by JNC Co., Ltd.), and a mixture (1-) obtained in Synthesis Example 1. 1) A mixture A was prepared by mixing 22.5 g, 116.0 g of methyl methacrylate, 10.0 g of 2-hydroxyethyl methacrylate, and 298.3 g of MIBK as a solvent.
25% by mass of the mixed solution A, 94.9 g of MIBK, and 5.0 g of the initiator Perbutyl O (manufactured by NOF CORPORATION) were placed in a glass flask, and the temperature was raised to 80 ° C. over 30 minutes in a nitrogen atmosphere. After the temperature was raised, 30.0 g of MIBK and 15.0 g of perbutyl O were added to 75% by mass of the mixed solution A to prepare a dropping solution, which was added dropwise at 80 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 3 hours and then at 110 ° C. for 2.5 hours. Then, the solvent was removed to a solid content of 65% and diluted with MIBK to obtain a solution containing 50% by mass of the polyoxyalkylene compound (5).
As a result of analyzing the copolymer polyoxyalkylene compound (5) by GPC, the weight average molecular weight Mw was 18,600. The glass transition temperature of the polyoxyalkylene compound (5) was 34 ° C.

Synthesis example 8
83.0 g of the compound (2-2) obtained in Synthesis Example 2, 11.8 g of a monomethacrylate compound having a polysiloxane bond (Cyraplane FM-0721K, manufactured by JNC Co., Ltd.), and a mixture (1-) obtained in Synthesis Example 1. 1) 22.5 g, 116.0 g of methyl methacrylate, 25.2 g of 4-hydroxybutyl acrylate, and 298.3 g of MIBK as a solvent were mixed to prepare a mixed solution A.
25% by mass of the mixed solution A, 94.9 g of MIBK, and 5.0 g of the initiator Perbutyl O (manufactured by NOF CORPORATION) were placed in a glass flask, and the temperature was raised to 80 ° C. over 30 minutes in a nitrogen atmosphere. After the temperature was raised, 30.0 g of MIBK and 15.0 g of perbutyl O were added to 75% by mass of the mixed solution A to prepare a dropping solution, which was added dropwise at 80 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 3 hours and then at 110 ° C. for 2.5 hours. Then, the solvent was removed to a solid content of 65% and diluted with MIBK to obtain a solution containing 50% by mass of the polyoxyalkylene compound (6).
As a result of analyzing the copolymer polyoxyalkylene compound (6) by GPC, the weight average molecular weight Mw was 23,300. The glass transition temperature of the polyoxyalkylene compound (6) was 8 ° C.

Example 1
For 100 parts of solid content of acrylic pressure-sensitive adhesive (CT-3088: manufactured by DIC Corporation), 2.9 parts of D-100K (manufactured by DIC Corporation) as a curing agent (crosslinking agent) and the obtained polyoxyalkylene compound 0.5 part of (1) was added, diluted with methyl ethyl ketone so that the solid content was 35%, and sufficiently mixed to obtain a pressure-sensitive adhesive composition.
The obtained pressure-sensitive adhesive composition was applied to the coroner-treated surface of a polyester film having a thickness of 50 μm as a base material so that the thickness of the pressure-sensitive adhesive layer after formation was 20 μm. Directly coated using (manufactured by). Then, it was dried at 85 ° C. for 3 minutes to form an adhesive layer, and then the adhesive layer was coated with a silicone-coated 38 μm-thick polyester film separator to prepare a laminated film. This laminated film was further cured at 40 ° C. for 3 days and used as a sample for an evaluation test.
The following evaluation was performed on the obtained laminated film. The results are shown in Table 1.

<Initial adhesive strength evaluation>
The obtained laminated film was pressure-bonded to a glass plate with one reciprocating 2 kgf roller to be attached as an evaluation sample. Twenty-four hours after the application, the adhesive strength of the evaluation sample was measured using the adhesive / film peeling analyzer VPA-3 (manufactured by Kyowa Interface Science). The measurement conditions are as follows. The adhesive strength was evaluated in two patterns, one in which the tensile speed and the peeling speed were set to 150 mm / min and the other in which the tensile speed and the peeling speed were set to 1200 mm / min.
-Tensile speed: 150 mm / min, 1200 mm / min
-Peeling speed: 150 mm / min, 1200 mm / min
・ Peeling direction: 180 °
-Sample size: 25 mm x 70 mm

<Adhesive strength evaluation after 60 ° C x 90% RH x 14 days>
A sample used for the initial adhesive strength evaluation was separately prepared, and the evaluation sample was placed at a temperature of 60 ° C. and a humidity of 90% RH and stored for 14 days. The adhesive strength of the evaluation sample after storage (after the moist heat test) was evaluated by the same method as the initial adhesive strength evaluation.

Example 2
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyeoxyethylene compound (2) was used instead of the polyoxyalkylene compound (1). The results are shown in Table 1.

Example 3
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyeoxyethylene compound (3) was used instead of the polyoxyalkylene compound (1). The results are shown in Table 1.

Example 4
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyeoxyethylene compound (4) was used instead of the polyoxyalkylene compound (1). The results are shown in Table 1.

Comparative Example 1
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyoxyalkylene compound (1) was not used. The results are shown in Table 1.

Comparative Example 2
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyeoxyethylene compound (5) was used instead of the polyoxyalkylene compound (1). The results are shown in Table 1.

Comparative Example 3
A laminated film was produced and evaluated in the same manner as in Example 1 except that the polyeoxyethylene compound (6) was used instead of the polyoxyalkylene compound (1). The results are shown in Table 1.

From the results in Table 1, it can be seen that the pressure-sensitive adhesive composition of Example 1-4 can have a small pressure-sensitive adhesive force even at a tensile speed of 1200 mm / min and a peeling speed of 1200 mm / min. Further, it can be seen that the pressure-sensitive adhesive composition of Examples 1-4 has little change in adhesive strength even after the moist heat test and is excellent in performance stability.

Claims (10)

A pressure-sensitive adhesive composition containing a polyoxyalkylene compound (A) having a polyoxyalkylene chain (a1) and a silicone chain (a2) and having a glass transition temperature of 0 ° C. or lower, and a pressure-sensitive adhesive (B). The pressure-sensitive adhesive composition according to claim 1, wherein the polyoxyalkylene compound (A) has a fluorinated alkyl group (a3) having 1 to 6 carbon atoms. The invention according to claim 1 or 2, wherein the polyoxyalkylene compound (A) has at least one selected from a repeating unit represented by the following formula (a4) and a repeating unit represented by the following formula (a5). Adhesive composition.

(During the ceremony,
R ₁ is a hydrocarbon group which may have a substituent.
R ₂ is an alkyl group having 4 or more carbon atoms.
* Represents a bond. ) The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the glass transition temperature of the polyoxyalkylene compound (A) is in the range of −20 ° C. to −50 ° C. The polyoxyalkylene compound (A) is a copolymer containing a polyoxyalkylene chain-containing ethylenically unsaturated monomer (x1) and a silicone chain-containing ethylene unsaturated monomer (x2) as essential raw materials. The pressure-sensitive adhesive composition according to any one of claims 1 to 4. The polyoxyalkylene compound (A) further includes an ethylenically unsaturated monomer (x3) containing a fluorinated alkyl group, a monomer (x4) represented by the following formula, and a monomer represented by the following formula (x3). The pressure-sensitive adhesive composition according to claim 5, which is a copolymer containing at least one selected from x5) as an essential raw material.

(During the ceremony,
R ₁ is a hydrocarbon group which may have a substituent.
R ₂ is an alkyl group having 4 or more carbon atoms. ) The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the content of the polyoxyalkylene compound (A) is 0.01 to 20% by mass in the solid content of the pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive (B) is an acrylic pressure-sensitive adhesive (b1) and / or a urethane-based pressure-sensitive adhesive (b2). A laminated film having an adhesive layer and a base material layer of the adhesive composition according to any one of claims 1 to 8. The laminated film according to claim 9, which is a surface protective film for an optical member.