KR20210068524A - Adhesive composition and laminated film using same - Google Patents

Abstract

It is easy to adjust the adhesive force of the pressure-sensitive adhesive, and provides a pressure-sensitive adhesive composition with less adhesive residue after peeling. Specifically, it contains a polyoxyethylene compound (A) having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2), and an adhesive (B). A pressure-sensitive adhesive composition.

Description

Adhesive composition and laminated film using same

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

In the field of the electronic industry, at the time of manufacture, conveyance, use of an electronic device and an electronic component, etc. WHEREIN: The surface protection is aimed at by sticking an adhesive protective film on the surface of an electronic device and an electronic component.

For the same reason, adhesion of an adhesive protective film is performed also on the surface of optical members, such as a polarizing plate used for a liquid crystal display, an organic electroluminescent display, a touch panel, retardation plate, an optical compensation film, and a transparent conductive film.

The adhesive used for the said protective film is calculated|required both the non-adhesiveness which can peel with a small force, and the re-peelability which can peel again cleanly even if it sticks once. Especially, the protective film for optical members has the tendency for an area to become large, and the additional non-tackiness and re-peelability are calculated|required.

Since the purpose of surface protection is to protect the surface, the protective film needs to be able to be peeled off easily from the adherend after the purpose is achieved and the base material and the pressure-sensitive adhesive are integrated into one, but the pressure-sensitive adhesive increases with the passage of time. It is known generally, and an adhesive may remain at the time of peeling, or the defect which a base film cut|disconnects may generate|occur|produce.

As a method of preventing the above-described defect, for example, a method of mixing a release agent such as a wax or a long-chain alkyl group-containing compound with a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is provided (see, for example, Patent Document 1).

As a surface protection film with little contamination originating in an adhesive component, the surface protection film which used acrylic resin for an adhesive layer is known. However, when an acrylic resin is used for the pressure-sensitive adhesive layer, there is a problem that glue residue is easily generated at the time of peeling, and as a surface protection film for protecting the surface of a member that does not particularly want foreign substances to be mixed, such as an optical member or an electronic member. There is a problem with using it.

As a means to solve the above problem, for example, a method of using a urethane-based resin formed of a specific polyfunctional polyol as an adhesive is provided (see, for example, Patent Document 2), but optimization of residual glue and adhesive strength There was a lack of compatibility with

Although the function as a surface protection film has been improved in various ways, with respect to an optical member used for a display that is increasing in size in recent years, while the method of peeling the surface protection film by a machine has become mainstream, peeling speed is different depending on the process In many cases, adjustment of peeling force (adhesive force) is easy, and there is little adhesive composition after peeling and the laminated|multilayer film which has this as an adhesive layer are calculated|required.

Japanese Patent Laid-Open No. 2017-019158 Japanese Patent Laid-Open No. 2014-111701

The problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition that is easy to adjust the adhesive strength of the pressure-sensitive adhesive and has less adhesive residue after peeling, and a laminated film that can be used suitably as a surface protection film by using it for the pressure-sensitive adhesive layer. .

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors used the polyoxyethylene compound which has one or more and a polyoxyethylene chain selected from a C1-C6 fluorinated alkyl group and a silicone chain together with an adhesive, It found out that the subject could be solved, and came to complete this invention.

The present invention relates to a polyoxyethylene compound (A) having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2), and a pressure-sensitive adhesive (B). An adhesive composition and the laminated|multilayer film which used this for an adhesive layer are provided.

ADVANTAGE OF THE INVENTION According to this invention, adjustment of the adhesive force is easy with respect to various adhesives, and there are few changes in adhesive force even after storage, peelability is favorable, and the laminated|multilayer film with few adhesive residues after peeling can be provided. Moreover, the laminated|multilayer film of this invention can be used conveniently as surface protection films, such as various optical members and an electronic member.

<Adhesive composition>

The pressure-sensitive adhesive composition of the present invention comprises a polyoxyethylene compound (A) having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2), and an adhesive (B) ) contains

It is well known that the adhesive force can be lowered by using together the compound which has a fluorine atom or a silicon atom, the compound which has a long-chain alkyl group, etc. with respect to an adhesive. However, in such a generally known compound, particularly a compound known as a mold release agent or a surfactant, the adhesive strength can be easily adjusted even with a small amount added, the adhesion strength is small even after long-term storage, the peelability is excellent, and the adhesive strength is excellent. It has not been confirmed so far that the detailed structure of the compound excellent also in anti-residue property has been studied in depth.

In the present invention, as a result of studying such a subject, a polyoxyethylene compound (A) having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2) was found to be a valid solution.

Hereinafter, each component contained in the adhesive composition of this invention is demonstrated.

[Polyoxyethylene compound (A)]

The polyoxyethylene compound (A) is a compound having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2). There are three types of polyoxyethylene compounds (A), specifically, a compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a2); a compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyethylene chain (a2), and a silicone chain (a3); and a compound having a polyoxyethylene chain (a2) and a silicone chain (a3).

A polyoxyethylene compound (A) is a C1-C6 fluorinated alkyl group (a1) from a viewpoint of being able to reduce the contamination after peeling to a to-be-adhered body when it is set as a surface protection film using the adhesive composition of this invention It is preferable to include Accordingly, the polyoxyethylene compound (A) is a compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a2), or a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyethylene chain ( A compound having a2) and a silicone chain (a3) is preferable, and a compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a2) is most preferable.

The fluorinated alkyl group (a1) having 1 to 6 carbon atoms in the polyoxyethylene compound (A) indicates that the number of carbon atoms directly bonded to the fluorine atom is in the range of 1 to 6, and a part of the atoms bonded to the carbon atoms is hydrogen. It may be an atom. The alkyl group of the fluorinated alkyl group may be either branched or linear.

Moreover, the structure formed by connecting several said fluorinated alkyl group (a1) by an ether bond, a thioether bond, or an alkylene chain which does not have a fluorine atom may be sufficient.

In the fluorinated alkyl group (a1) having 1 to 6 carbon atoms, the adhesive strength of the pressure-sensitive adhesive (B) can be easily adjusted, and the number of carbon atoms directly bonded to the fluorine atom from the viewpoint of effectively suppressing the adhesive residue during peeling, etc. It is preferable that it is the range of 3-6, and it is more preferable that it is 4 or 6. From the same viewpoint, the fluorinated alkyl group (a1) having 1 to 6 carbon atoms is more preferably a perfluoroalkyl group containing no hydrogen atom.

A polyoxyethylene compound (A) is preferable from a viewpoint that adjustment of adhesive force is easier if two or more fluorinated alkyl groups (a1) are contained in 1 molecule.

The polyoxyethylene chain (a2) in the polyoxyethylene compound (A) means a structure in which two or more oxyethylene groups are connected, and the polyoxyethylene chain (a2) may be linear or branched.

The polyoxyethylene compound (A) may have a polyoxyethylene chain (a2), and may further have a C1-C6 polyoxyalkylene chain, such as polyoxypropylene and polyoxybutylene from which the polyoxyethylene chain was removed. . When a polyoxyethylene compound (A) has a C1-C6 polyoxyalkylene chain from which the polyoxyethylene chain|strand was removed, it is preferable that a C1-C6 polyoxyalkylene chain is a polyoxypropylene chain.

It is preferable that it is the range of 2-50 as an average value of the repeating number of a polyoxyethylene chain (a2).

Further, when the polyoxyethylene compound (A) has a polyoxyethylene chain and a polyoxyalkylene chain having 1 to 6 carbon atoms, and the ethylene unit and the alkylene unit are bonded by an ether bond, the format may be a block or random. and the number of repetitions is preferably within the above range in the sum of each unit.

It does not specifically limit as a silicone chain (a3) in a polyoxyethylene compound (A), For example, the silicone chain represented by a following formula is mentioned.

(Wherein, R, R', R'' and R''' each independently represent an alkyl group having 1 to 18 carbon atoms or a phenyl group. A plurality of R, R', R'' and R''' may be the same as or different from each other.

n is the number of repeating units, and each independently represents an integer from 1 to 200)

As a weight average molecular weight of a silicone chain (a3), it is preferable from a viewpoint of peelability that it is the range of 200-50,000, and it is more preferable that it is the range of 200-30,000.

Although the content of fluorine atoms in the polyoxyethylene compound (A) is not particularly limited, it is in the range of 1 to 50 mass% from the viewpoint of compatibility with the adhesive (B) described later, ease of adjustment of adhesive force, and ease of manufacture. It is preferable, and it is more preferable that it is the range of 1-30 mass %.

In addition, although the said fluorine atom content rate is computable from the input ratio of the raw material of a polyoxyethylene compound (A), it can also measure actually by combustion ion chromatography of a polyoxyethylene compound (A). In this invention, it is preferable that it is the said range in the latter actual value.

The weight average molecular weight of the polyoxyethylene compound (A) is not particularly limited, but is in the range of 3,000 to 300,000 from the viewpoint of compatibility with the adhesive (B) described later, ease of adjustment of adhesive force, and reduction of adhesive residue, etc. It is preferable, it is more preferable that it is the range of 3,000-200,000, It is most preferable from a viewpoint of the uniformity of peeling force when it is the range of 4,000-100,000 used as surface protection films, such as an optical member of a large area.

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

(GPC measurement conditions)

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mmID × 4 cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mmID × 30 cm) manufactured by Shiki Corporation + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation (7.8 mm ID × 30 cm) + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation TSK-GEL GMHHR-N” (7.8㎜ID×30㎝)

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℃

Developing solvent tetrahydrofuran (THF)

Flow rate 1.0ml/min

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

Standard sample: According to the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30", the following monodisperse polystyrene with known molecular weight was used.

(monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

"F-40" made by Tosoh Corporation

"F-80" made by Tosoh Corporation

"F-128" made by Tosoh Corporation

"F-288" made by Tosoh Corporation

"F-550" made by Tosoh Corporation

When a fluorinated compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a2) is used as the polyoxyethylene compound (A), compatibility with the pressure-sensitive adhesive is particularly good, and the adhesive strength of the pressure-sensitive adhesive is adjusted From this easy viewpoint, the polyoxyethylene compound (A) is preferably a copolymer comprising a fluorinated alkyl group-containing ethylenically unsaturated monomer (x1) and a polyoxyethylene chain-containing ethylenically unsaturated monomer (x2) as essential raw materials. .

When a fluorinated compound having a fluorinated alkyl group (a1) having 1 to 6 carbon atoms, a polyoxyethylene chain (a2), and a silicone chain (a3) is used as the polyoxyethylene compound (A), compatibility with the pressure-sensitive adhesive is particularly good. And from the viewpoint of easy adjustment of the adhesive strength of the pressure-sensitive adhesive, the polyoxyethylene compound (A) contains a fluorinated alkyl group-containing ethylenically unsaturated monomer (x1), a polyoxyethylene chain-containing ethylenically unsaturated monomer (x2), and a silicone chain It is preferable that it is a copolymer which uses an ethylenically unsaturated monomer (x3) as an essential raw material.

When a polyoxyethylene compound having a polyoxyethylene chain (a2) and a silicone chain (a3) is used as the polyoxyethylene compound (A), the compatibility with the pressure-sensitive adhesive is particularly good, and the pressure-sensitive adhesive strength adjustment is easy. It is preferable that it is a copolymer which uses a polyoxyethylene chain containing ethylenically unsaturated monomer (x2) and a silicone chain containing ethylenically unsaturated monomer (x3) as essential raw materials.

Each of these monomers may consist of a single thing, may be copolymerized by using multiple types together, and a block may be sufficient as a copolymerization format, and random may be sufficient as it.

As an ethylenically unsaturated group which the said monomer has, the carbon-carbon unsaturated double bond which has radical polymerization property is preferable, and a (meth)acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. Among these, a (meth)acryloyl group and a vinyl group are preferable, and a (meth)acryloyl group is especially preferable since the availability of a raw material, compatibility with respect to the adhesive (B) mentioned later, or polymerization reactivity is favorable.

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

[wherein, A' is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a substituent It is also an aralkyl group having 6 to 24 carbon atoms, and is a divalent linking group formed alone or in combination of two or more;

A is an oxygen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or may have a substituent is an aralkyl group having 6 to 24 carbon atoms, and is a divalent linking group formed alone or in a plurality of combinations thereof;

R ⁶ is a hydrogen atom or a methyl group.

Rf is -C _n F _2n+1 (provided that n is an integer of 1 to 6)]

Examples of the fluorinated alkyl group-containing ethylenically unsaturated monomer (x1) include fluorinated urethane (meth)acrylates represented by the following formula (x1-3).

[Wherein, each Rf is independently -(C _x F _2x -O) _p -(C _y F _2y -O) _q -C _n F _2n+1 A group represented by (p and q are each independently an integer of 0 or more, and 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 Rf is -(C _x F _2x -O ) _p -(C _y F _2y -O) _q -C _n F _2n+1 .

R ⁵ is each independently an alkylene chain having 1 to 3 carbon atoms or a direct bond.

Y ¹ is each 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 fluorinated urethane (meth)acrylate represented by the formula (x1-3) has good compatibility with the adhesive (B) to be described later, particularly the acrylic adhesive (b1) or the urethane adhesive (b2), and may form an adhesive layer It is preferable from a viewpoint from which transparency at the time of being can also be maintained and adjustment of adhesive force becomes easy.

The monomer represented by the above formula (x1-3) is obtained by, 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.

(In the formula, Rf, R ⁵ , Y ¹ are the same as in the above formula (x1-3))

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-, 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.

As a specific example of the fluorine compound which has the said hydroxyl group, the compound represented by a following formula is mentioned.

Although it does not specifically limit as a manufacturing method of the fluorine compound which has a hydroxyl group represented by the said formula, For example, Unexamined-Japanese-Patent No. 1-193236, Unexamined-Japanese-Patent No. 9-67334, Unexamined-Japanese-Patent No. 2002-3428, etc. It can be prepared by the method described.

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

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

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

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

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

When making the fluorine compound which has the said hydroxyl group and the (meth)acrylate which has the said isocyanate group react, with respect to 1 mol of the fluorine compound which has the said hydroxyl group, the (meth)acrylate which has the said isocyanate group is injected|thrown-in so that it may become 0.80-1.20 mol. It is preferable to add it so that it may become 0.98-1.00 mol more preferably.

In the reaction (urethanization reaction) of the fluorine compound having a hydroxyl group and the (meth)acrylate having an isocyanate group, the terminal of (meth)acrylate having a secondary hydroxyl group and the isocyanate group of the fluorine compound having a hydroxyl group In order to accelerate reaction of an isocyanate group, For example, tertiary amines, such as triethylamine and benzyl dimethylamine; Dilaurates, such as dibutyltin dilaurate and dioctyltin dilaurate, can be used as a catalyst.

As for the addition amount of a catalyst, 0.001-5.0 mass % is preferable with respect to the whole reaction mixture, More preferably, it is 0.01-1.1 mass %. The reaction time is preferably 1 to 10 hours. Moreover, as for reaction temperature, 30-120 degreeC is preferable, More preferably, it is 30-100 degreeC.

In the above reaction, solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene that are inactive to an isocyanate group can be used as the reaction solvent.

Specific examples of the monomer represented by the formula (x1-3) obtained by the above reaction include the monomer represented by the following formula.

As said polyoxyethylene chain containing ethylenically unsaturated monomer (x2), the compound represented by a following formula (x2-1) is mentioned.

[Wherein, R' is a polyoxyalkylene group whose terminal of the polyoxyalkylene chain including the polyoxyethylene chain is a hydrogen atom or an alkyl group.

R ¹ is a (meth)acryloyl group. Moreover, in this invention, a (meth)acryloyl group is used as a generic name of one of an acryloyl group and a methacryloyl group, or its mixture.

R ² is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms.

r is an integer from 1 to 3, s is an integer from 0 to 2, and r+s=3]

As said polyoxyethylene chain containing ethylenically unsaturated monomer (x2), the compound represented by a following formula (x2-2) is mentioned.

R ¹ O-R''-OR ¹ (x2-2)

(In the formula, both R ¹ are the same or different (meth)acryloyl groups. In addition, the (meth)acryloyl group means both an acryloyl group and a methacryloyl group.

R'' is a polyoxyalkylene chain including a polyoxyethylene chain)

As said polyoxyethylene chain containing ethylenically unsaturated monomer (x2), the compound represented by a following formula (x2-3), and a compound represented by a following formula (x2-4) are mentioned.

(In the formula, R ³ is a hydrogen atom or a methyl group. A plurality of R ³ may be the same as or different from each other.

R ⁴ and R ⁵ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms.

R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

n is an integer greater than or equal to 2;

m is an integer greater than or equal to 0.

k is an integer greater than or equal to 0)

In the formulas (x2-3) and (x2-4), the ^{alkylene group having 1 to 6 carbon atoms for R 4} and R ⁵ is preferably an alkylene group having 2 or 3 carbon atoms.

As the compound (x2-1), (x2-2), (x2-3), and (x2-4), for example, ethylene oxide (hereinafter, abbreviated as EO) modified 1,6-hexanedioldi(meta) ) acrylates (for example, RCC13-361 manufactured by San Nopco Co., Ltd., etc.), diethylene glycol di(meth)acrylate (for example, Brenma ADE-100 manufactured by Nichiyo Co., Ltd.), EO Modified neopentyl glycol di(meth) acrylate (for example, Photomar 4160 manufactured by Sannov Co., Ltd., etc.), polyethylene glycol di(meth) acrylate (eg, Brenma manufactured by Nichiyu Corporation) ADE-200, etc.), polyethylene glycol-propylene glycol-polyethylene glycol di (meth) acrylate (for example, Nichi Oil Co., Ltd. Brenma ADC series, etc.), polyethylene glycol di (meth) acrylate (for example, , light acrylate 3EG-A manufactured by Kyoei Corporation), EO modified glycerol acrylate (for example, New Frontier GE3A manufactured by Daiichi Kogyo Chemical Co., Ltd.), EO modified phosphate triacrylic rate (eg, Viscot 3A manufactured by Osaka Yuki Chemical Co., Ltd.), (EO) modified trimethylolpropane triacrylate (eg, New Frontier TMP-3P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) etc.), methoxy polyethylene glycol methacrylate (For example, the Shin-Nakamura Chemical Co. make, M230G) etc. are mentioned.

These compounds may be used individually, or may mix and use the some compound from which (meth)acryloyl group number differs, and may mix and use the some compound from which a structure also differs.

Moreover, as said compound which can generally be obtained commercially, with respect to the target compound used as a main component, it is a mixture of compounds from which the number of (meth)acryloyl groups differ in many cases. In use, although the compound of the number of (meth)acryloyl groups made into the objective may be taken out and used by purification methods, such as various chromatography and extraction, you may use with a mixture.

As the polyoxyethylene chain-containing ethylenically unsaturated monomer (x2), a polyoxyethylene chain-containing (meth)acrylate represented by the following general formula may be used.

[wherein, A is an oxygen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a substituent is an aralkyl group having 6 to 24 carbon atoms which may have

R ⁶ is a hydrogen atom or a methyl group.

R' is a polyoxyalkylene group whose terminal of the polyoxyalkylene chain including the polyoxyethylene chain is a hydrogen atom or an alkyl group]

As said polyoxyethylene chain containing (meth)acrylate, for example, a commercially available hydroxypoly(oxyethylene) material, for example, a brand name "Pluronic" [Pluronic (made by ADEKA), Adeka Poly), Ether (manufactured by ADEKA, Ltd.), "Carbowax" [Carbowax (Glico Products)], "Triton" [Toriton (manufactured by Rohm and Haas), PEG (Daichi Kogyo Seiyaku) It can be produced by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride, acrylic acid anhydride or methacrylic acid anhydride, etc. by various methods by various methods. The polyoxyalkylene diacrylate etc. containing the polyoxyethylene chain|strand obtained can also be used.

As a commercially available polyoxyethylene chain-containing (meth)acrylate, for example, as a hydroxyl-terminated polyalkylene glycol mono(meth)acrylate manufactured by Nichiyo Co., Ltd., Brenma PE-90, Brenma PE-200 , Brenma PE-350, Brenma AE-90, Brenma AE-200, Brenma AE-400, Brenma 50PEP-300, Brenma 70PEP-350B, Brenma AEP series, Brenma 55PET-400, Brenma 30PET-800, Brenma 55PET-800, Brenma AET series, etc. are mentioned.

Similarly, as alkyl-terminated polyalkylene glycol mono(meth)acrylates manufactured by Nichi Oil Corporation, Brenma PME-100, Brenma PME-200, Brenma PME-400, Brenma PME-1000, and Brenma PME-4000 , Brenma AME-400, Brenma 50POEP-800B, Brenma 50AOEP-800B, Brenma PLE-200, Brenma ALE-200, Brenma ALE-800, Brenma PSE-400, Brenma PSE-1300, Brenma PSE-1300, Brenma Ma ASEP series, Brenma PKEP series, Brenma AKEP series, Brenma ANE-300, Brenma ANE-1300, Brenma PNEP series, Brenma PNPE series, Brenma 43ANEP-500, Brenma 70ANEP-550, etc., and also Light Ester MC, Light Ester 130MA, Light Ester 041MA, Light Acrylate BO-A, Light Acrylate EC-A, Light Acrylate MTG-A, Light Acrylate 130A, Light Acrylic, manufactured by Kyoeisha Chemical Co., Ltd. Rate DPM-A, light acrylate P-200A, light acrylate NP-4EA, light acrylate NP-8EA, etc. are mentioned.

As these polyoxyethylene chain containing (meth)acrylates, you may use only 1 type, and may use 2 or more types together.

As the polyoxyethylene chain-containing ethylenically unsaturated monomer (x2), a compound having a vinyl ether structure represented by the following general formula may be used.

[wherein, A' is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a substituent It is also an aralkyl group having 6 to 24 carbon atoms, and is a divalent linking group formed alone or in combination of two or more.

R ⁶ is a hydrogen atom or a methyl group.

R' is a polyoxyalkylene group whose terminal of the polyoxyalkylene chain including the polyoxyethylene chain is a hydrogen atom or an alkyl group]

As a silicone chain containing ethylenically unsaturated monomer (x3), the monomer containing a vinyl ether structure may be sufficient, and the monomer containing a (meth)acrylate structure may be sufficient.

The silicone chain-containing ethylenically unsaturated monomer (x3) is preferably the same system as the copolymerized fluorinated alkyl group-containing ethylenically unsaturated monomer (x1) and the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x2).

From the viewpoint of the availability of raw materials, it is preferable to use a monomer having a (meth)acrylate structure as the silicone chain-containing ethylenically unsaturated monomer (x3).

As a specific example of a silicone chain containing ethylenically unsaturated monomer (x3), the monomer represented by the following general formula is mentioned.

(In formula, R<^1> represents a hydrogen atom or a methyl group.

R ³ to ^{R 6} and R ¹⁰ to ^{R 17} each independently represent an alkyl group having 1 to 18 carbon atoms or a phenyl group.

R ² , R ⁷ to ^{R 9} and R ¹⁸ to ^{R 20} each independently represent an alkyl group having 1 to 8 carbon atoms or a phenyl group.

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 are each independently an integer of 1 to 250 represents)

As the silicone chain-containing ethylenically unsaturated monomer (x3), commercially available products can be used. Examples of the commercially available products include Cylaplane FM-0711, Cylaplane FM-0721K, and Cylaplane FM-0725, which are polysiloxane monomers containing an ethylenically unsaturated group. , Sila Plane TM-0701T (all are manufactured by JNC Corporation).

The polyoxyethylene compound (A) contains at least one selected from a polyoxyethylene chain-containing ethylenically unsaturated monomer (x2), a fluorinated alkyl group-containing ethylenically unsaturated monomer (x1), and a silicone chain-containing ethylenically unsaturated monomer (x3) When preparing by copolymerization, you may use other monomers as a raw material of a copolymer in the range which does not impair the effect of this invention other than these monomers.

Other monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

As said other monomer, for example, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, itaconic acid dialkyls and dialkyl esters or monoalkyl esters of fumaric acid.

More specifically, the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, Furfuryl acrylate, tetrahydrofurfuryl acrylate, etc. are mentioned.

Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, and benzyl methacrylate. , methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like.

Examples of the acrylamides include acrylamide, N-alkylacrylamide (the alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), and N,N-dialkylacrylamide (a carbon atom as the alkyl group). 1 to 3 atoms), N-hydroxyethyl-N-methylacrylamide, and N-2-acetamideethyl-N-acetylacrylamide.

Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (the alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), N,N-dialkyl methacrylamide ( Examples of the alkyl group include those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, and N-2-acetamideethyl-N-acetylmethacrylamide.

Examples of the allyl compound include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) , and allyloxyethanol.

Examples of the vinyl ethers include alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1- Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl Vinyl ether, tetrahydrofurfuryl vinyl ether, etc. are mentioned.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate. tate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like.

Examples of the dialkyl itaconate include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

As dialkyl esters or monoalkyl esters of the said fumaric acid, dibutyl fumarate etc. are mentioned.

In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleylonitrile, styrene, etc. are mentioned.

Although it does not specifically limit as a usage ratio of the monomers to be used when synthesizing the copolymer of a polyoxyethylene compound (A), A fluorinated alkyl group containing ethylenically unsaturated monomer (x1) in a total of 100 mass parts of monomers is It is preferable that 5-90 mass parts is contained, It is more preferable that 5-80 mass parts is contained, It is more preferable that 5-70 mass parts is contained.

It is preferable that 5-95 mass parts of polyoxyethylene chain containing ethylenically unsaturated monomers (x2) are contained, and it is more preferable that 5-80 mass parts is contained.

It is preferable that 5-95 mass parts of silicone chain containing ethylenically unsaturated monomers (x3) are contained, and it is more preferable that 5-80 mass parts is contained.

The copolymer can be prepared by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc., in particular, the radical polymerization method is simple, industrially preferred. For example, it can manufacture by adding a general-purpose radical polymerization initiator in an organic solvent, and polymerizing a monomer mixture. Depending on the polymerizability of the monomer to be used, a dropwise polymerization method in which monomers and an initiator are added dropwise to a reaction vessel while polymerization is also effective, in order to obtain a copolymer having a uniform composition.

As the polymerization initiator, various kinds can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane, Mn ( metal chelate compounds, such as acac) ₃ , and a transition metal catalyst which raise|generates living radical polymerization, etc. are mentioned.

If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, or octylthioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane as a chain transfer agent You may use as additives, such as

Although polymerization can be performed either in the presence or absence of a solvent, it is preferable to carry out in the presence of a solvent from the point of workability|operativity.

Examples of the solvent used for polymerization include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone. Esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate, 2-oxymethyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-oxypropionate butyl, 2-methyl Monocarboxylic acid esters such as methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone; Ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol and ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol and its esters such as propylene glycol monobutyl ether acetate, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, benzene, toluene, and xylene Aromatics, such as perfluorooctane, and fluorinated inert liquids, such as perfluoro tri-n-butylamine, etc. are mentioned.

These solvents may be used individually by 1 type, and may be used together 2 or more types.

The solvent used for superposition|polymerization of a polyoxyethylene compound (A) is good also as a solvent of the adhesive composition of this invention.

[Adhesive (B)]

The pressure-sensitive adhesive (B) can be used without particular limitation as long as it has adhesiveness, and examples thereof include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive. It is preferable to use an acrylic adhesive (b1) and/or a urethane type adhesive (b2) among these adhesives.

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 said (meth)acrylic-type monomer can use 1 type, or 2 or more types as a main component. By using the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is easy to control low adhesion to an adherend (subject to be protected), and a surface protection film excellent in light peelability and re-peelability this is obtained

In addition, the "main component" in the present invention means the most components in the total amount of components constituting, the "main component" preferably exceeds 40 mass%, more preferably exceeds 50 mass%, , more preferably exceeding 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, s-butyl (meth)acryl Rate, 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-tri Decyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc. are mentioned.

Among the (meth)acrylic monomers, 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 A (meth)acrylic monomer having an alkyl group having 6 to 14 carbon atoms, such as (meth)acrylate, is preferable from the viewpoint of easily controlling the adhesive force to an adherend to be low and excellent in re-peelability.

It is preferable to contain 50 mass % or more of the (meth)acrylic-type monomer which has a C1-C14 alkyl group with respect to 100 mass % of monomer components which comprise the said (meth)acrylic-type polymer, More preferably, 60 mass % As mentioned above, More preferably, it is 70-99 mass %, Most preferably, it is 80-97 mass %.

It is preferable that the said (meth)acrylic-type polymer which comprises an acrylic adhesive (b1) contains the (meth)acrylic-type monomer which has a hydroxyl group as a raw material monomer. As a (meth)acrylic-type monomer which has the said hydroxyl group, 1 type(s) or 2 or more types can be used.

By using the (meth)acrylic monomer having a hydroxyl group, it is easy to control the crosslinking of the pressure-sensitive adhesive composition, and further, it is easy to control the balance between the improvement of wettability by flow and the reduction of the adhesive force in peeling, and It is preferable also from a viewpoint of antistatic.

As a (meth)acrylic-type monomer which has the said hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclo Hexyl) methyl (meth) acrylate, N-methylol (meth) acrylamide, etc. are mentioned. In particular, by using a (meth)acrylic monomer having a hydroxyl group having 4 or more carbon atoms in the alkyl group, light peeling at the time of high-speed peeling becomes easy, which is preferable.

It is preferable to contain 15 mass parts or less of the (meth)acrylic-type monomer which has the said hydroxyl group with respect to 100 mass parts of the (meth)acrylic-type monomer which has the said C1-C14 alkyl group, More preferably, it is 1-13 mass parts. , More preferably, it is 2-10 mass parts, Most preferably, it is 3-8 mass parts. When it exists in the said range, since it becomes easy to control the balance of the wettability of an adhesive composition, and the cohesion force of the adhesive layer obtained, it is preferable.

As another polymerizable monomer component, for the reason that it is easy to balance the adhesion performance, the Tg is set to 0 ° C. or less (usually -100 ° C. or higher), and to adjust the glass transition temperature and peelability of the (meth)acrylic polymer. A polymerizable monomer etc. can be used.

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

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

The (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 3 parts by mass with respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Less than a part is more preferable, less than 0.2 mass part is still more preferable, Most preferably, it is 0.01 mass part or more and less than 0.1 mass part. If it is in the said range, a rise in adhesive force over time can be prevented (adhesive force increase prevention property), and it is preferable.

It is also possible to use the (meth)acrylic monomer having a hydroxy group and the (meth)acrylic monomer having a carboxy group in combination for the purpose of making the peeling electrification property and the adhesive strength increase prevention property compatible.

In addition, 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 used in the (meth)acrylic polymer The polymerizable monomer is not particularly limited and can be used. For example, components for improving cohesive strength and heat resistance such as cyano group-containing monomers, vinyl ester monomers and aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, N-acryloylmorpholine , a component having a functional group acting as an adhesive strength improvement or crosslinking origin, such as a vinyl ether monomer, can be appropriately used. Especially, it is preferable to use nitrogen-containing monomers, such as a cyano group containing monomer, an amide group containing monomer, an imide group containing monomer, an amino group containing monomer, and N-acryloylmorpholine. The use of the nitrogen-containing monomer is useful because it is possible to secure a suitable adhesive force that does not cause floating, peeling, etc., and to obtain a surface protection film excellent in shearing force. These polymerizable monomers may be used independently and may mix and use 2 or more types.

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

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

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

Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N -Diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetoneacrylamide amide etc. are mentioned.

As said imide group containing monomer, cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaconimide etc. are mentioned, for example.

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

As said epoxy group containing monomer, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, allyl glycidyl ether, etc. are mentioned, for example.

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

Polymerizable monomers 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 carboxy group include ( It is preferable that it is 0-40 mass parts with respect to 100 mass parts of meth)acrylic-type monomers, and it is preferable that it is 0-30 mass parts from a viewpoint which can control favorable re-peelability suitably.

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

As an average of the oxyalkylene units of the said polyoxyalkylene group containing reactive monomer, it is preferable that it is 1-40, It is more preferable that it is 3-40, It is more preferable that it is 4-35, It is especially preferable that it is 5-30. Do.

When the said average added mole number is 1 or more, there exists a tendency for the contamination reduction effect of a to-be-adhered body (to-be-protected object) to be acquired efficiently. Moreover, when the said average added mole number is larger than 40, there exists a tendency for the viscosity of an adhesive composition to rise and coating becomes difficult. Moreover, the terminal of an oxyalkylene chain|strand may be substituted with a hydroxyl group as it is, another functional group, etc.

The polyoxyalkylene chain-containing reactive monomer may be used alone or in combination of two or more, but the content as a whole is preferably 20% by mass or less based on the total amount of the monomer component of the (meth)acrylic polymer, It is more preferable that it is 10 mass % or less, It is still more preferable that it is 5 mass % or less, It is still more preferable that it is 4 mass % or less, It is especially preferable that it is 3 mass % or less, It is still more preferable that it is 1 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, for example, an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, etc. can be heard The hydrocarbon group of the oxyalkylene chain may be linear or may be branched.

It is more preferable that the said polyoxyalkylene chain containing reactive monomer is a reactive monomer which has an ethylene oxide group. By using a (meth)acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, compatibility between the base polymer and the polyoxyethylene compound (A) is improved, and bleeding to the adherend is suitably suppressed, A low-staining adhesive composition is easily obtained.

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

As a specific example of the said (meth)acrylic-acid alkylene oxide adduct, for example, polyethyleneglycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethyleneglycol- polypropylene glycol (meth)acrylate, polyethyleneglycol- poly Butylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) Acrylate, octoxy polyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, stearic polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) ) acrylate, octoxy polyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

Moreover, as a specific example of the said reactive surfactant, the anionic reactive surfactant, nonionic reactive surfactant, cationic reactive surfactant etc. which have a (meth)acryloyl group or an allyl group are mentioned, for example.

As for the (meth)acrylic polymer which comprises an acrylic adhesive (b1), as a weight average molecular weight (Mw), 100,000-5 million are preferable, More preferably, 200,000-2 million, More preferably, 300,000-800,000 All. When a weight average molecular weight is larger than 100,000, there exists a tendency for the cohesion force of an adhesive layer to become appropriate, and to suppress a glue residue. On the other hand, when the weight average molecular weight is 5 million or less, the fluidity of the polymer is appropriate, the wettability to the adherend is sufficient, and the occurrence of puffiness between the adherend and the pressure-sensitive adhesive layer of the surface protection film can be suppressed. .

In addition, the said weight average molecular weight says what was obtained by measuring by GPC (gel permeation chromatography).

As for the glass transition temperature (Tg) of the (meth)acrylic-type polymer which comprises an acrylic adhesive (b1), 0 degreeC or less is preferable, More preferably, it is -10 degreeC or less (usually -100 degreeC or more). When the glass transition temperature is higher than 0°C, the polymer is difficult to flow and the wetting tends to be insufficient. In particular, the adhesive layer excellent in wettability and light-peelability becomes easy to be obtained by making a glass transition temperature into -61 degreeC or less.

Moreover, the glass transition temperature of a (meth)acrylic-type polymer can be adjusted within the said range by changing the monomer component and composition ratio to be used suitably.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and polymerization can be performed by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. From the viewpoint of properties such as low contamination to protective body), solution polymerization is a more preferable aspect. In addition, any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, etc. may be sufficient as the polymer obtained.

When using a urethane-type adhesive (b2) as an adhesive (B), what is necessary is just to employ|adopt any suitable urethane-type adhesive. As a urethane-type adhesive (b2), Preferably, what consists of a urethane resin (urethane-type polymer) obtained by making a polyol and a polyisocyanate compound react is mentioned.

Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.

As said polyisocyanate compound, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate etc. are mentioned, for example.

When a silicone pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer, any appropriate silicone pressure-sensitive adhesive may be employed. As such a silicone adhesive, Preferably, the thing obtained by blending or making a silicone resin (silicone type polymer, a silicone component) agglomerate is employable.

Moreover, as said silicone adhesive, an addition reaction hardening type silicone adhesive and a peroxide hardening type silicone adhesive are mentioned. Among these silicone adhesives, since a peroxide (benzoyl peroxide etc.) is not used and a decomposition product does not generate|occur|produce, an addition reaction hardening type silicone adhesive is preferable.

As a curing reaction of the said addition reaction curable silicone pressure sensitive adhesive, for example, when obtaining a polyalkyl silicone pressure sensitive adhesive, the method of hardening a polyalkyl hydrogen siloxane composition with a platinum catalyst is generally mentioned.

The adhesive composition of this invention WHEREIN: What is necessary is just to set the compounding ratio of a polyoxyethylene compound (A) and an adhesive (B) suitably according to desired adhesive force. When using the adhesive composition of this invention for the adhesive layer of a surface protection film, it is preferable that the content rate of a polyoxyethylene compound (A) is 0.01-20 mass % in solid content of an adhesive composition, It is more preferable that it is 0.1-5.0 mass % desirable.

In addition, in this invention, "solid content" means the component which removed the solvent from the adhesive composition.

[Other Ingredients]

The adhesive composition of this invention should just contain a polyoxyethylene compound (A) and an adhesive (B), and it is the range which does not impair the effect of this invention. WHEREIN: Other components, such as various additives, can be included arbitrarily.

It is preferable that the adhesive composition of this invention contains a crosslinking 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), by further including a crosslinking agent, the structural units of the (meth)acrylic polymer, the proportion, the selection of the crosslinking agent and By appropriately adjusting the addition ratio or the like and crosslinking, an adhesive layer having more excellent heat resistance can be easily obtained.

As said crosslinking agent, an isocyanate compound, an epoxy compound, a melamine-type resin, an aziridine derivative, a metal chelate compound, etc. may be used, and use of an isocyanate compound especially becomes a preferable aspect. In addition, these compounds may be used independently and may mix and use 2 or more types.

As said isocyanate compound, For example, aliphatic polyisocyanates, such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone di Alicyclic isocyanates, such as isocyanate (IPDI), aromatic isocyanates, such as 2,4-tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, and xylylene diisocyanate (XDI), These isocyanate compounds are allophanate and polyisocyanate modified products modified by a bond, a biuret bond, an isocyanurate bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretonimine bond, an oxadiazinetrione bond, and the like.

As a commercial item of the said isocyanate compound, For example, brand name Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, Takedayakuhin Kogyo Co., Ltd. make), Sumijul T80, Sumijul L, Death. Module N3400 (above, manufactured by Sumika Bayer Urethane), Myrionate MR, Myrionate MT, Coronate L, Coronate HL, Coronate HX (above, manufactured by Nippon Polyurethane Kogyo), etc. are mentioned.

These isocyanate compounds may be used individually, may be used in mixture of 2 or more types, and it is also possible to use them in combination with a bifunctional isocyanate compound and a trifunctional or more than trifunctional isocyanate compound. By mixing and using 2 or more types of crosslinking agents, it becomes possible to make adhesiveness and repulsion resistance (adhesiveness to a curved surface) compatible, and the laminated|multilayer film excellent in adhesive reliability more can be obtained.

Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-m-xylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemicals) and 1,3-bis(N, N-diglycidylaminomethyl) cyclohexane (trade name: TETRAD-C, Mitsubishi Gas Chemical make) etc. are mentioned.

Hexamethylolmelamine etc. are mentioned as said melamine-type resin.

As said aziridine derivative|guide_body, the brand name HDU, TAZM, TAZO (above, the Sogoyak Kosha make) etc. as a commercial item are mentioned, for example.

As said metal chelate compound, aluminum, iron, tin, titanium, nickel etc. as a metal component, acetylene, methyl acetoacetate, ethyl lactate etc. are mentioned as a chelate component.

The content of the crosslinking agent is, for example, preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass, with respect to 100 parts by mass of the (meth)acrylic polymer used for the acrylic pressure-sensitive adhesive (b1). It is more preferable, containing 0.5-10 mass parts is more preferable, and containing 1.0-6 mass parts is the most preferable. By using a crosslinking agent in this range, the cohesive force of the adhesive layer obtained is appropriate, sufficient heat resistance is easy to be obtained, and an adhesive residue is also suppressed.

A crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types.

The pressure-sensitive adhesive composition may contain a crosslinking catalyst for more effectively advancing any of the crosslinking reactions described above.

Examples of the crosslinking catalyst include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonato)iron, tris(hexane-2,4-dionato)iron, tris(heptane- 2,4-Dionato)iron, tris(heptane-3,5-dionato)iron, tris(5-methylhexane-2,4-dionato)iron, tris(octane-2,4-dionato)iron , tris(6-methylheptane-2,4-dionato)iron, tris(2,6-dimethylheptane-3,5-dionato)iron, tris(nonane-2,4-dionato)iron, tris( Nonane-4,6-dionato)iron, tris(2,2,6,6-tetramethylheptane-3,5-dionato)iron, tris(tridecane-6,8-dionato)iron, tris( 1-phenylbutane-1,3-dionato)iron, tris(hexafluoroacetylacetonato)iron, tris(ethyl acetoacetate)iron, tris(acetoacetate-n-propyl)iron, tris(isopropyl acetoacetate) )Iron, tris(acetoacetate-n-butyl)iron, tris(acetoacetate-sec-butyl)iron, tris(acetoacetate-tert-butyl)iron, tris(propionylmethylacetate)iron, tris(propionylacetic acid) ethyl)iron, tris(propionylacetate-n-propyl)iron, tris(propionylisopropylacetate)iron, tris(propionylacetate-n-butyl)iron, tris(propionylacetate-sec-butyl)iron, Tris(propionylacetate-tert-butyl)iron, tris(benzylacetate)iron, tris(dimethyl malonate)iron, tris(diethylmalonate)iron, trimethoxyiron, triethoxyiron, triisopropoxy An iron-based catalyst such as iron or ferric chloride may be used. The number of these crosslinking catalysts may be one, and they may use 2 or more types together.

Although content in particular of the said crosslinking catalyst is not restrict|limited, For example, it is preferable to set it as about 0.0001-1 mass part with respect to 100 mass parts of said (meth)acrylic-type polymers, and 0.001-0.5 mass part is more preferable. When it exists in the said range, when an adhesive layer is formed, the speed|rate of a crosslinking reaction is quick, the pot life of an adhesive composition also becomes long, and it becomes a preferable aspect.

<Lamination film>

The laminated|multilayer film of this invention has an adhesion layer and a base material layer, The said adhesion layer is a layer formed using the adhesive composition of this invention.

The laminated|multilayer film of this invention can be manufactured by apply|coating and bridge|crosslinking the adhesive composition of this invention on at least one surface of a base material layer. Moreover, the laminated|multilayer film of this invention can be manufactured also by transcribe|transferring the adhesive layer which crosslinked the adhesive composition of this invention previously on the at least one surface of a base material layer.

The method of forming the pressure-sensitive adhesive layer on the substrate layer is not particularly limited. For example, the pressure-sensitive adhesive composition (solution) of the present invention is applied to the substrate, and the polymerization solvent is dried and removed to form the pressure-sensitive adhesive layer on the substrate. do. Then, you may cure for the purpose of adjustment of the component migration of an adhesive layer, adjustment of a crosslinking reaction, etc.

When apply|coating an adhesive composition on a base material and producing a laminated|multilayer film, you may newly add 1 or more types of solvents other than a polymerization solvent in the said adhesive composition so that it may apply|coat uniformly on a base material layer.

As a formation method of the adhesive layer at the time of manufacturing the laminated|multilayer film of this invention, the well-known method used for manufacture of adhesive tapes is used. Specific examples thereof include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and extrusion coating using a die coater.

Usually, the laminated|multilayer film of this invention is 1-200 micrometers in thickness of the said adhesive layer, Preferably it produces so that it may become about 3-100 micrometers. When the thickness of an adhesive layer exists in the said range, since it will be easy to obtain the suitable balance of re-peelability and adhesiveness, it is preferable.

It is preferable that total thickness is 1-400 micrometers, as for the laminated|multilayer film of this invention, it is more preferable that it is 10-200 micrometers, It is most preferable that it is 20-150 micrometers. When the total thickness of laminated|multilayer film is in the said range, it is excellent in adhesive characteristics (re-peelability, adhesiveness, etc.), workability|operativity, and an external appearance characteristic, and it becomes a preferable aspect.

In addition, "total thickness" means the sum total of the thickness including all layers, such as a base material layer of a laminated|multilayer film, an adhesive layer, and an antistatic layer.

Although it does not specifically limit as a base material layer which comprises the laminated|multilayer film of this invention, For example, it is excellent in characteristics, such as transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, flexibility, dimensional stability. It is preferred to use a substrate. In particular, since a base material has flexibility, an adhesive composition can be apply|coated by a roll coater etc., can be wound up in roll shape, and it is useful.

What can be used as said base material, For example, Polyester-type polymers, such as a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), and a polybutylene terephthalate; Cellulose polymers, such as a diacetyl cellulose and a triacetyl cellulose; polycarbonate-based polymers; and a plastic film composed of a resin material containing an acrylic polymer such as polymethyl methacrylate as the main resin component (the main component in the resin component, typically a component accounting for 50 mass% or more).

As another example of the said resin material, Styrene-type polymers, such as polystyrene and an acrylonitrile-styrene copolymer; olefinic polymers such as polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and an ethylene-propylene copolymer; vinyl chloride-based polymers; Examples of the resin material include those using an amide-based polymer such as nylon 6, nylon 6, 6 or aromatic polyamide.

As another example of the resin material, an imide-based polymer, a sulfone-based polymer, a polyethersulfone-based polymer, a polyetheretherketone-based polymer, a polyphenylenesulfide-based polymer, a vinyl alcohol-based polymer, a vinylidene chloride-based polymer, a vinyl buty A ral-type polymer, an arylate-type polymer, a polyoxymethylene-type polymer, an epoxy-type polymer, etc. are mentioned.

It may be a base material composed of a blend of two or more of the above-mentioned polymers.

As said base material, the plastic film which consists of a transparent thermoplastic resin material is employable preferably. It is a more preferable aspect to use a polyester film among the said plastic film. Here, the polyester film is 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 (polyester resin) as the main resin component. say to do with Such a polyester film has characteristics suitable as a base material of a surface protection film, such as being excellent in an optical characteristic and dimensional stability.

Various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents and antiblocking agents may be blended with the resin material constituting the base material as needed. Further, the surface of the film used as the substrate may be subjected to a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoating agent.

The laminated|multilayer film of this invention may have an antistatic layer on a base material layer, and it is also possible to use the plastic film formed by antistatic treatment as said base material. By using such a base material, since charging of the film itself at the time of peeling is suppressed, it is preferable.

In addition, the base material is a plastic film, and by subjecting the plastic film to an antistatic treatment, a laminated film itself is reduced in electrification and excellent in antistatic ability to an adherend is obtained. In addition, there is no restriction|limiting in particular as a method of providing an antistatic function, A conventionally well-known method can be used, For example, the antistatic resin which consists of an antistatic agent and a resin component, a conductive polymer, or electroconductivity containing a conductive substance. A method of applying a resin, a method of vapor-depositing or plating a conductive material, and a method of inserting an antistatic agent or the like may be mentioned. When using an antistatic agent, a lubricating agent can also be used together.

As thickness of the said base material layer, it is 5-200 micrometers normally, Preferably it is about 10-100 micrometers. When the thickness of the said base material layer exists in the said range, since it is excellent in bonding workability|operativity to a to-be-adhered body, and peeling workability from a to-be-adhered body, it is preferable.

In the laminated|multilayer film of this invention, as needed, in order to protect an adhesive surface, it is possible to bond a separator to the adhesive layer surface.

Although there exist paper and a plastic film as a material which comprises the said separator, a plastic film is used suitably at the point which is excellent in surface smoothness. The film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and 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 film. A copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the said separator is 5-200 micrometers normally, Preferably it is about 10-100 micrometers. When it exists in the said range, since it is excellent in the bonding workability|operativity to an adhesive layer and peeling workability from an adhesive layer, it is preferable. If necessary, the separator may be subjected to a release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl- or fatty acid amide-based release agent, silica powder, or the like, or an antistatic treatment such as a coating type, continuous insertion type, or vapor deposition type.

The laminated|multilayer film of this invention can be used conveniently as surface protection films, such as an optical member. Since the laminated|multilayer film of this invention is excellent also in temporal stability and can be used for surface protection uses, such as a process, conveyance, and shipment, it becomes useful for the use which protects the surface of optical members, such as a polarizing plate.

(Example)

Hereinafter, some examples related to the present invention will be described, but it is not intended to limit the present invention to those shown in these examples. In addition, unless it specifically limits, "part" and "%" in the following description and a table|surface are mass standards, and represent solid content or an active ingredient.

In addition, evaluation in an Example was performed according to the following.

<Adhesiveness>

On a glass plate, the obtained laminated|multilayer film is crimped|compressed and affixed by 1 reciprocating 2 kgf roller, respectively, and 24 hours after sticking, adhesive force is measured using adhesion and film peeling analyzer VPA-3 (made by Kyowa Gaimen Chemicals). did. Measurement conditions are as follows. The adhesive force was evaluated by two patterns when the tensile rate and the peeling rate were 150 mm/min, and the tensile rate and the peeling rate were 1200 mm/min.

Tensile speed: 150mm/min, 1200mm/min

Peeling speed: 150mm/min, 1200mm/min

·Peeling direction: 180°

・Sample size: 25mm×70mm

<Evaluation of adhesion permutation>

From the measurement result of adhesive force, the following reference|standard evaluated the adhesive force of laminated|multilayer film.

(double-circle) : The adhesive force of 150 mm/min of tensile speed is 50 mN/25 mm or less, Moreover, the adhesive force of 1200 mm/min of tensile speed is 100 mN/25 mm or less.

○: Adhesive force at a tensile rate of 150 mm/min is 50 mN/25 mm or less, or an adhesive force at a tensile rate of 1200 mm/min is 100 mN/25 mm or less

x: The adhesive force of 150 mm/min of tensile speed exceeds 50 mN/25 mm, and the adhesive force of 1200 mm/min of tensile speed exceeds 100 mN/25 mm.

<full leftover>

It carried out similarly to the time of adhesive force measurement, and affixed the obtained laminated|multilayer film on the glass plate. After 1 week storage at 40 degreeC, the film was peeled off, and the following reference|standard evaluated the remaining paste on a glass plate visually.

○: No glue residue on the glass plate

×: Glue remains in part of the glass plate

Synthesis Example 1

In a glass flask equipped with a stirring device, 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, 64 g of toluene as a solvent, 0.03 g of phenothiazine as a polymerization inhibitor and 0.6 g of methanesulfonic acid as a catalyst were added, stirring was started under an air stream, and the mixture was heated to 120° C. and dehydrated under reflux. After confirming dehydration of 0.63 g, it was cooled to 65°C and neutralized with triethylamine. After neutralization, it heated up to 85 degreeC, 2.3 g of ion-exchange water was added, and liquid separation and lower layer extraction were performed. The pH of the lower layer was measured, and washing|cleaning operation was repeated until pH became 7 or more. It diluted with toluene after cooling and obtained the toluene solution containing 55 mass % of 3 types of mixture (1-1) represented by following formula (1-1-1) - (1-1-3).

300.00 g of toluene was added to the glass flask, and it heated up at 105 degreeC, stirring in nitrogen stream. Next, a dripping solution obtained by mixing 14.25 g of 2-(perfluorohexyl)ethyl acrylate, 194.73 g of mixture (1-1), 99.05 g of toluene, and 11.25 g of initiator perbutyl O (manufactured by Nichiyu Co., Ltd.), polysiloxane A dropping solution obtained by dissolving 28.65 g of a monomethacrylate compound having a bond (manufactured by JNC Corporation, Silaplane FM-0721K) in 30.00 g of toluene was set in a dropping device, respectively, and the amount of the flask was maintained at 105°C. The dripping liquid was dripped over 4 hours. After completion|finish of dripping, it stirred at 105 degreeC for 10 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (1).

As a result of analyzing the polyoxyethylene compound (1) as a copolymer by a gel permeation graph (hereinafter abbreviated as GPC), the weight average molecular weight Mw was 16,200.

Synthesis Example 2

300.00 g of toluene was added to the glass flask, and it heated up at 105 degreeC, stirring in nitrogen stream. Next, a dripping solution prepared by mixing 42.90 g of 2-(perfluorohexyl)ethyl acrylate, 194.73 g of mixture (1-1), 129.05 g of toluene, and 11.25 g of initiator perbutyl O (manufactured by Nichiyu Co., Ltd.) was added dropwise. It set in the apparatus, and the dripping liquid was dripped over 4 hours, maintaining the inside of a flask at 105 degreeC. After completion|finish of dripping, it stirred at 105 degreeC for 10 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (2).

As a result of analyzing the polyoxyethylene compound (2) which is a copolymer by GPC, the weight average molecular weight Mw was 12,700.

Synthesis Example 3

300.00 g of toluene was added to the glass flask, and it heated up at 105 degreeC, stirring in nitrogen stream. Subsequently, 42.90 g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Corporation, Silaplane FM-0721K), 194.73 g of mixture (1-1), 129.05 g of toluene, and perbutyl O (Nichiyo Co., Ltd.) The dripping liquid which mixed 11.25 g of Corporation make) was set in the dripping apparatus, and the dripping liquid was dripped over 4 hours, maintaining the inside of a flask at 105 degreeC. After completion|finish of dripping, it stirred at 105 degreeC for 10 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (3).

As a result of analyzing the polyoxyethylene compound (3) which is a copolymer by GPC, the weight average molecular weight Mw was 19,100.

Synthesis Example 4

225.00 g of methyl ethyl ketone (MEK) was added to the glass flask, and it heated up at 80 degreeC, stirring in nitrogen stream. Next, 22.50 g of 2-(perfluorohexyl)ethyl acrylate, 82.65 g of polyethylene glycol monoacrylate (Brenma AE-400, manufactured by Nichi Oil Co., Ltd.), 150.00 g of MEK, 2,2'-azobis initiator (Isobutyric acid) A dripping solution mixed with 7.50 g of dimethyl (manufactured by Wako Pure Chemical Industries, Ltd., MAIB), a monomethacrylate compound having polysiloxane bonds (manufactured by JNC Corporation, Silaplane FM-0721K) 44.85 The dripping liquid which melt|dissolved g in MEK 75.00g was set to the dripping apparatus, respectively, and both dripping liquid were dripped over 4 hours, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 2 hours. Then, the liquid mixture of 0.75g of MAIB and 7.50g of MEK was dripped over 15 minutes, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 9 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (4).

As a result of analyzing the polyoxyethylene compound (4) which is a copolymer by GPC, the weight average molecular weight Mw was 9,100.

Synthesis Example 5

225.00 g of methyl ethyl ketone (MEK) was added to the glass flask, and it heated up at 80 degreeC, stirring in nitrogen stream. Then, 67.35 g of 2-(perfluorohexyl)ethyl acrylate, 82.65 g of polyethylene glycol monoacrylate (Brenma AE-400, manufactured by Nichi Oil Co., Ltd.), 225.00 g of MEK, 2,2'-azobis initiator (Isobutyric acid) A dripping solution mixed with 7.50 g of dimethyl (manufactured by Wako Pure Chemical Industries, Ltd., MAIB), a monomethacrylate compound having polysiloxane bonds (manufactured by JNC Corporation, Silaplane FM-0721K) 44.85 The dripping liquid which melt|dissolved g in MEK 75.00g was set in the dripping apparatus, and both dripping liquid were dripped over 4 hours, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 2 hours. Then, the liquid mixture of 0.75g of MAIB and 7.50g of MEK was dripped over 15 minutes, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 9 hours. The solvent was distilled off after completion|finish of reaction, and the solution containing 25 mass % of polyoxyethylene compound (5) was obtained.

As a result of analyzing the polyoxyethylene compound (5) which is a copolymer by GPC, the weight average molecular weight Mw was 9,600.

Synthesis Example 6

225.00 g of methyl ethyl ketone (MEK) was added to the glass flask, and it heated up at 80 degreeC, stirring in nitrogen stream. Subsequently, 67.35 g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., Ltd., Silaplane FM-0721K), 82.65 g of polyethylene glycol monoacrylate (manufactured by Nichiyu Co., Ltd., Brenma AE-400), A dripping solution of 225.00 g of MEK, 7.50 g of initiator 2,2'-azobis(isobutyric acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd., MAIB), a monomethacrylate compound having a polysiloxane bond (JNC Co., Ltd.) The dripping liquid which melt|dissolved 44.85 g of the ShilaPlain FM-0721K) made by Shiki Corporation in 75.00 g of MEK was set in the dripping apparatus, and both dripping liquid were dripped over 4 hours, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 2 hours. Then, the liquid mixture of 0.75g of MAIB and 7.50g of MEK was dripped over 15 minutes, maintaining the inside of a flask at 80 degreeC. After completion|finish of dripping, it stirred at 80 degreeC for 9 hours. The solvent was distilled off after completion|finish of reaction, and the solution containing 25 mass % of polyoxyethylene compounds (6) was obtained.

As a result of analyzing the polyoxyethylene compound (6) which is a copolymer by GPC, the weight average molecular weight Mw was 10,200.

Synthesis Example 7

100.00 g of butyl acetate was added to the glass flask, and it heated up at 95 degreeC, stirring in nitrogen stream. Next, a dripping solution in which 35.00 g of 2-(perfluorohexyl)ethyl acrylate, 65.00 g of methoxypolyethylene glycol #1000 methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., M230G), and 170.00 g of butyl acetate were mixed, and perbutyl The dripping liquid which melt|dissolved 10.00 g of O in 30.00 g of butyl acetate was set in the dripping apparatus, respectively, and both dripping liquid were dripped over 3 hours, maintaining the inside of a flask at 95 degreeC. The solution containing 25 mass % of polyoxyethylene compounds (7) was obtained by stirring at 95 degreeC after completion|finish of dripping for 9 hours.

As a result of analyzing the polyoxyethylene compound (7) which is a copolymer by GPC, the weight average molecular weight Mw was 12,700.

Synthesis Example 8

128.29 g of methyl isobutyl ketone (MIBK) was added to the glass flask, and it heated up at 90 degreeC, stirring in nitrogen stream. Next, 30.40 g of 2-(perfluorohexyl) ethyl acrylate, 65.85 g of propylene glycol/polybutylene glycol-monomethacrylate (Nichiyo Co., Ltd., Brenma 10PPB-500B), and 76.94 g of MIBK were mixed. The dripping solution prepared by mixing the previously prepared dripping solution, 19.34 g of MIBK, and 5.77 g of the initiator Perbutyl O (manufactured by Nichi Oil Co., Ltd.) was set in a dropping device, respectively, and both drops were added in 2 hours while maintaining the inside of the flask at 90°C. dropped across. After completion|finish of dripping, it stirred at 90 degreeC for 10 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyalkylene compound (8).

As a result of analyzing the polyoxyalkylene compound (8) which is a copolymer by GPC, the weight average molecular weight Mw was 9,100.

Synthesis Example 9

306.36 g of methyl isobutyl ketone (MIBK) was added to the glass flask, and it heated up at 105 degreeC, stirring in nitrogen stream. Next, a dripping solution obtained by mixing 97.11 g of 2-(perfluorohexyl)ethyl acrylate, 209.24 g of polypropylene glycol monomethacrylate (Brenma PP-1000, manufactured by Nichi Oil Co., Ltd.) and 222.35 g of MIBK, MIBK The dripping liquid which mixed 153.18 g and 15.32 g of initiator perbutyl O (made by Nichiyo Co., Ltd.) were respectively set in the dripping apparatus, and both dripping liquid were dripped over 3 hours, maintaining the inside of a flask at 105 degreeC. After completion|finish of dripping, it stirred at 105 degreeC for 3 hours. Then, the liquid mixture of 1.53g of perbutylO and 15.32g of MIBK was dripped over 15 minutes, maintaining the inside of a flask at 105 degreeC. After completion|finish of dripping, it stirred at 105 degreeC for 7.5 hours. After completion of the reaction, the solvent was distilled off to obtain a polyoxyalkylene compound (9).

As a result of analyzing the polyoxyalkylene compound (9) which is a copolymer by GPC, the weight average molecular weight Mw was 5,900.

Synthesis Example 10

100.00 g of butyl acetate was added to the glass flask, and it heated up at 95 degreeC, stirring in nitrogen stream. Next, a dripping solution of 30.00 g of 2-(perfluorohexyl)ethyl acrylate, 60.00 g of hydroxyethyl acrylate, 10.00 g of methyl methacrylate, and 170.00 g of butyl acetate, and 10.00 g of perbutyl O were mixed with 30.00 g of butyl acetate. The dripping liquid dissolved in g was respectively set in the dripping apparatus, and both dripping liquid were dripped over 3 hours, maintaining the inside of a flask at 95 degreeC. After completion|finish of dripping, it stirred at 95 degreeC for 9 hours. After completion of the reaction, the solvent was distilled off to obtain a fluorinated compound (10).

As a result of GPC analysis of the fluorinated compound (10) as a copolymer, the weight average molecular weight Mw was 4,200.

Example 1

To 100 parts of the solid content of the acrylic pressure-sensitive adhesive (CT-3088: manufactured by DIC), 2.9 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) and 0.5 parts of the obtained polyoxyethylene compound (1) in solid content are added, and methyl ethyl It diluted so that solid content might be 35 % with ketone, it thoroughly mixed, and obtained the adhesive composition.

The obtained pressure-sensitive adhesive composition was directly coated on the corona-treated surface of a polyester film having a thickness of 50 µm as a base material using an automatic coating device bar coater (PI-1210: manufactured by Tester Corporation) so that the thickness of the pressure-sensitive adhesive layer after formation was 20 µm. . Then, after drying at 85 degreeC for 3 minutes and forming an adhesion layer, the silicone-coated polyester film separator of the 38 micrometers thickness by which the said adhesion layer was coat|covered and laminated|multilayer film was produced. This laminated|multilayer film was further cured at 40 degreeC for 3 days, and it was set as the sample of the evaluation test.

About the obtained laminated|multilayer film, adhesive force and adhesiveness were evaluated. A result is shown in Table 1.

Example 2

Except having used the polyoxyethylene compound (2) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Example 3

Except having used the polyoxyethylene compound (3) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Example 4

Except having used the polyoxyethylene compound (4) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Example 5

Except having used the polyoxyethylene compound (5) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Example 6

Except having used the polyoxyethylene compound (6) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Example 7

Except having used the polyoxyethylene compound (7) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Moreover, although the obtained adhesive composition showed some haze, haze was not recognized by the laminated|multilayer film, and there was no problem in actual use.

Comparative Example 1

Except not having used the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Comparative Example 2

Except having used the polyoxyalkylene compound (8) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Comparative Example 3

Except having used the polyoxyalkylene compound (9) instead of the polyoxyethylene compound (1), it carried out similarly to Example 1, the laminated|multilayer film was manufactured and evaluated. A result is shown in Table 1.

Comparative Example 4

A laminated film was prepared and evaluated in the same manner as in Example 1 except that the fluorinated compound (10) was used instead of the polyoxyethylene compound (1). A result is shown in Table 1.

[Table 1]

Claims (12)

A pressure-sensitive adhesive composition comprising a polyoxyethylene compound (A) having at least one selected from a C1-C6 fluorinated alkyl group (a1) and a silicone chain (a3) and a polyoxyethylene chain (a2), and an adhesive (B). According to claim 1,
The adhesive composition in which the said polyoxyethylene compound (A) has the said C1-C6 fluorinated alkyl group (a1). 3. The method of claim 1 or 2,
The pressure-sensitive adhesive composition wherein the silicone chain (a3) has a molecular weight in the range of 200 to 50,000. 4. The method according to any one of claims 1 to 3,
The adhesive composition whose average value of the repeating number of the said polyoxyethylene chain (a2) is the range of 2-50. 5. The method according to any one of claims 1 to 4,
The adhesive composition whose fluorine atom content rate of the said polyoxyethylene compound (A) is the range of 1-50 mass %. 6. The method according to any one of claims 1 to 5,
The weight average molecular weight of the said polyoxyethylene compound (A) is the range of 3,000-300,000, The adhesive composition. 7. The method according to any one of claims 1 to 6,
The pressure-sensitive adhesive composition wherein the polyoxyethylene compound (A) is a copolymer comprising a fluorinated alkyl group-containing ethylenically unsaturated monomer (x1) and a polyoxyethylene chain-containing ethylenically unsaturated monomer (x2) as essential raw materials. 8. The method according to any one of claims 1 to 7,
The polyoxyethylene compound (A) contains an ethylenically unsaturated monomer containing a fluorinated alkyl group (x1), a polyoxyethylene chain containing ethylenically unsaturated monomer (x2), and a silicone chain containing ethylenically unsaturated monomer (x3) as essential raw materials The adhesive composition which is a copolymer made into 9. The method according to any one of claims 1 to 8,
The adhesive composition whose content rate of the said polyoxyethylene compound (A) is 0.01-20 mass % in solid content of an adhesive composition. 10. The method according to any one of claims 1 to 9,
The pressure-sensitive adhesive composition wherein the pressure-sensitive adhesive (B) is an acrylic pressure-sensitive adhesive (b1) and/or a urethane-based pressure-sensitive adhesive (b2). The laminated|multilayer film which have the adhesive layer of the adhesive composition in any one of Claims 1-10, and a base material layer. 12. The method of claim 11,
The laminated|multilayer film which is a surface protection film of an optical member.