CN113166606B

CN113166606B - Adhesive composition and laminated film using same

Info

Publication number: CN113166606B
Application number: CN201980079942.4A
Authority: CN
Inventors: 野口润; 高野启
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2018-12-03
Filing date: 2019-11-26
Publication date: 2023-02-03
Anticipated expiration: 2039-11-26
Also published as: JPWO2020116229A1; KR102480720B1; JP6923092B2; TW202031840A; WO2020116229A1; CN113166606A; KR20210068524A; TWI819152B

Abstract

Provided is an adhesive composition which can easily adjust the adhesive force of an adhesive and has little adhesive residue after peeling. Specifically disclosed is an adhesive composition containing a polyoxyethylene compound (A) and an adhesive (B), wherein the polyoxyethylene compound (A) has: at least 1 selected from fluorinated alkyl groups (a 1) having 1 to 6 carbon atoms and silicone chains (a 3), and polyoxyethylene chains (a 2).

Description

Adhesive composition and laminated film using same

Technical Field

The present invention relates to: a laminated film which 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 for forming a pressure-sensitive adhesive layer of the laminated film.

Background

In the field of electronic industry, when manufacturing, transporting, using, or the like electronic devices and electronic components, a protective film having adhesive properties is attached to the surfaces of the electronic devices and electronic components, thereby protecting the surfaces.

For the same reason, a protective film having adhesive properties is attached to the surface of an optical member such as a polarizing plate, a retardation plate, an optical compensation film, or a transparent conductive film used in a liquid crystal display, an organic EL display, a touch panel, or the like.

The pressure-sensitive adhesive used for the protective film is required to have both of a micro-pressure-sensitive adhesive property enabling peeling even with a small force and a removability enabling re-beautiful peeling even with one-time application. Among these, the protective film for an optical member tends to have a large area, and further micro-adhesiveness and removability are required.

Since the purpose of surface protection is achieved, it is necessary for the protective film to be easily peelable from the adherend and for the substrate and the pressure-sensitive adhesive to be integrated after the purpose is achieved, but it is generally known that the pressure-sensitive adhesive has a large adhesive force with the passage of time, and there are cases where the pressure-sensitive adhesive remains during peeling or the substrate film is broken.

As a method for preventing the above-described inconvenience, for example, there is provided a method of: a release agent such as a wax or a long-chain alkyl group-containing compound is mixed with the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer (see, for example, patent document 1).

As a surface protection film having little contamination derived from a binder component, a surface protection film using an acrylic resin for a binder layer is known. However, when an acrylic resin is used for the pressure-sensitive adhesive layer, there is a problem that scum is likely to occur at the time of peeling, and there is a problem when the acrylic resin is used as a surface protective film for protecting the surface of a member, such as an optical member or an electronic member, in which foreign matter is particularly troublesome to be mixed.

As a means for solving the above problems, for example, a method is provided which uses a urethane resin using a specific polyfunctional polyol as a binder (for example, see patent document 2), but there is a lack of compatibility between residual glue and optimization of adhesive strength.

While various improvements have been made in the function as a surface protective film, in the process of making optical members used in recent large-sized displays mainstream by a method of mechanically peeling off a surface protective film, the peeling rate often varies depending on the process, and a pressure-sensitive adhesive composition which is easier to adjust the peeling force (adhesive force) and has less adhesive residue after peeling off, and a laminated film having the same as a pressure-sensitive adhesive layer have been desired.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-019158

Patent document 2: japanese patent laid-open publication No. 2014-111701

Disclosure of Invention

Problems to be solved by the invention

The problem to be solved by the present invention is to provide: an adhesive composition which can be easily adjusted in adhesive force and has little adhesive residue after peeling, and a laminated film which can be suitably used as a surface protective film when used for an adhesive layer.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by solving the above problems by using a combination of a polyoxyethylene compound having 1 or more selected from fluorinated alkyl groups having 1 to 6 carbon atoms and silicone chains and a polyoxyethylene chain, and a binder.

The present invention provides an adhesive composition containing a polyoxyethylene compound (a) and an adhesive (B), the polyoxyethylene compound (a) having: at least 1 selected from fluorinated alkyl groups (a 1) having 1 to 6 carbon atoms and silicone chains (a 3), and polyoxyethylene chains (a 2).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: the laminated film is easy to adjust the adhesive force of various adhesives, has little change of the adhesive force after storage, good stripping performance and little residual glue after stripping. The laminated film of the present invention can be suitably used as a surface protective film for various optical members, electronic members, and the like.

Detailed Description

< adhesive composition >

The adhesive composition of the present invention contains a polyoxyethylene compound (a) and an adhesive (B), the polyoxyethylene compound (a) having: 1 or more selected from fluorinated alkyl groups (a 1) having 1 to 6 carbon atoms and silicone chains (a 3), and polyoxyethylene chains (a 2).

It is known that, with respect to the adhesive, the adhesive force thereof can be reduced by using a compound having a fluorine atom, a silicon atom, a compound having a long chain alkyl group, or the like in combination. However, no detailed structure has been found for a compound which is generally known, particularly a compound known as a release agent or a surfactant, and which is easily adjusted in adhesive force even with a small amount of addition, little enhances adhesive force even after long-term storage, is excellent in releasability, and is also excellent in residual adhesion prevention.

The present invention has been made in view of such problems, and as a result, has found that: it is an effective solution to use a polyoxyethylene compound (a) having 1 or more selected from fluorinated alkyl groups (a 1) having 1 to 6 carbon atoms and silicone chains (a 3), and polyoxyethylene chains (a 2).

The components contained in the adhesive composition of the present invention will be described below.

[ polyoxyethylene Compound (A) ]

The polyoxyethylene compound (a) is a compound having 1 or more selected from a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms and a silicone chain (a 3), and a polyoxyethylene chain (a 2). The polyoxyethylene compound (a) has 3 kinds, specifically: a compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a 2); a compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms, a polyoxyethylene chain (a 2) and a silicone chain (a 3); and, a compound having a polyoxyethylene chain (a 2) and a silicone chain (a 3).

The polyoxyethylene compound (a) preferably contains a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms, from the viewpoint that when a surface protection film is formed using the pressure-sensitive adhesive composition of the present invention, contamination after peeling off an adherend can be reduced. Therefore, the polyoxyethylene compound (a) is preferably a compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a 2), or a compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms, a polyoxyethylene chain (a 2) and a silicone chain (a 3), and is most preferably a compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a 2).

The fluorinated alkyl group (a 1) having 1 to 6 carbon atoms in the polyoxyethylene compound (a) means that the number of carbon atoms to which fluorine atoms are directly bonded is in the range of 1 to 6, and a part of atoms bonded to carbon atoms may be hydrogen atoms. The alkyl group as the fluorinated alkyl group may be either branched or linear.

The plurality of fluorinated alkyl groups (a 1) may have a structure in which they are connected by an ether bond, a thioether bond, or an alkylene chain having no fluorine atom.

The number of carbon atoms to which fluorine atoms are directly bonded to the fluorinated alkyl group (a 1) having 1 to 6 carbon atoms is preferably in the range of 3 to 6, more preferably 4 or 6, from the viewpoint of easily adjusting the adhesive force of the adhesive (B) and effectively suppressing the adhesive residue at the time of peeling. From the same viewpoint, the fluorinated alkyl group (a 1) having 1 to 6 carbon atoms is more preferably a perfluoroalkyl group containing no hydrogen atom.

From the viewpoint of easier adjustment of the adhesive force, it is preferable that the polyoxyethylene compound (a) contains 2 or more fluorinated alkyl groups (a 1) in 1 molecule.

The polyoxyethylene chain (a 2) in the polyoxyethylene compound (a) has a structure in which 2 or more oxyethylene groups are bonded, and the polyoxyethylene chain (a 2) may be linear or branched.

The polyoxyethylene compound (a) may have a polyoxyethylene chain (a 2), and may have a polyoxyalkylene chain having 1 to 6 carbon atoms such as polyoxypropylene or polyoxybutylene other than the polyoxyethylene chain. When the polyoxyethylene compound (a) has a polyoxyalkylene chain having 1 to 6 carbon atoms other than the polyoxyethylene chain, the polyoxyalkylene chain having 1 to 6 carbon atoms is preferably a polyoxypropylene chain.

The average value of the number of repetitions of the polyoxyethylene chain (a 2) is preferably in the range of 2 to 50.

When the polyoxyethylene compound (a) has a polyoxyethylene chain and a polyoxyalkylene chain having 1 to 6 carbon atoms and ethylene units and alkylene units are bonded to each other by an ether bond, the form thereof may be a block or a random, and the number of repetitions is preferably in the range described above in the total of the units.

The silicone chain (a 3) in the polyoxyethylene compound (a) is not particularly limited, and examples thereof include silicone chains represented by the following formulae.

(in the formula, wherein, R, R ', R ", and R'" each independently represent an alkyl group having 1 to 18 carbon atoms or a phenyl group, and a plurality of R, R ', R ", and R'" are optionally the same as or different from each other, respectively.

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

The weight average molecular weight of the silicone chain (a 3) is preferably in the range of 200 to 50000, more preferably in the range of 200 to 30000, from the viewpoint of peelability.

The content of the fluorine atom in the polyoxyethylene compound (a) is not particularly limited, but is preferably in the range of 1 to 50 mass%, more preferably in the range of 1 to 30 mass%, from the viewpoints of compatibility with the binder (B) described later, easiness of adjustment of adhesive strength, and easiness of production.

The fluorine atom content can be calculated from the charge ratio of the raw material of the polyoxyethylene compound (a), but may be actually measured by combustion ion chromatography of the polyoxyethylene compound (a). In the present invention, the above range is preferable among the measured values of the latter.

The weight average molecular weight of the polyoxyethylene compound (a) is not particularly limited, but is preferably in the range of 3000 to 300000, more preferably 3000 to 200000, from the viewpoint of compatibility with the binder (B) described later, ease of adjustment of adhesive force, and balance between reduction of residual gum, and the like, and is most preferably in the range of 4000 to 100000 from the viewpoint of uniformity of peeling force when used as a surface protection film for a large-area optical member or the like.

The weight average molecular weight in the present invention is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.

(GPC measurement conditions)

A measuring device: HLC-8220GPC manufactured by Tosoh corporation,

Column: "HHR-H" (6.0mmI.D.. Times.4 cm) protective column manufactured by Tosoh corporation, "TSK-GEL GMHHR-N" (7.8mmI.D.. Times.30 cm) manufactured by Tosoh corporation and "TSK-GEL GMHHR-N" (7.8mmI.D.. Times.30 cm) manufactured by Tosoh corporation

A detector: evaporative light scattering Detector (ELSD 2000, manufactured by Alltech Japan K.K.)

Data processing: "GPC-8020 type II data analysis 4.30 edition" manufactured by Tosoh corporation "

The measurement conditions were as follows: column temperature 40 deg.C

Tetrahydrofuran (THF) as developing solvent

Flow rate 1.0 ml/min

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

Standard sample: the following monodisperse polystyrene having a known molecular weight was used according to the manual of measurement of "GPC-8020 type II data analysis 4.30 edition".

(monodisperse polystyrene)

"A-500" made by Tosoh corporation "

"A-1000" manufactured by Tosoh corporation "

"A-2500" made by Tosoh corporation "

"A-5000" manufactured by Tosoh corporation "

"F-1" manufactured 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" manufactured by Tosoh corporation "

"F-550" made by Tosoh corporation "

When a fluorine-containing compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms and a polyoxyethylene chain (a 2) is used as the polyoxyethylene compound (a), the polyoxyethylene compound (a) is particularly preferably a copolymer having, as essential raw materials, an ethylenically unsaturated monomer (x 1) having a fluorinated alkyl group and an ethylenically unsaturated monomer (x 2) having a polyoxyethylene chain, from the viewpoints of good compatibility with the adhesive and easy adjustment of the adhesive strength of the adhesive.

When a fluorine-containing compound having a fluorinated alkyl group (a 1) having 1 to 6 carbon atoms, a polyoxyethylene chain (a 2) and a silicone chain (a 3) is used as the polyoxyethylene compound (a), the polyoxyethylene compound (a) is particularly preferably a copolymer having, as essential raw materials, an ethylenically unsaturated monomer (x 1) containing a fluorinated alkyl group, an ethylenically unsaturated monomer (x 2) containing a polyoxyethylene chain and an ethylenically unsaturated monomer (x 3) containing an organosilicon chain, from the viewpoints of good compatibility with a binder and easy adjustment of adhesive strength of a binder.

When a polyoxyethylene compound having a polyoxyethylene chain (a 2) and a silicone chain (a 3) is used as the polyoxyethylene compound (a), a copolymer in which an ethylenically unsaturated monomer having a polyoxyethylene chain (x 2) and an ethylenically unsaturated monomer having an organosilicon chain (x 3) are used as essential raw materials is particularly preferable from the viewpoint of good compatibility with the adhesive and easy adjustment of the adhesive strength of the adhesive.

These monomers may be used alone or in combination of two or more, and they may be copolymerized, and the copolymerization form may be a block or a random.

The ethylenically unsaturated group of the monomer is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and examples thereof include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, (meth) acryloyl group and vinyl group are preferable, and (meth) acryloyl group is particularly preferable, from the viewpoint of easiness of obtaining raw materials, compatibility with the binder (B) described later, and good polymerization reactivity.

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

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 an optionally substituted aralkyl group having 6 to 24 carbon atoms, and these are divalent linking groups composed of one or more of these groups,

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 an optionally substituted aralkyl group having 6 to 24 carbon atoms, which are divalent linking groups composed of one or more of these groups,

R ⁶ is a hydrogen atom or a methyl group.

Rf is-C _n F _2n+1 (wherein n is an integer of 1 to 6.). Angle (c)

As the fluorinated alkyl group-containing ethylenically unsaturated monomer (x 1), there may be mentioned a fluorinated urethane (meth) acrylate represented by the following formula (x 1-3).

[ in the formula, rf is independently- (C) _x F _2x -O) _p -(C _y F _2y -O) _q -C _n F _2n+1 The group (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 2 Rf is- (C) _x F _2x -O) _p -(C _y F _2y -O) _q -C _n F _2n+1 The groups shown.

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

Y ¹ Each independently being 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. Angle (c)

The fluorine-containing urethane (meth) acrylate represented by the formula (x 1-3) is preferable from the viewpoint that the compatibility with the pressure-sensitive adhesive (B) described later, particularly with the acrylic pressure-sensitive adhesive (B1) or the urethane pressure-sensitive adhesive (B2) is good, the transparency at the time of forming the pressure-sensitive adhesive layer can be maintained, and the adjustment of the adhesive strength is also easy.

The monomer represented by the formula (x 1-3) can be obtained, for example, by reacting a fluorine compound having a hydroxyl group represented by the following formula with a compound having an isocyanate group and a (meth) acryloyl group.

(Rf, R in the formula ⁵ 、Y ¹ The same as the above formula (x 1-3). )

As Rf-R in the above formula ⁵ -Y ¹ Specific examples of (3) 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-, etc.

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

The method for producing the fluorine compound having a hydroxyl group represented by the above formula is not particularly limited, and the fluorine compound can be produced by, for example, the methods described in Japanese patent application laid-open Nos. 1-193236, 9-67334, and 2002-3428.

Examples of the compound having an isocyanate group and a (meth) acryloyl group (i.e., the (meth) acrylate having an isocyanate group) include compounds represented by the following formulae.

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

A' in the formula represents an alkylene group having 2 to 3 carbon atoms, and specifically, an ethylene group (-CH) ₂ CH ₂ -) propylene (-CH) ₂ CH ₂ CH ₂ -, or branched propylene (-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 above compounds, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate in which A' in the formula is ethylene are preferable.

When the fluorine compound having a hydroxyl group is reacted with the (meth) acrylate having an isocyanate group, the (meth) acrylate having an isocyanate group is preferably added in an amount of 0.80 to 1.20 mol, more preferably 0.98 to 1.00 mol, based on 1 mol of the fluorine compound having a hydroxyl group.

In the reaction (urethanization reaction) of the fluorine compound having a hydroxyl group and the (meth) acrylate having an isocyanate group, for example, tertiary amines such as triethylamine and benzyldimethylamine; dilaurate esters such as dibutyltin dilaurate and dioctyltin dilaurate are used as catalysts.

The amount of the catalyst to be added is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.1% by mass, based on the whole reaction mixture. The reaction time is preferably 1 to 10 hours. The reaction temperature is preferably 30 to 120 ℃ and more preferably 30 to 100 ℃.

The reaction may be carried out in the absence of a solvent, or a solvent inactive to isocyanate groups such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, or xylene may be used as the reaction solvent.

Specific examples of the monomer represented by the formula (x 1-3) obtained by the above reaction include monomers represented by the following formulae.

Examples of the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2) include compounds represented by the following formula (x 2-1).

In the formula, R' is a polyoxyalkylene group in which the end of the polyoxyalkylene chain containing a polyoxyethylene chain is a hydrogen atom or an alkyl group.

R ¹ Is a (meth) acryloyl group. In the present invention, a (meth) acryloyl group is used as a generic term for one or a mixture of an acryloyl group and a methacryloyl group.

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. Angle (c)

Examples of the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2) include compounds represented by the following formula (x 2-2).

R ¹ O-R”-OR ¹ (x2-2)

(in the formula, 2R ¹ Are the same or different (methyl) propanesAn alkenoyl group. The term "meth (acryloyl group" means both an acryloyl group and a methacryloyl group.

R' is a polyoxyalkylene chain comprising a polyoxyethylene chain. )

Examples of the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2) include a compound represented by the following formula (x 2-3) and a compound represented by the following formula (x 2-4).

(in the formula, R ³ Is a hydrogen atom or a methyl group. Plural R ³ Optionally identical to or different from each other.

R ⁴ And R ⁵ Each independently is 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 of 2 or more.

m is an integer of 0 or more.

k is an integer of 0 or more. )

In the above formulae (x 2-3) and (x 2-4), R ⁴ And R ⁵ The alkylene group having 1 to 6 carbon atoms in (b) is preferably an alkylene group having 2 or 3 carbon atoms.

Examples of the compounds (x 2-1), (x 2-2), (x 2-3) and (x 2-4) include: ext> ethyleneext> oxideext> (ext> hereinafterext> abbreviatedext> asext> EOext>)ext> modifiedext> 1,6ext> -ext> hexanediolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> RCCext> 13ext> -ext> 361ext>,ext> manufacturedext> byext> Sanext> Nopcoext> corporationext>)ext>,ext> diethyleneext> glycolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> blumerext> ADEext> -ext> 100ext>,ext> manufacturedext> byext> noppoext> corporationext>)ext>,ext> EOext> modifiedext> neopentylext> glycolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> Photomerext> 4160ext>,ext> manufacturedext> byext> Sanext> Nopcoext> corporationext>)ext>,ext> polyethyleneext> glycolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> blumerext> ADEext> -ext> 200ext>,ext> manufacturedext> byext> noppoext> corporationext>)ext>,ext> polyethyleneext> glycolext> -ext> propyleneext> glycolext> -ext> polyethyleneext> glycolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> blumerext> ADCext> seriesext>,ext> manufacturedext> byext> noppoext> corporationext>)ext>,ext> polyethyleneext> glycolext> diext> (ext> methext>)ext> Acrylateext> (ext> forext> exampleext>,ext> Lightext> acrylteext> 3ext> EGext> -ext> aext>,ext> manufacturedext> byext> coyoboext> chemicalext> corporationext>)ext>,ext> EOext> modifiedext> glycerolext> Acrylateext> (ext> forext> exampleext>,ext> newfrotherext> 3ext> aext>,ext> manufacturedext> byext> seikouverext> chemicalext> corporationext>)ext>,ext> EOext> modifiedext> phosphateext> triacrylateext> (ext> forext> exampleext>,ext> newfrotherext> 3ext> aext>,ext> manufacturedext> byext> sakagakaext> chemicalext> corporationext>)ext>,ext> andext> theext> likeext>,ext> (ext> forext> exampleext>,ext> newext> trimethylolpropaneext> methacrylateext> -ext> basedext> onext> tmpext>,ext> manufacturedext> byext> newyowaext> chemicalext> companyext>,ext> andext> theext> likeext>.ext>

These compounds may be used alone, or a plurality of compounds having different (meth) acryloyl groups may be mixed and used, or a plurality of compounds having different structures may be mixed and used.

In addition, the above-mentioned compounds which are generally commercially available are often mixtures of compounds having different (meth) acryloyl groups relative to the target compound as a main component. When used, the compound having the target (meth) acryloyl group number may be extracted and used by various purification methods such as chromatography and extraction, or the mixture may be used as it is.

As the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2), a polyoxyethylene chain-containing (meth) acrylate represented by the following general formula can also be used.

Wherein A is an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, a cycloalkyl group having 3 to 12 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, or an aralkyl group having 6 to 24 carbon atoms which may be substituted, and these are divalent linking groups composed of one or more of these groups.

R ⁶ Is a hydrogen atom or a methyl group.

R' is a polyoxyalkylene group in which the end of a polyoxyalkylene chain containing a polyoxyethylene chain is a hydrogen atom or an alkyl group. Angle (c)

The polyoxyethylene chain-containing (meth) acrylate may be produced by reacting a commercially available hydroxypoly (oxyethylene) material, for example, a material sold under the trade name "Pluronic" (manufactured by ADEKA corporation), "ADEKA polyethylene" (manufactured by ADEKA corporation), "Carbowax" (グリコ, プロダクス), "Toriton" (manufactured by Rohm and Haas), or p.e.g. (manufactured by first industrial pharmaceutical company) with acrylic acid, methacrylic acid, acryloyl chloride, methacryloyl chloride, acrylic anhydride, methacrylic anhydride, or the like in various ways, or a polyoxyalkylene diacrylate containing a polyoxyethylene chain obtained by various production methods may be used.

Examples of commercially available (meth) acrylates containing a polyoxyethylene chain include Blemmer PE-90, blemmer PE-200, blemmer PE-350, blemmer AE-90, blemmer AE-200, blemmer AE-400, blemmer50 PEP-300, blemmer 70PEP-350B, blemmer AEP series, blemmer 55PET-400, blemmer 30PET-800, blemmer 55PET-800, and Blemmer AET series, which are hydroxyl-terminated polyalkylene glycol mono (meth) acrylates manufactured by Nippon oil Co.

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These polyoxyethylene chain-containing (meth) acrylates may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2), a compound having a vinyl ether structure represented by the following general formula can 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 an optionally substituted aralkyl group having 6 to 24 carbon atoms, and these are divalent linking groups composed of one or more of these groups.

R ⁶ Is a hydrogen atom or a methyl group.

The organosilicon chain-containing ethylenically unsaturated monomer (x 3) may be a monomer having a vinyl ether structure or a monomer having a (meth) acrylate structure.

The organosilicon chain-containing ethylenically unsaturated monomer (x 3) is preferably of the same series as the copolymerized fluorinated alkyl-containing ethylenically unsaturated monomer (x 1) and the polyoxyalkylene chain-containing ethylenically unsaturated monomer (x 2).

From the viewpoint of easy availability of raw materials, it is preferable to use a monomer having a (meth) acrylate structure as the organosilicon chain-containing ethylenically unsaturated monomer (x 3).

Specific examples of the organosilicon chain-containing ethylenically unsaturated monomer (x 3) include monomers represented by the following general formula.

(in the formula, R ¹ Represents a hydrogen atom or a methyl group.

R ³ ～R ⁶ 、R ¹⁰ ～R ¹⁷ Each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group.

R ² 、R ⁷ ～R ⁹ And R ¹⁸ ～R ²⁰ Each independently represents 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 each independently represent an integer of 1 to 250. )

As the ethylenically unsaturated monomer (x 3) having an organosilicon chain, commercially available products can be used, and examples thereof include Silaplane FM-0711, silaplane FM-0721K, silaplane FM-0725 and Silaplane TM-0701T (both manufactured by JNC K.K.) which are ethylenically unsaturated group-containing polysiloxane monomers.

When the polyoxyethylene compound (a) is produced by copolymerizing 1 or more selected from the group consisting of the polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2) and the fluorinated alkyl group-containing ethylenically unsaturated monomer (x 1) and the organosilicon chain-containing ethylenically unsaturated monomer (x 3), other monomers may be used as the raw materials of the copolymer in addition to these monomers within the range in which the effects of the present invention are not impaired.

The other monomers may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

Examples of the other monomer include acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, dialkyl fumarates and monoalkyl fumarates.

More specifically, the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

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

Examples of the acrylamide compound include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, and propyl group), N-dialkylacrylamide (alkyl group having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, and N-2-acetamidoethyl-N-acetylacrylamide.

Examples of the methacrylamide include methacrylamide, N-alkylmethacrylamide (having 1 to 3 carbon atoms as an alkyl group, for example, a methyl group, an ethyl group, and a propyl group), N-dialkylmethacrylamide (having 1 to 3 carbon atoms as an alkyl group), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide, and the like.

Examples of the allyl compound include allyl esters (e.g., allyl acetate, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, and the like.

Examples of the vinyl ethers include alkyl vinyl ethers such as 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, and the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl- β -phenyl-butyrate, and vinyl cyclohexylcarboxylate.

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

Examples of the dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate.

Furthermore, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, and the like can be mentioned.

When synthesizing the copolymer of the polyoxyethylene compound (a), the ratio of the monomers to be used is not particularly limited, and the fluorinated alkyl group-containing ethylenically unsaturated monomer (x 1) is contained in an amount of preferably 5 to 90 parts by mass, more preferably 5 to 80 parts by mass, and still more preferably 5 to 70 parts by mass, based on 100 parts by mass of the total monomers.

The polyoxyethylene chain-containing ethylenically unsaturated monomer (x 2) is preferably contained in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass.

The organosilicon chain-containing ethylenically unsaturated monomer (x 3) is contained preferably in an amount of 5 to 95 parts by mass, more preferably 5 to 80 parts by mass.

The copolymer can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, or the like. For example, the monomer mixture can be produced by adding a general-purpose radical polymerization initiator to an organic solvent and polymerizing the initiator. The dropping polymerization method is also effective for obtaining a copolymer having a uniform composition, depending on the polymerizability of the monomer used, or the polymerization is carried out while dropping the monomer and the initiator into the reaction vessel.

As the polymerization initiator, various ones can be used, and examples thereof include peroxides such as benzoyl peroxide and diacetyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate and phenylazotriphenylmethane, and Mn (acac) ₃ Metal chelates, transition metal catalysts for initiating living radical polymerization, and the like.

If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or the like, or a thiol compound having a coupling group such as γ -mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

The polymerization may be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent from the viewpoint of handling.

Examples of the solvent used in the polymerization include alcohols such as ethanol, isopropanol, N-butanol, isobutanol, and t-butanol, 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, monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, methyl Cellosolve, butyl carbitol, ethers such as Ethyl Cellosolve Acetate (Ethyl Cellosolve), ethers such as propylene glycol, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether Acetate, propylene glycol monobutyl ether Acetate, and esters thereof, halogen-based solvents such as 8978-trichloroethane, chloroform, aromatic solvents such as tetrahydrofuran, N-xylene, and perfluoroxylene, and inert liquids such as perfluoroxylene.

These solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The solvent used in the polymerization of the polyoxyethylene compound (a) may be used as the solvent of the adhesive composition of the present invention.

[ adhesive (B) ]

The pressure-sensitive adhesive (B) may be used without particular limitation as long as it has adhesiveness, and examples thereof include acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, synthetic rubber pressure-sensitive adhesives, natural rubber pressure-sensitive adhesives, and silicone pressure-sensitive adhesives. Among these adhesives, the acrylic adhesive (b 1) and/or the urethane adhesive (b 2) are preferably used.

The (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b 1) is obtained from a raw material monomer containing, as a main component monomer, a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms.

The (meth) acrylic monomer may be used in 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, the adhesive strength to an adherend (protected object) can be easily controlled to be low, and a surface protective film having excellent light peelability and removability can be obtained.

The term "main component" in the present invention means the component that constitutes the largest amount of the total components, and means that the "main component" is preferably more than 40% by mass, more preferably more than 50% by mass, and still more preferably more than 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, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate.

Among the (meth) acrylic monomers, preferred are (meth) acrylic monomers having an alkyl group having 6 to 14 carbon atoms such as 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, and n-tetradecyl (meth) acrylate, from the viewpoint of making it easier to control the adhesive strength to an adherend and making removability excellent.

The (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is contained preferably in an amount of 50% by mass or more, more preferably 60% by mass or more, even more preferably 70 to 99% by mass, and most preferably 80 to 97% by mass, based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer.

The (meth) acrylic polymer constituting the acrylic adhesive (b 1) preferably contains a (meth) acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth) acrylic monomer having a hydroxyl group, 1 or 2 or more species can be used.

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

Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and N-methylol (meth) acrylamide. In particular, the use of a (meth) acrylic monomer having a hydroxyl group with an alkyl group having 4 or more carbon atoms is preferable because light peeling can be easily performed at the time of high-speed peeling.

The hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 1 to 13 parts by mass, even more preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass, based on 100 parts by mass of the hydroxyl group-containing (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. When the content is within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the pressure-sensitive adhesive layer to be obtained can be easily controlled, and therefore, the content is preferable.

As other polymerizable monomer components, polymerizable monomers for adjusting the glass transition temperature and the peelability of the (meth) acrylic polymer can be used so that the Tg becomes 0 ℃ or lower (usually-100 ℃ or higher) because balance of the adhesive properties is easily obtained.

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

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

The amount of the (meth) acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably less than 1 part by mass, even more preferably less than 0.2 part by mass, and most preferably 0.01 part by mass or more and less than 0.1 part by mass, per 100 parts by mass of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Within the above range, the increase in adhesive strength with time (adhesion strength increase preventing property) can be prevented, and therefore, it is preferable.

The hydroxyl group-containing (meth) acrylic monomer and the carboxyl group-containing (meth) acrylic monomer may be used in combination for the purpose of achieving both of the peeling electrification property and the adhesion force increase prevention property.

Further, the polymerizable monomer other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic monomer having a hydroxyl group, and the (meth) acrylic monomer having a carboxyl group used in the (meth) acrylic polymer may be used without particular limitation. For example, a component having a functional group that functions as a base point for crosslinking, which improves adhesion, such as a cohesive strength/heat resistance-improving component including a cyano group-containing monomer, a vinyl ester monomer, or an aromatic vinyl monomer, or a component having a functional group that functions as a base point for crosslinking, such as an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloylmorpholine, or a vinyl ether monomer, can be suitably used. Among them, 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 are preferably used. By using the nitrogen-containing monomer, a suitable adhesive force that does not cause floating, peeling, or the like can be secured, and a surface-protecting film having excellent shear force can be obtained. And is therefore useful. These polymerizable monomers may be used alone, or two or more of them may be used in combination.

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.

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

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

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

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

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

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

The polymerizable monomer other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic monomer having a hydroxyl group, and the (meth) acrylic monomer having a carboxyl group is preferably 0 to 40 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, and is preferably 0 to 30 parts by mass from the viewpoint that good removability can be appropriately adjusted.

As for the aforementioned (meth) acrylic polymer, a reactive monomer containing a polyoxyalkylene chain may be further contained as a monomer component.

The average c of the oxyalkylene units of the polyoxyalkylene group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, still more preferably 4 to 35, particularly preferably 5 to 30.

When the average addition mole number is 1 or more, the stain reducing effect of the adherend (protected object) tends to be obtained efficiently. When the average addition mole number is more than 40, the viscosity of the adhesive composition increases, and the application tends to be difficult. The terminal of the oxyalkylene chain may be a hydroxyl group as it is, or may be substituted with another functional group or the like.

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

Examples of the oxyalkylene unit of the reactive monomer having a polyoxyalkylene chain include alkylene groups having 1 to 6 carbon atoms, and examples thereof include oxymethylene, oxyethylene, oxypropylene and oxybutylene groups. The hydrocarbon group of the oxyalkylene chain may be a straight chain or a branched chain.

The reactive monomer having a polyoxyalkylene chain is more preferably a reactive monomer having an ethylene oxide group. By using a (meth) acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, the compatibility of the base polymer with the polyoxyethylene compound (a) is improved, bleeding out to an adherend is suitably suppressed, and a pressure-sensitive adhesive composition having low staining properties is easily obtained.

Examples of the reactive monomer having a polyoxyalkylene chain include alkylene oxide (meth) acrylate adducts, and reactive surfactants having a reactive substituent such as an acryloyl group, a methacryloyl group, or an allyl group in the molecule.

Specific examples of the (meth) acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

Specific examples of the reactive surfactant include anionic reactive surfactants having a (meth) acryloyl group or allyl group, nonionic reactive surfactants, and cationic reactive surfactants.

The weight average molecular weight (Mw) of the (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b 1) is preferably 10 to 500 ten thousand, more preferably 20 to 200 ten thousand, and still more preferably 30 to 80 ten thousand. When the weight average molecular weight is more than 10 ten thousand, the cohesive force of the adhesive layer becomes appropriate, and the residual adhesive tends to be suppressed. On the other hand, when the weight average molecular weight is 500 ten thousand or less, the fluidity of the polymer is appropriate, and the wetting of the adherend is sufficient, so that the foaming occurring between the adherend and the pressure-sensitive adhesive layer of the surface protective film can be suppressed.

The weight average molecular weight is a value measured by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer constituting the acrylic adhesive (b 1) is preferably 0 ℃ or lower, more preferably-10 ℃ or lower (usually-100 ℃ or higher). When the glass transition temperature is higher than 0 ℃, the polymer does not flow easily and the wetting tends to be insufficient. In particular, by setting the glass transition temperature to-61 ℃ or lower, an adhesive layer having excellent wettability and light peelability can be easily obtained.

The glass transition temperature of the (meth) acrylic polymer can be adjusted within the above range by appropriately changing the monomer components and the composition ratio to be used.

The method of polymerization of the (meth) acrylic polymer is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization, and solution polymerization is a more preferable mode particularly from the viewpoint of handling properties and characteristics such as low staining property to an adherend (protected object). The polymer obtained may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.

When the urethane adhesive (B2) is used as the adhesive (B), any suitable urethane adhesive may be used. The urethane adhesive (b 2) preferably includes a urethane resin (urethane polymer) obtained by reacting a polyol with a polyisocyanate compound.

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

Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.

When a silicone adhesive is used for the adhesive layer, any suitable silicone adhesive can be used. As such a silicone adhesive, one obtained by mixing or aggregating silicone resins (silicone polymers, silicone components) can be preferably used.

Examples of the silicone adhesive include addition reaction-curable silicone adhesives and peroxide-curable silicone adhesives. Among these silicone-based adhesives, addition reaction curing type silicone-based adhesives are preferred in that peroxides (e.g., benzoyl peroxide) are not used and decomposition products are not generated.

As the curing reaction of the addition reaction curing type silicone-based adhesive, for example, when a polyalkyl silicone-based adhesive is obtained, a method of curing a polyalkyl hydrogen siloxane composition using a platinum catalyst is generally exemplified.

In the adhesive composition of the present invention, the blending ratio of the polyoxyethylene compound (a) and the adhesive (B) may be appropriately set according to the desired adhesive force. When the pressure-sensitive adhesive composition of the present invention is used in a pressure-sensitive adhesive layer of a surface protective film, the content of the polyoxyethylene compound (a) is preferably 0.01 to 20% by mass, more preferably 0.1 to 5.0% by mass, in the solid content of the pressure-sensitive adhesive composition.

In the present invention, the "solid component" refers to a component obtained by removing a solvent from a pressure-sensitive adhesive composition.

[ other ingredients ]

The binder composition of the present invention may contain the polyoxyethylene compound (a) and the binder (B), and may optionally contain other components such as various additives within a range not to impair the effects of the present invention.

The adhesive composition of the present invention preferably 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), a crosslinking agent is further contained, and the crosslinking is performed by appropriately adjusting the structural unit, the composition ratio, the selection and addition ratio of the crosslinking agent, and the like of the (meth) acrylic polymer, whereby a pressure-sensitive adhesive layer having more excellent heat resistance can be easily obtained.

As the crosslinking agent, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, and the like can be used, and particularly, the use of an isocyanate compound is a preferable embodiment. These compounds may be used alone or in combination of two or more.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene Diisocyanate (HDI) and dimer acid diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate (IPDI), aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4' -diphenylmethane diisocyanate and Xylene Diisocyanate (XDI), and polyisocyanate modifications obtained by modifying these isocyanate compounds by allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonimine bond and oxadiazinetrione bond.

Examples of commercially available products of the isocyanate compound include tradenames Takenate 300S, takenate, takenate 600, takenate D165N, takenate D178N (manufactured by Takara Shuzo Co., ltd.), SIMIDUR T80, SIMIDUR L, DESMOSAIL N3400 (manufactured by Sumitomo-Bayer Urethane K.K.), millino MR, millino MT, CORONATE L, CORONATE HL, and CORONATE (manufactured by Nippon Polyurethane Industry Co. Ltd.).

These isocyanate compounds may be used alone, or two or more kinds thereof may be used in combination, or a 2-functional isocyanate compound and a 3-functional isocyanate compound may be used in combination. When 2 or more kinds of crosslinking agents are mixed and used, both adhesiveness and repulsion resistance (adhesiveness to a curved surface) can be achieved, and a laminated film having more excellent adhesion reliability can be obtained.

Examples of the epoxy compound include N, N, N ', N' -tetraglycidyl-m-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi gas chemical Co., ltd.), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi gas chemical Co., ltd.), and the like.

Examples of the melamine resin include hexamethylolmelamine.

Examples of the aziridine derivative include trade names HDU, TAZM and TAZO (available from CRKOKAI Co., ltd.) which are commercially available.

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

The content of the crosslinking agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass, based on 100 parts by mass of the (meth) acrylic polymer used in the acrylic pressure-sensitive adhesive (b 1). By using a crosslinking agent in this range, the cohesive strength of the obtained pressure-sensitive adhesive layer is appropriate, sufficient heat resistance is easily obtained, and the residual adhesive is suppressed.

The crosslinking agent may be used alone in 1 kind, or two or more kinds may be used in combination.

The adhesive composition may contain a crosslinking catalyst for allowing any of the above crosslinking reactions to proceed more efficiently.

<xnotran> , , , ( ) , ( -5283 zxft 5283- ) , ( -5329 zxft 5329- ) , ( -5657 zxft 5657- ) , (5- -3264 zxft 3264- ) , ( -3282 zxft 3282- ) , (6- -3434 zxft 3434- ) , (3825 zxft 3825- -3638 zxft 3638- ) , ( -3724 zxft 3724- ) , ( -4924 zxft 4924- ) , (6242 zxft 6242- -8583 zxft 8583- ) , ( -9843 zxft 9843- ) , (1- -3524 zxft 3524- ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , ( ) , </xnotran> Iron-based catalysts such as iron tris (sec-butyl propionylacetate), iron tris (tert-butyl propionylacetate), iron tris (benzyl acetoacetate), iron tris (dimethyl malonate), iron tris (diethyl malonate), trimethoxyiron, triethoxy iron, triisopropoxy iron, iron chloride and the like. One kind of these crosslinking catalysts may be used, or two or more kinds may be used in combination.

The content of the crosslinking catalyst is not particularly limited, and is, for example, preferably about 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylic polymer. When the content is within the above range, the crosslinking reaction speed is high and the pot life of the pressure-sensitive adhesive composition is long in forming the pressure-sensitive adhesive layer, which is a preferable embodiment.

< laminated film >

The laminated film of the present invention includes an adhesive layer and a base material layer, and the adhesive layer is a layer formed using the adhesive composition of the present invention.

The laminate film of the present invention can be produced by coating the pressure-sensitive adhesive composition of the present invention on at least one surface of a base material layer and crosslinking the coating. The laminate film of the present invention may be produced by transferring a pressure-sensitive adhesive layer obtained by previously crosslinking the pressure-sensitive adhesive composition of the present invention onto at least one side of a base material layer.

The method for forming the pressure-sensitive adhesive layer on the base layer is not particularly limited, and for example, the pressure-sensitive adhesive composition (solution) of the present invention is applied to a base material, and the polymerization solvent or the like is dried and removed to form the pressure-sensitive adhesive layer on the base material. After that, curing may be performed for the purpose of adjusting the migration of components of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like.

When the pressure-sensitive adhesive composition is applied to a substrate to prepare a laminate film, one or more solvents other than the polymerization solvent may be newly added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive composition can be uniformly applied to the substrate.

As a method for forming the pressure-sensitive adhesive layer in the production of the laminated film of the present invention, a known method used for producing pressure-sensitive adhesive tapes can be used. Specifically, for example, extrusion coating methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The laminated film of the present invention is usually produced so that the thickness of the pressure-sensitive adhesive layer is about 1 to 200. Mu.m, preferably about 3 to 100. Mu.m. When the thickness of the pressure-sensitive adhesive layer is within this range, a proper balance between removability and adhesiveness can be easily obtained, and therefore, the pressure-sensitive adhesive layer is preferable.

The total thickness of the laminated film of the present invention is preferably 1 to 400. Mu.m, more preferably 10 to 200. Mu.m, and most preferably 20 to 150. Mu.m. When the total thickness of the laminated film is within this range, the adhesive properties (removability, adhesiveness, etc.), handling properties, and appearance properties are excellent, and this is a preferred embodiment.

The "total thickness" refers to the total thickness of all layers including the base layer, the pressure-sensitive adhesive layer, and the antistatic layer of the laminated film.

The substrate layer constituting the laminated film of the present invention is not particularly limited, and for example, a substrate excellent in characteristics such as transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, flexibility, and dimensional stability is preferably used. In particular, by imparting flexibility to the base material, the adhesive composition can be applied by a roll coater or the like and can be wound up in a roll form, which is useful.

Examples of the substrate include polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetylcellulose and triacetylcellulose; a polycarbonate-series polymer; acrylic polymers such as polymethyl methacrylate; and the like as a main resin component (a component constituting the main component of the resin component, typically 50 mass% or more).

Other examples of the resin material include styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; a vinyl chloride polymer; polyamide polymers such as nylon 6, nylon 6,6, and aromatic polyamides.

Examples of the resin material include imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, and epoxy polymers.

The base material may be a mixture of 2 or more of the above polymers.

As the substrate, a plastic film made of a transparent thermoplastic resin material can be preferably used. Among the plastic films, a polyester film is more preferable. The polyester film is mainly composed of a polymer material (polyester resin) having a main skeleton based on ester bonds, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. The polyester film has preferable characteristics as a base material of a surface protective film, such as excellent optical characteristics and dimensional stability.

The resin material constituting the substrate may contain various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a colorant (a pigment, a dye, or the like), an antistatic agent, and an antiblocking agent, as needed. 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, or coating with a primer.

The laminated film of the present invention may have an antistatic layer on a base material layer, and a plastic film subjected to antistatic treatment may be used as the base material. The use of such a base material is preferable because electrification of the film itself at the time of peeling is suppressed.

Further, the base material is a plastic film, and by subjecting the plastic film to antistatic treatment, a plastic film which is reduced in electrification of the laminated film itself and has excellent antistatic ability against an adherend can be obtained. The method for imparting the antistatic function is not particularly limited, and conventionally known methods can be used, and examples thereof include a method of applying an antistatic resin containing an antistatic agent and a resin component, a conductive polymer, and a conductive resin of a conductive substance, a method of vapor deposition or plating of a conductive substance, and a method of kneading an antistatic agent. When an antistatic agent is used, a lubricant may also be used in combination.

The thickness of the substrate layer is usually 5 to 200. Mu.m, preferably about 10 to 100. Mu.m. When the thickness of the substrate layer is within the above range, the adhesion workability to an adherend and the peeling workability from an adherend are excellent, and therefore, the thickness is preferable.

In the laminated film of the present invention, a separator may be bonded to the surface of the pressure-sensitive adhesive layer as necessary for the purpose of protecting the pressure-sensitive adhesive surface.

The material constituting the separator may be paper or a plastic film, and a plastic film is suitably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

The thickness of the separator is usually 5 to 200. Mu.m, preferably about 10 to 100. Mu.m. When the content is within the above range, the adhesion workability to the pressure-sensitive adhesive layer and the peeling workability from the pressure-sensitive adhesive layer are excellent, and therefore, the content is preferable. If necessary, the separator may be subjected to a mold release or antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agent, silica powder or the like, or an antistatic treatment such as a coating type, a kneading type, or a vapor deposition type.

The laminated film of the present invention can be suitably used as a surface protective film for optical members and the like. The laminated film of the present invention is also excellent in stability over time and can be used for surface protection in processing, transportation, shipment, and the like, and therefore is useful for protecting the surface of an optical member such as a polarizing plate.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the following description and tables, "part" and "%" represent a mass basis, a solid content or an effective component unless otherwise specified.

The evaluation in the examples was performed as follows.

< adhesion >

The obtained laminated films were respectively pressure-bonded to a glass plate by reciprocating a 2kgf roller 1 time, and after 24 hours from the bonding, the adhesive force was measured by using an adhesion/film peeling analyzer VPA-3 (manufactured by synechiae). The measurement conditions are as follows. The adhesive force was evaluated in 2 modes of a case where the stretching speed and the peeling speed were set to 150 mm/min and a case where the stretching speed and the peeling speed were set to 1200 mm/min.

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

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

Peeling direction: 180 degree

Sample size: 25mm x 70mm

< evaluation of adhesion alignment >

From the measurement results of the adhesive force, the adhesive force of the laminated film was evaluated according to the following criteria.

Very good: an adhesive force of 50mN/25mm or less at a drawing speed of 150 mm/min and an adhesive force of 100mN/25mm or less at a drawing speed of 1200 mm/min

O: an adhesive force of 50mN/25mm or less at a drawing speed of 150 mm/min, or an adhesive force of 100mN/25mm or less at a drawing speed of 1200 mm/min

X: an adhesive force at a drawing speed of 150 mm/min exceeds 50mN/25mm, and an adhesive force at a drawing speed of 1200 mm/min exceeds 100mN/25mm

< residual gum >

The obtained laminated film was attached to a glass plate in the same manner as in the measurement of the adhesive force. After storage at 40 ℃ for 1 week, the film was peeled off, and the residue on the glass plate was visually evaluated according to the following criteria.

O: no residual glue on the glass plate

X: a part of the glass plate is provided with residual glue

Synthesis example 1

30g of a block copolymer of ethylene oxide and propylene oxide represented by the following formula (1-1-1), 2.8g of acrylic acid, 64g of toluene as a solvent, 0.03g of phenothiazine as a polymerization inhibitor, and 0.6g of methanesulfonic acid as a catalyst were put into a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, and stirring was started under an air stream, and the flask was heated to 120 ℃ and refluxed to dehydrate. After confirming that 0.63g was dehydrated, it was cooled to 65 ℃ and neutralized with triethylamine. After neutralization, the temperature was raised to 85 ℃, 2.3g of ion-exchanged water was added, and liquid separation was performed to extract the lower layer. The pH of the lower layer was measured, and the washing operation was repeated until the pH was 7 or more. After cooling, the mixture was diluted with toluene to obtain a toluene solution containing 55 mass% of a mixture (1-1) of 3 kinds represented by the following formulae (1-1-1) to (1-1-3).

300.00g of toluene was added to a glass flask, and the temperature was raised to 105 ℃ under a nitrogen stream with stirring. Next, the following dropping liquids were respectively mounted on the dropping device: a dropping solution prepared by mixing 14.25g of 2- (perfluorohexyl) ethyl acrylate, 194.73g of the mixture (1-1), 99.05g of toluene and 11.25g of PERBUTYL O (manufactured by Nichikoku corporation) as an initiator, and a dropping solution prepared by dissolving 30.00g of toluene in 28.65g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC Co., ltd., silaplane FM-0721K), were added dropwise over 4 hours while keeping the temperature in the flask at 105 ℃. After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 10 hours. After the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (1).

The polyoxyethylene compound (1) as a copolymer was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC), and the weight average molecular weight Mw was 16200.

Synthesis example 2

A glass flask was charged with 300.00g of toluene, and the temperature was raised to 105 ℃ under a nitrogen stream with stirring. Next, the following dropping liquids were mounted on the dropping device: a dropping solution prepared by mixing 2- (perfluorohexyl) ethyl acrylate 42.90g, a mixture (1-1) 194.73g, toluene 129.05g, and an initiator PERBUTYL O (manufactured by Nichikoku Co., ltd.) 11.25g was added dropwise over 4 hours while maintaining the inside of the flask at 105 ℃. After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 10 hours. After the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (2).

The polyoxyethylene compound (2) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 12700.

Synthesis example 3

A glass flask was charged with 300.00g of toluene, and the temperature was raised to 105 ℃ under a nitrogen stream with stirring. Next, the following dropping liquids were mounted on the dropping device: a dropping solution was prepared by mixing 42.90g of a monomethacrylate compound having a polysiloxane bond (Silaplane FM-0721K, JNC K Co., ltd.), 194.73g of a mixture (1-1), 129.05g of toluene, and 11.25g of an initiator PERBUTYL O (manufactured by Nichikoku Co., ltd.), and the dropping solution was added dropwise over 4 hours while keeping the temperature in the flask at 105 ℃. After the end of the dropwise addition, the mixture was stirred at 105 ℃ for 10 hours. After the reaction, the solvent was distilled off to obtain a polyoxyethylene compound (3).

The polyoxyethylene compound (3) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 19100.

Synthesis example 4

Methyl Ethyl Ketone (MEK) 225.00g was added to a glass flask and the temperature was raised to 80 ℃ with stirring in a nitrogen stream. Next, the following dropping liquids were respectively mounted on the dropping device: a dropping solution prepared by mixing 22.50g of 2- (perfluorohexyl) ethyl acrylate, 7.50g of polyethylene glycol monoacrylate (Blemmer AE-400, manufactured by Nippon oil Co., ltd.), 82.65g, MEK 150.00g, and 2,2' -azobis (isobutyric acid) dimethyl ester (MAIB, manufactured by Wako pure chemical industries, ltd.), 44.85g of a monomethacrylate compound having a polysiloxane bond (JNC, manufactured by Silaplane FM-0721K) was dissolved in 75.00g of MEK, and two dropping solutions were added dropwise over 4 hours while keeping the temperature in the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 2 hours. Thereafter, a mixture of 0.75g of MAIB and 7.50g of MEK was added dropwise over 15 minutes while keeping the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 9 hours. After the reaction was completed, the solvent was distilled off to obtain a polyoxyethylene compound (4).

The polyoxyethylene compound (4) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 9100.

Synthesis example 5

Methyl Ethyl Ketone (MEK) 225.00g was added to a glass flask and the temperature was raised to 80 ℃ with stirring in a nitrogen stream. Next, the following dropping liquids were mounted on the dropping device: a dropping solution prepared by mixing 7.50g of 2- (perfluorohexyl) ethyl acrylate, polyethylene glycol monoacrylate (Blemmer AE-400, manufactured by Nichikoku K.K.), 82.65g, MEK 225.00g, and 2,2' -azobis (isobutyric acid) dimethyl ester (MAIB, manufactured by Wako pure chemical industries, ltd.) and a dropping solution prepared by dissolving 44.85g of a monomethacrylate compound having a polysiloxane bond (JNC, manufactured by Silaplane FM-0721K) in 75.00g of MEK were added dropwise over 4 hours while keeping the temperature in the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 2 hours. Thereafter, a mixture of MAIB0.75g and MEK7.50g was added dropwise over 15 minutes while keeping the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 9 hours. After the reaction was completed, the solvent was distilled off to obtain a solution containing 25 mass% of the polyoxyethylene compound (5).

The polyoxyethylene compound (5) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 9600.

Synthesis example 6

Methyl Ethyl Ketone (MEK) 225.00g was charged to a glass flask and heated to 80 ℃ with stirring in a stream of nitrogen gas. Next, the following dropping liquids were set on the dropping device: a dropping solution prepared by mixing 67.35g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC K.K., silaplane FM-0721K), 67.35g of polyethylene glycol monoacrylate (manufactured by Nikkiso K.K., blemmer AE-400), 82.65g, MEK 225.00g, and 7.50g of an initiator 2,2' -azobis (isobutyric acid) dimethyl ester (manufactured by Wako pure chemical industries, inc., MAIB) and 44.85g of a monomethacrylate compound having a polysiloxane bond (manufactured by JNC K.K., silaplane FM-0721K) were dissolved in 75.00g of MEK was added dropwise to the mixture, and two kinds of dropping solutions were added dropwise over 4 hours while keeping the temperature in the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 2 hours. Thereafter, a mixture of 0.75g of MAIB and MEK7.50g of MEK7 was added dropwise over 15 minutes while keeping the flask at 80 ℃. After the completion of the dropwise addition, the mixture was stirred at 80 ℃ for 9 hours. After the reaction was completed, the solvent was distilled off to obtain a solution containing 25 mass% of the polyoxyethylene compound (6).

The polyoxyethylene compound (6) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 10200.

Synthesis example 7

A glass flask was charged with 100.00g of butyl acetate, and the temperature was raised to 95 ℃ under a nitrogen stream with stirring. Next, the following dropping liquids were respectively mounted on the dropping device: a mixture of 35.00G of 2- (perfluorohexyl) ethyl acrylate, 65.00G of methoxypolyethylene glycol #1000 methacrylate (M230G, manufactured by Mizhongcun chemical industry Co., ltd.), and 5363G of butyl acetate (170.00G), and a mixture of 10.00G of PERBUTYL O dissolved in 30.00G of butyl acetate were added dropwise over 3 hours while keeping the temperature in the flask at 95 ℃. After the end of the dropwise addition, stirring was carried out at 95 ℃ for 9 hours, thereby obtaining a solution containing 25 mass% of the polyoxyethylene compound (7).

The polyoxyethylene compound (7) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 12700.

Synthesis example 8

A glass flask was charged with methyl isobutyl ketone (MIBK) 128.29g and heated to 90 ℃ with stirring in a stream of nitrogen gas. Next, the following dropping liquids were respectively installed in the dropping device: two kinds of drips were added dropwise over 2 hours while keeping the temperature in the flask at 90 ℃ while mixing 30.40g of 2- (perfluorohexyl) ethyl acrylate, 65.85g of propylene glycol/polytetramethylene glycol monomethacrylate (manufactured by Nippon oil Co., ltd., blemmer 10 PPB-500B), 65.85g of MIBK 76.94g of MIBK K19.34g and 5.77g of PERBUTYL O (manufactured by Nippon oil Co., ltd.). After the completion of the dropwise addition, the mixture was stirred at 90 ℃ for 10 hours. After the completion of the reaction, the solvent was distilled off to obtain polyoxyalkylene compound (8).

Polyoxyalkylene compound (8) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 9100.

Synthesis example 9

A glass flask was charged with methyl isobutyl ketone (MIBK) 306.36g and heated to 105 ℃ with stirring in a stream of nitrogen gas. Next, the following dropping liquids were respectively mounted on the dropping device: a mixture of 97.11g of 2- (perfluorohexyl) ethyl acrylate, 209.24g of polypropylene glycol monomethacrylate (manufactured by Nippon oil Co., ltd., blemmer PP-1000), and 3242 g of MIBK 222.35g, and a mixture of 15.32g of MIBK K153.18g of initiator PERBUTYL O (manufactured by Nippon oil Co., ltd.), and both were added dropwise over 3 hours while keeping the temperature in the flask at 105 ℃. After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 3 hours. Thereafter, a mixture of 1.53g of PERBUTYL O and 15.32g of MIBK was added dropwise over 15 minutes while keeping the flask at 105 ℃. After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 7.5 hours. After the reaction was completed, the solvent was distilled off to obtain polyoxyalkylene compound (9).

The polyoxyalkylene compound (9) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 5900.

Synthesis example 10

A glass flask was charged with 100.00g of butyl acetate, and the temperature was raised to 95 ℃ under a nitrogen stream with stirring. Next, the following dropping liquids were respectively mounted on the dropping device: a dropping solution prepared by mixing 30.00g of 2- (perfluorohexyl) ethyl acrylate, 60.00g of hydroxyethyl acrylate, 10.00g of methyl methacrylate and 5363 g of butyl acetate 170.00g and a dropping solution prepared by dissolving 10.00g of PERBUTYL O in 30.00g of butyl acetate were added dropwise over 3 hours while keeping the temperature in the flask at 95 ℃. After the completion of the dropwise addition, the mixture was stirred at 95 ℃ for 9 hours. After the reaction, the solvent was distilled off to obtain a fluorine-containing compound (10).

The fluorine-containing compound (10) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 4200.

Example 1

2.9 parts of D-100K (manufactured by DIC Co., ltd.) as a curing agent (crosslinking agent) and 0.5 part of the solid content of the obtained polyoxyethylene compound (1) were added to 100 parts of the solid content of an acrylic pressure-sensitive adhesive (manufactured by CT-3088 DIC Co., ltd.), and diluted with methyl ethyl ketone so that the solid content became 35%, followed by thorough mixing.

The obtained adhesive composition was directly applied to a corona-treated surface of a polyester film having a thickness of 50 μm as a base material using a bar coater (PI-1210: テスタ Co.) as an automatic coating apparatus so that the thickness of the adhesive layer after formation became 20 μm. After that, the film was dried at 85 ℃ for 3 minutes to form an adhesive layer, and then a 38 μm thick polyester film separator was coated with silicone to form a laminate film. The laminated film was further aged at 40 ℃ for 3 days to prepare a sample for evaluation test.

For the obtained laminated film, adhesion and residual gum were evaluated. The results are shown in Table 1.

Example 2

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

Example 3

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

Example 4

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

Example 5

A laminated film was produced and evaluated in the same manner as in example 1, except that the polyoxyethylene compound (5) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

Example 6

A laminated film was produced and evaluated in the same manner as in example 1, except that the polyoxyethylene compound (6) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

Example 7

A laminated film was produced and evaluated in the same manner as in example 1, except that the polyoxyethylene compound (7) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

The obtained pressure-sensitive adhesive composition was slightly cloudy, but cloudiness was not observed in the laminated film, and there was no problem in actual use.

Comparative example 1

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

Comparative example 2

A laminated film was produced and evaluated in the same manner as in example 1, except that the polyoxyalkylene compound (8) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

Comparative example 3

A laminated film was produced and evaluated in the same manner as in example 1, except that the polyoxyalkylene compound (9) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

Comparative example 4

A laminated film was produced and evaluated in the same manner as in example 1, except that the fluorine-containing compound (10) was used instead of the polyoxyethylene compound (1). The results are shown in Table 1.

[ Table 1]

Claims

1. An adhesive composition comprising a polyoxyethylene compound (a) and an adhesive (B), the polyoxyethylene compound (a) having: 1 or more selected from fluorinated alkyl groups (a 1) having 1 to 6 carbon atoms and silicone chains (a 3), and polyoxyethylene chains (a 2),

the polyoxyethylene compound (A) is a copolymer which uses 1 or more selected from (methyl) acrylate (x 1) with fluorinated alkyl of carbon number 1-6 and (methyl) acrylate (x 3) with organosilicon chain, and (methyl) acrylate (x 2) with polyoxyethylene chain with average value of repetition number of 2-50 as essential raw material.

2. The adhesive composition according to claim 1, wherein the polyoxyethylene compound (a) has the fluorinated alkyl group (a 1) having 1 to 6 carbon atoms.

3. The adhesive composition according to claim 1 or 2, wherein the molecular weight of the silicone chain (a 3) is in the range of 200 to 50000.

4. The binder composition according to claim 1 or 2, wherein the polyoxyethylene compound (a) has a fluorine atom content in a range of 1 to 50 mass%.

5. The adhesive composition according to claim 1 or 2, wherein the polyoxyethylene compound (a) has a weight average molecular weight in the range of 3000 to 300000.

6. The adhesive composition according to claim 1 or 2, wherein the (meth) acrylate (x 2) having a polyoxyethylene chain is a compound represented by the following formula (x 2-3) and/or (x 2-4),

in the formulae (x 2-3), (x 2-4), R ³ Is a hydrogen atom or a methyl group, a plurality of R ³ Optionally the same or different from each other,

R ⁴ and R ⁵ 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 of 2 or more,

m is an integer of 0 or more,

k is an integer of 0 or more,

n + m + k is in the range of 2 to 50.

7. The adhesive composition according to claim 1 or 2, wherein the (meth) acrylate (x 3) having a silicone chain is at least 1 of the compounds represented by the following formulae (x 3-1) to (x 3-7),

in the formulae (x 3-1) to (x 3-7), R ¹ Represents a hydrogen atom or a methyl group,

R ³ ～R ⁶ 、R ¹⁰ ～R ¹⁶ each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group,

R ² 、R ⁷ ～R ⁹ and R ¹⁸ ～R ¹⁹ Each independently represents 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 and y each independently represent an integer of 1 to 250.

8. The binder composition according to claim 1 or 2, wherein the content of the polyoxyethylene compound (a) is 0.01 to 20% by mass in the solid content of the binder composition.

9. The adhesive composition according to claim 1 or 2, wherein the adhesive (B) is an acrylic adhesive (B1) and/or a urethane-based adhesive (B2).

10. A laminated film, comprising: a bonding layer of the adhesive composition according to any one of claims 1 to 9, and a substrate layer.

11. The laminate film according to claim 10, which is a surface protective film for an optical member.