KR101807258B1 - Fluorine containing silylated polyurethane pressure sensitive adehesive and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a fluorine-containing silylated polyurethane pressure sensitive adhesive and, more specifically, to a pressure sensitive adhesive which has higher adhesiveness and less stickiness than existing silylated polyurethane pressure sensitive adhesives.

Description

FIELD OF THE INVENTION The present invention relates to a fluorinated silylated polyurethane pressure-sensitive adhesive, and a method for producing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a fluorine-containing silylated polyurethane pressure-sensitive adhesive, and relates to a pressure-sensitive adhesive having a tackiness equal to or higher than that of a conventional silylated polyurethane pressure-sensitive adhesive and having a lower tackiness.

Silylated Polyurethane (SLPU) Pressure Sensitive Adhesive (PSA) is excellent in solvent resistance, Applications to the label, aviation, automotive and electronics industries are continuously expanding. A very important factor in this application field is the chemical resistance and solvent resistance to jet fuel, hydraulic oil, lubricating oil and the like.

The SLPU adhesive has a hybrid structure in the polymer chain, which is summarized as polyurethane that is crosslinked with silane, so that the unique properties of silicon and urethane are combined. SLPU adhesives are characterized by various chemical and physical properties of silicone and urethane, which are not found in other organic adhesives.

Alkoxy silane bonded at the terminal of SLPU enables a curing reaction at a low temperature in the presence of moisture, so that " one-component type room temperature curable pressure-sensitive adhesive " In addition, the silicone-introduced pressure-sensitive adhesive can also improve the adhesive properties to inorganic materials as compared with other organic pressure-sensitive adhesives. The polyurethane forming the basic skeleton of the SLPU adhesive has a polar bond with a functional group (N-H) capable of hydrogen bonding in the molecule, and thus provides strong adhesion to various adherends. In addition, polyurethane materials are more economical because they are cheaper than other adhesive materials.

However, SLPU adhesive increases surface tackiness as adhesive strength increases. If surface tackiness is high, workability is poor. If tape is repeatedly tacked off, contamination will occur and defects in the punching process are likely to occur.

An object of the present invention is to provide a pressure-sensitive adhesive which is less sticky than conventional silylated polyurethane (SLPU) and which has an adhesive strength equal to or higher than that of conventional silylated polyurethane (SLPU).

Another object of the present invention is to provide a novel fluorine-containing silylated polyurethane pressure-sensitive adhesive which comprises an alkoxysilane as a terminal and introducing fluorine into the main chain of the polyurethane.

The inventors of the present invention have found that by introducing fluorine into the main chain of polyurethane, the stickiness is further reduced by the reduction of the surface energy, thereby completing the present invention.

The present invention relates to a fluorine-containing silylated polyurethane pressure-sensitive adhesive containing a fluorine-containing compound structure in the main chain of a polyurethane and containing a hydrolyzable silyl group represented by the following general formula (1) at both ends.

[Chemical Formula 1]

* -OCONH-R ₁ -Si (R ₂ ) _a (OR ₃ ) _3-a

Wherein R ₁ is an alkylene group containing from 1 to 12 carbon atoms, R ₂ is an alkyl group containing from 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having from 1 to 6 carbon atoms , a is 0, 1 or 2;

The present invention also relates to a curable pressure-sensitive adhesive composition comprising the polyurethane pressure-sensitive adhesive and the curing catalyst.

The present invention also relates to a pressure-sensitive adhesive tape in which the curable pressure-sensitive adhesive composition is applied to the surface of a tape substrate or sheet substrate and laminated.

The present invention also relates to a process for producing a fluorine-containing silylated polyurethane pressure-sensitive adhesive, which comprises the steps of: a) reacting an isocyanate-terminated urethane prepolymer (A) with a fluorine-containing diol compound (B) to prepare a hydroxyl group-terminated fluorinated urethane prepolymer A first reaction step; And

b) a second reaction step of reacting the hydroxyl group-terminated fluorinated urethane prepolymer (C) with an isocyanate group-containing silane compound (D) to prepare a fluorine-containing silylated polyurethane (E);

.

The fluorine-containing silylated polyurethane pressure-sensitive adhesive according to the present invention exhibits physical properties equal to or higher than that of conventional silylated polyurethane (SLPU), and the tackiness is further reduced.

The fluorine-containing silylated polyurethane pressure-sensitive adhesive according to the present invention has improved wettability of a pressure-sensitive adhesive film as the tack is reduced, and workability is improved. The adhesive tape is easily peeled off and reattached, This has a low effect.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described more fully hereinafter with reference to the accompanying drawings, It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

One embodiment of the present invention is a fluorine-containing silylated polyurethane pressure-sensitive adhesive containing a fluorine-containing compound structure in a main chain of a polyurethane and containing a hydrolyzable silyl group represented by the following formula (1)

[Chemical Formula 1]

-OCONH-R ₁ -Si (R ₂ ) _a (OR ₃ ) _{3 -a}

Wherein R ₁ is an alkylene group containing from 1 to 12 carbon atoms, R ₂ is an alkyl group containing from 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having from 1 to 6 carbon atoms , a is 0, 1 or 2;

In one embodiment of the present invention, the fluorine-containing compound may have a structure represented by the following formula (2).

(2)

-OR ₄ -R ₅ -R ₆ -O- *

In Formula 2, R ₄ is selected from C ₁ to C ₁₀ alkylene, C ₁ to C ₁₀ alkoxysilene, and - (R ₇ O) _a R ₈ -

Wherein R ₅ is _{C 1 ~ (R f2 O)} C 10 in whole or in part, a fluorinated alkylene group, C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkoxyl xylene and _f3 -R O (R O _f1) of a _{b c} R _f3 -, < / RTI >

Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (R ₇ O) _d R ₈ -

The R < ₇ & R ₈ is alkylene of each independently a C ₁ ~ C _4,

_Wherein R _f1 and R _f2 are each independently a prefluorinated or partially fluorinated C ₁ -C ₈ alkylene and R _f3 is a prefluorinated or partially fluorinated C ₁ -C ₄ alkylene,

A and d are integers of 1 to 30, b and c are integers of 1 to 50,

Still another embodiment of the present invention is a curable pressure-sensitive adhesive composition comprising the polyurethane pressure-sensitive adhesive and the curing catalyst.

Further, another embodiment of the present invention is a pressure-sensitive adhesive tape wherein the curable pressure-sensitive adhesive composition is applied to the surface of a tape base material or a sheet base material and laminated.

The present invention also relates to a process for producing a fluorine-containing silylated polyurethane pressure-sensitive adhesive, which comprises the steps of: a) reacting an isocyanate-terminated urethane prepolymer (A) with a fluorine-containing diol compound (B) to prepare a hydroxyl group-terminated fluorinated urethane prepolymer A first reaction step; And

b) a second reaction step of reacting the hydroxyl group-terminated fluorinated urethane prepolymer (C) with an isocyanate group-containing silane compound (D) to prepare a fluorine-containing silylated polyurethane (E);

.

In one embodiment of the production process of the present invention, the isocyanate-terminated urethane prepolymer (A) is prepared by reacting a polyester polyol with a diisocyanate or a polyisocyanate in the presence of a urethane-forming reaction catalyst, wherein the NCO / OH equivalent ratio is more than 1 And the like.

In one embodiment of the production process of the present invention, the NCO / OH equivalence ratio of the polyester polyol and the diisocyanate or polyisocyanate during the preparation of the isocyanate-terminated urethane prepolymer (A) 1.01 to 4.0.

In one embodiment of the production method of the present invention, the isocyanate group-containing silane compound (D) may be represented by the following general formula (3).

(3)

OCN-R ₁ -Si (R ₂ ) _a (OR ₃ ) _{3 -a}

Wherein R ₁ is an alkylene group having from 1 to 12 carbon atoms, R ₂ is an alkyl group having from 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having from 1 to 6 carbon atoms And a is 0, 1 or 2.

In one embodiment of the production method of the present invention, the isocyanate group-containing silane compound (D) is at least one member selected from the group consisting of isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyl Isocyanato-1,1-dimethylethyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, Isocyanato-n-butyltrimethoxysilane, isocyanato-n-butyltriethoxysilane, isocyanatoethyltriethoxysilane, isocyanatoethyltriethoxysilane, isocyanatoethyltriethoxysilane, t-butyltriethoxysilane, isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, isocyanatomethyltriethoxysilane, 1-isocyanatomethyltrimethoxysilane, Ethoxy silane, 3-isocyanatopropyl triethoxy silane, isocyanato methyl methyl di 2-isocyanato-2-methylethyltriethoxysilane, isocyanatoisopropyltriethoxysilane, 4-isocyanato-n-isocyanatoethyltriethoxysilane, Butyl triethoxy silane, isocyanato-t-butyl triethoxy silane, or a mixture of two or more thereof.

In one embodiment of the production process of the present invention, the fluorine-containing diol compound (B) may be represented by the following general formula (4).

[Chemical Formula 4]

HO-R ₄ -R ₅ -R ₆ -OH

In Formula 4, R ₄ is selected from C ₁ to C ₁₀ alkylene, C ₁ to C ₁₀ alkoxysilene and - (R ₇ O) _a R ₈ -

Wherein R ₅ is _{C 1 ~ (R f2 O)} C 10 in whole or in part, a fluorinated alkylene group, C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkoxyl xylene and _f3 -R O (R O _f1) of a _{b c} R _f3 -, < / RTI >

Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (R ₇ O) _d R ₈ -

The R < ₇ & R ₈ is alkylene of each independently a C ₁ ~ C _4,

_Wherein R _f1 and R _f2 are each independently a prefluorinated or partially fluorinated C ₁ -C ₈ alkylene and R _f3 is a prefluorinated or partially fluorinated C ₁ -C ₄ alkylene,

A and d are integers of 1 to 30, b and c are integers of 1 to 50,

In one embodiment of the production method of the present invention, the fluorine-containing diol compound (B) may be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the isocyanate-terminated urethane prepolymer (A).

In one embodiment of the production method of the present invention, the isocyanate group-containing silane compound (D) has an NCO / OH equivalent ratio of It may be added in a content ranging from 0.01 to 0.90.

Hereinafter, the fluorine-containing silylated polyurethane pressure-sensitive adhesive of the present invention and a method for producing the same will be described in more detail.

The method for producing the fluorine-containing silylated polyurethane pressure-sensitive adhesive of the present invention can be briefly described in the following reaction formula (1). The following Reaction Scheme 1 is intended to illustrate one example only, but is not limited thereto.

[Reaction Scheme 1]

1) Synthesis of hydroxy group-terminated fluorinated urethane prepolymer (C)

2) Synthesis of fluorine-containing silylated polyurethane (E)

First, the process for producing the hydroxyl group-terminated fluorinated urethane prepolymer (C), which is the first reaction step of the present invention, will be described. The first reaction is a reaction in which the fluorine-containing diol compound (B) is reacted with the isocyanate-terminated urethane prepolymer .

The isocyanate-terminated urethane prepolymer (A) may be one prepared by a polymerization reaction of a polyester polyol with a diisocyanate or a polyisocyanate. Wherein the polymerization is carried out in the presence of a urethane-forming reaction catalyst by reacting an excess of diisocyanate or polyisocyanate with the polyester polyol. The NCO / OH equivalent ratio of the polyester polyol to the diisocyanate or polyisocyanate is more than 1, more specifically, A urethane prepolymer having an isocyanate group as a terminal group in the range of 1.01 to 4.0 can be prepared. When the NCO / OH equivalent ratio is less than 1, a hydroxy-terminated urethane prepolymer may be prepared. The reaction temperature may be 60 ° C to 90 ° C, and the reaction time may be 2 to 48 hours.

The polyisocyanate means an organic compound having two or more isocyanate groups. Specific examples of the polyisocyanate include, but are not limited to, those commonly used in the art, and specific examples thereof include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate , Various liquid diphenylmethane diisocyanates including mixtures of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,4-isomers and 4,4'-isomers, Desmodur N ), And the like, and mixtures thereof.

The polyester polyol may have at least two or more hydroxy end groups. More preferably, a polyester polyol having 2 to 5 hydroxyl group terminal groups can be used.

The polyester polyol may be one obtained by reacting a polybasic acid component and a polyhydric alcohol component.

Examples of the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2- 2-cyclohexane dicarboxylic acid, 2-cyclohexanedicarboxylic acid, 2-cyclohexanedicarboxylic acid, 2-cyclohexane dicarboxylic acid, 2-cyclohexane dicarboxylic acid, 5-norbornanecarboxylic acid, 1,4-naphthalic acid, diphenic acid, 4,4'-oxybenzoic acid, diglycolic acid, thiodipropionic acid and 2,5-naphthalenedicarboxylic acid. The polybasic acid may be in the form of an acid anhydride, an ester, or a chloride.

Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , Neopentanediol, 2-methyl-1,3-propanol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, Ethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) Methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, Dihydroxyphenol, o-, m- and p-dihydroxybenzene, 4,4 '- (2-norbornylidene) - isopropylidene diphenol, 4,4'-isopropylidene bis (2,6-dichloro Phenol), 2,5-naphthalene diol, p-xylene diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and bisphenol A- And etherified diphenols such as water. A small amount of a polyhydric alcohol having three or more hydroxy groups may be optionally used in combination.

Examples of polyhydric alcohols having three or more hydroxyl groups include glycerin, trimethylol propane, 1,2,6-hexanetriol, trimethylol ethane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol. .

The polyester polyol may have a weight average molecular weight of 500 to 15,000 g / mol, more preferably 1000 to 10,000 g / mol. The weight average molecular weight is measured by gel permeation chromatography after dissolving the sample in tetrahydrofuran (THF), which is a mobile phase solvent, and the measurement is made using polymethyl methacrylate standard material as a standard material .

The catalyst used in the synthesis of the polyurethane prepolymer is not limited as long as it is a urethane forming reaction catalyst commonly used in the field, and specifically, for example, a catalyst of organic amine and organotin can be used. Specifically, it may include, for example, dialkyltin dicarboxylate, a tertiary amine, a primary tin salt of a carboxylic acid such as stannous octylate and stannous acetate, and the like. More specifically, there can be mentioned, for example, tin octylate, monobutyltin triacetate, monobutyltin monoctylate, monobutyltin monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, Organic tin compounds such as dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate, organic titanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate, and organic titanium compounds such as triethylamine, N, N, N, N ', N'-tetramethylethylenediamine, and triethylenediamine. These may be used alone or in admixture of two or more.

In order to prepare an isocyanate-terminated polyurethane prepolymer, a polyester polyol and / or a copolymer having an isocyanate group is terminated by using at least a slight excess of an isocyanate equivalent (NCO group) relative to the hydroxyl group equivalent (OH group). Advantageously, the molar ratio of NCO to OH depends on the choice of the particular hydroxy-terminated polyester polyol and / or copolymer, optional chain extender and optional non-butadiene-based polyol, but may be from 1.01 to 4.0 .

Next, the step of reacting the isocyanate-terminated urethane prepolymer (A) with the fluorine-containing diol compound (B) may be carried out under reflux conditions, specifically at 40 to 100 ° C for 1 to 10 hours have.

The fluorine-containing diol compound (B) means a compound containing fluorine in the molecule and having at least two or more hydroxy end groups, and may be represented by the following formula (4).

[Chemical Formula 4]

HO-R ₄ -R ₅ -R ₆ -OH

In Formula 4, R ₄ is selected from C ₁ to C ₁₀ alkylene, C ₁ to C ₁₀ alkoxysilene and - (R ₇ O) _a R ₈ -

Wherein R ₅ is _{C 1 ~ (R f2 O)} C 10 in whole or in part, a fluorinated alkylene group, C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkoxyl xylene and _f3 -R O (R O _f1) of a _{b c} R _f3 -, < / RTI >

Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (R ₇ O) _d R ₈ -

The R < ₇ & R ₈ is alkylene of each independently a C ₁ ~ C _4,

_Wherein R _f1 and R _f2 are each independently a prefluorinated or partially fluorinated C ₁ -C ₈ alkylene and R _f3 is a prefluorinated or partially fluorinated C ₁ -C ₄ alkylene,

A and d are integers of 1 to 30, b and c are integers of 1 to 50,

More specifically, in Formula 4,

Wherein R ₄ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (CH ₂ CH ₂ O) _a CH ₂ -

Wherein R ₅ is C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkylene, C all or a portion of the ₁ ~ C ₁₀ fluorinated alkoxyl xylene and _{CF 2 O (CF 2 CF 2} O) b (CF 2 O) of _c CF ₂ -, < / RTI >

Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (CH ₂ CH ₂ O) _d CH ₂ -

A and d may be an integer of 1 to 30, and b and c may be an integer of 1 to 50. [

More specifically, for example, those represented by the following formulas (5) and (6) can be used, but are not limited thereto.

[Chemical Formula 5]

HOCH ₂ (CF ₂ ) n CH ₂ OH

In Formula 5, n is an integer of 1 to 10.

[Chemical Formula 6]

HO (CH ₂ CH ₂ O) _a CH ₂ CF ₂ O (CF ₂ CF ₂ O) _b (CF ₂ O) _c CF ₂ CH ₂ (OCH ₂ CH ₂ ) _d OH

In the above formula (6), a and d are an integer of 1 to 30, and b and c are an integer of 1 to 50.

The fluorine-containing diol compound (B) may be added in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the isocyanate-terminated urethane prepolymer (A) It is preferable since the adhesive strength improvement and the stickiness reduction effect are excellent.

(FLUOROLINK E 10 / H (EW; 941 g / OHmol, MW = about 1882 g / mol) of Solvay, and the like.

When necessary, the polyester polyols are further added to the fluorine-containing diol compound (B) or the fluorine-containing diol compound (B), and the NCO / OH equivalents ratio is finally controlled. To participate in the reaction. In this case, the polyester polyol may be added in such an amount that the final NCO / OH equivalence ratio becomes 0.5 to 0.99.

If the NCO peak (2,267-2,270 cm ^-1 ) is not confirmed using FR-IR including the above procedure, it is the end point of the first step reaction.

Next, the second reaction step will be described.

The second reaction step is a step of reacting the hydroxyl group-terminated fluorinated urethane prepolymer (C) prepared by the first reaction step with an isocyanate group-containing silane compound (D) to prepare a fluorine-containing silylated polyurethane (E) 1 After the reaction temperature in the reaction step is lowered to 60 to 70 ° C, the isocyanate group-containing silane compound (D) is added and reacted under reflux conditions. In the second reaction step, the silylation may be carried out by reacting substantially all the hydroxyl groups of the hydroxyl group-terminated fluorinated urethane prepolymer (C) to obtain a completely silylated polyurethane polymer. In some cases, the pressure- It may be partially silylated to control the degree of crosslinking. It may be desirable to include a primary monoamine such as N-ethylbutylamine or a similar capping reagent in conjunction with the silane at the time of the partial silylation reaction since this amine readily capsules the isocyanate group to form a Which may interfere with the reaction. In order to achieve an operation that does not complete the silylation, the optimal amount of silane and optionally selected amine can be readily determined for a given isocyanate-terminated prepolymer using conventional experimental techniques.

In one embodiment of the present invention, 90% or more, more preferably 95% or more of the total hydroxyl groups present in the hydroxyl group-terminated fluorinated urethane prepolymer (C) may be silylated and suitable for use as a carcinogen . From the above viewpoint, the isocyanate group-containing silane compound (D) has an NCO / OH equivalent ratio of It is preferably added in a content of 0.01 to 0.90.

The isocyanate group-containing silane compound (D) may be represented by the following general formula (3), but is not limited thereto.

(3)

OCN-R ₁ -Si (R ₂ ) _a (OR ₃ ) _3-a

Wherein R ₁ is an alkylene group having 1 to 12 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having 1 to 6 carbon atoms And a is 0, 1 or 2;

More specifically, the isocyanate group-containing silane compound (D) is at least one selected from the group consisting of isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 2 -Isocyanato-1,1-dimethylethyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, iso Isocyanato-n-propyltriethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, 4-isocyanato-n-butyltriethoxysilane, isocyanato- Isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, 3-isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, 3-isocyanatomethyltrimethoxysilane, Cyanato propyl triethoxy silane, isocyanato methyl methyl diethoxy silane, 3-iso Isocyanato-2-methylethyltriethoxysilane, isocyanatoisopropyltriethoxysilane, 4-isocyanato-n-butyltriethoxysilane, isocyanatoethyltriethoxysilane, Isocyanato-t-butyltriethoxysilane, and isocyanato-t-butyltriethoxysilane.

If the NCO peak (2,267-2,270 cm ^-1 ) is not confirmed using FR-IR including the above procedure, it is the end point of the second step reaction.

The present invention includes a curable pressure-sensitive adhesive composition comprising the fluorine-containing silylated polyurethane pressure-sensitive adhesive prepared by the above-mentioned production method.

The pressure-sensitive adhesive composition of the present invention may contain 20 to 50% by weight, more preferably 30 to 40% by weight, of the fluorine-containing silylated polyurethane pressure-sensitive adhesive in terms of solid content, It is not.

The pressure-sensitive adhesive composition of the present invention includes a curing catalyst. In addition to the curing catalyst, one or more of a filler, a tackifier, a silane adhesion promoter, a plasticizer, a solvent, a thixotropic agent, a UV stabilizer, .

During the curing process of the fluorine-containing silylated polyurethane pressure-sensitive adhesive, the alkoxy group of the silane group is hydrolyzed in the presence of water and condensed to form a stable Si-O-Si bond to form a crosslinked structure. The curing catalyst may be used without limitation as long as it is commonly used in a pressure-sensitive adhesive composition, and specifically, for example, a tin-based catalyst or an amine-based catalyst may be used. Specifically, it may include, for example, dialkyltin dicarboxylate, a tertiary amine, a primary tin salt of a carboxylic acid such as stannous octylate and stannous acetate, and the like. More specifically, for example, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannic acid, tin octylate, monobutyltin triacetate, monobutyltin monoctylate, monobutyltin mono Organic tin compounds such as acetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate, Titanate and tetra-n-butyl titanate, and organic titanium compounds such as triethylamine, N, N-diethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine and triethylenediamine. Tertiary amine and the like can be used, and any one or two or more kinds of them can be mixed and used. The content of the catalyst may be 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total solid content of the pressure-sensitive adhesive composition. But the curing rate can be appropriately controlled within the above range.

Further, the present invention includes the pressure-sensitive adhesive tape in which the curable pressure-sensitive adhesive composition is applied to the surface of the tape base material or sheet base material and laminated thereon.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

In the following Examples and Comparative Examples, physical properties were measured as follows.

1. Viscosity

The sample was prepared at 25 ° C and measured with a Brookfield viscometer DV2T LV at spindle # 64 at 50 rpm.

2. End point

The end point was determined by confirming the NCO peak (2,267-2,270 cm ^-1 ) using FT-IR. The instrument used was JASCO FT-IR 4100 and the sample was measured in the neat state.

3. Adhesion

A self-pressing device (Model: KP-M2290-2) equipped with a rubber roller having a weight of 2,000 ± 50 g was used as a test plate of the polished SUS 304 steel plate.

The pressure-sensitive adhesive films prepared in Examples and Comparative Examples were cut into sharp test pieces having a width of 1 inch to prepare five test pieces. The test piece was placed on a test plate within 15 seconds after the collection, and pressed at 5 mm / s. The test plate with the test specimen was allowed to stand for 10 minutes at a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5%.

Thereafter, a 180 ° peel test was performed at a speed of 300 ± 30 mm / min using an adhesion measuring device (Universal Testing Machine) to measure the adhesive strength.

4. Initial adhesion

A width of 10 mm and a length of 300 mm was cut out with a sharp blade to prepare four or more test pieces. After the angle of the swash plate of the ball tack tester (Ball Tack Tester) is 30 degrees, attach the test piece to the test plate and roll the ball at the starting line. The number of the ball was recorded by maximizing the non-movement. The larger the number of balls, the larger the size and weight of the ball.

[Example 1]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050

150 g of SS20N (neopentylglycol adipate) and 350 g of ethyl acetate were fed into a four-necked 1 L reactor equipped with a stirrer, a condenser, a nitrogen injection device and a heating device and having an OH value of 57.33 mgKOH / g as a polyester diol component. To reduce the moisture content of the mixture, the mixture was refluxed at 75 ± 2 ° C., cooled to 70 ° C., and 0.03 g of dibutyl tin dilaurate was added as a catalyst, followed by mixing for 15 minutes. Next, 21.15 g (NCO / OH = 1.44) of isophorone diisocyanate (IPDI) was added and stirred at 75 占 폚 for 2 hours under reflux conditions.

Then, 3 g of FLUOROLINK E 10 / H (Solvay, EW; 941 g / OHmol, MW = about 1882 g / mol) was added with stirring and reacted under reflux conditions for 2 hours.

150 g (cumulative NCO / OH = 0.72) of SS20N (Neopentylglycol adipate, OH value: 57.33 mgKOH / g) was added thereto and stirred under reflux conditions for 2 hours. When the NCO peak (2,267 ~ 2,270 cm ^-1 ) was not confirmed using FT-IR, the end point of the first step reaction was determined.

The reactor temperature was lowered to 70 캜, and 17.9 g (NCO / OH = 0.28) of 3-isocyanatopropyltrimethoxysilane (ICPTMS) was added thereto and stirred at reflux while maintaining the temperature at 75 ± 2 ° C. When the NCO peak was not confirmed using FT-IR, the reaction was terminated in the second step reaction.

When the solid content was out of the range of 50 ± 2%, the solid content was adjusted to 50 ± 2% by using ethyl acetate to obtain a viscosity of 140 cured fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050 was obtained.

2) Production of pressure-sensitive adhesive film

30 g of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050 (adjusted to a coating solid content of 36% by weight) and 13 g of ethyl acetate were put into a 200 ml beaker and sufficiently stirred with a glass rod.

0.13g of 1,3-Diacetoxy-1,1,3,3-tetrabutyl distannoxane was added as a curing catalyst and mixed thoroughly. Then, 0.19g of distilled water was added and thoroughly mixed. The mixture was allowed to stand at room temperature for 10 minutes to remove bubbles, Prepared.

The surface of the B3 size corona treated 38 μm thick PET film was coated with a baker (Baker Applicator YBA-5 type) to a thickness of 50 μm and then dried at room temperature for 30 minutes. After curing for 1 hour in a convection oven set at 120 ° C, the silicone coated release film was covered and stored at room temperature. The dry film thickness measured with a thickness gauge was 20 ± 2 μm.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 2]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 2050

In Example 1, 27.65 g (cumulative NCO / OH = 0.79) of isophorone diisocyanate (IPDI) was used in the first step reaction and 3-isocyanatopropyltrimethoxysilane (ICPTMS) 13.4 g (NCO / OH = 0.21) was used in place of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 2050 having a viscosity of 175 cps.

2) Production of pressure-sensitive adhesive film

Except that the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 2050 prepared in Example 1 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 3]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 3050

In Example 1, 30.05 g (cumulative NCO / OH = 0.86) of isophorone diisocyanate (IPDI) was used in the first step reaction and 3-isocyanatopropyltrimethoxysilane (ICPTMS) 8.9 g (NCO / OH = 0.14) was used in place of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 3050 having a viscosity of 150 cps.

2) Production of pressure-sensitive adhesive film

Except that the produced fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 3050 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 4]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 4050

In Example 1, 30.35 g (cumulative NCO / OH = 0.87) of isophorone diisocyanate (IPDI) was used in the first step reaction and 3-isocyanatopropyltrimethoxysilane (ICPTMS) 8.29 g (NCO / OH = 0.13) was used in place of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 4050 having a viscosity of 180 cps.

2) Production of pressure-sensitive adhesive film

Except that the produced fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 4050 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 5]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 5050

In Example 1, 31.05 g (cumulative NCO / OH = 0.89) of isophorone diisocyanate (IPDI) was used in the first step reaction and 3-isocyanatopropyltrimethoxysilane (ICPTMS) 7.0 g (NCO / OH = 0.11) was used in place of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 5050 having a viscosity of 200 cps.

2) Production of pressure-sensitive adhesive film

Except that the produced fluorinated silylated polyurethane pressure-sensitive adhesive FSLPU PSA 5050 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 6]

1) Production of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 6050

In Example 1, 31.75 g (cumulative NCO / OH = 0.91) of isophorone diisocyanate (IPDI) was used in the first step reaction and 3-isocyanatopropyltrimethoxysilane (ICPTMS) 5.7 g (NCO / OH = 0.09) was used in place of the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 6050 having a viscosity of 210 cps.

2) Production of pressure-sensitive adhesive film

Except that the produced fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 6050 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 7]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-2

A fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-2 having a viscosity of 145 cps was prepared in the same manner as in Example 1 except that 6 g of FLUOROLINK E 10 / H was used in the first step reaction in Example 1, .

2) Production of pressure-sensitive adhesive film

Except that the fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-2 prepared in Example 1 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Example 8]

1) Preparation of fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-3

A fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-3 having a viscosity of 150 cps was prepared in the same manner as in Example 1, except that 9 g of FLUOROLINK E 10 / H was used in the first reaction in Example 1, .

2) Production of pressure-sensitive adhesive film

Except that the produced fluorine-containing silylated polyurethane pressure-sensitive adhesive FSLPU PSA 1050-3 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 1]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 1080

A four liter 1 L reactor equipped with a stirrer, a condenser, a nitrogen injection device and a heating device was charged with 300 g of SS20N (Neopentylglycol adipate) and 85 g of ethyl acetate as polyester diol components with an OH value of 57.33 mgKOH / g and stirred. After refluxing to reduce the water content of the mixture, the mixture was cooled to 70 ° C and 0.03 g of dibutyl tin dilaurate was added as a catalyst, followed by mixing for 15 minutes. Next, 24.8 g (NCO / OH = 0.72) of isophorone diisocyanate (IPDI) was added, and the mixture was stirred at a temperature of 75 ± 2 ° C. When the NCO peak (2,267 ~ 2,270 cm-1) was not confirmed using FT-IR, the end point of the first step reaction was determined.

The reactor temperature was lowered to 70 占 폚, and 17.9 g (NCO / OH = 0.28) of 3-isocyanatopropyltrimethoxysilane (ICPTMS) was added thereto and stirred while maintaining the temperature at 75 占 占. When the NCO peak was not confirmed using FT-IR, the reaction was terminated in the second step reaction.

When the solid content was out of the range of 80 ± 2%, the solid content was adjusted to 80 ± 2% by using ethyl acetate to obtain a viscosity of 2,700 cps silylated polyurethane pressure-sensitive adhesive SLPU PSA 1080 was obtained.

2) Production of pressure-sensitive adhesive film

25 g of the prepared silylated polyurethane pressure-sensitive adhesive SLPU PSA 1080 and 30 g of ethyl acetate were placed in a 200 ml beaker and sufficiently stirred with a glass rod.

0.13g of 1,3-Diacetoxy-1,1,3,3-tetrabutyl distannoxane was added as a curing catalyst and mixed thoroughly. Then, 0.19g of distilled water was added and thoroughly mixed. The mixture was allowed to stand at room temperature for 10 minutes to remove bubbles, Prepared.

The surface of the B3 size corona treated 38 μm thick PET film was coated with a baker (Baker Applicator YBA-5 type) to a thickness of 50 μm and then dried at room temperature for 30 minutes. After curing for 1 hour in a convection oven set at 120 ° C, the silicone coated release film was covered and stored at room temperature. The dry film thickness measured with a thickness gauge was 20 ± 2 μm.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 2]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 2080

In Comparative Example 1, 27.3 g (NCO / OH = 0.79) of isophorone diisocyanate (IPDI) was used in the first step reaction and 13.4 g of 3-isocyanatopropyltrimethoxysilane (ICPTMS) (NCO / OH = 0.21) was used as the initiator, to obtain a silylated polyurethane pressure-sensitive adhesive SLPU PSA 2080 having a viscosity of 6,030 cps.

2) Production of pressure-sensitive adhesive film

Was prepared in the same manner as in Comparative Example 1, except that the silylated polyurethane pressure-sensitive adhesive SLPU PSA 2080 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 3]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 3080

In Comparative Example 1, 29.7 g (NCO / OH = 0.86) of isophorone diisocyanate (IPDI) was used in the first step reaction, and 8.9 g of 3-isocyanatopropyltrimethoxysilane (ICPTMS) (NCO / OH = 0.14) was used as the initiator, to obtain a silylated polyurethane pressure-sensitive adhesive SLPU PSA 3080 having a viscosity of 8,760 cps.

2) Production of pressure-sensitive adhesive film

Was prepared in the same manner as in Comparative Example 1, except that the silylated polyurethane pressure-sensitive adhesive SLPU PSA 3080 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 4]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 4080

In Comparative Example 1, 30.0 g (NCO / OH = 0.87) of isophorone diisocyanate (IPDI) was used in the first step reaction, 8.29 g of 3-isocyanatopropyltrimethoxysilane (ICPTMS) (NCO / OH = 0.13) was used as the initiator, to obtain a silylated polyurethane pressure-sensitive adhesive SLPU PSA 4080 having a viscosity of 8,760 cps.

2) Production of pressure-sensitive adhesive film

Was prepared in the same manner as in Comparative Example 1, except that the silylated polyurethane pressure-sensitive adhesive SLPU PSA 4080 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 5]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 5080

In Comparative Example 1, 30.7 g (NCO / OH = 0.89) of isophorone diisocyanate (IPDI) was used in the first step reaction, 7.02 g of 3-isocyanatopropyltrimethoxysilane (ICPTMS) (NCO / OH = 0.11) was used as the initiator, to obtain a silylated polyurethane pressure-sensitive adhesive SLPU PSA 5080 having a viscosity of 8,760 cps.

2) Production of pressure-sensitive adhesive film

Was prepared in the same manner as in Comparative Example 1, except that the silylated polyurethane pressure-sensitive adhesive SLPU PSA 5080 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

[Comparative Example 6]

1) Preparation of Silylated Polyurethane Pressure Sensitive Adhesive SLPU PSA 6080

In Comparative Example 1, 31.4 g (NCO / OH = 0.91) of isophorone diisocyanate (IPDI) was used in the first step reaction, 5.70 g of 3-isocyanatopropyltrimethoxysilane (ICPTMS) (NCO / OH = 0.09) was used in place of the silylated polyurethane pressure-sensitive adhesive SLPU PSA 6080 having a viscosity of 8,760 cps.

2) Production of pressure-sensitive adhesive film

Was prepared in the same manner as in Comparative Example 1, except that the silylated polyurethane pressure-sensitive adhesive SLPU PSA 6080 was used.

All physical properties were measured after one week and after post-curing, and are shown in Table 1 below.

First-step reaction
NCO / OH ratio Two-step reaction
NCO / OH ratio adhesiveness Initial adhesion
(Ball number) Example 1 0.72 0.28 600 4 Example 2 0.79 0.21 1,145 4 Example 3 0.86 0.14 1,418 5 Example 4 0.87 0.13 1,428 5 Example 5 0.89 0.11 1,777 6 Example 6 0.91 0.09 2,945 7 Example 7 0.72 0.28 600 3 Example 8 0.72 0.28 605 3 Comparative Example 1 0.72 0.28 423 7 Comparative Example 2 0.79 0.21 899 9 Comparative Example 3 0.86 0.14 1,332 11 Comparative Example 4 0.87 0.13 1,413 11 Comparative Example 5 0.89 0.11 1,656 12 Comparative Example 6 0.91 0.09 2,707 12

As shown in Table 1, it was found that the surface tack was reduced in Examples 1 to 6 as compared with Comparative Examples by containing fluorine in the polyurethane main chain as compared with Comparative Examples 1 to 6. Further, it was confirmed that the adhesive strength was further increased.

As the content of IPDI increases and the molecular weight increases, the adhesion tends to increase. The initial tack increases as the content of ICPTMS which introduces alkoxysilane into the molecule and introduces cross-linking structure by moisture curing increases Respectively.

Claims (12)

Containing silylated polyurethane containing a fluorine-containing compound structure in the main chain of the polyurethane and containing a hydrolyzable silyl group represented by the following formula (1) at both ends and the fluorine-containing compound has a structure represented by the following formula (2) adhesive.
[Chemical Formula 1]
* -OCONH-R ₁ -Si (R ₂ ) _a (OR ₃ ) _3-a
Wherein R ₁ is an alkylene group having 1 to 12 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having 1 to 6 carbon atoms Alkyl group, and a is 0, 1 or 2.
(2)
-OR ₄ -R ₅ -R ₆ -O- *
In Formula 2, R ₄ is selected from C ₁ to C ₁₀ alkylene, C ₁ to C ₁₀ alkoxysilene, and - (R ₇ O) _a R ₈ -
Wherein R ₅ is _{C 1 ~ (R f2 O)} C 10 in whole or in part, a fluorinated alkylene group, C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkoxyl xylene and _f3 -R O (R O _f1) of a _{b c} R _f3 -, < / RTI >
Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (R ₇ O) _d R ₈ -
The R < ₇ & R ₈ is alkylene of each independently a C ₁ ~ C _4,
Wherein R _f1 and R _f2 are each independently a prefluorinated or partially fluorinated C ₁ -C ₈ alkylene and R _f3 is a prefluorinated or partially fluorinated C ₁ -C ₄ alkylene,
A and d are integers of 1 to 30, b and c are integers of 1 to 50, delete A curable pressure-sensitive adhesive composition comprising the polyurethane pressure-sensitive adhesive of claim 1 and a curing catalyst. A pressure-sensitive adhesive tape according to claim 3, wherein the curable pressure-sensitive adhesive composition is applied to the surface of a tape base material or a sheet base material and laminated. a) a first reaction step of reacting an isocyanate-terminated urethane prepolymer (A) with a fluorine-containing diol compound (B) to prepare a hydroxyl group-terminated fluorinated urethane prepolymer (C); And
b) a second reaction step of reacting the hydroxyl group-terminated fluorinated urethane prepolymer (C) with an isocyanate group-containing silane compound (D) to prepare a fluorine-containing silylated polyurethane (E);
Containing silylated polyurethane pressure-sensitive adhesive. 6. The method of claim 5,
The isocyanate-terminated urethane prepolymer (A) is prepared by reacting a polyester polyol and a polyisocyanate in the presence of a urethane-forming reaction catalyst, and is produced by reacting an NCO / OH equivalent ratio of more than 1. The fluorinated silylated polyurethane A method for producing an adhesive. The method according to claim 6,
When the NCO / OH equivalent ratio is Containing silylated polyurethane pressure-sensitive adhesive of 1.01 to 4.0. 6. The method of claim 5,
Wherein the isocyanate group-containing silane compound (D) is represented by the following formula (3).
(3)
OCN-R ₁ -Si (R ₂ ) _a (OR ₃ ) _3-a
Wherein R ₁ is an alkylene group having 1 to 12 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, and R ₃ is independently an alkyl group having 1 to 6 carbon atoms And a is 0, 1 or 2; 9. The method of claim 8,
The isocyanate group-containing silane compound (D) is at least one compound selected from the group consisting of isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 2- 1,1-dimethylethyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, isocyanatoiso Propyltriethoxysilane, isocyanato-n-butyltrimethoxysilane, isocyanato-n-butyltriethoxysilane, isocyanato-t-butyltriethoxysilane, iso Isocyanatomethyltrimethoxysilane, 1-isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, isocyanatomethyltrimethoxysilane, 3-isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, Triethoxysilane, isocyanatomethylmethyldiethoxysilane, 3-isocyanatopropylmethyl Diethoxy silane, 2-isocyanato-2-methylethyl triethoxy silane, isocyanatoisopropyl triethoxy silane, 4-isocyanato-n-butyl triethoxy silane, isocyanato -t-butyltriethoxysilane, and t-butyltriethoxysilane. 2. The fluorinated silylated polyurethane pressure-sensitive adhesive according to claim 1, 6. The method of claim 5,
Wherein the fluorine-containing diol compound (B) is represented by the following formula (4).
[Chemical Formula 4]
HO-R ₄ -R ₅ -R ₆ -OH
In Formula 4, R ₄ is selected from C ₁ to C ₁₀ alkylene, C ₁ to C ₁₀ alkoxysilene and - (R ₇ O) _a R ₈ -
Wherein R ₅ is _{C 1 ~ (R f2 O)} C 10 in whole or in part, a fluorinated alkylene group, C ₁ ~ C ₁₀ in whole or in part, a fluorinated alkoxyl xylene and _f3 -R O (R O _f1) of a _{b c} R _f3 -, < / RTI >
Wherein R ₆ is selected from C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ alkoxysilene and - (R ₇ O) _d R ₈ -
The R < ₇ & R ₈ is alkylene of each independently a C ₁ ~ C _4,
Wherein R _f1 and R _f2 are each independently a prefluorinated or partially fluorinated C ₁ -C ₈ alkylene and R _f3 is a prefluorinated or partially fluorinated C ₁ -C ₄ alkylene,
A and d are integers of 1 to 30, b and c are integers of 1 to 50, 6. The method of claim 5,
Wherein the fluorine-containing diol compound (B) is added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the isocyanate-terminated urethane prepolymer (A). 6. The method of claim 5,
The isocyanate group-containing silane compound (D) has an NCO / OH equivalent ratio of 0.01 to 0.9, based on the total amount of the fluorinated silylated polyurethane pressure-sensitive adhesive.