WO2016003239A1

WO2016003239A1 - Adhesive composition for optical film, adhesive layer, adhesive type optical film, and display device

Info

Publication number: WO2016003239A1
Application number: PCT/KR2015/006882
Authority: WO
Inventors: 스와타츠히로; 오가와히로시
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-07-03
Filing date: 2015-07-03
Publication date: 2016-01-07

Abstract

An adhesive composition of the present invention includes an adhesive composition for an optical film, which contains an adhesive resin having an acid value of about 0 mgKOH/g to about 20.0 mgKOH/g, and a silicate oligomer represented by chemical formula 1, thereby allowing the compatibility of reworkability and reliability.

Description

Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive optical film and display device for optical film

The present invention relates to an adhesive composition for an optical film, an adhesive layer, an adhesive optical film, and a display device including the same.

The display device includes a display element such as a liquid crystal cell. Such display elements may affix various films according to a desired function and objective. For example, the liquid crystal cell includes a polarizing film on both sides in accordance with a unique image forming method. In addition to the polarizing film, the liquid crystal cell may further include a retardation plate, a viewing angle expanding film, a brightness enhancing film, various protective films, and the like for improving the image quality. Hereinafter, the film affixed on a display element is called an optical film collectively.

In general, the display element may include one or more optical films. For example, the optical film may be directly attached to the display element, or a plurality of optical films may be laminated to the display element. In such a case, the optical film may be attached to the display element or another optical film using an adhesive.

At this time, the optical film is often used in the form of an adhesive optical film having an adhesive layer formed on at least one surface. In the case of using the pressure-sensitive adhesive optical film, there is an advantage such that the drying step of the pressure-sensitive adhesive can be omitted.

However, when affixing an adhesive optical film to a display element, an error may arise at a bonding position or a foreign material may enter a bonding surface. In such a case, the display element is reused by peeling the optical film from the display element. Therefore, re-peelability (rework property) is calculated | required by the adhesive for optical films. Specifically, reworkability means that the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive for optical film does not destroy the display element during peeling, and does not leave contamination such as a residual adhesive on the display element during peeling.

In order to improve the rework property of the pressure-sensitive adhesive layer, the adhesive force of the pressure-sensitive adhesive for optical film should be lowered. This reworkability is more important for thinner optical films and display devices as in recent trends. For example, when the thickness of an optical film and a display element becomes thin due to thinning, their breaking strength becomes small. Therefore, the adhesive used for a thin optical film and a display element needs to further reduce adhesive force in order to prevent damage.

On the other hand, the adhesive also requires the reliability (durability) which can stably bind an optical film and an optical film or an optical film and a display element. However, in order to secure the reworkability of the pressure-sensitive adhesive layer, if the adhesive force of the pressure-sensitive adhesive is greatly reduced, the adhesion reliability may be greatly impaired. Thus, there exists a problem that it is very difficult to make reworkability and reliability of the adhesive for optical films compatible. This problem was not particularly easy to solve when the optical film and the display element were thin.

In JP2010-275524 A (hereinafter referred to as Patent Document 1), JP2008-503638 A (hereinafter referred to as Patent Document 2), JP1996-199130 A (hereinafter referred to as Patent Document 3) and JP1996-209103 A (hereinafter referred to as Patent Document 4), an adhesive A technique is disclosed. However, in the technique disclosed in Patent Documents 1 to 4, the aforementioned problems could not be solved.

In patent document 1, the adhesive composition for optical films containing the (meth) acrylic-type polymer and the polyether which has a reactive silyl group is proposed. However, the pressure-sensitive adhesive disclosed in Patent Literature 1 could not lower the adhesive force to a degree sufficient to rework the thin, thin optical film and the display element.

In addition, Patent Document 2 discloses an acrylic pressure-sensitive adhesive composition comprising an acrylic copolymer containing a hydroxyl group, but not containing a carboxyl group, a crosslinking agent, and a polyether modified polydimethylsiloxane copolymer having an HLB value of 4 to 13. . However, in the technique disclosed in Patent Document 2, it was difficult to secure durability.

Patent document 3 and 4 disclose the adhesive composition characterized by mix | blending a crosslinking agent and a silicate oligomer in acrylic resin. However, when the amount of carboxyl groups in the acrylic resin was large, the adhesive force could not be sufficiently lowered. For this reason, the technique of patent documents 3 and 4 was not able to ensure rework property with respect to especially a thin soft optical film and a display element.

An object of the present invention is to provide a pressure-sensitive adhesive composition for an optical film that is not only capable of achieving reworkability and reliability but also excellent in workability.

Another object of the present invention is to provide an adhesive layer formed of the pressure-sensitive adhesive composition for an optical film, an adhesive optical film, and a display device including the same.

The above and other objects of the present invention can be achieved by the present invention described below.

The pressure-sensitive adhesive composition for an optical film of the present invention includes an adhesive resin having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g, a silicate oligomer represented by the following Chemical Formula 1, and a crosslinking agent.

[Formula 1]

In Formula 1, R ₁ to R ₄ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100.

The pressure-sensitive adhesive layer of one embodiment of the present invention may be formed of the pressure-sensitive adhesive composition for the optical film.

A pressure-sensitive adhesive layer of another embodiment of the present invention is a pressure-sensitive adhesive layer formed of a composition comprising a (meth) acrylic polymer, a urethane polymer and a pressure-sensitive resin containing at least one of polyester, a silicate oligomer represented by the following formula (1) and a peroxide-based crosslinking agent And at a temperature of 23 ° C. and a humidity of 65% RH, the gel fraction according to Formula 1 may be about 40 wt% to about 95 wt% after being left for about 1 hour from the pressure-sensitive adhesive layer formation.

[Formula 1]

In Formula 1, R ₁ to R ₄ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, having 1 to 20 carbon atoms. An alkyl group or an aryl group having 6 to 20 carbon atoms, n is an integer of 1 to 100,

[Equation 1]

Gel fraction (% by weight) = {(Wc-Wa) / (Wb-Wa)} × 100

In Formula 1, Wb is a weight of about 0.2g of the adhesive layer wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin. In addition, Wc immersed the adhesive layer wrapped with the fluorine resin in about 40 ml of ethyl acetate at about 23 ° C. for about 7 days to extract the soluble component, and the adhesive layer wrapped with the fluorine resin on the aluminum cup at about 130 ° C. for about 2 hours. After drying, it is the weight of the adhesive layer wrapped with the fluorine resin from which the soluble component is removed.

The pressure-sensitive adhesive optical film of the present invention may include one of a polarizer, a protective layer formed on one surface of the polarizer, and the adhesive layer formed on the other surface of the polarizer.

The display device of the present invention may include the adhesive optical film.

The present invention is not only capable of achieving both reworkability and reliability, but also has an effect of providing a pressure-sensitive adhesive composition for an optical film, a pressure-sensitive adhesive layer, a pressure-sensitive adhesive optical film, and a display device including the same.

1 is a cross-sectional view showing a pressure-sensitive adhesive optical film according to an embodiment.

2 is a cross-sectional view showing a pressure-sensitive adhesive optical film of another embodiment.

3 is a cross-sectional view illustrating a display device according to one embodiment.

4 is a cross-sectional view illustrating a display device of another embodiment.

<광학 필름용 점착제 조성물><Adhesive composition for optical film>

The pressure-sensitive adhesive composition for an optical film of the present invention includes a pressure-sensitive resin, a silicate oligomer and a crosslinking agent having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g. Hereinafter, the composition for forming the adhesive composition for optical films of a specific example is demonstrated.

(A) adhesive resin

The adhesive resin of one embodiment has an acid value of about 0 mgKOH / g to about 20 mgKOH / g. Specifically, the adhesive resin has an acid value of about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mgKOH / g can be. In addition, the adhesive resin may have an acid value in a range of at least one of the above values and at most one of the above values. For example, the acid value of the adhesive resin may be about 10 mgKOH / g or less, more specifically about 3 mgKOH / g or less, and more specifically about 1 mgKOH / g or less. For example, the adhesive resin may have an acid value of more than about 0 mgKOH / g and about 20 mgKOH / g or less. The adhesive resin in the above range is excellent in the adhesion and reliability of the pressure-sensitive adhesive composition, it can be balanced with the reworkability.

Adhesive resin can contain as a structural unit the monomer containing a hydroxyl-containing monomer as a structural unit. For example, the hydroxyl group-containing monomer may include (meth) acrylate having a hydroxyl group, polyol, and the like, but is not limited thereto.

The adhesive resin is not particularly limited as long as it is adhesive and has an acid value of about 0 mgKOH / g to about 20 mgKOH / g. Such adhesive resins may include, for example, one or more of (meth) acrylic polymers, urethane polymers, and polyesters. The adhesive resin may be composed of any one of these, or may be composed of a mixture of these resins. Moreover, the adhesive resin may be a copolymer of these resins. When using such an adhesive resin, the adhesive composition is advantageous to satisfy the optical properties of the optical film.

The adhesive resin of one embodiment may include a (meth) acrylic polymer. The (meth) acrylic polymer includes a polymer containing an alkyl (meth) acrylate monomer as a polymerized unit constituting the main skeleton; Or a copolymer comprising an alkyl (meth) acrylate monomer and other comonomers as a polymerized unit (hereinafter, an alkyl (meth) acrylate copolymer).

The alkyl (meth) acrylate may be exemplified that the monomer has 1 to 18 carbon atoms of a linear or branched alkyl group. For example, the alkyl group is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, furnace A nil group, a decyl group, an isodecyl group, a dodecyl group, an isomyristyl, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. can be illustrated. These can be used individually or in combination. Specifically, the average carbon number of these alkyl groups may be 3 to 9.

The alkyl (meth) acrylate copolymer may be prepared by copolymerizing an alkyl (meth) acrylate monomer and one or more comonomers. The comonomer means a monomer polymerizable with an alkyl (meth) acrylate monomer, and is not particularly limited as long as it is polymerizable with the alkyl (meth) acrylate monomer. The at least one comonomer may have a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. In such a case, the adhesive resin may have improved adhesiveness or heat resistance.

The comonomer is, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as 8-hydroxyoctyl acrylic acid, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid, and (4-hydroxymethylcyclohexyl) -methyl acrylate; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; Styrene sulfonic acid or aryl sulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylic amido propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonate Sulfonic acid group-containing monomers such as phonic acid; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate and the like.

In addition, the comonomer is, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methyl (N-substituted) amide monomers such as allpropane (meth) acrylamide; (Meth) acrylic-acid alkylaminoalkyl type monomers, such as amino ethyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; Alkoxy alkyl (meth) acrylate monomers, such as (meth) acrylic-acid methoxyethyl and (meth) acrylate ethoxyethyl; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, N Succinimide-based monomers such as acryloyl morpholine; Maleimide monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenylmaleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itacon Itacone imide type monomers, such as mead and N-lauryl itacone imide; And the like. In this case, there may be a modification effect of the pressure-sensitive adhesive composition.

The comonomers are, for example, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole as modified monomers. Vinyl monomers such as vinylimidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, styrene, α-methyl styrene, and N-vinyl caprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Glycol-based acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, and (meth) acrylic acid methoxy polypropylene glycol; Acrylic ester ester monomers, such as (meth) acrylic acid tetrahydrofurfuryl, a fluorine (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate, can also be used. Moreover, isoprene, butadiene, isobutylene, vinyl ether, etc. can also be used.

In addition, the comonomer may include, for example, a silane monomer containing a silicon atom. Examples of the silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, and 4-vinylbutyltriethoxysilane. -Vinyl octyl trimethoxysilane, 8-vinyl octyl triethoxy silane, 10-methacryloyl oxydecyl trimethoxy silane, 10-acryloyl oxydecyl trimethoxy silane, 10-methacryloyl jade Cedyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

In addition, the comonomer is tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl Ether di (meth) acrylate, neopentylglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate (Meth) acrylic acid, such as a dipentaerythritol penta (meth) acrylate, a dipentaerythritol hexa (meth) acrylate, and a caprolactone modified dipentaerythritol hexa (meth) acrylate; (Meth) acryloyl groups, such as esterified substance with an polyhydric alcohol; And vinyl groups; It may contain a polyfunctional monomer having two or more unsaturated double bonds, such as.

The comonomer is a polyester (meth) acrylate in which two or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups are added to a skeleton such as polyester, epoxy, urethane, or the like as the monomer component. , Epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

The content of the comonomer is about 0% to about 20% by weight, about 0.1% to about 15% by weight, based on the total weight of the total monomers (monomers used as polymerized units of the alkyl (meth) acrylate copolymer), Specifically, about 0.1% to about 10% by weight. Within this range, the pressure-sensitive adhesive composition is advantageous for achieving both reworkability and reliability.

The (meth) acrylic copolymer of one embodiment may use a hydroxyl group-containing monomer as a comonomer. In this case, the adhesiveness and durability of the pressure-sensitive adhesive composition can be improved. Since the hydroxyl group-containing monomer is rich in reactivity with the crosslinking agent, the cohesiveness and heat resistance of the pressure-sensitive adhesive composition can be further improved. In addition, the hydroxyl group-containing monomer may further improve the reworkability of the pressure-sensitive adhesive composition. When containing a hydroxyl group-containing monomer as a comonomer, the ratio is about 0.01% to about 15%, about 0.03% to about 10%, about 0.05% to about 7% by weight based on the total weight of the total monomers. Weight percent.

The (meth) acrylic copolymer of another embodiment may use a carboxyl group-containing monomer as a comonomer. In such a case, the comonomer can form a reaction point with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. In addition, the comonomer may further improve the reworkability of the pressure-sensitive adhesive composition. When the copolymer monomer contains a carboxyl group-containing monomer, the ratio is about 0.05% to about 10%, about 0.1% to about 8%, about 0.2% to about 6% by weight based on the total weight of the total monomers. Weight percent.

The (meth) acrylic copolymer of another embodiment may use a combination of a hydroxyl group-containing monomer and a carboxyl group-containing monomer as a comonomer.

In embodiments, the (meth) acrylic polymer may have a weight average molecular weight of about 300,000 to about 3 million. Specifically, the weight average molecular weight of the (meth) acrylic polymer may be about 500,000 to about 2.5 million, more specifically about 800,000 to about 2.3 million. In this case, the pressure-sensitive adhesive composition can be improved in durability and heat resistance. More specifically, the weight average molecular weight of the (meth) acrylic polymer may be about 700,000 to about 2.3 million. Within this range, the pressure-sensitive adhesive composition may further improve heat resistance, and the viscosity may be appropriate, which may be advantageous for coating. In addition, the process of adding a large amount of diluting solvent can be omitted, thereby reducing the cost. In this specification, a weight average molecular weight means the value computed by polystyrene conversion measured by GPC (gel permeation chromatography).

In one embodiment, the glass transition temperature of the (meth) acrylic polymer may be about −10 ° C. or less and about −25 ° C. or less. Within this range, the pressure-sensitive adhesive composition can improve flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure. In addition, the lower limit of the glass transition temperature may be about −100 ° C. or more, about −80 ° C. or more, or about −70 ° C. or more. Within such a range, the heat resistance of polyester can be prevented from falling.

As a polymerization method of a (meth) acrylic-type polymer, well-known polymerization methods, such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerization, can be selected suitably. In addition, the (meth) acrylic-type polymer obtained by the said polymerization method may be any of a random copolymer, a block copolymer, and a graft copolymer.

In one embodiment, the (meth) acrylic polymer can be prepared by solution polymerization. In this case, for example, ethyl acetate, toluene or the like may be used as the polymerization solvent. Specifically, solution polymerization may be carried out under reaction conditions of about 5 hours to about 30 hours, usually about 50 ° C. to about 85 ° C., by adding a polymerization initiator under an inert gas stream such as nitrogen.

In another embodiment, the (meth) acrylic polymer may be prepared by radical polymerization. A polymerization initiator, a chain transfer agent, an emulsifier, etc. used for radical polymerization are not specifically limited, It can select suitably and can use. The polymerization initiator, the chain transfer agent, etc. can control the weight average molecular weight of a (meth) acrylic-type polymer by adjusting the usage-amount, reaction conditions, etc. The polymerization initiator is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5- Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-di Azo initiators such as methylene isobutyl amidine) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (from Wako Pure Chemical Industries, Ltd., VA-057); Redox initiators such as a combination of a peroxide and a reducing agent such as an initiator, a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like, may be used.

The said polymerization initiator can be used individually, and can mix and use 2 or more types. The content of the polymerization initiator may be, for example, about 0.005 parts by weight to about 1 part by weight and about 0.02 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total monomers. For example, the (meth) acrylic polymer (A) of the said weight average molecular weight can be manufactured using 2,2'- azobisisobutyronitrile as a polymerization initiator. In this case, the specific amount of the polymerization initiator may be about 0.06 parts by weight to about 0.2 parts by weight, or about 0.08 parts by weight to about 0.175 parts by weight based on 100 parts by weight of the total amount of the monomer components.

As the chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglucolic acid 2-ethylhexyl, 2,3-dimercapto-1 Propanol and the like. A chain transfer agent can be used individually, and can mix and use 2 or more types. Content of a chain transfer agent may be about 0.1 weight part or less with respect to 100 weight part of all monomer components.

Examples of the emulsifier include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene. And nonionic emulsifiers such as alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene-polyoxypropylene block polymers. These emulsifiers may be used independently or may use 2 or more types together. Moreover, as an emulsifier into which radically polymerizable functional groups, such as a propenyl group and an allyl ether group, were introduce | transduced as a reactive emulsifier, For example, Aquaron HS-10, HS-20, KH-10, BC-05, BC-10 and BC-20 (all of which are manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N, SR-10N (ADEKA CHEMICAL Co., Ltd.), and the like. Since the emulsifier is introduced into the polymer chain after polymerization, the water resistance can be improved.The amount of the emulsifier used is about 0.3 parts by weight to about 5 parts by weight based on 100 parts by weight of the total amount of the monomer components, and from about polymerization stability or mechanical stability, 0.5 parts to about 2 parts by weight.

Next, the urethane polymer will be described. In one embodiment, the urethane polymer that may be used as the adhesive resin may be, for example, a reaction of a polyol and an isocyanate. Specifically, examples of the polyol include polyester polyols and polyether polyols.

As the polyester polyol, a known polyester polyol may be used.

The polyester polyol of one embodiment may be obtained by dehydration polymerization of an acid component and a bivalent or higher polyol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like. The divalent or higher polyol component is, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentane Diol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, 2-butyl-3-ethyl-1 Dihydric alcohols including, 5-pentanediol, 2-butyl-4-ethyl-1,5-pentanediol and the like; Trihydric alcohols including glycerine, trimethylolpropane; And one or more of tetrahydric alcohols including pentaerythritol and the like.

The polyester polyol of another specific example may be a polyester polyol obtained by ring-opening-polymerizing lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

The molecular weight of the polyester polyol can be used from low molecular weight to high molecular weight. Specifically, polyester polyols having a molecular weight of about 1,000 to about 5,000, more specifically polyester polyols having a molecular weight of about 2,500 to about 3,500 can be used. Within this range, the polyester polyol can prevent gelation of the polyurethane and improve the cohesion of the polyurethane itself. The amount of the polyester polyol may be about 10 mol% to about 70 mol%, more specifically about 35 mol% to about 65 mol% of the polyol constituting the polyurethane.

As the polyether polyol, a known polyether polyol may be used.

In one embodiment, the polyether polyol is a low molecular weight polyol such as propylene glycol, ethylene glycol, glycerine, trimethylolpropane, and the like, for example, ethylene oxide, propylene oxide, butylene oxide, It may be a polyether polyol obtained by polymerizing oxirane compounds such as tetrahydrofuran. Specifically, the polyether polyol may be exemplified by having two or more functional groups including polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and the like.

In another embodiment, the initiator is a glycol such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerine, trimethylolpropane, pentaerythritol ; And polyhydric amines such as ethylene diamine, N-aminoethylethanol amine, isophorone diamine, xylylene diamine, and the like.

The molecular weight of the polyether polyol can be used from low molecular weight to high molecular weight. The polyether polyol may specifically have a weight average molecular weight of about 1,000 to about 5,000, more specifically about 2,500 to about 3,500. Within this range, the polyether polyol can prevent gelation of the urethane polymer and improve the cohesion of the polyurethane itself.

The content of the polyether polyol may be about 20 mol% to about 80 mol%, more specifically about 40 mol% to about 65 mol% of the polyol constituting the polyurethane.

In one embodiment, the polyether polyols may also utilize bifunctional polyether polyols. In other embodiments, the polyether polyols may comprise polyether polyols having a molecular weight of about 1,000 to about 5,000 and at the same time having at least three or more hydroxyl groups in one molecule. In this case, the polyether polyol may implement a balance of adhesion and re-peelability to the urethane polymer. In another embodiment, the polyether polyols may utilize some or all of the polyols having a molecular weight of about 2,500 to about 3,500 and at the same time at least trifunctional. In this case, the polyether polyol can prevent gelation of the urethane polymer, improve reactivity, and improve cohesion of the polyurethane itself.

The isocyanate used in one embodiment may be an organopolyisocyanate compound including known aromatic polyisocyanates, aliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

The aromatic polyisocyanate is, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate , 4,4'-diphenylether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, and the like.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

The aromatic aliphatic polyisocyanate is ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-di Ethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

Alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl -2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4- Bis (isocyanatemethyl) cyclohexane and the like.

Moreover, isocyanate can also use together the trimethylolpropane adduct of the said polyisocyanate, the biuret reacted with water, and the trimer which has an isocyanurate ring.

In one embodiment, the polyisocyanate is, for example, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) ) Can be used.

A well-known catalyst can be used as a catalyst used for the synthesis | combination of a urethane polymer. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned.

Examples of the tertiary amine compound include triethylamine, triethylene diamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.

Examples of the organometallic compound include tin compounds and non-tin compounds. Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexane Acid tin etc. are mentioned as an example.

Examples of the non-tin compound include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate; Examples thereof include iron-based irons such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based zinc such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. Can be mentioned.

When synthesizing the urethane polymer of one embodiment, when using one or more catalysts of the above examples, it is possible to shorten the reaction time of the urethane polymer.

When synthesizing the urethane polymer of another embodiment, when using a combination of two or more catalysts of the above examples, it is possible to prevent the gelation of the urethane polymer and lower the turbidity of the reaction solution. In particular, when synthesizing a urethane polymer using a polyester polyol and a polyether polyol having a difference in reactivity as a polyol, the anti-gelling effect may be more excellent. In addition, when using two or more catalysts in the above examples, it is possible to control the reaction rate of the urethane polymer synthesis, the selectivity of the catalyst and the like. Tertiary amine / organic metal-based, tin-based / tin-based, tin-based / tin-based, etc. may be used as the two or more catalyst combinations, specifically, tin-based / tin-based, more specifically, dibutyltin dilaurate and Combinations of tin 2-ethylhexanoate can be used.

In one embodiment, when a combination of dibutyltin dilaurate and tin 2-ethylhexanoate is used as a catalyst for urethane polymer synthesis, the weight ratio of dibutyltin dilaurate: tin 2-ethylhexanoate is about 1: May be less than one. Specifically, about 1: 0.2 to about 1: 0.6. Within this range, the effect of lowering the gelation of the urethane polymer can be further improved.

The amount of the aforementioned catalyst may be about 0.01% to about 1.0% by weight based on the total amount of polyol and isocyanate.

The polyurethane of one embodiment may be used in admixture with a polyfunctional isocyanate compound. The polyfunctional isocyanate compound may include, for example, the aforementioned organopolyisocyanate compound and trimethylolpropane adducts thereof, a biuret reacted with water, or a trimer having an isocyanurate ring.

In one embodiment, when a combination of the urethane polymer and the polyfunctional isocyanate is used, the polyfunctional isocyanate may be included in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the urethane polymer. Specifically, it is about 2 parts by weight to about 10 parts by weight. Within this range, the adhesion and cohesion of the adhesive resin containing the urethane polymer can be further improved.

In the synthesis of the urethane polymer of one embodiment, the reaction temperature may be about 100 ° C. or less. More specifically, it may be about 85 ℃ to about 95 ℃. Within this range, it is advantageous to control the crosslinked structure of the urethane polymer, through which a polyurethane having a predetermined molecular weight and chemical structure can be obtained.

In one embodiment, the polyurethane may have a weight average molecular weight of about 10,000 to about 200,000, specifically about 15,000 to about 100,000, more specifically about 20,000 to about 50,000. Within this range, it is possible to further improve the adhesion and cohesion of the pressure-sensitive adhesive resin containing a urethane polymer, it is possible to further improve the heat resistance and mechanical strength. In addition, within the above range, the flexibility of the adhesive resin can prevent the loss, thereby improving the initial adhesiveness and overall adhesion. In such a case, the pressure-sensitive adhesive composition can be easily adhered even at low pressure.

The glass transition temperature of the polyurethane of one embodiment may be about −10 ° C. or less and about −25 ° C. or less. Within this range, the flexibility of the adhesive resin can prevent the loss, thereby improving the initial adhesiveness and overall adhesive strength. In such a case, the pressure-sensitive adhesive composition can be easily adhered even at low pressure. In addition, the glass transition temperature may specifically have a lower limit of about -100 ° C or more, about -80 ° C or more and about -70 ° C or more. Within this range, the heat resistance of the adhesive resin can be further improved.

In one embodiment, a solvent used for dilution of the urethane polymer may be a known solvent. For example, water, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. In one embodiment, toluene may be used as the solvent. In such a case, the solubility of a urethane polymer, the boiling point of a solvent, etc. may be excellent.

Next, a polyester is demonstrated. The polyester of one embodiment can be obtained by using what consists of a polyol component and a carboxylic acid component as a raw material, and polycondensing them.

In one embodiment, the polyol component used in the synthesis of the polyester may include at least one of a diol having an alkoxy group in the side chain and a polyol other than the diol having an alkoxy group in the side chain.

The diol having an alkoxy group in the side chain is methoxyethylene glycol, methoxypropylene glycol, methoxybutylene glycol, ethoxyethylene glycol, ethoxypropylene glycol, ethoxybutylene glycol Lycol, dimethoxyethylene glycol, dimethoxypropylene glycol, dimethoxybutylene glycol, diethoxyethylene glycol, diethoxypropylene glycol, diethoxybutylene glycol and the like can be used. It is not limited thereto.

As polyols other than the diol which has an alkoxy group in a side chain, ethylene glycol, a propylene glycol, 1, 3- propanediol, 1, 4- butanediol, 1, 5- pentanediol, for example Linear aliphatic diols such as 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; Neopentylglycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5- Aliphatic diols having a hydrocarbon group side chain, such as pentanediol, 1,3,5-trimethyl-1,3-pentanediol, and 2-methyl-1,6-hexanediol, can be used. These can use 1 type, or 2 or more types.

In one embodiment, polyols other than diols having an alkoxy group in the side chain include straight-chain aliphatic diols having 2 to 6 carbon atoms, specifically 1,4-butanediol, 1,6-hexanediol, ethylene glycol However, an aliphatic diol having a hydrocarbon group side chain having 1 to 4 carbon atoms, more specifically, neopentyl glycol can be used. In such a case, the initial adhesiveness, mechanical strength, and heat resistance of the pressure-sensitive adhesive composition can be well balanced.

In addition, if necessary, the polyol component used in the synthesis of the polyester may further include at least one of polyetherdiol and a trivalent or higher polyhydric alcohol.

As polyetherdiol, polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, etc. which ring-opened-polymerized ethylene oxide, a propion oxide, tetrahydrofuran, etc. are mentioned, These are mentioned 1 type or It can use 2 or more types.

Examples of the trihydric or higher polyhydric alcohol include trimethylolethane, trimethylolpropane, glycerine, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2, 6-hexane triol etc. can be mentioned as an example, These can be used 1 type, or 2 or more types. In one embodiment, trimethylolpropane may be used in the above-described trivalent or higher polyhydric alcohol. In this case, the polyester can be further improved in heat resistance. The content of the trihydric or higher polyhydric alcohol is not particularly limited, but may be, for example, about 0.1 mol% to about 5.0 mol%, specifically about 0.5 mol% to about 3.0 mol%.

The carboxylic acid component used in the synthesis of the polyester is not particularly limited. For example, the carboxylic acid which has an alkoxy group in a side chain can be included. In such a case, an alkoxy group can be introduce | transduced into the side chain of polyester resin obtained.

Of course, any of the above-mentioned polyol component and carboxylic acid component can use the raw material component which contains an alkoxy group in a side chain.

As a carboxylic acid which has an alkoxy group in a side chain, polyvinyl ether etc. which are described in Unexamined-Japanese-Patent No. 2004-307462 are mentioned as an example.

In one embodiment, among the examples of carboxylic acids described above, carboxylic acids having a number average molecular weight of about 500 to about 3,000 and having an alkoxy group can be used. In this case, the polyester can be made to have a good balance of initial adhesiveness, mechanical strength, and heat resistance.

Moreover, carboxylic acids other than the carboxylic acid which has an alkoxy group in a side chain, For example, aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, orthophthalic acid, 1, 5- naphthalene dicarboxylic acid, 2, 6- naphthalene dicarboxylic acid, p-oxybenzoic acid, Saturated dicarboxylic acids such as aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and octadecanedicarboxylic acid; Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, tetracurolphthalic acid, hexahydrophthalic acid, dimer acids, and the like, and the like, and these may be used alone or in combination of two or more thereof.

The carboxylic acid component of one embodiment may be, for example, trivalent or more such as trimellitic acid, trimesic acid, pyromellitic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, or the like, as necessary. It may further comprise a carboxylic acid. In one embodiment, among these, aromatic dicarboxylic acid, specifically terephthalic acid, isophthalic acid, aliphatic dicarboxylic acid having 6 to 12 carbon atoms (including carbon of carboxyl group), and more specifically sebacic acid can be used. In such a case, polyester can make the initial adhesiveness of an adhesive composition, mechanical strength, and heat resistance compatible with a good balance.

Although the content of the alkoxy group in the polyester resin of one specific example is not specifically limited, About 5 to about 300 alkoxy groups and about 60 to about 150 alkoxy groups can be introduce | transduced per molecule of polyester resin. Within this range, the initial adhesive force, mechanical strength, and heat resistance of the pressure-sensitive adhesive composition can be further improved.

In the synthesis of the polyester, the blending ratio of the polyol component may be about 1 equivalent or more, about 1.2 equivalents or more, and about 2.0 equivalents or less of the polyol component per 1 equivalent of the carboxylic acid component. Within this range, the molecular weight of the polyester can be adjusted to an appropriate range, and the yield can be further improved.

At the time of the polycondensation reaction of polyester, a polymerization (esterification) reaction may be performed first, and then a condensation reaction may be performed. In such a polymerization (esterification) reaction, a catalyst can be used. Specifically, the catalyst for the esterification reaction is a catalyst such as titanium-based such as tetraisopropyl titanate or tetrabutyl titanate, antimony-based such as antimony trioxide, germanium-based such as germanium oxide, zinc acetate, manganese acetate, dibutyltin, or the like. An oxide etc. can be mentioned as an example, These 1 type, or 2 or more types can be used.

The blending amount of the esterification catalyst may be about 1 ppm to about 10,000 ppm, about 10 ppm to about 5,000 ppm, and about 10 ppm to about 3,000 ppm with respect to the total of the total reactants. Within this range, it is possible to implement the effect of improving the degree of polymerization of the reaction, shortening the reaction time, and further lowering side reactions.

The reaction temperature in the polymerization (esterification) reaction may be about 160 ° C to about 260 ° C, specifically about 180 ° C to about 250 ° C, more specifically about 200 ° C to about 250 ° C. Within this range, it is possible to implement the effect of improving the degree of polymerization of the reaction, shortening the reaction time, and further lowering side reactions. In addition, the polymerization (esterification) reaction can be carried out under normal pressure.

In one embodiment, after the polymerization (esterification) reaction is carried out, the condensation reaction can be carried out. At this time, an additional catalyst may be further added. The catalyst used for the condensation reaction in the synthesis of polyester can be used in the same amount as the same kind of catalyst that can be used in the above-described esterification reaction. Specifically, the condensation reaction may be carried out at a reaction temperature of about 220 ° C. to about 260 ° C., more specifically about 230 ° C. to about 250 ° C., to gradually depressurize the reaction system and finally react at about 5 hPa or less. Within this reaction temperature range, the reactivity of the reactants can be improved, and side reactions such as decomposition of the polyester can be further lowered.

In one embodiment, the polyester has a weight average molecular weight of about 10,000 to about 200,000, specifically about 15,000 to about 100,000, more specifically about 20,000 to about 50,000. Within the range of the weight average molecular weight, sufficient cohesive force can be obtained when applied to the pressure-sensitive adhesive composition, and further excellent heat resistance and mechanical strength can be ensured. In addition, within the above range, the pressure-sensitive adhesive composition can be improved in flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure.

The glass transition temperature of the polyester of one embodiment may be about −10 ° C. or less and about −25 ° C. or less. Within this range, the pressure-sensitive adhesive composition can improve flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure. In addition, the lower limit of the glass transition temperature may be about −100 ° C. or more, about −80 ° C. or more, or about −70 ° C. or more. Within such a range, the heat resistance of polyester can be prevented from falling.

In one embodiment, a solvent used for dilution of the polyester may be a known solvent. For example, water, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. In one embodiment, methyl ethyl ketone and ethyl acetate may be used as the solvent. In this case, the solubility of polyester, the boiling point of a solvent, etc. may be excellent.

(B) Silicate Oligomer

The silicate oligomer of one embodiment is represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₄ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100. The alkyl group and the aryl group may or may not be substituted. In addition, the alkyl group may be linear or branched structure. Specifically, R ₁ to R ₄ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. It may be an aryl group of 12. For example, R ₁ to R ₄ may be each independently a methyl group, an ethyl group, or a phenyl group.

Specifically, the silicate oligomer may be a single species of oligomer or a mixture of plural kinds of oligomers.

The weight average molecular weight of the silicate oligomer may be about 300 to about 30,000. When the weight average molecular weight of the silicate oligomer becomes a value within this range, the pressure-sensitive adhesive composition can be compatible with even more excellent reworkability and adhesion.

In an embodiment, the silicate oligomer is a silicate oligomer having R ₁ to R ₄ , X ₁ and X ₂ in the formula (1) is a methyl group and a weight average molecular weight of about 300 to about 20,000, R ₁ to R ₄ , X ₁ in the formula ( ₁₎ And a silicate oligomer having X ₂ a methyl group and a weight average molecular weight greater than about 20,000 and up to about 30,000, and a silicate oligomer comprising R ₁ , R ₂ , R ₃ , R ₄ , X _1, or X ₂ in the formula (1). It may contain the above.

Methyl silicate oligomer having the weight average molecular weight of about 300 to about 20,000, Methyl silicate oligomer having a weight average molecular weight of greater than about 20,000 or less than about 30,000 or R ₁ , R ₂ , R ₃ , R ₄ , X ₁ or X ₂ of Formula 1 In the case where the oligomer comprises one or more silicate oligomers containing a phenyl group, the pressure-sensitive adhesive composition may be compatible with more excellent reworkability and adhesion.

The weight average molecular weight of the silicate oligomer may be specifically about 500 to about 25,000, more specifically about 600 to about 5,000, more specifically about 800 to about 3,500.

With adhesive resin Silicate Mixing ratio of oligomer

The pressure-sensitive adhesive composition according to one embodiment may include about 0.01 part by weight to about 50 parts by weight of the silicate oligomer based on 100 parts by weight of the adhesive resin. The pressure-sensitive adhesive composition has a silicate oligomer of about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6 based on 100 parts by weight of the adhesive resin. , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 parts by weight. In addition, the pressure-sensitive adhesive composition, with respect to 100 parts by weight of the adhesive resin, the silicate oligomer may be in the range of at least one of the above numerical values and at most one of the above numerical values. For example, about 0.01 parts by weight to about 50 parts by weight of silicate oligomer, specifically about 0.5 parts by weight to about 20 parts by weight, more specifically about 0.5 parts by weight to about 10 parts by weight, more preferably 100 parts by weight of the tacky resin. More specifically, about 1 part to about 5 parts by weight. Within this range, the initial reworkability of the pressure-sensitive adhesive composition and the adhesion after heating may be further improved. Within this range, the pressure-sensitive adhesive composition may be compatible with more excellent reworkability and adhesion.

Crosslinking agent

The pressure-sensitive adhesive composition of one embodiment may contain a crosslinking agent.

As a crosslinking agent, an organic type crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic crosslinking agent include isocyanate crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, imine crosslinking agents and the like. Examples of the polyfunctional metal chelate include those in which a polyvalent metal is covalently or coordinating with an organic compound. Examples of the polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be. As an atom in an organic compound covalently bonded or coordinated, an oxygen atom etc. can be illustrated, An alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. can be illustrated as an organic compound.

In an embodiment, the crosslinking agent may use at least one of an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and a peroxide crosslinking agent. When using a peroxide crosslinking agent, the adhesive layer which does not need aging can be manufactured. In the manufacturing process of an adhesive layer, the adhesive layer which does not need aging is strongly requested | required from a viewpoint of handling improvement. Therefore, the need for aging of the pressure-sensitive adhesive layer is a great advantage in the manufacturing process. The adhesive layer, which does not require aging, has an advantage in that reworkability and reliability are excellent, and handleability of the adhesive layer manufacturing process is improved.

Isocyanate-based crosslinking agents include, for example, isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate or the above isocyanate monomers. Isocyanate compound which added to trimethylol propane etc .; And urethane prepolymer isocyanates obtained by addition reaction of isocyanurate or isocyanate biuret compound with polyether polyol or polyester polyol, acryl polyol, polybutadiene polyol, polyisoprene polyol and the like; It may include one or more of.

Specifically, the isocyanate-based crosslinking agent may be a polyisocyanate compound, and more specifically, may be one or a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. . The one or more polyisocyanate compounds selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate are hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified hexa Methylene diisocyanate, polyol modified hydrogenated xylylene diisocyanate, trimer type hydrogenated xylylene diisocyanate, polyol modified isophorone diisocyanate and the like. The polyisocyanate compounds exemplified above may have excellent crosslinking reaction rates with hydroxyl groups. In addition, the exemplified polyisocyanate compound can accelerate the crosslinking reaction by using the acid and the base contained in the polymer as a catalyst, and thus can contribute particularly to the accelerated crosslinking.

The carbodiimide-based crosslinking agent may be specifically used a compound having two or more carbodiimide groups (-N = C = N-) in a molecule, and a known polycarbodiimide compound may be used. The carbodiimide compound may be, for example, a high molecular weight polycarbodiimide produced by decarbonation condensation of diisocyanate in the presence of a carbodiimide catalyzed catalyst. More specifically, the polycarbodiimide compound may be one obtained by decarboxylation of the following diisocyanate.

As the diisocyanate used for the polycarbodiimide compound, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-di Methyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate, 2,4-tolylene di One of isocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate The above can be used. Moreover, the mixture of 2 or more types in the said illustration can also be used.

At this time, as a catalyst used for the carbodiimidation reaction, 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2- Phosphorene oxides, such as a phosphorene-1-oxide, a 1-ethyl- 2-phosphorene-1-oxide, or these 3-phosphorene isomers, can be used.

In a specific example, the high molecular weight polycarbodiimide compound includes the carbodilite series manufactured by Nisshin Boseiki Co., Ltd. Especially, when carbodilite V-01, 03, 05, 07, 09 is used, compatibility with an organic solvent may be excellent.

The peroxide crosslinking agent can be used without limitation as long as it generates radically active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition. Specifically, a peroxide crosslinking agent having a half-life temperature of about 50 ° C to about 160 ° C or about 60 ° C to about 140 ° C for 1 minute can be used. In such a case, workability or stability may be improved.

Specifically, the peroxide crosslinking agent may be, for example, di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: about 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life). Temperature: about 92.1 ° C.), di-sec-butylperoxydicarbonate (1 minute half-life temperature: about 92.4 ° C.), t-butylperoxy neodecanoate (1 minute half-life temperature: about 103.5 ° C.), t-hex Silperoxypivalate (1 minute half-life temperature: about 109.1 ° C), t-butylperoxy pivalate (1 minute half-life temperature: about 110.3 ° C), dilauroyl peroxide (1 minute half-life temperature: about 116.4 ° C), die -n-octanoyl peroxide (1 minute half-life temperature: about 117.4 ° C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: about 124.3 ° C), die (4-methylbenzoyl) peroxide (1 minute half-life temperature: about 128.2 ° C), dibenzoylperoxide (1 minute half-life temperature: about 130.0 ° C), t-part Peroxy iso-butyrate and the like (one-minute half-life temperature: about 136.1 ℃), 1,1- di (t--hexylperoxy) cyclohexane (one-minute half-life temperature of about 149.2 ℃). Especially, since crosslinking reaction efficiency is favorable, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half life temperature: about 92.1 degreeC), dilauroyl peroxide (1 minute half life temperature: about 116.4 degreeC) ), Dibenzoyl peroxide (1 minute half-life temperature: about 130.0 ° C.), and the like are specifically used.

The peroxide half life is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide is half. In one embodiment, the decomposition temperature, half-life, and the like of the peroxide may be as described, for example, in each manufacturer catalog or the like. For example, it is described in Nihon Yushi Co., Ltd. "The organic peroxide catalog ninth edition (May 2003)" etc.

The oxazoline-based crosslinking agents are specifically 2-isopropyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxa May include one or more of sleepy, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline This is not restrictive. An oxazoline type crosslinking agent can use what is commercially available. For example, oxazoline group-containing acrylic polymers such as epocros WS-300, epocros WS-500, epocros WS-700, epocros K-1000 series, and epocros K-2000 series from Japan Catalyst Co., Ltd. can be used alone or in combination of two or more. It can be used, but is not limited thereto.

The amount of the crosslinking agent may be about 0.01 parts by weight to about 20 parts by weight, and about 0.03 parts by weight to about 10 parts by weight based on 100 parts by weight of the adhesive resin. Within the above range, the cohesive force of the pressure-sensitive adhesive composition is excellent, it is possible to lower the foaming incidence upon heating, excellent moisture resistance, reworkability can be improved in reliability tests and the like.

In one embodiment, one type of isocyanate type crosslinking agent may be used alone or two or more types may be used as a crosslinking agent. The content of the isocyanate-based crosslinking agent in this embodiment is about 0.01 parts by weight to about 2 parts by weight, about 0.02 parts by weight to about 2 parts by weight, about 0.05 parts by weight to about 1.5 parts by weight based on 100 parts by weight of the adhesive resin. Can be. Within this range, the cohesion force of the pressure-sensitive adhesive composition, the reworkability in the durability test, and the like can be further improved.

In another specific example, a peroxide type crosslinking agent can be used individually by 1 type or in mixture of 2 or more types as a crosslinking agent. When using a peroxide crosslinking agent, the adhesive layer which does not need aging can be manufactured. In the manufacturing process of an adhesive layer, the adhesive layer which does not require an aging from a viewpoint of handling improvement is strongly demanded. Therefore, the need for aging of the pressure-sensitive adhesive layer is a great advantage in the manufacturing process. The adhesive layer, which does not require aging, has an advantage in that reworkability and reliability are excellent, and handleability of the adhesive layer manufacturing process is improved.

The content of the peroxide crosslinking agent in this embodiment is about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, It may contain 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0 parts by weight. In addition, the peroxide-based cross-linking agent content may be in the range of about one or more of the above values and about one or less of the above values based on 100 parts by weight of the adhesive resin. For example, the peroxide-based crosslinking agent content is about 0.01 parts by weight to about 2 parts by weight, specifically about 0.02 parts by weight to about 2 parts by weight, and more specifically about 0.04 parts by weight to about 1.5 parts by weight of the adhesive resin. By weight, even more specifically from about 0.05 part by weight to about 1 part by weight. Within this range, processability, reworkability, crosslinking stability, reworkability, and the like of the pressure-sensitive adhesive composition can be further improved.

Silane coupling agent

The pressure-sensitive adhesive composition of one embodiment may further contain a silane coupling agent. When using a silane coupling agent, the durability of an adhesive composition can be improved further. Silane coupling agents are, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxy Epoxy group-containing silane coupling agents such as cyclohexyl) ethyl trimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl Amino group-containing silane coupling agents such as -N- (1,3-dimethylbutylidene) propylamine and N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-metha Isocyanate group containing silane coupling agents, such as (meth) acryl group containing silane coupling agents, such as a krilloxy propyl triethoxysilane, and 3-isocyanate propyl triethoxysilane, etc. can be used. The said silane coupling agents may be used independently, and can mix and use 2 or more types.

The content of the silane coupling agent is about 0.001 parts by weight to about 10 parts by weight, about 0.001 parts by weight to about 5 parts by weight, about 0.01 parts by weight to about 1 parts by weight, and about 0.02 parts by weight based on 100 parts by weight of the above-mentioned adhesive resin. To about 1 part by weight, about 0.05 part by weight to about 0.6 part by weight. Within the above range, durability of the pressure-sensitive adhesive composition can be improved, and adhesive strength to optical members such as liquid crystal cells can be ensured.

In addition, the pressure-sensitive adhesive composition of one embodiment may further include an additive other than the above-described components. For example, additives include polyether compounds of polyalkylene glycols such as polypropylene glycol, powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, It can add suitably according to the use which uses antioxidant, antioxidant, a light stabilizer, a ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, metal powder, a particle form, a foil form, etc. Moreover, the redox-type additive which added the reducing agent can also be used within the range which can be controlled.

<< 점착층의Adhesive layer 형성 및 Formation and 점착층의Adhesive layer 적용예Application example >>

Using the pressure-sensitive adhesive composition in the above-described embodiments, the pressure-sensitive adhesive layer can be formed on various optical films. The optical film in which such an adhesion layer was formed is also called adhesive optical film. The method of forming an adhesion layer includes the method of apply | coating the said adhesive composition to the separator (1st separator) etc. which the release agent processed, the method of transferring to an optical film after drying and removing a polymerization solvent etc. to form an adhesion layer; Or the method of apply | coating the said adhesive composition to an optical film, drying a polymeric solvent, etc., and forming an adhesive layer in an optical film; And the like. At the time of application | coating of an adhesive composition, you may add a 1 or more types of solvent other than a polymerization solvent newly.

As the separator, for example, a silicone liner may be specifically used. Such a liner may be, for example, a silicone-based release agent on one side of the liner. Such a silicone type release agent can facilitate the transfer of the adhesive composition formed in the separator to an optical film.

The method of forming a specific adhesive layer may include a method of applying a pressure-sensitive adhesive composition on a separator or an optical film to form a coating film. It may also include a method of heating and drying the coating film after the formation of the coating film. The heat drying temperature may be about 40 ° C to about 200 ° C, specifically about 50 ° C to about 180 ° C, and more specifically about 70 ° C to about 170 ° C. By making heating temperature into the said range, the adhesive composition which has the outstanding adhesive characteristic can be obtained.

As for a drying time, appropriate time can be employ | adopted suitably. The drying time may be specifically about 5 seconds to about 20 minutes, more specifically about 5 seconds to about 10 minutes, in particular about 10 seconds to about 5 minutes.

In one embodiment, when the pressure-sensitive adhesive composition is applied to the surface of the optical film, the adhesive layer is formed on the surface of the optical film after various kinds of easy adhesion treatment such as forming treatment, corona treatment, plasma treatment, etc. (adhesive auxiliary layer) )can do. Moreover, you may perform an easy adhesion | attachment process on the surface of an adhesion layer.

The coating method of the pressure-sensitive adhesive composition is not particularly limited, but for example, a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, an air knife coat, a curtain coat, Methods, such as the extrusion coating method by a lip coat and a die coat, are mentioned.

Crosslinking treatment may be performed when the adhesive layer is formed. Such a crosslinking process may be performed at the temperature at the time of the drying process of an adhesion layer, and you may provide and perform a crosslinking treatment process separately after a drying process. The said crosslinking process can fully consider the influence of crosslinking process temperature and crosslinking process time, while adjusting the addition amount of the whole crosslinking agent.

Specifically, the crosslinking treatment temperature, the crosslinking treatment time and the like can be adjusted according to the crosslinking agent to be used. In one embodiment, the crosslinking treatment temperature in the formation of the pressure-sensitive adhesive composition may be about 170 ° C or less and specifically about 130 ° C or less. Energy efficiency may be improved when the pressure-sensitive adhesive layer is formed in the above range. In addition, when using a specific separator (for example, PET) as the base material for forming the adhesive layer, there is an advantage that foreign substances such as oligomers can suppress the production. The foreign material (eg, oligomer) may be produced at about 30 ppm or less, specifically about 10 ppm or less. It is suitable to use it as an adhesive for optical films in the said range.

The crosslinking treatment time can be set in consideration of productivity and workability. In one embodiment, the crosslinking treatment time in forming the pressure-sensitive adhesive composition may be about 0.2 minutes to about 20 minutes, about 0.5 to about 10 minutes.

In one embodiment, the cross-linking treatment may be performed by performing a peroxide crosslinking treatment with a peroxide-based crosslinking agent to form an adhesive layer.

The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed by a crosslinking treatment of a pressure-sensitive adhesive composition comprising a pressure-sensitive resin comprising at least one of a (meth) acrylic polymer, a urethane polymer, and a polyester, a silicate oligomer represented by the following general formula (1), and a peroxide-based crosslinking agent, At a temperature of 23 ° C. and a humidity of 65% RH, the gel fraction according to Equation 1 may be about 40 wt% to about 95 wt% after being left for about 1 hour from adhesion layer formation.

[Formula 1]

[Equation 1]

Gel fraction (% by weight) = {(Wc-Wa) / (Wb-Wa)} × 100

When the pressure-sensitive adhesive composition forms a pressure-sensitive adhesive layer by peroxide crosslinking treatment, the gel fraction after about 1 hour is about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 or 95%. Also, the gel fraction after 1 hour may be in the range of one or more of the above values and one or less of the above values. For example, when the pressure-sensitive adhesive composition forms a pressure-sensitive adhesive layer by peroxide crosslinking, the gel fraction after 1 hour is about 40 wt% to about 95 wt%, specifically about 65 wt% to about 95 The range of weight% may be satisfied. In the above range, the pressure-sensitive adhesive layer has no fear of crushing and deterioration of durability, does not require aging, and therefore has an advantage of excellent workability.

The peroxide crosslinking treatment time may be a peroxide crosslinking treatment of at least a half-life time corresponding to a peroxide crosslinking treatment temperature (about 170 ° C. or less, specifically about 130 ° C. or less).

The adhesive resin has an acid value of about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mgKOH / can be g. In addition, the adhesive resin may have an acid value in a range of at least one of the above values and at most one of the above values. For example, the acid value of the tacky resin may range from about 0 mgKOH / g to about 20.0 mgKOH / g, specifically from about 0 mgKOH / g to about 10.0 mgKOH / g, more specifically from about 0 mgKOH / g to about 5.0 mgKOH / g, even more specifically about 0 mgKOH / g to about 3.0 mgKOH / g. In the above range, the pressure-sensitive adhesive composition is excellent in adhesive strength and reliability, and can achieve a balance between rework properties.

The composition may include a peroxide crosslinking agent to form an adhesive layer by peroxide crosslinking.

The peroxide crosslinking treatment can decompose at least about 50% by weight of the peroxide crosslinking agent. By decomposing at least about 50% by weight of the peroxide crosslinking agent, the gel fraction of the pressure-sensitive adhesive layer may be about 40% by weight to about 95% by weight.

The adhesive layer may have a difference between an initial adhesive force and an adhesive force after heating about 1 N / 25 mm or less. It is excellent in the rework property and reliability of an adhesion layer in the said range.

The initial adhesive force is the adhesive force to the following initial glass plate, the adhesive force after heating is the adhesive force to the glass plate after the heating, the initial glass plate and the glass plate after heating are produced as follows.

An adhesive polarizing film (sample) is cut out to about 25 mm in width x about 100 mm in length, and affixed on the alkali free glass plate (Corning Corporation product, Eagle XG) of thickness about 0.5 mm using a laminator. Next, the polarizing film is completely stuck to the alkali free glass by autoclaving the glass plate with a polarizing film at about 50 degreeC and about 5 atm for about 15 minutes. Thereby, an initial glass plate is produced. And the said initial glass plate is heated for about 48 hours under about 50 degreeC dry conditions, and a glass plate is produced after heating. And the adhesive force of an initial glass plate and a glass plate after a heating is measured by the following method.

The adhesive force (N / 25mm) at the time of removing a polarizing film from each glass plate is measured using the tensile tester (Tensilon Universal Testing Machine STA-1150 by Orient Tech Co., Ltd.). Measurement conditions are about 23 degreeC, relative humidity about 50%, peeling angle about 180 degrees, and peeling rate about 300 mm / min. In addition, peeling is based on the method of the adhesive tape and adhesive sheet test of JISZ0237.

The adhesive layer may have an adhesive strength of about 3 N / 25 mm or less, specifically about 2.5 N / 25 mm or less after heating. It is excellent in the rework property and reliability of an adhesion layer in the said range.

The thickness of the adhesive layer is not particularly limited, but may be, for example, about 1 μm to about 100 μm. Specifically, it is about 2 μm to about 50 μm, more specifically about 2 μm to about 40 μm, and more specifically about 5 μm to about 35 μm. Within this range, the adhesive force and the rework property of the adhesive layer can be effectively compatible.

When the surface of the adhesive layer is to be exposed during storage, a release agent-treated separator (second separator) may be further formed to protect the adhesive layer. This second separator is used after removing the adhesive layer.

<점착형 광학 필름><Adhesive type optical film>

The adhesive optical film of the present invention may include an optical film and the adhesive layer formed on one or both surfaces of the optical film.

As said optical film, what is used for formation of image display apparatuses, such as a liquid crystal display device, is used, The kind in particular is not restrict | limited. For example, a polarizer is mentioned as an optical film. Specifically, the adhesive optical film may include a polarizer, a protective layer formed on one surface of the polarizer, and an adhesive layer formed on the other surface of the polarizer, and the adhesive layer may be formed of the pressure-sensitive adhesive composition for the optical film.

The polarizer may include a transparent protective film on at least one side of the polarizer. Although a polarizer is not specifically limited, For example, the dichroism of an iodine or a dichroic dye is used for hydrophilic polymer films, such as a polyvinyl alcohol film, a partially foamed polyvinyl alcohol film, and an ethylene-vinyl acetate copolymerization partially saponified film. Polyene type orientation films, such as the thing which made the material adsorb | suck and uniaxially stretched, the dehydration process of polyvinyl alcohol, and the dehydrochlorination process of polyvinyl chloride, etc. are mentioned. In a specific embodiment, a polarizer made of a divinyl substance such as a polyvinyl alcohol film and iodine may be used as the polarizer. In this case, the degree of opticality and handleability of the polarizing film may be further excellent. The thickness of the polarizer is not particularly limited, but may be, for example, about 5 μm to about 80 μm.

The protective layer is not limited as long as it can protect the polarizer. Specifically, the protective layer may be a transparent protective film. The transparent protective film may be bonded to one or both sides of the polarizer by an adhesive layer. An adhesive agent is used for the adhesion | attachment process of a polarizer and a transparent protective film. As an adhesive agent, an isocyanate adhesive, a polyvinyl alcohol adhesive, a gelatin adhesive, a vinyl latex type, an aqueous polyester, etc. can be illustrated. The adhesive is usually used as an adhesive consisting of an aqueous solution, and may contain, for example, about 0.5% by weight to about 60% by weight solids. In addition to the above, an ultraviolet curable adhesive, an electron beam curable adhesive, etc. are mentioned as an adhesive agent of a polarizer and a transparent protective film. The adhesive agent for electron beam hardening type polarizing films shows suitable adhesiveness with respect to the said various transparent protective films. The adhesive for bonding the polarizer and the transparent protective film of one embodiment may further contain a metal compound filler.

As a material which comprises a transparent protective film, the thermoplastic resin which is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is used, for example. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins. , Cyclic polyolefin resin (norbornene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. Moreover, although one side of a polarizer has a transparent protective film bonded by an adhesive bond layer, on the other side, it is a thermosetting resin, such as a (meth) acrylic-type, urethane type, an acryl urethane type, an epoxy type, a silicone type, or ultraviolet curing type as a transparent protective film. Resin can be used. One or more types of arbitrary appropriate additives may be contained in the transparent protective film. As an additive, a ultraviolet absorber, antioxidant, a lubricating agent, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent, etc. are mentioned, for example. The content of the thermoplastic resin in the transparent protective film is specifically about 50 to about 100% by weight, more specifically about 50 to about 99% by weight, more specifically about 60 to about 98% by weight, particularly specifically From about 70 to about 97 weight percent. When content of the said thermoplastic resin in a transparent protective film is about 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

Although the thickness of a transparent protective film can be suitably determined, it is generally about 1 micrometer-about 500 micrometers in terms of workability, thinness, etc., such as strength and handleability. In particular from about 1 μm to about 300 μm, from about 5 μm to about 200 μm. In particular, the pressure-sensitive adhesive layer is suitable when a pressure-sensitive adhesive layer is directly formed on a thin transparent protective film having a thickness of about 40 μm or less.

In other embodiments, the protective layer can be a protective coating layer. The protective coating layer may be formed of an active energy ray curable resin composition comprising an active energy ray curable compound and an initiator. The active energy ray curable compound may include at least one of an acrylic compound, an epoxy compound, and an isocyanurate compound.

The protective coating layer may have a thickness of about 5 μm to about 200 μm, specifically about 5 μm to about 20 μm, and more specifically about 4 μm to about 10 μm. In the above range, the protective coating layer can be formed directly on the polarizer without using an adhesive, and can thin the polarizing plate.

Moreover, the said adhesive optical film can be laminated | stacked with another optical film. As another optical film, formation of a liquid crystal display device, such as a reflecting plate, a semi-transmissive plate, a retardation film (including wavelength plates, such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc. The thing used as the optical layer which may be used for is mentioned. These can be laminated | stacked on the said polarizing film at the time of practical use, and can use 1 layer or 2 or more layers. For example, the adhesive optical film may further include a retardation film formed on the adhesive layer.

Although the optical film which laminated | stacked the said optical layer on the adhesive optical film can also be formed also by the method of laminating | stacking separately in the manufacturing process of a liquid crystal display device etc., what laminated | stacked previously and made it into the optical film is stability of quality and granulation. Excellent work and the like has the advantage of improving the manufacturing process, such as a liquid crystal display device. Suitable lamination means, such as an adhesion layer, can be used for lamination. At the time of adhering the polarizing film to another optical layer, the optical axis can be set to an appropriate placement angle in accordance with a desired phase difference characteristic or the like.

The polarizer which dyed a polyvinyl alcohol-type film with iodine and uniaxially stretched can be created by dyeing polyvinyl alcohol by immersing it in the aqueous solution of iodine, and extending | stretching 3 to 7 times the original length, for example. As needed, it can also be immersed in aqueous solution, such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride, etc. If necessary, the polyvinyl alcohol-based film may be dipped in water and washed with water before dyeing. In addition to washing the polyvinyl alcohol-based film with water, the contamination of the polyvinyl alcohol-based film and the blocking agent can be washed. In addition, swelling of the polyvinyl alcohol-based film can also prevent the unevenness of dyeing and the like. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be dyed with iodine after stretching. It can extend | stretch also in aqueous solution, such as boric acid and potassium iodide, or a water bath.

Moreover, as an optical film, liquid crystal displays, such as a reflecting plate, a semi-transmissive plate, a retardation film (including wavelength plates, such as 1/2 and a quarter), a visual compensation film, a brightness enhancement film, a surface treatment film, etc. The thing used as the optical layer which may be used for formation of an apparatus etc. is mentioned. These can be used independently as an optical film, can be laminated | stacked on the said polarizing film at the time of practical use, and can use 1 layer or 2 or more layers. For example, the pressure-sensitive adhesive optical film including the optical film and the pressure-sensitive adhesive layer may further include a phase difference film formed on the pressure-sensitive adhesive layer.

Although the film thickness of the various optical films enumerated above is not restrict | limited, The adhesive composition which concerns on one Embodiment is a rework property with respect to an optical film even if an optical film is thin (for example, about 100 micrometers or less). While securing, it has high reliability. Moreover, you may form an adhesion | attachment auxiliary layer in an optical film, and may form an adhesion layer on this adhesion | attachment auxiliary layer. The adhesion auxiliary layer is a layer whose wettability with respect to the adhesion layer is larger than the optical film. An adhesion | attachment auxiliary layer is produced by corona-processing an optical film, for example. You may prepare an adhesion | attachment auxiliary layer separately, and stick this to an optical film. Specifically, the adhesive auxiliary layer may be formed on at least one of the optical film surface and the adhesive layer surface. By forming an adhesion | attachment auxiliary layer, an adhesion layer can be easily formed on an optical film.

1 and 2 show examples of the pressure-sensitive adhesive optical film. The adhesive optical film 10 shown in FIG. 1 includes an optical film 11 and an adhesive layer 12 formed on one surface of the optical film 11. The adhesive layer 12 is formed on the optical film 11 by apply | coating the solution of an adhesive composition to one side of the optical film 11, and removing a solvent after that, for example. The optical film 11 may be a polarizer, for example. Thus, the adhesive composition may be used as an adhesive layer previously formed on an optical film. In addition, the adhesion layer 12 may be formed on both surfaces of the optical film 11. 2 shows a modification of the adhesive optical film 10. The adhesive optical film 10 shown in FIG. 2 has the adhesion | attachment auxiliary layer 11a formed between the optical film 11 and the adhesion layer 12. As shown in FIG. The adhesion auxiliary layer 11a is a layer whose wettability with respect to the adhesion layer 12 is larger than the optical film 11.

The display device of the present invention may include the adhesive optical film. Examples of the display device include a liquid crystal display device, an organic electroluminescent display device, and the like.

3 and 4 show a configuration example of a display device in which an adhesive layer according to one embodiment is formed. The display device 20 shown in FIG. 3 includes a display element 21, an adhesive layer 22, and an optical film 23. The optical film 23 is arrange | positioned on both surfaces of the display element 21, and the adhesion layer 22 adhere | attaches the display element 21 and the optical film 23. As shown in FIG. You may produce the display apparatus 20 by affixing the adhesive optical film which consists of the adhesion layer 22 and the optical film 23 to both surfaces of the display element 21. FIG. Moreover, you may form the adhesive bond layer 22 on both surfaces of the display element 21, and may affix the optical film 23 to the adhesive bond layer 22. FIG.

4 is a modification of the display device 20. As shown in FIG. 4, you may provide the multiple optical film on the display element 21. In the display device 20 shown in FIG. 4, the adhesive layer 24 and the optical film 25 are further provided on the optical film 23 of the display device 20 shown in FIG. 3. The adhesion layer 24 and the optical film 25 are provided on the optical film 23 by the method similar to the adhesion layer 22 and the optical film 23.

As described above, the display device 20 may be, for example, a liquid crystal display device, an organic EL display device, or the like. When the display device 20 becomes a liquid crystal display device, the display element 21 becomes a liquid crystal cell, and the optical film 23 becomes a polarizing film. Moreover, the optical film 25 becomes a viewing angle enlargement film, a brightness improving film, various protective films, etc., for example. In addition, when the display device 20 becomes a liquid crystal display device, you may arrange | position a phase difference plate between the adhesion layer 22 and the display element 21. FIG. In addition, the retardation plate and the display element 21 may be bonded by an adhesive layer. Although the film thickness of the display element 21 is not specifically limited, Although the adhesive composition which concerns on one Embodiment is a case where the display element 21 is thin (for example, 200 micrometers or less), it is not necessary for the display element 21 to be retained. While ensuring workability, it has high reliability. That is, even when either or both of an optical film and a display element is thin, the adhesive composition which concerns on one Embodiment has high reliability, ensuring rework property for these.

<< 점착층Adhesive layer 제조방법> Manufacturing Method>

The pressure-sensitive adhesive layer manufacturing method of the present invention includes the step of forming an adhesive layer with a pressure-sensitive adhesive composition for an optical film on one or both sides of the substrate, the pressure-sensitive adhesive composition for the optical film has an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g It may include a pressure-sensitive adhesive resin and a silicate oligomer represented by the formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₄ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100. Specifically, R ₁ to R ₄ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. It may be an aryl group of 12. For example, R ₁ to R ₄ may be a methyl group, an ethyl group, or a phenyl group.

The substrate may be an optical film. As said optical film, what is used for formation of image display apparatuses, such as a liquid crystal display device, is used, The kind in particular is not restrict | limited. The optical film is substantially the same as described in the pressure-sensitive adhesive layer. For example, a polarizing film is mentioned as an optical film.

The forming of the pressure-sensitive adhesive layer may include forming a layer including the pressure-sensitive adhesive composition for an optical film on one or both sides of the substrate, and performing a peroxide crosslinking treatment on the layer including the pressure-sensitive adhesive composition for the optical film.

Peroxide crosslinking may be performed in the preparation of the adhesive layer. This crosslinking treatment is substantially the same as described in the adhesive layer formation process, and specifically, the peroxide crosslinking treatment may be decomposed about 50 wt% or more of the peroxide crosslinking agent, and may be performed at about 130 ° C. or less, and the adhesive layer. The gel fraction may be from about 40% to about 95% by weight.

In one embodiment, the pressure-sensitive adhesive composition for an optical film includes about 0.01 part by weight to about 2 parts by weight, and about 0.02 part by weight to about 2 parts by weight, and about 0.04 parts by weight, based on about 100 parts by weight of the adhesive resin. About 1.5 parts by weight, about 0.05 parts by weight to about 1 part by weight may be further included.

In another embodiment, the pressure-sensitive adhesive composition for an optical film may contain about 0.01 parts by weight to about 50 parts by weight, specifically about 0.5 parts by weight to about 20 parts by weight, and more specifically about 0.5 parts by weight of the silicate oligomer based on 100 parts by weight of the adhesive resin. To about 10 parts by weight, even more specifically about 1 part to about 5 parts by weight. Within this range, the initial reworkability of the pressure-sensitive adhesive composition and the adhesion after heating may be further improved.

In another embodiment, the pressure-sensitive adhesive composition for an optical film may further include a crosslinking agent. The crosslinking agent may be an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, an imine crosslinking agent, or the like, but is not limited thereto.

Next, the Example of one specific Example is described. In the following examples, the concentration of the solution is expressed in weight percent relative to the total weight of the solution.

[[ 실시예Example ]]

<A. <A. 리워크성Reworkability 및 신뢰성 평가를 위한 And reliability assessment 실시예Example >>

The following examples and comparative examples were carried out to evaluate the reworkability and reliability of the adhesive layer.

제조예Production Example 1(아크릴 수지의 1 (acrylic resin 제조예Production Example ))

By the following process, the acrylic resin (polymer A1) which is an example of adhesive resin was produced. In a four-necked flask equipped with a stirring vane, a thermometer, a nitrogen gas introduction tube, and a cooler, 99 parts by weight of butyl acrylate, 1 part by weight of 4-hydroxybutyl acrylate, and 2,2'-azobis isobutyro as a polymerization initiator 0.15 parts by weight of nitrile was injected together with 100 parts by weight of ethyl acetate. And nitrogen gas was introduce | transduced into the four neck flask by nitrogen stirring, stirring a mixed solution gently. Thereafter, the liquid temperature in the flask was maintained at about 55 ° C, and the monomers were allowed to undergo a polymerization reaction for 5 hours. This produced the solution of the polymer A1. The weight average molecular weight (Mw) of the polymer A1 was 2.1 million. In addition, the acid value of the polymer A1 was 0 mgKOH / g. Table 1 shows the composition of the polymer A1 (weight ratio of the monomers constituting the polymer A1), the weight average molecular weight and the acid value.

Here, the weight average molecular weight of polymer A1 was measured by GPC (gel permeation chromatography). The measuring apparatus and measuring conditions are as follows.

Analysis device: Tosoh Corporation, HLC-8120GPC

Column: Tosoh Corporation, G7000HXL + GMHXL + GMHXL

Column size: Each 7.8 mm diameter x 30 cm 90 cm

Column temperature: 40 ℃

Flow rate: 0.8 ml / min

Injection volume: 100 μl

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: Polystyrene

In addition, the acid value of the polymer A1 was measured by the following process. A mixed solvent containing toluene, isopropyl alcohol, and distilled water in a weight ratio of 50: 49.5: 0.5 was prepared. Next, about 0.5 g (based on solids) of Polymer A1 was precisely weighed and dissolved in 50 g of the mixed solvent. This prepared the sample solution for titration. This sample solution was neutralized and titrated with a 0.1% KOH aqueous solution using a titration device manufactured by Hiranma (MA), form "COMTITE-550". The acid value of the polymer A1 was computed by the obtained result and following [formula 2].

[Equation 2]

Acid value [mgKOH / g] = (a-b) × 5.611 × F / S

In equation 2,

a: amount of KOH aqueous solution required for titration of the sample solution [ml]

b: Amount of KOH aqueous solution required for titration of the blank (mixed solvent) [ml]

F: Activity of KOH Aqueous Solution

S: Weight of Resin Contained in Sample Solution Provided for Titration [g]

to be.

제조예Production Example 2 내지 7(아크릴 수지의 2 to 7 (acrylic resin 제조예Production Example ))

Except having changed the kind and weight ratio of the monomer put into a four neck flask as Table 1, polymer A2-A6 were produced by performing the process similar to Production Example 1. In addition, the weight average molecular weights and the acid value of polymers A2 to A7 were measured by the same method as in Production Example 1. The results are summarized in Table 1.

제조예Production Example 8(우레탄 수지의 8 (of urethane resin 제조예Production Example ))

The urethane resin (polymer A8) was produced by the following process. 51.9 g of polyester polyol P-1010 (bifunctional polyester polyol, OH of 112 mg / g, manufactured by Kuraray Co., Ltd.) in a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introducing tube, a thermometer, and a dropping funnel; Adeka polyether G-1500 (trifunctional polyether poly, trifunctional, OH value 109 mg / g, manufactured by ADEKA Corporation) 32.2 g, isophorone diisocyanate (IPDI) (manufactured by Sumitomo Bayer Corporation) 15.9 g, 66.7 g of toluene, 0.03 g of iron 2-ethylhexanoate and 0.04 g of lead naphthenate were added as a catalyst.

Next, the mixed solution was gradually heated up to 90 ° C, and the monomers were polymerized for 4 hours. The residual isocyanate group was confirmed by an infrared spectrophotometer (IR), the reaction was terminated at the timing when the peak corresponding to the isocyanate group disappeared, and the mixed solution after the reaction, that is, the solution of the urethane resin was cooled. The solution of urethane resin was colorless transparent and 60 weight% of solid content. The weight average molecular weight and the acid value were measured by the same method as in Production Example 1, and the weight average molecular weight was 50,000 and the acid value was 0.5 KOHmg / g. Table 2 shows the composition (weight ratio of monomers constituting polymer A8), weight average molecular weight and acid value of polymer A8.

제조예Production Example 9(폴리에스테르 수지의 9 (of polyester resin 제조예Production Example ))

The polyester resin (polymer A9) was produced with the following process. In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 11.7 g of ethylene glycol, 18.6 g of neopentyl glycol, 11.8 g of isophthalic acid, 57.9 g of sebacic acid, and tetra-n-butyl titanate 0.15 g was added. Then, esterification reaction was performed by heating a mixed solution at 150-270 degreeC for 150 minutes, and then the pressure of the reaction system was gradually lowered to 133 Pa after 30 minutes, and reaction was performed for 180 minutes, continuing pressure reduction. Next, the solution of the polyester resin was obtained by diluting the mixed solution after reaction with ethyl acetate. Solid content of this solution was 60 weight%. The weight average molecular weight and the acid value of the polyester resin were measured by the same method as in Production Example 1, and the weight average molecular weight was 38,000 and the acid value was 0.3 KOHmg / g. The composition (weight ratio of the monomers which comprise Polymer A8), the weight average molecular weight, and the acid value of polymer A9 are shown in Table 3.

제조예Production Example	폴리머Polymer	폴리머종류Polymer type	BABA	2HEA2HEA	4HBA4HBA	AAAA	분자량(Mw)Molecular Weight (Mw)	산가(mgKOH/g)Acid value (mgKOH / g)
1One	A1A1	아크릴acryl	9999	--	1One	--	210만2.1 million	00
22	A2A2	아크릴acryl	9999	0.10.1	--	0.90.9	210만2.1 million	77
33	A3A3	아크릴acryl	96.696.6	--	1One	2.42.4	210만2.1 million	18.718.7
44	A4A4	아크릴acryl	9595	--	--	55	210만2.1 million	38.938.9
55	A5A5	아크릴acryl	9696	--	1One	33	210만2.1 million	23.423.4
66	A6A6	아크릴acryl	9999	--	--	1One	210만2.1 million	7.87.8
77	A7A7	아크릴acryl	9999	--	1One	--	80만800,000	00
BA: 부틸아크릴레이트, 2HEA: 2-하이드록시 에틸아크릴레이트,4HBA: 4-하이드록시 부틸아크릴레이트, AA: 아크릴산BA: Butyl acrylate, 2HEA: 2-hydroxy ethyl acrylate, 4HBA: 4-hydroxy butyl acrylate, AA: Acrylic acid

제조예Production Example	폴리머Polymer	폴리머종류Polymer type	P-1010P-1010	G-1500G-1500	IPDIIPDI	분자량(Mw)Molecular Weight (Mw)	산가(mgKOH/g)Acid value (mgKOH / g)
88	A8A8	우레탄urethane	51.951.9	32.232.2	15.915.9	5.0만5.0 million	0.50.5
P-1010: 폴리에스테르폴리올, G-1500: 아데카 폴리에테르IPDI: 이소-포론 다이-아이소-사이아네이트P-1010: polyester polyol, G-1500: adeka polyether IPDI: iso-phoron di-iso-cyanate

제조예Production Example	폴리머Polymer	폴리머종류Polymer type	EGEG	NPGNPG	IPAIPA	SASA	분자량(Mw)Molecular Weight (Mw)	산가(mgKOH/g)Acid value (mgKOH / g)
99	A9A9	폴리에스테르Polyester	11.711.7	18.618.6	11.811.8	57.957.9	3.8만3.8 million	0.30.3
EG:에틸렌 글라이콜, NPG:네오펜틸 글라이콜IPA: 아이소 프탈산, SA:세바스산EG: ethylene glycol, NPG: neopentyl glycol IPA: isophthalic acid, SA: sebacic acid

Component contents of Tables 1 to 3 are expressed in parts by weight.

제조예Production Example 10(고분자량 타입의 10 (of high molecular weight type 제조예Production Example ))

By the following process, the high molecular weight type silicate oligomer B1 was produced. 152 g (1 mol, 4 equivalents) of tetramethoxysilane was dissolved in 500 g of tetrahydrofuran (hereinafter also referred to as "THF"). Next, 72 g (8 equivalents) of 0.35% by weight aqueous hydrochloric acid solution was added to the obtained solution and mixed. Next, the tetramethoxysilane was hydrolyzed by standing the mixed solution at 20 ° C for 1 hour. Next, 450 g of polymethoxysiloxane ("MKC silicate MS-51" by Mitsubishi Chemical Co., Ltd.) was added to the solution after hydrolysis, ie, the reaction solution, and refluxed for 2 hours. Then, THF was made to flow out by raising the temperature of the reaction solution to 150 degreeC. This gave the silicate oligomer B1 of the colorless and transparent liquid form. The weight average molecular weight of the silicate oligomer B1 was 25,000. In addition, the polymethoxysiloxane ("MKC silicate MS-51") of a raw material is an oligomer of 900 with a weight average molecular weight. Thus, the hydrolyzed tetramethoxysilane and polymethoxysiloxane were bonded to each other, resulting in a high molecular weight silicate oligomer. R ₁ to R ₄ , X ₁ and X ₂ of the silicate oligomer B1 are all represented by Formula 1, which is a methyl group.

In addition, the measurement of the weight average molecular weight of the silicate oligomer B1 was measured by GPC (gel permeation chromatography).

The measuring apparatus and measuring conditions are as follows.

Analysis device: Tosoh Corporation, HLC-8120GPC

Column: TSKgel, SuperHZM-H / HZ4000 / HZ2000

Column size: 6.0 mm (inner diameter) x 150 mm

Column temperature: 40 ℃

Flow rate: 0.6 ml / min

Injection volume: 20 μl

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: Polystyrene

제조예Production Example 11( 11 ( 페녹시Phenoxy 타입의 Type of 제조예Production Example ))

In the following steps, silicate oligomer B2 in which R ₁ to R ₄ , X ₁ and X ₂ are phenyl groups or methyl groups (R ₁ to R ₄ , X _1, or X ₂ is a phenyl group) was prepared. 400 g (1 mole, 4 equivalents) of tetraphenoxysilane was dissolved in 500 g of THF. Next, 72 g (8 equivalents) of 0.35% by weight aqueous hydrochloric acid solution was added to the obtained solution and mixed. Next, the tetraphenoxysilane was hydrolyzed by standing the mixed solution at 20 ° C for 1 hour. Next, 450 g of polymethoxysiloxane ("MKC silicate MS-51" by Mitsubishi Chemical Co., Ltd.) was added to the solution after hydrolysis, ie, the reaction solution, and refluxed for 2 hours. Then, THF was made to flow out by raising the temperature of the reaction solution to 150 degreeC. This obtained the silicate oligomer B2 which is a colorless and transparent liquid form. The weight average molecular weight of the silicate oligomer B2 was measured in the same manner as in Production Example 10, and the weight average molecular weight of the silicate oligomer B2 was 5,000. Moreover, polymethoxysiloxane ("MKC silicate MS-51") which is a raw material is an oligomer of 900 molecular weight. Thus, the hydrolyzed tetraphenoxysilane and the polymethoxysiloxane were bonded to each other to produce a silicate oligomer B2 wherein R ₁ to R ₄ , X ₁ and X ₂ are phenyl groups or methyl groups.

Moreover, this inventor obtained several silicate oligomers in addition to the above, and provided for each following experiments.

광학 필름의 Of optical film 제조예Production Example

제조예Production Example 12( 12 ( 편보호Protection 편광 필름) Polarizing film)

By the following process, the single protection polarizing film was produced as an optical film. A 20-micrometer-thick polyvinyl alcohol film was stretched up to three times while dyeing in a 0.3 wt% iodine solution at 30 ° C for 1 minute between rolls having different speed ratios. Thereafter, the stretched film was stretched to 6 times while immersing the stretched film in an aqueous solution containing 60 ° C., 4 wt% boric acid, and 10 wt% potassium iodide for 0.5 minute. Next, the stretched film was washed by immersion for 10 seconds in an aqueous solution containing 30 ° C and 1.5% by weight of potassium iodide, and then dried at 50 ° C for 4 minutes. This obtained the polarizer. And the acrylic film (lactone modified acrylic resin film) of 20 micrometers in thickness was bonded to one surface of the polarizer with the polyvinyl alcohol-type adhesive agent. An acrylic film is an example of a protective film. This produced the single protection polarizing film whose total thickness is 27 micrometers.

<< 실시예Example 1> 1>

Preparation of pressure-sensitive adhesive composition

5 parts by weight of methyl silicate 51 (weight average molecular weight 550), manufactured by COLCOAT CO. LTD, as the silicate oligomer B, based on 100 parts by weight of the polymer A1 solution obtained in Production Example 1, isocyanate-based crosslinking agent carbonate D110N (75 wt% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, number of isocyanate groups in 1 molecule: 3, manufactured by Mitsui Chemical Co., Ltd.) 0.1 part by weight and silane coupling agent (trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) 0.1 parts by weight of the product, 3-glycidoxypropyltrimethoxysilane). This obtained the adhesive composition solution (solid content 15weight%). Table 4 shows the composition of the pressure-sensitive adhesive composition.

Preparation of adhesive polarizing film (adhesive optical film)

The thickness of the adhesive layer after drying was carried out on one side of the polyethylene terephthalate (PET) film (Mitsubishi Chemical Co., Ltd. product, MRF38, the oligomer prevention layer) of 38 micrometers in thickness which siliconized the said adhesive composition solution. It applied so that it might become 20 micrometers. Next, the coating layer was dried at 100 ° C. for 2 minutes to form an adhesive layer. A pressure-sensitive adhesive polarizing film was produced by bonding an adhesive layer to a polarizer surface (corona treated surface) subjected to corona treatment at a corona discharge amount of 80 [W · min / m 2] to the single protective polarizing film prepared in Production Example 12. It was.

실시예Example 2 내지 22, 2 to 22, 비교예Comparative example 1 내지 8 1 to 8

Except having changed the composition of adhesive resin into the composition shown in Table 4, Table 5, and Table 6, it carried out similarly to Example 1, and produced the adhesive polarizing film.

	접착 성 수지Adhesive resin		실리케이트 올리고머 BSilicate Oligomer B			가교제 1Crosslinking agent 1		가교제 2Crosslinking agent 2		실란 커플 링제Silane coupling agent
	종류Kinds	질량 부Mass parts	종류Kinds	첨가량Amount	MwMw	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount
	종류Kinds	질량 부Mass parts	종류Kinds	(중량 부)(Parts by weight)	MwMw	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)
실시예1Example 1	A1A1	100100	B3B3	55	550550	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	0.10.1
실시예2Example 2	A1A1	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--
실시예3Example 3	A1A1	100100	B4B4	0.50.5	900900	D-110ND-110N	0.10.1	--	--	--	--
실시예4Example 4	A1A1	100100	B4B4	3030	900900	D-110ND-110N	0.10.1	--	--	--	--
실시예5Example 5	A1A1	100100	B6B6	55	13001300	D-110ND-110N	0.10.1	--	--	--	--
실시예6Example 6	A1A1	100100	B7B7	55	14001400	D-110ND-110N	0.10.1	--	--	--	--
실시예7Example 7	A1A1	100100	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.10.1	--	--
실시예8Example 8	A1A1	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	0.010.01
실시예9Example 9	A1A1	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	0.10.1
실시예10Example 10	A1A1	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	1One
실시예11Example 11	A1A1	100100	B1B1	1One	2500025000	D-110ND-110N	0.10.1	--	--	--	--

	접착 성 수지Adhesive resin		실리케이트 올리고머 BSilicate Oligomer B			가교제 1Crosslinking agent 1		가교제 2Crosslinking agent 2		실란 커플 링제Silane coupling agent
	종류Kinds	질량 부Mass parts	종류Kinds	첨가량Amount	MwMw	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount
	종류Kinds	질량 부Mass parts	종류Kinds	(중량 부)(Parts by weight)	MwMw	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)
실시예12Example 12	A1A1	100100	B2B2	33	50005000	D-110ND-110N	0.10.1	--	--	--	--
실시예13Example 13	A1A1	100100	B5B5	55	32003200	D-110ND-110N	0.10.1	--	--	--	--
실시예14Example 14	A2A2	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--
실시예15Example 15	A2A2	100100	B4B4	55	900900	V-05V-05	0.10.1	--	--	--	--
실시예16Example 16	A1A1	100100	B5B5	55	32003200	WS-700WS-700	0.10.1	--	--	--	--
실시예17Example 17	A1A1	100100	B5B5	55	32003200	Tetrad XTetrad X	0.10.1	--	--	--	--
실시예18Example 18	A3A3	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--
실시예19Example 19	A3A3	100100	B4B4	55	900900	V-05V-05	0.10.1	--	--	--	--
실시예20Example 20	A8A8	100100	B4B4	55	900900	D-110ND-110N	1010	--	--	--	--
실시예21Example 21	A9A9	100100	B4B4	55	900900	D-110ND-110N	1010	--	--	--	--
실시예22Example 22	A6A6	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--

	접착 성 수지Adhesive resin		실리케이트 올리고머 BSilicate Oligomer B			가교제 1Crosslinking agent 1		가교제 2Crosslinking agent 2		실란 커플 링제Silane coupling agent
	종류Kinds	질량 부Mass parts	종류Kinds	첨가량Amount	MwMw	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount	종류Kinds	첨가량Amount
	종류Kinds	질량 부Mass parts	종류Kinds	(중량 부)(Parts by weight)	MwMw	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)	종류Kinds	(중량 부)(Parts by weight)
비교예1Comparative Example 1	A1A1	100100	없음none	00	--	D-110ND-110N	0.10.1	--	--	--	--
비교예2Comparative Example 2	A4A4	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--
비교예3Comparative Example 3	A4A4	100100	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.10.1	--	--
비교예4Comparative Example 4	A4A4	100100	없음none	00	--	D-110ND-110N	0.10.1	--	--	--	--
비교예5Comparative Example 5	A5A5	100100	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	--	--
비교예6Comparative Example 6	A5A5	100100	없음none	00	--	D-110ND-110N	0.10.1	--	--	--	--
비교예7Comparative Example 7	A8A8	100100	없음none	00	--	D-110ND-110N	1010	--	--	--	--
비교예8Comparative Example 8	A9A9	100100	없음none	00	--	D-110ND-110N	1010	--	--	--	--

In Tables 4, 5 and 6, the silicate oligomer B3 is methyl silicate 51 having R ₁ to R ₄ , X ₁ and X ₂ all being methyl groups and having a weight average molecular weight of 600. The silicate oligomer B4 is methyl silicate 53A (manufactured by Cole Coat Co., Ltd.), wherein R ₁ to R ₄ , X ₁ and X ₂ are all methyl groups and a weight average molecular weight is 900. Silicate oligomer B5 is R ₁ to R ₄ , X ₁ and X ₂ are butyl groups (15%), the rest are methyl groups (85%), and MKC silicate MS58B15 (manufactured by Mitsubishi Kagaku Co., Ltd.) with a weight average molecular weight of 3,200. . A silicate oligomer B6 is R ₁ to R _4, X ₁ and X ₂ is a methyl group (50%) and an ethyl group (50%), and a weight average molecular weight of 1,300 of EMS-485 (Cole Coat Co., Ltd.). The silicate oligomer B7 is ethyl silicate 48 (manufactured by Cole Coat Co., Ltd.), wherein R ₁ to R ₄ , X ₁ and X ₂ are all ethyl groups and have a weight average molecular weight of 1,400.

In addition, PEROYL TCP is a peroxide crosslinking agent manufactured by NOF CORPORATION.

<물성평가방법><Property evaluation method>

(1) 신뢰성 평가 시험(1) reliability evaluation test

The reliability evaluation test was done about the adhesive polarizing film (adhesive optical film) which concerns on each Example and the comparative example. Specifically, the pressure-sensitive adhesive polarizing film (sample) is cut out into a 37-inch size (56.4 cm x 75.2 cm size) and laminated to an alkali-free glass (Corning Company, Eagle XG) having a thickness of 0.5 mm. It was attached using a laminater (laminating machine). Moreover, an alkali free glass is used as a liquid crystal cell glass substrate. In addition, what attached two sheets of alkali free glass of thickness 0.25mm is used for an actual liquid crystal cell. And in this test and the adhesive force and rework property evaluation test mentioned later, an adhesive type polarizing film is affixed on both surfaces of such an alkali free glass. Therefore, what is excellent in these characteristics means that an adhesive type polarizing film can be used suitably as a polarizing film of a liquid crystal cell.

Subsequently, the sample was completely adhered to the alkali free glass by autoclaving the glass plate with a polarizing film at 50 degreeC and 0.5 Mpa for 15 minutes. The glass plate with a polarizing film (henceforth a "initial glass plate" hereafter) with which this process was performed was hold | maintained at 85 degreeC for 500 hours (heating test). In addition, the initial stage glass plate was processed for 500 hours in 60 degreeC / 95% RH (relative humidity) atmosphere (humidification test). Moreover, the heat cycle which hold | maintains an initial glass plate at 85 degreeC for 30 minutes and -40 degreeC for 30 minutes was performed (heat shock test). After each test, the appearance between the polarizing film and the glass was visually evaluated based on the following criteria. The evaluation results are shown in Table 7, Table 8 and Table 9.

(Double-circle): There is no change in external appearance, such as foaming, peeling, and no lifting.

(Circle): Although there exists peeling or foaming at the edge part although it is slightly, there is no problem practically.

(Triangle | delta): Although there exists peeling or foaming at the edge part, if there is no special use, there is no problem practically.

X: There exists a peeling remarkably at the edge part, and there exists a problem practically.

(2) 접착력 및 (2) adhesion and 리워크성Reworkability 평가 시험 Evaluation test

The adhesive force evaluation test was done about the adhesive polarizing film (adhesive optical film) which concerns on each Example and the comparative example. Specifically, the adhesive polarizing film (sample) was cut out to width 25mm x length 100mm, and was affixed on the alkali free glass plate (Corning Company, Eagle XG) of thickness 0.5mm using a laminator. Next, the polarizing film was completely stuck to the alkali free glass by autoclaving a glass plate with a polarizing film at 50 degreeC and 5atm for 15 minutes. This produced the initial glass plate. Next, the initial glass plate was heated for 48 hours under 50 ° C drying conditions. This produced the glass plate after heating. And the adhesive force of the initial glass plate and the glass plate after heating was measured by the following method.

That is, the adhesive force (N / 25mm) at the time of removing a polarizing film from each glass plate was measured using the tensile tester (Tensilon universal material tester STA-1150 by Orient Tech Co., Ltd.). Measurement conditions were made into 23 degreeC, 50% of a relative humidity, 180 degree of peeling angles, and 300 mm / min of peeling rates. In addition, peeling was performed based on the method of the adhesive tape and adhesive sheet test of JISZ0237.

Moreover, the rework property evaluation test was done about the adhesive polarizing film (sample). Specifically, the initial glass plate and the glass plate after heating were produced by first performing the process similar to the adhesive force evaluation test with respect to an adhesive polarizing film (sample). However, the magnitude | size of the adhesive polarizing film (sample) was made into 420 mm in width x 320 mm in length. Thereafter, the polarizing film was peeled off by the human hand from the initial glass plate and the glass plate after heating. And the process similar to the above was repeated 3 times. That is, three sheets of an initial glass plate and a glass plate after heating were each created, and the polarizing film was peeled off from each glass plate. And the reworkability (actual reworkability) of each adhesive composition is evaluated on the following reference | standard, and it shows in Table 7, Table 8, and Table 9.

(Double-circle): All three sheets can peel easily, without full residue and the breakage of a polarizing film. There was no breakage of the alkali free glass.

(Circle): Although some of 3 sheets broke a film, it peeled again by peeling again. There was no breakage of the alkali free glass.

(Triangle | delta): Although all three films broke, it peeled by peeling again. There was no breakage of the alkali free glass.

X: Even if all 3 sheets had pull residue, or peeled several times, a film broke and it could not peel. Moreover, there existed a case where an alkali free glass broke.

	신뢰성responsibility			리 워크 성Lee Walk Castle
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)	가열 후 실제 리워크성Actual rework after heating
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)
실시예1Example 1	◎◎	◎◎	◎◎	1.11.1	◎◎	1.91.9	○○
실시예2Example 2	◎◎	◎◎	◎◎	0.50.5	◎◎	0.80.8	◎◎
실시예3Example 3	○○	○○	○○	1.61.6	◎◎	2.52.5	○○
실시예4Example 4	○○	○○	○○	0.20.2	◎◎	0.40.4	○○
실시예5Example 5	◎◎	◎◎	◎◎	1.91.9	○○	2.82.8	○○
실시예6Example 6	◎◎	◎◎	◎◎	2.32.3	○○	2.92.9	△△
실시예7Example 7	◎◎	◎◎	◎◎	0.40.4	◎◎	1One	◎◎
실시예8Example 8	◎◎	◎◎	◎◎	0.50.5	◎◎	0.80.8	◎◎
실시예9Example 9	◎◎	◎◎	◎◎	0.60.6	◎◎	1One	◎◎
실시예10Example 10	◎◎	◎◎	◎◎	1.21.2	◎◎	2.22.2	○○
실시예11Example 11	◎◎	◎◎	◎◎	0.30.3	◎◎	0.90.9	◎◎

	신뢰성responsibility			리 워크 성Lee Walk Castle
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)	가열 후 실제 리워크성Actual rework after heating
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)
실시 예 12Example 12	◎◎	◎◎	◎◎	0.50.5	◎◎	1.31.3	◎◎
실시 예 13Example 13	◎◎	◎◎	◎◎	0.40.4	◎◎	0.90.9	◎◎
실시 예 14Example 14	◎◎	◎◎	◎◎	1.31.3	◎◎	22	○○
실시 예 15Example 15	◎◎	○○	◎◎	1One	◎◎	1.51.5	◎◎
실시 예　16Example # 16	◎◎	○○	◎◎	0.80.8	◎◎	1.31.3	◎◎
실시 예　17Example 17	◎◎	○○	◎◎	0.70.7	◎◎	1.21.2	◎◎
실시 예 18Example 18	◎◎	◎◎	◎◎	2.62.6	○○	3.53.5	△△
실시 예 19Example 19	◎◎	○○	◎◎	2.22.2	○○	2.72.7	○○
실시 예　20 Example # 20	◎◎	○○	◎◎	0.90.9	◎◎	1.21.2	◎◎
실시 예　21Example 21	◎◎	○○	◎◎	1.21.2	◎◎	1.81.8	◎◎
실시 예 22Example 22	○○	○○	○○	0.50.5	◎◎	0.80.8	◎◎

	신뢰성responsibility			리 워크 성Lee Walk Castle
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)	가열 후 실제 리워크성Actual rework after heating
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기접착력(N/25mm)Initial adhesive force (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)
비교 예 1Comparative Example 1	○○	○○	○○	33	△△	6.56.5	××
비교 예 2Comparative Example 2	◎◎	◎◎	◎◎	4.54.5	××	9.29.2	××
비교 예 3Comparative Example 3	◎◎	◎◎	◎◎	5.25.2	××	10.910.9	××
비교 예 4Comparative Example 4	○○	○○	○○	6.26.2	××	11.511.5	××
비교 예 5Comparative Example 5	◎◎	◎◎	◎◎	3.63.6	△△	5.15.1	××
비교 예 6Comparative Example 6	◎◎	○○	◎◎	3.23.2	△△	4.54.5	××
비교 예 7Comparative Example 7	○○	△△	○○	2.22.2	○○	4.54.5	××
비교 예 8Comparative Example 8	○○	△△	○○	3.53.5	△△	5.85.8	××

As shown in Table 7 and Table 8, it was confirmed that the pressure-sensitive adhesive composition according to the present example is compatible with reworkability and reliability. In particular, both the polarizing film and the alkali free glass used in the evaluation test were thin, but when the pressure-sensitive adhesive composition according to the present example was used, the polarizing film and the alkali free glass could be peeled off from the alkali free glass almost without destroying it. Moreover, according to Table 9, when adhesive force exceeds 3 N / 25mm, it may be a thing which tends to be inferior to rework property.

<B. <B. 리워크성Reworkability , 신뢰성 및 작업성에 관한 , Reliability and workability 실시예Example >>

The following examples and comparative examples were carried out to evaluate the reworkability, reliability and workability of the pressure-sensitive adhesive layer (whether or not aging of the adhesive film).

실리케이트Silicate 올리고머 Oligomer

As silicate oligomers, the silicate oligomers used in the Examples for A. Reworkability and Reliability Evaluation were prepared. Specifically, the above-mentioned silicate oligomer B1 (preparation example 10), B2 (preparation example 11), 트 methyl silicate 51 (silicate oligomer B3), methyl silicate 53A (silicate oligomer B4) MKC silicate MS58B15 (silicate oligomer B5), EMS-485 ( Silicate oligomer B6) and ethyl silicate 48 (silicate oligomer B7).

과산화물 가교제Peroxide Crosslinking Agent

As peroxide-based crosslinking agent, A. Perbutyl ND (1 minute half-life temperature 103.5 ° C) in addition to peroyl TCP (1 minute half-life temperature 92.1 ° C.) used in Examples for reworkability and reliability evaluation And perbutyl PV '(1 minute half life temperature of 110.3 ° C) was prepared.

광학 필름의 제조Manufacture of optical film

A. The optical film (fragmentation protective polarizing film) used by the Example for reworkability and reliability evaluation was prepared.

실시예Example 23 내지 47 및 23 to 47 and 비교예Comparative example 9 내지 15 9 to 15

A pressure-sensitive adhesive polarizing film was produced in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition was changed to the composition shown in Tables 10 and 11 and the drying temperature was applied at the temperatures shown in Tables 10 and 11. Specifically, the drying temperature was applied differently depending on the type of peroxide crosslinking agent. For example, Example 23 applied a drying temperature of peroyl TCP, 120 ° C. (2 minutes), with a 1 minute half life temperature of 92.1 ° C. At least 50% by weight of the peroxide crosslinking agent was decomposed by this drying treatment.

	점착성 수지Adhesive resin	실리케이트 올리고머(B)Silicate oligomer (B)			가교제Crosslinking agent		과산화물계 가교제Peroxide Crosslinking Agent		실란 커플링제Silane coupling agent		건조온도(℃)/시간(분)Drying temperature (℃) / hour (minutes)
	100 중량부100 parts by weight	종류Kinds	함량(중량부)Content (parts by weight)	분자량(Mw)Molecular Weight (Mw)	종류Kinds	함량(중량부)Content (parts by weight)	종류Kinds	함량(중량부)Content (parts by weight)	종류Kinds	함량(중량부)Content (parts by weight)	건조온도(℃)/시간(분)Drying temperature (℃) / hour (minutes)
실시예23Example 23	A1A1	B3B3	55	550550	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예24Example 24	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예25Example 25	A1A1	B4B4	0.50.5	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예26Example 26	A1A1	B4B4	3030	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예27Example 27	A1A1	B6B6	55	13001300	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예28Example 28	A1A1	B7B7	55	14001400	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예29Example 29	A1A1	B1B1	1One	2500025000	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예30Example 30	A1A1	B2B2	33	50005000	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예31Example 31	A1A1	B5B5	55	32003200	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예32Example 32	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.050.05	--	--	120/5120/5
실시예33Example 33	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	1.51.5	--	--	120/2120/2
실시예34Example 34	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼부틸NDPerbutylND	0.30.3	--	--	130/2130/2
실시예35Example 35	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼부틸PVPerbutyl PV	0.30.3	--	--	130/2130/2
실시예36Example 36	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	KBM-403KBM-403	0.010.01	120/2120/2
실시예37Example 37	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	KBM-403KBM-403	0.10.1	120/2120/2
실시예38Example 38	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	KBM-403KBM-403	1One	120/2120/2

	점착성 수지Adhesive resin	실리케이트 올리고머(B)Silicate oligomer (B)			가교제Crosslinking agent		과산화물계 가교제Peroxide Crosslinking Agent		실란 커플링제Silane coupling agent		건조온도(℃)/시간(분)Drying temperature (℃) / hour (minutes)
	100 중량부100 parts by weight	종류Kinds	함량(중량부)Content (parts by weight)	분자량(Mw)Molecular Weight (Mw)	종류Kinds	함량(중량부)Content (parts by weight)	종류Kinds	함량(중량부)Content (parts by weight)	종류Kinds	함량(중량부)Content (parts by weight)	건조온도(℃)/시간(분)Drying temperature (℃) / hour (minutes)
실시예39Example 39	A1A1	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	140/2140/2
실시예40Example 40	A7A7	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예41Example 41	A2A2	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예42Example 42	A2A2	B4B4	55	900900	V-05V-05	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예43Example 43	A2A2	B4B4	55	900900	WS-500WS-500	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예44Example 44	A2A2	B4B4	55	900900	Tetrad XTetrad X	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예45Example 45	A3A3	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예46Example 46	A8A8	B4B4	55	900900	D-110ND-110N	1010	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
실시예47Example 47	A9A9	B4B4	55	900900	D-110ND-110N	1010	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
비교예9Comparative Example 9	A1A1	--	--	--	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	0.10.1	120/2120/2
비교예10Comparative Example 10	A4A4	B4B4	55	900900	D-110ND-110N	0.10.1	--	--	KBM-403KBM-403	0.10.1	120/2120/2
비교예11Comparative Example 11	A4A4	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	KBM-403KBM-403	0.10.1	120/2120/2
비교예12Comparative Example 12	A4A4	--	--	--	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
비교예13Comparative Example 13	A5A5	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	KBM-403KBM-403	0. 10. 1	120/2120/2
비교예14Comparative Example 14	A5A5	B4B4	55	900900	D-110ND-110N	0.10.1	퍼로일TCPPeroyl TCP	0.30.3	--	--	120/2120/2
비교예15Comparative Example 15	A5A5	--	--	--	D-110ND-110N	0.10.1	--	--	--	--	120/2120/2

In Table 11, V-05 is a carbodiimide crosslinking agent manufactured by NISSHINBO Co., Ltd., WS-500 is an oxazoline crosslinking agent of Nippon Catalyst, and Tetrad X is an epoxy crosslinking agent of Mitsubishi Gas Chemical.

(1) Reliability, Adhesion, and Reworkability Evaluation Tests: A. Evaluation was carried out in the same manner as in Example for reworkability and reliability evaluation, and is shown in Tables 12 and 13.

(2) Calculation of gel fraction: The gel fraction was dried for 2 minutes at 100 ° C. and crosslinked to form a pressure-sensitive adhesive layer so that the thickness after drying the pressure-sensitive adhesive composition was 20 μm, and the pressure-sensitive adhesive layer had a temperature of 23 ° C. and a humidity of 65% RH. After leaving for 1 hour under the condition of can be calculated by the following formula (1).

[Equation 1]

Gel fraction (% by weight) = {(Wc-Wa) / (Wb-Wa)} × 100

In Formula 1, Wb is a weight in which 0.2g of the adhesive layer is wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin. In addition, Wc was immersed in 40 ml of ethyl acetate at 23 ° C. for 7 days to extract the soluble component, and Wc was dried on an aluminum cup at 130 ° C. for 2 hours, and then soluble. It is the weight of the adhesion layer wrapped with the fluorine resin from which the powder was removed.

(3) Evaluation of Need for Aging (Workability): If the gel fraction calculated above is 40% by weight or more, there is no concern about crushing and deterioration of durability, so no aging treatment is required. Therefore, evaluation of the necessity of aging according to the gel fraction was carried out as follows. The evaluation results are shown in Table 12 and Table 13.

○: If the gel fraction is 65% or more, there is no fear of crushing, workability or durability deterioration.

(Triangle | delta): When the gel fraction is 40% or more and less than 65%, there is no fear of crushing phenomenon.

X: When the gel fraction is less than 40%, crushing may occur, and workability and durability deteriorate.

In this case, the pressing phenomenon means that when pressed together with a pressure-sensitive adhesive optical film (sample) for evaluation of reworkability and reliability, the pressing is visually confirmed on the surface of the optical film. Manufactured as a pressure-sensitive adhesive optical film (sample) for evaluation of the reliability and reliability (420mmX320mm), and within one hour through a square hole with a side length of 270mm in the optical film, the hand and the naked eye on the side of the polarizing film This means that adhesiveness is observed or surface contamination of the polarizing film is observed.

(4) Determination of PET oligomer deposition amount: The separator was removed after leaving the above-mentioned adhesive polarizing film (including separator) at 60 ° C. and 90% RH for 500 hours. Subsequently, about 0.025 g of the adhesive layer was taken from the adhesive type polarizing film, 1 ml of chloroform was added, and after shaking for 18 hours at room temperature, 5 ml of acetonitrile was further extracted and shaken for 3 hours. The obtained solution was filtered with a 0.45 ml membrane filter, a standard product of PET oligomer of trimer was adjusted to a constant concentration to prepare a calibration curve, and the calibration curve was used to request the amount (ppm) of PET oligomer contained in the pressure-sensitive adhesive. The calibration curve was determined by HPLC (high performance liquid chromatography) using a sample of known PET oligomer concentration (ppm). HPLC apparatus, HPLC measurement conditions, and PET oligomer amount quantification method are as follows.

HPLC instrument: Agilent Technologies 1200 Series

Measuring conditions

Column: ZORBAX SB-C18 from Agilent Technologies

Column temperature: 40 ℃

Heat flow rate: 0.8ml / min

Eluent composition: water / acetonitrile reverse phase gradient conditions

Injection volume: 5 μl

Detector: PDA (photo diode array)

Quantitative method: A standard sample of PET oligomer trimer was dissolved in chloroform and diluted with acetonitrile to adjust the sample to a constant concentration. The calibration curve was created in the HPLC area and the adjusted concentration. The sample PET oligomer amount (the amount of oligomer deposited on the adhesive layer) was determined along the calibration curve. The results are shown in Table 12 and Table 13.

	신뢰성responsibility			리워크성Reworkability				겔분율(질량%)Gel fraction (mass%)	작업성Workability	올리고머 석출양(ppm)Oligomer precipitation amount (ppm)
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기 접착력(N/25mm)Initial Adhesion (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)	가열 후 실제 리워크성Actual rework after heating	겔분율(질량%)Gel fraction (mass%)	작업성Workability	올리고머 석출양(ppm)Oligomer precipitation amount (ppm)
실시예23Example 23	◎◎	◎◎	◎◎	1.11.1	◎◎	1.91.9	○○	6969	○○	88
실시예24Example 24	◎◎	◎◎	◎◎	0.50.5	◎◎	0.80.8	◎◎	7070	○○	88
실시예25Example 25	○○	○○	○○	1.61.6	◎◎	2.52.5	○○	7272	○○	88
실시예26Example 26	○○	○○	○○	0.20.2	◎◎	0.40.4	○○	7171	○○	88
실시예27Example 27	◎◎	◎◎	◎◎	1.91.9	○○	2.82.8	○○	7575	○○	88
실시예28Example 28	◎◎	◎◎	◎◎	2.32.3	○○	2.92.9	△△	7373	○○	88
실시예29Example 29	◎◎	◎◎	◎◎	0.30.3	◎◎	0.90.9	◎◎	7474	○○	88
실시예30Example 30	◎◎	◎◎	◎◎	0.50.5	◎◎	1.31.3	◎◎	7272	○○	88
실시예31Example 31	◎◎	◎◎	◎◎	0.40.4	◎◎	0.90.9	◎◎	7474	○○	88
실시예32Example 32	◎◎	◎◎	◎◎	0.60.6	◎◎	1.51.5	○○	4242	○○	88
실시예33Example 33	◎◎	◎◎	◎◎	0.40.4	◎◎	0.80.8	◎◎	9292	○○	88
실시예34Example 34	◎◎	◎◎	◎◎	0.50.5	◎◎	0.90.9	◎◎	5555	○○	88
실시예35Example 35	◎◎	◎◎	◎◎	0.40.4	◎◎	0.90.9	◎◎	4545	○○	88
실시예36Example 36	◎◎	◎◎	◎◎	0.50.5	◎◎	1.31.3	◎◎	7474	○○	88
실시예37Example 37	◎◎	◎◎	◎◎	0.80.8	◎◎	1.61.6	○○	7676	○○	88
실시예38Example 38	◎◎	◎◎	◎◎	1.51.5	○○	3.33.3	△△	7575	○○	88

	신뢰성responsibility			리워크성Reworkability				겔분율(질량%)Gel fraction (mass%)	작업성Workability	올리고머 석출양(ppm)Oligomer precipitation amount (ppm)
	가열 시험Heating test	가습 시험Humidification test	히트쇼크 시험Heat shock test	초기 접착력(N/25mm)Initial Adhesion (N / 25mm)	초기 실제 리워크성Initial real reworkability	가열 후 접착력(N/25mm)Adhesive force after heating (N / 25mm)	가열 후 실제 리워크성Actual rework after heating	겔분율(질량%)Gel fraction (mass%)	작업성Workability	올리고머 석출양(ppm)Oligomer precipitation amount (ppm)
실시예39Example 39	◎◎	○○	◎◎	1One	◎◎	1.51.5	△△	8585	○○	4040
실시예40Example 40	◎◎	◎◎	◎◎	1.81.8	○○	3.53.5	△△	7777	○○	88
실시예41Example 41	◎◎	◎◎	◎◎	2.22.2	○○	3.83.8	△△	7979	○○	88
실시예42Example 42	◎◎	○○	◎◎	1.91.9	○○	2.72.7	○○	8181	○○	88
실시예43Example 43	◎◎	○○	◎◎	1.71.7	○○	2.82.8	○○	8282	○○	88
실시예44Example 44	◎◎	○○	◎◎	1.91.9	○○	2.72.7	○○	8181	○○	88
실시예45Example 45	◎◎	○○	◎◎	1.81.8	○○	3.73.7	△△	8585	○○	88
실시예46Example 46	◎◎	○○	◎◎	0.70.7	◎◎	1.11.1	◎◎	7272	○○	88
실시예47Example 47	◎◎	○○	◎◎	1One	◎◎	1.61.6	◎◎	7070	○○	88
비교예9Comparative Example 9	○○	○○	○○	33	△△	6.56.5	××	00	××	88
비교예10Comparative Example 10	◎◎	◎◎	◎◎	4.54.5	××	9.29.2	××	00	××	88
비교예11Comparative Example 11	◎◎	◎◎	◎◎	5.25.2	××	10.910.9	××	7575	○○	88
비교예12Comparative Example 12	○○	○○	○○	6.26.2	××	11.511.5	××	6868	○○	88
비교예13Comparative Example 13	◎◎	◎◎	◎◎	3.63.6	△△	5.15.1	××	7272	○○	88
비교예14Comparative Example 14	◎◎	○○	◎◎	3.23.2	△△	4.54.5	××	6969	○○	88
비교예15Comparative Example 15	○○	△△	○○	2.22.2	○○	4.54.5	××	00	××	88

As shown in Table 12 and Table 13, the pressure-sensitive adhesive composition according to the embodiment contains an adhesive resin (A), a silicate oligomer (B), and a peroxide-based crosslinking agent having an acid value of 0 mgKOH / g to 20.0 mgKOH / g as a base polymer. . And in the adhesive optical film which has the adhesion layer obtained from such an adhesive composition, since the said adhesion layer contains a silicate oligomer (B), the adhesive force immediately after sticking an adhesive optical film to a liquid crystal cell etc. can be made low. In addition, even if a long time passes or stored at a high temperature through various processes, there is no increase in adhesion to the liquid crystal cell and the like, and the adhesive optical film can be easily peeled from the liquid crystal cell and the like, and the reworkability is excellent. That is, the adhesive optical film can be reused without damaging or contaminating the liquid crystal cell. Although peeling of the planar adhesive optical film was difficult for the large liquid crystal cell especially, according to this invention, a planar adhesive optical film can be easily peeled also in a large liquid crystal cell.

In addition, in the present embodiment, when the coating film of the adhesive composition solution is heated and dried by including a peroxide-based crosslinking agent in a pressure-sensitive adhesive composition at a specific ratio, it does not require aging, so it is excellent in workability, excellent in reworkability and reliability, and manufactured. Provides an adhesive optical film having excellent handling properties in terms of process. In addition, the deposition temperature of the oligomer in the pressure-sensitive adhesive layer can be reduced by setting the drying temperature to 130 ° C or lower.

As mentioned above, although preferred embodiment of this invention was described in detail, referring an accompanying drawing, this invention is not limited to this example. Those skilled in the art to which the present invention pertains can clearly think of various changes or modifications within the scope of the technical idea described in the claims. It is, of course, understood to be within the technical scope of the present invention.

Claims

Adhesive resins having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g;

Silicate oligomers represented by Formula 1 below; And

Crosslinking agents;

Pressure-sensitive adhesive composition for an optical film comprising:

[Formula 1]

In Formula 1, R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100.
The pressure-sensitive adhesive composition for an optical film according to claim 1, wherein the pressure-sensitive resin comprises at least one of a (meth) acrylic polymer, a urethane polymer, and a polyester.
The pressure-sensitive adhesive composition for an optical film of claim 2, wherein the (meth) acrylic polymer has a weight average molecular weight of about 300,000 to about 3 million.
The pressure-sensitive adhesive composition for an optical film of claim 2, wherein the urethane polymer or the polyester has a weight average molecular weight of about 10,000 to about 200,000.
The said adhesive resin is an adhesive composition for optical films of Claim 1 containing a hydroxyl-containing monomer as a structural unit.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive resin has a glass transition temperature (Tg) of about -100 ° C to about -10 ° C.
The pressure-sensitive adhesive composition for an optical film of claim 1, wherein the weight average molecular weight of the silicate oligomer is about 300 to about 30,000.
According to claim 1, wherein the silicate oligomer is a silicate oligomer of R 1 to R 4 , X 1 and X 2 in the formula 1 and a weight average molecular weight of about 300 to about 20,000, in the formula 1 R 1 to R 4 , X 1 and X 2 is a methyl group, a silicate oligomer having a weight average molecular weight greater than about 20,000 and up to about 30,000, and in Formula 1 R 1 , R 2 , R 3 , R 4 , X 1 or X 2 comprises a phenyl group Adhesive composition for optical films containing at least one of a silicate oligomer.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition comprises about 0.01 to about 50 parts by weight of the silicate oligomer based on 100 parts by weight of the pressure-sensitive adhesive resin.
According to claim 1, wherein the pressure-sensitive adhesive composition is about one or more of isocyanate crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, epoxy crosslinking agent and peroxide crosslinking agent as about the crosslinking agent, about 100 parts by weight of the adhesive resin Adhesive composition for optical films containing 0.01 to about 20 parts by weight.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition contains about 0.02 to about 2 parts by weight of a peroxide crosslinking agent based on 100 parts by weight of the pressure-sensitive adhesive resin.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further comprises about 0.001 to about 10 parts by weight of the silane coupling agent, based on 100 parts by weight of the pressure-sensitive adhesive resin.
The adhesive layer formed from the adhesive composition for optical films of Claim 1.
Adhesive resin containing at least one of (meth) acrylic polymer, urethane polymer and polyester;

Silicate oligomers represented by Formula 1 below; And

Peroxide crosslinking agents;

It is an adhesive layer formed by the crosslinking treatment of the pressure-sensitive adhesive composition comprising a,

A pressure-sensitive adhesive layer is formed and the pressure-sensitive adhesive layer having a gel fraction of about 40% by weight to about 95% by weight after 23 hours at a temperature of 23 ℃, humidity 65% RH about 1 hour

[Formula 1]

In Formula 1, R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. An alkyl group or an aryl group having 6 to 20 carbon atoms, n is an integer of 1 to 100,

[Equation 1]

Gel fraction (% by weight) = {(Wc-Wa) / (Wb-Wa)} × 100

In Formula 1, Wb is a weight of about 0.2g of the adhesive layer wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin. In addition, Wc immersed the adhesive layer wrapped with the fluorine resin in about 40 ml of ethyl acetate at about 23 ° C. for about 7 days to extract the soluble component, and the adhesive layer wrapped with the fluorine resin on the aluminum cup at about 130 ° C. for about 2 hours. After drying, it is the weight of the adhesive layer wrapped with the fluorine resin from which the soluble component is removed.
15. The adhesive layer of claim 14 wherein the viscous resin has an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g.
The pressure-sensitive adhesive layer of claim 13 or 14, wherein the pressure-sensitive adhesive layer is left to stand for about 1 hour at a temperature of 23 ° C. and a humidity of 65% RH, and then a gel fraction of about 65% by weight to about 95% by weight according to Equation 1 below. layer:

[Equation 1]

Gel fraction (% by weight) = {(Wc-Wa) / (Wb-Wa)} × 100

In Formula 1, Wb is a weight of about 0.2g of the adhesive layer wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin. In addition, Wc immersed the adhesive layer wrapped with the fluorine resin in about 40 ml of ethyl acetate at about 23 ° C. for about 7 days to extract the soluble component, and the adhesive layer wrapped with the fluorine resin on the aluminum cup at about 130 ° C. for about 2 hours. After drying, it is the weight of the adhesive layer wrapped with the fluorine resin from which the soluble component is removed.
The pressure-sensitive adhesive layer of claim 13 or 14, wherein the pressure-sensitive adhesive layer has a difference between the initial adhesive strength and the adhesive force after heating about 1 N / 25 mm or less.
The adhesive layer according to claim 13 or 14, wherein the adhesive layer has an adhesive force of about 3 N / 25 mm or less after heating.
The adhesive layer according to claim 13 or 14, wherein the adhesive layer has a thickness of about 2 μm to about 40 μm.
Polarizer;

A protective layer formed on one surface of the polarizer;

An adhesive layer formed on the other side of the polarizer;

Including,

The pressure-sensitive adhesive layer is a pressure-sensitive adhesive optical film of any one of claim 13 or 14.
The pressure-sensitive adhesive optical film of claim 20, wherein an adhesive auxiliary layer is formed between the polarizer and the pressure-sensitive adhesive layer.
The method of claim 21, wherein the adhesion auxiliary layer is formed on at least one of the surface of the polarizer and the surface of the adhesive layer,

The adhesive auxiliary layer is a pressure-sensitive adhesive optical film formed by corona treatment.
The pressure-sensitive adhesive optical film of claim 20, wherein the protective layer is a transparent protective film or a protective coating layer.
A display device comprising the pressure-sensitive adhesive optical film of claim 20.