TWI825244B - Polarizing film with adhesive layer - Google Patents

Abstract

The present invention provides a polarizing film with an adhesive layer that has high durability and reworkability. The present invention provides a polarizing film with an adhesive layer, which is provided with a polarizing film and an adhesive layer, and the adhesive layer includes a base polymer and a polysiloxane oligomer, and the base polymer is (meth)acrylic acid. is a polymer, the above-mentioned polysiloxane oligomer contains 0.1 to 20 parts by weight relative to 100 parts by weight of the above-mentioned (meth)acrylic polymer, and the Tg of the above-mentioned polysiloxane oligomer is -50°C or more and 100°C or less, The polysiloxy functional group equivalent of the side chain is 1,000 to 20,000 g/mol, and the weight average molecular weight is between 10,000 and 300,000.

Description

Polarizing film with adhesive layer

The invention relates to a polarizing film with an adhesive layer.

For a liquid crystal display device, it is indispensable to arrange polarizing films on both sides of the glass substrate that forms the surface of the liquid crystal panel depending on the image forming method. Polarizing films generally use a protective film bonded to one or both sides of a polarizing element containing a polyvinyl alcohol-based film and a dichroic material such as iodine using a polyvinyl alcohol-based adhesive or the like.

When bonding the above-mentioned polarizing film to a liquid crystal cell, etc., an adhesive is usually used. In addition, since the adhesive has the advantage of being able to instantly fix the polarizing film and does not require a drying step for fixing the polarizing film, it is pre-disposed on one side of the polarizing film as an adhesive layer. That is, a polarizing film with an adhesive layer attached is generally used for laminating polarizing films (Patent Documents 1 and 2).

In addition, when the polarizing film or the polarizing film with an adhesive layer is bonded to the glass substrate of the liquid crystal panel, durability is required, for example, in a durability test using heating and humidification that is commonly performed as an environmental acceleration test. , undesirable phenomena such as peeling or swelling caused by the adhesive layer will not occur.

In this way, adhesives used for polarizing films are required to have high durability. On the other hand, in order to improve defects or bonding errors caused by poor steps when bonding polarizing plates, expectations for reworkability have also increased. In recent years, as panels become thinner or larger, expectations for panel recycling have increased, so reprocessability is an important item. However, there is a trade-off between high durability and reworkability, which is a very difficult characteristic to balance. [Prior technical documents] [Patent documents]

[Patent Document 1] Japanese Patent Publication No. 2011-219765 [Patent Document 2] Japanese Patent Publication No. 2018-169612

[Problem to be solved by the invention]

In view of the above background technology, there is a strong demand for a polarizing film that can have an adhesive layer that has a trade-off relationship between high durability and reworkability. [Technical means to solve problems]

The present inventors conducted intensive research and found that the above-mentioned problems can be solved by the polarizing film with an adhesive layer of the present invention, and thus completed the present invention.

That is, the present invention includes the following embodiments.

(1) A polarizing film with an adhesive layer, which has a polarizing film and an adhesive layer, and the adhesive layer includes a base polymer and a polysiloxane oligomer Ps, and the base polymer is (methyl) Acrylic polymer, the above-mentioned polysilicone oligomer Ps contains 0.1 to 20 parts by weight relative to 100 parts by weight of the above-mentioned (meth)acrylic polymer, and the Tg of the above-mentioned polysilicone oligomer Ps is -50°C or above 100 ℃ or below, the polysiloxy functional group equivalent of the side chain is 1000~20000 g/mol, and the weight average molecular weight Mw is between 10000 and 300000.

(2) The polarizing film with an adhesive layer as described in (1) above, wherein the polysiloxane oligomer Ps includes monomer S1 having a polyorganosiloxane skeleton, and the glass transition temperature of the homopolymer is -Monomers above 70℃ and below 180℃ are used as monomer units.

(3) The polarizing film with an adhesive layer as described in the above (1) or (2), which contains an alkyl (meth)acrylate (meth)acrylate ( A) More than 80% by weight as monomer units of the above-mentioned base polymer.

(4) The polarizing film with an adhesive layer as described in (3) above, which further contains at least one polar monomer selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). 0 to 20% by weight of body (B) is used as the monomer unit of the above-mentioned base polymer.

(5) The polarizing film with an adhesive layer as described in any one of the above (1) to (4), wherein the weight average molecular weight Mw of the above-mentioned base polymer is 500,000 to 2.5 million.

(6) The polarizing film with an adhesive layer as described in any one of (1) to (5) above, wherein the melting temperature of the polysiloxy oligomer Ps is 0 to 100°C. [The effect of the invention]

According to the present invention, it is possible to provide a polarizing film with an adhesive layer that can provide reworkability immediately after lamination and can provide durability by increasing the adhesive force after heating.

Hereinafter, preferred embodiments of the present invention will be described. Those in the industry can understand the circumstances necessary for the implementation of the invention other than the matters specifically mentioned in this specification based on the teachings related to the implementation of the invention described in this specification and the technical common sense at the time of filing. The present invention can be implemented based on the content disclosed in this specification and the technical common sense in the field.

<Polarizing film with adhesive layer> The polarizing film with adhesive layer of the present invention includes a polarizing film and an adhesive layer. In the present invention, the adhesive layer can be present on one side of the polarizing film or on both sides.

The structure of a polarizing film with an adhesive layer according to one embodiment is schematically shown in FIG. 1 . The polarizing film 10 with an adhesive layer is configured as a polarizing film including a polarizing film 3 and an adhesive layer 4 provided on one side of the polarizing film. In Figure 1, the polarizing film 3 includes a polarizing element 1 and protective films 2 and 2' provided on both sides of the polarizing element 1, but the protective film can also be provided on only one side of the polarizing element. The adhesive layer 4 is fixedly disposed on one side of the polarizing film 3 , that is, there is no intention to dispose the adhesive layer 4 separately from the polarizing film 3 . The polarizing film 10 with an adhesive layer is used to attach the adhesive layer 4 to an adherend. As the separator 5, for example, a structure in which a release layer obtained by using a release treatment agent is provided on one side of a sheet-like base material (gasket base material) so that the one side becomes a release layer can be suitably used. noodle. The structure of the polarizing film with the adhesive layer is not limited to the embodiment schematically shown in FIG. 1 .

＜Polarizing element＞ The polarizing element is not particularly limited, and various polarizing elements can be used. Examples of polarizing elements include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films that adsorb iodine or dichroic dyes. Dichroic substances obtained by uniaxial extension; polyene alignment films such as dehydrated polyvinyl alcohol or dehydrochlorinated polyvinyl chloride. Among them, a polarizing element containing a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred. The thickness of these polarizing elements is not particularly limited, generally ranging from 2 to 25 μm.

A polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be produced, for example, by immersing a polyvinyl alcohol-based film in an aqueous solution of iodine, dyeing it, and stretching it. to 3 to 7 times its original length. It can also be immersed in boric acid or an aqueous solution of potassium iodide or the like that may contain zinc sulfate, zinc chloride, etc. if necessary. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed before dyeing. By washing the polyvinyl alcohol-based film, the dirt or anti-adhesive agent on the surface of the polyvinyl alcohol-based film can be washed away. In addition, by swelling the polyvinyl alcohol-based film, it can also prevent uneven dyeing and other uneven staining. Uniform effect. The stretching may be carried out after dyeing with iodine, the stretching may be carried out while dyeing, or the dyeing with iodine may be carried out after stretching. It can be extended in aqueous solutions such as boric acid or potassium iodide or in water baths.

<Adhesive layer> The adhesive layer used in the present invention includes a base polymer and polysiloxane oligomer Ps.

The adhesive constituting the adhesive layer used in the present invention is not particularly limited. Rubber adhesives, acrylic adhesives, polysiloxane adhesives, urethane adhesives, and vinyl alkyl adhesives can be used. Ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. A variety of base polymers can be used depending on the adhesive used.

Among the above-mentioned adhesives, those having excellent optical transparency, exhibiting appropriate adhesive properties of wettability, cohesiveness, and adhesiveness, and having excellent weather resistance or heat resistance are preferably used. As one exhibiting such characteristics, an acrylic adhesive is preferably used. As the base polymer of the acrylic adhesive, a (meth)acrylic polymer is used. In addition, (meth)acrylate includes acrylate and/or methacrylate.

<Base polymer> In the present invention, a (meth)acrylic polymer is generally used as the base polymer.

(1) (Meth)acrylic acid alkyl ester (A) (Meth)acrylic acid-based polymers usually contain (meth)acrylic acid alkyl ester as a monomer unit as a main component. As the (meth)acrylic acid alkyl ester (A) constituting the main skeleton of the (meth)acrylic polymer, a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used. Examples of C1 to C20 (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, (meth)acrylate )Amyl acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, eleven (meth)acrylate Alkyl ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, (meth)acrylate Cetyl acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nineteen (meth)acrylate Alkyl ester, eicosanyl (meth)acrylate, etc., but are not limited to these. These alkyl (meth)acrylates can be used alone or in combination.

In one embodiment of the present invention, the (meth)acrylic polymer preferably contains one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as monomer units. . Examples of other (meth)acrylic acid alkyl esters that can be preferably used as monomer units of (meth)acrylic polymers include: methyl acrylate, methyl methacrylate (MMA), methyl acrylate n-Butyl acrylate (BMA), 2-ethylhexyl methacrylate (2EHMA), etc.

In one embodiment of the present invention, the glass transition temperature of the homopolymer of the alkyl (meth)acrylate (A) used as the monomer unit of the base polymer is -80°C or more and not more than 0°C. The glass transition temperature of the homopolymer of alkyl (meth)acrylate (A) is preferably -70°C to -5°C, more preferably -60°C to -10°C.

In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as the monomer unit of the base polymer may contain 80% by weight or more based on the weight of the base polymer. The alkyl (meth)acrylate (A) is preferably 85% by weight or more based on the weight of the base polymer, more preferably 90% by weight or more.

In a preferred embodiment of the present invention, more than 80% by weight of (meth)acrylic acid alkyl ester (A) whose homopolymer has a glass transition temperature of -60°C or more and 0°C or less can be contained as a monomer of the base polymer. unit.

In one embodiment of the present invention, in addition to the (meth)acrylic acid alkyl ester (A) as the main component, the (meth)acrylic acid polymer may further include (meth)acrylic acid alkyl esters that can be combined with the (meth)acrylic acid alkyl ester if necessary. Other monomers (copolymerizable monomers) for ester copolymerization. As the copolymerizable monomer, a monomer having a polar group (such as a carboxyl group, a hydroxyl group, a nitrogen atom-containing ring, etc.) can be preferably used. Monomers with polar groups can be beneficial in introducing cross-linking points into acrylic polymers or improving the cohesion of (meth)acrylic polymers. A copolymerizable monomer can be used individually by 1 type, or in combination of 2 or more types.

Non-limiting specific examples of copolymerizable monomers include carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, sulfonic acid group- or phosphate group-containing monomers, epoxy group-containing monomers, Cyano monomers, isocyanate-containing monomers, amide-containing monomers, monomers with nitrogen-containing rings, monomers with succinimide skeleton, maleimides, Ikonium imines, (meth)acrylic acid aminoalkyl esters, (meth)acrylic acid alkoxyalkyl esters, vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, etc. (Meth)acrylates with alicyclic hydrocarbon groups, (meth)acrylates with aromatic hydrocarbon groups, and heterocyclic (meth)acrylates such as (meth)acrylic acid tetrahydrofuran methyl ester, chlorine-containing (meth)acrylates containing halogen atoms such as ethylene or fluorine atom-containing (meth)acrylates, (meth)acrylates containing silicon atoms such as polysiloxy (meth)acrylates, derivatives of terpene compounds (meth)acrylate obtained from alcohol.

Examples of carboxyl group-containing monomers include: acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc.; Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride; Examples of the hydroxyl group-containing monomer include: (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxyl Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylate ) 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc. (methyl )Hydroxyalkyl acrylate, etc.; As a monomer containing a sulfonic acid group or a phosphate group, examples include: styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2-(meth)acrylamide -2-Methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, (meth)sulfopropyl acrylate, (meth)acryloxynaphthalenesulfonic acid, 2-hydroxyethylacrylylphosphate esters, etc.; As the epoxy group-containing monomer, for example, epoxy group-containing acrylates such as (meth)glycidyl acrylate or (meth)acrylic acid-2-ethyl glycidyl ether, allyl Glycidyl ether, (meth)acrylic acid glycidyl ether, etc.; Examples of the cyano group-containing monomer include: acrylonitrile, methacrylonitrile, etc.; Examples of the isocyanate group-containing monomer include: (methyl ) 2-isocyanatoethyl acrylate, etc.; Examples of the amide group-containing monomer include: (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N -Diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-bis(n- Butyl)(meth)acrylamide, N,N-di(tert-butyl)(meth)acrylamide and other N,N-dialkyl(meth)acrylamide; N-ethyl( N-alkyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-n-butyl(meth)acrylamide, etc. Meth)acrylamide; N-vinylcarboxamides such as N-vinylacetamide; in addition, N,N-dimethylaminopropyl (meth)acrylamide, hydroxyethyl Acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxymethylpropane(meth)acrylamide, N-methoxymethane (meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(meth)acrylamide, etc. ; As a monomer having a ring containing a nitrogen atom, for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone , N-vinyl pyrimidine, N-vinyl piperazine, N-vinyl pyrrole, N-vinyl pyrrole, N-vinylimidazole, N-vinyl 㗁azole, N-(meth)acrylyl- 2-pyrrolidinone, N-(meth)acrylylpiperidine, N-(meth)acrylylpyrrolidine, N-vinyl𠰌line, N-vinyl-3-𠰌linone, N- Vinyl-2-caprolactam, N-vinyl-1,3-㗁𠯤-2-one, N-vinyl-3,5-𠰌lindione, N-vinylpyrazole, N-ethylene Isothiazole, N-vinyl thiazole, N-vinyl isothiazole, N-vinyl thiazole, etc. (for example, lactams such as N-vinyl-2-caprolactam); Examples of monomers with an imine skeleton include: N-(meth)acryloxymethylenesuccinimide, N-(meth)acrylyl-6-oxyhexamethylenebutane Diamine, N-(meth)acryl-8-oxyhexamethylenesuccinimine, etc.; Examples of maleimines include: N-cyclohexylmaleimine Endedimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, etc.; as econimide Classes, for example, include: N-methyliconimide, N-ethyl itonimide, N-butyl itonimide, N-octyl itonimide, N-2- Ethylhexyl itaconidimide, N-cyclohexyl itaconidimide, N-lauryl itaconidimide, etc.; Examples of (meth)acrylic acid aminoalkyl esters include: (meth) )Aminoethyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, tert-butyl (meth)acrylate Aminoethyl ester; Examples of (meth)acrylic acid alkoxyalkyl esters include: (meth)acrylic acid methoxyethyl, (meth)acrylic acid ethoxyethyl, (meth)acrylic acid Propoxyethyl ester, (meth)butoxyethyl acrylate, (meth)ethoxypropyl acrylate, etc.; As vinyl esters, examples include: vinyl acetate, vinyl propionate, etc.; As ethylene Examples of ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether; examples of aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, etc.; Examples of olefins include: ethylene, butadiene, isoprene, isobutylene, etc. Examples of (meth)acrylate having an alicyclic hydrocarbon group include: (meth)cyclopentyl acrylate, (meth)acrylate base) cyclohexyl acrylate, (meth)isoacrylate, dicyclopentyl (meth)acrylate, etc.; Examples of (meth)acrylate having an aromatic hydrocarbon group include: (meth)benzene acrylate ester, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc.

When such a copolymerizable monomer is used, the usage amount is not particularly limited, but is usually preferably 0.01% by weight or more of the total amount of monomer components. From the viewpoint of better exerting the effect obtained by using the copolymerizable monomer, the usage amount of the copolymerizable monomer may be 0.1% by weight or more of the total amount of the monomer components, or may be 1% by weight or more. In addition, the usage amount of the copolymerizable monomer can be 50% by weight or less of the total amount of monomer components, preferably 40% by weight or less. This can prevent the cohesion of the adhesive from being too high and improve the tackiness at normal temperature (25°C).

In one embodiment of the present invention, in addition to the alkyl (meth)acrylate as the main component, the (meth)acrylic polymer may also optionally contain the above-mentioned hydroxyl-containing monomer (typically a hydroxyl-containing monomer). (meth)acrylic monomer) as the monomer unit. Examples of the hydroxyl-containing monomer include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester )3-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate esters, (meth)acrylic acid hydroxyalkyl esters such as 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc., (meth) can be preferably used 2-hydroxyethyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. Among them, preferred examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA). By using hydroxyl-containing monomers, the cohesion or polarity of the adhesive can be adjusted, thereby improving the adhesion after heating. In addition, the hydroxyl-containing monomer can also be beneficial in suppressing the decrease in transparency caused by moisture by improving the hydrophilicity of the adhesive layer. When a hydroxyl-containing monomer is included, the usage amount of the hydroxyl-containing monomer is not particularly limited. It is usually based on the total amount of monomer units used to prepare the (meth)acrylic polymer, for example, it can be set to 0.01 weight. % or more, 0.1 wt% or more, 0.5 wt% or more, etc.

Furthermore, in one embodiment of the present invention, the (meth)acrylic polymer contains, in addition to the alkyl (meth)acrylate as the main component, a multifunctional monomer if necessary to form an adhesive layer. Cohesion adjustment, etc. Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate ) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetrakis Hydroxymethylmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate Ester, butylene glycol (meth)acrylate, hexylene glycol di(meth)acrylate, etc. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type, or in combination of 2 or more types. The usage amount of the polyfunctional monomer varies depending on its molecular weight, the number of functional groups, etc., but is usually preferably 0.01% by weight to 3.0% based on the total amount of monomer components used to prepare alkyl (meth)acrylate (A). The range of weight % can be 0.02 weight % to 2.0 weight %, or 0.03 weight % to 1.0 weight %.

(2) Polar monomer (B) In one embodiment of the present invention, the base polymer may further include at least one selected from the group consisting of carboxyl group-containing monomer (b1) and nitrogen-containing monomer (b2) The polar monomer (B) serves as a copolymerizable monomer unit.

In one embodiment of the present invention, the above-mentioned polar monomer (B) may contain 0 to 20% by weight based on the weight of the base polymer. The polar monomer (B) is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.

(2-1) Carboxyl group-containing monomer (b1) In the present invention, the base polymer may contain carboxyl group-containing monomer (b1) as a copolymerizable monomer unit. Examples of the carboxyl group-containing monomer (b1) include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isobutylene. acid, etc., but is not limited to these. In a preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) can be acrylic acid or methacrylic acid. In a more preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) can be acrylic acid (AA).

(2-2) Nitrogen-containing monomer (b2) In the present invention, the base polymer may contain nitrogen-containing monomer (b2) as a copolymerizable monomer unit. Examples of the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone). , and vinyl lactam monomers having lactam rings such as β-lactam ring, δ-lactam ring, and ε-lactam ring, etc.); Maleic imine, N -Maleimide-based monomers such as cyclohexylmaleimide and N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl( Meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methyl(meth)acrylamide, N-butyl( Meth)acrylamide, N-butyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethylpropane(meth)acrylamide, etc. (N-substituted )amide monomer; (meth)acrylic acid aminoethyl ester, (meth)acrylic acid aminopropyl ester, (meth)acrylic acid N,N-dimethylaminoethyl ester, (meth)acrylic acid third (Meth)acrylic acid aminoalkyl ester monomers such as tributyl aminoethyl ester and 3-(3-pyridyl)propyl (meth)acrylate; N-(meth)acryloxymethylene Succinimide, N-(meth)acryl-6-oxyhexamethylenesuccinimide, N-(meth)acryl-8-oxyoctamethylenebutane Succinimide monomers such as diimide; cyano (meth)acrylate monomers such as acrylonitrile and methacrylonitrile; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl Pipepan, vinyl pyrrole, vinyl pyrrole, vinyl imidazole, vinyl ytazole, vinyl pyridine, N-vinyl carboxamides, etc.; but are not limited to these. In a preferred embodiment of the present invention, the nitrogen-containing monomer (b2) can be N-vinylpyrrolidone, methylvinylpyrrolidone, or N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.

The method for obtaining the (meth)acrylic polymer is not particularly limited. Solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, photopolymerization, etc. can be appropriately used as the synthesis method of the acrylic polymer. Various polymerization methods are well known. In some aspects, solution polymerization may be preferred. The polymerization temperature during solution polymerization can be appropriately selected depending on the types of monomers and solvents used, the types of polymerization initiators, etc., and can be, for example, about 20°C to 170°C (typically about 40°C to 140°C).

The initiator used for polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, and the like according to the polymerization method. A polymerization initiator can be used individually by 1 type, or in combination of 2 or more types.

Examples of thermal polymerization initiators include azo polymerization initiators (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2 ,2'-azobis(2-methylpropionate)dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 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'-dimethyleneisobutylamidine) dihydrochloride, etc.); potassium persulfate, etc. Sulfate; peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl peroxymaleate, lauryl peroxide, etc.); redox-based polymerization initiator, etc. The usage amount of the thermal polymerization initiator is not particularly limited. For example, it can be 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight based on 100 parts by weight of the monomer components used to prepare the acrylic polymer. Amount within the range of parts by weight.

The photopolymerization initiator is not particularly limited. For example, benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketool photopolymerization initiators, and aromatic sulfonyl initiators can be used. Chlorine-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzil-based photopolymerization initiator, benzophenone-based photopolymerization initiator, Ketal photopolymerization initiator, 9-oxosulfide𠮿 It is a photopolymerization initiator, a phosphine oxide photopolymerization initiator, etc. The usage amount of the photopolymerization initiator is not particularly limited. For example, it can be 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight relative to 100 parts by weight of the monomer component used to prepare the acrylic polymer. Amount within the range of parts by weight.

In one embodiment of the present invention, the (meth)acrylic polymer can be polymerized in a mixture in which a polymerization initiator is blended with the monomer components as described above. For example, ethyl acetate, toluene, etc. can be used as the polymerization agent. Solvent to obtain (meth)acrylic polymer through solution polymerization. As an example of solution polymerization, a polymerization initiator is added under a flow of inert gas such as nitrogen, and the reaction is usually carried out under reaction conditions of about 50 to 70° C. for about 5 to 30 hours. The adhesive layer disclosed in this specification can be formed, for example, using an adhesive composition containing the above-mentioned (meth)acrylic polymer, the following polysiloxane oligomer Ps, and other additives.

In the present invention, the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2.5 million. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer is preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.

<Polysilicone oligomer Ps> In the present invention, the adhesive layer contains polysilicone oligomer Ps. Due to the low polarity and mobility of the siloxane structure, the polysiloxane oligomer Ps can function as an adhesion rise delaying agent that helps suppress the initial adhesion and increase the adhesion rise ratio. As the polysiloxane oligomer Ps, a polymer having a siloxane structure in the side chain can be suitably used.

The glass transition temperature (Tg) of the polysiloxane oligomer Ps used in the present invention is in the range of -50°C or more and 100°C or less. In one embodiment of the present invention, the Tg of the polysiloxane oligomer Ps is preferably -30°C or more and 70°C or less, more preferably -20°C or more and 60°C or less. If the Tg of the polysiloxane oligomer Ps is within the above range, it can achieve both initial low adhesion and increased adhesion during use (strong adhesion) at a high level.

The weight average molecular weight Mw of the polysiloxy oligomer Ps used in the present invention is in the range of 10,000 to 300,000. In one embodiment of the present invention, the weight average molecular weight Mw of the polysiloxy oligomer Ps is preferably from 12,500 to 2,500,000, and more preferably from 15,000 to 2,000,000. If the weight average molecular weight Mw of the polysiloxane oligomer Ps is within the above range, it is easy to adjust the compatibility or mobility within the adhesive layer to an appropriate range, and thus it is easy to achieve a high level of initial low adhesion. Adhesive sheet with strong adhesiveness during use.

In a preferred embodiment of the present invention, the Tg of the polysiloxy oligomer Ps is -70°C or above and below 30°C, the polysiloxy functional group equivalent of the side chain is 1000-20000 g/mol, and the weight average molecular weight Mw can be It is above 10,000 and below 300,000.

In one embodiment of the present invention, the polysiloxane oligomer Ps may include monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer with a glass transition temperature of -70°C or more and 180°C or less. Single unit.

(1) Monomer S1 having a polyorganosiloxane skeleton. The monomer S1 having a polyorganosiloxane skeleton that can be used in the polysiloxane oligomer Ps of the present invention is not particularly limited. Polyorganosiloxane monomer S1 can be used. Any monomer of an alkane skeleton. Examples of the polyorganosiloxane skeleton include: trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), etc., but are not limited thereto. to such.

As the monomer S1 having a polyorganosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, the single-end reactive polysiloxane oil manufactured by Shin-Etsu Chemical Industry Co., Ltd. includes: X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X- 22-174BX, X-22-2404, etc. The monomer S1 having a polyorganosiloxane skeleton can be used alone or in combination of two or more types. [Chemical 1] [Chemicalization 2] Wherein, R ³ in the above general formulas (1) and (2) is hydrogen or methyl group, R ⁴ is methyl group or monovalent organic group, m and n are integers above 0.

The polysiloxy functional group equivalent of the side chain of the polysiloxy oligomer Ps used in the present invention is 1,000 to 20,000 g/mol. In one embodiment of the present invention, the polysiloxy functional group equivalent of the side chain of the polysiloxy oligomer Ps is preferably 1200 to 18000 g/mol, and more preferably 1500 to 15000 g/mol. If the polysiloxane functional group equivalent of the side chain of the polysiloxane oligomer Ps is within the above range, the compatibility (such as the compatibility with the base polymer) or mobility in the adhesive layer can be easily adjusted. to a moderate range, making it easy to realize an adhesive sheet that has a high level of initial low adhesion and strong adhesion during use.

Here, "functional group equivalent" refers to the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. Regarding the labeling unit g/mol, it is converted into 1 mol of functional group. The functional group equivalent of monomer S1 having a polyorganosiloxane skeleton can be calculated, for example, from the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). Calculation of the functional group equivalent (g/mol) of the monomer S1 with a polyorganosiloxane skeleton based on the spectral intensity of 1 H-NMR can be based on the general structural analysis method of ¹ H ^- NMR spectral analysis, as needed. This was performed with reference to the description of Japanese Patent No. 5951153.

Furthermore, when two or more types of monomers with different functional group equivalents are used as the monomer S1 having a polyorganosiloxane skeleton, the arithmetic mean value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of monomer S1 including n types of monomers (monomer S1 ₁ , monomer S1 ₂ . . . monomer S1 _n ) with different functional group equivalents can be calculated by the following formula. The functional group equivalent of monomer S1 (g/mol) = (the functional group equivalent of monomer S1 ₁ × the blending amount of monomer S1 ₁ + the functional group equivalent of monomer S1 ₂ × the blending amount of monomer S1 ₂ +...+ Functional group _{equivalent of monomer S1 n}

The content of the monomer S1 having a polyorganosiloxane skeleton relative to all the monomer components used to prepare the polysiloxane oligomer Ps can be, for example, 5% by weight or more, so that it can better function as an adhesion increase retardant. From the viewpoint of the effect, the content is preferably 10% by weight or more, and may be 15% by weight or more. In some aspects, the content of the above-mentioned monomer S1 may also be, for example, 20% by weight or more. In addition, from the viewpoint of polymerization reactivity or compatibility, the content of monomer S1 having a polyorganosiloxane skeleton is suitably set to 60% relative to all monomer components used to prepare the polysiloxane oligomer Ps. It may be 50% by weight or less, 40% by weight or less, or 30% by weight or less. If the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize an adhesive sheet that has a high level of initial low adhesiveness and increased adhesive force during use (strong adhesiveness).

(2) Monomers with a homopolymer with a glass transition temperature of above -70°C and below 180°C. The polysiloxane oligomer Ps of the present invention includes (methane) which can be copolymerized with the above-mentioned monomer S1 having a polyorganosiloxane skeleton. base) acrylic monomer or other copolymerizable monomer. As the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the polysiloxy oligomer Ps of the present invention, a homopolymer with a glass transition temperature of -70°C or more and 180°C or less can be used. Examples of the monomer include (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group, but are not limited thereto. Examples of (meth)acrylic acid alkyl esters include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate ( BA), 2-ethylhexyl acrylate (2-EHA), examples of (meth)acrylates having an alicyclic hydrocarbon group include: 2-((3-hydroxymethyl)-adamantane methacrylate) -1-yl)methoxy-2-pentoxyethyl ester (2EHAMA), cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate (meth)acrylate, 1-adamantyl (meth)acrylate, etc., but are not limited to these. In one embodiment of the present invention, it may contain 2-((3-hydroxymethyl)-adamant-1-yl)methoxy-2-pentoxyethyl methacrylate (2EHAMA), and At least one kind of isobiyl methacrylate (IBXMA) is used as a monomer unit. In another embodiment of the present invention, at least one selected from the group consisting of dicyclopentyl methacrylate, isobiyl methacrylate, and cyclohexyl methacrylate can be included as a monomer unit. These monomers can be used individually by 1 type, or in combination of 2 or more types.

The usage amount of the above-mentioned alkyl (meth)acrylate and the above-mentioned (meth)acrylate having an alicyclic hydrocarbon group may be, for example, 10% by weight relative to all monomer components used to prepare the polysiloxy oligomer Ps. It may be more than 95% by weight and not more than 20% by weight and not more than 95% by weight, it may be not less than 30% by weight and not more than 90% by weight, it may be not less than 40% by weight and not more than 90% by weight, or it may be not less than 50% by weight and not more than 85% by weight. .

As another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the polysiloxy oligomer Ps, the above-mentioned monomer that can be used for the (meth)acrylic acid alkyl ester (A) can be cited. Specifically, carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, isocyanato group-containing monomers, amide group-containing monomers, and Nitrogen atom ring monomers, monomers with succinimide skeleton, maleic imines, icosimines, (meth)acrylic acid aminoalkyl esters, vinyl esters , vinyl ethers, olefins, (meth)acrylates with aromatic hydrocarbon groups, (meth)acrylates containing heterocyclic rings, (meth)acrylates containing halogen atoms, obtained from terpene compound derivative alcohols (meth)acrylate, etc.

As another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the polysiloxane oligomer Ps, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol Oxyalkylene di(meth)acrylate such as di(meth)acrylate; at the end of the polyoxyalkylene chain of a monomer with a polyoxyalkylene skeleton, such as polyethylene glycol or polypropylene glycol. It is a polymerizable polyoxyethylene extension having polymerizable functional groups such as (meth)acrylyl group, vinyl group, and allyl group, and having an ether structure (alkyl ether, aryl ether, aralkyl ether, etc.) at the other end. Alkyl ether; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, (meth)acrylate (meth)acrylic acid alkoxyalkyl esters such as ethoxypropyl acrylate; (meth)acrylic acid alkali metal salts and other salts; trimethylolpropane tri(meth)acrylate and other poly(meth)acrylates Acrylates; vinylidene chloride, 2-chloroethyl (meth)acrylate and other halogenated vinyl compounds; 2-vinyl-2-ethyl azoline, 2-vinyl-5-methyl-2-ethyl azolate oxazoline-containing monomers such as phosphine and 2-isopropenyl-2-ethazoline; nitrogen-containing monomers such as (meth)acrylaziridine and (meth)acrylic acid-2-aziridinylethyl ester. Propidyl monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, adducts of lactones and 2-hydroxyethyl (meth)acrylate, etc. Hydroxyl-containing vinyl monomers; fluorine-containing vinyl monomers such as fluorine-substituted alkyl (meth)acrylate; reactive halogen-containing vinyl monomers such as 2-chloroethylvinyl ether, vinyl monochloroacetate; Vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethyl Silicone-containing vinyl monomers such as oxytrimethoxysilane; and macromonomers having radically polymerizable vinyl groups at the terminal ends of monomers obtained by polymerizing vinyl groups. These can be copolymerized with monomer S1 singly or in combination with monomer S1.

In the aspect where the monomer component used to prepare the polysiloxy oligomer Ps includes monomer S1 and a (meth)acrylic acid monomer, the monomer S1 and the (meth)acrylic acid monomer are in the above monomer components. The total amount in the whole may be, for example, 50% by weight or more, 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight. %.

The composition of the (meth)acrylic monomer included in the monomer component can be set such that the glass transition temperature T _m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example. Here, the glass transition temperature T _m1 based on the composition of the (meth)acrylic monomer refers to the composition based only on the (meth)acrylic monomer among the monomer components used to prepare the polysiloxy oligomer Ps. , use Fox's formula to find Tg. T _m1 can only take the (meth)acrylic acid-based monomers among the monomer components used to prepare the polysiloxy oligomer Ps as the target, and apply the above-mentioned Fox formula to obtain the average value of each (meth)acrylic acid-based monomer. The glass transition temperature of the polymer and the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer were calculated. If polysiloxane oligomer Ps whose glass transition temperature T _m1 is higher than 0°C is used, the initial adhesion force will be easily suppressed. In addition, by using the polysiloxane oligomer Ps whose glass transition temperature T _m1 is higher than 0°C, it is easy to obtain an adhesive sheet with a relatively large increase in adhesive force.

In some aspects, T _m1 can be above -20°C, above -10°C, above 0°C, or above 10°C. As T _m1 becomes higher, the adhesive force at the initial stage of adhesion tends to be better suppressed. Moreover, T _m1 may be, for example, 90°C or lower, 80°C or lower, or 70°C or lower or less than 70°C. If T _m1 becomes low, the adhesive force tends to increase easily due to heating. The technology disclosed herein can be preferably implemented using polysiloxane oligomer Ps with T _m1 in the range of, for example, -20°C to 90°C, or -10°C to 80°C, or 0°C to 70°C.

The polysiloxane oligomer Ps can be produced by polymerizing the above-mentioned monomer using known methods such as solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, and photopolymerization.

In order to adjust the molecular weight of the polysiloxane oligomer Ps, a chain transfer agent can be used. Examples of chain transfer agents used include compounds having mercapto groups such as octyl mercaptan, lauryl mercaptan, tertiary nonyl mercaptan, tertiary dodecyl mercaptan, mercaptoethanol, α-thioglycerol, etc.; thioglycolic acid , methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, tert-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, thioglycolic acid Decyl ester, lauryl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate and other thioglycolic acid esters; α-methylstyrene dimer Things etc.

There is no particular restriction on the amount of chain transfer agent used. It is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and further preferably 0.2 parts by weight relative to 100 parts by weight of the monomer. Parts by weight ~ 10 parts by weight. By adjusting the amount of chain transfer agent added in this way, polysiloxane oligomer Ps with suitable molecular weight can be obtained. In addition, a chain transfer agent can be used individually by 1 type, or in combination of 2 or more types.

In one embodiment of the present invention, the polysiloxane oligomer Ps may contain 0.1 to 20 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. In the embodiment of the present invention, the polysiloxane oligomer Ps is preferably included in an amount of 0.25 to 10 parts by weight, more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. share. If the content of the polysiloxane oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed and higher post-heating adhesive force can be obtained.

Furthermore, by being formulated in the adhesive layer, the polysiloxane oligomer Ps as mentioned above can function better as an adhesive force increase retardant. The adhesive sheet disclosed herein can be preferably implemented in the following aspect: the adhesive constituting the adhesive layer includes a base polymer and an adhesion increase delaying agent, and the adhesion increase delaying agent includes polysiloxane oligomer Ps . Here, it is believed that the reason why the polysiloxane oligomer Ps functions as an adhesive force increase delaying agent is that the adhesive sheet that exists on the surface of the adhesive layer is used from before it is attached to the adherend to the initial stage of attachment. The polysilicone oligomer Ps suppresses the initial adhesion, and the adhesive flows due to time or heating after attachment, thereby reducing the amount of the polysilicone oligomer Ps on the surface of the adhesive layer, and the polysilicone oligomer Ps The oxygen oligomer Ps is compatible with the adhesive, and the adhesive force increases. Therefore, as the above-mentioned adhesion rise retardant in the technology disclosed herein, other materials that can perform the same function can be used to replace the polysiloxane oligomer Ps, or be combined with the polysiloxane oligomer Ps. Non-limiting examples of such materials include polymers having a polyoxyalkylene structure in the molecule (hereinafter also referred to as "polymer Po"). The polymer Po may, for example, be a polymer containing monomer units derived from monomers having a polyoxyalkylene skeleton. As a specific example, any single polymer or a copolymer of two or more types of monomers having a polyoxyalkylene skeleton as described above, or one or two types of monomers having a polyoxyalkylene skeleton can be used. Copolymers of the above and other monomers (such as (meth)acrylic monomers) are used as polymer Po. The usage amount of the monomer having a polyoxyalkylene skeleton is not particularly limited. For example, the usage amount of the monomer S1 in the polysiloxy oligomer Ps can also be applied to the polyoxyalkylene skeleton in the polymer Po. The amount of monomer used in the basic skeleton. In addition, the usage amount of the polymer Po in the adhesive layer is not particularly limited. For example, the usage amount of the polysiloxane oligomer Ps relative to the base polymer can also be applied to the usage of the polymer Po relative to the base polymer. quantity. Alternatively, the above-mentioned polysilicone oligomer Ps may be used as part of the usage amount of the base polymer (for example, about 5% to 95% by weight, or 15% by weight of the total usage amount of the polysiloxane oligomer Ps). About 85% by weight or about 30% by weight to 70% by weight) is replaced by polymer Po.

In one embodiment of the present invention, the melting temperature of the polysiloxane oligomer Ps may be -20°C to 120°C. In another embodiment of the present invention, the melting temperature of the polysiloxane oligomer Ps can be -10°C to 90°C, or 0°C to 80°C.

＜Other ingredients＞ (Cross-linking agent) For the adhesive layer disclosed in this manual, a cross-linking agent can be used to adjust the cohesive force. As the cross-linking agent, commonly used cross-linking agents can be used. For example, epoxy cross-linking agents, isocyanate cross-linking agents, polysiloxy cross-linking agents, tetrazoline cross-linking agents, and aziridine cross-linking agents can be used. Linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, metal chelate-based cross-linking agents, etc. In particular, isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents can be preferably used. A cross-linking agent can be used individually by 1 type, or in combination of 2 or more types.

Specifically, examples of isocyanate-based crosslinking agents include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and diisocyanate. Phenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylene isocyanate, and those related to trimethylol Adducts of polyhydric alcohols such as propane. Or a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule. Specifically, 2-isocyanatoethyl (meth)acrylate, etc. can also be used as the isocyanate system. Cross-linking agent. These can be used individually by 1 type, or in combination of 2 or more types.

Examples of epoxy cross-linking agents include bisphenol A, epichlorohydrin-type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glyceryl triglycidyl ether. Glyceryl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl -m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc. These can be used individually by 1 type, or in combination of 2 or more types.

Regarding the metal chelate compound, examples of the metal component include aluminum, iron, tin, titanium, nickel, etc., and examples of the chelate compound include acetylene, methyl acetyl acetate, ethyl lactate, and the like. These can be used individually by 1 type, or in combination of 2 or more types.

The usage amount of the cross-linking agent can be, for example, 0.01 parts by weight or more, preferably 0.05 parts by weight or more, based on 100 parts by weight of the base polymer. By increasing the amount of cross-linking agent used, there is a tendency to obtain higher cohesion. In some aspects, the usage amount of the cross-linking agent relative to 100 parts by weight of the base polymer may be more than 0.1 parts by weight, may be more than 0.5 parts by weight, or may be more than 1 part by weight. On the other hand, from the perspective of avoiding a decrease in touch tack due to an excessive increase in cohesive force, the usage amount of the cross-linking agent relative to 100 parts by weight of the base polymer is usually 15 parts by weight or less, and may be 10 parts by weight or less. , it can also be set to 5 parts by weight or less. In adhesives containing polysiloxane oligomer Ps or other adhesion rise delay agents, the cross-linking agent is not used in too much and the fluidity of the adhesive is used to better demonstrate the use effect of the adhesion rise delay agent. From the point of view, it can also be beneficial.

The technology disclosed in this specification can be preferably implemented by using at least an isocyanate-based cross-linking agent as a cross-linking agent. From the perspective of easily realizing an adhesive sheet with higher cohesion after heating and a relatively large increase in adhesive force, in some aspects, the usage amount of the isocyanate cross-linking agent relative to 100 parts by weight of the base polymer can be set to 5, for example. It may be 3 parts by weight or less, it may be 1 part by weight or less, it may be 0.7 parts by weight or less, or it may be 0.5 parts by weight or less.

In order to carry out any of the above cross-linking reactions more efficiently, a cross-linking catalyst can also be used. As the cross-linking catalyst, for example, a tin-based catalyst (especially dioctyltin dilaurate) can be preferably used. The usage amount of the cross-linking catalyst is not particularly limited. For example, it can be approximately 0.0001 to 1 part by weight relative to 100 parts by weight of the base polymer.

(Silane coupling agent) The adhesive layer disclosed in this specification may further contain a silane coupling agent. By using silane coupling agent, durability can be improved. As the silane coupling agent, one having any appropriate functional group can be used. Specifically, examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetyl acetyl group, an isocyanato group, a styryl group, and a polysulfide group. Key et al. Specific examples include vinyl-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; γ -glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-cyclo Silane coupling agents containing epoxy groups such as oxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N-(1,3-dimethylbutylene amine group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropylmethyldimethoxysilane and other mercapto-group-containing silane coupling agents; Silane coupling agents containing styrene groups such as p-styryltrimethoxysilane; γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. containing (methyl silane coupling agents containing isocyanate groups; silane coupling agents containing isocyanate groups such as 3-isocyanatopropyltriethoxysilane; bis(triethoxysilylpropyl)tetrasulfide, etc. Polysulfide-based silane coupling agents, etc. As the silane coupling agent, preferably γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane -Mercaptopropylmethyldimethoxysilane.

The above-mentioned silane coupling agent can be used alone, or two or more kinds can be mixed and used. The total content is preferably 0.001 to 5 parts by weight of the above-mentioned silane coupling agent based on 100 parts by weight of the base polymer, and more preferably 0.01 ~1 part by weight, more preferably 0.02-1 part by weight, more preferably 0.05-0.6 part by weight.

In addition, the adhesive layer in the technology disclosed herein may also contain adhesion-imparting agents, leveling agents, plasticizers, softeners, colorants (dyes, pigments, etc.) as necessary within the scope that does not significantly hinder the effects of the present invention. ), fillers, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers, preservatives and other well-known additives that can be used in adhesives.

(Formation of the adhesive layer) As a method of forming the adhesive layer, for example, it can be produced by the following method: applying the above-mentioned adhesive composition to a peeled separator, etc., and drying and removing the polymerization solvent, etc. to form The adhesive layer is then transferred to the polarizing film; or the above-mentioned adhesive composition is applied to the polarizing film, and the polymerization solvent is dried and removed to form an adhesive layer on the polarizing film. Furthermore, when applying the adhesive, one or more solvents other than the polymerization solvent may be added appropriately.

As the release-treated separator, a silicone release liner is preferably used. In the step of applying the adhesive composition of the present invention on such a liner and drying it to form an adhesive layer, an appropriate method can be appropriately used according to the purpose as a method for drying the adhesive. It is preferable to use a method of heating and drying the above-mentioned coating film. The heating and drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature within the above range, an adhesive having excellent adhesive properties can be obtained.

The drying time can be appropriately adjusted. The drying time is preferably from 5 seconds to 20 minutes, more preferably from 5 seconds to 10 minutes, and particularly preferably from 10 seconds to 5 minutes.

In addition, an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after performing various easy-adhesion treatments such as corona treatment and plasma treatment. In addition, the surface of the adhesive layer may be treated to facilitate adhesion.

As a method of forming the adhesive layer, various methods can be used. Specific examples include roller coating, contact roll coating, gravure coating, reverse coating, roller brush coating, spray coating, dip roll coating, rod coating, blade coating, and air knife coating. , curtain coating, die lip coating, extrusion coating method using die nozzle coating machine, etc.

The thickness of the adhesive layer is not particularly limited, but is, for example, about 1 to 100 μm. Preferably it is 2-50 micrometers, More preferably, it is 2-40 micrometers, Still more preferably, it is 5-35 micrometers.

When the above-mentioned adhesive layer is exposed, a peeled sheet (spacer) can also be used to protect the adhesive layer until actual use.

Examples of materials constituting the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabrics, mesh materials, and foam sheets. , metal foils, and laminates thereof, etc., plastic films are suitable for use in terms of excellent surface smoothness.

The plastic film is not particularly limited as long as it can protect the adhesive layer. Examples include polyethylene film, polypropylene film, polybutylene film, polybutadiene film, and polymethylpentene. Film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the above-mentioned spacer is usually 5 to 200 μm, preferably about 5 to 100 μm. For the above-mentioned separators, mold release and antifouling treatment using polysilicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silica powder, etc. can also be carried out if necessary; or coating type , kneading type, evaporation type and other antistatic treatments. In particular, peelability from the adhesive layer can be further improved by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator.

Furthermore, the peeled sheet used in making the polarizing film with the adhesive layer can be directly used as a spacer for the polarizing film with the adhesive layer, thereby simplifying the steps. [Example]

The present invention will be described below with reference to examples, but the present invention is not limited to the examples shown below. Furthermore, parts and % in each example are based on weight. The following room temperature storage conditions without special regulations are all 23℃65%RH.

In addition, the weight average molecular weight Mw of each of the following polymers was measured using a GPC (Gel Permeation Chromatograph, gel permeation chromatography) device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and was measured by polyphenylene glycol Calculate the ethylene conversion.・Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution) ・Sample injection volume: 10 μl ・Eluent: THF ・Flow rate: 0.6 ml/min ・Measurement temperature: 40℃

<Preparation of polarizing element> Dip a 75 μm thick polyvinyl alcohol film with an average degree of polymerization of 2400 and a saponification degree of 99.9 mol% into warm water at 30°C for 60 seconds to swell. Then, it was immersed in an aqueous solution with a concentration of 0.3% of iodine/potassium iodide (weight ratio = 0.5/8), extended to 3.5 times, and the membrane was stained. Thereafter, the film was stretched in a borate ester aqueous solution at 65° C. so that the total stretching ratio became 6 times. After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a PVA (polyvinyl alcohol) polarizing element (SP value 32.8, thickness 23 μm). The moisture content is 14% by weight.

<Preparation of transparent protective film> Corona treatment is applied to the easy-adhesion surface of an acrylic resin film (SP value 22.2) with a thickness of 40 μm and a moisture permeability of 60 g/m ² /24 h.

＜Active energy rays＞ As active energy rays, use: ・Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Light HAMMER10 manufactured by Fusion UV Systems, Inc. ・Lamp: V bulb; ・Peak illuminance: 1600 mW/ cm ² ; ・Cumulative irradiation dose 1000/mJ/cm ² (wavelength 380～440 nm). In addition, the illuminance of ultraviolet rays was measured using the Sola-Check system manufactured by Solatell.

<Preparation of active energy ray curable adhesive> 38.3 parts of N-hydroxyethylacrylamide (SP value 29.6, homopolymer Tg 123°C, manufactured by Kojin Co., Ltd.) as the radical polymerizable compound (A) 19.1 parts of tripropylene glycol diacrylate (trade name: ARONIX M-220, SP value 19.0, homopolymer Tg 69°C, manufactured by Toagosei Co., Ltd.) as the radically polymerizable compound (B), as the radically polymerizable compound (B) Compound (C): 38.3 parts of acrylamide (SP value 22.9, Tg of homopolymer 150°C, manufactured by Kojin Co., Ltd.), and photopolymerization initiator (trade name: KAYACURE DETX-S, diethyl 9 -oxygen sulfur , manufactured by Nippon Kayaku Co., Ltd.), mix 1.4 parts and stir at 50°C for 1 hour to obtain an active energy ray-hardening adhesive.

<Preparation of Polarizing Film A> After forming a urethane-based easy-adhesive layer with a thickness of 0.5 μm on the above-mentioned acrylic resin film, use an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (unit shape: honeycomb; gravure) Number of roller lines: 1000/inch, rotation speed 140%/relative linear speed), apply the above-mentioned active energy ray-hardening adhesive to the easy-adhesive layer so that the thickness of the adhesive layer becomes 0.5 μm. Then, the acrylic resin film is used as a transparent protective film on the viewing side and the panel side and is bonded to both sides of the polarizing element via the adhesive agent using a rolling machine. Thereafter, an IR heater is used to heat both sides of the laminated acrylic resin film to 50°C, and both sides are irradiated with the ultraviolet rays to harden the active energy ray curable adhesive. Furthermore, it was hot air dried at 70 degreeC for 3 minutes, and the polarizing film A which has a transparent protective film on both sides of a polarizing element was obtained (Table 1). Carry out at a laminating linear speed of 25 m/min. [Table 1] Polarizing film polarizing plate Visual side protective film Polarizing element Panel side protective film Polarizing film A Acrylic resin film 40 μm 23 μm Acrylic resin film 40 μm

<Preparation of adhesive> (Preparation of polymer solution A) Mix 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.075 parts of 2-hydroxyethyl acrylate and 0.3 parts of 2,2'-azobisisobutyronitrile with ethyl acetate The ester is added together to a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device to prepare a solution. Then, the solution was stirred while blowing nitrogen gas into it, and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer with a weight average Mw of 2.2 million. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution A in which the solid content concentration was adjusted to 30%.

To 100 parts of the solid content of the acrylic polymer solution A, 0.6 parts of a cross-linking agent containing a compound having an isocyanate group as a main component (manufactured by Nippon Polyurethane Co., Ltd., Trade name "Coronate L"), and 0.075 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-403") as a silane coupling agent to prepare an adhesive Agent polymer solution A.

(Preparation of polymer solution B) Add 94 parts of 2-ethylhexyl acrylate (2EHA), 6 parts of acrylic acid and 0.3 parts of 2,2'-azobisisobutyronitrile together with ethyl acetate into a cooling tube. Nitrogen gas is introduced into the reaction vessel of the tube, thermometer and stirring device to prepare the solution. Then, the solution was stirred while blowing nitrogen gas into it, and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer with a weight average molecular weight Mw of 2.2 million. Furthermore, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution (B) in which the solid content concentration was adjusted to 30%.

To 100 parts of the solid content of the acrylic polymer solution (B), 0.6 parts of a cross-linking agent containing a compound having an isocyanate group as a main component (Japan Polyurethane Co., Ltd.) was prepared as a cross-linking agent. Manufactured, trade name "Coronate L"), and 0.075 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-403") as a silane coupling agent, thereby Prepare adhesive polymer solution B.

The compositions of the acrylic polymer solution (A) (polymer A) and the acrylic polymer solution (B) (polymer B) are shown in Table 2 below. [Table 2] Adhesive main agent Monomer composition of polymer solution weight average molecular weight Cross-linking agent Silane coupling agent BA 2EHA AA 2HEA Kind content Kind content Polymer A 100 - 5 0.075 2.2 million Coronate L 0.6 phr KBM-403 0.075phr Polymer B - 94 6 - 2.2 million Coronate L 0.6 phr KBM-403 0.075 phr

(Preparation of polysilicone oligomer A) Put 100 parts of ethyl acetate, 40 parts of MMA, and n-butyl methacrylate into a four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, a cooler, and a dropping funnel. (BMA) 20 parts, 2-ethylhexyl methacrylate (2EHMA) 20 parts, a methacrylate monomer containing a polyorganosiloxane skeleton with a functional group equivalent of 900 g/mol (trade name: X- 22-174ASX, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 8.7 parts of methacrylate monomer containing polyorganosiloxane skeleton with a functional group equivalent of 4600 g/mol (trade name: KF-2012, Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd.) and 0.2 parts of methyl thioglycolate as a chain transfer agent. Then, after stirring for 1 hour at 70°C in a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was added, and the reaction was carried out at 70°C for 2 hours, and then added 0.1 part of 2,2'-azobisisobutyronitrile was used as a thermal polymerization initiator, and then reacted at 80° C. for 3 hours. A solution of polysiloxane oligomer is thus obtained. The weight average molecular weight Mw of the polysiloxy oligomer is 18,000.

(Preparation of other polysilicone oligomers B to F) Regarding polysilicone oligomers B to F, the monomer composition and mass parts were changed to the structural components described in Table 3. Otherwise, the same as polysilicone oligomers B to F. Oxygen oligomer A was prepared in the same manner.

[table 3] reprocessing agent Oligomer composition MMA BMA 2EHMA BA 2EHA X-22-174ASX KF-2012 Si oligomer A 40 20 20 8.7 11.3 Si oligomer B 50 15 15 8.7 11.3 Si oligomer C 60 10 10 8.7 11.3 Si oligomer D 10 35 35 8.7 11.3 Si oligomer E 70 5 5 8.7 11.3 Si oligomer F twenty two 20 38 8.7 11.3

(Preparation of adhesive solution) 1 part of polysiloxane oligomer A was prepared into the adhesive polymer solution A prepared above to prepare the acrylic adhesive solution used in Example 1. The acrylic adhesive solutions used in Examples 2 to 19 were prepared in the same manner using the adhesive polymer solution and polysiloxane oligomer described in Table 4 below.

(Preparation of polarizing film with adhesive layer) [Example 1] ~ [Example 19] Then, the above-mentioned acrylic adhesive solution was evenly coated on the polyterephthalate treated with a polysiloxy release agent. The surface of the ethylene formate film (separator film) was dried in an air circulation constant temperature oven at 155°C for 2 minutes to form an adhesive layer with a thickness of 20 μm on the surface of the separator film. The separator formed with the adhesive layer is moved to one side of the above-mentioned polarizing film to prepare a polarizing film with an adhesive layer.

[Comparative Example 1] In Comparative Example 1, except that the polysiloxane oligomer A was removed, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.

[Comparative Example 2] ~ [Comparative Example 5] In Comparative Examples 2 to 5, ether group-containing polysiloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "modified polysiloxane KF-353") was used ) instead of polysiloxane oligomer A, and except that the compounding amount was changed as shown in Table 4, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.

[Reference Example 1] In Reference Example 1, another reprocessing enhancer (trade name "SAT10" manufactured by Kaneka Co., Ltd.) was used instead of polysiloxane oligomer A, and the blending amount was changed as shown in Figure 4, except that Otherwise, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.

The polarizing films with adhesive layers obtained in Examples 1 to 19, Comparative Examples 1 to 5, and Reference Example 1 were evaluated as follows. The results are shown in Table 4.

<Evaluation of durability> Peel off the separator film of the polarizing film (37 inches) with the adhesive layer, and use a laminating machine to laminate it to alkali-free glass with a thickness of 0.7 mm (made by Corning Co., Ltd., EG-XG ). Then, perform an autoclave treatment at 50°C and 0.5 MPa for 15 minutes to completely adhere the polarizing film to the alkali-free glass. Then, each was placed in a heating oven (heating) at 80°C, and the presence or absence of peeling of the polarizing plate after 500 hours was evaluated according to the following criteria. A: No peeling was observed at all. B: Foaming is observed to a degree that cannot be visually confirmed. C: Peeling is observed to a degree that cannot be visually confirmed. D: Minor bubbling or peeling that can be visually confirmed is observed. E: Obvious foaming or peeling is observed.

＜Evaluation of Adhesion＞ (1) Measurement of Initial Adhesion Under the standard environment of 23℃ and 50% RH, cut the produced polarizing film with adhesive layer into a length of 120 mm×width 25 mm, and use the result as sample. The sample was pressure-bonded to an alkali-free glass plate (manufactured by Corning Co., Ltd., EG-XG) with a thickness of 0.7 mm by making a 2 kg roller reciprocate once, and then the adhesion force of the sample was measured. The adhesion force is measured by using a tensile testing machine (Autograph SHIMAZU AG-1 10KN) to peel off the sample at a peeling angle of 90° and a peeling speed of 300 mm/min (N/25 mm, measuring length 80 mm). Find it by measuring it. The measurement system samples 200 times at intervals of 1 time/0.5 s, and the average value is used as the measured value. It was carried out when the number of specimens was 3 specimens. The average value is shown in the "2 kg roller" column of Table 4 as the initial adhesive force. Furthermore, the reworkability is judged based on the level of adhesion according to the following criteria. A: Below 4 N/25 mm, reprocessing is 90% successful. B: More than 4 N/25 mm and less than 5 N/25 mm, reprocessing success is over 80%. C: More than 5 N/25 mm and less than 6 N/25 mm, reprocessing success is over 70%. D: More than 6 N/25 mm and less than 7 N/25 mm, reprocessing success is over 60%. E: More than 7 N/25 mm, more than 40% of reprocessing failures.

(2) Measurement of adhesion after heating: Cut the produced polarizing film with adhesive layer into 120 mm length × 25 mm width, and use the result as a sample. The sample was attached to a 0.7 mm thick alkali-free glass plate (EG-XG manufactured by Corning Corporation) using a laminating machine, and then autoclaved at 50°C and 5 atm for 15 minutes to achieve complete adhesion, and then measured. The adhesion of this sample. The adhesion force is measured by using a tensile testing machine (Autograph SHIMAZU AG-1 10KN) to peel off the sample at a peeling angle of 90° and a peeling speed of 300 mm/min (N/25 mm, measuring length 80 mm). Find it by measuring it. The measurement system samples 200 times at intervals of 1 time/0.5 s, and the average value is used as the measured value. It was carried out when the number of specimens was 3 specimens. In Table 4, "60℃×2 h" and "60℃×24 h" represent the adhesion after being placed at 60℃ for 2 hours and 24 hours respectively.

[Table 4] Adhesive reprocessing agent Glass transition temperature Tg Melting temperature weight average molecular weight Si functional group amount g/mol content Alkali-free glass adhesion Reprocessing Durability 2 kg roller 60℃×2h 60℃×24h Alkali-free Alkali-free Example 1 Polymer A Si oligomer A 47 53 18000 2990 0.5phr 5.7 7.5 13.6 C A Example 2 Polymer A Si oligomer A 47 53 18000 2990 1.0phr 4.8 8.7 12.1 B A Example 3 Polymer A Si oligomer A 47 53 18000 2990 2.0phr 4.5 8.1 11.0 B A Example 4 Polymer A Si oligomer A 47 53 18000 2990 5.0phr 3.9 7.8 10.1 A C Example 5 Polymer A Si oligomer B 60 64 18000 2990 0.5phr 5.8 8.8 14.1 D A Example 6 Polymer A Si oligomer B 60 64 18000 2990 1.0phr 4.8 8.7 13.0 B A Example 7 Polymer A Si oligomer B 60 64 18000 2990 2.0phr 3.9 9.5 12.0 A A Example 8 Polymer A Si oligomer B 60 64 18000 2990 5.0phr 2.2 9.2 10.1 A C Example 9 Polymer A Si oligomer C 73 77 18000 2990 0.5phr 5.8 10.3 15.5 D A Example 10 Polymer A Si oligomer C 73 77 18000 2990 1.0phr 51 11.4 15.8 C A Example 11 Polymer A Si oligomer C 73 77 18000 2990 2.0phr 2.7 9.7 13.5 A A Example 12 Polymer A Si oligomer C 73 77 18000 2990 5.0phr 1.1 5.5 7.2 A D Example 13 Polymer A Si oligomer D 14 twenty one 18000 2990 1.0phr 4.9 9.2 11.9 B A Example 14 Polymer A Si oligomer D 14 twenty one 18000 2990 2.0phr 3.5 8.5 11.0 A A Example 15 Polymer A Si oligomer E 89 93 19000 2990 1.0phr 3.9 9.1 11.9 A A Example 16 Polymer A Si oligomer E 89 93 19000 2990 2.0phr 1.3 5.4 7.2 A D Example 17 Polymer B Si oligomer A 47 53 18000 2990 1.0phr 2.2 10.1 9.6 A D Example 18 Polymer A Si oligomer F -35 -31 18000 2990 1.0phr 5.0 7.6 10.9 C B Example 19 Polymer A Si oligomer F -35 -31 18000 2990 2.0phr 4.6 7.3 9.1 B D Comparative example 1 Polymer A - - - - - - 7.6 10.9 15.5 E A Comparative example 2 Polymer A KF-353 - - 7700 non-reactive 0.5phr 1.8 2.5 5.9 A E Comparative example 3 Polymer A KF-353 - - 7700 non-reactive 1.0phr 0.8 1.6 4.8 A E Comparative example 4 Polymer A KF-353 - - 7700 non-reactive 2.0phr 0.3 1.4 5.1 A E Comparative example 5 Polymer A KF-353 - - 7700 non-reactive 5.0phr 0.3 1.8 6.1 A E Reference example 1 Polymer A SAT10 - - 6000 1.0phr 5.1 7.5 10.9 C C

As described above, according to the present invention, it is possible to provide a polarizing film with an adhesive layer that has both high durability and reworkability.

1:Polarizing element 2: Protective film 2':Protective film 3:Polarizing film 4: Adhesive layer 5: spacer 10: Polarizing film with adhesive layer

FIG. 1 is an example of a schematic cross-sectional view of a polarizing film with an adhesive layer according to the present invention.

1:Polarizing element

2: Protective film

2':Protective film

3:Polarizing film

4: Adhesive layer

5: spacer

10: Polarizing film with adhesive layer

Claims (6)

A polarizing film with an adhesive layer, which has a polarizing film and an adhesive layer, and the adhesive layer includes a base polymer and a polysiloxane oligomer Ps, and the base polymer is a (meth)acrylic polymer , the above-mentioned (meth)acrylic polymer is a (meth)acrylic polymer containing a hydroxyl-containing monomer as a monomer unit, and the above-mentioned polysiloxy oligomer Ps is relative to the above-mentioned (meth)acrylic polymer 100 The parts by weight include 1 to 5 parts by weight. The Tg of the above polysiloxy oligomer Ps is -30°C or above and below 70°C, the polysiloxy functional group equivalent of the side chain is 1000~20000g/mol, and the weight average molecular weight Mw is 10000 Above 300,000 and below. The polarizing film with an adhesive layer as claimed in claim 1, wherein the polysiloxane oligomer Ps includes monomer S1 having a polyorganosiloxane skeleton, and the glass transition temperature of the homopolymer is -70°C or above and 180°C. The following monomers are used as monomer units. For example, the polarizing film with an adhesive layer according to claim 1 or 2 contains at least 80% by weight of alkyl (meth)acrylate (A) which is a homopolymer with a glass transition temperature of -80°C or more and 0°C or less as the above-mentioned Monomeric units of the base polymer. The polarizing film with an adhesive layer as claimed in claim 3 further contains at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). 20% by weight as monomer units of the above-mentioned base polymer. For example, the polarizing film with an adhesive layer according to claim 1 or 2, wherein the weight average molecular weight Mw of the above-mentioned base polymer is 500,000 to 2.5 million. For example, the polarizing film with an adhesive layer according to claim 1 or 2, wherein the melting temperature of the polysiloxane oligomer Ps is -20~120°C.