KR101242336B1 - Adhesive composition for optical member, adhesive layer for optical member, adhesive optical member, transparent conductive laminate, touch panel, and image display device - Google Patents

Abstract

The adhesive composition for optical members of this invention contains 0.2-20 weight part of carboxyl group-containing monomer as a copolymerization component with respect to 100 weight part of alkyl (meth) acrylates which have a C4-C14 alkyl group as a monomer unit (meth). It contains 0.02-2 weight part of peroxides and 0.005-5 weight part of epoxy type crosslinking agents with respect to an acryl-type polymer and 100 weight part of said (meth) acrylic-type polymers as a crosslinking agent. Such an adhesive composition for optical members of the present invention can form a pressure-sensitive adhesive layer capable of suppressing yellowing under high temperature and high temperature and high humidity environment, and also suppressing foaming, peeling, and the like under high temperature and high temperature and high humidity environment.

Description

Adhesive composition for optical members, adhesive layer for optical members, adhesive optical member, transparent conductive laminate, touch panel and image display device {ADHESIVE COMPOSITION FOR OPTICAL MEMBER, ADHESIVE LAYER FOR OPTICAL MEMBER, ADHESIVE OPTICAL MEMBER, TRANSPARENT CONDUCTIVE LAMINATE, TOUCH PANEL, AND IMAGE DISPLAY DEVICE}

This invention relates to the adhesive composition for optical members, and the adhesive layer for optical members formed with the said adhesive composition. Moreover, this invention relates to the adhesive optical member in which the adhesive layer for optical members is formed in the at least single side | surface of an optical member. As an adhesive optical member, a transparent conductive film with an adhesive layer is mentioned, for example, After the processing process is given suitably, the said transparent conductive film with an adhesive layer is a new display system, such as a liquid crystal display and an electroluminescent display. Or a transparent electrode in a touch panel or the like. In addition, the transparent conductive film with an adhesive layer is used for antistatic and electromagnetic wave blocking of a transparent article, liquid crystal dimming glass, and a transparent heater. Moreover, as an adhesive optical member, the optical film with an adhesive layer is mentioned, for example, The said optical film with an adhesive layer is used for image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display. As said optical film, a polarizing plate, a retardation plate, an optical compensation film, a brightness improving film, and also those in which these are laminated can be used.

Conventionally, as a transparent conductive thin film, what is called a conductive glass which formed the indium oxide thin film on glass is well known, but since conductive substrate is glass, flexibility and workability are inferior, and it may not be usable depending on a use. . Therefore, in recent years, in addition to flexibility and workability, a transparent conductive film based on various plastic films including polyethylene terephthalate films has been used in terms of excellent impact resistance and light weight.

The transparent conductive film forms a transparent conductive thin film on one surface of the transparent plastic film base material, and is a transparent substrate via the adhesive layer of the transparent conductive film with an adhesive layer having an adhesive layer on the other side of the transparent plastic film base material. It is used as a transparent conductive laminated body which adhered to (patent document 1).

Moreover, optical films, such as a polarizing plate, are also generally used as an optical film with an adhesive layer which previously formed the adhesive layer in the single side | surface of an optical film (patent document 2).

Patent Document 1: Japanese Patent Application Laid-open No. Hei 6-309990

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-316181

DISCLOSURE OF INVENTION

Problems to be solved by the invention

Acrylic adhesive is mainly used for the adhesive layer applied to optical members, such as the said transparent conductive film and a polarizing plate. As an acrylic adhesive, what mix | blended crosslinking agents, such as an isocyanate type crosslinking agent, with the acrylic polymer which is a base polymer is used normally. However, when using an isocyanate crosslinking agent, yellowing occurs in a high temperature and high temperature and high humidity environment, and there exists a problem that visibility falls. In particular, when an isocyanate crosslinking agent and a peroxide are used as the crosslinking agent, yellowing is remarkable. Moreover, in patent document 2, using an epoxy type crosslinking agent and a peroxide as a crosslinking agent is described in the acryl-type polymer which is a base polymer. However, when the epoxy crosslinking agent and the peroxide are used, there is no problem of yellowing, but the crosslinking reaction with the crosslinking agent is insufficient in relation to the acrylic polymer, and the pressure-sensitive adhesive layer causes foaming and peeling under high temperature and high temperature and high humidity environment. There is another problem.

Moreover, when a transparent conductive laminated body is used for pen input touch panel substrates, such as a resistive film system, it is also required to satisfy the pen trace resistance which does not generate | occur | produce a trace with respect to an input pen.

An object of the present invention is to provide a pressure-sensitive adhesive composition for an optical member capable of forming a pressure-sensitive adhesive layer capable of suppressing yellowing under a high temperature and high temperature and high humidity environment, and also suppressing foaming and peeling under a high temperature and high temperature and high humidity environment. do. Moreover, an object of this invention is to provide the adhesive layer for optical members formed with the said adhesive composition for optical members.

Moreover, an object of this invention is to provide the adhesive optical member in which the adhesive layer for optical members is formed in the at least single side | surface of an optical member. Moreover, it aims at providing the transparent conductive film with an adhesive layer which can satisfy | fill pen trace resistance as an adhesive optical member. Moreover, an object of this invention is to provide the transparent conductive laminated body using the said transparent conductive film with an adhesive layer, and to provide the touch panel using the said transparent conductive film with an adhesive layer or a transparent conductive laminated body.

Moreover, it aims at providing the optical film with an adhesive layer as an adhesive optical member, and providing the image display apparatus using the optical film with an adhesive layer.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said objective can be achieved by the following adhesive composition for optical members, and came to complete this invention.

That is, this invention is a (meth) acrylic-type polymer which contains 0.2-20 weight part of carboxyl group-containing monomer as a copolymerization component with respect to 100 weight part of alkyl (meth) acrylates which have a C4-C14 alkyl group as a monomer unit,

And it is related with the adhesive composition for optical members which consists of 0.02-2 weight part of peroxides and 0.005-5 weight part of epoxy type crosslinking agents with respect to 100 weight part of said (meth) acrylic-type polymers.

In the said adhesive composition for optical members, 0.01-0.5 weight part of isocyanate type crosslinking agents can be contained further as a crosslinking agent with respect to 100 weight part of said (meth) acrylic-type polymers.

In the said adhesive composition for optical members, 0.01-1 weight part of silane coupling agents can be contained further with respect to 100 weight part of said (meth) acrylic-type polymers.

In the said adhesive composition for optical members, what contains 0.01-5 weight part of hydroxyl-group containing monomers further with respect to 100 weight part of alkyl (meth) acrylates as a monomeric unit as said (meth) acrylic-type polymer can be used. .

Moreover, this invention relates to the adhesive layer for optical members characterized by being formed by the said adhesive composition for optical members.

It is preferable that the storage elastic modulus (G ') in 23 degreeC of the said adhesive layer for optical members is 20000-50000 Pa.

It is preferable that the gel fraction of the said adhesive layer for optical members is 70 to 98 weight%.

Moreover, this invention relates to the adhesive optical member characterized by the above-mentioned adhesive layer for optical members being formed in at least one surface of an optical member.

In the said adhesive optical member, it is preferable that the adhesive layer and the optical member are laminated | stacked through the anchor layer. The anchor layer preferably contains a polymer.

As said adhesive optical member, For example, the adhesive layer has an adhesive layer in one surface of a 1st transparent plastic film base material, and has a transparent conductive thin film in the other surface of the said 1st transparent plastic film base material A film is mentioned.

In the said transparent conductive film with an adhesive layer, a transparent conductive thin film can be formed in one surface of a 1st transparent plastic film base material through at least one undercoat layer.

Moreover, this invention relates to the transparent conductive laminated body further characterized by the 2nd transparent plastic film base material adhere | attached on the adhesive layer in the said transparent conductive film with an adhesive layer.

In the transparent conductive laminate, the second transparent plastic film base material may have a hard coat layer on one side or both sides.

Moreover, this invention relates to the touchscreen characterized by the said transparent conductive film with an adhesive layer or a transparent conductive laminated body being used as a transparent conductive film for touch panels.

Moreover, as said adhesive optical member, the optical film with an adhesive layer which an adhesive optical member has an adhesive layer in at least one surface of the optical film for image display apparatus is mentioned, for example. As said optical film, a polarizing plate or a retardation plate can be used preferably.

Moreover, this invention relates to the image display apparatus characterized by the at least 1 adhesive type optical member which concerns on the said optical film with an adhesive layer being used.

Effects of the Invention

In the pressure-sensitive adhesive composition for an optical member of the present invention, a predetermined amount of peroxide and an epoxy-based crosslinking agent are blended as a crosslinking agent with respect to the (meth) acrylic polymer containing a predetermined amount of a carboxyl group-containing monomer. Yellowing under a high humidity environment can be suppressed, and an adhesive layer capable of suppressing foaming, peeling, etc. under a high temperature and a high temperature and high humidity environment can be formed. Moreover, although the said adhesive layer is used in various adhesive optical members, when applied to the transparent conductive film with an adhesive layer, pen trace resistance can be satisfy | filled, for example.

Conventional isocyanate crosslinking agents tend to cause hydrogen drawing reactions under high temperature and high temperature and high humidity environments, and especially in aromatic isocyanate crosslinking agents, it is easy to take a quinone imide structure (yellowish structure), and thus an adhesive using an isocyanate crosslinking agent Is prone to yellowing. In particular, when an isocyanate crosslinking agent is used in the presence of a peroxide, yellowing of the pressure-sensitive adhesive is remarkable. On the other hand, in this invention, yellowing is suppressed also when a peroxide is used by using an epoxy type crosslinking agent as a crosslinking agent of an adhesive. Moreover, when an epoxy type crosslinking agent is used, yellowing can be suppressed even when a predetermined amount isocyanate type crosslinking agent is used together.

The peroxide generates radicals by heating to generate crosslinking with respect to the main chain of the (meth) acrylic polymer, while the epoxy crosslinking agent is a carboxyl group derived from a carboxyl group-containing monomer introduced into the (meth) acrylic polymer as a copolymerization component. The crosslinking is caused by the reaction. Thus, the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition containing a peroxide and an epoxy-based crosslinking agent as a crosslinking agent is easy to set the gel fraction and storage elastic modulus high, and can suppress the occurrence of foaming and peeling under a high temperature and high temperature and high humidity environment, Moreover, in the transparent conductive film with an adhesive layer, it is preferable in order to improve pen trace resistance. Moreover, about the carboxyl group-containing (meth) acrylic-type polymer like this invention, the adhesive composition which used a peroxide and an epoxy crosslinking agent as a crosslinking agent is an adhesive by mix | blending a small amount of crosslinking agent rather than the adhesive composition which used a peroxide and an isocyanate type crosslinking agent as a crosslinking agent. It is easy to set the gel fraction and storage elastic modulus of a layer high. Therefore, even when using an isocyanate type crosslinking agent together with an epoxy type crosslinking agent, the ratio of an isocyanate type crosslinking agent can be suppressed and foaming and peeling in high temperature, high temperature, high humidity environment can be suppressed, suppressing yellowing. Moreover, in the transparent conductive film with an adhesive layer, pen trace resistance can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the adhesive optical member of this invention.

2 is a cross-sectional view showing an example of the pressure-sensitive adhesive optical member of the present invention.

3 is a cross-sectional view showing an example of the pressure-sensitive adhesive optical member of the present invention.

It is sectional drawing which shows an example of the transparent conductive film with an adhesive layer of this invention.

It is sectional drawing which shows an example of the transparent conductive film with an adhesive layer of this invention.

It is sectional drawing which shows an example of the transparent conductive laminated body of this invention.

It is sectional drawing which shows an example of the transparent conductive laminated body of this invention.

Best Mode for Carrying Out the Invention

Hereinafter, the adhesive composition for optical members of this invention is demonstrated.

The adhesive composition for optical members of this invention contains 0.2-20 weight part of carboxyl group-containing monomer as a copolymerization component with respect to 100 weight part of alkyl (meth) acrylates which have a C4-C14 alkyl group as a monomer unit (meth). An acrylic polymer is used as a base polymer.

As alkyl (meth) acrylate, the alkyl group of an alkyl (meth) acrylate may be a linear or branched chain. 4-12 are preferable and, as for carbon number of the said alkyl group, a C4-9 thing is more preferable. In addition, (meth) acrylate refers to acrylate and / or methacrylate, and has the same meaning as (meth) of this invention.

As a specific example of alkyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (Meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl ( Meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dode Sil (meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) Acrylates and the like. Especially, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. can be illustrated, These can be used individually or in combination.

As a carboxyl group-containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a carboxyl group can be used without a restriction | limiting in particular. Examples of the carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. It can be used in combination. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.

A carboxyl group-containing monomer is used in the ratio of 0.2-20 weight part with respect to 100 weight part of alkyl (meth) acrylates. The said ratio of a carboxyl group-containing monomer becomes like this. Preferably it is 1-15 weight part, Furthermore, it is more preferable that it is 3-10 weight part. When the ratio of the carboxyl group-containing monomer is too small, the crosslinking reaction with the epoxy-based crosslinking agent is insufficient, and the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is formed on a transparent conductive film with a pressure-sensitive adhesive layer in addition to foaming and peeling under a high temperature and high temperature and high humidity environment. In the case of application, pen traces tend to occur, which is not preferable as an adhesive layer for touch panels. On the other hand, when the ratio of the carboxyl group-containing monomer is excessively large, crosslinking becomes excessive and adhesiveness is inferior, which is not preferable.

In addition to the carboxyl group-containing monomer, a hydroxyl group-containing monomer can be used as the copolymerization component in the (meth) acrylic polymer. As a hydroxyl group containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a hydroxyl group can be used without a restriction | limiting in particular. As a hydroxyl group containing monomer, it is 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates; Hydroxyethyl (meth) acrylamide, in addition, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, allyl alcohol, 2- Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. are mentioned, These can be used individually or in combination. Among these, hydroxyalkyl (meth) acrylate is preferable.

It is preferable to use the hydroxyl group containing monomer in 5 weight part or less with respect to 100 weight part of alkyl (meth) acrylates. It is preferable that the said ratio of a hydroxyl group containing monomer is 0.01-5 weight part, Furthermore, it is preferable that it is 0.01-2 weight part. By using a hydroxyl group containing monomer in the said range, durability can be improved more.

As a copolymerization component which forms the said (meth) acrylic-type polymer, in addition to the said monomer, alkyl (meth) acrylate is used for the monomer of that excepting the above in the range which does not impair the objective of this invention for the purpose of improvement of adhesiveness, etc. It can be used in the range of 50 parts by weight or less based on 100 parts by weight. It is preferable that the ratio of an arbitrary monomer is also 20 weight part or less.

As said arbitrary monomer, For example, Acid anhydride group containing monomers, such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; Containing sulfonic acid group such as styrene sulfonic acid or allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Monomers; And a phosphoric acid group-containing monomer such as 2-hydroxyethyl acryloyl phosphate.

Moreover, (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol propane (meth) acrylamide, etc. (N-substituted) amide monomers; Alkyl (meth) acrylate alkylaminoalkyl monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; 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-based monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itacon Itaconic imide type monomers, such as mead and N-lauryl itaconimide, etc. are mentioned as a monomer example for a purpose of modification.

-메틸스티렌, N-비닐카프로락탐 등의 비닐계 모노머 ; 아크릴로니트릴, 메타크릴로니트릴 등의 시아노아크릴레이트계 모노머 ; (메트)아크릴산글리시딜 등의 에폭시기 함유 아크릴계 모노머 ; (메트)아크릴산폴리에틸렌글리콜, (메트)아크릴산폴리프로필렌글리콜, (메트)아크릴산메톡시에틸렌글리콜, (메트)아크릴산메톡시폴리프로필렌글리콜 등의 글리콜계 아크릴에스테르 모노머 ; (메트)아크릴산테트라히드로푸르푸릴, 불소(메트)아크릴레이트, 실리콘(메트)아크릴레이트나 2-메톡시에틸아크릴레이트 등의 아크릴산에스테르계 모노머 등도 사용할 수 있다. As the modified monomer, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, Vinyl oxazole, vinyl morpholine, N-vinylcarboxylic acid amides, styrene,

Vinyl monomers such as 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 polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; Acrylic ester ester monomers, such as (meth) acrylic acid tetrahydrofurfuryl, fluorine (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate, can also be used.

As for the (meth) acrylic-type polymer of this invention, the thing of the range of 1 million-3 million in weight average molecular weight is used normally. In consideration of durability, especially heat resistance, it is preferable to use a weight average molecular weight of 1.5 million to 2.5 million. Moreover, it is more preferable that it is 1.7 million-2.5 million, and it is still more preferable that it is 1.8 million-2.5 million. If the weight average molecular weight is less than 1.5 million, it is not preferable in terms of heat resistance. Moreover, when a weight average molecular weight becomes larger than 3 million, it is also unpreferable also in the point which adhesiveness and adhesive force fall. In addition, a weight average molecular weight measures by GPC (gel permeation chromatography) and says the value computed by polystyrene conversion.

In the production of such a (meth) acrylic polymer, a known production method such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. Moreover, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the obtained (meth) acrylic-type polymer.

In solution polymerization, for example, ethyl acetate, toluene or the like is used as the polymerization solvent. In a specific solution polymerization example, the reaction is carried out under an inert gas stream such as nitrogen to add a polymerization initiator, and is usually performed at reaction conditions of about 5 to 30 hours at about 50 to 70 ° C.

The polymerization initiator, chain transfer agent and emulsifier used in the radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled with the usage-amount and reaction conditions of a polymerization initiator, a chain transfer agent, and the usage-amount is adjusted suitably according to these types.

Moreover, the adhesive composition for optical members of this invention contains a peroxide and an epoxy type crosslinking agent as a crosslinking agent.

The peroxide of the present invention can be suitably used as long as it generates radically active species by heating to advance the crosslinking of the (meth) acrylic polymer in the pressure-sensitive adhesive composition. However, in consideration of workability and stability, the half-life temperature is 80 ° C for 1 minute. It is preferable to use the peroxide which is -160 degreeC, and it is more preferable to use the peroxide which is 90 degreeC-140 degreeC. If the half-life temperature is too low for 1 minute, the reaction may proceed at the time of storage before application drying, and the viscosity may become high and coating may be impossible. On the other hand, if the half-life temperature is too high for 1 minute, the temperature during the crosslinking reaction becomes high. It is not preferable because side reactions occur, and many unreacted peroxides remain and crosslinking progresses over time.

Peroxides used in the present invention include, for example, di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature). : 92.1 ° C.), di-sec-butylperoxydicarbonate (1 minute half life temperature: 92.4 ° C.), t-butyl peroxy neodecanoate (1 minute half life temperature: 103.5 ° C.), t-hexyl peroxy pivalate ( 1 minute half-life temperature: 109.1 ° C), t-butylperoxypivalate (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C), di-n-octanoylperoxide ( 1 minute half life temperature: 117.4 ° C., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half life temperature: 124.3 ° C.), di (4-methylbenzoyl) peroxide (1 Minute half-life temperature: 128.2 ° C), dibenzoylperoxide (1 minute half-life temperature: 130.0 ° C), t-butylperoxyisobutylate (1 minute half-life temperature: 136.1 degreeC), 1,1-di (t-hexyl peroxy) cyclohexane (1 minute half-life temperature: 149.2 degreeC), etc. are mentioned. Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C), dibe Crude peroxide (1 minute half life temperature: 130.0 ° C.) and the like are preferably used.

In addition, the half-life of a peroxide is an index which shows the decomposition rate of a peroxide, and means the time until the residual amount of a peroxide becomes half. The decomposition temperature for obtaining a half-life at any time and the half-life time at an arbitrary temperature are described in a manufacturer catalog or the like, and described in, for example, Nippon Oil Holding Co., Ltd. May) ”and the like.

Although the said peroxide may be used individually by 1 type, and may mix and use 2 or more types, The total compounding quantity of a peroxide is 0.02-2 weight part with respect to 100 weight part of said (meth) acrylic-type polymers, and is 0.04-1.5 It is preferable to comprise by weight part, and it is more preferable to contain 0.05-1 weight part. When the said compounding quantity is too small, crosslinking formation will become inadequate and durability will not be enough. On the other hand, when the said compounding quantity is too large, since it becomes excess crosslinking and adhesiveness falls, it is unpreferable.

In the case where a peroxide is used as the polymerization initiator, the remaining peroxide can be used for the crosslinking reaction, which is not used for the polymerization reaction. Can be.

In addition, as a measuring method of the residual amount of peroxide decomposition after reaction processing, it can measure by HPLC (high speed liquid chromatography), for example.

More specifically, for example, about 0.2 g of the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, shaken and extracted at 120 rpm at 25 ° C. for 3 hours, followed by standing at room temperature for 3 days. ) Subsequently, 10 ml of acetonitrile were added, shaken at 120 rpm for 30 minutes at 25 ° C, and about 10 µl of the extract obtained by filtration with a membrane filter (0.45 µm) was injected into HPLC, analyzed, and the amount of peroxide after the reaction treatment. can do.

Moreover, as an epoxy type crosslinking agent, the epoxy compound which has two or more epoxy groups (glycidyl group) in 1 molecule is mentioned. As an epoxy type crosslinking agent, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester, spiroglycol diglycidyl ether, diglycidylaminomethylcyclohexane, tetra Glycidyl xylenediamine, polyglycidyl metaxylenediamine, etc. are mentioned. These epoxy crosslinking agents may be used independently, and may mix and use 2 or more types.

The compounding quantity of the said epoxy type crosslinking agent is 0.005-0.5 weight part with respect to 100 weight part of said (meth) acrylic-type polymers, It is preferable to contain 0.01-0.2 weight part, It is more preferable to contain 0.02-0.1 weight part Do. When the compounding amount is too small, the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is not only foamed and peeled off under high temperature and high temperature and high humidity environment, but also applied to the transparent conductive film with pressure-sensitive adhesive layer, and pen traces tend to occur. It is not preferable as an adhesive layer. On the other hand, when the said compounding quantity is too large, since it becomes excess crosslinking and adhesiveness falls, it is unpreferable.

Moreover, in the adhesive composition of this invention, in addition to a peroxide and an epoxy type crosslinking agent as a crosslinking agent, another crosslinking agent can be used together and the generation | occurrence | production of foaming and peeling can be suppressed in high temperature, high temperature, high humidity environment. As another crosslinking agent, an isocyanate crosslinking agent, an amine crosslinking agent, an aldehyde crosslinking agent, a hydrazine crosslinking agent, an aziridine crosslinking agent, an imine crosslinking agent, a polyvalent metal salt, a polyvalent metal alkoxide, a polyvalent ammonium salt, or the like can be used. As a crosslinking agent which can be used together, since an adhesiveness with a 1st transparent plastic film base material can be improved, an isocyanate type crosslinking agent is preferable. The optional crosslinking agent is usually used in the range of 0.5 parts by weight or less based on 100 parts by weight of the (meth) acrylic polymer.

As an isocyanate type crosslinking agent, aromatic diisocyanate, such as tolylene diisocyanate, chlorophenylene diisocyanate, 2, 4-tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, etc. ; Lower aliphatic isocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate; Alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate and hydrogenated products of the aromatic diisocyanates; Moreover, the adduct type isocyanate compound, the isocyanurate compound, the biuret type compound which added the said various isocyanate and polyhydric alcohols, such as a trimethylol propane, a polyether polyol, polyester polyol, acryl polyol, polybutadiene polyol, The urethane prepolymer type polyisocyanate etc. which addition-reacted polyisoprene polyol etc. are mentioned. An isocyanate type crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types. Among these isocyanate-based crosslinking agents, adduct-based isocyanates to which aromatic diisocyanates such as the tolylene diisocyanate and polyhydric alcohols such as trimethylolpropane are added from the viewpoint of adhesion improvement with the first transparent plastic film base material.

When using an isocyanate type crosslinking agent as said arbitrary crosslinking agent, 0.01-0.5 weight part is preferable with respect to 100 weight part of said (meth) acrylic-type polymers, It is more preferable to contain 0.05-0.3 weight part. When the said compounding quantity exceeds 0.5 weight part, an adhesive layer yellows under high temperature and high temperature, high humidity environment, and visibility will fall.

Moreover, a silane coupling agent can be used for the adhesive composition of this invention in order to raise adhesive force and durability. As the silane coupling agent, known ones may be appropriately used without particular limitation.

Specifically, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- Amino group-containing silane coupling agents such as (1,3-dimethylbutylidene) propylamine and N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Isocyanate group containing silane coupling agents, such as (meth) acryl group containing silane coupling agents, such as ethoxysilane, and 3-isocyanate propyl triethoxysilane, etc. are mentioned. Using such a silane coupling agent is preferable for improvement of durability.

Although the said silane coupling agent may be used independently and may be used in mixture of 2 or more type, It is preferable that the total content is 1 weight part or less of the said silane coupling agent with respect to 100 weight part of said (meth) acrylic-type polymers, and it is 0.01 It is preferable to contain-1 weight part, It is more preferable to contain 0.02-0.6 weight part, It is still more preferable to contain 0.05-0.3 weight part. When the compounding quantity of a silane coupling agent exceeds 1 weight part, when an adherend is glass, there exists a possibility that adhesive force may increase too much and it may cause a rework defect.

Moreover, the adhesive composition of this invention may contain other well-known additives, For example, powder, such as a coloring agent and a pigment, dye, surfactant, a plasticizer, a tackifier, surface lubricant, a leveling agent, a softener, and antioxidant , Anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils and the like can be appropriately added. Moreover, you may employ | adopt the redox system which added the reducing agent within the range which can be controlled.

The pressure-sensitive adhesive layer is formed by the pressure-sensitive adhesive composition of the present invention. For example, what provided the adhesive layer in the at least one surface of the optical member is used as an adhesive optical member. As a method of forming an adhesive layer, for example, after apply | coating the said adhesive composition to a release film etc., drying-removing a polymerization solvent etc. and forming an adhesive layer, in an optical member (for example, a transparent conductive film with an adhesive layer), 1st transparent plastic film base material, the optical film for image display apparatuses in the optical film with an adhesive layer), or apply | coating the said adhesive composition to an optical member, drying a polymerization solvent, etc., and forming an adhesive layer in an optical member It is manufactured by the method. In addition, in application | coating of an adhesive, you may add a 1 or more types of solvent other than a polymerization solvent suitably.

Various methods are used as a formation method of an adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Methods, such as an extrusion coat method, are mentioned.

The thickness of an adhesive layer is not specifically limited, For example, it is about 1-100 micrometers. Preferably it is 5-50 micrometers, More preferably, it is 10-30 micrometers.

Moreover, when the thickness of an adhesive layer becomes too thin, when it applies to the transparent conductive film with an adhesive layer, a pen trace will generate easily and it is not preferable as an adhesive layer for touch panels. On the other hand, when it is too thick, it will be difficult to obtain a good result also in terms of transparency, the formation of an adhesive layer, the adhesive workability with respect to various to-be-adhered bodies, and cost.

When the said adhesive layer is exposed, you may protect an adhesive layer with a release film (separator) until it is provided for actual use.

As a constituent material of the release film, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous materials such as paper, textiles, nonwoven fabrics, nets, foam sheets, metal foils, and laminates thereof Although an appropriate thin body etc. are mentioned, A plastic film is used preferably at the point which is excellent in surface smoothness.

It will not specifically limit, if it is a film which can protect the said adhesive layer as this plastic film, For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethyl pentene film, a polyvinyl chloride film, A vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the release film is usually 5 to 200 占 퐉, preferably 5 to 100 占 퐉. The release film may also be subjected to antistatic treatment such as silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder or the like, and antistatic treatment such as coating type, kneading type and vapor deposition type. . In particular, the peelability from the pressure-sensitive adhesive layer can be further improved by appropriately performing a peeling treatment such as silicone treatment, long chain alkyl treatment, or fluorine treatment on the surface of the release film.

The release film used in manufacture of the said adhesive layer can be used as a release film of an adhesive layer as it is, and can simplify it from a process surface.

In addition, in formation of the said adhesive layer, an adhesive layer is bridge | crosslinked by a crosslinking agent. In this invention, although a peroxide and an epoxy type crosslinking agent are used as a crosslinking agent, it is preferable to fully consider the influence of crosslinking process temperature and crosslinking process time, adjusting these addition amounts.

The adjustment of the crosslinking treatment temperature and the crosslinking treatment time is preferably set such that the decomposition amount of the peroxide contained in the pressure-sensitive adhesive composition is 50% by weight or more, more preferably 60% by weight or more. It is more preferable to set it so that it may become weight% or more. When the amount of decomposition of the peroxide is less than 50% by weight, the amount of the peroxide remaining in the pressure-sensitive adhesive composition increases, and there are cases where a crosslinking reaction occurs over time even after the crosslinking treatment.

More specifically, for example, when the crosslinking treatment temperature is half-life temperature for 1 minute, the decomposition amount of the peroxide is 50% by weight for 1 minute, and the decomposition amount of the peroxide is 2% for 75 minutes, and the crosslinking treatment time of 1 minute or more is required. Do. For example, when the half-life (half-life time) of the peroxide at the crosslinking treatment temperature is 30 seconds, the crosslinking treatment time is 30 seconds or more, and for example, the half-life (half-life time) of the peroxide at the crosslinking treatment temperature is required. Is 5 minutes, the crosslinking treatment time of 5 minutes or more is required.

In this way, the crosslinking treatment temperature and the crosslinking treatment time can be calculated by the theoretical calculation from the half-life (half-life time) on the assumption that the peroxide is first proportional, and the amount of addition can be appropriately adjusted by the peroxide to be used. On the other hand, the higher the temperature, the higher the possibility that side reactions occur, so that the crosslinking treatment temperature is preferably 170 ° C or lower.

Moreover, such crosslinking process may be performed at the temperature at the time of the drying process of an adhesive layer, and you may provide and perform a crosslinking process process separately after a drying process.

Moreover, about crosslinking treatment time, although it can set in consideration of productivity and workability, it is normally about 0.2 to 20 minutes, and it is preferable that it is about 0.5 to 10 minutes.

It is preferable that the storage elastic modulus (G ') in 23 degreeC of the said adhesive layer is 20000-50000 Pa. When applying the said adhesive layer as a transparent conductive film with an adhesive layer, it is more preferable that the storage elastic modulus (G ') of the said adhesive layer is 70000-200000 Pa, Furthermore, it is preferable that it is 80000-180000 Pa. On the other hand, when applying the said adhesive layer to optical films, such as a polarizing plate, it is more preferable that the storage elastic modulus (G ') of the said adhesive layer is 30000-200000 Pa from a viewpoint of suppressing a nonuniformity etc., Furthermore, It is preferable that it is 70000-200000 Pa, and also it is preferable that it is 75000-150000 Pa. When the said storage elastic modulus (G ') is too small than 20000 GPa, it is unpreferable in external defects, foaming at the time of heating, etc., and when applying it as a transparent conductive film with an adhesive layer, a pen trace tends to arise and it is for a touch panel. It is not preferable as an adhesive layer. On the other hand, when the said storage elastic modulus (G ') is too large than 500000 GPa, since adhesiveness will fall, it is unpreferable.

In addition, storage elastic modulus (G ') in this invention is described in JIS-K-7244-1 testing method of plastics-dynamic mechanical characteristics-Part 1: General as one of dynamic mechanical characteristics, G 'means the value obtained by the torsional deformation mode in the part 2 of this JIS-K7244-1 Table 4. In addition, it implemented by the method as described in an Example specifically.

Considering the stress as the amount of energy per unit volume, when mechanical energy is applied to the polymer test piece from the outside to perform sine motion, a part of the applied energy is stored in the polymer by elasticity, and the rest by internal friction. Converted to heat and lost. At this time, the temperature rise due to the heat generation during the test is very small and approximated as the temperature constant. Here, in the case of the storage modulus G ', it corresponds to the stored part, and the loss modulus G "corresponds to the part lost by the internal friction, so that G' represents the degree of hardness and G" represents the degree of viscosity. It can be thought of as showing.

In the case of an adhesive, G 'represents the grade of the stress with respect to the force which an adhesive layer receives from the exterior, and when G' is large, the stress which generate | occur | produces becomes large and the curvature of glass also becomes large. On the contrary, when too small, it is too soft and will be inferior to workability and workability.

Moreover, it is preferable that the gel fraction of the said adhesive layer is 70 to 98 weight%. It is preferable that the gel fraction of the said adhesive layer is 85 to 98 weight%, Furthermore, it is preferable that it is 88 to 95 weight%. When the said gel fraction is too small, when applying as a transparent conductive film with an adhesive layer, a pen trace will generate easily and it is not preferable as an adhesive layer for touch panels. On the other hand, when the said gel fraction becomes large too much, since adhesiveness falls, it is unpreferable. The gel fraction was measured in accordance with the description of the examples.

In the pressure-sensitive adhesive optical member, in the formation of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be formed after the anchor layer is formed on the surface of the optical member or various easy adhesion treatments such as corona treatment and plasma treatment are performed. Moreover, you may perform an easy adhesion | attachment process on the surface of an adhesive layer.

As said easily bonding process, an anchor layer is preferable and it is preferable to laminate | stack an adhesive layer and an optical member with an anchor layer. The adhesive layer can improve the anchoring force by the anchor layer. The anchor layer is usually formed on the optical member side.

The forming agent of the anchor layer is not particularly limited as long as it is a layer capable of improving the anchoring force of the pressure-sensitive adhesive. Specifically, for example, a silane coupling agent having a reactive functional group such as an amino group, a vinyl group, an epoxy group, a mercapto group, and a chlor group in the same molecule and a hydrolyzable alkoxysilyl group, and a hydrolyzable hydrophilic group containing titanium in the same molecule And a so-called coupling agent such as a titanate coupling agent having an organic functional group and a hydrolyzable hydrophilic group containing aluminum in the same molecule and an aluminate coupling agent having an organic functional group, an epoxy resin, an isocyanate resin, and a polyurethane type Resin (polymer) which has organic reactive groups, such as resin, polyester resin, polymer containing an amino group in a molecule | numerator, and ester urethane type resin, can be used.

Anchor layer can be suitably selected and used according to the adhesive optical member, For example, when an adhesive optical member is a transparent conductive film with an adhesive layer, it is a silane coupling agent from a viewpoint of being industrially easy to handle. Particularly preferred is a layer containing.

On the other hand, when an adhesive optical member is an optical film with an adhesive layer, as a formation material of the said anchor layer, a polymer is preferable and it is a polymer containing an amino group in polyurethane resin, polyester resin, and a molecule | numerator, for example. And the like. Polymers containing an amino group in a molecule ensure good adhesion because the amino group in the molecule exhibits an interaction such as a carboxyl group or the like in the pressure-sensitive adhesive or an ionic interaction.

Polymers containing amino groups in the molecule include, for example, polymers of amino group-containing monomers such as polyethyleneimine, polyallylamine, polyvinylamine, polyvinylpyridine, polyvinylpyrrolidine, dimethylamino ethylacrylate, and the like. Can be mentioned.

An antistatic agent can also be added to the said anchor layer in order to provide antistatic property. Examples of antistatic agents for imparting antistatic properties include conductive polymers such as ionic surfactants, polyaniline, polythiophene, polypyrrole, and polyquinoxaline, and metal oxides such as tin oxide, antimony oxide, and indium oxide. In particular, in view of optical properties, appearance, antistatic effect, and stability during heating and humidification of the antistatic effect, a conductive polymer type is preferably used. Among them, water-soluble conductive polymers such as polyaniline and polythiophene or water-dispersible conductive polymers are particularly preferably used. When water-soluble conductive polymers or water-dispersible conductive polymers are used as the material for forming the antistatic layer, deterioration to the optical member due to the organic solvent at the time of coating can be suppressed.

The thickness of the anchor layer is not particularly limited and is, for example, about 2 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm. In addition, formation of an anchor layer can be performed by apply | coating and drying the formation material of an anchor layer to an optical member, for example.

EMBODIMENT OF THE INVENTION Below, the adhesive optical member of this invention is demonstrated, referring drawings. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the adhesive optical member of this invention. As for the adhesive optical member of FIG. 1, the release film 4 is formed in the single side | surface of the optical member 1 through the adhesive layer 3 for optical members. As shown in FIG. 2, the other layer 2 can be formed on the other single side of the optical member 1. The other layer 2 may be the adhesive layer 3. Moreover, as shown in FIG. 3, the adhesive layer 3 and the optical member 1 may be laminated | stacked through the anchor layer (a).

Hereinafter, the transparent conductive film with an adhesive layer of this invention is demonstrated, referring FIGS. 4 and 5. FIG. It is sectional drawing which shows an example of the transparent conductive film with an adhesive layer of this invention. The transparent conductive film with an adhesive layer of FIG. 4 has the transparent conductive thin film 12 in one surface of the 1st transparent plastic film base material 11 which is an optical member, and the other surface of the 1st transparent plastic film base material 11 The release film 14 is formed through the adhesive layer 13 in the inside. In the transparent conductive film with an adhesive layer of FIG. 4, when the transparent conductive thin film 12 is formed in one surface of the 1st transparent plastic film base material 11 via the undercoat layer 15. FIG. to be. In addition, although the undercoat layer 15 is described in one layer in FIG. 5, the undercoat layer 15 can be formed in multiple layers. The release film 14 is formed in the other surface of the film base material 11 in which the said transparent conductive thin film 12 was formed through the adhesive layer 13.

Although it does not restrict | limit especially as said 1st transparent plastic film base material 11, Various plastic films which have transparency are used. The said plastic film is formed of the film of one layer. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, and polyolefin resins , (Meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like. Particularly preferred among these are polyester resins, polyimide resins, and polyether sulfone resins.

Moreover, in the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO10 / 37007), for example, the thermoplastic resin which has a substituted and / or unsubstituted imide group in (A) side chain, and (B) side chain And resin compositions containing a substituted and / or unsubstituted phenyl and a thermoplastic resin having a nitrile group. Specifically, the polymer film of the resin composition containing the alternating copolymer which consists of isobutylene and N-methyl maleimide, and an acrylonitrile styrene copolymer can be used.

It is preferable that it is 15-200 micrometers, and, as for the thickness of the said film base material 11, it is more preferable that it is 25-188 micrometers. If the thickness of the film base material 11 is less than 15 micrometers, the mechanical strength of the film base material 11 will be insufficient, and operation which continuously forms the transparent conductive thin film 12 by making this film base material 11 into a roll shape is difficult. There may be a case. On the other hand, when thickness exceeds 200 micrometers, in the film forming process of the transparent conductive thin film 12, input amount may be reduced, it may cause a deterioration in a process of removing gas and water, and may inhibit productivity.

The film substrate 11 is subjected to etching or undercoat treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or the like on the surface of the transparent conductive thin film 12 formed thereon. Or you may make it improve the adhesiveness of the undercoat layer 15 with respect to the said film base material 11. Moreover, before forming the transparent conductive thin film 12 or the undercoat layer 15, you may damp and clean by solvent washing, ultrasonic cleaning, etc. as needed.

It does not specifically limit as a constituent material of the said transparent conductive thin film 12, For example, metal oxides, such as indium oxide containing tin oxide and tin oxide containing antimony, are used preferably.

As a constituent material of the transparent conductive thin film 12, indium oxide containing tin oxide is preferable. It is preferable that the said metal oxide contains 90-99 weight% of indium oxide and 1-10 weight% of tin oxide.

Although the thickness of the transparent conductive thin film 12 is not specifically limited, In order to make the surface resistance into the continuous film which has the favorable electroconductivity of 1 * 10 <^3> ohm / square or less, it is preferable to set it as thickness 10nm or more. It is preferable that it is 15-35 nm, More preferably, it exists in the range of 20-30 nm, since a film thickness becomes too thick and causes a fall of transparency. If the thickness is less than 15 nm, the surface electrical resistance is high, and it is difficult to form a continuous film. Moreover, when it exceeds 35 nm, transparency will fall.

It does not specifically limit as a formation method of the transparent conductive thin film 12, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. Moreover, the appropriate method can also be employ | adopted according to the film thickness required.

The undercoat layer 15 can be formed of an inorganic substance, an organic substance, or a mixture of inorganic substances and organic substances. For example, as inorganic materials, NaF (1.3), Na ₃ AlF ₆ (1.35), LiF (1.36), MgF ₂ (1.38), CaF ₂ (1.4), BaF ₂ (1.3), SiO ₂ (1.46), LaF Inorganic substances, such as ₃ (1.55), CeF ₃ (1.63), and Al ₂ O ₃ (1.63), in which the numerical values in parentheses of the above materials are the refractive indices of light. Among these, SiO ₂ , MgF ₂ , Al ₂ O ₃ Etc. are used preferably. In particular, SiO ₂ is preferable. In addition to the above, a complex oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide can be used relative to indium oxide.

The undercoat layer formed of an inorganic substance can be formed by dry processes, such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a wet method (coating method). An inorganic material for forming the undercoat layer, the SiO ₂ is preferable as described above. In the wet method, a SiO ₂ film can be formed by coating a silica sol or the like.

Examples of the organic substance include acrylic resins, urethane resins, melamine resins, alkyd resins, siloxane polymers, and organic silane condensates. At least one of these organic substances is used. As an organic substance, it is preferable to use thermosetting resin which consists of a mixture of a melamine resin, an alkyd resin, and an organosilane condensate.

When forming the multiple layers of the undercoat layer 15, the undercoat layer of the 1st layer from the transparent plastic film base material 11 is formed of organic substance, and the undercoat layer which is furthest from the transparent plastic film base material 11 is an inorganic substance. It is preferable that it is formed from the point of the workability of the transparent conductive film with an adhesive layer obtained. Therefore, when the undercoat layer 15 is two layers, it is preferable that the undercoat layer of the 1st layer from the transparent plastic film base material 11 is formed with the organic substance, and the 2nd layer is formed with the inorganic substance.

Although the thickness of the undercoat layer 15 is not specifically limited, From an optical design and the viewpoint of the oligomer generation prevention effect from the said film base material 11, it is about 1-300 nm normally, Preferably it is 5-300 nm. to be. In addition, when forming two or more layers of the undercoat layer 15, the thickness of each layer is about 5-250 nm, Preferably it is 10-250 nm.

In addition, although not shown in FIG. 4, 5, it is preferable to form an oligomer shift prevention layer between the film base material 11 and the adhesive layer 13. As shown in FIG. In addition, an inorganic substance, an organic substance, or those composite materials may be used as a formation material of the said migration prevention layer using the suitable thing which can form a transparent film. It is preferable that the film thickness is 0.01-20 micrometers. In addition, the coating method, the spray method, the spin coat method, the in-line coat method, etc. using a coater are often used for formation of the said transfer prevention layer, The vacuum vapor deposition method, sputtering method, ion plating method, spray pyrolysis method, chemical plating method, electroplating method The same method may be used. In the coating method, resin components such as acrylic resins, urethane resins, melamine resins, UV curable resins and epoxy resins, and mixtures of inorganic particles such as alumina, silica and mica may be used. Alternatively, the polymer substrate may have a function of a migration prevention layer on the substrate component by coextrusion of two or more layers. In addition, in methods such as vacuum deposition, sputtering, ion plating, spray pyrolysis, chemical plating and electroplating, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt or tin Or other metal compounds made of metal oxides made of indium oxide, tin oxide, titanium oxide, cadmium oxide or a mixture thereof, steel iodide, or the like.

As shown in FIG. 3, the said adhesive layer 13 can improve the anchoring force by the anchor layer (a) as mentioned above. The anchor layer is usually formed on the film substrate 11 side.

The manufacturing method of the transparent conductive film with an adhesive layer of this invention will not be restrict | limited especially if the thing of the said structure is obtained. Usually, the said adhesive layer 13 forms a transparent conductive thin film 12 (when the undercoat layer 15 is included) in one surface of the 1st transparent plastic film base material 11, and forms a transparent conductive film. After manufacture, it is formed in the other surface of the said transparent conductive film. As described above, the pressure-sensitive adhesive layer 13 may be directly formed on the film base material 11, or the pressure-sensitive adhesive layer 13 may be formed on the release film 14, and the pressure-sensitive adhesive layer 13 may be adhered to the film base material 11. In the latter method, since the formation of the pressure-sensitive adhesive layer 13 can be carried out continuously by making the film base material 11 into a roll shape, it is further advantageous in terms of productivity.

The transparent conductive film with a pressure-sensitive adhesive layer can further adhere the second transparent plastic film base material 11 'to the pressure-sensitive adhesive layer 13 to form a transparent conductive laminate as shown in FIG. 6.

In addition, the adhesion of the 2nd transparent plastic film base material 11 'may form the adhesive layer 13 in the 2nd transparent plastic film base material 11' side, and may make it adhere | attach the film base material 11 to this, and conversely The adhesive layer 13 may be formed on the film substrate 11 side, and the second transparent plastic film substrate 11 'may be attached thereto. In the latter method, formation of the adhesive layer 13 can be performed continuously by making the film base material 11 into a roll shape, and is further advantageous in terms of productivity.

As shown in FIG. 6, the 2nd transparent plastic film base material 11 'has a single layer structure, Comprising: The composite structure which adhere | attached 2 or more 2nd transparent plastic film base material 11' with the transparent adhesive layer. In this way, the mechanical strength and the like of the entire laminate can be further improved. In addition, although the 2nd transparent plastic film base material 11 'is adhere | attached on the transparent conductive film with an adhesive layer in FIG. 4 in FIG. 6, the 2nd transparent plastic film similarly also about the transparent conductive film with an adhesive layer in FIG. It can be set as the transparent conductive laminated body which adhere | attached the base material 11 '.

The case where a single layer structure is employ | adopted as said 2nd transparent plastic film base material 11 'is demonstrated. When the transparent conductive laminate is required to be flexible even after the second transparent plastic film base material 11 'having a single layer structure is bonded, the thickness of the second transparent plastic film base material 11 is usually about 6 to 300 µm. Plastic films are used. When flexibility is not specifically requested, the glass of about 0.05-10 mm, the film shape, or plate-shaped plastic is used for the thickness of a transparent base material normally. The material similar to the said film base material 11 is mentioned as a material of plastics. In the case where a plurality of structures are employed as the second transparent plastic film base 11 ', the thickness is preferably the same.

In the said transparent conductive laminated body, a hard-coat layer can be formed in the single side | surface or both surfaces of a 2nd transparent plastic film base material. In FIG. 7, the hard-coat layer 16 is formed in the single side | surface (surface which is not adhere | attached to the adhesive layer 13) of the 2nd transparent plastic film base material 11 '. The said hard coat layer is obtained by giving a hard-coat process to a 2nd transparent plastic film base material. Hard coat processing can be performed by the method of apply | coating hardening processes, such as acrylic urethane resin and siloxane resin, and hardening process, etc., for example. At the time of hard coat processing, silicone resin etc. are mix | blended with hard resins, such as said acrylic urethane resin and siloxane resin, and the surface is roughened, and when it is actually used as a touch panel etc., reflection by mirror action can be prevented. Non-glare surfaces may be formed at the same time.

If the thickness of the hard coat layer is thin, the hardness is insufficient, while if the thickness is too thick, cracks may occur. Moreover, in consideration of the prevention property of curl, etc., the thickness of a preferable hard-coat layer is about 0.1-30 micrometers.

In addition to the hard coat layer, an antiglare treatment layer and an antireflection layer for the purpose of improving visibility are provided on the outer surface (surface not adhered to the adhesive layer 13) of the second transparent plastic film base material as described above. It may be formed.

The transparent conductive film or transparent conductive laminated body with an adhesive layer of this invention is used in formation of various apparatuses, such as a touchscreen and a liquid crystal display. In particular, it can use suitably as an electrode plate for touch panels. The touch panel is preferably used by various detection methods (for example, resistive film type, capacitive type, etc.).

In the resistive touch panel, an electrode plate for a touch panel having a transparent conductive thin film and an electrode plate for a display panel having a transparent conductive thin film are disposed to face each other via spacers so that the transparent conductive thin films face each other. The electrode panel for touch panels which consists of a transparent conductive film of this invention can be used also for the electrode panels for touch panels on a touch side and a display side. In particular, the electrode panel for touch panels using the transparent conductive film with an adhesive layer or the transparent conductive laminated body of this invention is a point which suppresses generation | occurrence | production of a Newton ring, satisfy | fills durability, display characteristics, and the thickness of a touch panel. It is preferable to use it as an electrode plate for touch panels on the display side.

On the other hand, in the capacitive touch panel, the transparent conductive film provided with the transparent conductive thin film which has a predetermined pattern shape normally is formed in the whole surface of a display display part. In FIGS. 4-7, although the transparent conductive thin film 12 is not patterned, what was suitably patterned is used and the said patterned transparent conductive film is used by laminating suitably.

Moreover, the adhesive optical member of this invention can be used as an optical film with an adhesive layer using the optical film for image display apparatuses as the optical member 1 in FIG.

As an optical film, what is used for formation of image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display, is used, The kind in particular is not restrict | limited. For example, a polarizing plate is mentioned as an optical film. As for the polarizing plate, one having a transparent protective film is generally used on one side or both sides of the polarizer.

The polarizer is not particularly limited, and various kinds of polarizers can be used. As the polarizer, for example, a dichroic substance of iodine or a dichroic dye is adsorbed onto hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymerized partial saponified films. And polyene oriented films such as monoaxially stretched, dehydrated polyvinyl alcohol and dehydrochloric acid treated polyvinyl chloride. Among these, the polarizer which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 占 퐉.

The polarizer which dyed a polyvinyl alcohol-type film with iodine and uniaxially stretched can be manufactured, for example, by dyeing polyvinyl alcohol by immersing it in the iodine aqueous solution, and extending | stretching 3 to 7 times the original length. It can also be immersed in aqueous solution, such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride, etc. as needed. If necessary, the polyvinyl alcohol-based film may be immersed in water and washed 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 also prevents unevenness such as dyeing. The stretching may be carried out after dyeing with iodine, stretching while dyeing, and dyeing with iodine after stretching. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

As a material which comprises a transparent protective film, the thermoplastic resin 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, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acryl Resins, cyclic polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. In addition, a transparent protective film is bonded to one side of the polarizer by an adhesive layer, and on the other side, a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, silicone, or ultraviolet curable resin is used as the transparent protective film. 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. Content of the said thermoplastic resin in a transparent protective film becomes like this. Preferably it is 50-100 weight%, More preferably, it is 50-99 weight%, More preferably, it is 60-98 weight%, Especially preferably, it is 70-97 weight% . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

Moreover, as an optical film, liquid crystal display devices, such as a reflecting plate, a semi-transmissive plate, a retardation plate (including wavelength plates, such as 1/2 or 1/4), an optical compensation film, a visual compensation film, and a brightness enhancement film, for example The thing used as the optical layer used for formation of these etc. is mentioned. In addition to being able to be used as an optical film independently, these can be laminated | stacked on the said polarizing plate at the time of actual use, and can use 1 layer or 2 or more layers.

Although the optical film which laminated | stacked the said optical layer on the polarizing plate can also be formed also by the method of laminating | stacking separately, one by one in the manufacturing process of a liquid crystal display device, etc., what laminated | stacked previously was made into the optical film, such as stability of quality, assembly work, etc. It is excellent in this and there exists an advantage which can improve manufacturing processes, such as a liquid crystal display device. Appropriate adhesion means, such as an adhesion layer, can be used for lamination. At the time of adhering the polarizing plate to another optical layer, these optical axes can be set to an appropriate placement angle in accordance with a desired phase difference characteristic or the like.

The optical film with an adhesive layer of this invention can be used suitably for formation of various image display apparatuses, such as a liquid crystal display device. Formation of a liquid crystal display device can be carried out in accordance with a conventional method. In other words, a liquid crystal display device is generally formed by assembling a component such as a liquid crystal cell, an optical film with a pressure-sensitive adhesive layer, and a lighting system, if necessary, and mounting a drive circuit, but in the present invention, the pressure-sensitive adhesive layer according to the present invention It does not specifically limit except the point which uses an attached optical film, and can follow conventionally. As for the liquid crystal cell, any type of TN type, STN type, pi type, VA type, IPS type or the like can be used, for example.

Suitable liquid crystal display devices, such as the liquid crystal display device which arrange | positioned the optical film with an adhesive layer on the one side or both sides of a liquid crystal cell, and the thing which used the backlight or the reflecting plate for the illumination system, can be formed. In that case, the optical film by this invention can be provided in the one side or both sides of a liquid crystal cell. When providing an optical film in both sides, they may be the same and may differ. Further, at the time of forming the liquid crystal display device, appropriate parts such as a diffusion plate, an anti-glare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, Can be deployed.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In addition, in each case, all parts and% are basis of weights.

&Lt; Measurement of molecular weight &

Molecular weight was measured by GPC (gel permeation chromatography).

Analysis device: manufactured by Tosoh Corporation, HLC-8120 GPC

Data processing device: manufactured by Tosoh Corporation, GPC-8020

column :

Sample column; Made by Tosoh Corporation, G7000H _XL -H + GMH _XL -H + GMH _XL

Column size; Each 7.8 mmΦ × 30 cm (90 cm in total)

Flow rate: 0.8 ml / min

Injection sample concentration: about 0.1% by weight

Injection volume: 100 μl

Column temperature: 40 DEG C

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

In addition, molecular weight was computed by polystyrene conversion.

<Measurement of gel fraction>

About 0.1 g of the pressure-sensitive adhesive layer immediately after the crosslinking treatment prepared in each Example and Comparative Example was taken, and weighed thereto, and the weight W ₁ (g) was measured. Subsequently, the pressure-sensitive adhesive layer was immersed in about 50 ml of ethyl acetate at 23 ° C. for 7 days, and then the soluble component was extracted. Thereafter, the pressure-sensitive adhesive layer taken out from ethyl acetate, it was dried for 2 hours at 120 ℃ was measured the total weight W ₂ (g). In these measurements,

Formula: Gel fraction (% by weight) = [(W ₁ -W ₂ ) / W ₁ ] × 100

The value computed by was made into the gel fraction (weight%) of an adhesive layer. After coating, the gel fraction was measured after storage at room temperature (under about 23 ° C.) for 7 days.

&Lt; Measurement of storage elastic modulus &

The storage elastic modulus was measured by ARES (viscoelastic spectrometer, rheometallic scientific company) using the adhesive layer manufactured in each Example and the comparative example.

Deformation mode: torsion

Measuring frequency: constant frequency 1 ㎐

Temperature rise rate: 5 ℃ / min

Measurement temperature: measured up to 200 ° C near the glass transition temperature (Tg) of the acrylic polymer

Shape: Parallel Plate 7.9 mmΦ

Sample thickness: about 1.8 mm (initial installation)

In addition, the storage elastic modulus (G ') at 23 degreeC was read.

Example 1

(Preparation of acrylic polymer)

In a four-necked flask equipped with a stirring vane, a thermometer, a nitrogen gas introduction tube, and a cooler, 100 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid and 0.075 parts by weight of 2-hydroxyethyl acrylate, and 2,2'- as a polymerization initiator. 0.2 parts by weight of azobisisobutyronitrile and 200 parts by weight of ethyl acetate as a polymerization solvent were injected, and after nitrogen was sufficiently substituted, the liquid temperature in the flask was kept at about 55 ° C while stirring under a nitrogen stream, followed by a polymerization reaction for 10 hours. And acrylic polymer solution were prepared. The weight average molecular weight of the said acrylic polymer was 2.2 million.

(Preparation of pressure-sensitive adhesive composition)

0.2 parts by weight of dibenzoyl peroxide (Nipa BMT, Nippon Oil & Fats Co., Ltd.) as a peroxide, 100 parts by weight of the acrylic polymer solution, and diglycidylaminomethylcyclohexane (Mitsubishi Gas Chemical Co., Ltd.) as an epoxy crosslinking agent. 0.1 part by weight of an adduct of trimethylolpropane / tolylene diisocyanate (Nippon Polyurethane Industry Co., Ltd., Colonate L) as a Manufacture, tetrad C) 0.05 part by weight and an isocyanate-based crosslinking agent, and a silane coupling agent ( Shin-Etsu Chemical Co., Ltd. product, KBM403) 0.075 weight part was mixed and stirred uniformly, and the acrylic adhesive solution (solid content 10.9 weight%) was prepared.

(Formation of pressure-sensitive adhesive layer)

The said acrylic adhesive solution was apply | coated on the separator of the polyethylene terephthalate film (thickness: 38 micrometers) which performed the mold release process, it heated at 155 degreeC for 1 minute, and formed the adhesive layer whose thickness after drying is 22 micrometers. The gel fraction of the pressure-sensitive adhesive layer was 92% by weight, and the storage elastic modulus (G ′) at 23 ° C. was 118000 GPa.

(Formation of Undercoat Layer)

As a film base material, what formed by forming a transition prevention layer (formation with urethane acrylic type ultraviolet curable resin, thickness 1 micrometer) in one surface of the 25-micrometer-thick polyethylene terephthalate film (henceforth a PET film) was used. On the other side of the said film base material, the undercoat layer of the 1st layer whose thickness is 180 nm was formed with the thermosetting resin of weight ratio 2: 2: 1 of melamine resin: alkyd resin: organosilane condensate. Subsequently, SiO ₂ was vacuum-deposited on the undercoat layer of the first layer with a vacuum of 1.33 × 10 ⁻² to 2.67 × 10 ⁻² Pa by an electron beam heating method, and the undercoat of the second layer having a thickness of 40 nm ( SiO ₂ film).

(Formation of Transparent Conductive Thin Film)

Next, on the undercoat layer of the second layer, in a reactive sputtering method using 95% by weight of indium oxide and 5% by weight of tin oxide in an atmosphere of 5.33 × 10 ⁻² Pa composed of 80% argon gas and 20% oxygen gas. Thus, an ITO film having a thickness of 20 nm was formed to obtain a transparent conductive film. The obtained ITO membrane was amorphous.

(Manufacture of the transparent conductive film with an adhesive layer)

The said transparent conductive film (surface of the side which does not form an ITO film | membrane) was adhere | attached on the adhesive layer formed on the said release film, and the transparent conductive film with an adhesive layer was manufactured. The surface resistance of the ITO film was 300 Ω / square. The surface resistance value ((ohm / square)) of an ITO film | membrane was measured using the Mitsubishi Chemical Co., Ltd. product Lorestar resistance meter.

Example 2

In Example 1, the transparent conductive film with an adhesive layer was produced like Example 1 except not having added the isocyanate type crosslinking agent in preparation of an adhesive composition.

Comparative Example 1

In Example 1, the transparent conductive film with an adhesive layer was manufactured like Example 1 except not having added the epoxy type crosslinking agent in preparation of an adhesive composition.

Comparative Example 2

In Example 1, the transparent conductive film with an adhesive layer was manufactured like Example 1 except not having added the isocyanate type crosslinking agent and the epoxy type crosslinking agent in preparation of an adhesive composition.

Comparative Example 3

In Example 1, the transparent conductive film with an adhesive layer was manufactured like Example 1 except not having added the epoxy type crosslinking agent in preparation of an adhesive composition, and changing the compounding quantity of the isocyanate type crosslinking agent to 0.6 weight part. It was.

The following evaluation was performed about the transparent conductive film with an adhesive layer obtained in Examples 1 and 2 and Comparative Examples 1-3. The results are shown in Table 1. In addition, in Table 1, content of the carboxyl group-containing monomer (acrylic acid) in the acryl-type polymer used in Examples 1 and 2 and Comparative Examples 1-3, the kind of crosslinking agent, a compounding quantity, the gel fraction of the adhesive layer manufactured, at 23 degreeC The storage modulus (G ') of the following is shown.

<Optical characteristics>

After heating the transparent conductive film with an adhesive layer for 90 minutes at 140 degreeC, the adhesive layer side of the transparent conductive film with an adhesive layer was stuck on the glass substrate, and the sample was manufactured. This sample was left to stand 500 hours in 85 degreeC, 85% RH atmosphere, and 100 degreeC atmosphere, respectively. The color b ^* before leaving (initial stage) and after standing was measured with the high speed spectrophotometer (DOT-3 type | mold, Murakami Color Research Institute). In Table 1, the difference (Δb ^* ) of the measured color b ^* is shown with the measured value before leaving (initial stage) and after leaving.

<Appearance>

Three transparent conductive films with an adhesive layer were prepared and heated at 140 degreeC for 90 minutes. The adhesive layer side is laminated | stacked on the glass substrate on the transparent conductive film with one adhesive layer, and then the other two transparent conductive films with an adhesive layer are laminated | stacked on the transparent conductive film with an adhesive layer on which the adhesive layer side is laminated | stacked. Samples were prepared by adhering on the ITO membrane in order. This sample was left to stand for 500 hours in the atmosphere of 85 degreeC, 85% RH, and 100 degreeC atmosphere, respectively. After the said standing, foaming and peeling between a glass and an adhesive layer between the transparent conductive film with a 1st (or 2nd) adhesive layer, and the transparent conductive film with a 2nd (or 3rd) adhesive layer in a sample are performed. Visual evaluation was made based on the following criteria.

○: No foaming or peeling.

X: Foaming and peeling can be confirmed.

&Lt; Adhesion >

The pressure-sensitive adhesive layer side of the transparent conductive film with a pressure-sensitive adhesive layer cut to a width of 25 mm on the treated surface of the polyethylene terephthalate film (125 tetrate OES, thickness 125 μm, manufactured by Oike Industry Co., Ltd.) on which the indium tin oxide was deposited. 1 reciprocating crimping | compression-bonding with a 2 kg roller, and after curing at 23 degreeC for 20 minutes, the adhesive strength (N / 25mm) at the time of peeling the said polyethylene terephthalate film at 300 mm / min in 180 degree direction of an adhesive layer is tensile Measured with a tester. Evaluation was performed based on the following criteria.

○: 7.0 N / 25 mm or more

△: less than 3.0 to 7.0 N / 25 mm

<Npen traces>

A polyethylene terephthalate film (G1SPU, manufactured by Kimoto Co., Ltd.) having a hard coat layer is bonded to the pressure-sensitive adhesive layer of the transparent conductive film with a pressure-sensitive adhesive layer so that the hard coat layer becomes the outer side, and the transparent conductive laminate (FIG. 7 and The same configuration, except that the undercoat layer is not shown in Fig. 7). The transparent conductive laminate was placed on a glass plate via a spacer (180 μm) such that the hard coat layer side was upward. After a certain load (250 g x 30 minutes) was applied to the pen (polyacetal agent) on the hard coat layer side, and left for 1 day after the release of the load, pen traces were visually evaluated on the ITO membrane side based on the following criteria.

(Circle): Pen trace cannot be confirmed.

X: Pen trace can be confirmed.

Example 3

(Manufacture of Polarizing Plate)

The 80-micrometer-thick polyvinyl alcohol film was extended | stretched 5 times in 40 degreeC iodine aqueous solution, and it dried at 50 degreeC for 4 minutes, and obtained the polarizer. The 80-micrometer-thick triacetyl cellulose film was adhere | attached on both sides of this polarizer using the polyvinyl alcohol-type resin adhesive, and the polarizing plate was obtained.

(Manufacture of Anchor Layer)

The aqueous solution of 0.8% of solid content concentration was prepared using the polyurethane resin which is a formation material (binder) of an anchor layer, and water-soluble polythiophene type conductive polymer. The ratio of a polyurethane resin and a water-soluble polythiophene conductive polymer was made into the former: latter = 10: 1. The said aqueous solution was apply | coated to the single side | surface of the said polarizing plate so that thickness after drying might be set to 100 nm, and it dried at 80 degreeC for 2 minutes, and formed the anchor layer.

(Manufacture of a polarizing plate with an adhesive layer)

In the above, the adhesive layer formed on the release film in Example 1 (formation of an adhesive layer) was adhere | attached to the anchor layer formed on the polarizing plate, and the polarizing plate with an adhesive layer was manufactured.

Comparative Example 4

In the manufacture of the polarizing plate with an adhesive layer of Example 3, the polarizing plate with an adhesive layer was produced like Example 3 except having used the thing manufactured by the comparative example 3 as an adhesive layer formed on the release film.

Comparative Example 5

In the manufacture of the polarizing plate with an adhesive layer of Example 3, the polarizing plate with an adhesive layer was produced like Example 3 except having used the thing manufactured by the comparative example 1 as an adhesive layer formed on the release film.

Comparative Example 6

(Formation of pressure-sensitive adhesive layer)

In the preparation of the acrylic polymer of Example 1, an acrylic polymer was prepared in the same manner as in Example 1 except that 5 parts of acrylic acid was not used. Moreover, except having used the said acryl-type polymer, the adhesive composition was prepared like Example 1, and the adhesive layer was formed using the said adhesive composition.

(Manufacture of a polarizing plate with an adhesive layer)

In the manufacture of the polarizing plate with an adhesive layer of Example 3, the polarizing plate with an adhesive layer was produced like Example 3 except having used the thing manufactured above as the adhesive layer formed on the release film.

The following evaluation was performed about the polarizing plate with an adhesive layer obtained in Example 3 and Comparative Examples 4-6. The results are shown in Table 2. In addition, in Table 2, similarly to Table 1, the content of the carboxyl group-containing monomer (acrylic acid) in the acrylic polymer used in Example 3 and Comparative Examples 4 to 6, the type of crosslinking agent, the compounding amount, the gel fraction of the pressure-sensitive adhesive layer produced, 23 The storage modulus (G ') at ° C is shown.

<Optical characteristics>

The adhesive layer side of the polarizing plate with an adhesive layer was stuck on the glass substrate, and the sample was produced. This sample was left to stand 500 hours in 60 degreeC, 95% RH atmosphere, and 100 degreeC atmosphere, respectively. (DELTA) ab was measured by the high speed spectrophotometer (DOT-3 type | mold, Murakami Color Research Institute) by the amount of color change before (initial) and after leaving.

<Appearance>

The adhesive layer side of the polarizing plate with an adhesive layer was stuck on the glass substrate, and it was set as the sample (size 32 cm x 24 cm). This sample was left to stand 500 hours in 60 degreeC, 95% RH atmosphere, and 100 degreeC atmosphere, respectively. After the said standing, foaming and peeling between the polarizing plate with an adhesive layer and an adhesive layer, and a glass and an adhesive layer in a sample were evaluated visually on the following reference | standard.

○: No foaming or peeling.

X: Foaming and peeling can be confirmed.

&Lt; Adhesion >

2 kg of the pressure-sensitive adhesive layer side of the polarizing plate with pressure-sensitive adhesive layer cut to a width of 25 mm on the treated surface of the polyethylene terephthalate film (125 tetrat OES, thickness 125 µm, manufactured by Oike Industry Co., Ltd.) on which the indium tin oxide was deposited. After reciprocating with a roller for 1 minute and curing at 23 ° C. for 20 minutes, the adhesive strength (N / 25 mm) at the time of peeling the polyethylene terephthalate film at 300 mm / min in the 180 ° direction of the pressure-sensitive adhesive layer was measured by a tensile tester. Measured. Evaluation was performed based on the following criteria.

○: 7.0 N / 25 mm or more

△: less than 3.0 to 7.0 N / 25 mm

Explanation of symbols

1 optical member (optical film)

2 different layers

3 pressure sensitive adhesive layer

4 release film

11 first transparent plastic film base material

11 'second transparent plastic film base

12 transparent conductive thin film layer

13 pressure-sensitive adhesive layer

14 release film

15 undercoat layers

16 hard coat floors

Claims (19)

(Meth) acrylic polymer which contains 0.2-20 weight part of carboxyl group-containing monomer as a copolymerization component with respect to 100 weight part of alkyl (meth) acrylates which have a C4-C14 alkyl group as a monomer unit, And with respect to 100 weight part of said (meth) acrylic-type polymers, the adhesive layer for optical members formed with the adhesive composition for optical members containing 0.02-2 weight part of peroxides as a crosslinking agent, and 0.005-5 weight part of epoxy type crosslinking agents. As The adhesive layer for optical members is a storage elastic modulus (G ') in 23 degreeC of 80000-500000 Pa, The adhesive layer for optical members characterized by the above-mentioned. The method of claim 1, 0.01-0.5 weight part of isocyanate type crosslinking agents are further contained with respect to 100 weight part of said (meth) acrylic-type polymers, The adhesive layer for optical members characterized by the above-mentioned. The method of claim 1, 0.01-1 weight part of silane coupling agents are further contained with respect to 100 weight part of said (meth) acrylic-type polymers, The adhesive layer for optical members characterized by the above-mentioned. The method of claim 1, The said (meth) acrylic-type polymer contains 0.01-5 weight part of hydroxyl-group containing monomers further with respect to 100 weight part of alkyl (meth) acrylates as a monomer unit, The adhesive layer for optical members characterized by the above-mentioned. The method of claim 1, It is applied to the transparent conductive film which has a transparent conductive thin film in one surface of a 1st transparent plastic film base material, The adhesive layer for optical members characterized by the above-mentioned. The method of claim 1, The said adhesive layer for optical members is 70-98 weight% of gel fraction, The adhesive layer for optical members characterized by the above-mentioned. The adhesive layer for optical members of Claim 1 is formed in at least one surface of an optical member, The adhesive optical member characterized by the above-mentioned. The method of claim 7, wherein The said adhesive layer and an optical member are laminated | stacked through the anchor layer, The adhesive optical member characterized by the above-mentioned. 9. The method of claim 8, The adhesive optical member, wherein the anchor layer contains a polymer. The method of claim 7, wherein An adhesive optical member is a transparent conductive film with an adhesive layer which has an adhesive layer in one surface of a 1st transparent plastic film base material, and has a transparent conductive thin film in the other surface of the said 1st transparent plastic film base material, It is characterized by the above-mentioned. Adhesive optical member. 11. The method of claim 10, The transparent conductive thin film is formed in one surface of a 1st transparent plastic film base material through the at least 1 undercoat layer, The adhesive optical member characterized by the above-mentioned. A 2nd transparent plastic film base material is further adhere | attached on the adhesive layer in the adhesive optical member which concerns on the transparent conductive film with an adhesive layer of Claim 10, The transparent conductive laminated body characterized by the above-mentioned. 13. The method of claim 12, The 2nd transparent plastic film base material has a hard-coat layer in the single side | surface or both surfaces, The transparent conductive laminated body characterized by the above-mentioned. The adhesive optical member which concerns on the transparent conductive film with an adhesive layer of Claim 10, or the transparent conductive laminated body of Claim 12 is used as a transparent conductive film for touch panels, The touchscreen characterized by the above-mentioned. The method of claim 7, wherein The adhesive optical member is an optical film with an adhesive layer which has an adhesive layer on at least one surface of the optical film for image display apparatuses, The adhesive optical member characterized by the above-mentioned. 16. The method of claim 15, The said optical film is a polarizing plate or retardation plate, The adhesive optical member characterized by the above-mentioned. At least one adhesive optical member which concerns on the optical film with an adhesive layer of Claim 15 is used, The image display apparatus characterized by the above-mentioned. delete delete

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