JP2010065217A - Self-adhesive composition for optical member, self-adhesive for optical member, and optical member with self-adhesive layer obtained by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly durable adhesive composition for optical members having excellent antistatic performance, exhibiting superior adhesiveness between optical laminates, in particular between a polarizing plate and a glass substrate, even under the high-temperature high-humidity conditions to prevent foaming and separation between an adhesive layer and the glass substrate, and preventing a light leakage phenomenon occurring due to shrinkage of a polarlizing film. <P>SOLUTION: The adhesive resin composition for optical members includes (A) an acrylic resin obtained by polymerizing polymerizable components containing 15 wt.% or more of a hydroxy group-containing monomer, and (B) at least one of an alkali metal salt and an alkaline-earth metal salt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is an optical film (polarizing film, retardation film, optical compensation film, brightness enhancement film, etc.) suitably used for image display devices such as liquid crystal display devices, organic EL display devices, and PDPs. Optical member pressure-sensitive adhesive resin composition used for bonding a polarizing film with an optical laminate coated with a protective film such as a cellulose triacetate film and a glass substrate of a liquid crystal cell, and an optical member pressure-sensitive adhesive, and this The present invention relates to an optical member with an adhesive layer in which an adhesive layer made of an adhesive for optical members is formed, particularly a polarizing plate with an adhesive layer. More specifically, it has excellent antistatic performance, and also has excellent adhesion between the optical laminate and the glass substrate even under high temperature and high humidity conditions, and foaming or peeling between the adhesive layer and the glass substrate is possible. In addition, the optical member pressure-sensitive adhesive resin composition excellent in durability, such as being capable of preventing light leakage caused by shrinkage of the optical film, and the optical member pressure-sensitive adhesive, and obtained using the same The present invention relates to an optical member with an adhesive layer.

  Conventionally, a polarizing film, for example, a polarizing plate coated with a cellulose film, for example, a cellulose triacetate film, on both sides of a polarizing film, for example, a polyvinyl alcohol film having a polarizing property, is a liquid crystal component that is aligned between two glass plates. Lamination is carried out on the surface of the sandwiched liquid crystal cell to form a liquid crystal display panel. This lamination to the liquid crystal cell surface is performed by bringing the pressure-sensitive adhesive layer provided on the polarizing plate surface into contact with the liquid crystal cell surface. This is usually done by pressing.

  The pressure-sensitive adhesive layer provided on the surface of the optical member such as the polarizing plate is provided with a separator for the purpose of preventing scratches or dirt, or the surface for the purpose of preventing scratches or dirt generated during processing and transporting processes. Although a protective film or the like is provided, these separators and the surface protective film are not necessary and are peeled and removed when they are bonded to a liquid crystal cell or the like. Static electricity is generated when the separator or the surface protection film is peeled off from such an optical member, and this static electricity causes dust to adhere to the optical member, causes an abnormal display due to disorder of the liquid crystal alignment, and peripheral circuit elements. There is a problem that problems such as electrostatic breakdown occur.

  In addition, when an optical member provided with the above-mentioned pressure-sensitive adhesive layer is bonded to a liquid crystal cell, if foreign matter is mixed, damaged, or an adhesion error occurs, it will be peeled off and re-bonded. As described above, static electricity is generated and a problem occurs. As a countermeasure for preventing the occurrence of defects due to the generation of static electricity, for example, in an adhesive composition used for an optical member, it has been proposed to blend an ionic liquid with a base polymer (see Patent Document 1). In addition, it has been proposed that an acrylic base polymer is blended with an antistatic agent in which a polymer having a polyalkylene structure and a hydroxyl group is mixed with an ionic substance (see Patent Document 2).

JP 2006-11365 A JP 2006-199873 A

  However, in the disclosed technique of Patent Document 1, although the effect of antistatic performance is recognized, there is a possibility that bleeding occurs over time because the ionic liquid is blended, and the base polymer itself is charged. It is a general one that does not have a preventive ability, and relies on the antistatic performance of only the ionic liquid. Further, the durability and light leakage prevention performance, which are important for the optical members to be used, particularly for polarizing plate applications, have not been considered at all.

  On the other hand, in the disclosed technology of Patent Document 2, the effect of antistatic performance is recognized as in Patent Document 1, but the antistatic agent blended in the base polymer may bleed over time. It was unbearable for practical use.

  By the way, liquid crystal display panels using polarizing plates are widely used as display devices for personal computers, liquid crystal televisions, car navigation systems, etc., and the use environment has become very harsh. It is required to be excellent in durability even in use, for example, there is no phenomenon such as foaming or peeling between the pressure-sensitive adhesive layer and the glass plate even under a severe environment such as high temperature and high humidity, In a high-temperature, high-humidity environment, the polarizing film contracts, whereas the adhesive layer cannot follow the contraction of the polarizing film, and light leaks from the peripheral edge of the liquid crystal display panel. It is required that there is no so-called light leakage phenomenon.

  The present invention has been made in view of such circumstances, and is excellent in antistatic performance, and further excellent in adhesion between an optical laminate, particularly a polarizing plate and a glass substrate, even under high temperature and high humidity conditions. In addition, the pressure-sensitive adhesive resin composition for optical members has excellent durability, such as no foaming or peeling between the pressure-sensitive adhesive layer and the glass substrate, and prevention of light leakage caused by contraction of the polarizing film. It is another object of the present invention to provide an adhesive for an optical member and an optical member with an adhesive layer obtained by using the adhesive.

  In order to solve the above-mentioned object, the present inventors, in the course of intensive studies, first, when a large amount of antistatic agent is added for the purpose of imparting antistatic ability, the durability of the adhesive itself is significantly reduced. Conversely, in order to reduce the addition amount of the antistatic agent and maintain the antistatic performance, it has been found that the resin itself constituting the pressure-sensitive adhesive needs to be improved. Based on this knowledge, as a result of repeated research, the antistatic ability is exhibited by increasing the use ratio of the hydroxyl group-containing acrylic monomer that is a polymerization component of the resin. It has been found that the durability decreases when the amount is too large. Therefore, as a result of further research to obtain an antistatic agent capable of imparting excellent antistatic ability without causing a decrease in the durability of the pressure-sensitive adhesive, various antistatic agents have been obtained. In particular, when at least one of an alkali metal salt and an alkaline earth metal salt, which is an antistatic agent having a small particle diameter, is used, the pressure-sensitive adhesive resin composition for optical members is excellent in durability, light leakage prevention property and antistatic ability. The present invention has been found.

  That is, the present invention provides an optical resin containing an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer, and at least one of an alkali metal salt and an alkaline earth metal salt (B). The pressure-sensitive adhesive resin composition for members is the first gist.

  And this invention makes the 2nd summary the adhesive for optical members formed by bridge | crosslinking the adhesive resin composition [I] for optical members which is the said 1st summary.

  Furthermore, this invention makes the 3rd summary the optical member with an adhesive layer which is a laminated body which consists of the adhesive layer which consists of an adhesive for optical members which is the said 2nd summary, and an optical member.

  Thus, the present invention contains an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer, and at least one of an alkali metal salt and an alkaline earth metal salt (B). The optical member pressure-sensitive adhesive resin composition [I] is an optical member pressure-sensitive adhesive obtained by crosslinking the optical member pressure-sensitive adhesive resin composition [I]. For this reason, it has an excellent balance between adhesive physical properties and antistatic performance, and also has excellent adhesive properties between the optical laminate, particularly the polarizing plate and the glass substrate, even under high temperature and high humidity conditions. In addition, the liquid crystal display panel having excellent durability, such as no foaming or peeling, can be prevented, and the light leakage phenomenon caused by the contraction of the polarizing film can be prevented.

  When the pressure-sensitive adhesive resin composition [I] for an optical member contains a cross-linking agent (C) and is cross-linked by the cross-linking agent (C), the durability and light leakage prevention properties are further improved. can get.

  The pressure-sensitive adhesive resin composition [I] for optical members contains an unsaturated group-containing compound (D) as a polymerizable component, and also contains a polymerization initiator (E), and is crosslinked by active energy rays and / or heat. As a result, even better durability and light leakage prevention properties can be obtained.

  When the gel fraction of the pressure-sensitive adhesive for optical members is 80% or more, further excellent durability and light leakage prevention properties can be obtained.

  In the present invention, (meth) acrylic acid is acrylic acid or methacrylic acid, (meth) acryl is acrylic or methacrylic, (meth) acryloyl is acryloyl or methacryloyl, and (meth) acrylate is acrylate or methacrylate. Each means something.

  The pressure-sensitive adhesive resin composition [I] for optical members of the present invention comprises an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer, an alkali metal salt, and an alkaline earth metal salt. It is obtained using at least one of (B). And the adhesive for optical members of this invention consists of this crosslinked body formed by bridge | crosslinking this adhesive resin composition [I] for optical members.

First, the said adhesive resin composition [I] for optical members is demonstrated.
As described above, the pressure-sensitive adhesive resin composition for optical members (hereinafter also simply referred to as “resin composition”) [I] is obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer. An acrylic resin (A) and at least one (B) of an alkali metal salt and an alkaline earth metal salt are contained.

  The acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer has a hydroxyl group-containing monomer as an essential component as a polymerization component and is homopolymerized or co-polymerized with other copolymer components. It is obtained by polymerization.

  Examples of the hydroxyl group-containing monomer in the present invention include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8- Hydroxyalkyl esters of (meth) acrylic acid such as hydroxyoctyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, and oxyalkylene modifications such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate Monomer, other primary hydroxyl group-containing monomers such as 2- (meth) acryloyloxyethyl 2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide; 2- Droxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) ) Secondary hydroxyl group-containing monomers such as acrylate; tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth) acrylate.

  Among the hydroxyl group-containing monomers, it is preferable to use a primary hydroxyl group-containing monomer in terms of excellent reactivity with the crosslinking agent, and it is more preferable to use 2-hydroxyethyl (meth) acrylate. It is particularly preferable in that it is easy to manufacture because of few impurities such as.

  In addition, as a hydroxyl-containing monomer used by this invention, it is preferable to use the content rate of di (meth) acrylate which is an impurity 0.5% or less.

  Examples of other copolymer components other than the hydroxyl group-containing monomer include functional group-containing monomers other than the hydroxyl group-containing monomer, (meth) acrylic acid ester monomers, and, if necessary, other copolymerizable monomers.

  Examples of the functional group-containing monomer include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, (meth) acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. Michael adducts (for example, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyldicarboxylic acid monoester (for example, 2- Acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydroph Carboxyl group-containing monomers such as phosphoric acid monoester and 2-methacryloyloxyethyl hexahydrophthalic acid monoester); glycidyl group-containing monomers such as glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate; (meth) acrylamide, N Amide group-containing monomers such as-(n-butoxyalkyl) (meth) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide; Amino group-containing monomers such as (meth) acrylamide-3-methylbutylmethylamine and dimethylaminoalkyl (meth) acrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, 2- (meth) a Riruamido 2-methylpropane sulfonic acid, sulfonic acid group-containing monomers such as styrenesulfonic acid or salts thereof; and the like. These may be used either alone or in combination.

  Among the functional group-containing monomers, a carboxyl group-containing monomer, a glycidyl group-containing monomer, and an amide group-containing monomer are preferably used, and further, the carboxyl group-containing monomer particularly increases the adhesive strength and durability. Preferably used.

  Examples of the (meth) acrylic acid ester monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid phenyl ester, and the like. About the said (meth) acrylic-acid alkylester, it is preferable that carbon number of an alkyl group is 1-12 normally, Especially 1-8, Furthermore, 4-8 are preferable, Specifically, methyl (meth) acrylate , Ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and the like.

  Among the above (meth) acrylic acid alkyl esters, n-butyl acrylate is particularly preferably used because it is excellent in tackiness, antistatic performance, compatibility when mixed with an antistatic agent, and the like.

  Examples of the other copolymerizable monomers include N- (meth) acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, and chloride. Examples thereof include vinylidene, vinyl acetate, styrene, α-methylstyrene and the like.

  In the present invention, it is also preferable to copolymerize a compound having an antistatic property as a copolymerizable monomer in order to further improve the antistatic property of the acrylic resin (A). .

  The compound having antistatic performance may be any compound having a hydrophilic structural portion, and examples of the hydrophilic group include compounds having an ionic group and a nonionic group. Examples of the compound having an ionic group include a quaternized product such as dimethylaminoethyl (meth) acrylate, an ionic liquid and an ionic solid having a polymerizable group such as (meth) acrylate of an imidazolium salt, and a quaternary ammonium base. Examples thereof include ionic group-containing polymerizable compounds such as urethane (meth) acrylate-based compounds, and examples of compounds having nonionic groups include nonionic polymerizable compounds such as alkylene oxide structure-containing polymerizable monomers. it can.

  It is also possible to introduce a compound having antistatic performance into the side chain of the acrylic resin (A) once produced by copolymerization by grafting reaction. In this case, for example, a compound containing a hydroxyl group is selected from the compounds having a structural portion exhibiting hydrophilicity, reacted with a polyisocyanate compound to form a urethane prepolymer, and then reacted with a hydroxyl group of the acrylic resin (A). Can be introduced.

  In the present invention, the specific acrylic resin (A) is produced by polymerizing the monomer component, and the polymerization can be performed by a conventionally known method. For example, in an organic solvent, the above hydroxyl group-containing monomer, other functional group-containing monomer, acrylate monomer, other copolymerizable monomer, and other polymerization monomers, polymerization initiators (azobisisobutyronitrile, azobisiso) (Valeronitrile, benzoyl peroxide, etc.) may be mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 2 to 20 hours.

  Such an acrylic resin (A) can be produced, for example, by radical polymerization in an organic solvent. Examples of the organic solvent used for the radical polymerization include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; esters such as ethyl acetate and butyl acetate; n-propyl alcohol, iso- Examples include aliphatic alcohols such as propyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  As the radical polymerization initiator used for the radical polymerization, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, which are usual radical polymerization initiators, Azo compounds such as 4'-azobis (4-cyanovaleric acid), 2,2'azobis (2-methylpropionic acid), benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide And other peroxide compounds.

  And in the said acrylic resin (A), it is required to contain 15 weight% or more of hydroxyl-containing monomers with respect to the whole polymerization component as a polymerization component. That is, if the amount of the hydroxyl group-containing monomer is too small, sufficient antistatic performance cannot be obtained. A preferable range of the hydroxyl group-containing monomer is 15 to 70% by weight, more preferably 17 to 60% by weight, and particularly preferably 20 to 50% by weight.

  Moreover, as a content rate of the said other polymerization component, it is 0-5 weight% especially functional group containing monomers other than a hydroxyl-containing monomer, It is 0-3 weight%, Furthermore, it is 0.2-1 weight%. Preferably, the (meth) acrylic acid ester monomer is 0 to 85% by weight, particularly 30 to 85% by weight, more preferably 40 to 80% by weight, and other copolymerization monomers are 0 to 30% by weight, In particular, it is preferably 0 to 15% by weight, more preferably 0 to 10% by weight.

  The weight average molecular weight (Mw) of the acrylic resin (A) obtained by polymerizing the polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer thus obtained is the balance between durability and light leakage prevention performance. Therefore, it is usually preferably 200,000 to 2,500,000, particularly preferably 500,000 to 1,600,000. If the weight average molecular weight is too small, there is a tendency that sufficient cohesive force cannot be obtained even by crosslinking treatment such as irradiation with active energy rays described below or reaction with a crosslinking agent, and if it is too large, a large amount of dilution solvent is required. In addition, an undesirable tendency is seen in terms of coatability and cost.

  In addition, the said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column is used for a high performance liquid chromatography (The product of Japan Waters, "Waters 2695 (main body)" and "Waters 2414 (detector)"). Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 7, separation range: 100 to 2 × 10 7, theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: It is measured by using three series of 10 μm).

  The degree of dispersion (Mw / Mn) of the acrylic resin (A) is not particularly limited, but is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less. When the degree of dispersion is too high, the pressure-sensitive adhesive layer tends to be inferior in durability performance such as heat resistance and light leakage. The lower limit of the degree of dispersion is usually 2 from the viewpoint of production limit. The dispersity is a value obtained from a weight average molecular weight and a number average molecular weight, and the Mn indicates a number average molecular weight of the acrylic resin (A), and the number average molecular weight (Mn) is It is calculated | required by the method similar to the said weight average molecular weight (Mw).

  Furthermore, the glass transition temperature of the acrylic resin (A) is preferably −80 to −20 ° C., particularly −75 to −25 ° C., more preferably −55 to −30 ° C. If the glass transition temperature is too high, tack tends to be insufficient, and if it is too low, heat resistance tends to be poor. The glass transition temperature is calculated from the Fox equation.

Further, the viscosity of the acrylic resin (A) obtained by polymerizing the polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer thus obtained is diluted with ethyl acetate so that the nonvolatile content becomes 30%. The viscosity is usually 10 to 1,000,000 mPa · s / 25 ° C, more preferably 500 to 100,000 mPa · s / 25 ° C, and particularly preferably 2000 to 50,000 mPa · s / 25 ° C. That is, if the viscosity is too high, it tends to cause uneven coating, which is difficult to process as an adhesive, and if it is too low, it tends to be inferior in cohesion.
In addition, the measurement of the said viscosity can be performed according to the 4.5.3 rotational viscometer method of JISK5400 (1990).

  At least one of the alkali metal salt and the alkaline earth metal salt (B) (hereinafter sometimes referred to as “antistatic agent (B)”) used together with the acrylic resin (A) is used as an antistatic agent. Although it has an effect, it also has an effect of not causing a decrease in durability.

Examples of the cation moiety in the alkali metal salt and alkaline earth metal salt include Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , and Ca ²⁺ . Among these, the antistatic performance is excellent. Li ⁺ , Na ⁺ and K ⁺ are preferred.

Examples of the anion moiety in the alkali metal salt and alkaline earth metal salt include Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ COO ⁻ , SbF ₆ ⁻ , and NbF ₆ ^−. , TaF ₆ ⁻ , F (HF) n ⁻ , C ₄ F ₉ SO ₃ ⁻ , C ₃ F ₇ COO ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO _{^{-, CH 3 SO 3 -,}} AsF 6 -, (CN) 2 N -, but like can be mentioned. among _{^{them, BF 4 -, PF 6 -}} , CF 3 COO -, SbF 6 -, NbF 6 -, TaF ₆ ⁻ , F (HF) n ⁻ , C ₄ F ₉ SO ₃ ⁻ , C ₃ F ₇ COO ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) It is preferably a fluorine atom-containing anion such as ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ , particularly preferably (CF ₃ SO ₂ ). ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ^{− and} other sulfonyl groups and fluorine atom-containing anions More preferably, a sulfonyl group having an imide structure such as (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ and a fluorine atom Containing anions.

  Among at least one of the alkali metal salt and alkaline earth metal salt (B) obtained by combining the cation and the anion, trifluoromethanesulfonyl is capable of imparting antistatic performance without deteriorating physical properties other than antistatic performance. It is particularly preferable to use imidolithium or potassium trifluoromethanesulfonylimide.

  The content of at least one of the alkali metal salt and alkaline earth metal salt (B) is usually set to 0.001 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin (A). More preferably, it is 0.1-10 weight part, Most preferably, it is 1-5 weight part. That is, if the content of at least one of the alkali metal salt and the alkaline earth metal salt (B) is too small, it becomes difficult to impart sufficient antistatic ability, and if it is too much, the durability tends to decrease. Because it is.

  In the present invention, the pressure-sensitive adhesive resin composition [I] for optical members generally contains the acrylic resin (A) as a main component, and at least one of the alkali metal salt and the alkaline earth metal salt. Although it contains (B), the said main component is normally 50 weight% or more with respect to the adhesive resin composition [I] optical member [I] whole quantity, Preferably it is 60 weight% or more, More preferably, it is 70. It means that it is contained by weight% or more.

  In the present invention, an optical resin containing an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer, and at least one of an alkali metal salt and an alkaline earth metal salt (B). It becomes a pressure-sensitive adhesive by crosslinking the pressure-sensitive adhesive resin composition [I] for members.

  The pressure-sensitive adhesive resin composition [I] for optical members of the present invention comprises an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer, an alkali metal salt, and an alkaline earth metal salt. It may consist of at least one of (B), and contains a crosslinking agent (C), an active energy ray-polymerizable unsaturated group-containing compound (D), and a polymerization initiator (E), which will be described later. Is also preferable.

Below, the adhesive for optical members of this invention is demonstrated.
The pressure-sensitive adhesive for optical members of the present invention comprises an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer, and at least one of the alkali metal salt and alkaline earth metal salt ( The pressure-sensitive adhesive resin composition [I] for optical members containing B) is crosslinked. For the acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of the hydroxyl group-containing monomer and at least one of the alkali metal salt and alkaline earth metal salt (B), the resin composition This is the same as described in the article.

  As a method of crosslinking the above pressure-sensitive adhesive resin composition [I] for optical members, [α] a method of crosslinking using a crosslinking agent (C), [β] an unsaturated group-containing compound (D) and a polymerization initiator ( Examples thereof include a method of containing E) and crosslinking with active energy rays and / or heat. As for the degree of cross-linking, a sufficient product can be obtained only by the method [β]. However, from the viewpoint that the cross-linking of the pressure-sensitive adhesive is made more dense and the light leakage prevention property is improved, It is particularly preferable to use the methods [β] in combination.

First, a method for crosslinking using the [α] crosslinking agent (C) will be described.
When crosslinking is performed using the crosslinking agent (C), the resin composition [I] is added to at least one of the acrylic resin (A), alkali metal salt, and alkaline earth metal salt (B), and further crosslinked. Resin composition [I] containing agent (C) is used.

  When the crosslinking agent (C) is used, crosslinking (chemical crosslinking) is performed by reacting the functional group of the acrylic resin (A) with the crosslinking agent (C).

  The crosslinking agent (C) may be any compound having a functional group that reacts with the functional group contained in the acrylic resin (A). For example, bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol , Epoxy compounds such as diglycerol polyglycidyl ether, tetramethylolmethane-tri-β-aziridinyl propionate, Roll propane-tri-β-aziridinyl propionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), N, N′-hexamethylene-1,6-bis (1 -Aziridine compounds such as -aziridinecarboxyamide), melamines such as hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, melamine resin Compound, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate, diphen Rumethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and their polyisocyanate compounds and tri Adducts with polyol compounds such as methylolpropane, isocyanate compounds such as bullets and isocyanurates of these polyisocyanate compounds, glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, Aldehyde compounds such as benzaldehyde, hexamethylenediamine, triethyldiamine, polyethyleneimine, hexane Many amine compounds such as methylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, polyamide, aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, zirconium, etc. Examples include metal chelate compounds such as metal acetylacetone and acetoacetyl ester coordination compounds. Among them, isocyanate compounds are preferably used in terms of improving adhesion to the base material and reactivity with the base polymer. It is done. These crosslinking agents (C) may be used alone or in combination of two or more.

  The content of the crosslinking agent (C) can be appropriately selected depending on the amount of the functional group contained in the acrylic resin (A), the molecular weight of the acrylic resin (A), and the purpose of use. (A) It is preferable that it is 0.1-15 weight part with respect to 100 weight part, Furthermore, 0.2-12 weight part, Especially 0.3-3 weight part, Especially 0.5- The amount is preferably 1 part by weight. When the amount of the crosslinking agent (C) is too small, there is a tendency that the cohesive force is insufficient and sufficient durability cannot be obtained, and when the amount is too large, the flexibility and the adhesive strength are lowered, the durability is deteriorated, and peeling is caused. Tends to occur, and it tends to be difficult to bond to an optical film.

  In the present invention, in order to further improve the antistatic performance of the pressure-sensitive adhesive obtained by crosslinking the resin composition [I], a compound having an antistatic performance is partly included in the crosslinking agent (C). It is also preferable to use an introduced crosslinking agent. As the compound having antistatic performance, the same compound as the compound having antistatic performance introduced into the side chain of the acrylic resin (A) by grafting reaction can be used.

  As a method for introducing a compound having antistatic performance into such a crosslinking agent, for example, when a polyisocyanate compound is used as the crosslinking agent, a compound having a hydroxyl group in its structure as a compound having antistatic performance. And a crosslinking agent in which a compound having antistatic performance is partially introduced can be produced by the reaction of the hydroxyl group and the isocyanate group.

  In addition, regarding the introduction of the compound having antistatic performance into the crosslinking agent, a compound having antistatic performance may be introduced into the crosslinking agent in advance and mixed with the acrylic resin (A), or the acrylic resin. (A) At the time of mixing with the crosslinking agent (C), a compound having antistatic performance may be added at the same time to react with the crosslinking agent (C).

  Next, the unsaturated group-containing compound (D) and the polymerization initiator (E), which are the methods of [β], are contained, and the resin composition [I] is subjected to active energy rays and / or heat (active energy ray irradiation). And / or a method of crosslinking by heating) will be described.

  In the case of crosslinking by the active energy ray and / or heat (irradiation with active energy ray and / or heating), the resin composition [I] is the acrylic resin (A), alkali metal salt and alkaline earth metal described above. In addition to at least one of the salts (B), a resin composition [I] containing an unsaturated group-containing compound (D) and a polymerization initiator (E) is used. Thus, by containing an unsaturated group containing compound (D), hardening can be adjusted and it becomes possible to implement | achieve the adhesive physical property suitable for an optical member use. Moreover, the reaction at the time of active energy ray irradiation can be stabilized by containing the said polymerization initiator (E).

  In the case of the cross-linking, the unsaturated group-containing compound (D) is polymerized (polymerized) by active energy rays and / or heat to cross-link (physical cross-linking) with the acrylic resin (A). When the acrylic resin (A) is an unsaturated group-containing acrylic resin, the unsaturated group-containing acrylic is not limited to polymerization of the unsaturated group-containing compound (D) by active energy rays and / or heat. Polymerization of the resin (A) and the unsaturated group-containing compound (D) will be considered.

  The unsaturated group-containing compound (D) may be a monofunctional unsaturated group-containing compound having one unsaturated group in one molecule, or two or more unsaturated groups in one molecule. It may be a polyfunctional unsaturated group-containing compound having an unsaturated group-containing compound having two or more unsaturated groups, more preferably an unsaturated group-containing compound having three or more unsaturated groups. In particular, an unsaturated group-containing compound having 3 to 10 unsaturated groups is preferred from the viewpoint of curability during irradiation with active energy rays.

Examples of the structure of the unsaturated group-containing compound (D) include urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and one or more ethylene in one molecule. An ethylenically unsaturated monomer containing a polymerizable unsaturated group, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher functional monomer, and the like can be used. Among these, it is preferable to use the urethane (meth) acrylate compound (d1) and the ethylenically unsaturated monomer (d2) from the viewpoint of excellent curing speed and ultimate physical properties.
Moreover, it is more preferable from the surface of antistatic performance or compatibility that the said unsaturated group containing compound (D) contains structural parts which show hydrophilicity, such as an oxyalkylene chain and a hydroxyl group.

  The urethane (meth) acrylate compound (d1) is a (meth) acrylate compound having a urethane bond in the molecule, and can be produced by reacting a (meth) acrylic compound containing a hydroxyl group with a polyvalent isocyanate compound. .

  The (meth) acrylic compound containing the hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, Caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, capro Examples include kuton-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, and ethylene oxide-modified pentaerythritol tri (meth) acrylate. Among them, hydroxyl group-containing (meta) having three or more acryloyl groups ) Acrylic compounds are preferably used. Moreover, these can be used 1 type or in combination of 2 or more types.

  The polyvalent isocyanate compound is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates. Among them, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, Polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanato) Methyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate And polyisocyanates such as naphthalene diisocyanate or trimer compounds or multimeric compounds of these polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, “Aquanate 100” manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.), or the reaction products of these polyisocyanates and polyols.

  Examples of the polyol include, but are not limited to, alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, and polybutylene glycol. Compounds, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, Multivalent alcohols such as glycerin, polyglycerin, polytetramethylene glycol A polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization; the polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, anhydrous Polyester polyols that are condensates with polybasic acids such as itaconic acid, itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; polybutadiene-based polyols such as hydrogenated polybutadiene polyols Etc. Among these, polyethylene glycol derivatives are preferably used, and polyethylene glycol and polyethylene glycol monomethyl ether are particularly preferably used.

  Furthermore, as the polyol, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid Also included are carboxyl group-containing polyols such as homogentisic acid, sulfonic acid group or sulfonate group-containing polyols such as sodium 1,4-butanediolsulfonate.

  And when using the reaction product of the said polyisocyanate and a polyol, what is necessary is just to use as terminal isocyanate group containing polyisocyanate obtained by making the said polyol and polyisocyanate react, for example. In the reaction between the polyisocyanate and the polyol, a metal catalyst such as dibutyltin dilaurate or an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7 is used for the purpose of promoting the reaction. Is also preferable.

  In addition, it is also preferable that an oxyalkylene chain-containing urethane (meth) acrylate compound is used as the urethane (meth) acrylate compound (d1) in view of excellent antistatic performance.

  The oxyalkylene chain-containing urethane (meth) acrylate compound is obtained by using an alkylene glycol compound among the polyols, and the structure of the oxyalkylene chain-containing urethane (meth) acrylate compound is as follows. One of the hydroxyl groups at both ends of the alkylene glycol compound reacts with an isocyanate group, and the other is a urethane (meth) acrylate having an oxyalkylene chain structure that remains as a hydroxyl group. Even after the treatment, the oxyalkylene chain has a high degree of freedom and is easy to transport ions, which is preferable in that it exhibits excellent antistatic performance.

  The oxyalkylene chain-containing urethane (meth) acrylate compound is obtained by using an alkylene glycol compound having only one hydroxyl group in place of the polyol alkylene glycol compound having a plurality of hydroxyl groups. It may be a thing. Examples of the alkylene glycol compounds having only one hydroxyl group include polyethylene glycol monomethyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol tridecyl ether, and polyethylene glycol. Examples include alkyl group-containing polyalkylene glycol derivatives such as oleyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol derivatives such as polyoxyethylene oleyl cetyl ether, and polypropylene glycol derivatives such as polypropylene glycol monomethyl ether.

  The method for producing the urethane (meth) acrylate compound is not particularly limited, and for example, a hydroxyl group-containing (meth) acrylic compound and a polyvalent isocyanate compound are mixed in an inert gas atmosphere, and 30 to 80 ° C., 2 to An example is a method of reacting for 10 hours. In this reaction, it is preferable to use a urethanization catalyst such as tin octenoate, di-n-butyltin dilaurate, lead octylate, potassium octylate, potassium acetate, stannous octoate, or triethylenediamine.

  The weight average molecular weight of the urethane (meth) acrylate compound is preferably 300 to 4000, more preferably 400 to 3500, and particularly preferably 500 to 3000. That is, if the weight average molecular weight is too small, the cohesive force tends to be insufficient after curing, and if it is too large, the viscosity becomes too high and production tends to be difficult.

  The monofunctional monomer may be any monomer that contains one ethylenically unsaturated group, such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth). Acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) ) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Conductor half ester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester, and the like.

  Examples of the ethylenically unsaturated monomer (d2) include, in addition to the above, a Michael adduct of acrylic acid or a 2-acryloyloxyethyldicarboxylic acid monoester. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid Examples thereof include acid dimers, acrylic acid trimers, methacrylic acid trimers, acrylic acid tetramers, and methacrylic acid tetramers. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester that is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxy. Examples thereof include ethylphthalic acid monoester, 2-methacryloyloxyethylphthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene Oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di ( (Meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester It is done.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol (Meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate Etc.

  The said urethane (meth) acrylate type compound, ethylenically unsaturated monomer, etc. which comprise these unsaturated group containing compounds (D) may be used independently, and may use 2 or more types together.

  As content of the said unsaturated group containing compound (D), 5-100 weight part is preferable with respect to 100 weight part of acrylic resin (A), More preferably, it is 7-50 weight part, More preferably, it is 10-30. Parts by weight. When there is too much content of the said unsaturated group containing compound (D), a softness | flexibility will fall, antistatic performance will worsen, and since it will become easy to peel, the tendency for it to become difficult to bond with an optical film is seen. If the amount is too small, the crosslinking density of the pressure-sensitive adhesive becomes insufficient, and the light leakage prevention property tends to deteriorate.

  In order to further improve the antistatic performance of the adhesive obtained in the present invention, it is also effective to increase the antistatic performance of the unsaturated group-containing compound (D). In order to obtain the effect of improving the antistatic performance, a compound having an antistatic performance may be used as the ethylenically unsaturated monomer, and a hydrophilic component as a constituent component of the urethane (meth) acrylate compound. You may use the compound which has both the structural site | part which shows this, and the antistatic performance which has a hydroxyl group.

  As the polymerization initiator (E), for example, various polymerization initiators such as a photopolymerization initiator (E1) and a thermal polymerization initiator (E2) can be used, and in particular, a photopolymerization initiator ( Use of E1) is preferable in that it can be crosslinked (cured) by irradiation with active energy rays such as ultraviolet rays for a very short time.

  Moreover, when using the said photoinitiator (E1), resin composition [I] is bridge | crosslinked by active energy ray irradiation, and when using a thermal polymerization initiator (E2), resin composition [I] is heated. It is also preferable to use both in combination, if necessary.

  The photopolymerization initiator (E1) is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2 -Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoy Benzoins such as isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxy Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoyl) Benzophenones such as (benzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethyl Thioxanthones such as mino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Acylphosphones such as -2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, these photoinitiators (E1) may be used individually by 1 type, and 2 or more types may be used together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

  Examples of the thermal polymerization initiator (E2) include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide). ) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1, 1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1- Bis (t-butylperoxy) butane, 2,2-bis (4 -Di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroper Oxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-Butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexa Noyl peroxide, octanoyl per Oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) (Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-te Lamethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxy Pivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylper) Oxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2 -Ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5 -Bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilylper Oxide, 3,3 ', 4,4'-tetra Organic peroxide initiators such as (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1- [(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′- Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl- N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] Hydride chloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) Lopan] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3 , 4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] ] Propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-me Til-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'- Azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl ) Propionitrile] and the like; and the like. In addition, only 1 type may be used independently for these thermal polymerization initiators, and 2 or more types may be used together.

  About content of the said polymerization initiator (E), 0.01-10 weight part with respect to 100 weight part of said acrylic resins (A), Especially 0.1-7 weight part, Furthermore, 0.3 It is preferably ~ 3 parts by weight. If the content of the polymerization initiator (E) is too small, the curability tends to be poor and the physical properties tend to become unstable, and if it is too much, no further effect can be obtained.

  In the active energy ray irradiation, in addition to rays such as far ultraviolet rays, ultraviolet rays and near ultraviolet rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price. In addition, when performing electron beam irradiation, it can harden | cure without using the said photoinitiator (E1).

As the light source for the ultraviolet irradiation, a high pressure mercury lamp, an electrodeless lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, or the like is used. In the case of the high-pressure mercury lamp, for example, it is performed under conditions of 5 to 3000 mJ / cm ² , preferably 10 to 1000 mJ / cm ² . Moreover, in the case of the said electrodeless lamp, it is performed on the conditions of 2-1500 mJ / cm < ² >, for example, Preferably it is 5-500 mJ / cm < ² >. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it may usually be several seconds to several tens of seconds, and in some cases, may be a fraction of a second. On the other hand, in the case of the electron beam irradiation, for example, an electron beam having energy in the range of 50 to 1000 Kev is used, and the irradiation amount is preferably 2 to 50 Mrad.

  Moreover, when using a thermal-polymerization initiator (E2) as said polymerization initiator (E), a polymerization reaction is started and advanced by heating. The treatment temperature and treatment time at the time of crosslinking by heating vary depending on the type of the thermal polymerization initiator (E2) used, and are usually calculated from the half-life of the initiator, but the treatment temperature is usually The temperature is preferably 70 ° C to 170 ° C, and the treatment time is usually preferably 0.2 to 20 minutes, and particularly preferably 0.5 to 10 minutes.

  When performing the crosslinking, either crosslinking by irradiation with active energy rays or thermal crosslinking may be used, but crosslinking by irradiation with active energy rays and thermal crosslinking may be used in combination as necessary.

  In the present invention, sufficient crosslinking can be obtained only by the above [β] active energy rays and / or heat (irradiation with active energy rays and / or heating). By using together, the crosslink density of the pressure-sensitive adhesive is increased, the cohesive force is increased, and a further superior one in terms of prevention of light leakage and durability can be obtained.

  In the present invention, it is preferable that the resin composition [I], which is a pressure-sensitive adhesive forming material, further contains a silane coupling agent (F) from the viewpoint of improving adhesion to an optical member. As content of the said silane coupling agent (F), it is normally set to 0.001-10 weight part with respect to 100 weight part of acrylic resin (A), More preferably, 0.01-1 weight part Particularly preferred is 0.03 to 0.8 parts by weight. When there is too little content of the said silane coupling agent (F), there exists a tendency for an addition effect not to be acquired, and when too much, compatibility with acrylic resin (A) is bad and adhesive force and cohesive force are obtained. There is a tendency to disappear.

  Examples of the silane coupling agent (F) include epoxy silane coupling agents, acrylic silane coupling agents, mercapto silane coupling agents, hydroxyl group silane coupling agents, carboxyl group silane coupling agents, amino Examples thereof include a base silane coupling agent, an amide group silane coupling agent, and an isocyanate group silane coupling agent. These may be used alone or in combination of two or more. Among these, an epoxy silane coupling agent and a mercapto silane coupling agent are preferably used. In particular, the combined use of an epoxy silane coupling agent and a mercapto silane coupling agent improves wet heat durability and adhesive strength. Is preferable in that it does not rise too much.

  Specific examples of the epoxy-based silane coupling agent include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycid. Examples include xylpropylmethyldimethoxysilane, methyltri (glycidyl) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. -Glycidoxypropyltrimethoxysilane, [gamma] -glycidoxypropyltriethoxysilane, [gamma] -glycidoxypropylmethyldiethoxysilane, [beta]-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Specific examples of the mercapto silane coupling agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyldimethoxymethylsilane.

  In the present invention, the pressure-sensitive adhesive composition [I], which is a pressure-sensitive adhesive-forming material, further contains an alkylene oxide group-containing compound (G) [excluding the unsaturated group-containing compound (D) described above] [ Hereinafter, it may be simply referred to as an alkylene oxide group-containing compound (G). It is preferable that the adhesiveness to the optical member is improved.

  As content of the said alkylene oxide group containing compound (G), it is normally set to 1-90 weight part with respect to 100 weight part of acrylic resin (A), Preferably it is 2-30 weight part, Especially preferably, it is. 3 to 10 parts by weight, in particular 4 to 5 parts by weight. When there is too little content of the said alkylene oxide group containing compound (G), there exists a tendency for it to be inferior to antistatic ability, and when there is too much, there exists a tendency for adhesive physical property to deteriorate.

  The oxyalkylene group-containing compound (G) may be any compound having an oxyalkylene group (excluding unsaturated group-containing compounds), and various oxyalkylene group-containing compounds can be used. For example, polyoxyalkylene alkyl Such as amine, polyoxyalkylene diamine, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether, etc. Nonionic surfactant, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl ether phosphate, polyoxyalkyl Anionic surfactants such as alkyl phenyl ether sulfates and polyoxyalkylene alkyl phenyl ether phosphates, cationic surfactants having both oxyalkylene groups and amphoteric surfactants, polyethers containing oxyalkylene groups Examples include esters.

  Among these, oxyethylene group-containing compounds are preferable. Specifically, polyoxyethylene alkylamines, polyoxyethylene diamines, oxyethylene group-containing polyether polymers, oxyethylene group-containing polyether ester amides, oxyethylene group-containing polymers are preferred. Examples include ether amide imide, polyoxyethylene glycol fatty acid ester, polyoxysorbitan acid fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, etc., and polyether polymers or acrylic polymers having an oxyethylene group, It is preferably used because it is easy to balance the compatibility with the base polymer.

  Examples of the oxyethylene group-containing polyether polymer include a polypropylene glycol-polyethylene glycol-polypropylene glycol block copolymer, a polypropylene glycol-polyethylene glycol block copolymer, and a polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer. And random copolymers and block copolymers of polyethylene glycol and polypropylene glycol, such as polypropylene glycol-polyethylene glycol random copolymers. The end of the glycol chain may be a hydroxyl group or may be substituted with an alkyl group, a phenyl group or the like.

  The polyethylene glycol ratio in the random copolymer or block copolymer of polyethylene glycol and polypropylene glycol is preferably 5 to 75% by weight, more preferably 10 to 70% by weight. If the polyethylene glycol ratio is too small, the compatibility with the ionic liquid tends to be poor, and sufficient antistatic properties tend to be difficult to obtain. If the ratio is too large, the crystallinity becomes high and the compatibility with the acrylic polymer becomes poor. It tends to be difficult to obtain sufficient antistatic properties.

  These compounds may be used alone or in combination of two or more. Among the oxyethylene group-containing compounds, the polyoxyethylene alkyl ether is preferable from the viewpoint of effectively increasing the antistatic ability.

  As the polyoxyethylene alkyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether and the like having 2 repetitions, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether and the like are repeated. No. 3, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, higher polyoxyethylene dimethyl ether, and the like. Among these, tetraethylene glycol dimethyl ether is preferably used.

  Moreover, in this invention, it is preferable that the oxyalkylene group content rate in the said oxyalkylene group containing compound (G) is 5-85 weight%, It is more preferable that it is 7-80 weight%, 9-75 More preferably, it is% by weight. When the content is too low, the antistatic performance tends to be inferior, and when the content is too high, the composition becomes hydrophilic and tends to be inferior in heat and moisture resistance.

  The molecular weight of the oxyalkylene group-containing compound (G) is preferably a number average molecular weight of 100 to 10,000, particularly preferably 180 to 1,000. In addition, the said number average molecular weight is calculated | required by the method similar to the above-mentioned weight average molecular weight.

  In the present invention, at least one of the alkali metal salt and the alkaline earth metal salt (B) is used by dissolving it in the oxyalkylene group-containing compound (G) in advance, so that the salt can be efficiently converted into the acrylic resin (A). It is preferable at the point which can melt | dissolve in. If this operation is not performed, the antistatic agent (B) may be difficult to dissolve in the acrylic resin (A).

  In the present invention, the resin composition [I], which is a pressure-sensitive adhesive-forming material, has a charge other than at least one of the alkali metal salt and alkaline earth metal salt (B) as long as the effect of the present invention is not impaired. An inhibitor (B ′) may be blended. Examples of the antistatic agent (B ′) include cationic antistatic agents of quaternary ammonium salts such as tetraalkylammonium sulfonates, aliphatic sulfonates, higher alcohol sulfates, and higher alcohol alkylene oxide additions. Anionic antistatic agents such as sulfuric acid ester salts, higher alcohol phosphoric acid ester salts, higher alcohol alcohol alkylene oxide adduct phosphoric acid ester salts, alkali metal salts of organic or inorganic acids such as lithium perchlorate and lithium chloride, Examples include alkaline earth metal salts, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters, and the like.

  The content of the antistatic agent (B ′) is usually set to 0.001 to 20 parts by weight, more preferably 0.01 to 7 parts by weight with respect to 100 parts by weight of the acrylic resin (A). Particularly preferred is 0.02 to 1 part by weight. If the content of the antistatic agent (B ′) is too small, the effect of addition tends not to be obtained, and if it is too large, the durability may deteriorate or the antistatic agent may bleed out.

  In the present invention, the resin composition [I], which is a pressure-sensitive adhesive-forming material, further includes other acrylic pressure-sensitive adhesives, other pressure-sensitive adhesives, urethane resins, rosins, and rosin esters as long as the effects of the present invention are not impaired. , Hydrogenated rosin ester, phenolic resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin, tackifier, colorant, filler, anti-aging agent Conventionally known additives such as ultraviolet absorbers, and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation can be added.

  Thus, in this invention, the adhesive for optical members formed by bridge | crosslinking said resin composition [I] is obtained. And the optical member with an adhesive layer can be obtained by laminating | stacking the adhesive layer which consists of the said adhesive, and an optical member (optical laminated body).

  The optical member with the pressure-sensitive adhesive layer is preferably further provided with a release sheet on the surface opposite to the surface of the optical member on which the pressure-sensitive adhesive layer is provided.

  Examples of the method for producing the optical member with the pressure-sensitive adhesive layer include [1] a method in which the resin composition [I] is applied on the optical member and dried, and then a release sheet is pasted, or [2] the release. After applying and drying the resin composition [I] on the mold sheet, it can be produced by a method of bonding an optical member or the like. Especially, the manufacturing method which apply | coats resin composition [I] on a release sheet which is the method of said [2] is preferable at the point with a low possibility of degrading a base material with a dilution solvent.

  Moreover, when using the optical member with an adhesive layer for practical use, the said release sheet is peeled and used. And as said release sheet, it is preferable to use a silicon-type release sheet.

  Further, when the resin composition [I] is crosslinked by at least one of active energy ray irradiation and heating, [1] the resin composition [I] is coated on the optical member, dried, and then released. A method of pasting sheets and performing treatment by at least one of active energy ray irradiation and heating, [2] On the release sheet, after applying and drying the resin composition [I], the optical members are pasted, Method of performing treatment by active energy ray irradiation and heating, [3] Applying and drying resin composition [I] on the optical member, further performing treatment by irradiation of active energy ray and heating, and then attaching a release sheet [4] The pressure-sensitive adhesive layer by the method of [4] applying the resin composition [I] on the release sheet, drying, and further applying the active energy ray and heating and then bonding the optical member. With It is possible to produce a faculty member.

  In applying the resin composition [I], the resin composition [I] is preferably diluted with a solvent, and the dilution concentration is preferably 10 to 50% by weight, particularly preferably 11 to 25%. % By weight. The solvent is not particularly limited as long as it dissolves the resin composition [I]. For example, ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, acetone, Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene can be used. Among these, ethyl acetate and methyl ethyl ketone are preferably used from the viewpoints of solubility, drying property, price, and the like.

  The application of the resin composition [I] is performed by a conventional method such as roll coating, die coating, gravure coating, comma coating, or screen printing.

  The gel fraction of the pressure-sensitive adhesive layer produced by the above method is preferably 80% or more, particularly 90% or more from the viewpoint of durability performance and light leakage prevention performance. If the gel fraction is too low, the durability and light leakage phenomenon due to insufficient cohesive force tend to be deteriorated. In general, the upper limit of the gel fraction is 100%.

  In adjusting the gel fraction of the optical member pressure-sensitive adhesive to the above range, for example, adjusting the irradiation amount and irradiation intensity of the active energy ray, adjusting the type of polymerization initiator and the combination ratio thereof, This is achieved by adjusting the blending amount of the polymerization initiator. Moreover, since the gel fraction changes by each interaction, the irradiation amount and irradiation intensity | strength of said active energy ray, the composition ratio of a polymerization initiator, and addition amount need to balance each.

  The gel fraction is a measure of the degree of crosslinking, and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (not provided with a separator) formed by forming a pressure-sensitive adhesive layer on a polyethylene terephthalate film as a base material is wrapped in a 200-mesh SUS metal mesh and immersed in toluene at 23 ° C. for 24 hours. The weight percentage of the insoluble pressure-sensitive adhesive component remaining therein is defined as the gel fraction. However, the weight of the substrate is subtracted.

  Moreover, 10-40 micrometers is preferable, for example, and, as for the thickness of the adhesive layer in the optical member with an adhesive layer obtained, 12-30 micrometers is preferable. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, adhesive residue tends to occur.

  The optical member with the pressure-sensitive adhesive layer of the present invention has a release sheet directly or after the release sheet is peeled off, and then the surface of the pressure-sensitive adhesive layer is bonded to a glass substrate and used for a liquid crystal display panel, for example. .

  The adhesive strength of the pressure-sensitive adhesive layer of the present invention is appropriately determined according to the material of the adherend. For example, when sticking on a glass substrate, it preferably has an adhesive strength of 0.2 N / 25 mm to 20 N / 25 mm, and more preferably 0.5 N / 25 mm to 10 N / 25 mm.

  The adhesive strength is calculated as follows. About a polarizing plate with an adhesive layer, it cut | judged to width 25mm width, peels a release film, presses the adhesive layer side to a non-alkali glass plate (Corning company make, "Corning 1737"), and a polarizing plate A glass plate is bonded. Then, after autoclaving (50 ° C., 0.5 MPa, 20 minutes), a 180 ° C. peel test is performed 24 hours later. In addition, in peelability, it is desired that adhesive force is small.

  The optical member in the present invention is not particularly limited, and an optical film suitably used for an image display device such as a liquid crystal display device, an organic EL display device, or a PDP, such as a polarizing plate, a retardation plate, or an elliptical polarizing plate. , Optical compensation films, brightness enhancement films, and those in which these are laminated. Among them, a polarizing plate is particularly effective in the present invention.

  The polarizing plate used in the present invention is usually a laminate of a cellulose triacetate film as a protective film on both sides of a polarizing film. The polarizing film has an average degree of polymerization of 1,500 to 10,000, A uniaxially stretched film dyed with an aqueous solution of iodine-potassium iodide or a dichroic dye using a film made of a polyvinyl alcohol resin having a degree of conversion of 85 to 100 mol% as a raw film (usually 2 to 10 times, preferably Is a stretching ratio of about 3 to 7 times.

  The polyvinyl alcohol resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but a small amount of unsaturated carboxylic acid (including salt, ester, amide, nitrile, etc.), olefins, vinyl ether And a component copolymerizable with vinyl acetate, such as an unsaturated sulfonate. Moreover, what is called polyvinyl acetal resin and polyvinyl alcohol derivatives, such as polybutyral resin and polyvinyl formal resin, which are obtained by reacting polyvinyl alcohol with an aldehyde in the presence of an acid can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” mean weight basis unless otherwise specified.

First, various acrylic resins were prepared as follows. In addition, regarding the measurement of the weight average molecular weight of acrylic resin and a glass transition temperature, it measured according to the above-mentioned method.
[Preparation of acrylic resins (A-1) to (A-3), (A′-1), (A′-2)]
In a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer, butyl acrylate (BA), 2-hydroxyethyl acrylate (HEA), and acrylic acid (AAc) are shown in the table below. 1 was added so that the ratio (wt%) shown in 1 was reached, and after heating to reflux, 0.03 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was reacted at ethyl acetate reflux temperature for 3 hours. An acrylic resin solution was prepared by diluting with ethyl. In addition, the weight average molecular weight (Mw), dispersity (Mw / Mn), and glass transition temperature of the obtained acrylic resin are shown together in Table 1.

[Antistatic agent (B-1)]
Lithium perchlorate [Antistatic agent (B-2)
Bis (trifluoromethanesulfonyl) imidolithium [Li (CF ₃ SO ₂ ) ₂ N] (Morita Chemical Co., Ltd.)
[Antistatic agent (B-3)
Bis (trifluoromethanesulfonyl) imide potassium [K (CF ₃ SO ₂ ) ₂ N] (Morita Chemical Co., Ltd.)
[Antistatic agent (B'-1)]
MOI + Br-: methacryloyloxyethyl octylimidazolium bromide

[Crosslinking agent (C-1)]
55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (manufactured by Nippon Polyurethane Co., Ltd., Coronate L-55E)

[Unsaturated group-containing compound (D-1)]
In a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer, 19.2 parts of isophorone diisocyanate, 0.05 part of di-t-butylhydroxyphenol, 0.02 of dibutyltin dilaurate 80.8 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate PE-3A, hydroxyl value 120 mg KOH / g) was added at 70 ° C. Then, the unsaturated group-containing compound (C-1) was obtained by continuing the reaction.
[Unsaturated group-containing compound (D-2)]
Pentaerythritol tetraacrylate (Nippon Kayaku Co., Ltd., “Kayarad DPHA”)

[Polymerization initiator (E-1)]
A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1: 1 (Ciba Specialty Chemicals, "Irgacure 500")

[Silane compound (F-1)]
γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM403”)

[Oxyalkylene group-containing compound (G-1)]
Tetraethylene glycol dimethyl ether

[Examples 1 to 10, Comparative Examples 1 to 5]
A resin composition to be a pressure-sensitive adhesive forming material for an optical member is prepared by blending each of the blended components prepared and prepared as described above in the ratio shown in Table 2 below, and this is coated with ethyl acetate. It diluted to the viscosity which can be made [1000-10000 mPa * s (25 degreeC)], and produced the adhesive resin composition solution for optical members.

  And after apply | coating the said resin composition solution to the polyester-type release sheet so that the thickness after drying may be set to 25 micrometers, and drying for 3 minutes at 90 degreeC, the formed resin composition layer side is made into the polarizing plate ( The film was transferred onto a 190 μm thick electrode, and irradiated with ultraviolet rays at a peak illuminance of 600 mW / cm 2 and an integrated exposure of 240 mJ / cm 2 with an electrodeless lamp [H bulb of LH6UV lamp (effective irradiation width 150 mm × 1 row)]. Conducted, 23 ° C. × 65% R.C. H. The film was aged for 14 days to obtain a polarizing plate with an adhesive layer. The polarizing plate is laminated with a cellulose triacetate film having a thickness of 80 μm on both sides of a 30 μm-thick polyvinyl alcohol polarizing film (average polymerization degree 1700, average saponification degree 99 mol%, iodine staining, 4-fold stretching). The polarizing plate (the polyvinyl alcohol polarizing film was cut into 100 mm × 100 mm by tilting the direction of the stretching axis by 45 °) was used.

  On the other hand, by using a polyethylene terephthalate (PET) film (thickness 38 μm) in place of the polarizing plate in the same manner as described above, a gel fraction, surface resistivity, and adhesive strength measurement sample were prepared.

  Using the thus obtained polarizing plate with the pressure-sensitive adhesive layer or PET film with the pressure-sensitive adhesive layer, its physical properties [surface resistivity, gel fraction, durability (heat resistance test, moist heat resistance test), adhesive strength] Were measured and evaluated according to the following methods. These results are also shown in Table 3 below.

[Surface resistivity]
The obtained PET film with the pressure-sensitive adhesive layer was cut into a size of 40 × 40 mm, and this was left to stand for 3 hours under conditions of a temperature of 23 ° C. and a relative humidity of 65%, and then the release sheet was peeled off. About the adhesive layer after 10 to 20 seconds, the surface resistivity was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Hallistar UP). In addition, it means that antistatic performance is so high that surface resistivity is small.

[Gel fraction]
After the obtained PET film with the pressure-sensitive adhesive layer is cut into 40 × 40 mm, the release sheet is peeled off and the pressure-sensitive adhesive layer side is bonded to a 50 × 100 mm SUS mesh sheet (200 mesh), and then the SUS mesh sheet. The sample was wrapped from the center with respect to the longitudinal direction, and the sample was wrapped. Then, the gel fraction was measured by weight change when immersed in a sealed container containing 250 g of toluene.

〔durability〕
The release sheet of the obtained polarizing plate with the pressure-sensitive adhesive layer was peeled off, and the pressure-sensitive adhesive layer side was pressed against a non-alkali glass plate (Corning 1737, manufactured by Corning) to bond the polarizing plate and the glass plate. After that, autoclave treatment (50 ° C., 0.5 MPa, 20 minutes) was performed, and thereafter, foaming, peeling, and light leakage phenomenon (heat resistance test only) were evaluated in the following durability tests (heat resistance test, moist heat resistance test). .

〔An endurance test〕
(1) Heat resistance test 80 ° C., 100 hour durability test (2) Moist heat resistance test 60 ° C., 90% R.D. H. 100 hours durability test

〔Evaluation criteria〕
(Foam)
○ ... No foaming △ ... Slight foaming is observed × ... Many foaming is observed (peeling)
○ ・ ・ ・ No peeling, or peeling less than 0.5 mm, or generation of a lift mark Δ ・ ・ ・ Peeling of 0.5 mm or more and less than 10 mm, or generation of a lift mark × ... Peeling of 10 mm or more, or 10 mm Occurrence of the above-mentioned sway (light leakage)
○ ・ ・ ・ No or almost no light leakage △ ・ ・ ・ Slight leakage occurred × ・ ・ ・ Large light leakage on 4 sides

〔Adhesive force〕
About the prepared polarizing plate with an adhesive layer, it cut | judged to width 25mm width, peels a release film, presses an adhesive layer side to a non-alkali glass plate (Corning company make, Corning 1737), and a polarizing plate The said glass plate was bonded. Thereafter, autoclave treatment (50 ° C., 0.5 MPa, 20 minutes) was performed, and a 180 ° C. peel test was performed 24 hours later. In addition, in peelability, it is desirable that the adhesive strength is small, and the target is 10 N / 25 mm or less after one day.

  From the above results, the examples have low surface resistivity and excellent antistatic performance, and good evaluation results are obtained in any of the items of heat resistance test and moist heat resistance test (foaming, peeling, light leakage only in heat resistance test). It is clear that it has excellent durability. Moreover, a sufficiently satisfactory value with no problem with respect to adhesive strength was obtained.

  Further, in Examples 6 to 10 using an imide salt containing a fluorine atom and a sulfonyl group as the antistatic agent (B), the antistatic performance and the heat resistance test / moisture heat resistance test can be achieved at a high level. It can also be confirmed that it is preferable.

  On the other hand, Comparative Example 1 using an ionic liquid as an antistatic agent caused foaming in a moist heat resistance test and had a low level in general durability, and a sufficient antistatic performance was not obtained. . In Comparative Example 2 using an acrylic resin obtained by polymerizing a polymerization component containing 12% by weight of a hydroxyl group-containing monomer and using an ionic liquid as an antistatic agent, foaming occurs in a moisture and heat resistance test, and durability The overall level was low, and the antistatic performance was not satisfactory. Comparative Examples 3 and 4 using an acrylic resin obtained by polymerizing a polymerization component containing 1.5% by weight of a hydroxyl group-containing monomer had no particular problem regarding durability, but had high surface resistivity and The prevention performance was inferior. Further, an acrylic resin obtained by polymerizing a polymerization component containing 1.5% by weight of a hydroxyl group-containing monomer is used, and more lithium perchlorate as an antistatic agent is blended than in Comparative Examples 3 and 4. In Comparative Example 5, a good result was obtained with respect to the antistatic performance, but the compatibility between the acrylic resin and the antistatic agent deteriorated due to the low hydrophilicity of the acrylic resin. In particular, the evaluation of foaming and peeling in the heat and humidity resistance test was poor, resulting in poor durability.

  The pressure-sensitive adhesive for optical members of the present invention is less likely to be charged with static electricity generated in each step, and has excellent adhesion between the optical laminate and the glass substrate even under high temperature and high humidity conditions. Since foaming and peeling do not occur between the glass substrate and the light leakage phenomenon caused by the contraction of the optical film can be suppressed, a liquid crystal display panel with excellent durability can be obtained, which is very useful. is there.

Claims (10)

  An optical member comprising an acrylic resin (A) obtained by polymerizing a polymerization component containing 15% by weight or more of a hydroxyl group-containing monomer, and at least one of an alkali metal salt and an alkaline earth metal salt (B) Adhesive resin composition. The pressure-sensitive adhesive resin composition for an optical member according to claim 1, wherein the cation portion of at least one of the alkali metal salt and the alkaline earth metal salt (B) is any one of Li ⁺ , Na ⁺ , and K ⁺ .   The pressure-sensitive adhesive composition for an optical member according to claim 1 or 2, wherein the anion part (B) of at least one of the alkali metal salt and the alkaline earth metal salt is an anion containing a fluorine atom and a sulfonyl group.   A pressure-sensitive adhesive for optical members, wherein the pressure-sensitive adhesive resin composition [I] for optical members according to any one of claims 1 to 3 is crosslinked.   The pressure-sensitive adhesive resin composition [I] for optical members contains a crosslinking agent (C) and is crosslinked by the crosslinking agent (C).   The pressure-sensitive adhesive resin composition [I] for optical members contains an unsaturated group-containing compound (D) as a polymerizable component, and also contains a polymerization initiator (E), and is crosslinked by active energy rays and / or heat. The pressure-sensitive adhesive for optical members according to claim 4 or 5. The pressure-sensitive adhesive resin composition [I] for optical members further comprises an oxyalkylene group-containing compound (G) [
However, the pressure-sensitive adhesive for optical members according to any one of claims 4 to 6, comprising an unsaturated group-containing compound (D).   The pressure-sensitive adhesive for optical members according to any one of claims 4 to 7, wherein the gel fraction of the pressure-sensitive adhesive for optical members is 80% or more.   An optical member is a polarizing plate, The adhesive for optical members as described in any one of Claims 4-8.   An optical member with an adhesive layer, wherein the optical member is a laminate comprising an adhesive layer made of the adhesive for optical members according to any one of claims 4 to 9, and an optical member.