JP5493158B2 - Optical pressure-sensitive adhesive composition and optical functional film - Google Patents

Description

  The present invention relates to an optical pressure-sensitive adhesive composition used for adhering an optical functional film such as a polarizing plate or a retardation plate to an optical component such as a liquid crystal cell of a liquid crystal display device, and an adhesive formed from the composition. The present invention relates to an optical functional film having an agent layer.

  A liquid crystal cell constituting a liquid crystal display device includes a liquid crystal component oriented in a predetermined direction sandwiched between two glass substrates, and an adhesive layer formed from an optical adhesive composition on the outside of these glass substrates. An optical functional film such as a polarizing plate or a laminate of a polarizing plate and a retardation plate is attached. In recent years, liquid crystal display devices have been widely used due to the reduction in weight and thickness of displays for vehicles, outdoor instruments, displays such as personal computers, and televisions, and their demand is increasing. As a result, the usage environment of liquid crystal display devices has become extremely harsh, both indoors and outdoors.

  A polarizing plate used in a liquid crystal display device has a three-layer structure in which both surfaces of a polyvinyl alcohol polarizer are sandwiched between triacetyl cellulose protective films, but has poor dimensional stability due to the characteristics of these materials. In addition, since an optical functional film such as a polarizing plate is formed by stretching, it tends to expand and contract over time. For this reason, in the liquid crystal display device, the internal stress generated by the expansion and contraction of the optical functional film cannot be absorbed and relaxed by the adhesive layer, and the distribution of residual stress acting on the optical functional film becomes non-uniform, In particular, stress concentrates on the peripheral edge. As a result, the peripheral edge of the liquid crystal display device becomes brighter or darker than the center, which causes color unevenness and white spots in the liquid crystal display device.

  Further, as another factor that causes color unevenness and white spot phenomenon in the liquid crystal display device, optical distortion (such as generation of birefringence) generated in the optical functional film or the pressure-sensitive adhesive layer due to stress can be considered.

  Many means have been studied to solve the above problems. For example, in Patent Document 1, the pressure-sensitive adhesive layer of the optical functional film is composed of a main polymer having a weight average molecular weight of 600,000 to 2,000,000 and a plasticizer of 0.1 to 60 parts by mass. Is disclosed. However, although this technique relieves stress by adding a plasticizer, it does not disclose a technique for correcting optical distortion by limiting the structure of the polymer and the plasticizer. In the display element, white spots cannot be sufficiently suppressed.

In patent document 2, it is a polarizing plate which has an adhesive layer, Comprising: The absolute value of the photoelastic coefficient of the adhesive layer is 500 * 10 < ^-12 > (1 / Pa) or less, The adhesive layer is an aromatic ring. A polarizing plate is disclosed which is an acrylic pressure-sensitive adhesive containing an acrylic monomer containing as a monomer component. However, in this technique, optical distortion generated in the pressure-sensitive adhesive layer due to stress is reduced. However, since a technique for relaxing the stress is not disclosed, white spots cannot be sufficiently suppressed.
Japanese Patent No. 3272721 JP 2006-259664 A

  An object of the present invention is a pressure-sensitive adhesive composition used for a liquid crystal cell constituting a liquid crystal display device, which can prevent occurrence of uneven color and white spots in a liquid crystal display device due to expansion and contraction of an optical functional film. It is providing the optical adhesive composition for forming an agent layer.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that the above-described object can be achieved by the present invention described below.
That is, the present invention is a mixture of a monomer represented by the following general formula (I) where n is 1 and n is 2 or more, wherein n is a content of 2 or more monomer (Meth) acrylate copolymer (A) having a weight average molecular weight of 1 to 2 million and containing 10 to 40 mass% of a monomer mixture occupying 1 to 5 mass% of the total amount of the mixture and aromatic An optical pressure-sensitive adhesive composition comprising a plasticizer (B) containing two groups as an essential component, wherein the plasticizer (B) comprises diethylene glycol dibenzoate, dipropylene glycol dibenzoate, benzyl benzoate, 1,4 - cyclohexanedimethanol dibenzoate, at least one selected from the group consisting of benzyl benzoate and butyl benzyl phthalate, 3-5 of the plasticizer (B) content is above copolymer (a) To provide an optical pressure-sensitive adhesive composition, which is a mass%. The composition preferably further contains an antistatic agent, and is particularly useful for laminating optical functional films.

  Moreover, this invention provides the optical functional film with an adhesive layer characterized by having the adhesive layer which consists of an optical adhesive composition of the said invention on an at least one surface. A polarizing plate is useful as the optical functional film. In the case of a polarizing plate coated with a discotic liquid crystal as the polarizing plate, the content of the plasticizer (B) in the optical pressure-sensitive adhesive composition of the present invention is 20 to 50% by mass of the copolymer (A). Preferably, when the polarizing plate is a polarizing plate based on a stretched triacetylcellulose-based film, a polycycloolefin-based film or a stretched cellulose acetate propionate film, the optical pressure-sensitive adhesive composition of the present invention described above It is preferable that content of the plasticizer (B) of a thing is 3-20 mass% of a copolymer (A).

According to the present invention, the pressure-sensitive adhesive composition of the present invention is coated with a glass substrate and an optical functional film constituting a liquid crystal cell of a liquid crystal display device, particularly a discotic liquid crystal having a layer structure as shown in FIG. 2 and a stretched film as shown in FIG. 2, for example, a stretched triacetyl cellulose film, a polycycloolefin film or a stretched cellulose acetate propionate film and a polarizing plate between the polarizing plate. As a result, in the liquid crystal display device, it is possible to effectively prevent the occurrence of a unique frame-type or diagonal-type color unevenness / whiteout phenomenon as shown in FIG. FIG. 3a shows a phenomenon in which the peripheral part of the black display screen becomes white as shown in the figure, and FIG. 3b shows a phenomenon in which the diagonal part of the black display screen becomes white as shown in the figure. In FIG. 2, both sides of the iodine-doped PVA are in contact with the stretched film for convenience, but the present invention is not limited to FIG. 2, and one of the stretched films may be an unstretched film.
The pressure-sensitive adhesive composition of the present invention not only relieves the stress generated by the expansion and contraction of the polarizing plate, but also seems to correct the optical distortion generated in the polarizing plate by the stress in a well-balanced manner.

  Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The term “(meth) acryl” in the claims and the specification of the present invention means both “acryl” and “methacryl”, and the term “(meth) acrylate” ”And“ methacrylate ”.

The copolymer A used in the present invention is a mixture of a monomer represented by the following general formula (I) wherein n is 1 and n is 2 or more, and n is a monomer having 2 or more. (Meth) acrylic acid ester having a weight average molecular weight of 1,000,000 to 2,000,000 containing 10 to 40% by weight of the monomer mixture (a) in which the content of the monomer occupies 1 to 5% by weight of the total amount of the mixture Copolymer.

  In the monomer a, when a mixture in which the content of the monomer having n of 2 or more exceeds 5% by mass is used, the viscosity of the finally obtained copolymer A tends to be deteriorated, etc., Therefore, the viscosity of the pressure-sensitive adhesive composition also deteriorates. Further, if the content of the monomer having n of 2 or more is less than 1%, it is not preferable because the purification cost during production is high and expensive. The monomer a needs to be contained in an amount of 10 to 40% by mass when the total amount of monomer units constituting the copolymer A is 100% by mass. When the content of the monomer a unit is less than 10% by mass and exceeds 40% by mass, uneven color and white spots cannot be sufficiently suppressed in the finally obtained pressure-sensitive adhesive composition.

  Other acrylic monomers b that may be copolymerized with the monomer a include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include alkyl (meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate. These may be used alone or in combination.

  In addition to these other monomers b, when the total amount of monomer units constituting the copolymer A is 100% by mass, the carboxyl group, hydroxyl group, acetyl group, amide group or substituted group having reactivity with the crosslinking agent C It is preferable to use a monomer c containing a functional group such as an amide group, amino group or substituted amino group, epoxy group or mercapto group. The monomer c is typically a carboxyl group-containing monomer such as (meth) acrylic acid or carboxyethyl acrylate, or a hydroxyl group-containing monomer such as hydroxyethyl acrylate. These may be used alone or in combination. These monomers c are all known in the field of pressure-sensitive adhesives, and any known monomer c can be used in the present invention.

  The content of the monomer c in the copolymer A is preferably 10 to 0.2% by mass when the copolymer A is 100% by mass. When the usage-amount of the monomer c is less than 0.2 mass%, durability will become inadequate when the adhesive composition formed with the copolymer A is used. Moreover, when it exceeds 10 mass%, when the adhesive composition formed with the copolymer A is used, generation | occurrence | production of a color nonuniformity and a white spot phenomenon cannot be suppressed.

  Further, the copolymer A needs to have a weight average molecular weight (GPC measurement, standard polystyrene conversion) of 1,000,000 to 2,000,000, and a preferable weight average molecular weight of 1,300,000 to 1,800,000. When the weight average molecular weight is less than 1,000,000, when the pressure-sensitive adhesive composition is formed and the pressure-sensitive adhesive layer is formed, the durability of the pressure-sensitive adhesive layer becomes insufficient. On the other hand, if the weight average molecular weight exceeds 2 million, it is not preferable because the suppression of the occurrence of uneven color and white spots is insufficient.

  The copolymer A used in the present invention preferably has the above molecular weight and a glass transition temperature (Tg) (calculated value) of −60 ° C. to 0 ° C. If the Tg of the copolymer A is lower than −60 ° C., the copolymer A is too soft when the plasticizer is added to the copolymer A, and the pressure-sensitive adhesive composition using the copolymer A When the pressure-sensitive adhesive layer is formed, the durability of the pressure-sensitive adhesive layer becomes insufficient. In this case, if the amount of the plasticizer B to be added is reduced to suppress the peeling or foaming of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer has insufficient followability with respect to the contraction of the polarizing plate. Can not be prevented.

  On the other hand, when the Tg of the copolymer A exceeds 0 ° C., even when the plasticizer B is added to the copolymer A when the molecular weight of the copolymer A is 1 million or more, Adhesiveness is not expressed, and the performance as a preferable adhesive cannot be obtained. In addition, Tg in this invention is a calculated value from the monomer used for the synthesis | combination of the copolymer A. FIG.

  The copolymer A satisfying the above conditions can be produced by ordinary solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, or the like, but can be produced by solution polymerization in which the copolymer A is obtained as a solution. preferable. By obtaining the copolymer A as a solution, it can be used as it is for producing the pressure-sensitive adhesive composition of the present invention. Examples of the solvent used for the solution polymerization include organic solvents such as ethyl acetate, toluene, n-hexane, acetone, and methyl ethyl ketone.

  Examples of the polymerization initiator used in the polymerization include peroxides such as benzoyl peroxide and lauryl peroxide, azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile, and polymer azo polymerization initiators. These can be used alone or in combination. Moreover, in the said superposition | polymerization, in order to adjust the molecular weight of the copolymer A, a conventionally well-known chain transfer agent can be used.

  The plasticizer B used in the present invention is a compound containing two aromatic groups, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, benzyl benzoate, 1,4-cyclohexanedimethanol as a benzoate ester system. And dibenzoate. The number of “aromatic groups” is counted as one condensed ring such as a naphthalene ring.

  The content of the plasticizer is required to be 3 to 50 parts by mass per 100 parts by mass of the copolymer A, and a preferable content is 20 to 50 parts by mass per 100 parts by mass of the copolymer A. If the amount of the plasticizer B used is too small, the occurrence of uneven color and white spots is insufficiently suppressed. On the other hand, if the amount of the plasticizer used is too large, the durability is insufficient.

  As the antistatic agent used in the present invention, the following antistatic agents can be used. For example, surfactants, alkali metal salts, ionic liquids and the like can be mentioned, and at least one selected from these groups can be used. Specific examples of the surfactant include, for example, an alkylene oxide homopolymer, an alkylene oxide copolymer, an aliphatic alcohol / alkylene oxide adduct, a long-chain aliphatic substituted phenol / alkylene oxide adduct polymer, and a polyhydric alcohol. Nonionic surfactants such as aliphatic esters and long-chain aliphatic amide alcohols, compounds having a quaternary ammonium salt, compounds having an alkylpyridinium salt, and cationic surfactants can be mentioned. Preferably, it is a solvent-soluble cationic surfactant.

  Examples of alkali metal salts include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium nitrate, Examples include inorganic salts such as sodium carbonate and sodium thiocyanate, and organic salts such as sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, and lithium perchlorate is preferable.

As the ionic liquid, a nitrogen-containing onium salt, a sulfur-containing onium salt, or a phosphorus-containing onium salt is used, and an organic cation component and an anion component are preferably used. Organic cation components include pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyriminium cation, dihydropyrimidinium cation, pyrazolium cation , A virazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, etc., and the anion component includes Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF. ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF _{3 ^{SO 2) 3 C -, AsF}} 6 -, SbF 6 -, NbF 6 - ^{_{TaF 6 -, F (HF)}} n -, (CN) 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2 ) (CF ₃ CO) N ⁻ , hexafluorophosphate ion, tris (pentafluoroethyl) trifluorophosphate, bis (fluorosulfonyl) imide and the like.

  The usage-amount of an antistatic agent is 0.2-10 mass parts per 100 mass parts of said copolymers A, Preferably it is 1-5 mass parts. If the amount used is in the range of 0.2 to 10 parts by mass, good antistatic properties can be obtained while maintaining the transparency of the pressure-sensitive adhesive layer without impairing the physical properties of the pressure-sensitive adhesive composition finally obtained. Therefore, the antistatic agent does not bleed out on the surface of the resulting pressure-sensitive adhesive composition.

  In the present invention, it is preferable to use the crosslinking agent C. Examples of the crosslinking agent C to be used include a polyglycidyl compound having two or more glycidyl groups in one molecule, a polyisocyanate compound having two or more isocyanate groups in one molecule, and two or more aziridinyl groups in one molecule. A polyaziridine compound having one, a polyoxazoline compound having two or more oxazoline groups in one molecule, a metal chelate compound, a butylated melamine compound, or the like can be used. A polyglycidyl compound, a polyisocyanate compound, or a polyaziridine compound is preferably used in that the durability of the pressure-sensitive adhesive composition can be further improved. These crosslinking agents are all known in the field of pressure-sensitive adhesives, and any known crosslinking agent can be used in the present invention.

  It is preferable that content of the said crosslinking agent C is 0.01-3.0 mass parts with respect to 100 mass parts of said copolymers A, More preferably, it is 0.1-2.0 mass parts. When the said content is less than 0.01 mass part, the cohesion force of an adhesive composition becomes low and durability is inferior compared with the said range. On the other hand, when the amount used exceeds 3.0 parts by mass, the resulting pressure-sensitive adhesive composition has excessive cohesive strength, which causes peeling of the optical functional film to be adhered.

  Moreover, in this invention, the durability of the adhesive layer formed from an adhesive composition can further be improved by containing the silane coupling agent D. These silane coupling agents are all known in the field of pressure-sensitive adhesives, and any known silane coupling agent can be used in the present invention. The content of the silane coupling agent D is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the copolymer A. When the content is less than 0.01 parts by mass, the adhesive strength of the copolymer A cannot be appropriately reduced, and the reworkability is inferior compared with the above range, When content exceeds 5 mass parts, although the adhesive force of the said copolymer A is reduced, durability will be inferior compared with the said range.

  Moreover, the adhesive composition of this invention may mix | blend various additives in the range which does not impair the effect of this invention according to required characteristics, such as the objective of adjusting adhesive force. For example, terpene, terpene-phenol, coumarone indene, styrene, rosin, xylene, phenol, or petroleum tackifier resins, antioxidants, UV absorbers, fillers, pigments, etc. can do. The production method of the pressure-sensitive adhesive composition of the present invention may be a known method and is not particularly limited, but is preferably in the form of a solution containing an organic solvent. In this case, the pressure-sensitive adhesive layer can be easily formed.

  The optical functional film of the present invention is characterized in that the pressure-sensitive adhesive composition of the present invention is laminated on one side or both sides of an optical functional film (raw film) on which no pressure-sensitive adhesive layer is formed. For this reason, the optical functional film of the present invention does not peel off from the glass substrate or the like even under high temperature or high temperature and high humidity, and does not cause foaming in the pressure-sensitive adhesive layer (durability) and has a long time. It can be easily peeled off even after a lapse of time, and also has a property (reworkability) that does not cause residue on the substrate after peeling.

  Although there is no limitation in particular as the kind of said raw film, For example, a film light-guide plate, an antireflection film, an electroconductive film, a viewing angle expansion film, a phase difference film, a polarizing plate, or the film which combined these etc. are mentioned. . Moreover, in order to improve the adhesiveness with respect to the original film of the said adhesive composition, surface treatments, such as a corona treatment, can be performed to the surface of an original film.

  Moreover, there is no restriction | limiting in particular in the thickness of the said raw film, Although any thing can be used, For example, the thing of 5 micrometers-300 micrometers can be used, These differ with uses or the objectives.

  When the raw film is a polarizing plate, the pressure-sensitive adhesive composition of the present invention exhibits the most excellent effect. When the polarizing plate is a polarizing plate coated with a discotic liquid crystal, an uncoated polarizing plate (generally, an untreated triacetylcellulose (TAC) film, usually a contact angle of 60 to 70 ° ), The contact angle is high at 85 to 95 °, and the adhesiveness with the adhesive is inferior. Therefore, foaming between the adhesive layer and the panel glass surface, or floating and peeling of the polarizing plate are likely to occur, and There are problems such as light leakage.

A polarizing plate coated with a discotic liquid crystal means that a triphenylene discotic compound having a cross-linking group at the end of a side chain as shown below is cross-linked on a TAC film and maintained in an aligned state. The polarizing plate formed by integrating the viewing angle widening film and the polarizing film of the discotic layer, for example, one side of a polarizing film obtained by laminating a TAC film on both sides of a polyvinyl alcohol polarizer (PVA). In addition, for example, a viewing angle widening functional layer made of a discotic liquid crystal is provided by coating, or a viewing angle widening film is bonded with an adhesive.
In particular, a polarizing plate coated with a discotic liquid crystal is used for a monitor (usually 7 to 26 inches) and is used to expand a viewing angle as described above.

  The said subject was solved by use of the adhesive composition of this invention. The pressure-sensitive adhesive composition used here preferably has a plasticizer content of 20 to 50 parts by weight per 100 parts by weight of copolymer A. When the content of the plasticizer is less than 20 parts by mass, the occurrence of uneven color and white spots is insufficiently suppressed. On the other hand, when the content of the plasticizer exceeds 50 parts by mass, the uneven colors and white spots are generated. Although the occurrence of the phenomenon can be prevented, foaming, floating of the polarizing plate, and peeling are likely to occur. In particular, the above phenomenon occurs in a frame type.

  When the polarizing plate is a polarizing film based on a stretched film, for example, a stretched triacetyl cellulose film, a polycycloolefin film or a stretched cellulose acetate propionate film, Compared to those using a treated TAC film), the film is stretched, so the shrinkage rate is large, and in particular, the color unevenness and white spot phenomenon occurs in the diagonal type, which is insufficient to suppress it. There are some issues. The polarizing plate is used for a television (usually 15 to 60 inches) to improve hue and contrast and eliminate a phase difference. Such a problem is caused by the use of the pressure-sensitive adhesive composition of the present invention. It was solved. The pressure-sensitive adhesive composition used here preferably has a plasticizer content of 3 to 20 parts by weight per 100 parts by weight of copolymer A. When the content of the plasticizer is less than 3 parts by mass, the occurrence of uneven color and white spots is insufficiently suppressed. On the other hand, when the content of the plasticizer exceeds 20 parts by mass, the uneven colors and white spots are generated. Although the occurrence of the phenomenon can be prevented, foaming, floating of the polarizing plate, and peeling are likely to occur.

  The optical functional film of the present invention is coated by applying the pressure-sensitive adhesive composition of the present invention on one or both sides of the original film using a commonly used coating apparatus such as a roll coating apparatus. It can be produced by drying the layer. If necessary, the pressure-sensitive adhesive layer can be subjected to heat crosslinking or curing with light such as ultraviolet rays. The optical functional film of the present invention is prepared by first applying an adhesive composition to a protective film such as a polyethylene terephthalate film (PET film) coated with a release agent such as a silicone resin and drying the adhesive layer. After forming, it can also be produced by laminating the original film on the pressure-sensitive adhesive layer.

  The coating amount of the pressure-sensitive adhesive composition of the present invention is preferably such that the thickness of the pressure-sensitive adhesive layer after drying is 10 to 50 μm. By setting the thickness of the pressure-sensitive adhesive layer within the above range, an optical functional film having a better balance between durability and reworkability is obtained.

  The above-mentioned optical functional film of the present invention can be stuck on a glass substrate of a liquid crystal display device by means usually used. Further, the optical functional film of the present invention can be further laminated and stuck on the optical functional film stuck on the glass substrate.

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “part” is based on mass.
<Preparation of adhesive solution>
[Adhesive solutions 1-14]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 88 parts of butyl acrylate, 10 parts of phenoxyethyl acrylate (n ≧ 1 in the general formula (1)), 2 parts of acrylic acid, 0.1 part of azobisisobutyronitrile and 100 parts of ethyl acetate were added to the reactor. Part was added. While stirring this, a reaction was carried out at 68 ° C. for 8 hours in a nitrogen gas stream to obtain a solution of an acrylic copolymer having a weight average molecular weight of 1,200,000. To this acrylic copolymer solution, 20 parts of benzyl benzoate was added and further diluted with ethyl acetate to obtain a pressure-sensitive adhesive solution 1 having a solid content of 20%. Similarly, pressure-sensitive adhesive solutions 2 to 14 were obtained with the monomer compositions shown in Table 1.

MA: methyl acrylate EA: ethyl acrylate BA: butyl acrylate PHEA: phenoxyethyl acrylate AA: acrylic acid BB: benzyl benzoate DPDB: dipropylene glycol dibenzoate DEDB: diethylene glycol dibenzoate BBP: butyl benzyl phthalate

  In the above, the value of the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene measured by GPC (GEL Permeation Chromatography) method. Specifically, the coating film obtained by drying the copolymer at room temperature was dissolved in tetrahydrofuran, and measured with a high performance liquid chromatograph (manufactured by Shimadzu Corporation, LC-10ADvp, column KF-G + KF-806 × 2). The weight average molecular weight (Mw) in terms of polystyrene was determined.

<Production and evaluation of pressure-sensitive adhesive composition and optical functional film>
[Examples 1 to 10, Comparative Examples 1 to 6 ]
By applying a solution prepared by mixing 0.2 parts of Coronate L and 0.1 part of KBM-803 to 100 parts of the solid content of the pressure-sensitive adhesive 1 on a PET film coated with a silicone resin, and drying at 90 ° C. The solvent was removed, and an adhesive layer having a thickness of 25 μm was formed. After the 180 μm-thick polarizing plate (EWV) was bonded to the surface on which the pressure-sensitive adhesive layer was formed, the optical functional film of Example 1 was cured by curing for 7 days in an atmosphere of 23 ° C. and 50% RH. Produced. In the same manner as in Example 1, the components shown in Table 2 were mixed to obtain optical functional films of Examples 1 to 10 and Comparative Examples 1 to 6 .

Coronate L: Polyisocyanate Takenate D-160N manufactured by Nippon Polyurethane Industry Co., Ltd .: Polyisocyanate tetrad C manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: Polyglycidyl compound KBM-803 manufactured by Mitsubishi Gas Chemical Co., Ltd .: Shin-Etsu Chemical Co., Ltd. ) KBM-802: Shin-Etsu Chemical Co., Ltd. γ-mercaptopropylmethyltrimethoxysilane X-41-1810: Shin-Etsu Chemical Co., Ltd. methyl mercapto-based alkoxy oligomer X-41-1805: Shin-Etsu Chemical Co., Ltd. ) Mercapto alkoxy oligomer AS agent: lithium trifluoromethanesulfonate (antistatic agent)
EWV: polarizing plate coated with discotic liquid crystal TAC: polarizing plate using a stretched triacetyl cellulose film CAP: polarizing plate using a stretched cellulose acetate propionate film COP: using a polycycloolefin film Polarizer

  This optical functional film was evaluated for white spots, durability, and surface resistance by a test method described later. The evaluation results of the examples were good in all items. The evaluation results are shown in Table 3.

<Test methods and evaluation criteria>
[Durability test]
The optical functional films in Examples and Comparative Examples were each cut to 200 mm × 300 mm, and after the PET film was peeled off, it was affixed on a glass substrate and subjected to autoclave treatment to produce an evaluation sample. About the obtained sample for evaluation, the test of the following item was performed, respectively.

(1) 80 ° C
The sample for evaluation was allowed to stand in an atmosphere of 80 ° C. (DRY) for 500 hours, and then visually confirmed for foaming and peeling. The evaluation criteria are as follows.
(2) 60 ° C / 90% RH
The sample for evaluation was allowed to stand in an atmosphere of 60 ° C. and 90% RH for 500 hours, and then visually confirmed for foaming and peeling. The evaluation criteria are as follows.

Evaluation criteria (1) Foaming ○: Foaming is not confirmed in the optical functional film.
Δ: Slight foaming was confirmed in the optical functional film.
X: Foaming was confirmed in the optical functional film.
(2) Peeling ○: Peeling is not confirmed on the optical functional film.
Δ: Slight peeling was confirmed on the optical functional film.
X: Peeling was confirmed on the optical functional film.

[Light leakage test]
Two of the same samples after the 80 ° C. endurance test using the optical functional films in Examples and Comparative Examples were bonded together in crossed Nicols, placed on the backlight of a liquid crystal monitor, and the state of light leakage was visually observed.

-Evaluation criteria ○: No white spots were observed in the optical functional film.
Δ: Slight white spots were observed in the optical functional film.
X: White spots were observed in the optical functional film.

[Antistatic test]
The optical functional films in Examples and Comparative Examples were cut to a size of 100 mm × 100 mm, and then the separator was peeled off. A high resistance meter and a measuring electrode were placed in a constant temperature and humidity chamber at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH. The surface resistance value is measured. The high resistance meter uses HIGH RESISTANCE METER 4329A manufactured by YOKOGAWA-HEWLETT • PACKARD, and the measurement electrode uses RESISTIVITY CELL 16008A manufactured by HEWLETT • PACKARD.

  According to the present invention, the pressure-sensitive adhesive composition of the present invention comprises a glass substrate and an optical functional film constituting a liquid crystal cell of a liquid crystal display device, a polarizing plate coated with a discotic liquid crystal in particular, and a stretched film, for example, stretched By using it for forming an adhesive layer between a triacetyl cellulose-based film, a polycycloolefin-based film or a stretched cellulose acetate propionate film and a polarizing plate as a base material, It is possible to effectively prevent the occurrence of square color unevenness and white spots. The pressure-sensitive adhesive composition of the present invention not only relieves the stress generated by the expansion and contraction of the polarizing plate, but also seems to correct the optical distortion generated in the polarizing plate by the stress in a well-balanced manner.

The figure explaining the liquid crystal panel containing the polarizing plate coated with the discotic liquid crystal. The figure explaining the liquid crystal panel containing the polarizing plate using a stretched film. The figure explaining the white spot phenomenon in a liquid crystal panel.

Claims (7)

N is a mixture of a monomer represented by the following general formula (I) and a monomer having n of 2 or more, and the content of the monomer having n of 2 or more is 1 to 1 of the total amount of the mixture. Contains 10 to 40% by mass of a monomer mixture occupying 5% by mass and contains a (meth) acrylic acid ester copolymer (A) having a weight average molecular weight of 1 to 2 million and 2 aromatic groups An optical pressure-sensitive adhesive composition comprising a plasticizer (B) as an essential component,
The plasticizer (B) is at least one selected from the group consisting of diethylene glycol dibenzoate, dipropylene glycol dibenzoate, benzyl benzoate (benzyl benzoate), 1,4-cyclohexanedimethanol dibenzoate and butyl benzyl phthalate. And
Content of the said plasticizer (B) is 3-50 mass% of the said copolymer (A), The optical adhesive composition characterized by the above-mentioned.

  Furthermore, the optical adhesive composition of Claim 1 containing an antistatic agent.   The optical pressure-sensitive adhesive composition according to claim 1 or 2, which is used for bonding an optical functional film.   An optical functional film with an adhesive layer, comprising an adhesive layer comprising the optical adhesive composition according to claim 1 on at least one surface.   The optical functional film according to claim 4, wherein the optical functional film is a polarizing plate.   The polarizing plate is a polarizing plate coated with a discotic liquid crystal, and the content of the plasticizer (B) in the optical pressure-sensitive adhesive composition according to claim 1 is 20 to 50 of the copolymer (A). The optical functional film according to claim 5, wherein the content is% by mass.   The plasticizer of the optical pressure-sensitive adhesive composition according to claim 1, wherein the polarizing plate is a polarizing plate based on a stretched triacetylcellulose-based film, a polycycloolefin-based film, or a stretched cellulose acetate propionate film. The optical functional film according to claim 5, wherein the content of (B) is 3 to 20% by mass of the copolymer (A).

Images