KR20100100602A - Cation-polymerizable adhesive and polarizing plate using the same - Google Patents

Abstract

PURPOSE: A cationically polymerizable adhesive and a polarizing plate using thereof are provided to use the cationically polymerizable adhesive as an adhesive for an optical material, and a construction material. CONSTITUTION: A cationically polymerizable adhesive contains an oxetane compound with more than two oxetanyl groups, aromatic glycidyl ether, and a cationic polymerization initiator. The amount of chlorine inside the total amount of the adhesive is less than 1,500 ppm. A polarizing plate includes a protective film formed with either triacetyl cellulose or cycloolefin, a polarizer formed with polyvinylalcohol, and the cationically polymerizable adhesive.

Description

Cationic polymerizable adhesive and polarizing plate obtained using the same {CATION-POLYMERIZABLE ADHESIVE AND POLARIZING PLATE USING THE SAME}

This invention relates to the cationically polymerizable adhesive which can be used for various uses, including manufacture of optical members, such as a polarizing plate, for example.

As a polarizing plate used for a liquid crystal display etc., what laminated | stacked the transparent protective film which consists of triacetyl cellulose, a thermoplastic saturated norbornene-type resin, etc. on the polarizer which generally consists of a polyvinyl alcohol-type film impregnated with dichroic materials, such as iodine, is used. Known. The adhesive used for adhesion of the polarizer and the protective film has excellent state adhesive strength with respect to both adherends of the polarizer and the protective film, and is independent of the influence of light or heat caused by the backlight of the liquid crystal display or the like. And it is demanded by the industry to be able to maintain the excellent state adhesive strength for a protective film for a long time.

On the other hand, as an adhesive, the cationic polymerizable adhesive which hardly produces hardening inhibition resulting from oxygen in air | atmosphere and which can advance hardening reaction even after stopping supply of energy, such as an ultraviolet-ray, is attracting attention, Applications to adhesive applications have also begun to be examined.

For example, as an adhesive agent used for adhesion | attachment of the said polarizer and a protective film, the adhesive agent which consists of a composition which has an epoxy resin which does not contain an aromatic ring as a main component is known, Specifically, a hydrogenated epoxy resin and an alicyclic epoxy resin, The adhesive agent containing an aliphatic epoxy resin and a photocationic polymerization initiator is known (for example, refer patent document 1).

However, the state adhesive strength of the adhesive to the polarizer made of polyvinyl alcohol or the like is less than the level required in the industry, and furthermore, the state adhesive strength due to the influence of light or heat due to the backlight or the like is decreased over time. This may cause peeling of the polarizer and the protective film in a relatively short period of time.

As described above, with the competition for the development of liquid crystal displays capable of displaying more clear images, the optical components constituting the same are required to have a very high level of various characteristics, and are superior in the levels that can be used for the adhesive use of polarizers and protective films. It was the situation which the cationically polymerizable adhesive which can maintain state adhesive strength for a long time has not yet been found.

Japanese Laid-Open Patent Publication No. 2004-245925

SUMMARY OF THE INVENTION An object of the present invention is to provide a cationic polymerizable adhesive capable of maintaining excellent state adhesive strength for a long time without being influenced by heat or light, and a polarizing plate to which a polarizer and a protective film are bonded using the adhesive. have.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors examined the combination of various compounds known as a cationically polymerizable compound, such as a hydroxyl group containing compound, an oxetanyl group containing compound, and an alicyclic epoxy compound.

Specifically, although the adhesive which combined the comparatively low molecular weight oxetanyl group containing compound, aromatic glycidyl ether, and a photocationic polymerization initiator was examined, it was difficult to fully prevent the fall of state adhesive strength over time with such an adhesive agent. .

Therefore, the present inventors have studied various combinations with the specific amount of the cationically polymerizable compound and the amount of residual chlorine that may be contained in the adhesive obtained, and thus, low molecular weight oxetane compound, aromatic glycidyl ether, and cationic polymerization It was found out that among the adhesive agents containing an initiator, an adhesive having 1500 ppm or less of chlorine remaining in the whole amount of the adhesive can solve the problem of the present invention.

That is, this invention is an adhesive agent containing the oxetane compound (A) of 100-800 molecular weight (A) which has two or more oxetanyl groups, an aromatic glycidyl ether (B), and a cationic polymerization initiator (C), The said The chlorine remaining in the whole amount of an adhesive agent is 1500 ppm or less, and it relates to the polarizing plate obtained by adhering a polarizer and a protective film using it.

Since the cationically polymerizable adhesive of the present invention can express excellent state adhesive strength over a long period of time without being influenced by heat or light, it is suitable for an adhesive for use in optical materials such as polarizing plates, construction materials, and automotive interior and exterior parts. Can be used. Moreover, since the cationically polymerizable adhesive agent of this invention has favorable state adhesive strength with respect to the polyvinyl alcohol film generally used for the material of a polarizer, it can be used only for manufacture of a polarizing plate, and especially the polarizer which comprises a polarizing plate It is possible to use suitably for adhesion | attachment of a protective film.

The present invention provides an oxetane compound (A) having a molecular weight of two or more oxetanyl groups (A), an aromatic glycidyl ether (B), a cationic polymerization initiator (C), and other additives as necessary. It is a cationically polymerizable adhesive agent which contains 1500 ppm or less of chlorine which remains in the whole quantity of the said adhesive agent as the adhesive agent to contain, and can be used suitably only for adhesion | attachment of the polarizer and protective film which comprise a polarizing plate. In addition, it shows that the said molecular weight is calculated | required by calculating based on foodstuff.

As an oxetane compound (A) used by this invention, it is important to use what has a molecular weight of 100-800. In order for adhesion of a polarizer and a protective film to fully advance hardening, the film thickness of an adhesive bond layer is usually performed by a thin film (thickness micrometer thickness), and in order to apply | coat an adhesive uniformly to the film thickness of the said grade, The adhesive needs to be low viscosity. And in order to obtain the said low viscosity adhesive agent, it is essential to use the said comparatively low molecular weight oxetane compound. Instead of the oxetane compound (A), for example, the adhesive obtained by using an oxetane compound having a molecular weight of about 1500 has a relatively high viscosity, which makes it difficult to form a thin film. May cause deterioration.

As said oxetane compound (A), it is more preferable to use the thing which has a molecular weight of the range of 100-500 from a viewpoint of further improving the coating workability and curability of the cationic polymerization adhesive of this invention, and is a range of 150-400. It is especially preferable to use what has a molecular weight of.

Moreover, as said oxetane compound (A), using what has two or more, preferably 2-4 oxetane ring structures which contribute to cation polymerization is preferable in order to give favorable curability and state adhesive strength. .

Specifically as an oxetane compound (A) used by this invention, the compound etc. which are represented by following General formula (1), (2), etc. can be used independently, or can use 2 or more types together, for example.

R ₁ in the general formulas (1) and (2) are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, an allyl group, an aryl group, an aralkyl group, a furyl group or a thio group having 1 to 6 carbon atoms A substituent group, R ₂ each independently represent a divalent organic residue, and each Z independently represents an oxygen atom or a sulfur atom.

As a linear, branched, or cyclic alkyl group of 1 to 6 carbon atoms represented by R ₁ in General Formulas (1) and (2), for example, a methyl group, an ethyl group, n- or i-propyl group, n- , i- or t-butyl group, pentyl group, hexyl group, cyclohexyl group and the like, and as the aryl group, for example, phenyl, naphthyl, tolyl, xylyl group and the like, and as the aralkyl group, For example, benzyl, a phenethyl group, etc. are mentioned.

Moreover, as a bivalent organic residue represented by R <_2> in the said General formula (1), For example, a linear, branched or cyclic alkylene group, the poly (oxyalkylene) group which has 4-30 carbon atoms, There exists a structure represented by a phenylene group, a xylylene group, and following General formula (3) and (4).

The linear, branched or cyclic alkylene group constituting R ₂ in General Formula (1) may be a methylene group, an ethylene group, a 1,2- or 1,3-propylene group, a butylene group, a cyclohexylene group, or the like. It is preferable that it is a C1-C15 alkylene group. Moreover, it is preferable that the poly (oxyalkylene) group which has 4-30 carbon atoms has 4-8 carbon atoms, For example, it is preferable that they are a poly (oxyethylene) group and a poly (oxypropylene) group. .

The formula (3) in R ₃ represents an oxygen atom, a sulfur atom, CH _2, NH, SO, SO _2, C (CF _{3) 2} or C (CH _{3) 2.}

R <_4> in the said General formula (4) represents the alkylene group which has 1-6 carbon atoms, an arylene group, and the functional group represented by following General formula (5).

A in the said General formula (5) shows the integer of 1-6, b shows the integer of 1-15.

As said General formula (5), it is preferable that b is an integer of 1-3.

As an oxetane compound which has the said 2-4 oxetane ring structure, For example, Aaron oxetane OXT-221, Aaron oxetane OXT-121, Aaron oxetane OXT-223 (above, Doagosei Co., Ltd. product), Etanacol OXBP (above, Ubegosan Co., Ltd. product) etc. are marketed.

As said oxetane compound (A), it is preferable to use what is represented by the said General formula (1), and bis [1-ethyl (3-) whose R <_1> in general formula (1) is an ethyl group and R <_2> is methylene Since oxetanyl)] methyl ether can make the film thickness of the adhesive agent after hardening thin, it can further improve sclerosis | hardenability, and also prevents the fall of the adhesive strength resulting from heat or light for a long time. It is preferable because it can be done.

Moreover, in this invention, it is a polarizer and a protective film to use combining the oxetane compound (D) which has one oxetanyl group as needed other than the oxetane compound (A) which has two or more oxetanyl groups as needed. It is preferable from the viewpoint of ensuring a sufficient open time for bonding together and preventing peeling due to heat, light, etc. of the polarizing plate obtained by bonding them together for a long time. In particular, the equivalent ratio of the oxetanyl group of the oxetane compound (A) and the oxetanyl group of the oxetane compound (D) is 0.1% of the oxetanyl group of (A) / (D) of oxetanyl group). It is preferable that it is -35.0, It is more preferable to use in the range of 0.2-10.0, It is especially preferable that it is the range of 1-5.

In addition, as an oxetane compound (D) which has one said oxetanyl group, the compound represented by following General formula (6) can be used, for example.

(R <_1> in General formula (6) represents a hydrogen atom, a C1-C8 alkyl group, a C1-C5 alkoxyalkyl group, or a C1-C6 hydroxyalkyl group. R <_2> represents , Hydrogen atom, alkyl group having 1 to 10 carbon atoms which may be branched, aliphatic cyclic structure, aromatic structure)

As an example of the C1-C8 alkyl group which can comprise R <_1> in the said General formula (6), a methyl group, an ethyl group, n-propyl group, i-propyl group, 2-ethylhexyl group, etc. are mentioned. .

Moreover, as an example of the C1-C5 alkoxyalkyl group which can comprise R <_1> in the said General formula (6), a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, propoxy Ethyl group etc. are mentioned.

Moreover, as an example of the C1-C6 hydroxyalkyl group which can comprise R <_1> in the said General formula (6), a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, etc. are mentioned.

Moreover, as a C1-C10 alkyl group which may be branched which can comprise R <_2> in the said General formula (6), linear alkyl groups, such as a methyl group, an ethyl group, and a propyl group, and 2-ethylhexyl group And branched alkyl groups may be mentioned.

Moreover, as an aliphatic cyclic structure which can comprise R <_2> in the said General formula (6), a cyclohexyl group etc. are mentioned, for example. The cyclohexyl group or the like may have an alkyl group or the like instead of a hydrogen atom.

Moreover, as an aromatic structure which can comprise R <_2> in the said General formula (6), a phenyl group etc. are mentioned, for example. The said phenyl group etc. may have an alkyl group etc. instead of a hydrogen atom.

As said oxetane compound (D), it is preferable to use what has a molecular weight of 100-500, and it is preferable to use what has a molecular weight of 150-500.

Moreover, as said oxetane compound (D), 3-hydroxymethyl-3-ethyl oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl It is more preferable to use one or more selected from the group consisting of oxetane and 3-ethyl-3- (cyclohexyloxy) methyloxetane.

In this invention, it is preferable to use the said oxetane compound (A) and (D) in 20-70 mass% with respect to whole quantity of a cationically polymerizable adhesive agent. Further, bis [1-ethyl (3-oxetanyl)] methyl ether as the oxetane compound (A) is preferably 20 to 70% by mass with respect to the total amount of the oxetane compounds (A) and (D). And 3-hydroxymethyl-3-ethyloxetane as the oxetane compound (D), with respect to the total amount of the oxetane compounds (A) and (D), preferably 20 to 70% by mass. It is preferable to use in combination, since the improvement of sclerosis | hardenability and the fall of the adhesive strength resulting from heat, light, etc. can be prevented for a long time.

Next, the aromatic glycidyl ether (B) used by this invention is demonstrated.

In this invention, an aromatic glycidyl ether (B) is used as what can be ring-opened by the cationic polymerization initiator (C) mentioned later and can form a crosslinked structure.

As said aromatic glycidyl ether (B), bisphenol-A glycidyl ether, bisphenol F-type glycidyl ether, bisphenol S-type glycidyl ether, bisphenol AD-type glycidyl ether can be used, and bisphenol is especially It is preferable to use A-type glycidyl ether or bisphenol F-type glycidyl ether.

As said aromatic glycidyl ether (B), bisphenol A-type glycidyl ether from a viewpoint of improving the curability of the cationically polymerizable adhesive agent of this invention further, and preventing the fall of the adhesive strength resulting from heat, light, etc. for a long time. It is preferable to use nabisphenol F-type glycidyl ether, and it is especially preferable to use bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.

As said aromatic glycidyl ether (B), it is preferable to use what has two or more glycidyl ether groups in order to provide favorable state adhesive strength, and it is more preferable to use 2-6 things.

Moreover, although the said aromatic glycidyl ether (B) can be manufactured by making bisphenol A or bisphenol F react with epichlorohydrin, etc., in the obtained aromatic glycidyl ether, chlorine resulting from the said epichlorohydrin etc. There may be some remaining. In general, in the commercially available glycidyl ether group-containing compound, chlorine in a few% to 10% by weight is usually left in many cases.

Therefore, when manufacturing the said aromatic glycidyl ether (B), performing treatment, such as removal of chlorine by rectification etc., gives more excellent state adhesive strength, and prevents discoloration of a polarizer, etc. It is preferable from a viewpoint. It is preferable to perform the said rectification for about 1 to 200 hours at the temperature of about 50-200 degreeC, for example. The amount of chlorine remaining in the aromatic glycidyl ether (B) can be measured based on JIS K1200-3-2: 00.

It is preferable that 5-50 mass% is contained in the whole amount of the cationically polymerizable adhesive agent of this invention, and the said aromatic glycidyl ether (B) contains the outstanding state adhesive strength that it is contained in the range of 10-40 mass%. It is more preferable for long term maintenance.

Moreover, in this invention, other glycidyl ether can be used as needed other than the said aromatic glycidyl ether (B).

As said other glycidyl ether, For example, aliphatic which has three glycidyl ether groups, such as trimethylol propane triglycidyl ether, glycerin triglycidyl ether, polyglycerol triglycidyl ether, and diglycerol triglycidyl ether, etc. Glycidyl compound (a1), trimethylolpropane diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether And glycidyl compounds having two glycidyl ether groups, such as propylene glycol diglycidyl ether and diethylene glycol diglycidyl ether.

Moreover, as said other glycidyl ether, hydrogenated hydrogenated bisphenol-A glycidyl ether, hydrogenated bisphenol F-type glycidyl ether of the said aromatic glycidyl ether (B), and other aromatic glycidyl Ether can be used.

Next, the cationic polymerization initiator (C) used by this invention is demonstrated.

The cationic polymerization initiator (C) used in the present invention is, for example, a photocationic polymerization initiator for generating an acid capable of initiating cationic polymerization by irradiation with energy rays such as ultraviolet rays, or a thermal cation for generating an acid by heating or the like. It is a polymerization initiator. Especially, when a polarizer and a protective film are adhere | attached and a polarizing plate is manufactured, or other optical material is manufactured, a photocationic polymerization initiator is used from a viewpoint of preventing deformation | transformation, discoloration, etc. of a base material by heat. It is preferable to use.

As said photocationic polymerization initiator, a cation part is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxanthium, (2, 4- cyclopentadiene-1, for example). -yl) - (1-methylethyl) benzene] -Fe cation, and the anion _{^{portion, BF 4 -, PF 6 -}} , SbF 6 -, [BX 4] - ( stage, X is at least two fluorine or trifluoromethyl Onium salt consisting of a phenyl group substituted with a romethyl group) may be used alone or in combination of two or more thereof.

Examples of the aromatic sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluorophosphate and bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroanti Monate, bis [4- (diphenylsulfonio) phenyl] sulfidebistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfidetetrakis (pentafluorophenyl) borate, di Phenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoro Borate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoro Roborate, Triphenylsulfonium Tetrakis (pentafluorophenyl) borei , Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfidebishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy )) Phenylsulfonio) phenyl] sulfidebishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfidebistetrafluoro Borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfidetetrakis (pentafluorophenyl) borate and the like can be used.

Moreover, as said aromatic iodonium salt, diphenyl iodonium hexafluoro phosphate, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium tetrafluoro borate, diphenyl iodonium tetra, for example. Kis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Roborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyl iodonium hexafluorophosphate, 4-methylphenyl-4- ( 1-methylethyl) phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyl iodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyl Iodonium tetrakis (pentafluorophenyl) borate and the like can be used. Can be.

Moreover, as said aromatic diazonium salt, a phenyl diazonium hexafluoro phosphate, a phenyl diazonium hexafluoro antimonate, a phenyl diazonium tetrafluoro borate, a phenyl diazonium tetrakis (pentafluorophenyl) borate, for example Etc. can be used.

Moreover, as said aromatic ammonium salt, 1-benzyl-2-cyano pyridinium hexafluoro phosphate, 1-benzyl-2-cyano pyridinium hexafluoro antimonate, 1-benzyl-2-cyano pyridinium tetra Fluoroborate, 1-benzyl-2-cyanopyridiniumtetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) 2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis ( Pentafluorophenyl) borate and the like can be used.

Moreover, S-biphenyl-2-isopropyl thioxanthone hexafluoro phosphate etc. can be used as said thioxanthium salt.

In addition, as said (2, 4- cyclopentadien- 1-yl) [(1-methylethyl) benzene] -Fe salt, it is (2, 4- cyclopentadien- 1-yl) [(1-methyl ethyl) Benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, 2,4- Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, 2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate and the like can be used.

As said photocationic polymerization initiator, for example, CPI-100P, CPI-101A, CPI-200K (above, San Apro Co., Ltd. product), a silocure photocuring initiator UVI-6990, a silocure photocuring initiator UVI-6992 , Silica Cure Photocuring Initiator UVI-6976 (above, manufactured by Dow Chemical Company), Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP -172, Adeka Optomer SP-300 (above, made by ADEKA Co., Ltd.), CI-5102, CI-2855 (above, made by Nihon Sotatsu Co., Ltd.), San-ade SI-60L, San-ade SI-80L , San Aid SI-100L, San Aid SI-110L, San Aid SI-180L, San Aid SI-110, San Aid SI-180 Above, product made by Lambertisa, omnicat 550 (product made by IMG resin), Irgacure 250 (product made in Chiba specialty chemicals), road seal photo initiator 2074 (RHODORSIL PHOTOINITIATOR 2074 (made in Rhodia Japan) ) And the like are commercially available.

As the thermal cation polymerization initiator, for example, benzylsulfonium salt, thiophenium salt, thiornium salt, benzyl ammonium salt, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, amineimide and the like can be used. .

As said thermal cationic polymerization initiator, "adeca optone CP77", "adeca optone CP66" (above, made by ADEKA Corporation), "CI-2639", "CI-2624" (above, Nihon Sotatsu Co., Ltd.) Commercially available products, such as "San Aid SI-60L", "San Aid SI-80L", and "San Aid SI-100L" (above, made by Sanshin Kagaku Kogyo Co., Ltd.).

Although the usage-amount of the said cationic polymerization initiator (C) is not specifically limited, Preferably it is the range of 0.1-20 mass% with respect to whole quantity of the said cationically polymerizable adhesive agent, More preferably, it is the range of 1-15 mass% It is preferable.

Moreover, in the cationically polymerizable adhesive agent of this invention, in addition to the said oxetane compound (A), the said aromatic glycidyl ether (B), and the said cationic polymerization initiator (C), if necessary, an alicyclic epoxy compound (E) is required. You may use together an epoxy group containing silane compound (F).

It is preferable to use the alicyclic epoxy compound (E) as the adhesive agent of this invention, in order to improve the adhesive strength in the initial stage of bonding, and to prevent a shift of a base material.

As said alicyclic epoxy compound (E), what has two or more alicyclic epoxy groups, Preferably 2-4 can be used.

As an alicyclic epoxy compound which has two alicyclic epoxy groups among the said alicyclic epoxy compounds (E), For example, 3, 4- epoxycyclohexenyl methyl-3, 4- represented by following General formula (7). Epoxycyclohexanecarboxylate (compound in which a is 0 in General Formula (7)), its caprolactone modified compound (compound in which a is 1 in General Formula (7)), the trimethylcaprolactone modified compound (Structure Formula ( 8) and Structural Formula (9)) and its valerolactone modified product (Structures (10) and (11)) or the compound represented by Structural Formula (12) can be used.

(A in General formula (7) represents 0 or 1)

Moreover, as an adipic acid ester alicyclic epoxy compound represented by the said General formula (12), Silcure UVR-6128 (above, Dow Chemical Nippon Corporation) etc. are marketed, for example.

Moreover, as the alicyclic epoxy compound which has two alicyclic epoxy groups, the compound represented by following General formula (13) can be used among the said alicyclic epoxy compounds (D).

(In General Formula (13), R ₁ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

As a compound represented by the said General formula (13), dicyclohexyl-3,3'- diepoxide can be used specifically ,.

As an alicyclic epoxy compound which has three alicyclic epoxy groups, the compound represented by following General formula (14) can be used.

In General formula (14), a and b are 0 or 1 each independently, and they may be same or different.

As the alicyclic epoxy compound represented by the general formula (14), for example, epoxide GT301, epoxide GT302 (manufactured by Daicel Chemical Co., Ltd.) and the like are commercially available.

As an alicyclic epoxy compound which has four alicyclic epoxy groups, the compound represented by following General formula (15) can be used, for example.

In the general formula (15), a to d each independently represent 0 or 1, and they may be the same or different.

As the alicyclic epoxy compound represented by the general formula (15), for example, epoxide GT401, epoxide GT403 (manufactured by Daicel Chemical Co., Ltd.) and the like are commercially available.

It is preferable to use the said alicyclic epoxy compound (E) in the range of 1-20 mass% with respect to whole quantity of the cationically polymerizable adhesive agent of this invention, and to use it in the range of 2-10 mass%, the initial stage of bonding It is preferable to improve the adhesive strength of the substrate and to prevent the misalignment of the substrate.

Moreover, since the said epoxy group containing silane compound (F) can further prevent the discoloration of a polarizer, etc., while improving the state adhesive strength of the adhesive agent obtained further, it is preferable to use it as the adhesive agent of this invention. When aminosilanes, such as 3-aminopropyltriethoxysilane, vinylsilanes, such as vinyltriacetoxysilane, etc. are used instead of the said compound (F), compared with the case where the said compound (F) is used, There exists a tendency for the discoloration prevention effect to fall slightly.

Examples of the epoxy group-containing silane compound (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidyl silane. It is preferable to use doxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) It is preferable to use 1 or more types chosen from the group which consists of ethyl triethoxysilane, in order to provide more excellent state adhesive strength, and to prevent the fading of a polarizer.

Moreover, as said epoxy group containing silane compound (F), the silicone oil represented by following General formula (16) and (17) can also be used.

(N in the said General formula (16) represents the integer of 1 or more.)

(R in said General formula (16) represents an organic group, n represents an integer of 1 or more.)

When the said epoxy group containing silane compound (F) is used in 0.1-1.5 mass% with respect to whole quantity of the cationically polymerizable adhesive agent of this invention, it does not cause the fall of the adhesive strength by influence of heat, etc., and it is a polarizer. It is preferable to prevent discoloration and the like.

In the cationically polymerizable adhesive used in the present invention, the amount of chlorine remaining in the whole amount of the cationically polymerizable adhesive is 1500 ppm or less, which provides more excellent heat-resistant adhesive strength and prevents discoloration of polarizers and the like. In view of the above, it is very preferable. When the said chlorine amount exceeds 1500 ppm, discoloration of an adhesive bond layer or the polarizer obtained and a fall of adhesive strength may be caused.

Herein, chlorine as used in the present invention refers to chlorine or chlorides derived from raw materials such as epichlorohydrin used in the production of the aromatic glycidyl ether (B), and various additives that can be used in the adhesive of the present invention. For example, it refers to inorganic chlorides such as sodium chloride.

By adjusting the amount of such chlorine to 1500 ppm or less, preferably 1000 ppm or less, and more preferably 800 ppm or less with respect to the total amount of the cationic polymerizable adhesive, it becomes possible to achieve discoloration such as polarizer and the like and long-term state adhesive strength. . The amount of chlorine remaining in the whole amount of the cationically polymerizable adhesive of the present invention can be measured based on JIS K1200-3-2: 00.

In particular, in order to further prevent discoloration and the like of the polarizer, it is preferable to adjust the amount of chlorine remaining in the cationically polymerizable adhesive to 1500 ppm or less while using the epoxy group-containing silane compound (F).

As a method of adjusting the amount of chlorine remaining in the cationically polymerizable adhesive agent of this invention to 1500 ppm or less, the method of removing chlorine by rectifying, using the capture | acquisition material which can capture | acquire the said chlorine, etc. are mentioned, for example. It is preferable to perform the said rectification for about 1 to 200 hours at the temperature of about 50-200 degreeC, for example.

The cationically polymerizable adhesive of the present invention can be produced, for example, by the following method.

The cationically polymerizable adhesive of the present invention is, for example, the oxetane compound (A), the aromatic glycidyl ether (B), and the cationic polymerization initiator (C) prepared in advance using a hermetic planetary mixer or the like. And it can manufacture by mixing and stirring the oxetane compound (D) which has said one oxetanyl group, the said alicyclic epoxy compound (E), and the said epoxy group containing silane compound (F) as needed. When using the said oxetane compound (D), you may use the thing in which the said oxetane compound (A) and (D) were mixed previously.

It is preferable that the cationically polymerizable adhesive obtained by the said method is a viscosity of 100 mPa * s or less at 25 degreeC from a viewpoint which makes thickness of the contact bonding layer to form as thin as possible. This viscosity can be adjusted mainly by using diluents, such as an oxetane compound and an alicyclic epoxy compound, or using a low molecular weight liquid phase thing as said aromatic glycidyl ether (B).

The cationically polymerizable adhesive agent of this invention may contain various additives in the range which does not lose the effect of this invention as needed.

Examples of the additives include thixotropic agents, sensitizers, various polyols described above, and other polyols other than those, leveling agents, antioxidants, tackifiers, waxes, heat stabilizers, light stabilizers, and fluorescent brighteners. , Foaming agent, thermoplastic resin, thermosetting resin, organic solvent, conductivity giving agent, antistatic agent, moisture permeability improver, water repellent, hollow foam, crystal water-containing compound, flame retardant, absorbent, moisture absorbent, deodorant, foam stabilizer, antifoaming agent, I), preservatives, preservatives, antiblocking agents, hydrolysis inhibitors, organic and inorganic water-soluble compounds and the like can be used in combination.

As said thixotropic agent, surface-treated calcium carbonate, fine powder silica, bentonite, zeolite, etc. can be used, for example.

When using the said various additives, the said additive uses the said oxetane compound (A), the said aromatic glycidyl ether (B), and the said cationic polymerization initiator (C) using a hermetic planetary mixer etc., for example. When mixing and stirring the said alicyclic epoxy compound (E) and the said epoxy group containing silane compound (F) as needed, it can mix together.

The cationically polymerizable adhesive agent of this invention can advance hardening by irradiation of energy rays, such as an ultraviolet-ray.

Energy beam irradiation, such as the ultraviolet ray is preferably 50~5000mJ / cm ^2, preferably of more preferably 100~3000mJ / cm ^2, particularly preferably in the range of 300~1500mJ / cm ^2.

As a source of ultraviolet rays, well-known lamps, such as a xenon lamp, a xenon mercury lamp, a metal halide lamp, a high pressure mercury lamp, and a low pressure mercury lamp, can be used, for example. In addition, the amount of ultraviolet irradiation was based on the value measured in the wavelength range of 300-390 nm using UV Sucker UVR-N1 (made by Nippon Denchi Co., Ltd.).

Moreover, you may further accelerate hardening by heating to about 40-80 degreeC after irradiation of the said energy beam as needed.

Next, the polarizing plate of this invention is demonstrated.

In the polarizing plate of the present invention, the protective film and the polarizer are bonded to each other via an adhesive layer made of the cationic polymerizable adhesive.

As a protective film which can be used for manufacture of the said polarizing plate, it is a film or sheet form which consists of cellulose resins, such as triacetyl cellulose, resin which has a cycloolefin structure, norbornene resin, etc. from a viewpoint of improving polarization characteristic, durability, etc. It is preferable to use cellulose resin, such as a triacetyl cellulose, among these.

As said cellulose resin, a cellulose acetate, a cellulose acetate propionate, a cellulose acetate butyrate, a cellulose acetate propionate butyrate, a cellulose acetate phthalate, cellulose nitrate, etc. can be used, for example, These can be used individually or in combination of 2 or more types It is possible to do this, and it is preferable to use cellulose acetate among them, since a film excellent in mechanical properties and transparency can be obtained.

The polarizer is not particularly limited and various kinds can be used. For example, a plastic substrate made of a hydrophilic polymer compound such as polyvinyl alcohol, partially formalized polyvinyl alcohol, and an ethylene-vinyl acetate copolymerized partial saponifier. Polyene oriented films, such as the thing uniaxially stretched by adsorb | sucking dichroic materials, such as iodine and a dichroic dye, and the dehydration process of polyvinyl alcohol, and the dehydrochlorination process of polyvinyl chloride, can be used. Especially, it is preferable to use the film which adsorb | sucked dichroic substances, such as a polyvinyl alcohol-type film and iodine.

Although the thickness of the said protective film used when manufacturing the polarizing plate of this invention changes with the use used, it is preferable that it is the range of about 20 micrometers-100 micrometers. Moreover, it is preferable that the thickness of the said polarizer is the range of 5 micrometers-50 micrometers normally.

In addition, the polarizing plate of this invention can be manufactured by apply | coating the said cationically polymerizable adhesive agent on the said protective film, and then irradiating the said ultraviolet-ray of the said quantity to the application surface, and then mounting and bonding a polarizer to the application surface. At this time, as for the thickness of the contact bonding layer which consists of said cationically polymerizable adhesive agent, the thinner is preferable so that optical characteristics may lose | disappear etc. Specifically, it is preferable that it is 5 micrometers or less.

The polarizing plate of this invention obtained by the above method can be used for the member which comprises displays, such as a mobile communication terminal, such as a mobile telephone, a liquid crystal television, a personal computer, a portable game machine, for example.

[Example]

Hereinafter, an Example and a comparative example demonstrate this invention further more concretely.

[Production Example 1]

The isomeric mixture (B'-6) of the bisphenol F type diglycidyl ether compound having a chlorine content of 3.5% determined according to JIS K1200-3-2: 00 was distilled under the conditions of 1.3 kPa and 185 ° C, and then By rectifying on the conditions of 0.02 Mpa and 70 degreeC, the glycidyl ether group containing compound (B-1) of chlorine content of 600 ppm was obtained. In addition, as chlorine content contained in the said glycidyl ether group containing compound (B-1), about 0.05% or more as sodium chloride, the value calculated | required by the Folhart improvement method is less than 0.05% about the ion chromatograph analysis method The value obtained by was used. In addition, the chlorine content of the glycidyl ether group containing compound (B-2), (B'-3), and (B'-4) of the following manufacture examples 2-3 was also measured by the method similar to the above. .

[Production Example 2]

The isomeric mixture of bisphenol A type diglycidyl ether having a chlorine content of 3.5% determined according to JIS K1200-3-2 was distilled under the conditions of 1.3 kPa and 185 ° C, and then rectified under the conditions of 0.02 MPa and 70 ° C. By carrying out, 600 ppm glycidyl ether group containing compound (B-2) was obtained by chlorine content.

[Production Example 3]

Cyclohexanedimethanol diglycidyl ether having a chlorine content of 6.5% determined according to JIS K1200-3-2 was distilled under the conditions of 1.3 kPa and 185 ° C, followed by sequential rectification under the conditions of 0.02 MPa and 70 ° C. The chlorine content is 500 ppm glycidyl ether group-containing compound (B'-3), the chlorine content is 1000 ppm glycidyl ether group-containing compound (B'-4), and the chlorine content is 10000 ppm glycidyl Ether group containing compound (B'-5) was obtained.

Example 1

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-4), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) 25.0 parts by mass and 50% by mass of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) Solution) The cationically polymerizable adhesive 1 was manufactured by mixing and stirring 4 mass parts. It was 247 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 1 was calculated | required by the method mentioned later.

Example 2

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) 25.0 parts by mass and 50% by mass of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) Solution) The cationically polymerizable adhesive 2 was manufactured by mixing and stirring 4 mass parts. It was 219 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 2 was calculated | required by the method mentioned later.

Example 3

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-2), 20.0 mass parts of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) 25.0 parts by mass and 50% by mass solution of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) ) 4 mass parts was mixed and stirred to prepare a cationically polymerizable adhesive 3. It was 211 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive agent 3 was calculated | required by the method mentioned later.

Example 4

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) 25.0 parts by mass, 0.5 parts by mass of KBE-403 (3-glycidoxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) as an epoxy group-containing silane compound (F), and a photocationic polymerization initiator (C ) 4 parts by mass of CPI-100P (50% by mass of propylene carbonate solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp.), followed by mixing and stirring (4) was manufactured. It was 218 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 4 was calculated | required by the method of mentioning later.

[Example 5]

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 25.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) as a 30.0 mass part and alicyclic epoxy compound (E), ceoxide 2021P (3, 4- epoxycyclohexenylmethyl-3 ', 4'- epoxycyclohexene carboxylate by Daicel Chemical Co., Ltd.) CPI-100P (50 mass% solution of propylene carbonate of diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate by the acid Apro Corporation) as 5.0 mass part and photocationic polymerization initiator (C) 4 The cationically polymerizable adhesive 5 was manufactured by mixing and stirring a mass part. It was 209 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 5 was calculated | required by the method mentioned later.

[Example 6]

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 45.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Bushing Co., Ltd. and 3-ethyl-3- (phenoxymethyl, manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-211 (Oxetane) 50 mass% of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate by the acid aprogas company made as 15.0 mass parts and photocationic polymerization initiator (C) Solution) The cationically polymerizable adhesive 6 was manufactured by mixing and stirring 4 mass parts. It was 212 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 6 was calculated | required by the method mentioned later.

Example 7

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Bushing Co., Ltd. and 3-ethyl-3- (phenoxymethyl, manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-211 (Oxetane) 25.0 parts by mass and 50 parts by mass of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) % Solution) The cationically polymerizable adhesive 7 was manufactured by mixing and stirring 4 mass parts. It was 214 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 7 was calculated | required by the method mentioned later.

Example 8

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-ethyl-3- (2-ethyl manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-212 Hexyloxymethyl) oxetane) and propylene of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) The cationic polymerizable adhesive 8 was manufactured by mixing and stirring 4 mass parts of carbonate 50 mass% solutions). It was 208 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive agent 8 was calculated | required by the method mentioned later.

Example 9

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-ethyl-3- (cyclohexyl jade manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-213 Propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate made from acid aprogas) as 25.0 parts by mass of methyl) oxetane) and photocationic polymerization initiator (C) 4 mass parts of 50 mass% solutions) were mixed and stirred, and the cationically polymerizable adhesive agent 9 was manufactured. It was 215 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 9 was calculated | required by the method mentioned later.

[Example 10]

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 25.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Bushing Co., Ltd. and 3-ethyl-3- (phenoxymethyl, manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-211 ) Oxetane) 30.0 mass parts and 3, 4- epoxycyclohexenyl methyl-3 ', 4'- epoxycyclohexene carboxyl of Daicel Chemical Co., Ltd. make as an alicyclic epoxy compound (E) Rate) 5.0 parts by mass, 0.5 parts by mass of KBE-403 (3-glycidoxypropyl triethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) as an epoxy group-containing silane compound (F), and a photocationic polymerization initiator (C Propylene carbonate 50-quality of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate made from San Afro Corporation % Solution) by mixing 4 parts by weight, stirred, to prepare a cationic polymerizable adhesive (10). It was 216 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive agent 10 was calculated | required by the method mentioned later.

Example 11

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-3), and aronoxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether, manufactured by Bushing Co., Ltd. and 3-ethyl-3- (phenoxymethyl, manufactured by Toagosei Co., Ltd.) and Aaron Oxetane OXT-211 ) Oxetane) As a 25.0 mass part and alicyclic epoxy compound (E), ceoxide 2021P (3, 4- epoxycyclohexenyl methyl-3 ', 4'- epoxycyclohexene carboxyl made from Daicel Chemical Co., Ltd.) Rate) 5.0 parts by mass, 0.5 parts by mass of KBE-403 (3-glycidoxypropyl triethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) as an epoxy group-containing silane compound (F), and a photocationic polymerization initiator (C Propylene carbonate 50-quality of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate made from San Afro Corporation % Solution) by mixing 4 parts by weight, stirred, to prepare a cationic polymeric adhesive 11. It was 216 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 11 was calculated | required by the method mentioned later.

[Comparative Example 1]

40.0 parts by mass of glycidyl ether group-containing compound (B'-3) in a hermetic planetary mixer, and biox [1-ethyl (3-oxetanyl manufactured by Toagosei Co., Ltd.) 35.0 parts by mass of methyl ether) and 25.0 parts by mass of oxoxane-OXT-101 (3-hydroxymethyl-3-ethyloxetane manufactured by Toagosei Co., Ltd.) and CPI as a photocationic polymerization initiator (C) Cationic polymerizable adhesive (1 ') by mixing and stirring 4 parts by mass of -100P (50% by mass of propylene carbonate solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, manufactured by San Apro Corp.) ). It was 194 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 1 'was calculated | required by the method mentioned later.

Comparative Example 2

40.0 parts by mass of glycidyl ether group-containing compound (B'-4) and biox [1-ethyl (3-oxetanyl manufactured by Toagosei Co., Ltd.) in a hermetic planetary mixer 35.0 parts by mass of methyl ether) and 25.0 parts by mass of oxoxane-OXT-101 (3-hydroxymethyl-3-ethyloxetane manufactured by Toagosei Co., Ltd.) and CPI as a photocationic polymerization initiator (C) Cationic polymerizable adhesive (2 ') by mixing and stirring 4 parts by mass of -100P (50% by mass of a propylene carbonate solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp.) ). It was 383 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive agent 2 'was calculated | required by the method mentioned later.

[Comparative Example 3]

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B'-3), 20.0 mass part of glycidyl ether group containing compounds (B-1), and aron oxetane OXT-191 (Doagosei Chemicals) 35.0 parts by mass of oxetanyl silicate manufactured by Bushiki Co., Ltd. and 25.0 parts by mass of Aaron oxetane OXT-101 (3-hydroxymethyl-3-ethyl oxetane manufactured by Toagosei Co., Ltd.), and a photocationic polymerization initiator Cationic polymerization by mixing and stirring 4 mass parts of CPI-100P (50 mass% solution of the propylene carbonates of the diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate by San Apro Corp.) as (C) A sex adhesive 3 'was prepared. It was 211 ppm when the chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive agent 3 'was calculated | required by the method mentioned later.

[Comparative Example 4]

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B'-3), 20.0 mass part of glycidyl ether group containing compounds (B-2), and aron oxetane OXT-191 (Doagosei Chemicals) 35.0 parts by mass of oxetanyl silicate manufactured by Bushiki Co., Ltd., 25.0 parts by mass of Aaron oxetane OXT-101 (3-hydroxymethyl-3-ethyl oxetane manufactured by Toagosei Co., Ltd.), and a photocationic polymerization initiator Cationic polymerization by mixing and stirring 4 mass parts of CPI-100P (50 mass% solution of the propylene carbonates of the diphenyl-4- (phenylthio) phenylsulfonium hexafluoro phosphate by San Apro Corp.) as (C) A sex adhesive 4 'was prepared. It was 213 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 4 'was calculated | required by the method mentioned later.

Comparative Example 5

In a hermetic planetary mixer, 20.0 mass parts of glycidyl ether group containing compounds (B-1), 20.0 mass part of glycidyl ether group containing compounds (B'-5), and aron oxetane OXT-221 (Doagosei Chemicals) 35.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether) manufactured by Bushing Co., Ltd. and 3-hydroxymethyl-3-ethyl jade by Aaron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Cetane) 25.0 parts by mass and 50% by mass solution of propylene carbonate of CPI-100P (diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp. as a photocationic polymerization initiator (C) ) 4 mass parts was mixed and stirred to prepare a cationically polymerizable adhesive 5 ′. It was 2019 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 5 'was calculated | required by the method mentioned later.

Comparative Example 6

40.0 parts by mass of glycidyl ether group-containing compound (B'-6) and biox [1-ethyl (3-oxetanyl, manufactured by Toagosei Co., Ltd.) in a hermetic planetary mixer 35.0 parts by mass of methyl ether) and 25.0 parts by mass of oxoxane-OXT-101 (3-hydroxymethyl-3-ethyloxetane manufactured by Toagosei Co., Ltd.) and CPI as a photocationic polymerization initiator (C) Cationic polymerizable adhesive (6 ') by mixing and stirring 4 parts by mass of -100P (50% by mass of propylene carbonate solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate manufactured by San Apro Corp.) ). It was 13462 ppm when chlorine content contained in the whole quantity of the obtained cationically polymerizable adhesive 6 'was calculated | required by the method mentioned later.

[Measurement Method of Total Chlorine Content]

The chlorine content contained in the cationically polymerizable adhesive agent of this invention was measured based on JISK1200-3-2: 00. Specifically, for the adhesive whose amount of chlorine in the present invention is 0.05% or more as sodium chloride, the value obtained by the Paul Hart improvement method is taken as the chlorine content of the adhesive, and for the adhesive having less than 0.05%, the ion chromatograph analysis method The value calculated | required by was made into the chlorine content of the adhesive agent.

[How to make polarizer]

The bar coater is used for the polyvinyl alcohol aqueous solution (8 mass% of non volatile matters) obtained by dissolving Kuraray foaming PVA-117H (polyvinyl alcohol, polymerization degree 1700, complete saponified product, powder form) made by Kuraray Co., Ltd. in water. And apply | coated on a release film, and drying for 5 minutes in 80 degreeC environment, the polyvinyl alcohol film of thickness 75micrometer was produced by removing the said release film.

Subsequently, the obtained polyvinyl alcohol film was fixed to the drawing machine, and it extended | stretched until the film became 3 times the magnitude | size in the uniaxial direction in 40 degreeC warm water.

After removing the water adhering to the surface of the stretched film obtained above, the said stretched film was immersed in the aqueous solution adjusted to 30 degreeC containing 0.02 mass part of iodine, 2 mass parts of potassium iodide, and 100 mass parts of water. .

Subsequently, the said stretched film was immersed in the aqueous solution adjusted to 56.5 degreeC containing 12 mass parts of potassium iodide, 5 mass parts of boric acid, and 100 mass parts of water.

After wash | cleaning in the pure water adjusted to 8 degreeC after the said immersion, the polarizer (polarizing film) which iodine adsorbed and orientated on the surface of the stretched film which consists of polyvinyl alcohol was obtained by drying in the environment of 65 degreeC.

[Production Method of Polarizing Plate]

On the one surface of two triacetyl cellulose films (80 μm thick, 297 mm wide, 210 mm wide) treated with corona treatment, the cationically polymerizable adhesives obtained in Examples and Comparative Examples using an applicator to have a thickness of about 2 μm. It coated, respectively, and the ultraviolet-ray of 30-100mJ / cm <^2> was irradiated to the coating surface using the conveyor type ultraviolet irradiation device CSOT-40 (The high pressure mercury lamp by Nihon Denchi Co., Ltd., intensity | strength 120W / cm).

Subsequently, the said two triacetylcellulose films were bonded together on both surfaces of 42 micrometers in thickness, 297 mm in length, and 210 mm in width | variety obtained by the said method, pressurized using a rubber roller, and they adhered, Then, 60 degreeC dryer The polarizing plate was produced by heating in 1 minute.

[Evaluation Method of State Adhesive Strength]

After leaving the polarizing plate obtained by the said method to 1500 degreeC in the dryer set to 85 degreeC for 1500 hours, each polarizing plate is comprised using a tensile tester (made by Imada Seisakusho, tension rate = 50 mm / min T type peeling). The peeling strength of the interface of triacetyl cellulose and polyvinyl alcohol was measured. The said peel strength of 10 N / 25mm or more or the fracture (MB) of a triacetyl cellulose film evaluated "good" and the thing less than 10 N / 25mm as "defect".

[Evaluation of Transmittance, Discoloration of Polarizer, etc.]

The degree of fading and discoloration of the polarizer under the influence of the cationically polymerizable adhesive was evaluated based on the rate of change of the transmittance of the polarizing plate before and after the polarizing plate produced by the above method was allowed to stand for 1500 hours under conditions of a temperature of 65 ° C and a humidity of 90%. did.

The transmittance | permeability of the polarizing plate was measured using the visible spectrophotometer (JASCO V-570 by Nippon Bunko Corporation, measurement wavelength 200-900 nm, scanning speed 400 nm / min). The change of the transmittance | permeability (%) of the polarizing plate after the said neglect was evaluated as "x" with respect to the transmittance | permeability (%) of the polarizing plate before the said neglect to "x", and that the change of the transmittance of the polarizing plate after the said neglect is less than +/- 5%. It evaluated with "(circle)".

TABLE 1

TABLE 2

[Table 3]

Claims (15)

An adhesive agent containing an oxetane compound (A) having a molecular weight of 100 to 800 having two or more oxetanyl groups (A), an aromatic glycidyl ether (B), and a cationic polymerization initiator (C), which remain in the total amount of the adhesive. A cationically polymerizable adhesive, characterized in that chlorine is 1500 ppm or less. The method of claim 1,
The said oxetane compound (A) is bis [1-ethyl (3-oxetanyl)] methyl ether, The cationically polymerizable adhesive agent. The method of claim 1,
A cationically polymerizable adhesive wherein said aromatic glycidyl ether (B) is at least one selected from the group consisting of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether. The method of claim 1,
It further contains an oxetane compound (D) which has one oxetanyl group, and is equivalent ratio of the oxetanyl group which the said oxetane compound (A) has, and the oxetanyl group which the said oxetane compound (D) has [[A] Oxetanyl group / (D) has a oxetanyl group] is 0.1 to 35.0 cationic polymerizable adhesive. The method of claim 4, wherein
The cationically polymerizable adhesive whose said oxetane compound (D) has a molecular weight of 100-500. The method of claim 4, wherein
The oxetane compound (D) is 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane And 3-ethyl-3- (cyclohexyloxy) methyloxetane. The cationic polymerizable adhesive selected from the group consisting of: The method of claim 4, wherein
20-70 mass% of bis [1-ethyl (3-oxetanyl)] methyl ether as the said oxetane compound (A) is contained with respect to the whole of the said cationically polymerizable adhesive agent, and the said oxetane compound (D 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3 as The cationically polymerizable adhesive agent containing 20-70 mass% of 1 or more types chosen from the group which consists of-(cyclohexyloxy) methyl oxetane. The method of claim 1,
A cationically polymerizable adhesive further containing an alicyclic epoxy compound (E). The method of claim 8,
The cationically polymerizable adhesive agent wherein the alicyclic epoxy compound (E) has a structure represented by the following general formula (7).

(A in General formula (7) represents 0 or 1) The method of claim 8,
The cationic polymerizable adhesive wherein the alicyclic epoxy compound (E) is 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate. The method according to any one of claims 1 to 8,
The cationically polymerizable adhesive which contains an epoxy group containing silane compound (F) further. The method of claim 11,
The cationically polymerizable adhesive agent with which the said epoxy group containing silane compound (F) is contained 0.1-1.5 mass% with respect to whole quantity of the said cationically polymerizable adhesive agent. The method of claim 11,
The epoxy group-containing silane compound (F) is 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethol Cationically polymerizable adhesive which is 1 or more types chosen from the group which consists of oxysilane, 2- (3, 4- epoxycyclohexyl) ethyltriethoxysilane, and 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane. The method according to any one of claims 1 to 13,
Cationically polymerizable adhesive agent used for adhesion | attachment of the polarizer and protective film which comprise a polarizing plate. A polarizing plate wherein a protective film made of triacetyl cellulose or a protective film made of cycloolefin and a polarizer made of polyvinyl alcohol are bonded to each other via a cationically polymerizable adhesive, wherein the cationic polymerizable adhesive is the cationic polymerizable agent according to claim 14. It is an adhesive agent, The polarizing plate characterized by the above-mentioned.