JP2015071740A - Acrylic adhesive composition, manufacturing method of acrylic adhesive layer and acrylic adhesive layer obtained by the manufacturing method, polarizing film with adhesive layer, laminate, image display device, and crosslinking acceleration method of acrylic adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic adhesive composition and the acrylic adhesive layer, a polarizing film with the adhesive layer, a laminate, and an image display device which contain an acrylic polymer, one type or more of a crosslinking agent selected from an organic peroxide-based crosslinking agent and an isocyanate-based crosslinking agent, and are capable of efficiently crosslinking the composition.SOLUTION: A acrylic adhesive composition contains a (meth)acrylic-based polymer, one type or more of crosslinking agents selected from an organic peroxide-based crosslinking agent and an isocyanate-based crosslinking agent, and a compound expressed by the general formula (1) at 0.005 to 5 pts.wt. with respect to 100 pts.wt. of the (meth)acrylic-based polymer. (Rand Rare hydrocarbon residues with C1 to 18 which may independently contain H or O.)

Description

  The present invention relates to an acrylic pressure-sensitive adhesive composition, a method for producing an acrylic pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive layer produced by the production method, and a pressure-sensitive adhesive having the acrylic pressure-sensitive adhesive layer. TECHNICAL FIELD The present invention relates to a polarizing film with a layer, a laminate in which the polarizing film with an acrylic pressure-sensitive adhesive layer and a transparent conductive substrate are laminated, an image display device using the laminated body, and a method for promoting crosslinking of the acrylic pressure-sensitive adhesive composition. .

  For image display devices such as liquid crystal display devices, it is indispensable to arrange various kinds of films on both sides of the liquid crystal cell from the image forming method, and when attaching various films to the liquid crystal cell, An adhesive is used. For example, since the adhesion between the polarizing film and the liquid crystal cell usually reduces the loss of light, the respective materials are adhered using an adhesive. In such a case, since it has the merit that a drying process is not required to fix various films, the pressure-sensitive adhesive is a film with a pressure-sensitive adhesive layer previously provided as a pressure-sensitive adhesive layer on one side of the various films. Is generally used.

  In the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer, a crosslinking agent is often blended together with a base polymer such as a (meth) acrylic polymer for the purpose of improving durability, for example, (meth) acrylic A pressure-sensitive adhesive containing a peroxide and an isocyanate-based compound in addition to a polymer has been proposed (see, for example, Patent Document 1). In addition to a (meth) acrylic polymer containing an acrylic monomer and a nitrogen-containing monomer, a pressure-sensitive adhesive composition containing a peroxide and an isocyanate crosslinking agent has been proposed (see, for example, Patent Document 2). .

JP 2006-183022 A JP 2007-138147 A

  As described in Patent Documents 1 and 2, the conventional acrylic pressure-sensitive adhesive compositions often employ crosslinking with organic peroxides or isocyanate crosslinking agents. However, in organic peroxide cross-linking, cross-linking efficiency may be lowered due to cross-linking inhibition by oxygen in the reaction system in atmospheric hot air cross-linking, and isocyanate cross-linking agents have low reactivity, so these cross-linking agents are used. In the case of cross-linking, the processability and productivity are insufficient. Specifically, for example, when a base material having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is punched into a predetermined size or slitted, the pressure-sensitive adhesive layer is taken by a cutting blade. In some cases, it protrudes from the cut surface. In addition, during the appearance inspection and conveyance of the punched base material with the adhesive layer, the adhesive layer may be removed or the base material may be soiled by the adhesive layer protruding from the cut surface.

  In addition, in order to increase the efficiency of the crosslinking reaction in the acrylic pressure-sensitive adhesive composition containing these crosslinking agents, a catalyst or the like that promotes the urethane reaction may be added. In some cases, the pot life may be very short. In addition, amine-based and metal-based additives may be used as a catalyst, but this has been a cause of product defects and physical property degradation due to amine odor.

Furthermore, in the acrylic pressure-sensitive adhesive composition containing these cross-linking agents, after the cross-linking treatment, the aging (aging) period may be provided to complete the cross-linking. The aging period is usually required for about 1 day to 1 week, and the productivity is lowered by providing an aging process.

  Thus, in an acrylic pressure-sensitive adhesive composition containing an acrylic polymer, an organic peroxide-based crosslinking agent and / or an isocyanate-based crosslinking agent, it is difficult to efficiently crosslink with the crosslinking agent.

  Therefore, the present invention includes an acrylic pressure-sensitive adhesive composition that includes one or more cross-linking agents selected from the group consisting of acrylic polymers, organic peroxide cross-linking agents, and isocyanate cross-linking agents, and can be efficiently cross-linked. The purpose is to provide goods. Also provided are a method for producing an acrylic pressure-sensitive adhesive layer using the acrylic pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive layer obtained by the production method, a polarizing film with a pressure-sensitive adhesive layer, a laminate, and an image display device. The purpose is to do. It is another object of the present invention to provide a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by using the following acrylic pressure-sensitive adhesive composition, and have completed the present invention.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基である）
で表される化合物を含有し、
前記一般式（１）で表される化合物の含有量が、前記（メタ）アクリル系ポリマー１００重量部に対して０．００５〜５重量部であることを特徴とするアクリル系粘着剤組成物に関する。 That is, the present invention includes at least one crosslinking agent selected from the group consisting of (meth) acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents, and the following general formula (1):

(Wherein, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
Containing a compound represented by
The acrylic pressure-sensitive adhesive composition is characterized in that the content of the compound represented by the general formula (1) is 0.005 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. .

  The compound represented by the general formula (1) is preferably a phosphate ester having an acid value of 80 to 900 mgKOH / g.

  It is preferable to contain 0.05 to 2 parts by weight of the organic peroxide crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.

  The acrylic pressure-sensitive adhesive composition contains an organic peroxide crosslinking agent and an isocyanate crosslinking agent, and the content of the isocyanate crosslinking agent is 5 to 1000 with respect to 100 parts by weight of the organic peroxide crosslinking agent. It is preferable that it is a weight part.

  The (meth) acrylic polymer preferably has a weight average molecular weight of 1,200,000 to 3,000,000.

Moreover, this invention includes the process of apply | coating the said acrylic adhesive composition on a base material, and the process of bridge | crosslinking the acrylic adhesive composition apply | coated on the base material, and forming an adhesive layer. The manufacturing method of the acrylic adhesive layer characterized by these.

  The acrylic pressure-sensitive adhesive composition is preferably crosslinked by heating at 70 to 170 ° C. for 30 to 240 seconds.

  The present invention also relates to an acrylic pressure-sensitive adhesive layer produced by the method for producing an acrylic pressure-sensitive adhesive layer.

  The gel fraction after 5 days after crosslinking is preferably 60 to 95% by weight, and the gel fraction after 2 hours after crosslinking is more preferably 55 to 85% by weight.

  Moreover, this invention relates to the polarizing film with an adhesive layer characterized by having the said acrylic adhesive layer on the at least single side | surface of a polarizing film.

  Moreover, the transparent conductive base material which has the said polarizing film with an adhesive layer and a transparent conductive film is laminated | stacked, and this invention is the transparent conductive of the adhesive layer of the said polarizing film with an adhesive layer, and a transparent conductive base material. The present invention relates to a laminate in which a film is in contact.

  The transparent conductive film is preferably formed from indium tin oxide.

  The present invention also relates to an image display device using a laminate.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基である）
で表される化合物を、前記（メタ）アクリル系ポリマー１００重量部に対して０．００５〜５重量部添加して、架橋することを特徴とするアクリル系粘着剤組成物の架橋促進方法に関する。 Furthermore, the present invention provides a crosslink of an acrylic pressure-sensitive adhesive composition comprising a (meth) acrylic polymer, and one or more crosslinking agents selected from the group consisting of an organic peroxide crosslinking agent and an isocyanate crosslinking agent. A promotion method,
In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1):

(Wherein, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
The present invention relates to a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition, which comprises adding 0.005 to 5 parts by weight of the compound represented by formula (100) by weight to 100 parts by weight of the (meth) acrylic polymer and crosslinking.

  The acrylic pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition comprising at least one crosslinking agent selected from the group consisting of acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents. By adding the compound represented by the general formula (1), the crosslinking reaction of the crosslinking agent is promoted, the three-dimensional crosslinking network of the pressure-sensitive adhesive layer is efficiently formed, and the crosslinking reaction can proceed efficiently. Specifically, when an organic peroxide-based crosslinking agent is used as the crosslinking agent, the addition of the compound represented by the general formula (1) suppresses radical crosslinking inhibition by oxygen and efficiently performs a crosslinking reaction. In addition, when an isocyanate-based crosslinking agent is used as the crosslinking agent, the compound represented by the general formula (1) serves as a catalyst for urethane reaction formation and can efficiently perform the crosslinking reaction. it can. As described above, by using the compound represented by the general formula (1), the crosslinking reaction of the organic peroxide crosslinking agent and / or the isocyanate crosslinking agent is promoted. It is suppressed, processability can be improved, and productivity is excellent.

  Further, the acrylic pressure-sensitive adhesive composition of the present invention has high crosslinking efficiency, and it is not necessary to perform an aging operation in a warmed state or at room temperature after crosslinking.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基である）で表される化合物を含有し、
前記一般式（１）で表される化合物の含有量が、前記（メタ）アクリル系ポリマー１００重量部に対して０．００５〜５重量部であることを特徴とする。 1. Acrylic pressure-sensitive adhesive composition The acrylic pressure-sensitive adhesive composition of the present invention is one or more cross-linking agents selected from the group consisting of (meth) acrylic polymers, organic peroxide-based cross-linking agents, and isocyanate-based cross-linking agents. And the following general formula (1):

(Wherein, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom). And
The content of the compound represented by the general formula (1) is 0.005 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.

In the present invention, phosphoric acid (H ₃ PO ₄ ) in which R ¹ and R ² are hydrogen atoms in general formula (1) can also be used, and the phosphoric acid salts (sodium, potassium, and Metal salts such as magnesium, ammonium salts, etc.) can also be suitably used.

In the present invention, a phosphate ester in which at least ^one of R ¹ and R ^{2 in} the general formula (1) may contain an oxygen atom and is a hydrocarbon residue having 1 to 18 carbon atoms is also suitable. Can be used. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,- (CH ₂ CH ₂ O) _n R ³ (R ³ is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15). The alkyl group and alkenyl group may be linear or branched.

（式中、Ｒ^１は、前記同様であり、Ｒ^３は、炭素数１〜１８のアルキル基、又は、アルケニル基であり、ｎは０〜１５の整数である。）で表されるリン酸エステルが好ましい。 In the present invention, examples of the compound represented by the general formula (1) include the following general formula (2):

(Wherein, R ¹ is the same as above, R ³ is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15). Esters are preferred.

Examples of R ³ include an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and an alkyl group having 1 to 18 carbon atoms is preferable. Moreover, n is an integer of 0-15, and it is preferable that it is an integer of 0-10.

In the present invention, two or more compounds represented by the general formula (1) may be mixed and used, and phosphoric acid (R ¹ = R ² = hydrogen atom), a mixture of monoester and diester May be used. In general, the phosphoric acid ester represented by the general formula (2) is a monoester (R ¹ = hydrogen atom) and a diester (R ¹ = a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom). As a mixture of

  In the present invention, a salt of a compound represented by the general formula (2) (a metal salt such as sodium, potassium and magnesium, an ammonium salt, etc.) can also be suitably used.

  In addition, the acid value of the phosphate ester used in the present invention is preferably 80 to 900 mgKOH / g, more preferably 80 to 700 mgKOH / g, still more preferably 80 to 600 mgKOH / g, More preferably, it is -500 mgKOH / g, More preferably, it is 100-400 gKOH / g, It is especially preferable that it is 150-300 mgKOH / g. If the acid value of the phosphate ester is too high, when an isocyanate crosslinking agent is used as the crosslinking agent, it may act as a crosslinking reaction catalyst for the isocyanate crosslinking agent, and the pressure-sensitive adhesive composition will gel. The pot life of the pressure-sensitive adhesive composition tends to be shortened. By making the acid value of the phosphate ester within the above range, the pot life of the pressure-sensitive adhesive composition can be sufficiently ensured, and in the crosslinking step, the crosslinking agent can be promoted to be crosslinked, from the initial stage of production, The gel fraction of the pressure-sensitive adhesive layer can be increased, and as a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.

As a commercial item of the phosphate ester represented by the general formula (2), “Phosphanol SM-172” (R ¹ = R ³ = C ₈ H of the general formula (2) manufactured by Toho Chemical Industry Co., Ltd.) ₁₇ , n = 0, mono-di mixture, acid value: 219 mg KOH / g), “phosphanol GF-185”
(R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 0, mono-di mixture, acid value: 158 mgKOH / g), “phosphanol BH-650” (in general formula (2) R ¹ = R ³ = C ₄ H ₉ , n = 1, mono-di mixture, acid value: 388 mgKOH / g), “phosphanol RS-410” (R ¹ = R ³ = C in formula (2) ₁₃ H ₂₇ , n = 4, mono-di mixture, acid value: 105 mg KOH / g), “phosphanol RS-610” (R ¹ = C ₁₃ H ₂₇ in general formula (2), R ³ = C ₁₃ H ₂₇ , n = 6, mono-di mixture, acid value: 82 mg KOH / g), “phosphanol ML-220” (R ¹ = R ³ = C ₁₂ H ₂₅ in general formula (2), n = 2, mono・ Dimix), “Phosphanol ML-200” (of general formula (2) _{^{1 = R 3 = C 12 H}} 25, n = 0, mono di _{^{mixture), R 1 = R 3 =}} C 8 H 17 of "Phosphanol ED-200" (the general formula (2), n = 1, Mono-di mixture), “phosphanol RL-210” (R ¹ = R ³ = C ₁₈ H _{37 of} general formula (2), n = 2, mono-di mixture), “phosphanol GF-339 ( R ¹ = R ³ = C ₆ H _{13 to} C ₁₀ H ₂₁ in formula (2), n = 0, mono-di mixture), “phosphanol GF-199” (R in formula (2) ¹ = R ³ = C ₁₂ H ₂₅ , n = 0, mono-di mixture), “phosphanol RL-310” (R ¹ = R ³ = C ₁₈ H ₃₇ in general formula (2), n = 3, R mono di mixture), Nikko Chemicals Co., Ltd. "Nikkol DDP-2" (formula (2) = Mixture of _{^{R 3 = C 12 H 25 ~C}} 15 H 31, n = 2), R 1 = R 3 = C 8 of Johoku Chemical Co., Ltd. "JP-508" (the general formula (2) _{H 17} , N = 0, mono-di mixture, acid value: 288 mg KOH / g), “JP-513” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 0, mono-di mixture) “JP-524R” (R ¹ = R ³ = C ₂₄ H ₄₉ in general formula (2), n = 0, mono-di mixture), “DBP” (R ¹ = R ^{3 in} general formula (2) = C ₄ H ₉ , n = 0, diester, acid value: 266 mg KOH / g), “LB-58” (R ¹ = R ³ = C ₈ H ₁₇ in general formula (2), n = 0, diester, acid value ^{: 173mgKOH / g), R 1} = R 3 = C 4 H 9 of Daihachi chemical industry Co., Ltd. "AP-4" (formula (2), = 0, mono di mixture acid value: 452mgKOH / g), "DP-4" _{^{R 1 = R 3 = C 4}} H 9, n = 0 in (formula (2), mono di mixture acid number : 290 mgKOH / g), “MP-4” (R ¹ = H, R ³ = C ₄ H ₉ , n = 0 in the general formula (2), mono-di mixture, acid value: 670 mgKOH / g), “AP −8 ”(R ¹ = R ³ = C ₈ H _{17 in} the general formula (2), n = 0, mono-di mixture, acid value: 306 mgKOH / g),“ MP-8 ”(in the general formula (2) R ¹ = R ³ = C ₁₀ H ₂₁ , n = 0, diester, acid value: 400 mgKOH / g) and the like and salts thereof. Incidentally, the "mono-di mixture" may include R ^{1 =} an oxygen atom (R ^{1 =} H in the general formula (2)) and diesters monoester (Formula (2), 1 carbon atoms For example, in the case of phosphanol SM-172, monoesters (R ¹ = H, R ³ = C ₈ H in the general formula (2)) are shown. ₁₇ , n = 0) and a diester (R ¹ = R ³ = C ₈ H _{17 in} the general formula (2), n = 0). The mixing ratio of the monoester and diester of the “mono / di mixture” can be calculated from the measurement result of ³¹ P-NMR. The measuring method is as described in the examples.

The phosphate ester used in the present invention is a compound selected from the group consisting of a compound represented by the general formula (1) (or a compound represented by the general formula (2)), or a salt or multimer thereof. May be used alone or in admixture of two or more. However, phosphoric acid, phosphoric acid monoester, and phosphorus may be used from the viewpoint of reducing the addition amount and obtaining a better effect. It is preferably a mixture of two or more selected from the group consisting of acid diesters. Moreover, it can also be used as a mixture containing phosphoric acid and phosphoric acid monoester. Here, the phosphoric acid monoester is a carbon atom having 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrogen residue (in the case of the general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} the general formula (1) are oxygen atoms A compound which is a hydrocarbon residue having 1 to 18 carbon atoms which may be contained (in the case of the general formula (2), R ¹ may contain an oxygen atom, and the hydrocarbon residue having 1 to 18 carbon atoms may be contained) Compound which is a group).

  In the present invention, phosphoric acid can be further added to the phosphoric ester compound, and the amount of phosphoric acid added in that case is the phosphoric ester compound 100 from the viewpoint of the pot life of the pressure-sensitive adhesive composition. The amount is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 20 parts by weight or less with respect to parts by weight. In addition, the lower limit of the addition amount of phosphoric acid is not particularly limited, and is added to the extent that it does not affect the pot life of the pressure-sensitive adhesive composition, and used to adjust the acid value of the phosphoric acid compound. Can do.

  In the present invention, a compound represented by the general formula (1) or a multimer such as a dimer or trimer of a phosphate ester represented by (2) can also be used.

  The addition amount of the compound represented by the general formula (1) is preferably 0.005 to 5 parts by weight, and 0.01 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer described later. More preferably, it is 0.01-3 weight part, More preferably, it is 0.01-2.5 weight part, It is especially preferable that it is 0.01-1 weight part. When the amount of the compound represented by the general formula (1) is less than 0.005 parts by weight, the effects of the present invention tend not to be obtained. Since the durability of the obtained pressure-sensitive adhesive layer tends to decrease, it is not preferable. In the present invention, two or more compounds represented by the general formula (1) can be used. In that case, the total amount can be added within the above range.

  The (meth) acrylic polymer used in the present invention is not particularly limited. For example, the (meth) acrylic polymer is preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate. It is preferably obtained by polymerizing a monomer component containing a (meth) acrylate and a hydroxyl group-containing monomer. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

  As the alkyl group related to the alkyl (meth) acrylate, various linear or branched ones can be used. Specific examples of the alkyl (meth) acrylate include, for example, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n- Nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-tride Le (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, or dodecyl (meth) acrylate and the like. These can be used alone or in combination. Among these, the alkyl (meth) acrylate which has a C4-C18 alkyl group is preferable, the (meth) acrylate which has a C4-C10 alkyl group is more preferable, n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate is more preferred, and n-butyl acrylate is particularly preferred.

  The alkyl (meth) acrylate is preferably 50 parts by weight or more, preferably 60 parts by weight or more, and 70 parts by weight or more with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Is more preferably 80 parts by weight or more, further preferably 90 parts by weight or more, and particularly preferably 95 parts by weight or more.

Moreover, as a hydroxyl group containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a hydroxyl group can be especially used without a restriction | limiting. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and the like. Can be used alone or in admixture of two or more. Among these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable. Moreover, when using an isocyanate type crosslinking agent as a crosslinking agent mentioned later, a crosslinking point with the isocyanate group of an isocyanate type crosslinking agent can be efficiently ensured by using 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer. This is preferable because it is possible.

  The hydroxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 1 to 3 parts by weight is more preferable.

  The monomer component forming the (meth) acrylic polymer used in the present invention may contain the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, and optionally the hydroxyl group-containing monomer. However, besides these monomers, a carboxyl group-containing monomer and other copolymerization monomers can be used as the monomer component.

  As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These may be used alone or in combination. Can be used.

  The carboxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 6 parts by weight or less, still more preferably 2 parts by weight or less, based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 0.5 parts by weight or less is particularly preferable. Moreover, although a lower limit is not specifically limited, For example, it is preferable that it is 0.01 weight part or more.

  The other copolymerization monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, for example, an alkyl having 1 to 3 carbon atoms. (Meth) acrylic alicyclic hydrocarbon esters such as alkyl (meth) acrylate having a group, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate; for example, (meth) acrylic acid (Meth) acrylic acid aryl esters such as phenyl; vinyl esters such as vinyl acetate and vinyl propionate; styrenic monomers such as styrene; for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate Epoxy group-containing monomers such as methoxy (meth) acrylate Alkyl group-containing monomers such as til and ethoxyethyl (meth) acrylate; for example, cyano group-containing monomers such as acrylonitrile and methacrylonitrile; for example, functional monomers such as 2-methacryloyloxyethyl isocyanate; for example, ethylene, propylene, Examples thereof include olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as vinyl ether; and halogen atom-containing monomers such as vinyl chloride.

Examples of copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N -Itacone imide monomers such as butyl itaconimide, N-octyl itacon imide, N-2-ethylhexyl itacon imide, N- cyclohexyl itacon imide, N- lauryl itacon imide; Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid, Examples include sulfonic acid group-containing monomers such as aryl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalene sulfonic acid. .

  In addition, as the copolymerizable monomer, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate Other examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.

  Furthermore, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc. (mono or poly) In addition to (mono or poly) alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate. In addition, as a polyfunctional monomer, polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.

  The proportion of the other copolymerization monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 10 parts by weight or less is particularly preferable. When the ratio of the copolymerization monomer is too large, the adhesive properties such as reduced adhesion to various adherends such as glass and film of the adhesive layer formed from the acrylic adhesive composition, and transparent conductive film, etc. May decrease.

  The weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1,200,000 to 3,000,000, more preferably 1,200,000 to 2,700,000, and even more preferably 1,200,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it may not be preferable in terms of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) acrylic polymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties. On the other hand, if the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range. The weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).

  The production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations, and is not particularly limited. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

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

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

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2). -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di sec-butyl peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t- Hexylperoxy) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, And redox initiators combined with reducing agents. But it is not limited thereto.

  The polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is 100 weight of monomer component forming the (meth) acrylic polymer. The amount is preferably about 0.005 to 1 part by weight with respect to parts.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to

  Various silane coupling agents can be added to the acrylic pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high-temperature and high-humidity conditions. As the silane coupling agent, one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N-phenyl-γ Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane; γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silane coupling agents; p-styryltrimethoxysilane and other styryl group-containing silane coupling agents; (Meth) acrylic group-containing silane coupling agents such as acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane; bis (triethoxysilyl) And polysulfide group-containing silane coupling agents such as propyl) tetrasulfide.

  The silane coupling agent may be used alone or in combination of two or more, but the total content is 100% of all monomer components constituting the (meth) acrylic polymer. The amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight, and more preferably 0.05 to Particularly preferred is 0.7 part by weight. When the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.

  In addition, when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. It is preferable that the ratio is 0.005-0.7 weight part with respect to 100 weight part of all the monomer components which comprise the said (meth) acrylic-type polymer.

  Furthermore, the acrylic pressure-sensitive adhesive composition of the present invention contains one or more types of cross-linking agents selected from the group consisting of organic peroxide cross-linking agents and isocyanate cross-linking agents. Addition is preferable because cohesive force related to the durability of the pressure-sensitive adhesive layer can be imparted.

  Any organic peroxide crosslinking agent can be used as long as it generates radical active species by heating or light irradiation to promote crosslinking of the base polymer of the pressure-sensitive adhesive composition. In view of the above, it is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C., more preferably 90 ° C. to 140 ° C.

  Examples of peroxides that can be used include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl Oxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C), dibenzoyl peroxide (half-minute for 1 minute) Period temperature: 130.0 ° C.), t-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C.). Among them, dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) is preferably used because of particularly excellent crosslinking reaction efficiency.

  The peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic Peroxide Catalog No. 9 of Nippon Oil & Fats Co., Ltd.” Edition (May 2003) ".

  The content of the organic peroxide crosslinking agent is preferably 0.05 to 2 parts by weight and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If the amount is less than 0.05 parts by weight, the required properties of the crosslinked structure tend not to be obtained. On the other hand, if the amount exceeds 2 parts by weight, the pressure-sensitive adhesive layer may contain peroxides or decomposition products thereof. Since durability characteristics tend to decrease, it is not preferable.

  The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in a molecule (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by a blocking agent or quantification).

  Examples of the isocyanate-based crosslinking agent include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and trimethylolpropane. And the like, and isocyanate compounds added with isocyanurates, burette type compounds, and urethane prepolymer type isocyanates such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols that have undergone addition reaction. . Particularly preferred is a polyisocyanate compound, which is one or a polyisocyanate compound derived from one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. Here, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified is selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom. Examples include hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate.

  Commercially available isocyanate crosslinking agents include trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct. (Product name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), Isocyanurate of hexamethylene diisocyanate (Product name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), xylylene diisocyanate trimethylol Examples thereof include a propane adduct (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), a trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals, Inc.), and the like.

  The content of the isocyanate crosslinking agent is preferably 0.02 to 2 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If the amount is less than 0.02 parts by weight, the required properties of the crosslinked structure tend not to be obtained. On the other hand, if the amount is more than 2 parts by weight, the pressure-sensitive adhesive becomes hard because the crosslinked structure becomes dense, As a result, there is a tendency that physical properties such as durability and adhesive strength tend not to be satisfied.

  In the present invention, either an organic peroxide crosslinking agent or an isocyanate crosslinking agent may be used, or may be used in combination, but an organic peroxide crosslinking agent or an isocyanate crosslinking agent is used in combination. By doing so, a crosslinking reaction can be efficiently performed, and adhesive residue at the time of processing is reduced, which is preferable.

  When using together an organic peroxide type crosslinking agent and an isocyanate type crosslinking agent, it is preferable that content of an isocyanate type crosslinking agent is 5-1000 weight part with respect to 100 weight part of organic peroxide type crosslinking agents. More preferably, it is 20 to 300 parts by weight.

  Moreover, as a crosslinking agent, another crosslinking agent can be used with the said peroxide type crosslinking agent and an isocyanate type crosslinking agent. As other crosslinking agents, polyfunctional compounds are used, and organic crosslinking agents and polyfunctional metal chelates are exemplified. Examples of the organic crosslinking agent include an epoxy crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide type crosslinking agent and an isocyanate type crosslinking agent are preferable, and it is more preferable to use these in combination.

  The addition amount of the other crosslinking agent is not particularly limited, and can be added within a range not impairing the effects of the present invention. For example, the amount of the (meth) acrylic polymer (solid content) is 100 parts by weight. On the other hand, it can mix | blend in the ratio of about 1 weight part or less.

  Furthermore, the acrylic pressure-sensitive adhesive composition used in the present invention includes, as necessary, a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others. Various kinds of fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, etc., which do not depart from the object of the present invention. These additives can also be used as appropriate. These additives can also be blended as an emulsion.

2. Method for producing acrylic pressure-sensitive adhesive layer The method for producing the acrylic pressure-sensitive adhesive layer of the present invention comprises a step of applying the acrylic pressure-sensitive adhesive composition on a substrate, and
It includes a step of forming a pressure-sensitive adhesive layer by crosslinking an acrylic pressure-sensitive adhesive composition applied on a substrate.

  As the acrylic pressure-sensitive adhesive composition, those described above can be used.

  The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.

  Various methods are used as a coating method on the substrate or polarizing film. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Daiko Examples of the method include an extrusion coating method using a catalyst.

  The crosslinking temperature can be appropriately set depending on the composition and concentration of the acrylic pressure-sensitive adhesive composition, but is preferably 70 to 170 ° C, more preferably 90 to 165 ° C, and further preferably 140 to 160 ° C. The crosslinking time can also be appropriately set depending on the composition, concentration, etc. of the acrylic pressure-sensitive adhesive composition, but is preferably 30 to 240 seconds, and more preferably 60 to 180 seconds. It is preferable that the crosslinking condition is within the above range because the crosslinking reaction is efficiently performed.

  The thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 μm, more preferably 10 to 60 μm, and further preferably 12 to 40 μm. When the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the acrylic pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer cannot be fully dried at the time of drying and air bubbles remain, or the pressure-sensitive adhesive layer There is a tendency that unevenness in thickness occurs on the surface of the surface, and problems in appearance tend to become obvious.

  Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.

  Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -A vinyl acetate copolymer film etc. are mentioned.

  The thickness of the release film is usually 5 to 200 μm, and more preferably about 5 to 100 μm. For the release film, if necessary, release agent and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.

  The transparent resin film substrate is not particularly limited, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

  The thickness of the film substrate is preferably 15 to 200 μm.

3. Acrylic pressure-sensitive adhesive layer The acrylic pressure-sensitive adhesive layer of the present invention is produced by the method for producing an acrylic pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive layer obtained by the method for producing an acrylic pressure-sensitive adhesive layer of the present invention is obtained by crosslinking an acrylic pressure-sensitive adhesive composition containing a compound represented by the general formula (1). Since the compound represented by the general formula (1) has a cross-linking promoting effect of a cross-linking agent such as an isocyanate cross-linking agent or an organic peroxide cross-linking agent, the acrylic pressure-sensitive adhesive layer of the present invention is produced from the initial stage of production. The gel fraction of the pressure-sensitive adhesive layer can be increased. As a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.

  The gel fraction of the acrylic pressure-sensitive adhesive layer of the present invention is preferably 60 to 95% by weight, more preferably 65 to 90% by weight, and 70 to 90% by weight 5 days after crosslinking. More preferably. The gel fraction after 2 hours after crosslinking is preferably 55 to 85% by weight, more preferably 60 to 85% by weight, and 65 to 85% by weight from the viewpoint of processability. Is more preferable. A gel fraction within the above range is preferable from the viewpoints of workability and productivity. In addition, when the gel fraction after 2 hours after crosslinking is less than 55% by weight, the pressure-sensitive adhesive layer is too soft. If processing is performed in this state, problems such as sticking of the blade during processing occur. Tend to. Furthermore, since a dent is generated in the winding process of the pressure-sensitive adhesive layer after cross-linking and a problem occurs in appearance, the productivity tends to be inferior. In addition, the measurement of the gel fraction of an adhesive layer can be performed by the method as described in an Example.

  The change rate of the gel fraction (the gel fraction after 5 days after cross-linking / the gel fraction after 2 hours after cross-linking) is preferably 1.35 or less, more preferably 1-1.35. 1 to 1.30 is more preferable, and 1 to 1.25 is particularly preferable. When the change rate of the gel fraction is within the above range, the cross-linking reaction proceeds quickly, and stable physical properties are obtained 2 hours after the cross-linking reaction, which is preferable from the viewpoint of aging and workability.

4). The polarizing film with an adhesive layer The polarizing film with an adhesive layer of this invention has the said acrylic adhesive layer on the at least single side | surface of a polarizing film, It is characterized by the above-mentioned.

  The method for laminating the pressure-sensitive adhesive layer on the polarizing film is not particularly limited. As described above, the acrylic pressure-sensitive adhesive layer is formed on various substrates, and the pressure-sensitive adhesive layer is transferred onto the polarizing film. Alternatively, the acrylic pressure-sensitive adhesive composition may be applied directly on the polarizing film to form a pressure-sensitive adhesive layer. In addition, the formation method of an adhesive layer is as above-mentioned.

  The polarizing film may be a single-sided protective polarizing film having a transparent protective film on one side of the polarizer or a double-sided protective polarizing film having transparent protective films on both sides of the polarizer. When is used, the pressure-sensitive adhesive layer can be directly provided on the surface of the polarizer on the side not having the transparent protective film.

  The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

  In the present invention, a thin polarizer having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing plate can be reduced.

  As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. , WO 2010/100917 pamphlet, or Patent 4751481 specification or JP 2012-073563 A, which is obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution which is described in the specification of 4751481 or Unexamined-Japanese-Patent No. 2012-073563 is preferable.

  As a material for forming a transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

  Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin film property.

  The polarizer and the transparent protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

  The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.

  Moreover, you may have an anchor layer between a polarizing film and an adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, polymers are particularly preferably used. The polymer may be used in any of a solvent-soluble type, a water-dispersed type, and a water-soluble type.

  Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, polystyrene resins, and the like. Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferable. These resins can be appropriately mixed with a crosslinking agent. These other binder components can be used singly or in combination of two or more as appropriate.

  When the anchor layer is formed of a water dispersion type material, a water dispersion type polymer is used. Examples of the water-dispersible polymer include those obtained by emulsifying various resins such as polyurethane and polyester using an emulsifier, and introducing a water-dispersible anionic group, cationic group, or nonionic group into the resin. Examples include self-emulsified ones.

  The anchor agent can contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material that can impart conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. Among these, a conductive polymer is preferable, and a water-dispersible conductive polymer is more preferable.

  Examples of water-soluble conductive polymers include polyaniline sulfonic acid (weight average molecular weight of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.). Examples of water-dispersible conductive polymers include polythiophene-based conductive polymers (Nagase Chemtech Co., Ltd.). ) And Denatron series).

  The blending amount of the antistatic agent is, for example, preferably 70 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the polymers used for the anchor agent. From the viewpoint of the antistatic effect, it is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more.

  The thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.

  The method for forming the anchor layer is not particularly limited and can be performed by a generally known method. In forming the anchor layer, the polarizing film can be activated. Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.

  The method for forming the pressure-sensitive adhesive layer on the anchor layer on the polarizing film is as described above.

  Moreover, when the adhesive layer of the polarizing film with an adhesive layer of this invention is exposed, you may protect an adhesive layer with a release film (separator) until it uses for practical use. The above-mentioned thing can be mentioned as a release film. When a release film is used as a base material in the production of the above-mentioned pressure-sensitive adhesive layer, the release film is polarized with a pressure-sensitive adhesive layer by laminating the pressure-sensitive adhesive layer on the release film and the polarizing film. It can be used as a release film for the pressure-sensitive adhesive layer of the film, and the process can be simplified.

  Moreover, the polarizing film with an adhesive layer of this invention can suppress corrosion of a transparent conductive film, when a transparent conductive film is laminated | stacked on the adhesive layer of the said polarizing film with an adhesive layer, The surface of a transparent conductive film It is possible to suppress an increase in resistance. This is because the phosphoric acid compound contained in the pressure-sensitive adhesive layer selectively adsorbs on the surface of the transparent conductive film to form a film, so that a substance that corrodes the transparent conductive film such as acid migrates to the surface of the transparent conductive film. As a result, it is considered that corrosion of the transparent conductive film is hindered.

5. Laminated body In the laminated body of the present invention, the polarizing film with an acrylic adhesive layer and a transparent conductive film are laminated, and the adhesive layer of the polarizing film with an acrylic adhesive layer and the transparent conductive film are in contact with each other. Features.

  The said polarizing film with an adhesive layer can use the above-mentioned thing.

  The substrate having a transparent conductive film is not particularly limited, and a known material can be used. Generally, a substrate having a transparent conductive film on a transparent substrate is used.

  The transparent substrate may be any material as long as it has transparency, and examples thereof include a resin film and a substrate made of glass (for example, a sheet-like, film-like, or plate-like substrate). A film is particularly preferred. Although the thickness of a transparent base material is not specifically limited, About 10-200 micrometers is preferable and about 15-150 micrometers is more preferable.

  Although it does not restrict | limit especially as a material of the said resin film, Various plastic materials which have transparency are mentioned. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

  In addition, the transparent base material is subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, and undercoating treatment on the surface in advance, and the transparent conductive film provided thereon You may make it improve the adhesiveness with respect to a transparent base material. Moreover, before providing a transparent conductive film, you may remove and clean by solvent washing | cleaning, ultrasonic cleaning, etc. as needed.

  The constituent material of the transparent conductive film is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide and tin oxide containing antimony are preferably used, and ITO is particularly preferably used. As ITO, it is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide.

  Examples of the ITO include crystalline ITO and non-crystalline (amorphous) ITO, both of which can be suitably used.

  The thickness of the transparent conductive film is not particularly limited, but is preferably 10 nm or more, more preferably 15 to 40 nm, and even more preferably 20 to 30 nm.

  It does not specifically limit as a formation method of the said transparent conductive film, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.

  As thickness of the base material which has the said transparent conductive film, 15-200 micrometers can be mentioned. Furthermore, it is preferable that it is 15-150 micrometers from a viewpoint of thin film formation, and it is more preferable that it is 15-50 micrometers. When the base material having the transparent conductive film is used in a resistive film method, for example, a thickness of 100 to 200 μm can be given. In addition, when used in the electrostatic capacity method, for example, a thickness of 15 to 100 μm is suitable, in particular, a thickness of 15 to 50 μm is more preferable, and a thickness of 20 to 50 μm is more preferable in accordance with the recent demand for further thinning. .

  Moreover, an undercoat layer, an oligomer prevention layer, etc. can be provided between a transparent conductive film and a transparent base material as needed.

6). Image display device The laminate of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) provided with an input device (touch panel, etc.), input device Although it can be used suitably in manufacture of the base material (member) which comprises apparatuses, such as (a touch panel etc.), or the base material (member) used for these apparatuses, it is especially suitable in manufacture of the optical base material for touch panels. Can be used. Moreover, it can be used irrespective of systems, such as a touch panel, such as a resistive film system and a capacitive system.

  The laminated body of the present invention is subjected to treatments such as cutting, resist printing, etching, and silver ink printing, and the resulting transparent conductive film can be used as a substrate for optical devices (optical member). The substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics. For example, an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), Examples include base materials (members) constituting devices such as electronic paper) and input devices (touch panels, etc.) or base materials (members) used in these devices.

  Moreover, the polarizing film with an adhesive layer of this invention can suppress corrosion of a transparent conductive film also when a transparent conductive film is laminated | stacked on the adhesive layer of the said polarizing film with an adhesive layer as above-mentioned. Therefore, it can be suitably used for an image display device having a configuration in which the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer is in contact with the transparent conductive film.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基である）で表される化合物を、前記（メタ）アクリル系ポリマー１００重量部に対して０．００５〜５重量部添加して、架橋することを特徴とする。 7). Method for promoting crosslinking of acrylic pressure-sensitive adhesive composition The method for promoting crosslinking of the acrylic pressure-sensitive adhesive composition of the present invention comprises a (meth) acrylic polymer, an organic peroxide-based crosslinking agent, and an isocyanate-based crosslinking agent. A method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition comprising one or more selected crosslinking agents,
In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1):

(Wherein R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom), 0.005-5 weight part is added with respect to 100 weight part of said (meth) acrylic-type polymers, It bridge | crosslinks, It is characterized by the above-mentioned.

  For the compound represented by the general formula (1), one or more crosslinking agents selected from the group consisting of (meth) acrylic polymers, organic peroxides, and isocyanate crosslinking agents, the aforementioned ones should be used. The blending ratio is also as described above. The crosslinking conditions are as described above.

In the crosslinking acceleration method of the acrylic pressure-sensitive adhesive composition of the present invention, one or more crosslinking agents selected from the group consisting of (meth) acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents. In addition, the acrylic pressure-sensitive adhesive composition containing can further promote crosslinking of the acrylic pressure-sensitive adhesive composition by containing the compound represented by the general formula (1). This is because when an organic peroxide-based crosslinking agent is used as a crosslinking agent, the addition of the compound represented by the general formula (1) suppresses radical crosslinking inhibition by oxygen and efficiently performs a crosslinking reaction. In addition, when an isocyanate-based crosslinking agent is used as the crosslinking agent, the compound represented by the general formula (1) serves as a catalyst for urethane reaction formation and can efficiently perform a crosslinking reaction. As described above, by using the compound represented by the general formula (1), the crosslinking reaction of the organic peroxide crosslinking agent and / or the isocyanate crosslinking agent is promoted. It is suppressed, processability can be improved, and productivity is excellent.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In each example, both parts and% are based on weight.

Production Example 1 (Production of Polarizing Film (1))
A stretched laminate was produced by subjecting a laminate in which a polyvinyl alcohol (PVA) layer having a thickness of 9 μm to a non-crystalline polyethylene terephthalate (PET) substrate to a stretching temperature of 130 ° C. by air auxiliary stretching. Next, a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio is 5.94 times. And an optical film laminate comprising a 4 μm thick PVA layer stretched together. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm that constitutes a highly functional polarizer. Furthermore, a 40 μm-thick acrylic resin film (transparent protective film (1)) subjected to saponification treatment was applied to one side of the polarizer of the optical film laminate while applying a polyvinyl alcohol-based adhesive, and then amorphous. The PET substrate was peeled off to produce a polarizing film using a single-side protected thin polarizer. Hereinafter, this is referred to as a polarizing film (1).

Production Example 2 (Production of Polarizing Film (2))
A PVA film having a thickness of 80 μm was stretched up to 3 times while being dyed in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the film was stretched so that the total stretch ratio was 6 times while immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 μm. Further, after applying a saponified 40 μm thick acrylic resin film (transparent protective film (1)) while applying a polyvinyl alcohol-based adhesive on the surface of the polarizer of the optical film laminate, amorphous PET After peeling off the base material, a norbornene-based film (transparent protective film (2)) having a thickness of 40 μm was bonded to the other surface with a polyvinyl alcohol-based adhesive to prepare a double-sided protective polarizing film. Hereinafter, this is referred to as a polarizing film (2).

Production Example 3 (Preparation of a solution containing an acrylic polymer (A-1))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2,2′-azobisisobutyroyl as an initiator 1 part of nitrile (AIBN) is added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate is added to the reaction solution to obtain a weight average. A solution containing an acrylic polymer (A-1) having a molecular weight of 150,000 was obtained (solid content concentration 30% by weight).

Production Examples 4 to 6 (Preparation of solutions containing acrylic polymers (A-2) to (A-4))
A solution containing acrylic polymers (A-2) to (A-4) was obtained in the same manner as in Production Example 3 except that the monomer composition was changed to the composition shown in Table 2 (for each solution, Solid content concentration 30% by weight).

Abbreviations in Table 2 are as follows.
BA: butyl acrylate AA: acrylic acid HEA: 2-hydroxyethyl acrylate HBA: 4-hydroxybutyl acrylate

Moreover, the weight average molecular weight of the acrylic polymer obtained in Production Examples 3 to 6 was measured by the following measuring method.
<Measurement of weight average molecular weight (Mw) of acrylic polymer>
The weight average molecular weight of the prepared acrylic polymer was measured by GPC (gel permeation chromatography).

Device: HLC-8220GPC, manufactured by Tosoh Corporation
column:
Sample column: TSK guard column Super HZ-H manufactured by Tosoh Corporation
(1) + TSKgel Super HZM-H (2)
Reference column; manufactured by Tosoh Corporation, TSKgel Super H-RC (1)
Flow rate: 0.6mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.

Example 1
(Adjustment of acrylic adhesive composition)
As an acrylic polymer (A-1) obtained in Production Example 3, as a crosslinking agent, per 100 parts of solid content of the acrylic polymer solution, an adduct of hexamethylene diisocyanate with trimethylolpropane (trade name: Takenate D160N, Mitsui Chemicals Co., Ltd.) 0.1 part, dibenzoyl peroxide 0.3 part, phosphate ester (trade name: Phosphanol SM-172, Toho Chemical Industry Co., Ltd.) 0.05 part, Γ-glycidoxypropylmethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.075 parts was mixed to obtain an acrylic pressure-sensitive adhesive composition.

(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator which formed the adhesive layer was transferred to the surface which does not have a protective film of a polarizing film (1), and the polarizing film with an adhesive layer was produced.

Examples 2-3
In Example 1 (Adjustment of acrylic pressure-sensitive adhesive composition), the adhesive amount was changed in the same manner as in Example 1 except that the amount of phosphate ester was changed from 0.05 parts to the number of parts shown in Table 3. A polarizing film with an agent layer was produced.

Examples 4-6
In Example 1 (Preparation of polarizing film with pressure-sensitive adhesive layer), except that the drying conditions were changed from 155 ° C. and 120 seconds to the conditions described in Table 3, the same as in Example 1 was followed. A polarizing film was produced.

Example 7
In Example 1 (adjustment of acrylic pressure-sensitive adhesive composition), 0.05 part of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was added to phosphanol RS-410 (trade name, A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the acid value was changed to 0.05 part (acid value: 105 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.).

Example 8
In Example 1 (Adjustment of acrylic pressure-sensitive adhesive composition), 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was added to phosphoric acid (special grade reagent) (Wako Pure Chemical Industries, Ltd.). A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the amount was changed to 0.05 part (produced by Kogyo Co., Ltd.).

Examples 9-11
In Example 1 (adjustment of the acrylic pressure-sensitive adhesive composition), the solutions containing the acrylic polymer (A-1) obtained in Production Example 3 were used as the acrylics obtained in Production Examples 4 to 6, respectively. Except for changing to a solution containing the polymers (A-2) to (A-4) and changing the blending amount of the phosphate ester from 0.05 part to 0.1 part, the same as in Example 1. Thus, a polarizing film with an adhesive layer was produced.

Example 12
In Example 1 (Preparation of polarizing film with pressure-sensitive adhesive layer), the polarizing film (1) was changed to the polarizing film (2) obtained in Production Example 2, and the same procedure as in Example 1 was followed. A polarizing film with an agent layer was produced.

Example 13
In Example 1 (production of polarizing film with pressure-sensitive adhesive layer), the addition amount of adduct body (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.) of hexamethylene diisocyanate with trimethylolpropane is from 0.1 part. A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.12 parts and dibenzoyl peroxide was not added.

Example 14
In Example 1 (production of polarizing film with pressure-sensitive adhesive layer), the amount of dibenzoyl peroxide added was changed from 0.3 part to 0.4 part, and hexamethylene diisocyanate was adducted with trimethylolpropane. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.) was not added.

Example 15
In Example 1 (adjustment of acrylic pressure-sensitive adhesive composition), 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) and MP-4 (trade name, acid value: A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.05 part (670 mg KOH / g, mono / di mixture, manufactured by Daihachi Chemical Industry Co., Ltd.).

Comparative Example 1
In Example 1 (Adjustment of acrylic pressure-sensitive adhesive composition), a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the phosphate ester was not added.

Comparative Example 2
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that phosphate ester and dibenzoyl peroxide were not added in (Adjustment of acrylic pressure-sensitive adhesive composition) in Example 1.

Comparative Examples 3 and 4
In Example 1 (Adjustment of acrylic pressure-sensitive adhesive composition), the phosphoric acid ester was not added, and in (Preparation of polarizing film with pressure-sensitive adhesive layer), the drying conditions were changed from 155 ° C. for 120 seconds to Table 3. A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the conditions were changed to those described in 1. above.

The phosphoric acid compounds used in Examples and Comparative Examples were analyzed as follows. The results are shown in Table 3.
(Analysis method)
The composition of the phosphoric acid compound used in Examples and Comparative Examples was calculated based on the measurement results of ³¹ P-NMR (Acetone-d6, room temperature). After calculating mol% from the integrated value of the peak obtained by measurement, the content ratio (% by weight) was calculated from the alkyl chain of the alcohol component of the ester.
⁽³¹ P-NMR measurement conditions)
Measuring apparatus: Bruker Biospin, AVANCE III-400
Observation frequency: 160 MHz ( ³¹ P)
Flip angle: 30 °
Measurement solvent: Acetone-d6 (heavy acetone)
Measurement temperature: room temperature chemical shift standard: P = (OCH ₃ ) ₃ in Acetone-d6 ( ³¹ P; 140 ppm external standard)

In Table 3, the phosphoric acid monoester has 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrocarbon residue (in the case of general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} general formula (1) are oxygen atoms A compound having a carbon residue of 1 to 18 carbon atoms (in the case of general formula (2), R ¹ may contain an oxygen atom and a hydrocarbon group having 1 to 18 carbon atoms) Compound that is a residue). For example, in the case of phosphanol SM-172, the “monoester” is a compound in which R ¹ = H, R ³ = C ₈ H ₁₇ and n = 0 in the general formula (2), A compound in which R ¹ = R ³ = C ₈ H ₁₇ in formula (2) and n = 0 is shown.

<Measurement of gel fraction>
About the acrylic adhesive composition obtained by the Example and the comparative example, it processed on the same dry conditions (temperature, time) as each Example and the comparative example, forms an adhesive layer, and also temperature 23 degreeC and humidity 65 Fluorine resin film (TEMISH NTF-1122, manufactured by Nitto Denko Corp.) after taking 0.2 g of the pressure-sensitive adhesive layer and measuring the weight in advance after leaving it under the condition of% RH for 2 hours and after leaving it for 5 days Wrapped in (weight: Wa) and tied so that the acrylic pressure-sensitive adhesive composition did not leak. This is a measurement sample. The measurement sample was weighed (weight: Wb) and placed in a sample bottle. 40 cc of ethyl acetate was added to the sample bottle and left for 7 days. Thereafter, a measurement sample (fluororesin film + acrylic pressure-sensitive adhesive composition) was taken out, and the measurement sample was dried on an aluminum cup at 130 ° C. for 2 hours. The weight (Wc) of the measurement sample was measured, and the gel fraction was determined by the following formula.

<Processability>
About the polarizing film with the pressure-sensitive adhesive layer obtained in the examples and the comparative examples, what was punched into a square having a length of 270 mm on one side within 24 hours after the production was observed visually and by hand, It was judged whether or not there was a sticky feeling and whether or not the surface of the polarizing film was soiled by the adhesive.
(Double-circle): The stain | pollution | contamination by an adhesive is not seen.
○: Stain due to adhesive is not problematic.
(Triangle | delta): There exists a feeling of adhesion and some stains are confirmed.
X: There is a sticky feeling, and dirt is confirmed on most of the end portions.

<Pot life>
In Examples and Comparative Examples, the sample was allowed to stand for 12 hours after the addition of the cross-linking agent, and then the coated material was judged according to the following criteria.
A: There was no problem in the appearance of the coated material.
○: Slightly irregularities are observed on the appearance of the coated material.
X: A large lump of gel is confirmed in appearance, or the blended solution is gelled.

<Durability test of adhesive (peeling and foaming)>
The separator film of the adhesive polarizing film sample obtained in Examples and Comparative Examples was peeled off and bonded to non-alkali glass, and after autoclaving at 50 ° C., 5 atm for 15 minutes, a 85 ° C. heating oven and 60 ° C. / 90% RH constant temperature and humidity machine. The peeling and foaming of the polarizing plate after 500 hours were visually observed and judged according to the following criteria.
A: No peeling or foaming was observed.
○: Exfoliation or foaming that could not be confirmed visually occurred.
Δ: Small peeling or foaming that can be visually confirmed occurred.
X: Clear peeling or foaming was recognized.

Abbreviations in Table 4 are as follows.
B-1: Phosphanol SM-172, acid value: 219 mg KOH / g (manufactured by Toho Chemical Industry Co., Ltd.)
B-2: Phosphanol RS-410, acid value: 105 mgKOH / g (manufactured by Toho Chemical Industry Co., Ltd.)
B-3: Phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.)
B-4: MP-4, acid value: 670 mg KOH / g, mono-di mixture, manufactured by Daihachi Chemical Industry Co., Ltd .: dibenzoyl peroxide isocyanate system: adduct form of hexamethylene diisocyanate with trimethylolpropane (Product name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.)
Silane coupling agent: γ-glycidoxypropylmethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (15)

One or more crosslinking agents selected from the group consisting of (meth) acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents, and the following general formula (1):

(Wherein, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
Containing a compound represented by
Content of the compound represented by the said General formula (1) is 0.005-5 weight part with respect to 100 weight part of said (meth) acrylic-type polymers, The acrylic adhesive composition characterized by the above-mentioned. The pressure-sensitive adhesive composition according to claim 1, wherein the compound represented by the general formula (1) is a phosphate ester having an acid value of 80 to 900 mgKOH / g. The acrylic pressure-sensitive adhesive composition according to claim 1 or 2, comprising 0.05 to 2 parts by weight of the organic peroxide-based crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer. . The acrylic pressure-sensitive adhesive composition contains an organic peroxide crosslinking agent and an isocyanate crosslinking agent, and the content of the isocyanate crosslinking agent is 5 to 1000 with respect to 100 parts by weight of the organic peroxide crosslinking agent. It is a weight part, The acrylic adhesive composition in any one of Claims 1-3 characterized by the above-mentioned. The acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the (meth) acrylic polymer has a weight average molecular weight of 1,200,000 to 3,000,000. The step of applying the acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 5 on a substrate, and the pressure-sensitive adhesive layer formed by crosslinking the acrylic pressure-sensitive adhesive composition applied on the substrate. The manufacturing method of the acrylic adhesive layer characterized by including a process. The method for producing an acrylic pressure-sensitive adhesive layer according to claim 6, wherein the crosslinking is performed by heating at 70 to 170 ° C. for 30 to 240 seconds. An acrylic pressure-sensitive adhesive layer produced by the method for producing an acrylic pressure-sensitive adhesive layer according to claim 6. The acrylic pressure-sensitive adhesive layer according to claim 8, wherein a gel fraction after crosslinking is 5 to 95% by weight after 5 days. The acrylic pressure-sensitive adhesive layer according to claim 8 or 9, wherein a gel fraction after crosslinking for 2 hours is 55 to 85% by weight. A polarizing film with a pressure-sensitive adhesive layer, comprising the acrylic pressure-sensitive adhesive layer according to claim 8 on at least one surface of the polarizing film. The polarizing film with an adhesive layer of Claim 11 and the transparent conductive base material which has a transparent conductive film are laminated | stacked, The adhesive layer of the polarizing film with an adhesive layer and the transparent conductive film of a transparent conductive base material A laminate characterized by contacting. The laminate according to claim 12, wherein the transparent conductive film is made of indium tin oxide. An image display device using the laminate according to claim 12 or 13. A method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition comprising a (meth) acrylic polymer, and at least one crosslinking agent selected from the group consisting of an organic peroxide crosslinking agent and an isocyanate crosslinking agent,
In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1):

(Wherein, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
A compound represented by
A method for promoting the crosslinking of an acrylic pressure-sensitive adhesive composition, comprising adding 0.005 to 5 parts by weight to 100 parts by weight of the (meth) acrylic polymer and crosslinking.