JP6505383B2 - Acrylic pressure-sensitive adhesive composition, method for producing acrylic pressure-sensitive adhesive layer, acrylic pressure-sensitive adhesive layer obtained by the production method, polarizing film with pressure-sensitive adhesive layer, laminate, image display device, and acrylic pressure-sensitive adhesive composition Method of promoting cross-linking - Google Patents

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 A layered polarizing film, a laminate in which the polarizing film with an acrylic pressure-sensitive adhesive layer and a transparent conductive substrate are laminated, an image display apparatus using the laminate, and a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition .

  In image display devices such as liquid crystal display devices, it is essential to arrange various films on both sides of the liquid crystal cell from the image forming system, and when bonding various films to the liquid crystal cell, An adhesive is used. For example, adhesion between a polarizing film and a liquid crystal cell is usually in close contact with a pressure-sensitive adhesive in order to reduce light loss. In such a case, the adhesive has a merit such that a drying step is not required to fix various films, so the pressure-sensitive adhesive is a film with a pressure-sensitive adhesive layer provided in advance as a pressure-sensitive adhesive layer on one side of various films. Is commonly 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 In addition to polymers, pressure-sensitive adhesives containing peroxides and isocyanate compounds have been proposed (see, for example, Patent Document 1). In addition to a (meth) acrylic polymer containing an acrylic monomer and a nitrogen-containing monomer, an 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, in the conventional acrylic pressure-sensitive adhesive composition, a large amount of crosslinking by an organic peroxide or an isocyanate-based crosslinking agent has been adopted. However, in organic peroxide crosslinking, in atmospheric pressure hot air crosslinking, the crosslinking efficiency may be lowered due to the inhibition of crosslinking by oxygen in the reaction system, and the reactivity is low in the case of isocyanate crosslinking agents. In the case of crosslinking, the processability and productivity are insufficient. Specifically, for example, when a substrate 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 removed by a cutting blade, or , There was a case to be out of the cutting plane. In addition, during the appearance inspection and transportation of the punched pressure-sensitive adhesive layer-attached substrate, the pressure-sensitive adhesive layer may be removed, or the pressure-sensitive adhesive layer protruding from the cut surface may stain the substrate.

  In addition, in the acrylic pressure-sensitive adhesive composition containing these crosslinking agents, in order to raise the efficiency of the crosslinking reaction, a catalyst or the like that accelerates the urethane reaction was sometimes added, but in such a case, it gelled at normal temperature. In some cases, the pot life may become very short. Moreover, although an amine-based or metal-based additive was used as a catalyst in some cases, it has been a cause of causing product defects or physical property deterioration due to amine odor.

Furthermore, in an acrylic pressure-sensitive adhesive composition containing such a crosslinking agent, there is a case where a curing (aging) period is provided after the crosslinking treatment to complete the crosslinking. The aging period is usually required for about one day to about one week, and by providing an aging step, the productivity is reduced.

  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 has been difficult to efficiently crosslink with the crosslinking agent.

  Therefore, the present invention comprises an acrylic pressure-sensitive adhesive composition that can be efficiently crosslinked, including one or more crosslinking agents selected from the group consisting of acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents. It aims to provide goods. Moreover, the method of manufacturing an acrylic adhesive layer using the said acrylic adhesive composition, the acrylic adhesive layer obtained by the said manufacturing method, the polarizing film with an adhesive layer, a laminated body, and an image display apparatus are provided. The purpose is to Furthermore, another object of the present invention is to provide a method for accelerating the crosslinking of the acrylic pressure-sensitive adhesive composition.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining this invention so that the said subject might be solved, the present inventors discover that the said objective can be achieved by setting it as the following acrylic adhesive composition, and came to complete this 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, in the present invention, 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 each independently represent 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. .

  It is preferable that the compound represented by the said General formula (1) is a phosphoric acid ester whose acid value is 80-900 mgKOH / g.

  It is preferable to contain 0.05-2 weight part of said organic peroxide type crosslinking agents with respect to 100 weight part of said (meth) acrylic-type polymers.

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

  The weight average molecular weight of the (meth) acrylic polymer is preferably 1.2 million to 3,000,000.

In addition, the present invention includes a step of applying the acrylic pressure-sensitive adhesive composition on a substrate, and a step of crosslinking the acrylic pressure-sensitive adhesive composition applied on the substrate to form a pressure-sensitive adhesive layer. The present invention relates to a method for producing an acrylic pressure-sensitive adhesive layer characterized by

  The crosslinking of the acrylic pressure-sensitive adhesive composition is preferably performed 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 more preferably 55 to 85% by weight after 2 hours after crosslinking.

  The present invention also relates to a pressure-sensitive adhesive layer-attached polarizing film having the above-mentioned acrylic pressure-sensitive adhesive layer on at least one surface of a polarizing film.

  In the present invention, the transparent conductive substrate having the pressure-sensitive adhesive layer-attached polarizing film and the transparent conductive film is laminated, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film and the transparent conductive substrate are transparent The present invention relates to a laminate characterized in that the films are in contact with each other.

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

  The present invention also relates to an image display apparatus characterized by 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 relates to a crosslinkable acrylic pressure-sensitive adhesive composition comprising a (meth) acrylic polymer and at least one crosslinker selected from the group consisting of an organic peroxide crosslinker and an isocyanate crosslinker. A promotion method,
In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1):

(Wherein, R ¹ and R ² each independently represent 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 is characterized in that 0.005 to 5 parts by weight of a compound represented by 100 parts by weight of the (meth) acrylic polymer is added for crosslinking.

  The acrylic pressure-sensitive adhesive composition of the present invention comprises an acrylic pressure-sensitive adhesive composition comprising one or more crosslinking agents selected from the group consisting of acrylic polymers, organic peroxide-based crosslinking agents, and isocyanate-based 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 be efficiently advanced. Specifically, when an organic peroxide crosslinking agent is used as the crosslinking agent, inhibition of radical crosslinking by oxygen is suppressed by the addition of the compound represented by the general formula (1), and the crosslinking reaction is efficiently performed. In the case where 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 efficiently performs the crosslinking reaction. it can. Thus, 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, and as a result, the adhesive residue at the time of processing, etc. It is suppressed, the processability can be improved, and the productivity is excellent.

  In addition, the acrylic pressure-sensitive adhesive composition of the present invention has high crosslinking efficiency, and it is not necessary to perform an aging operation by heating or leaving it 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 comprises 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 each independently represent 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 both of R ¹ and R ² in the general formula (1) are hydrogen atoms can be used, and salts of the phosphoric acid (sodium, potassium, and And metal salts such as magnesium, ammonium salts and the like) can also be suitably used.

In the present invention, it is also preferable to use a phosphoric acid ester having a hydrocarbon residue of 1 to 18 carbon atoms in which at least ^one of R ¹ and R ^{2 in} the general formula (1) may contain an oxygen atom. It can be used for The hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom includes 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, n is an integer of 0 to 15.), and the like. In addition, the alkyl group and the 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 as defined above, R ³ is an alkyl group having 1 to 18 carbon atoms, or an alkenyl group, and n is an integer from 0 to 15). Ester is preferred.

As R ³ , an alkyl group having 1 to 18 carbon atoms or an alkenyl group can be mentioned, and an alkyl group having 1 to 18 carbon atoms is preferable. In addition, n is an integer of 0 to 15, and preferably an integer of 0 to 10.

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

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

  The acid value of the phosphoric acid ester used in the present invention is preferably 80 to 900 mg KOH / g, more preferably 80 to 700 mg KOH / g, still more preferably 80 to 600 mg KOH / g, and 100 More preferably, it is 500 to 500 mg KOH / g, further preferably 100 to 400 g KOH / g, and particularly preferably 150 to 300 mg KOH / g. If the acid value of the phosphoric acid ester is too high, when using an isocyanate-based crosslinking agent as the crosslinking agent, it may act as a crosslinking reaction catalyst for the isocyanate-based crosslinking agent, causing the pressure-sensitive adhesive composition to gel. The pot life of the pressure-sensitive adhesive composition tends to be short. By setting the acid value of the phosphoric acid ester in the above range, the pot life of the pressure-sensitive adhesive composition can be sufficiently secured, and in the crosslinking step, the crosslinking of the crosslinking agent can be promoted. 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 the general formula phosphoric acid esters commercially available as indicated by ^{(2), R 1 = R} 3 = C 8 H of Toho Chemical Industry Co., Ltd. "Phosphanol SM-172" (the general formula (2) ₁₇ , n = 0, mono-di mixture, acid value: 219 mg KOH / g), "Phosphanol GF-185"
(R ¹ = R ³ = C ₁₃ H _{27 in} the general formula (2), n = 0, mono-di mixture, acid value: 158 mg KOH / g), “Phosphorol BH-650” (general formula (2) R ¹ = R ³ CC ₄ H ₉ , n = 1, mono-di mixture, acid value: 388 mg KOH / g, “Phosphorol RS-410” (general formula (2) R ¹ RR ³ CC ₁₃ H ₂₇ , n = 4, mono-di mixture, acid value: 105 mg KOH / g, “Phosphanol RS-610” (general formula (2) R ¹ CC ₁₃ H ₂₇ , R ³ CC ₁₃ H ₂₇ , n = 6, mono-di mixture, acid value: 82 mg KOH / g, “Phosphanol ML-220” (in the general formula (2), R ¹ = R ³ = C ₁₂ H ₂₅ , n = 2, mono・ Di-mixture), “Phosphanol ML-200” (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” (in the general formula (2), R ¹ = R ³ = C ₁₈ H ₃₇ , n = 2, mono-di mixture), “Phosphanol GF-339 ( A mixture of R ¹ = R ³ CC ₆ H _{13 to} C ₁₀ H _{21 in} the general formula (2), n = 0, a mono-di mixture), R of the “phosphonol GF-199” (general formula (2) _{^{1 = R 3 = C 12 H}} 25, n = 0, mono di mixture), "Phosphanol RL-310" (the general formula (2) _{^{R 1 = R 3 = C 18}} H 37, 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 of} the general formula (2), n = 0, mono-di mixture) , “JP-524R” (R ¹ = R ³ = C ₂₄ H _{49 in} the general formula (2), n = 0, mono-di mixture), “DBP” (R ¹ = R ^{3 in} the general formula (2) C ₄ H ₉ , n = 0, diester, acid value: 266 mg KOH / g, “LB-58” (general formula (2) R ¹ = R ³ = C ₈ H ₁₇ , 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 mg KOH / g), "MP-4" (R ¹ = H, R ³ = C ₄ H _{9 in} the general formula (2), n = 0, mono-di mixture, acid value: 670 mg KOH / g), "AP −8 ′ ′ (R ¹ RR ³ CC ₈ H _{17 in} the general formula (2), n = 0, mono-di mixture, acid value: 306 mg KOH / g), “MP-8” (general formula (2) R ¹ = R ³ = C ₁₀ H ₂₁ , n = 0, diester, acid value: 400 mg KOH / g) and the like, and salts thereof. The above “mono-di mixture” refers to a monoester (R ¹ = H in the general formula (2)) and a diester (R ^{1 in the} general formula (2) which may contain an oxygen atom; It is shown that it is a mixture of to 18 hydrocarbon residues, and, for example, in the case of phosphanol SM-172, a monoester (general formula (2) R ¹ H H, R ³ C C ₈ H) _17, n = 0) and indicates a mixture of diester _{^{R 1 = R 3 = C 8}} H 17, n = 0 in (formula (2)). The mixing ratio of monoester and diester of the "mono-di mixture" can be calculated from the measurement result of ³¹ P-NMR. The measurement method is as described in the examples.

The phosphate ester used in the present invention is a compound represented by the general formula (1) (or a compound represented by the general formula (2)), or a compound selected from the group consisting of salts and multimers thereof. These may be used alone or as a mixture of two or more, but from the viewpoint of being able to reduce the amount of addition and obtain better effects, phosphoric acid, phosphoric monoesters, and phosphorus It is preferred that it is 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 monoester. Here, with phosphoric acid monoester, one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom, and carbonization having 1 to 18 carbon atoms It is a compound which is a hydrogen residue (in the case of the general formula (2), a compound in which R ¹ is a hydrogen atom), and with phosphoric acid diester, 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), a hydrocarbon residue having 1 to 18 carbon atoms which R ¹ may contain an oxygen atom) A compound which is a group).

  Further, in the present invention, phosphoric acid can be further added to the phosphoric acid ester compound, and the amount of phosphoric acid added in that case is the phosphoric acid 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. In addition, the lower limit of the addition amount of phosphoric acid is not particularly limited, and it is added to an extent that 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.

  In the present invention, it is also possible to use a compound represented by the above-mentioned general formula (1) or a multimer such as a dimer or trimer of a phosphoric acid ester represented by (2).

  The 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. Is more preferable, 0.01 to 3 parts by weight is further preferable, 0.01 to 2.5 parts by weight is further preferable, and 0.01 to 1 part by weight is particularly preferable. When the addition amount of the compound represented by the general formula (1) is less than 0.005 parts by weight, the effect of the present invention tends to be unobtainable, and when it is more than 5 parts by weight, it is obtained after crosslinking. It is not preferable because the durability of the pressure-sensitive adhesive layer tends to decrease. Moreover, in this invention, although two or more compounds represented by General formula (1) can be used, in that case, it can add so that a total amount may become said 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 alkyl (meth) acrylate, and It is preferable that it is obtained by polymerizing a monomer component containing a meth) acrylate and a hydroxyl group-containing monomer. In addition, an alkyl (meth) acrylate means an alkyl acrylate and / or an alkyl methacrylate, and (meth) of this invention is 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, alkyl (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are preferable, (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, n-butyl (meth) acrylate, 2- Ethyl hexyl (meth) acrylate is more preferred, and n-butyl acrylate is particularly preferred.

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

Further, as the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomers 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 meta) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and the like. Can be used alone or in combination 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, using a 4-hydroxybutyl acrylate as a hydroxyl group containing monomer, a bridge | crosslinking point with the isocyanate group of an isocyanate type crosslinking agent is efficiently ensured. It is preferable because it can be done.

  The amount of 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 preferred.

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

  As the carboxyl group-containing monomer, one 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, crotonic acid and the like, which may be used alone or in combination Can be used.

  The amount of the carboxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 6 parts by weight or less, and still more preferably 2 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Particularly preferred is 0.5 parts by weight or less. The lower limit value is not particularly limited, but is preferably 0.01 parts by weight or more, for example.

  The other copolymerizable monomer is not particularly limited as long as it has a polymerizable functional group related to unsaturated double bond such as (meth) acryloyl group or vinyl group, and, for example, alkyl having 1 to 3 carbon atoms (Meth) acrylic acid alicyclic hydrocarbon ester such as alkyl (meth) acrylate having a group, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate; eg, (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; glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate Epoxy group-containing monomers such as; eg, methoxy (meth) acrylate Alkoxy group-containing monomers such as ethyl, ethoxyethyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; functional monomers such as 2-methacryloyloxyethyl isocyanate; for example, ethylene, propylene, Olefin monomers such as isoprene, butadiene and isobutylene; vinyl ether monomers such as vinyl ether; halogen atom-containing monomers such as vinyl chloride; and the like.

Moreover, as copolymerizable monomers, for example, maleimide monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like; for example, N-methyl itaconimide, N-ethyl itaconimide, N Itaconimide-based monomers such as -butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl itaconimide, N-laurylitaconimide; eg, N- (meth) acryloyloxymethylene succinimide, N- Succinimide-based monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, etc .; eg, styrene sulfonic acid, Examples include sulfonic acid group-containing monomers such as lylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid .

  Moreover, as copolymerizable monomers, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc. And others, for example, heterocyclic rings such as tetrahydrofurfuryl (meth) acrylate and fluorine (meth) acrylate, and acrylic acid ester monomers containing a halogen atom.

  Furthermore, polyfunctional monomers can be used as copolymerizable monomers. As a polyfunctional monomer, the compound etc. which have 2 or more of unsaturated double bonds, such as a (meth) acryloyl group and a vinyl group, are mentioned. For example, (mono or poly) such as 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. 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 Esters of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compounds such as divinyl benzene; allyl (meth) acrylate, (meth) The compound etc. which have reactive unsaturated double bonds, such as a vinyl acrylate, are mentioned. In addition, as a polyfunctional monomer, polyester (meta (meta) added with two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as a functional group similar to the monomer component to a skeleton of polyester, epoxy, urethane, etc. Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like can also be used.

  The proportion of the other copolymerizable monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still 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 proportion of the copolymerization monomer is too large, adhesion properties such as adhesion decrease to various adherends such as glass, film, transparent conductive film and the like of the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition It may decrease.

  The weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1.2 million to 3,000,000, more preferably 1.2 million to 2.7 million, and still more preferably 1.2 million to 2.5 million. If the weight average molecular weight is less than 1.2 million, there are cases where it is not preferable in terms of heat resistance. When the weight average molecular weight is less than 1.2 million, the low molecular weight component is increased in the pressure sensitive adhesive composition, and the low molecular weight component may bleed out from the pressure sensitive adhesive layer to impair the 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. In addition, when the weight average molecular weight is more than 3,000,000, 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 also from a corrosion-resistant and durability viewpoint by a weight average molecular weight being in the said range. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

  The production of such (meth) acrylic polymers can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, various radical polymerizations, etc., and is not particularly limited. In addition, the (meth) acrylic polymer to be 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 carried out under a stream of an inert gas such as nitrogen, usually with a polymerization initiator at about 50 to 70 ° C., for 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. The weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used can be appropriately adjusted according to the type of these.

  As a polymerization initiator, for example, 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'-dimethylene isobutylamidine), 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 peroxy dicarbonate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, 1,1-di (t- Peroxide initiators such as hexylperoxy) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, etc., combinations of persulfates and sodium bisulfite, peroxides such as combinations of peroxides and sodium ascorbate Examples include redox initiators combined with a reducing agent But it is not limited thereto.

  Although the said polymerization initiator may be used independently and may be used in mixture of 2 or more types, 100 weight of monomer components which form said (meth) acrylic-type polymer as a whole content It is preferable that it is about 0.005-1 weight part with respect to a part.

  Examples of chain transfer agents include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like. 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 the adhesion under high temperature and high humidity conditions. As a silane coupling agent, what has arbitrary appropriate functional groups can be used. As a functional group, a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth) acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, a polysulfide group etc. are mentioned, for example. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, etc .; γ-glycidoxypropyltrimethoxysilane, γ-gly Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 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; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; γ- (Meth) acrylic group-containing silane coupling agents such as acryloxypropyltrimethoxysilane, 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 the total monomer component 100 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 parts by weight, and more preferably 0.05 to 1 part by weight. Particularly preferred is 0.7 parts by weight. If the compounding amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable in terms of durability.

  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 crosslinking agents selected from the group consisting of organic peroxide crosslinking agents and isocyanate crosslinking agents, The addition is preferable because it can impart cohesive force related to the durability of the pressure-sensitive adhesive layer.

  As the organic peroxide-based crosslinking agent, any agent capable of generating radically active species by heating or light irradiation to promote the crosslinking of the base polymer of the pressure-sensitive adhesive composition can be suitably used, but the workability and stability are possible. 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.

  As a peroxide which can be used, for example, di (2-ethylhexyl) peroxydicarbonate (one-minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Half-life temperature: 92.1 ° C), di-sec-butylperoxydicarbonate (one-minute half-life temperature: 92.4 ° C), t-butyl peroxy neodecanoate (one-minute half-life temperature: 103) .5 ° C), t-hexylperoxypivalate (one-minute half-life temperature: 109.1 ° C), t-butylperoxypivalate (one-minute half-life temperature: 110.3 ° C), dilauroyl peroxide (one-minute half-life temperature: 110.3 ° C) 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 peroxide Oxy-2-ethylhexanoate (one-minute half-life temperature: 124.3 ° C), di (4-methylbenzoyl) peroxide (one-minute half-life temperature: 128.2 ° C), dibenzoyl peroxide (one-minute half-life Temperature: 130.0 ° C.), t-butyl peroxyisobutyrate (one-minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (one-minute half-life temperature: 149.2 ° C.) and the like. Among them, dibenzoyl peroxide (half-life temperature per minute: 130.0 ° C.) is preferably used because the crosslinking reaction efficiency is particularly excellent.

  In addition, the half life of peroxide is an index showing the decomposition rate of peroxide, and refers to the time until the remaining amount of peroxide is halved. The decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer catalog etc., for example, Nippon Organic Fat 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 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If it is less than 0.05 parts by weight, the physical properties of the required crosslinked structure tend not to be obtained, while if it is more than 2 parts by weight, peroxides or decomposition products thereof are present in the pressure-sensitive adhesive layer. It is not preferable because the durability tends to decrease.

  An isocyanate type crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group in which an isocyanate group is temporarily protected by a blocking agent or quantification or the like) in one molecule.

  Examples of isocyanate-based crosslinking agents include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and such isocyanate monomers as trimethylolpropane. These include isocyanate compounds and isocyanurate compounds added with etc., Burette type compounds, and further, polyurethane prepolymer type isocyanates subjected to an addition reaction such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. . Particularly preferred is a polyisocyanate compound, which is one or a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. Here, one or a polyisocyanate compound derived therefrom selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate includes hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and polyol modification. Hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate are included.

  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 (Trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), Isocyanate adduct of hexamethylene diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. Propane adduct (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals, Inc.), and the like can be mentioned.

  The content of the isocyanate crosslinking agent is preferably 0.02 to 2 parts by weight, and more preferably 0.05 to 1 parts 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 physical properties of the crosslinked structure tend not to be obtained, while if the amount is more than 2 parts by weight, the crosslinked structure becomes dense and the adhesive becomes hard. As a result, it is not preferable because physical properties such as durability and adhesion tend not to be satisfied.

  In the present invention, either one of an organic peroxide crosslinking agent and 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 this, the crosslinking reaction can be performed efficiently, and adhesive residue and the like at the time of processing can be reduced, which is preferable.

  When using an organic peroxide crosslinking agent and an isocyanate crosslinking agent in combination, the content of the isocyanate crosslinking agent is preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the organic peroxide crosslinking agent. And 20 to 300 parts by weight are more preferable.

  In addition to the peroxide-based crosslinking agent and the isocyanate-based crosslinking agent, other crosslinking agents can be used as the crosslinking agent. As other crosslinking agents, polyfunctional compounds are used, and organic crosslinking agents and polyfunctional metal chelates can be mentioned. As an organic type crosslinking agent, an epoxy type crosslinking agent, a carbodiimide type crosslinking agent, an imine type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent etc. are mentioned. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently bonded or coordinated with 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, etc. It can be mentioned. An oxygen atom etc. are mentioned as an atom in the organic compound which carries out covalent bond or coordinate bond, An alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound etc. are mentioned as an organic compound. These crosslinking agents can be used singly or in combination of two or more. Among these, peroxide type crosslinking agents and isocyanate type crosslinking agents are preferable, and it is more preferable to use them in combination.

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

  Furthermore, in the acrylic pressure-sensitive adhesive composition used in the present invention, if necessary, a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and the like Fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, UV absorbers, etc., without departing from the object of the present invention The following additives can also be used as appropriate. These additives can also be formulated as an emulsion.

2. Method for Producing Acrylic Pressure-Sensitive Adhesive Layer The method for producing an acrylic pressure-sensitive adhesive layer of the present invention comprises the steps of: applying the acrylic pressure-sensitive adhesive composition on a substrate;
A step of crosslinking the acrylic pressure-sensitive adhesive composition applied on the substrate to form a pressure-sensitive adhesive layer is characterized.

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

  It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, can be mentioned.

  Various methods are used as a method of applying to the substrate or the 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, Daikoh Methods such as extrusion coating using a rubber powder, etc.

  As a crosslinking temperature, although it can set suitably according to a composition of an acrylic adhesive composition, a density | concentration, etc., 70-170 degreeC is preferable, 90-165 degreeC is more preferable, 140-160 degreeC is more preferable. 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. When the crosslinking conditions are in the above range, the crosslinking reaction is efficiently performed, which is preferable.

  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 still more preferably 12 to 40 μm. If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the adhesion to the adherend is 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 can not be sufficiently dried at the time of application and drying, air bubbles remain, or the pressure-sensitive adhesive layer There is a tendency for thickness unevenness to occur on the surface of the surface, making appearance problems more likely to occur.

  As a constituent material of the release film, for example, resin film such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous material such as paper, cloth, non-woven fabric, net, foam sheet, metal foil, and laminate of these Although an appropriate thin leaf etc. can be mentioned, a resin film is used suitably from the point which is excellent in surface smoothness.

  As the resin film, for example, 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, ethylene film -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. The release film may be, if necessary, a release agent of silicone type, fluorine type, long chain alkyl type or fatty acid amide type, silica powder etc., release treatment and antifouling treatment, coating type, kneading type, It is also possible to carry out antistatic treatment such as deposition type. In particular, the releasability from the pressure-sensitive adhesive layer can be further enhanced by appropriately performing release treatment such as silicone treatment, long chain alkyl treatment, fluorine treatment and the like on the surface of the release film.

  The transparent resin film substrate is not particularly limited, but various resin films having transparency are used. The said resin film is formed of the film of one layer. For example, as the material, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like can be mentioned. Among 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 characterized by being 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 crosslinking promoting effect of a crosslinking agent such as an isocyanate crosslinking agent or an organic peroxide crosslinking agent, the acrylic pressure-sensitive adhesive layer of the present invention is 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 five days after crosslinking. Is more preferred. In addition, 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 preferred. When a gel fraction is in the said range, it is preferable from a viewpoint of processability and productivity. If the gel fraction after 2 hours after crosslinking is less than 55% by weight, the pressure-sensitive adhesive layer is too soft, and if processing is performed in this state, problems such as adhesion to the blade occur during processing There is a tendency to Furthermore, since dents occur in the winding-up process of the pressure-sensitive adhesive layer after cross-linking and a problem occurs in the appearance, the productivity tends to be poor. In addition, the measurement of the gel fraction of an adhesive layer can be performed by the method as described in an Example.

  The gel fraction change rate (gel fraction 5 days after crosslinking / gel fraction 2 hours after crosslinking) is preferably 1.35 or less, more preferably 1-1.35. Preferably, 1 to 1.30 is more preferable, and 1 to 1.25 is particularly preferable. When the rate of change in gel fraction is within the above range, the crosslinking reaction proceeds rapidly, and the physical properties become stable 2 hours after the crosslinking reaction, which is preferable from the viewpoint of aging and processability.

4. Pressure-Sensitive Adhesive Layer Attached Polarizing Film The pressure-sensitive adhesive layer-attached polarizing film of the present invention is characterized in that the acrylic pressure-sensitive adhesive layer is provided on at least one side of the polarizing film.

  The method of laminating the pressure-sensitive adhesive layer on the polarizing film is not particularly limited, but 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. The pressure-sensitive adhesive layer may be formed by directly applying the acrylic pressure-sensitive adhesive composition onto a polarizing film. 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 may be a double-sided protective polarizing film having a transparent protective film on both sides of the polarizer, but the single-sided protective polarizing film In the case where is used, the pressure-sensitive adhesive layer can be provided directly on the surface of the polarizer not having the transparent protective film.

  The polarizer is not particularly limited, and various types of polarizers can be used. As a polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene / vinyl acetate copolymer-based partially saponified film, dichroism of iodine or a dichroic dye Examples thereof include those obtained by adsorbing a substance and uniaxially stretched, and dehydrated products of polyvinyl alcohol and dehydrochlorinated products of polyvinyl chloride such as polyene-based oriented films. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. Although the thickness in particular of these polarizers is not restrict | limited, Generally it is about 5-80 micrometers.

  The polarizer which dye | stained the polyvinyl alcohol-type film with iodine, and uniaxially stretched it can be produced by, for example, dyeing | staining by immersing polyvinyl alcohol in the aqueous solution of iodine, and extending | stretching 3 to 7 times of original length. It can also be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride and the like as required. Furthermore, before dyeing, the polyvinyl alcohol-based film may be dipped in water and rinsed if necessary. In addition to being able to wash the stains and antiblocking agents on the surface of the polyvinyl alcohol film by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also effective in preventing nonuniformity such as unevenness in dyeing by swelling the film. is there. The stretching may be performed after staining with iodine, may be stretching while staining, or may be stretched and then stained with iodine. It can also be stretched in an aqueous solution of 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. It is preferable that such a thin polarizer has small thickness unevenness and excellent visibility, and also has small dimensional change, so that it is excellent in durability, and furthermore, the thickness as a polarizing plate can be reduced.

  Typical thin polarizers are disclosed in JP-A-51-069644, JP-A-2000-338329, WO 2010/100917, WO 2010/100917, or a patent. The thin-shaped polarizing film described in 4751481 specification and Unexamined-Japanese-Patent No. 2012-073563 can be mentioned. These thin polarizing films can be obtained by a manufacturing method including the steps of stretching a polyvinyl alcohol resin (hereinafter, also referred to as a PVA resin) layer and a stretching resin base material in the state of a laminate and dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it is possible to stretch without any trouble such as breakage due to stretching by being supported by the stretching resin base material.

  Among the thin polarizing films described above, among the process of drawing in the state of a laminate and the process of dyeing, it can be drawn at a high magnification and the polarization performance can be improved. WO 2010/100917 pamphlet, or those obtained by the process comprising stretching in a boric acid aqueous solution as described in Japanese Patent No. 4751481 or Japanese Patent Application Laid-Open No. 2012-073563 is preferable, particularly the patent What is obtained by the manufacturing method which includes the process of carrying out airborne extension auxiliary | assistant before extending | stretching in the boric-acid aqueous solution which is described in 4751481 specification 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, heat stability, water blocking property, isotropy and the like is preferable. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, and styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) Examples include system polymers and polycarbonate polymers. In addition, polyolefins having polyethylene, polypropylene, cyclo-based or norbornene structure, polyolefin-based polymers such as ethylene / propylene copolymer, vinyl chloride-based polymers, amide-based polymers such as nylon and aromatic polyamides, imide-based polymers, sulfone-based polymers , Polyether sulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or Blends of the above-mentioned polymers and the like are also mentioned as examples of the polymer forming the above-mentioned transparent protective film. The transparent protective film can also be formed as a cured layer of thermosetting resin such as acrylic resin, urethane resin, acrylic urethane resin, epoxy resin, and silicone resin, and ultraviolet curable resin.

  The thickness of the protective film can be appropriately determined, but in general, it is about 1 to 500 μm from the viewpoints of strength, workability such as handleability, and thin film properties.

  The polarizer and the transparent protective film are usually in close contact with each other via a water-based adhesive or the like. Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latexes, water-based polyurethanes, water-based polyesters, and the like. In addition to the above, as an adhesive agent of a polarizer and a transparent protective film, an ultraviolet curable adhesive, an electron beam curable adhesive, etc. are mentioned. The adhesive for electron beam-curable polarizing film exhibits suitable adhesion to the above 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 attached may be treated with a hard coat layer, an antireflective treatment, an antisticking treatment, or a treatment for diffusion or antiglare.

  In addition, an anchor layer may be provided between the polarizing film and the pressure-sensitive adhesive layer. Although the material which forms an anchor layer is not specifically limited, For example, various polymers, the sol of a metal oxide, silica sol etc. are mentioned. Among these, polymers are particularly preferably used. The use form of the polymers may be any of solvent-soluble type, water-dispersible type and water-soluble type.

  Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, and polystyrene resins. Among these, polyurethane resins, polyester resins and acrylic resins are particularly preferable. A crosslinking agent can be suitably blended with these resins. These other binder components may be used alone or in combination of two or more according to the application.

  When the anchor layer is formed of a water dispersible material, a water dispersible polymer is used. As a water dispersion type polymer, what made various resin, such as polyurethane and polyester, emulsified using an emulsifier, or in the said resin, introduces a water dispersible anion group, a cation group, or a nonionic group. A self-emulsified thing etc. are mentioned.

  The anchor agent can contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material capable of providing conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. Among them, preferred is a conductive polymer, more preferably a water-dispersible conductive polymer.

  As a water-soluble conductive polymer, polyaniline sulfonic acid (weight average molecular weight 150,000 based on polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.) and the like, and as a water-dispersible conductive polymer, a polythiophene conductive polymer (Nagase Chemtech (stock) And Denatron series).

  The compounding 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, the amount 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 carried out by a generally known method. In addition, in forming the anchor layer, the polarizing film can be subjected to an activation treatment. For the activation treatment, various methods can be adopted. For example, corona treatment, low pressure UV treatment, plasma treatment etc. can be adopted.

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

  When the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film of the present invention is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is practically used. As a release film, the above-mentioned thing can be mentioned. When a release film is used as a substrate for producing the above-mentioned pressure-sensitive adhesive layer, the release film is attached 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 of 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 polarizing film with the said adhesive layer, The surface of a transparent conductive film It is possible to suppress the rise 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 the corrosion of the transparent conductive film is prevented.

5. Laminate The laminate of the present invention is obtained by laminating the acrylic adhesive layer-attached polarizing film and a transparent conductive film, and the adhesive layer of the acrylic adhesive layer-attached polarizing film is in contact with the transparent conductive film. It features.

  As the polarizing film with the pressure-sensitive adhesive layer, those described above can be used.

  The substrate having the transparent conductive film is not particularly limited, and known materials can be used, but generally, those having the transparent conductive film on a transparent substrate are used.

  The transparent substrate may be any one having transparency, and examples thereof include resin films, substrates made of glass and the like (for example, sheet-like, film-like, and plate-like substrates), etc., and resins Films are particularly preferred. The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 μm, and more preferably about 15 to 150 μm.

  The material of the resin film is not particularly limited, and various plastic materials having transparency may be mentioned. For example, as the material, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like can be mentioned. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

  In addition, the transparent base material is previously subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical formation, oxidation or undercoating on the surface, and the transparent conductive film provided thereon The adhesion to the transparent substrate may be improved. Moreover, before providing a transparent conductive film, you may dust 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, tungsten Metal oxides of at least one metal are used. The said metal oxide may contain the metal atom further shown by the said group as needed. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

  Moreover, as said ITO, crystalline ITO and non-crystalline (amorphous) ITO can be mentioned, and all can be used suitably.

  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 still 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 evaporation method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted according to the required film thickness.

  As a thickness of the base material which has the said transparent conductive film, 15-200 micrometers can be mentioned. Furthermore, in view of thinning, the thickness is preferably 15 to 150 μm, and more preferably 15 to 50 μm. When the base material which has the said transparent conductive film is used by a resistive film system, the thickness of 100-200 micrometers can be mentioned, for example. When used in the capacitance method, for example, a thickness of 15 to 100 μm is preferable, and in particular, a thickness of 15 to 50 μm is more preferable, and a thickness of 20 to 50 μm is more preferable .

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

6. Image Display Device The laminate of the present invention is an image display device (a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), an electronic paper, etc.) including an input device (a touch panel etc.), an input device Although it can be used suitably in manufacture of a substrate (member) which constitutes apparatus, such as (touch panel etc.) or a substrate (member) used for these apparatuses, it is suitable suitably in manufacture of an optical substrate for touch panels especially It can be used for Moreover, it can be used irrespective of methods, such as a resistive film type and a capacitive type, such as a touch panel.

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

  In addition, as described above, the polarizing film with a pressure-sensitive adhesive layer of the present invention can suppress the corrosion of the transparent conductive film even when the transparent conductive film is laminated on the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film can be suitably used for an image display device having a configuration 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 accelerating crosslinking of acrylic pressure-sensitive adhesive composition The method for accelerating crosslinking of acrylic pressure-sensitive adhesive composition according to the present invention comprises (meth) acrylic polymer, and from the group consisting of organic peroxide crosslinking agent and isocyanate crosslinking agent A method for accelerating the crosslinking of an acrylic pressure-sensitive adhesive composition comprising one or more crosslinking agents selected, comprising:
In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1):

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

  (1) At least one crosslinking agent selected from the group consisting of (meth) acrylic polymers, organic peroxides and isocyanate crosslinking agents, and the compounds represented by the general formula (1) The mixing ratio is also as described above. The crosslinking conditions are also as described above.

In the method for accelerating crosslinking of the acrylic pressure-sensitive adhesive composition of the present invention, 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. By further containing the compound represented by the said General formula (1) in the acrylic adhesive composition containing these, the crosslinking of the said acrylic adhesive composition can be accelerated | stimulated. This is because, when an organic peroxide crosslinking agent is used as the crosslinking agent, inhibition of radical crosslinking by oxygen is suppressed by the addition of the compound represented by the general formula (1), and the crosslinking reaction is performed efficiently. In addition, when an isocyanate 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 the crosslinking reaction can be efficiently performed. Thus, 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, and as a result, the adhesive residue at the time of processing, etc. It is suppressed, the processability can be improved, and the productivity is excellent.

  Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In each example, parts and% are all based on weight.

Production Example 1 (Production of Polarizing Film (1))
A laminate obtained by forming a polyvinyl alcohol (PVA) layer having a thickness of 9 μm on an amorphous polyethylene terephthalate (PET) substrate was formed into a stretched laminate by air-assisted stretching at a stretching temperature of 130 ° C. Next, the stretched laminate is dyed to form a colored 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 becomes 5.94 times the amorphous PET substrate An optical film laminate was produced comprising a 4 μm thick PVA layer stretched integrally with it. The PVA molecules of the PVA layer formed on the amorphous PET substrate by such two-step drawing are oriented in high order, and the iodine adsorbed by dyeing is oriented in one direction in one direction as polyiodine ion complex An optical film laminate including a 4 μm-thick PVA layer, which constitutes a high-performance polarizer, could be produced. Furthermore, after applying a polyvinyl alcohol-based adhesive on one side of the polarizer of the optical film laminate, a 40 μm-thick saponified acrylic resin film (transparent protective film (1)) is laminated, and then it is amorphous. The PET substrate was peeled off to prepare a polarizing film using a thin polarizer with single-sided protection. Hereinafter, this is called a polarizing film (1).

Production Example 2 (Production of Polarizing Film (2))
An 80 μm-thick PVA film was stretched up to 3 times while being stained for 1 minute in a 0.3% iodine solution at 30 ° C. between rolls with different speed ratios. Then, it was drawn so as to have a total draw ratio of 6 while being immersed for 0.5 minutes in an aqueous solution containing 60% of boric acid at 4% concentration and potassium iodide at 10% concentration. Subsequently, after washing | cleaning by immersing in 30 degreeC and the aqueous solution containing 1.5% density | concentration potassium iodide for 10 seconds, drying was performed at 50 degreeC for 4 minutes, and the 20-micrometer-thick polarizer was obtained. Furthermore, after applying a polyvinyl alcohol-based adhesive to the surface of the polarizer of the optical film laminate, a 40 μm thick acrylic resin film (transparent protective film (1)) subjected to saponification treatment is laminated, and then amorphous PET After peeling the base material, a 40 μm thick norbornene-based film (transparent protective film (2)) was bonded to the other side with a polyvinyl alcohol-based adhesive to prepare a double-sided protective polarizing film. Hereinafter, this is called a polarizing film (2).

Production Example 3 (Preparation of Solution Containing Acrylic Polymer (A-1))
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2,2'-azobisisobutyro as an initiator. Add 1 part of nitrile (AIBN) to 100 parts of monomer (solid content) together with ethyl acetate, and react under nitrogen gas flow at 60 ° C. for 7 hours, add ethyl acetate to the reaction solution, and weight average A solution containing an acrylic polymer (A-1) having a molecular weight of 1.55 million was obtained (solid content concentration 30% by weight).

Production Examples 4 to 6 (Production of Solution Containing Acrylic Polymer (A-2) to (A-4))
Solutions containing acrylic polymers (A-2) to (A-4) were obtained in the same manner as in Production Example 3 except that the composition of the monomers was changed to the composition shown in Table 2 (about each solution, Solid concentration 30% by weight).

The 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 by manufacture example 3-6 was measured with the following measuring methods.
<Measurement of Weight Average Molecular Weight (Mw) of Acrylic Polymer>
The weight average molecular weight of the produced acrylic polymer was measured by GPC (gel permeation chromatography).

Device: Tosoh Corporation HLC-8220 GPC
column:
Sample column; Tosoh Corporation TSKguardcolumn Super HZ-H
(1) + TSKgel Super HZM-H (2)
Reference column; Tosoh TSKgel Super H-RC (1)
Flow rate: 0.6 mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: Differential Refractometer In addition, the weight average molecular weight was calculated by polystyrene conversion.

Example 1
(Preparation of acrylic pressure-sensitive adhesive composition)
The acrylic polymer (A-1) obtained in Production Example 3, an adduct of hexamethylene diisocyanate with trimethylolpropane as a crosslinking agent per 100 parts of the solid content of the acrylic polymer solution (trade name: Takenate D 160 N, 0.1 part of Mitsui Chemicals Co., Ltd., 0.3 parts of dibenzoyl peroxide, and 0.05 parts of phosphoric ester (trade name: Phosphanol SM-172, Toho Chemical Co., Ltd.) An acrylic pressure-sensitive adhesive composition was obtained by mixing 0.075 parts of γ-glycidoxypropyl methoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).

(Preparation of polarizing film with pressure-sensitive adhesive layer)
The acrylic pressure-sensitive adhesive composition is uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone release agent with a fountain coater, and dried in an air circulating constant temperature oven at 155 ° C. for 2 minutes. Then, a pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator on which the pressure-sensitive adhesive layer was formed was transferred to the surface of the polarizing film (1) having no protective film, to prepare a polarizing film with a pressure-sensitive adhesive layer.

Examples 2-3
In Example 1 (Preparation of acrylic pressure-sensitive adhesive composition), adhesion was performed in the same manner as in Example 1 except that the amount of addition of the phosphate was changed from 0.05 part to the number of parts described in Table 3. An agent layer-attached polarizing film was produced.

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

Example 7
In (Preparation of acrylic pressure-sensitive adhesive composition) of Example 1, 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.), Phosphanol RS-410 (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 acid value was changed to 105 mg KOH / g, Toho Chemical Industry Co., Ltd., 0.05 part.

Example 8
In (Preparation of acrylic pressure-sensitive adhesive composition) of Example 1, 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.), phosphoric acid (reagent special grade) (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 by Kogyo Co., Ltd.).

Examples 9 to 11
In (Preparation of acrylic pressure-sensitive adhesive composition) of Example 1, the solution containing the acrylic polymer (A-1) obtained in Production Example 3 is an acrylic type obtained in Production Examples 4 to 6, respectively. The same as Example 1, except that the solution containing the polymers (A-2) to (A-4) was changed and the blending amount of the phosphate was changed from 0.05 part to 0.1 part. Thus, a polarizing film with an adhesive layer was produced.

Example 12
Adhesion in the same manner as in Example 1 except that the polarizing film (1) was changed to the polarizing film (2) obtained in Production Example 2 in (Production of Polarizing Film with Pressure-Sensitive Adhesive Layer) in Example 1 An agent layer-attached polarizing film was produced.

Example 13
In (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, the addition amount of the adduct of hexamethylene diisocyanate with trimethylolpropane (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.) is 0.1 part A pressure-sensitive adhesive layer-carrying polarizing film was produced in the same manner as in Example 1 except that the amount was changed to 0.12 parts and no dibenzoyl peroxide was added.

Example 14
In (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, the addition amount of dibenzoyl peroxide is changed from 0.3 part to 0.4 part, and an adduct of hexamethylene diisocyanate with trimethylolpropane. A pressure-sensitive adhesive layer-carrying polarizing film 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 (Preparation of acrylic pressure-sensitive adhesive composition) of Example 1, 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.), 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 amount was changed to 670 mg KOH / g, a mono-di mixture, and 0.05 parts by Daihachi Chemical Industry Co., Ltd.

Comparative Example 1
A pressure-sensitive adhesive layer-attached polarizing film was produced in the same manner as in Example 1 except that the phosphoric acid ester was not added in (Preparation of acrylic pressure-sensitive adhesive composition).

Comparative example 2
A pressure-sensitive adhesive layer-attached polarizing film was produced in the same manner as in Example 1 except that the phosphate ester and dibenzoyl peroxide were not added in (Preparation of Acrylic Pressure-Sensitive Adhesive Composition).

Comparative Examples 3 and 4
In (Preparation of an acrylic pressure-sensitive adhesive composition) of Example 1, no phosphate was added, and in (Preparation of a polarizing film with a pressure-sensitive adhesive layer), the drying conditions were from 155 ° C. for 120 seconds, Table 3 A pressure-sensitive adhesive layer-carrying polarizing film was produced in the same manner as in Example 1 except that the conditions described in were changed.

The analysis was performed as follows about the phosphoric acid type compound used by the Example and the comparative example. The results are shown in Table 3.
(Analytical method)
The composition of the phosphoric acid type compound used by the Example and the comparative example was computed based on the measurement result of ³¹ P-NMR (Acetone-d6, room temperature). After calculating mol% from the integral 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 device: 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, with phosphoric monoester, one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom, and has 1 to 18 carbon atoms. It is a compound which is a hydrocarbon residue (in the case of the general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester refers to an oxygen atom in which R ¹ and R ^{2 in} the general formula (1) are In the case of a compound having a hydrocarbon residue of 1 to 18 carbon atoms (in the case of the general formula (2), a hydrocarbon having 1 to 18 carbons in which R ¹ may contain an oxygen atom) A compound that is a residue). For example, in the case of phosphanol SM-172, “monoester” is a compound in which R ¹ H H, R ³ C C ₈ H ₁₇ , n の in general formula (2), “diester” is a general compound shows the compound is _{^{R 1 = R 3 = C 8}} H 17, n = 0 in formula (2).

<Measurement of gel fraction>
The acrylic pressure-sensitive adhesive composition obtained in Examples and Comparative Examples is treated under the same drying conditions (temperature and time) as in each Example and Comparative Example to form a pressure-sensitive adhesive layer, and the temperature is 23 ° C. and the humidity is 65. After leaving it for 2 hours under% RH conditions and after leaving it for 5 days, 0.2 g of the pressure-sensitive adhesive layer is taken and its weight is measured in advance. Fluorine resin film (TEMISH NTF-1122, manufactured by Nitto Denko Corporation) It was wrapped in (weight: Wa) and bound so as not to leak the acrylic pressure-sensitive adhesive composition. Let this be a measurement sample. The weight of the measurement sample was measured (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 equation.

<Processability>
About the polarizing film with an adhesive layer obtained by the Example and the comparative example, it observes by visual observation and touch about what punched out in the square of 270 mm of 1 side length within 24 hours after preparation, It was judged whether or not there was a tackiness, and whether the surface of the polarizing film was soiled by the adhesive.
◎: no stain due to adhesive is observed.
:: Staining due to the adhesive is seen to some extent without any problem.
Fair: sticky feeling, some stains confirmed.
X: Stickiness is observed, and dirt is observed on most of the end.

<Pot life>
In the examples and comparative examples, it was allowed to stand for 12 hours after the addition of the crosslinking agent, and thereafter, those applied were judged according to the following criteria.
◎: There was no problem in the appearance of the coated material.
:: some appearance is confirmed in the appearance of the coated material.
X: A large gel clump is confirmed in appearance, or the formulated solution is gelled.

<Durability test of adhesive (Peeling and foaming)>
The separator film of the pressure-sensitive adhesive polarizing film sample obtained in Examples and Comparative Examples is peeled off, laminated to an alkali-free glass, autoclaved at 50 ° C., 5 atm for 15 minutes, and then heated at 85 ° C. and 60 ° C. It was introduced into a / 90% RH constant temperature and humidity chamber. Peeling and foaming of the polarizing plate after 500 h were visually observed and judged based on the following criteria.
◎: No peeling or foaming was observed at all.
○: Peeling or foaming occurred to an extent that could not be confirmed visually.
Δ: Small peeling or bubbling occurred visually.
X: clear peeling or foaming was observed.

The 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 mg KOH / g (manufactured by Toho Chemical Industry Co., Ltd.)
B-3: Phosphoric acid (reagent grade) (Wako Pure Chemical Industries, Ltd.)
B-4: MP-4, acid value: 670 mg KOH / g, mono-di mixture, peroxide manufactured by Daihachi Chemical Industry Co., Ltd .: dibenzoyl peroxide isocyanate type: adduct of hexamethylene diisocyanate with trimethylolpropane (Brand name: Takenate D 160 N, manufactured by Mitsui Chemicals, Inc.)
Silane coupling agent: γ-glycidoxypropyl methoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (10)

A pressure-sensitive adhesive layer-attached polarizing film having an acrylic pressure-sensitive adhesive layer on at least one side of a polarizing film,
The acrylic pressure-sensitive adhesive layer is
(Meth) acrylic polymer, an organic peroxide crosslinking agent, Lee isocyanate-based crosslinking, and the following general formula (1):

(Wherein, R ¹ and R ² each independently represent 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 content of the compound represented by the general formula (1) is, it said (meth) 0.005 parts by weight der per 100 parts by weight of the acrylic polymer,
The content of the organic peroxide crosslinking agent is 0.05 to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer,
An adhesive characterized in that it is formed from an acrylic pressure-sensitive adhesive composition in which the content of the isocyanate-based crosslinking agent is 5 to 1000 parts by weight with respect to 100 parts by weight of the organic peroxide-based crosslinking agent. Agent layer-attached polarizing film . The pressure-sensitive adhesive layer-attached polarizing film according to claim 1, wherein the compound represented by the general formula (1) is a phosphoric acid ester having an acid value of 80 to 900 mg KOH / g. The pressure-sensitive adhesive layer-attached polarizing film according to claim 1 or 2 , wherein a weight average molecular weight of the (meth) acrylic polymer is 1.2 million to 3,000,000. It is a manufacturing method of the polarizing film with an adhesive layer in any one of Claims 1-3, Comprising :
A step of applying on the substrate the acrylic pressure-sensitive adhesive composition, process by crosslinking the coated acrylic pressure-sensitive adhesive composition onto a substrate to form an adhesive layer, and the resulting polarization sensitive adhesive layer A process for producing a pressure-sensitive adhesive layer-attached polarizing film , comprising the step of laminating on a film . The method for producing a polarizing film with a pressure-sensitive adhesive layer according to claim 4 , wherein the crosslinking is performed by heating at 70 to 170 ° C. for 30 to 240 seconds. The acrylic pressure-sensitive adhesive layer is
The pressure-sensitive adhesive layer-attached polarizing film according to any one of claims 1 to 3 , wherein the gel fraction after 5 days after crosslinking is 60 to 95% by weight. The acrylic pressure-sensitive adhesive layer is
The pressure-sensitive adhesive layer-attached polarizing film according to any one of claims 1 to 3, wherein a gel fraction after 2 hours after crosslinking is 55 to 85% by weight. A pressure-sensitive adhesive layer-attached polarizing film according to any one of claims 1 to 3, and a transparent conductive substrate having a transparent conductive film are laminated, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film A laminate characterized in that a transparent conductive film of a transparent conductive substrate contacts. The said transparent conductive film is formed from an indium tin oxide, The laminated body of Claim 8 characterized by the above-mentioned. An image display apparatus using the laminate according to claim 8 or 9 .