JP6745596B2 - Adhesive composition - Google Patents

Description

The present invention relates to a pressure-sensitive adhesive composition useful for forming a pressure-sensitive adhesive layer having excellent durability in a pressure-sensitive adhesive layer-carrying optical film used for liquid crystal display devices and the like.

An optical film represented by a polarizing plate obtained by laminating and laminating a transparent resin film on one side or both sides of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device. An optical film such as a polarizing plate is often used by being attached to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). For this reason, as an optical film, an optical film with a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer provided in advance on one surface thereof is known.

JP, 2010-229321, A

2. Description of the Related Art In recent years, liquid crystal display devices have been developed for mobile device applications represented by smartphones and tablet-type terminals and in-vehicle device applications represented by car navigation systems. In such an application, there is a possibility of being exposed to a harsh environment as compared with the conventional indoor TV application, and therefore improvement of the durability of the device is a problem.

Similarly, durability is required for the pressure-sensitive adhesive layer-attached optical film that constitutes a liquid crystal display device or the like. That is, the pressure-sensitive adhesive layer incorporated in a liquid crystal display device or the like may be placed in a high temperature or high temperature and high humidity environment, or in an environment in which high and low temperatures are repeated. The optical film is required to be able to suppress problems such as floating or peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which it is bonded, foaming of the pressure-sensitive adhesive layer, etc., even under these environments, and It is also required that the optical characteristics do not deteriorate. In particular, when the optical film is a polarizing plate, the pressure-sensitive adhesive layer is required to have higher durability performance than a general optical film due to a strong shrinkage stress under a high temperature environment. Due to the increasing demand for improving the durability of the liquid crystal display device, the durability required for the pressure-sensitive adhesive layer has recently become extremely severe.

Therefore, the object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting excellent durability even under such severe durability conditions.

（式中、ｎは１〜４の整数を示し、Ａ^１は水素原子又はアルキル基を示し、Ｘ^１は置換基を有していてもよいメチレン基を示し、ｎが２以上のとき、前記置換基は同一又は異なっていてもよい）
で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位と、下記式（ａ２）

（式中、ｍは５以上の整数を示し、Ａ^２は水素原子又はアルキル基を示し、Ｘ^２は置換基を有していてもよいメチレン基を示し、前記置換基は同一又は異なっていてもよい）
で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位とを含み、
カルボキシル基含有（メタ）アクリレート由来の構成単位の割合が、（メタ）アクリル系樹脂を構成する全構成単位１００重量部に対して、１．０重量部以下である、粘着剤組成物。
［２］（メタ）アクリル系樹脂を構成する全構成単位１００重量部に対して、式（ａ１）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位の割合は１．５〜４．５重量部であり、式（ａ２）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位の割合は０．２５〜１．０重量部である［１］に記載の粘着剤組成物。
［３］（メタ）アクリル系樹脂は、ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ａ３−１）由来の構成単位と、ガラス転移温度が０℃以上のアルキルアクリレート（ａ３−２）由来の構成単位とを含有するアルキルアクリレート（ａ３）由来の構成単位を含む［１］又は［２］に記載の粘着剤組成物。
［４］ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ａ３−１）由来の構成単位と、ホモポリマーのガラス転移温度が０℃以上のアルキルアクリレート（ａ３−２）由来の構成単位との割合（重量比）は、（ａ３−１）／（ａ３−２）＝２０／８０〜９５／５である［３］に記載の粘着剤組成物。
［５］カルボキシル基含有（メタ）アクリレート由来の構成単位の割合は、（メタ）アクリル系樹脂を構成する全構成単位１００重量部に対して、０．００１〜０．５重量部である［１］〜［４］のいずれかに記載の粘着剤組成物。
［６］（メタ）アクリル系樹脂の重量平均分子量は、ポリスチレン換算で、６．０×１０^５〜２．５×１０^６である［１］〜［５］のいずれかに記載の粘着剤組成物。
［７］架橋剤（Ｂ）は、芳香族イソシアネート化合物及び／又は該芳香族イソシアネート化合物の多価アルコール化合物による付加体である［１］〜［６］のいずれかに記載の粘着剤組成物。
［８］架橋剤（Ｂ）の割合は、（メタ）アクリル系樹脂（Ａ）１００重量部に対して、０．０１〜１０重量部である［１］〜［７］のいずれかに記載の粘着剤組成物。
［９］シラン化合物（Ｃ）は、下記式（ｃ１）

（式中、Ｂは、炭素数１〜２０のアルカンジイル基又は炭素数３〜２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置換されてもよく、Ｒ^１は炭素数１〜５のアルキル基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基を示す）
で表されるシラン化合物である［１］〜［８］のいずれかに記載の粘着剤組成物。
［１０］式（ｃ１）のＢは炭素数１〜１０のアルカンジイル基であり、Ｒ^１は炭素数１〜５のアルキル基であり、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、炭素数１〜５のアルコキシ基である［９］に記載の粘着剤組成物。
［１１］シラン化合物（Ｃ）の割合は、（メタ）アクリル系樹脂（Ａ）１００重量部に対して、０．０１〜１０重量部である［１］〜［１０］のいずれかに記載の粘着剤組成物。
［１２］粘着剤組成物から形成される粘着剤のゲル分率は、５０〜９５％である［１］〜［１１］のいずれかに記載の粘着剤組成物。
［１３］ガラス基板に、前記粘着剤組成物から形成される粘着剤層を貼合し、温度２３℃、相対湿度５０％の条件下２４時間後の前記粘着剤層の粘着力は、剥離速度３００ｍｍ／分において、０．５〜１０Ｎ／２５ｍｍである［１］〜［１２］のいずれかに記載の粘着剤組成物。
［１４］光学フィルムに積層される粘着剤層の形成に用いられる、［１］〜［１３］のいずれかに記載の粘着剤組成物。 The present inventor has completed the present invention as a result of extensive studies to solve the above problems.
That is, the present invention includes the following.
[1] A pressure-sensitive adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth)acrylic resin (A) has the following formula (a1)

(In the formula, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, The substituents may be the same or different)
A structural unit derived from a hydroxy group-containing (meth)acrylate represented by the following formula (a2)

(In the formula, m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, X ² represents a methylene group which may have a substituent, and the substituents are the same or different. Good)
And a structural unit derived from a hydroxy group-containing (meth)acrylate represented by
The pressure-sensitive adhesive composition, wherein the proportion of the structural unit derived from a carboxyl group-containing (meth)acrylate is 1.0 part by weight or less, relative to 100 parts by weight of all the structural units constituting the (meth)acrylic resin.
[2] The ratio of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) to 100 parts by weight of all the structural units constituting the (meth)acrylic resin is 1.5 to 4. It is 5 parts by weight, and the ratio of the constituent unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is 0.25 to 1.0 parts by weight, the pressure-sensitive adhesive composition according to [1].
[3] The (meth)acrylic resin is a structural unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0°C, and an alkyl acrylate (a3-2) having a glass transition temperature of 0°C or more. The pressure-sensitive adhesive composition according to [1] or [2], which contains a structural unit derived from an alkyl acrylate (a3) containing a structural unit derived from.
[4] A structural unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0° C., and a structural unit derived from an alkyl acrylate (a3-2) having a homopolymer glass transition temperature of 0° C. or higher. The ratio (weight ratio) of (a3-1)/(a3-2)=20/80 to 95/5 is the pressure-sensitive adhesive composition according to [3].
[5] The proportion of the structural unit derived from the carboxyl group-containing (meth)acrylate is 0.001 to 0.5 part by weight, relative to 100 parts by weight of all the structural units constituting the (meth)acrylic resin. ] The adhesive composition in any one of [4].
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], which has a weight average molecular weight of 6.0×10 ^{5 to} 2.5×10 ⁶ in terms of polystyrene, in terms of polystyrene. Stuff.
[7] The pressure-sensitive adhesive composition according to any one of [1] to [6], wherein the crosslinking agent (B) is an aromatic isocyanate compound and/or an adduct of the aromatic isocyanate compound with a polyhydric alcohol compound.
[8] The proportion of the cross-linking agent (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylic resin (A). Adhesive composition.
[9] The silane compound (C) has the following formula (c1).

(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH ₂ — may be substituted with —O— or —CO—, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are respectively Independently, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
The pressure-sensitive adhesive composition according to any one of [1] to [8], which is a silane compound represented by.
[10] B in the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ Are each independently an alkoxy group having 1 to 5 carbon atoms, [9].
[11] The proportion of the silane compound (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylic resin (A), and the proportion is [1] to [10]. Adhesive composition.
[12] The pressure-sensitive adhesive composition according to any one of [1] to [11], wherein the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition has a gel fraction of 50 to 95%.
[13] A pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is attached to a glass substrate, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer after 24 hours under the conditions of a temperature of 23° C. and a relative humidity of 50% is a peeling speed The pressure-sensitive adhesive composition according to any one of [1] to [12], which has a viscosity of 0.5 to 10 N/25 mm at 300 mm/min.
[14] The pressure-sensitive adhesive composition according to any one of [1] to [13], which is used for forming a pressure-sensitive adhesive layer laminated on an optical film.

The pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer having excellent durability even under severe durability conditions.

It is a schematic sectional drawing which shows an example of the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate. FIG. 3 is a schematic cross-sectional view showing another example of the layer structure of the polarizing plate. FIG. 4 is a schematic cross-sectional view showing an example of an optical laminate including a pressure-sensitive adhesive layer-carrying optical film formed from the pressure-sensitive adhesive composition according to the present invention. FIG. 5: is a schematic sectional drawing which shows an example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. FIG. 6 is a schematic cross-sectional view showing still another example of the optical laminate including the optical film with a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention. FIG. 7 is a schematic cross-sectional view showing another example of the optical laminate including the pressure-sensitive adhesive layer-carrying optical film formed from the pressure-sensitive adhesive composition according to the present invention. FIG. 8 is a schematic cross-sectional view showing still another example of the optical laminate including the pressure-sensitive adhesive layer-carrying optical film formed from the pressure-sensitive adhesive composition according to the present invention.

[1] Adhesive Composition The adhesive composition of the present invention contains a (meth)acrylic resin (A), a cross-linking agent (B), and a silane compound (C).

（式中、ｎは１〜４の整数を示し、Ａ^１は水素原子又はアルキル基を示し、Ｘ^１は置換基を有していてもよいメチレン基を示し、ｎが２以上のとき、前記置換基は同一又は異なっていてもよい）

（式中、ｍは５以上の整数を示し、Ａ^２は水素原子又はアルキル基を示し、Ｘ^２は置換基を有していてもよいメチレン基を示し、前記置換基は同一又は異なっていてもよい） [1-1] (Meth)acrylic resin (A)
The (meth)acrylic resin (A) is a polymer or copolymer containing a structural unit derived from a (meth)acrylic monomer as a main component (preferably containing 50% by weight or more), and has the following formula (a1) ) And (a2), a structural unit derived from a hydroxy group-containing (meth)acrylate is included.

(In the formula, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, The substituents may be the same or different)

(In the formula, m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, X ² represents a methylene group which may have a substituent, and the substituents are the same or different. Good)

That is, since the (meth)acrylic resin (A) of the present invention has hydroxyalkyl groups having different carbon chain lengths (n and m) in the side chains, in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, ( It is estimated that the crosslink density between (meth)acrylic resins can be optimized. By optimizing the crosslinking density, a pressure-sensitive adhesive layer having an excellent balance of hardness and softness (or having an optimum hardness) can be formed, so that durability can be improved and the interface peels even in a high temperature environment. (Or floating) and foaming can be effectively suppressed. Moreover, even if a strong shrinkage stress is generated, the pressure-sensitive adhesive layer can effectively alleviate the stress, and therefore blank areas due to the shrinkage of the optical film (for example, the deflection plate) can be prevented. Further, the reworkability (peelability) can be improved by optimizing the crosslink density. In the present specification, durability means, for example, in an interface between the pressure-sensitive adhesive layer and an optical member adjacent thereto under a high temperature environment, a high temperature and high humidity environment, an environment in which high temperature and low temperature are repeated, and the like. The characteristics that can prevent floating and peeling (sometimes called peeling resistance) and the characteristics that can suppress problems such as foaming of the pressure-sensitive adhesive layer (sometimes called foaming resistance) are referred to. Further, in the present invention, the cohesive failure resistance refers to a property capable of suppressing cohesive failure (or breaking) of the pressure-sensitive adhesive layer.

In formulas (a1) and (a2), X ¹ and X ² represent a methylene group which may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t- C _1-10 alkyl group such as butyl group, pentyl group and hexyl group, preferably C _1-6 alkyl group, more preferably C _1-3 alkyl group), cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.) , Aryl group [phenyl group, alkylphenyl group (tolyl group, xylyl group, etc.)] aralkyl group (benzyl group, etc.), alkoxy group (eg, C _1-4 alkoxy group such as methoxy group, ethoxy group), polyoxyalkylene Group (for example, dioxyethylene group), cycloalkoxy group (for example, C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (for example, phenoxy group), aralkyloxy group (for example, , Benzyloxy group, etc.), alkylthio group (eg, C _1-4 alkylthio group such as methylthio group, ethylthio group, etc.), cycloalkylthio group (eg, cyclohexylthio group, etc.), arylthio group (eg, thiophenoxy group, etc.) ), an aralkylthio group (eg, a benzylthio group), an acyl group (eg, an acetyl group), a nitro group, a cyano group and the like. Of these, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group and the like are preferable, and an alkyl group (eg, methyl group, ethyl group, etc.) is particularly preferable.

A ¹ and A ² each represent a hydrogen atom or an alkyl group, and the alkyl group may be the alkyl group (preferably a methyl group etc.) exemplified in X ¹ and X ² .
In formula (a1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2. In the formula (a2), m is an integer of 5 or more (for example, an integer of 5 to 20), preferably 5 to 15 (for example, an integer of 5 to 11), and more preferably 5 to 9 (for example, an integer of 5 to 7). ), especially 5. Further, m may be an even number of 5 or more (for example, 6, 8, 10, 12, etc.) or an odd number of 5 or more (for example, 5, 7, 9, 11, etc.).

Specific examples of the hydroxy group-containing (meth)acrylate (a1) include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, and (meth)acrylic. Acid 1-hydroxybutyl, (meth)acrylic acid 1-hydroxypentyl, and other (meth)acrylic acid 1- _{hydroxyC 1-8} alkyl; (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl 2-hydroxy C _2-9 alkyl (meth)acrylate such as 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate; (meth)acrylic (Meth) such as 3-hydroxypropyl acid, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 3-hydroxyhexyl (meth)acrylate, and 3-hydroxyheptyl (meth)acrylate. 3-hydroxy C _3-10 alkyl acrylate; 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate , 4-hydroxy C _4-11 alkyl (meth)acrylate such as 4-hydroxyoctyl (meth)acrylate; 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2 (meth)acrylate -Hydroxypropyl, 2-hydroxy-3-phenoxypropyl (meth)acrylate and the like can be mentioned. Of these, a hydroxy-containing (meth)acrylate in which n is 2, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, from the viewpoint of durability; A hydroxy-containing (meth)acrylate in which n is 3 such as 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 3-hydroxypentyl (meth)acrylate is preferable. In particular, the hydroxy-containing (meth)acrylate in which n is 2 is preferable, and among these, 2-hydroxyethyl (meth)acrylate is preferable.

Specific examples of the hydroxy group-containing (meth)acrylate (a2) include 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, and (meth)acrylic. 5-hydroxyoctyl acid, 5-hydroxy C _5-12 alkyl (meth)acrylate such as 5-hydroxynonyl (meth)acrylate; 6-hydroxyhexyl (meth)acrylate, 6-hydroxyheptyl (meth)acrylate , (Meth)acrylic acid 6-hydroxyoctyl, (meth)acrylic acid 6-hydroxynonyl, (meth)acrylic acid 6-hydroxydecyl, and other (meth)acrylic acid 6-hydroxy C _6-13 alkyl; Acid 7-hydroxyheptyl, (meth)acrylic acid 7-hydroxyoctyl, (meth)acrylic acid 7-hydroxynonyl, (meth)acrylic acid 7-hydroxydecyl, (meth)acrylic acid 7-hydroxyundecyl and the like (meth ) 7-hydroxy C _7-14 alkyl acrylate; 8-hydroxyoctyl (meth)acrylate, 8-hydroxynonyl (meth)acrylate, 8-hydroxydecyl (meth)acrylate, 8-hydroxy (meth)acrylate Undecyl, 8-hydroxy C _8-15 alkyl (meth)acrylate such as 8-hydroxydodecyl (meth)acrylate; 9-hydroxynonyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, (meth ) 9-Hydroxyundecyl acrylate, 9-hydroxydodecyl (meth)acrylate, 9-hydroxytridecyl (meth)acrylate, etc. 9-hydroxy C _9-16 alkyl (meth)acrylate; (meth)acrylic acid (Meth)acryl such as 10-hydroxydecyl, 10-hydroxyundecyl (meth)acrylate, 10-hydroxydodecyl (meth)acrylate, 10-hydroxytridecyl acrylate, and 10-hydroxytetradecyl (meth)acrylate. Acid 10-hydroxy C _10-17 alkyl; (meth)acrylic acid 11-hydroxyundecyl, (meth)acrylic acid 11-hydroxydodecyl, (meth)acrylic acid 11-hydroxytridecyl, (meth)acrylic acid 11-hydroxy 10-hydroxy C _11-18 alkyl (meth)acrylate such as tetradecyl and 11-hydroxypentadecyl (meth)acrylate; 12-hydroxy (meth)acrylate 12-Hydroxy C _12-19 alkyl (meth)acrylate, such as dodecyl, 12-hydroxytridecyl (meth)acrylate, 12-hydroxytetradecyl (meth)acrylate; 13-hydroxypentamethacrylate Decyl, 13-hydroxytetradecyl (meth)acrylate, 13- _{hydroxyC13-20} alkyl (meth)acrylate such as 13-hydroxypentadecyl (meth)acrylate; 14-hydroxytetradecyl (meth)acrylate, 14-hydroxy C _14-21 alkyl (meth)acrylate such as 14-hydroxypentadecyl (meth)acrylate; 15-hydroxypentadecyl (meth)acrylate, 15-hydroxyheptadecyl (meth)acrylate and the like ( _Examples thereof include 15-hydroxy C _15-22 alkyl meth)acrylate. Among these, from the viewpoint of durability, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, 5-hydroxyoctyl (meth)acrylate, A hydroxy-containing (meth)acrylate having an n of 5 such as 5-hydroxynonyl (meth)acrylate is preferable, and 5-hydroxypentyl (meth)acrylate is particularly preferable.

The ratio of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight based on 100 parts by weight of all the structural units constituting the (meth)acrylic resin. Is preferred, and the proportion of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is preferably 0.25 to 1.0 part by weight. Further, the ratio (weight ratio) of the constitutional unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) to the constitutional unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is Although not particularly limited as long as it is within the above range, preferably (a1)/(a2)=13/1 to 3/1 (for example, 11/1 to 3/1), more preferably 9/1 to 4/1 , Especially 7/1 to 5/1. Within the above range, it is advantageous for forming an optimum crosslinked structure, and further, characteristics such as durability can be improved.

The (meth)acrylic resin (A) may include a structural unit derived from the alkyl acrylate (a3) and a structural unit derived from the substituent-containing alkyl acrylate (a4).

Among the alkyl acrylates (a3), examples of the alkyl acrylate (a3-1) having a homopolymer glass transition temperature (Tg) of less than 0° C. include ethyl acrylate, n- and i-propyl acrylate, n- and i-. Butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i- Examples thereof include linear or branched alkyl acrylates having an alkyl group with about 2 to 12 carbon atoms such as decyl acrylate and n-dodecyl acrylate. The alkyl acrylate (a3) may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but has 2 to 10 carbon atoms from the viewpoint of followability (or flexibility or adhesiveness) to the optical film. Alkyl acrylate of, preferably C 3-8 alkyl acrylate, more preferably C 4-6 alkyl acrylate, especially n-butyl alkyl acrylate. When n-butylalkyl acrylate is used, the followability can be increased, which is advantageous for peeling resistance, for example. These alkyl acrylates (a3-1) can be used alone or in combination of two or more.

Examples of the alkyl acrylate (a3-2) having a homopolymer Tg of 0° C. or higher include methyl acrylate, cycloalkyl acrylate (for example, cyclohexyl acrylate, isobornyl acrylate), stearyl acrylate, t-butyl acrylate, and the like. Methyl acrylate is particularly preferred. When methyl acrylate is used, the strength can be increased, which is advantageous for cohesive failure, for example. These alkyl acrylates (a3-2) can be used alone or in combination of two or more. For the Tg of the homopolymer of alkyl acrylate, reference can be made to literature values such as POLYMER HANDBOOK (Wiley-Interscience).

From the viewpoint of durability and reworkability of the pressure-sensitive adhesive layer, the proportion of the structural unit derived from alkyl acrylate in the (meth)acrylic resin (A) is 100% by weight of all structural units constituting the (meth)acrylic resin (A). For example, 40 parts by weight or more (eg, 50 to 98 parts by weight), preferably 60 parts by weight or more (eg, 70 to 95 parts by weight), and more preferably 70 parts by weight or more (eg, 80 parts by weight). ~90 parts by weight).

When an alkyl acrylate having a homopolymer Tg of less than 0° C. is used in combination with an alkyl acrylate having a homopolymer Tg of 0° C. or higher, cohesive failure resistance and followability (foaming resistance and peeling resistance) can be achieved at the same time The durability of the film (for example, a polarizing plate) against dimensional change can be improved.

Ratio (weight ratio) of the structural unit derived from the alkyl acrylate (a3-1) having a glass transition temperature of less than 0°C to the structural unit derived from the alkyl acrylate (a3-2) having a glass transition temperature of 0°C or higher. Is (a3-1)/(a3-2)=20/80 to 95/5 (for example, 30/70 to 90/10), preferably 40/60 to 85/15, more preferably 55/45 to 75/25. Within the above range, the durability can be further improved. The greater the proportion of the structural unit derived from the alkyl acrylate (a3-1) having a glass transition temperature of less than 0°C, the more the followability is improved. The larger the proportion of the structural unit derived from the alkyl acrylate (a3-2) having a glass transition temperature of 0° C. or higher, the higher the cohesive failure resistance.

Examples of the substituent-containing alkyl acrylate (a4) include an alkyl acrylate in which a substituent is introduced into the alkyl group in the alkyl acrylate (a3-1) (a hydrogen atom of the alkyl group is replaced by a substituent). .. The substituent may be, for example, an aryl group (phenyl group etc.), an aryloxy group (phenoxy group), an alkoxy group (eg methoxy group, ethoxy group etc.) and the like. Examples of the substituent-containing alkyl acrylate (a3-3) include alkoxyalkyl acrylate (eg, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), aryloxyalkyl acrylate (eg, phenoxyethyl acrylate, etc.), aryloxypolyalkylene glycol mono. Examples thereof include acrylate and polyalkylene glycol monoacrylate. These alkyl acrylates (a3-3) can be used alone or in combination of two or more. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, it is possible to improve white spots in the polarizing plate during the durability test. The alkylene group of the aryloxypolyalkylene glycol monoacrylate and polyalkylene glycol monoacrylate may be, for example, a C _1-6 alkylene group (preferably ethylene group etc.) such as methylene group, ethylene group, propylene group, and the like, The repeating unit of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 (particularly 2) from the viewpoint of durability of the adhesive layer formed from the adhesive composition. In the present invention, since the pressure-sensitive adhesive composition contains the (meth)acrylic resin (A) and the crosslinking agent (B) described below, an optimum crosslinked structure (or crosslink density) can be formed, and therefore the number of repeating units of the oxyalkylene group. Shows a good reworkability even if is relatively small. Specific examples include phenoxydi to hepta C _1-3 alkylene glycol acrylates such as phenoxydiethylene glycol acrylate, and di to hepta C _1-3 alkylene monoacrylates such as diethylene glycol monoacrylate.

The ratio of the constituent unit derived from the substituent-containing alkyl acrylate is, for example, 0 to 30 parts by weight (e.g., 1 to 25 parts by weight), relative to 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). It is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight.

The (meth)acrylic resin (A) is a monomer (a5) other than the hydroxy group-containing (meth)acrylates (a1) and (a2), the alkyl acrylate (a3) and the substituent-containing alkyl acrylate (a4). And a structural unit derived from The other monomers may be used alone or in combination of two or more. Examples of the other monomer (a5) include a monomer (a5-1) having a polar functional group other than a hydroxy group, an acrylamide monomer (a5-2), and a methacrylate (methacrylic acid ester) (a5- 3), a methacrylamide monomer (a5-4), a styrene monomer (a5-5), a vinyl monomer (a5-6), a single monomer having a plurality of (meth)acryloyl groups in the molecule. Examples thereof include a monomer (a5-7).

Examples of the monomer (a5-1) having a polar functional group other than a hydroxy group include (meth)acrylates having a substituent such as a carboxyl group, a substituted or unsubstituted amino group, and a heterocyclic group such as an epoxy group. .. Specifically, acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl Monomers having a heterocyclic group such as (meth)acrylate and 2,5-dihydrofuran; aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate and the like. Monomers having substituted or unsubstituted amino groups; (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth)acrylates (for example, carboxyethyl (meth)acrylate, carboxypentyl (meth ) Acrylate) and other monomers having a carboxyl group. These monomers can be used alone or in combination of two or more. From the viewpoint of preventing the peelability of the separate film that can be laminated on the pressure-sensitive adhesive layer from decreasing, it is preferable that the constitutional unit derived from the monomer having an amino group is not substantially contained. The term "substantially free from" means that the amount is less than 1.0 part by weight based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A).

In the present invention, the durability of the pressure-sensitive adhesive layer can be further improved by only containing a small amount of a structural unit derived from a monomer having a carboxyl group (a structural unit derived from a carboxyl group-containing (meth)acrylate). Even when is applied to the ITO substrate, it is possible to effectively suppress the corrosion of ITO and improve the durability. That is, both excellent durability and ITO corrosion resistance can be achieved. Even more surprisingly, when a small amount of the structural unit derived from the carboxyl group-containing (meth)acrylate is contained, reworkability may be improved.

The proportion of the structural unit derived from the carboxyl group-containing (meth)acrylate is, for example, 1.0 part by weight or less (for example, 0 to 0.8 part by weight), relative to 100 parts by weight of the structural unit derived from the (meth)acrylate. Preferably 0.5 parts by weight or less (eg 0.001 to 0.5 parts by weight), more preferably 0.3 parts by weight or less (eg 0.005 to 0.3 parts by weight), especially 0.2 parts by weight or less. (For example, 0.01 to 0.2 parts by weight), and particularly 0.15 parts by weight or less (for example, 0.05 to 0.15 parts by weight). When it is at most the upper limit, ITO corrosion can be suppressed, and when it is at least the lower limit, durability can be improved.

Examples of the acrylamide monomer (a5-2) include N-methylol acrylamide, N-(2-hydroxyethyl)acrylamide, N-(3-hydroxypropyl)acrylamide, N-(4-hydroxybutyl)acrylamide, N-(5-hydroxypentyl)acrylamide, N-(6-hydroxyhexyl)acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-(3-dimethylaminopropyl)acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-[2-(2-oxo-1-imidazolidinyl)ethyl]acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (Methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(1-methylethoxymethyl)acrylamide, N-(1-methylpropoxymethyl)acrylamide, N-(2-methyl Propoxymethyl)acrylamide [Alias: N-(isobutoxymethyl)acrylamide], N-(butoxymethyl)acrylamide, N-(1,1-dimethylethoxymethyl)acrylamide, N-(2-methoxyethyl)acrylamide, N- (2-Ethoxyethyl)acrylamide, N-(2-propoxyethyl)acrylamide, N-[2-(1-methylethoxy)ethyl]acrylamide, N-[2-(1-methylpropoxy)ethyl]acrylamide, N- [2-(2-Methylpropoxy)ethyl]acrylamide [Alias: N-(2-isobutoxyethyl)acrylamide], N-(2-butoxyethyl)acrylamide, N-[2-(1,1-dimethylethoxy)] Ethyl] acrylamide etc. Among these, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-(2-methylpropoxymethyl)acrylamide and the like are preferable.

Examples of the methacrylate (methacrylic acid ester) (a5-3) include linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; i-butyl methacrylate. Branched alkyl methacrylates such as 2-ethylhexyl methacrylate and i-octyl methacrylate; isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, t-butylcyclohexyl methacrylate, Examples thereof include mono- or dicycloalkyl methacrylates such as cyclohexylphenyl methacrylate; alkoxyalkyl methacrylates such as 2-methoxyethyl methacrylate and ethoxymethyl methacrylate; aralkyl methacrylates such as benzyl methacrylate.

Examples of the methacrylamide monomer (a5-4) include a methacrylamide monomer corresponding to the acrylamide monomer described in (a5-2).

Examples of the styrene-based monomer (a5-5) include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, etc. Alkyl styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene and the like.

Examples of the vinyl monomer (a5-6) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; halogen such as vinyl chloride and vinyl bromide. Vinylidene halide; vinylidene halide such as vinylidene chloride; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomer such as butadiene, isoprene and chloroprene; unsaturated nitrile such as acrylonitrile and methacrylonitrile And so on.

Examples of the monomer (a5-7) having a plurality of (meth)acryloyl groups in the molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. A monomer having a (meth)acryloyl group; a monomer having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate.

From the viewpoint of reworkability of the pressure-sensitive adhesive layer, the (meth)acrylic resin (A) is a methacrylic resin such as methacrylate (methacrylic acid ester) (a5-3) or methacrylamide monomer (a5-4). It is preferable that the ratio (or content) of the structural units derived from the monomer is small. That is, the ratio of the structural unit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of all the structural units constituting the (meth)acrylic resin (A). In particular, it may be 1 part by weight or less.
The proportion of the structural unit derived from the other monomer (a5) is, for example, 0 to 20 parts by weight, preferably 0 to 100 parts by weight of all the structural units constituting the (meth)acrylic resin (A). The amount may be about 10 to 10 parts by weight (for example, 0.001 to 10 parts by weight), and more preferably about 0 to 5 parts by weight (for example, 0.01 to 3 parts by weight).

The (meth)acrylic resin (A) has a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography GPC of, for example, 6.0×10 ^{5 to} 2.5×10 ⁶ (for example, 8. 0×10 ^{5 to} 2.5×10 ⁶ ), preferably 1.0×10 ^{6 to} 2.0×10 ⁶ , and more preferably 1.2×10 ^{6 to} 1.8×10 ⁶ (eg 1.3. It is in the range of x10 ^{6 to} 1.6x10 ⁶ . When the upper limit of Mw is less than or equal to it, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to the substrate, and when Mw is more than the lower limit thereof, the pressure-sensitive adhesive with respect to dimensional change of the optical film. This is advantageous for improving the trackability of the layers. The molecular weight distribution represented by the ratio (Mw/Mn) of the weight average molecular weight Mw and the number average molecular weight Mn is usually 2 to 10, preferably 3 to 8, and more preferably 4 to 6.

The (meth)acrylic resin (A) preferably has a single peak when the Mw on the discharge curve in GPC is in the range of 1.0×10 ^{3 to} 2.5×10 ⁶ . Use of the (meth)acrylic resin (A) having a peak number of 1 is advantageous for improving the durability of the pressure-sensitive adhesive layer.

In the above range of the obtained emission curve, “having a single peak” means having only one maximum value in the range of Mw 1.0×10 ^{3 to} 2.5×10 ⁶ . In this specification, in the GPC emission curve, one having an S/N ratio of 30 or more is defined as a peak. The peak number of the GPC emission curve and the Mw and Mn of the (meth)acrylic resin (A) can be determined by the GPC measurement conditions described in the section of Examples.

When the (meth)acrylic resin (A) is dissolved in ethyl acetate to obtain a solution having a concentration of 20% by weight, the viscosity at 25° C. is preferably 20 Pa·s or less, and 0.1 to 7 Pa·s. Is more preferable. A viscosity within this range is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate. The viscosity can be measured with a Brookfield viscometer.

The glass transition temperature (Tg) of the (meth)acrylic resin (A) is, for example, -60 to 0°C (for example, -50 to -10°C), preferably -50 to -20°C, and more preferably -40 to 40°C. It may be -20°C (for example, -40 to -25°C). Within this range, it is advantageous to improve durability. The glass transition temperature can be measured by a differential scanning calorimeter (DSC).

The (meth)acrylic resin (A) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method, and a solution polymerization method is particularly preferable. As the solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and a temperature condition of about 40 to 90° C. (preferably 50 to 80° C.) is 3 to A method of stirring for about 15 hours can be used. To control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer and the thermal initiator may be added to the organic solvent.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator or the like is used. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone. As the thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropio) Azo), 2,2′-azobis(2-hydroxymethylpropionitrile), and other azo compounds; lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide. Organic peroxides such as diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate and (3,5,5-trimethylhexanoyl) peroxide Examples thereof include inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide. Further, a redox type initiator in which a peroxide and a reducing agent are used in combination can also be used.

The proportion of the polymerization initiator is about 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of the monomers constituting the (meth)acrylic resin. The (meth)acrylic resin may be polymerized by a polymerization method using active energy rays (for example, ultraviolet rays).

Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. And the like.

[1-2] Crosslinking agent (B)
The pressure-sensitive adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) reacts with the polar functional group containing a hydroxy group in the (meth)acrylic resin (A). In the present invention, the OH group (hydroxyl group) of the hydroxyalkyl group having a predetermined different carbon chain introduced into the side chain of the (meth)acrylic resin (A) reacts with the cross-linking agent (B), resulting in durability. And a crosslinked structure advantageous for reworkability is formed.

Examples of the cross-linking agent (B) include conventional cross-linking agents (for example, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and particularly pot life of pressure-sensitive adhesive compositions and pressure-sensitive adhesive layer attachment. From the viewpoint of the durability of the optical film and the crosslinking speed, an isocyanate compound is preferable.

The isocyanate compound is preferably a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include an aliphatic isocyanate compound (e.g. hexamethylene diisocyanate) and an alicyclic isocyanate compound (e.g. isophorone diisocyanate). ), aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.) and the like. The cross-linking agent (B) is an adduct (adduct) of the above-mentioned isocyanate compound with a polyhydric alcohol compound [eg, an adduct with glycerol, trimethylolpropane, etc.], isocyanurate compound, buret type compound, polyether polyol, polyester. It may be a derivative such as a urethane prepolymer type isocyanate compound which has been subjected to an addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like. The cross-linking agent (B) can be used alone or in combination of two or more kinds. Of these, representatively, aromatic isocyanate compounds (eg tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (eg hexamethylene diisocyanate) or polyhydric alcohol compounds (glycerol, trimethylol propane) of these An adduct is mentioned. If the cross-linking agent (B) is an adduct of an aromatic isocyanate compound and/or a polyhydric alcohol compound thereof, it may be advantageous for the formation of an optimum cross-linking density (or cross-linking structure). It is possible to improve the property. In particular, when it is an adduct of a tolylene diisocyanate compound and/or a polyhydric alcohol compound thereof, durability (for example, durability when an adhesive layer is applied to an ITO substrate) can be further improved.

The proportion of the cross-linking agent (B) is, for example, 0.01 to 10 parts by weight (e.g., 0.05 to 5 parts by weight), preferably 0.1 to 100 parts by weight of the (meth)acrylic resin (A). It may be 3 parts by weight (eg 0.1 to 2 parts by weight), and more preferably 0.2 to 1 parts by weight (eg 0.3 to 0.8 parts by weight). When it is at most the upper limit, it is advantageous to improve the followability (or peeling resistance), and when it is at least the lower limit, it is advantageous to improve cohesion resistance (or foaming resistance) and reworkability.

[1-3] Silane compound (C)
The pressure-sensitive adhesive composition contains a silane compound (C). By including the silane compound (C), the adhesiveness (or adhesiveness) between the pressure-sensitive adhesive layer and the metal layer, transparent electrode, glass substrate or the like can be improved. The silane compound (C) may be any silane compound capable of binding to a reactive group (for example, an OH group of a hydroxyl group) of the (meth)acrylic resin (A), and examples thereof include vinyltrimethoxysilane and vinyltriethoxy. Silane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 1 , 3-bis(3′-trimethoxypropyl)urea and the like.

The silane compound (C) may be a silicone oligomer type compound, and when the silicone oligomer is expressed as a combination of monomers, for example, 3-mercaptopropyldi or trimethoxysilane-tetramethoxysilane oligomer, 3 -Mercaptoalkyl group-containing oligomers such as mercaptomethyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer An oligomer in which the mercaptoalkyl group of the mercaptoalkyl group-containing oligomer is replaced with another substituent [3-glycidoxypropyl group, (meth)acryloyloxypropyl group, vinyl group, amino group, etc.] ..

The silane compound (C) may be preferably a silane compound represented by the following formula (c1). When the pressure-sensitive adhesive composition contains the silane compound represented by the following formula (c1), the adhesiveness (or the adhesiveness) can be further improved, so that the pressure-sensitive adhesive layer having excellent peeling resistance can be formed. Furthermore, the pressure-sensitive adhesive layer is also excellent in reworkability. In particular, even when a pressure-sensitive adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate) under a high temperature environment, the adhesiveness (or adhesiveness) can be maintained and high durability can be exhibited.

（式中、Ｂは、炭素数１〜２０のアルカンジイル基又は炭素数３〜２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置換されてもよく、Ｒ^１は炭素数１〜５のアルキル基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基を示す）

(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH ₂ — may be substituted by —O— or —CO—, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each Independently, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)

In the formula (c1), B is an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group (for example, 1,2-cyclobutylene group), cyclopentylene group (eg, 1,2-cyclopentylene group), cyclohexylene group (eg, 1,2-cyclohexylene group), cyclooctylene group (eg, 1,2- A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as a cyclooctylene group); or —CH ₂ — constituting these alkanediyl groups and the alicyclic hydrocarbon group is —O— or A group substituted with —CO— is shown. Preferred B is an alkanediyl group having 1 to 10 carbon atoms. R ¹ represents an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, and a pentyl group, and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 5 carbon atoms exemplified in the above R ¹ ; or a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, an s-butoxy group. , T-butoxy group and other alkoxy groups having 1 to 5 carbon atoms. Preferred ^{R 2, R 3, R 4} , R 5 and ^{R 6} is an alkoxy group having 1 to 5 carbon atoms. These silane compounds (C) can be used alone or in combination of two or more.

Specific examples of the silane compound (c1) include (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis( Trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(trimethoxy) (Silyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl) Hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl)octane and other bis(triC _1-5 alkoxysilyl)C _1-10 alkane; bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethylsilyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1 ,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl)hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8 - bis bis (such as dimethoxyethyl silyl) octane (di _{C 1-5} alkoxy _{C 1-5} alkyl _{silyl) C 1-10} alkanes; 1,6-bis (methoxy dimethyl silyl) hexane, 1,8-bis (methoxy _Examples thereof include bis(mono C _1-5 alkoxy-di C _1-5 alkylsilyl) C _1-10 alkane such as dimethylsilyl)octane. Of these, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl) Bis(triC _1-3 alkoxysilyl)C _1-10 alkanes such as pentane, 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are preferable, and 1,6 is particularly preferable. -Bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are preferred.

The ratio of the silane compound (C) is, for example, 0.01 to 10 parts by weight (e.g. 0.03 to 5 parts by weight), preferably 0.05, relative to 100 parts by weight of the (meth)acrylic resin (A). -3 parts by weight, more preferably 0.1-1 parts by weight (e.g. 0.2-0.5 parts by weight). When it is at most the upper limit, it is advantageous for suppressing the bleed-out of the silane compound (C) from the pressure-sensitive adhesive layer, and when it is at least the lower limit, the adhesiveness between the pressure-sensitive adhesive layer and the metal layer, the glass substrate or the like ( Or, the adhesiveness) is easily improved, which is advantageous in improving peeling resistance.

[1-4] Antistatic Agent The pressure-sensitive adhesive composition may further include an antistatic agent. By including the antistatic agent, the antistatic property of the pressure-sensitive adhesive can be improved (for example, a defect due to static electricity that occurs when a release film, a protective film or the like is peeled off can be suppressed). Examples of the antistatic agent include conventional ones, and an ionic antistatic agent is preferable. Examples of the cation component constituting the ionic antistatic agent include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, a phosphonium cation, and the like. Examples of the inorganic cations include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. The anion component constituting the ionic antistatic agent may be either an inorganic anion or an organic anion, but an anion component containing a fluorine atom is preferable from the viewpoint of excellent antistatic performance. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion (PF ₆ − ), bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N −], bis(fluorosulfonyl)imide anion [(FSO _{2) 2} N-], tetra (pentafluorophenyl) borate anion _{[(C 6 F 5) 4} B-] , and the like. These antistatic agents can be used alone or in combination of two or more kinds. In particular, bis (trifluoromethanesulfonyl) imide anion _{[(CF 3 SO 2) 2} N-], bis (fluorosulfonyl) imide anion _{[(FSO 2) 2 N-]} , tetra (pentafluorophenyl) borate anion [(C ₆ F5) ₄ B-] is preferable.
An ionic antistatic agent that is solid at room temperature is preferable in that the antistatic performance of the pressure-sensitive adhesive composition is excellent in stability over time.
The proportion of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth)acrylic resin (A). May be

[1-5] Other Components To the pressure-sensitive adhesive composition, a solvent, a crosslinking catalyst, an ultraviolet absorber, a weather resistance stabilizer, a tackifier, a plasticizer, a softening agent, a dye, a pigment, an inorganic filler, light scattering fine particles, etc. are added. The agents may be used alone or in combination of two or more. It is also useful to blend an ultraviolet-curable compound into the pressure-sensitive adhesive composition, form the pressure-sensitive adhesive layer, and then irradiate it with ultraviolet rays to cure it to form a harder pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins and melamine resins.

The pressure-sensitive adhesive composition may contain a rust preventive agent from the viewpoint of enhancing the metal corrosion resistance of the pressure-sensitive adhesive layer. Examples of the rust preventive agent include triazole compounds such as benzotriazole compounds; thiazole compounds such as benzothiazole compounds; imidazole compounds such as benzylimidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; Pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoate; benzylmercapto compounds; di-sec-butyl sulfide; and diphenyl sulfoxide.

[2] Structure of pressure-sensitive adhesive layer and optical film with pressure-sensitive adhesive layer and manufacturing method The pressure-sensitive adhesive composition of the present invention is subjected to surface activation treatment (for example, plasma treatment, corona treatment, etc.) to form a pressure-sensitive adhesive layer. it can. Usually, the pressure-sensitive adhesive layer is laminated on at least one surface of the optical film.
FIG. 1 is a schematic cross-sectional view showing an example of an optical film with a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention. The pressure-sensitive adhesive layer-carrying optical film 1 shown in FIG. 1 is an optical film having an optical film 10 and a pressure-sensitive adhesive layer 20 laminated on one side of the optical film. The adhesive layer 20 is usually directly laminated on the surface of the optical film 10. The adhesive layer 20 may be laminated on both sides of the optical film 10.
When laminating the pressure-sensitive adhesive layer 20 on the surface of the optical film 10, a primer layer is formed on the bonding surface of the optical film 10 and/or the bonding surface of the pressure-sensitive adhesive layer 20, or the surface activation treatment ( For example, plasma treatment, corona treatment, etc.) are preferable, and corona treatment is particularly preferable.

When the optical film 10 is a single-sided protective polarizing plate as shown in FIG. 2, the pressure-sensitive adhesive layer 20 is usually laminated on the polarizer surface, that is, on the surface of the polarizer 2 opposite to the first resin film 3. (Preferably directly laminated). When the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the pressure-sensitive adhesive layer 20 may be laminated on either outer surface of the first and second resin films 3 and 4, and both outer surfaces may be laminated. It may be laminated.

An antistatic layer may be separately provided between the optical film 10 and the adhesive layer 20. As the antistatic layer, a silicon-based material such as polysiloxane, an inorganic metal-based material such as tin-doped indium oxide or tin-doped antimony oxide, or an organic polymer-based material such as polythiophene, polystyrene sulfonic acid, or polyaniline can be used.

The pressure-sensitive adhesive layer-carrying optical film 1 may include a separate film (release film) laminated on the outer surface of the pressure-sensitive adhesive layer 20. This separate film is usually peeled off when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on a transparent conductive electrode or a glass substrate). The separate film is, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarate, and the like, on the surface of which the adhesive layer 20 is formed, release treatment such as silicone treatment is performed. Good.

The pressure-sensitive adhesive layer-attached optical film 1 is obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, which is then applied to the surface of the optical film 10 and dried. Can be obtained by forming the pressure-sensitive adhesive layer 20. In the pressure-sensitive adhesive layer-attached optical film 1, the pressure-sensitive adhesive layer 20 is formed on the release-treated surface of the separate film in the same manner as described above, and the pressure-sensitive adhesive layer 20 is laminated (transferred) on the surface of the optical film 10. You can also get

The thickness of the pressure-sensitive adhesive layer is usually 2 to 40 μm, and preferably 5 to 30 μm, and more preferably 10 from the viewpoint of durability of the pressure-sensitive adhesive layer-attached optical film and reworkability of the pressure-sensitive adhesive layer-attached optical film. Is about 25 μm. When it is at most the upper limit, the followability (or conformability) of the pressure-sensitive adhesive layer to the dimensional change of the optical film will be good, and when it is at least the lower limit, reworkability will be good.

The pressure-sensitive adhesive layer preferably has a storage elastic modulus of 0.1 to 5 MPa in the temperature range of 23 to 80°C. Thereby, the durability of the pressure-sensitive adhesive layer-carrying optical film can be more effectively enhanced. The phrase “showing a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80° C.” means that the storage elastic modulus is a value within the above range at any temperature in this range. Since the storage elastic modulus generally gradually decreases with increasing temperature, if the storage elastic moduli at 23° C. and 80° C. are both within the above range, the storage elastic modulus within the above range is shown at this range of temperature. Can be assumed. The storage elastic modulus of the pressure-sensitive adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.

The gel fraction can be used as an index of the crosslink density. The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a predetermined crosslink density and therefore exhibits a predetermined gel fraction. That is, the gel fraction of the pressure-sensitive adhesive layer is, for example, 50 to 95% by weight (eg 55 to 93% by weight), preferably 60 to 90% by weight (eg 65 to 90% by weight), and more preferably 70 to 85%. It may be wt% (for example, 80 to 85 wt%). When the gel fraction is at least the lower limit value, it is advantageous in the foaming resistance (cohesive fracture resistance) and reworkability of the pressure-sensitive adhesive layer, and when the gel fraction is at most the upper limit value, it is advantageous in peeling resistance. .. The gel fraction can be measured by the method described in the section of Examples.

The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a predetermined adhesive force. That is, the adhesive force of the adhesive layer after bonding the adhesive layer to a glass substrate and at a temperature of 23° C. and a relative humidity of 50% for 24 hours is, for example, 0. It may be 5 to 25 N (for example, 0.5 to 20 N), preferably 0.5 to 10 N (for example, 1 to 10 N), and more preferably 1 to 8 N. When the adhesive strength is at least the lower limit value, the adhesiveness (or adhesiveness) is improved, which is advantageous for peeling resistance, and when the adhesive force is at most the upper limit value, it is advantageous for reworkability. The adhesive force can be measured by the method described in the section of Examples.

[2-1] Optical Film The optical film 10 constituting the pressure-sensitive adhesive layer-attached optical film 1 may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device. .. The optical film 10 may have a single-layer structure (for example, a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, an optical functional film such as a light collecting film, or the like), It may have a multilayer structure (for example, a polarizing plate, a retardation plate, etc.). The optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and particularly preferably a polarizing plate or a polarizer. In the present specification, the optical film means a film that functions to display an image (display screen or the like) (for example, a film that functions to improve visibility of an image). Further, in the present specification, a polarizing plate means a resin film or a resin layer laminated on at least one surface of a polarizer, and a retardation plate means a resin film on at least one surface of a retardation film. Alternatively, it means a laminate of resin layers.

[2-2] Polarizing Plate FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The polarizing plate 10a shown in FIG. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated (or laminated and laminated) on one surface of the polarizer 2, and the polarizing plate 10b shown in FIG. It is a double-sided protective polarizing plate in which the second resin film 4 is further laminated (or laminated and laminated) on the other surface of the polarizer 2. The first and second resin films 3 and 4 can be attached to the polarizer 2 via an adhesive layer or an adhesive layer (not shown). The polarizing plates 10a and 10b may include films and layers other than the first and second resin films 3 and 4.

The polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis). A film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used. Examples of the dichroic dye include iodine and dichroic organic dyes.

The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate-based resin include a homopolymer of vinyl acetate, polyvinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, ammonium group). And a vinyl acetate copolymer.

The saponification degree of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.

Usually, a film produced from a polyvinyl alcohol-based resin is used as a raw film of the polarizer 2. The polyvinyl alcohol resin can be formed into a film by a known method. The thickness of the raw film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of easiness of stretching and the like.

The polarizer 2 is, for example, a step of uniaxially stretching a raw film, a step of dyeing a film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water, and finally dried to be manufactured. The thickness of the polarizer 2 is usually 1 to 30 μm, and preferably 20 μm or less, more preferably 15 μm or less, and especially 10 μm or less from the viewpoint of thinning the pressure-sensitive adhesive layer-attached optical film 1.

The polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film uses 1) a single film of a polyvinyl alcohol-based resin film as a raw film, and a uniaxial stretching treatment and dichroism are applied to this film. In addition to the method of dyeing a dye, 2) a base film having a polyvinyl alcohol resin layer is obtained by applying a coating solution (aqueous solution, etc.) containing a polyvinyl alcohol resin to the base film and drying it. After that, this can also be obtained by a method of uniaxially stretching the whole base film, subjecting the stretched polyvinyl alcohol resin layer to a dyeing treatment with a dichroic dye, and then peeling and removing the base film. As the base film, a film made of the same thermoplastic resin as the thermoplastic resin that can form the first and second resin films 3 and 4 described later can be used, and preferably a polyester resin such as polyethylene terephthalate. , A polycarbonate resin, a cellulose resin such as triacetyl cellulose, a cyclic polyolefin resin such as a norbornene resin, and a polystyrene resin. If the method 2) is used, the thin film polarizer 2 can be easily manufactured, for example, the polarizer 2 having a thickness of 7 μm or less can be easily manufactured.

The first and second resin films 3 and 4 are independently transparent, preferably optically transparent thermoplastic resin, for example, chain polyolefin resin (polyethylene resin, polypropylene resin, etc.). Polyolefin resin such as cyclic polyolefin resin (norbornene resin etc.); Cellulose resin (cellulose ester resin etc.); Polyester resin (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate etc.); Polycarbonate resin (eg , Polycarbonates derived from bisphenols such as 2,2-bis(4-hydroxyphenyl)propane); (meth)acrylic resins; polystyrene resins; polyetheretherketone resins; polysulfone resins, or mixtures thereof. It may be a film made of a copolymer or the like. Of these, the first and second resin films 3 and 4 are films composed of cyclic polyolefin resin, polycarbonate resin, cellulose resin, polyester resin, (meth)acrylic resin, etc., respectively. Is preferable, and a film composed of a cellulose resin, a cyclic polyolefin resin, or the like is particularly preferable.

Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resin and polypropylene resin, and copolymers of two or more chain olefins.

The cyclic polyolefin-based resin is a general term for resins containing a cyclic olefin represented by norbornene, tetracyclododecene (alias: dimethanooctahydronaphthalene) or their derivatives as a polymerized unit. The cyclic polyolefin-based resin includes a ring-opening (co)polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin and a chain olefin such as ethylene or propylene, or an aromatic compound having a vinyl group. And modified (co)polymers obtained by modifying these with unsaturated carboxylic acids or their derivatives. Among these, norbornene-based resins using norbornene-based monomers such as norbornene and polycyclic norbornene-based monomers as the cyclic olefin are preferable.

The cellulose-based resin is preferably a cellulose ester-based resin, that is, a partially or completely esterified product of cellulose, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.

The polyester-based resin is a resin having an ester bond other than the above-mentioned cellulose ester-based resin, and is generally made of a polycondensate of a polyvalent carboxylic acid or its derivative and a polyhydric alcohol. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexane dimethyl terephthalate, polycyclohexane dimethyl naphthalate and the like.

Polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Of these, aromatic polycarbonates having diphenylalkane in the molecular chain are preferable from the viewpoints of heat resistance, weather resistance and acid resistance. Examples of the polycarbonate include 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1 Examples include polycarbonates derived from bisphenols such as 1,1-bis(4-hydroxyphenyl)isobutane and 1,1-bis(4-hydroxyphenyl)ethane.

The (meth)acrylic resin that can form the first and second resin films 3 and 4 can be a polymer mainly containing a structural unit derived from a methacrylic acid ester (for example, containing 50% by weight or more thereof). It is preferably a copolymer in which other copolymerization components are copolymerized. The (meth)acrylic resin may contain two or more kinds of structural units derived from methacrylic acid ester. Examples of the methacrylic acid ester include C ₁ -C ₄ alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

Acrylic acid ester is mentioned as a copolymerization component which can be copolymerized with a methacrylic acid ester. The acrylic acid ester is preferably a C ₁ -C ₈ alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate. Specific examples of other copolymerization components include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, vinyltoluene; and vinyl cyan such as (meth)acrylonitrile. Compounds: unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; unsaturated imides such as phenylmaleimide, cyclohexylmaleimide and the like, other than acrylic acid esters having one polymerizable carbon-carbon double bond in the molecule Compounds of A compound having two or more polymerizable carbon-carbon double bonds in the molecule may be used as a copolymerization component. The copolymerization components can be used alone or in combination of two or more.

The (meth)acrylic resin may have a ring structure in the polymer main chain, from the viewpoint of enhancing the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include glutaric anhydride structure, succinic anhydride structure and the like, and specific examples of the cyclic imide structure include glutarimide structure, succinimide structure and the like, specific examples of lactone ring structure. Examples include butyrolactone ring structure and valerolactone ring structure.

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoint of film-forming property on the film, impact resistance of the film, and the like. Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylic ester as an essential component, and have a single layer structure consisting essentially of this elastic polymer or a single layer of elastic polymer. A multilayer structure having Examples of the elastic polymer include a crosslinked elastic copolymer having an alkyl acrylate as a main component and another vinyl monomer and a crosslinkable monomer copolymerizable therewith. Examples of the alkyl acrylate as the main component of the elastic polymer include C ₁ -C ₈ alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The alkyl group preferably has 4 or more carbon atoms.

Examples of other vinyl monomers copolymerizable with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid such as methyl methacrylate. Examples thereof include esters, aromatic vinyl compounds such as styrene, vinyl cyan compounds such as (meth)acrylonitrile. Examples of the crosslinkable monomer include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di(meth)acrylate and butanediol di( Examples thereof include (meth)acrylate of polyhydric alcohol such as (meth)acrylate, alkenyl ester of (meth)acrylic acid such as allyl (meth)acrylate, and divinylbenzene.

The content of the acrylic rubber particles is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more with respect to 100 parts by weight of the (meth)acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film may be lowered, and the solvent resistance to the organic solvent in the surface treatment agent may be lowered when the film is subjected to the surface treatment. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, preferably 60 parts by weight or less, based on 100 parts by weight of the (meth)acrylic resin.

The 1st, 2nd resin films 3 and 4 can contain the additive normally used in the technical field of this invention. Examples of the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, and a heat stabilizer. Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano(meth)acrylate compounds, nickel complex salts and the like.

Each of the first and second resin films 3 and 4 may be either an unstretched film or a uniaxially or biaxially stretched film. The first resin film 3 and/or the second resin film 4 may be a protective film that plays a role of protecting the polarizer 2, or a protective film having an optical function such as a retardation film described later. Good. The first resin film 3 and the second resin film 4 may be the same or different films.

The first resin film 3 and/or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer on the outer surface (the surface opposite to the polarizer 2). A surface treatment layer (coating layer) such as an antifouling layer or a conductive layer may be provided. The thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, preferably 5 to 100 μm (eg 5 to 60 μm), more preferably 50 μm or less (eg 1 to 40 μm), and further It may be 30 μm or less (for example, 5 to 25 μm).

In particular, in the case of small and medium-sized polarizing plates such as smartphones and tablet terminals, a thin film having a thickness of 30 μm or less is often used as the first resin film 3 and/or the second resin film 4 because of the demand for thinning. Such a polarizing plate has a weak force for suppressing the contracting force of the polarizer 2 and tends to have insufficient durability. Even when such a polarizing plate is used as the optical film 10, the pressure-sensitive adhesive layer-carrying optical film 1 of the present invention has good durability.

The first and second resin films 3 and 4 can be attached to the polarizer 2 via an adhesive layer or a pressure-sensitive adhesive layer. A water-based adhesive or an active energy ray-curable adhesive can be used as the adhesive forming the adhesive layer.

As the water-based adhesive, a conventional water-based adhesive (for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, Crosslinking agents such as amine compounds and polyvalent metal salts). Of these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be preferably used. When a water-based adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying step is performed to remove water contained in the water-based adhesive. Preferably. After the drying step, a curing step of curing at a temperature of, for example, 20 to 45° C. may be provided.

The active energy ray-curable adhesive refers to an adhesive that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light. Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and the like, and an ultraviolet curable adhesive is preferable.

When an active energy ray-curable adhesive is used, the polarizer 2 and the first and second resin films 3 and 4 are bonded together, and then a drying step is performed if necessary, followed by irradiation with active energy rays. Thus, a curing step of curing the active energy ray-curable adhesive is performed. The light source of the active energy ray is not particularly limited, but ultraviolet rays having an emission distribution at a wavelength of 400 nm or less are preferable.

As a method of bonding the polarizer 2 and the first and second resin films 3 and 4 to the bonding surface of at least one of these, surface activation treatment such as saponification, corona treatment or plasma treatment is performed. The method of applying it may be mentioned. When resin films are attached to both surfaces of the polarizer 2, the adhesive for attaching these resin films may be the same kind of adhesive or different kinds of adhesives.

The polarizing plates 10a and 10b may further include other films or layers. Specific examples thereof include a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light condensing film, a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer 20, a coating layer, a protective film, and the like, in addition to the retardation film described below. .. The protect film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from scratches and stains. For example, the adhesive film-attached optical film 1 is peeled off after being stuck on a metal layer or a substrate. It is usually removed.

The protect film is usually composed of a base film and an adhesive layer laminated on the base film. The base film is composed of a thermoplastic resin, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth)acrylic resin or the like. be able to.

[2-3] Retardation Plate The retardation film included in the retardation plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and second resin films 3 and 4. In addition to the thermoplastic resins exemplified above as, for example, polyvinyl alcohol-based resin, polyarylate-based resin, polyimide-based resin, polyether sulfone-based resin, polyvinylidene fluoride/polymethylmethacrylate-based resin, liquid crystal polyester-based resin, It can be a stretched film obtained by stretching a resin film made of a saponified ethylene-vinyl acetate copolymer, a polyvinyl chloride resin or the like about 1.01 to 6 times. Of these, a polycarbonate-based resin film, a cyclic olefin-based resin film, a (meth)acrylic-based resin film or a cellulose-based resin film is preferably a uniaxially or biaxially stretched film. In the present specification, a zero retardation film is also included in the retardation film (however, it can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, or the like is also applicable as the retardation film.

The zero retardation film refers to a film having an in-plane retardation value R _e and a thickness direction retardation value R _th of −15 to 15 nm. This retardation film is suitably used for an IPS mode liquid crystal display device. Plane retardation value R _e and the thickness direction retardation R _th are preferably both -10～10Nm, more preferably both -5～5Nm. The in-plane retardation value R _e and the thickness direction retardation value R _th here are values at a wavelength of 590 nm.

The in-plane retardation value R _e and the thickness direction retardation value R _th are respectively represented by the following formulas:
_{R e = (n x -n y} ) × d
R _th =[(n _x + _ny )/2−n _z ]×d
Is defined by In the formula, n _x is the refractive index in the slow axis direction (x axis direction) in the film plane, and n _y is the fast axis direction in the film plane (y axis direction orthogonal to the x axis in the plane) Is the refractive index, _nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the film thickness.

As the zero retardation film, for example, a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin and a cyclic polyolefin resin, a polyethylene terephthalate resin or a (meth)acrylic resin can be used. In particular, a cellulose-based resin, a polyolefin-based resin or a (meth)acrylic-based resin is preferably used because the retardation value can be easily controlled and easily obtained.

Further, a film that exhibits optical anisotropy by coating/orienting a liquid crystal compound or a film that exhibits optical anisotropy by coating an inorganic layered compound can also be used as the retardation film. Such a retardation film is referred to as a temperature compensation type retardation film, and a rod-shaped liquid crystal sold under the trade name of “NH film” by JX Nikko Nisseki Energy Co., Ltd. is tilt-aligned. Film, a film with a disc-shaped liquid crystal that is sold under the brand name of "WV film" from Fujifilm Co., Ltd., and a complete biaxial marketed under the trade name of "VAC film" from Sumitomo Chemical Co., Ltd. There are orientation type films, biaxial orientation type films and the like, which are also sold by Sumitomo Chemical Co., Ltd. under the trade name of “new VAC film”. The resin film laminated on at least one surface of the retardation film can be, for example, the protective film described above.

[3] Optical Laminated Body FIGS. 4 to 8 are schematic cross-sectional views showing examples of an optical laminated body including an optical film with a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention.
In the optical layered body 5 shown in FIG. 4, the metal layer 30 (or the metal wiring layer 30) laminated on the substrate 40 is adhered to the pressure-sensitive adhesive layer-attached optical film 1a (or the pressure-sensitive adhesive layer-attached polarizing plate 1a). It is an optical laminated body laminated on the surface of the agent layer side. The pressure-sensitive adhesive layer-attached optical film 1a is obtained by laminating a pressure-sensitive adhesive layer 20 on the surface of the polarizing plate 10a on the side of the polarizer 2.

In the optical laminate 6 shown in FIG. 5, the metal layer 30 laminated on the substrate 40 is laminated on the surface of the pressure-sensitive adhesive layer-attached optical film 1b (or the pressure-sensitive adhesive layer-attached polarizing plate 1b) on the pressure-sensitive adhesive layer side. It is an optical laminated body. The pressure-sensitive adhesive layer-attached optical film 1b is an optical film in which the pressure-sensitive adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.

The optical laminates 5 and 6 can be obtained by laminating the pressure-sensitive adhesive layer-attached optical film (1 a, 1 b) on the metal layer 30 laminated on the substrate 40 via the pressure-sensitive adhesive layer 20.

Examples of the method of forming the metal layer 30 on the substrate 40 include a sputtering method. The substrate 40 may be a transparent substrate that constitutes a liquid crystal cell included in the touch input element, and is preferably a glass substrate. As the material for the glass substrate, soda lime glass, low alkali glass, non-alkali glass, or the like can be used. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof.

The metal layer 30 contains, for example, at least one metal element selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and alloys containing two or more of these metals. It may be a layer containing. Of these, a layer containing at least one metal element selected from aluminum, copper, silver and gold may be preferable from the viewpoint of conductivity, and more preferably aluminum from the viewpoint of conductivity and cost. It may be a layer containing an element, and more preferably a layer containing an aluminum element as a main component (50% by weight or more of all metal components constituting the metal layer 30).

The metal layer 30 may be a transparent electrode layer made of, for example, ITO (tin-doped indium oxide), or may have a transparent electrode layer made of a metal oxide such as ITO together with the metal layer 30. In addition, you may use the layer which added the metal mesh in which the fine metal wiring layer was arrange|positioned on the board|substrate, metal nanoparticles, and metal nanowire to the binder.

The method for preparing the metal layer 30 is not particularly limited, and may be a metal foil, or may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method. A metal layer formed by a sputtering method, an inkjet printing method, or a gravure printing method is preferable, and a metal layer formed by sputtering is more preferable. The thickness of the metal layer 30 is not particularly limited, but is usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm or less, and usually 0.01 μm or more. Further, when the metal layer 30 is a metal wiring layer (for example, a metal mesh), the line width of the metal wiring is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more. Is.

The optical laminate 7 shown in FIG. 6 is an optical laminate in which the pressure-sensitive adhesive layer 20 of the pressure-sensitive adhesive layer-attached optical film 1 is laminated on the substrate 40.

In the optical layered body 8 shown in FIG. 7, the resin layer 50 further laminated on the surface of the metal layer 30 laminated on the substrate 40 (on the surface opposite to the substrate 40) is provided with the adhesive layer. It is an optical laminated body laminated on the surface of the optical film 1 on the pressure-sensitive adhesive layer 20 side. Examples of the resin that forms the resin layer 50 include the resins that form the above-described first or second resin film.

In the optical laminated body 9 shown in FIG. 8, a plurality of metal layers 30 are laminated on a substrate 40 at predetermined intervals in the vertical and horizontal directions, and the metal layers 30 are arranged between (or between) the metal layers 30. The optical laminated body 7 is the same as the optical laminated body 7 except that the resin layer 50 is formed (or laminated) on the surface (on the surface opposite to the substrate 40). When the optical layered body 8 is in the form (the form in which the metal layer 30 is patterned into a predetermined shape), the metal layer 30 is, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in a touch input liquid crystal display device. ).

In the optical layered body 8, the plurality of metal layers 30 may or may not be in contact with the pressure-sensitive adhesive layer 20 in whole or in part. Further, the metal layer 30 may be a continuous film containing the above metal or alloy. The resin layer 50 may be omitted.

After the optical film (1, 1a, 1b) with the pressure-sensitive adhesive layer and the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) are adhered to each other to produce an optical layered body, some trouble occurs. If there is, an adhesive layer-attached optical film is peeled from the substrate 40 or the metal layer 30, and another adhesive layer-attached optical film 1 is reattached to the substrate 40 or the metal layer 30, so-called rework work is required. May be. The pressure-sensitive adhesive layer-carrying optical film 1 formed from the pressure-sensitive adhesive composition according to the present invention is less likely to cause clouding or adhesive residue on the surface of the glass substrate or the transparent electrode after peeling, and is excellent in reworkability.

[4] Liquid crystal display device The liquid crystal display device according to the present invention includes the pressure-sensitive adhesive layer-carrying optical film 1 formed from the pressure-sensitive adhesive composition according to the present invention, and more typically, the optical laminate. Is included. Therefore, the liquid crystal display device according to the present invention has excellent durability.

The liquid crystal display device according to the present invention may be a touch input type liquid crystal display device having a touch panel function. A touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel may be a well-known method (for example, an out-cell type, an on-cell type, an in-cell type, etc.), and the operation method of the touch panel is a well-known method [for example, a resistance film type, a capacitance type (surface type static type). Capacitance method, projection-type capacitance method, etc.). The pressure-sensitive adhesive layer-carrying optical film 1 according to the present invention may be arranged on the viewing side of the touch input element (liquid crystal cell), on the backlight side, or on both sides. The driving method of the liquid crystal cell may be any conventionally known method such as TN method, VA method, IPS method, multi-domain method, OCB method. In the liquid crystal display device according to the present invention, the substrate 40 included in the optical laminate may be a substrate included in the liquid crystal cell (typically a glass substrate).

Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, the amounts and the parts and the percentages representing the contents are based on weight unless otherwise specified.

<Production Example 1: Production of (meth)acrylic resin (A-1) for adhesive layer>
A monomer having the composition shown in Table 1 (numerical values in Table 1 are parts by weight) was mixed with 81.8 parts of ethyl acetate in a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer. The resulting solution was charged. After replacing the air in the reaction vessel with nitrogen gas, the internal temperature was set to 60°C. Then, a solution of 0.12 parts of azobisisobutyronitrile dissolved in 10 parts of ethyl acetate was added. After maintaining the same temperature for 1 hour, ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/Hr so that the concentration of the polymer was about 35% while maintaining the internal temperature at 54 to 56°C. I added it. After maintaining the internal temperature at 54 to 56° C. for 12 hours from the start of addition of ethyl acetate, ethyl acetate was further added to adjust the concentration of the polymer to 20%, and the (meth)acrylic resin ( An ethyl acetate solution of A-1) was obtained. The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-1) was 1.39 million, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32.

<Production Example 2-12: Production of (meth)acrylic resin (A-2 to 12) for adhesive layer>
An ethyl acetate solution of the (meth)acrylic resin (A-2 to 12) was obtained in the same manner as in Production Example 1 except that the composition of the monomer was changed to the composition shown in Table 1. (Resin concentration: 20%). The weight average molecular weights Mw of the obtained (meth)acrylic resins (A-2 to 12) were all in the range of 1.3 million to 1.5 million, and Mw/Mn was in the range of 4 to 6.

In the above production example, the weight average molecular weight Mw and the number average molecular weight Mn were 4 columns of "TSKgel XL" manufactured by Tosoh Corporation and "Shodex GPC KF-" manufactured by Showa Denko K.K. 802" is connected in series with a total of 5 tubes, and tetrahydrofuran is used as an eluent. Sample concentration is 5 mg/mL, sample introduction amount is 100 μL, temperature is 40° C., and flow rate is 1 mL/min. It was measured by. The conditions for obtaining the emission curve of GPC were also the same.

The glass transition temperature Tg was measured by using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII Nano Technology Co., Ltd. under a nitrogen atmosphere in a measurement temperature range of -80 to 50°C and a heating rate of 10°C/min. It was measured under the conditions.

The composition of the monomers in each production example (the numerical values in Table 1 are parts by weight) is shown in Table 1.

Abbreviations in the column of "monomer composition" in Table 1 mean the following monomers.
BA: butyl acrylate (glass transition temperature of homopolymer: −54° C.),
MA: methyl acrylate (glass transition temperature of homopolymer: 10° C.),
HEA: 2-hydroxyethyl acrylate.
4HBA: 4-hydroxybutyl acrylate 5HPA: 5-hydroxypentyl acrylate PEA: phenoxyethyl acrylate PEA2: phenoxydiethylene glycol acrylate BMAA: butoxymethyl acrylamide AA: acrylic acid

<Examples 1 to 12, Comparative Examples 1 to 9>
(1) Preparation of pressure-sensitive adhesive composition The results are shown in Table 2 for the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above Production Example, relative to 100 parts of solid content of the solution. A pressure-sensitive adhesive composition obtained by mixing amounts (parts by weight) of the crosslinking agent (B), the silane compound (C), and the ionic compound (D), and further adding ethyl acetate so that the solid content concentration is 14%. Got The blending amount of each blending component shown in Table 2 is the number of parts by weight as an active ingredient contained therein when the used product contains a solvent and the like.

Details of each compounding component represented by abbreviations in Table 2 are as follows.
(Crosslinking agent)
B-1: Ethylene acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration 75%), trade name “Coronate L” obtained from Tosoh Corporation.
B-2: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content concentration 75%), trade name “Takenate D-110N” obtained from Mitsui Chemicals, Inc.

(Silane compound)
C-1:1,6-bis(trimethoxysilyl)hexane, C-2:1,8-bis(trimethoxysilyl)hexane, C-3: methyl group/methoxy group-containing silicone oligomer, Shin-Etsu Chemical Co., Ltd. Trade name “X-40-9250”, C-4:1,3-bis(3′-trimethoxypropyl)urea, obtained from (4).

(Ionic compound)
D-1: N-decylpyridinium bis(fluorosulfonyl)imide, D-2: Potassium bis(fluorosulfonyl)imide, D-3: Lithium bis(trifluoromethylsulfonyl)imide, D-4: N-decyl Pyridinium tetra(pentafluorophenyl)borate.

(2) Preparation of pressure-sensitive adhesive layer Each pressure-sensitive adhesive composition prepared in the above (1) was separated from the polyethylene terephthalate film which had been subjected to a mold release treatment [trade name "PLR-382051 obtained from Lintec Co., Ltd.]. ]] was applied to the release-treated surface using an applicator so that the thickness after drying was 20 μm, and dried at 100° C. for 1 minute to prepare a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet).

(3) Preparation of optical film with pressure-sensitive adhesive layer (P-1) Polyvinyl alcohol film having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% and a thickness of 60 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.] -PE#6000"] was immersed in pure water at 37°C, and then an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) It was immersed in the solution at 30°C. Then, it was immersed at 56.5° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio)=12/3.6/100). The film was washed with pure water at 10° C. and then dried at 85° C. to obtain a polarizer having a thickness of about 23 μm in which iodine was adsorbed and oriented in polyvinyl alcohol. Stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

On one side of the obtained polarizer, a transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] composed of a 25 μm-thick triacetyl cellulose film was provided with an adhesive composed of an aqueous solution of polyvinyl alcohol resin. Pasted together. Then, on the surface of the above-mentioned polarizer on the side opposite to the triacetyl cellulose film, a zero retardation film [trade name "ZEONOR" manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 μm was used. A laminated polarizing plate was produced with an adhesive made of an aqueous solution of resin. Then, the surface of the zero retardation film opposite to the surface in contact with the polarizer is subjected to corona discharge treatment for improving the adhesion, and then the surface opposite to the separate film of the pressure-sensitive adhesive layer produced in (2) above. After sticking the side surface (adhesive layer surface) with a laminator, curing was performed for 7 days under the conditions of a temperature of 23° C. and a relative humidity of 65% to obtain an optical film with an adhesive layer (P-1).

(4) Durability evaluation of pressure-sensitive adhesive layer-attached optical film The pressure-sensitive adhesive layer-attached optical film (P-1) produced in (3) above was measured in 300 mm×220 mm so that the stretching axis direction of the polarizing plate was the long side. It was cut into a size, the separate film was peeled off, and the exposed adhesive layer surface was attached to a glass substrate or a glass substrate with ITO (tin-doped indium oxide). The test piece to which the glass substrate was attached (optical film with pressure-sensitive adhesive layer attached to the glass substrate) was placed in an autoclave at a temperature of 50° C. and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. Pressurized. As the glass substrate, non-alkali glass trade name "Eagle XG" manufactured by Corning was used. Further, as the glass substrate with ITO, an alkali-free glass [trade name "Eagle XG"] manufactured by Corning Co., Ltd. having an ITO layer of 30 nm formed by ITO vapor deposition was used.
The following three types of durability tests were performed on the obtained optical layered body.

[Durability test]
・Heat resistance test for 1000 hours under dry condition of 95℃ (glass substrate)
・Heat resistance test for 1000 hours under dry condition of 95°C (glass with ITO)
-Humidity heat resistance test (glass substrate) for 1000 hours in an environment of temperature 60°C and relative humidity 90%,
-Heat shock resistance (HS) test (glass substrate) in which an operation of holding for 30 minutes under a drying condition of a temperature of 85°C and then for 30 minutes under a drying condition of a temperature of -40°C is repeated 1000 cycles. ..

The optical laminate after each test was visually observed, and the presence or absence of appearance change such as floating, peeling and foaming of the pressure-sensitive adhesive layer was visually observed, and durability was evaluated according to the following evaluation criteria. The results are shown in Table 3.

5: No change in appearance such as floating, peeling, foaming,
4: Almost no change in appearance such as floating, peeling, foaming,
3: Changes in appearance such as floating, peeling, and foaming are slightly noticeable,
2: Appearance change such as floating, peeling, foaming is noticeable,
1: Appearance changes such as floating, peeling and foaming are noticeable.

(5) Evaluation of adhesive strength of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm x 150 mm. The separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to the glass substrate. The test piece to which the glass substrate was attached (optical film with pressure-sensitive adhesive layer attached to the glass substrate) was placed in an autoclave at a temperature of 50° C. and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere of a temperature of 23° C. and a relative humidity of 50%, the optical film was peeled from the test piece together with the adhesive layer in the 180° direction at a speed of 300 mm/min. Table 3 shows the average peeling force at the time of peeling as the adhesive force. When the adhesive strength is 10 N or less, reworkability is excellent, and when it is 0.5 N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.

[ITO Corrosion Evaluation of Optical Laminate]
The surface resistance (surface resistance value before the test) of the surface of the ITO layer of the glass substrate with the ITO layer was measured with a low resistivity meter [trade name "Loresta-AX" manufactured by Mitsubishi Chemical Analytech Co., Ltd.]. Next, the polarizing plate having the pressure-sensitive adhesive layer formed in the above (3) was cut into a test piece having a size of 20 mm×40 mm, which was attached to the ITO layer side of the glass substrate via the pressure-sensitive adhesive layer. did. The obtained optical laminate is stored in an oven at a temperature of 60° C. and a relative humidity of 90% for 500 hours, and then peeled between the ITO layer and the pressure-sensitive adhesive layer in an atmosphere of a temperature of 23° C. and a relative humidity of 50%. did. The surface resistance (post-test surface resistance value) of the ITO layer after peeling was measured. The rate of resistance change before and after the test was calculated by the following formula and evaluated according to the following criteria. The smaller the resistance change rate, the lower the ITO corrosiveness. The results are shown in Table 3.
Resistance change rate (%)=[(surface resistance value after test)-(surface resistance value before test)]/[surface resistance value before test]×100

<Evaluation criteria for ITO corrosion>
◯: An optical laminate having a resistance change rate of less than 50% and good ITO corrosivity.
X: The rate of change in resistance is 50% or more, and the ITO corrosiveness of the optical laminate is poor.

(6) Evaluation of antistatic property of optical film with adhesive layer
After peeling the separator of the obtained polarizing film with an adhesive layer, the surface resistance value of the adhesive is measured with a surface resistivity measuring device [Mitsubishi Chemical Corporation's "Hiresta-up MCP-HT450" (trade name)) It was measured by. The measurement was performed under the conditions of an applied voltage of 250 V and an applied time of 10 seconds. When the surface resistance value is 1.0×10 ¹² Ω/□ or less, good antistatic property can be obtained.

(Gel fraction of adhesive sheet)
The gel fraction evaluation method of the pressure sensitive adhesive sheet of the present invention is shown. The larger the gel fraction, the more the crosslinking reaction is progressing in the pressure-sensitive adhesive, which can be used as a measure of the crosslinking density. The gel fraction is a value measured according to the following (1) to (4).

(1) An adhesive sheet having an area of about 8 cm×about 8 cm and a metal mesh of SUS304 of about 10 cm×about 10 cm (whose weight is Wm) are laminated.
(2) The bonded product obtained in (1) above is weighed, its weight is set to Ws, and then the adhesive sheet is folded 4 times so as to wrap it, fastened with a stapler (stapler), and then weighed. Weight is Wb.
(3) The mesh stapled in (2) above is placed in a glass container, 60 mL of ethyl acetate is added and immersed, and the glass container is stored at room temperature for 3 days.
(4) The mesh is taken out from the glass container, dried at 120° C. for 24 hours and then weighed, and the weight is set to Wa, and the gel fraction is calculated based on the following formula.
Gel fraction (% by weight)=[{Wa-(Wb-Ws)-Wm}/(Ws-Wm)]×100

1, 1a, 1b... Optical film with adhesive layer, 2... Polarizer, 3... First resin film, 4... Second resin film, 5, 6, 7, 8, 9... Optical laminate, 10... Optical film 10a, 10b... Polarizing plate, 20... Adhesive layer, 30... Metal layer, 40... Substrate, 50... Resin layer.

Claims (16)

A pressure-sensitive adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth)acrylic resin (A) has the following formula (a1)

(In the formula, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, The substituents may be the same or different)
A structural unit derived from a hydroxy group-containing (meth)acrylate represented by the following formula (a2)

(In the formula, m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, X ² represents a methylene group which may have a substituent, and the substituents are the same or different. Good)
Including a constitutional unit derived from a hydroxy group-containing (meth)acrylate represented by and a constitutional unit derived from a carboxyl group-containing (meth)acrylate ,
The ratio of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight with respect to 100 parts by weight of all the structural units forming the (meth)acrylic resin. Parts, and the ratio of the constituent unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is 0.25 to 100 parts by weight of all constituent units constituting the (meth)acrylic resin. 1.0 parts by weight,
The pressure-sensitive adhesive composition, in which the proportion of the structural unit derived from a carboxyl group-containing (meth)acrylate is 0.001 to 0.5 part by weight, relative to 100 parts by weight of all the structural units constituting the (meth)acrylic resin. .. A pressure-sensitive adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth)acrylic resin (A) has the following formula (a1)

(In the formula, n represents an integer of 1 to 4, and A ¹ Represents a hydrogen atom or an alkyl group, X ¹ Represents a methylene group which may have a substituent, and when n is 2 or more, the substituents may be the same or different)
A structural unit derived from a hydroxy group-containing (meth)acrylate represented by the following formula (a2)

(In the formula, m represents an integer of 5 or more, and A ^Two Represents a hydrogen atom or an alkyl group, X ^Two Represents a methylene group which may have a substituent, and the substituents may be the same or different)
And a structural unit derived from a hydroxy group-containing (meth)acrylate represented by
The ratio (weight ratio) of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) to the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is ( a1)/(a2)=13/1 to 5/1,
The pressure-sensitive adhesive composition, wherein the proportion of the structural unit derived from a carboxyl group-containing (meth)acrylate is 1.0 part by weight or less, relative to 100 parts by weight of all the structural units constituting the (meth)acrylic resin. A pressure-sensitive adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth)acrylic resin (A) has the following formula (a1)

(In the formula, n represents an integer of 1 to 4, and A ¹ Represents a hydrogen atom or an alkyl group, X ¹ Represents a methylene group which may have a substituent, and when n is 2 or more, the substituents may be the same or different)
A structural unit derived from a hydroxy group-containing (meth)acrylate represented by the following formula (a2)

(In the formula, m represents an integer of 5 or more, and A ^Two Represents a hydrogen atom or an alkyl group, X ^Two Represents a methylene group which may have a substituent, and the substituents may be the same or different)
And a structural unit derived from a hydroxy group-containing (meth)acrylate represented by, a structural unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0° C., and a homopolymer glass transition temperature of 0° C. And a structural unit derived from the above alkyl acrylate (a3-2),
The proportion of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight with respect to 100 parts by weight of all the structural units forming the (meth)acrylic resin. Parts, and the ratio of the constituent unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a2) is 0.25 to 100 parts by weight of all constituent units constituting the (meth)acrylic resin. 1.0 parts by weight,
The structural unit derived from the alkyl acrylate (a3-1) having a glass transition temperature of less than 0° C. of the homopolymer consists only of a linear alkyl acrylate having 2 to 12 carbon atoms,
The pressure-sensitive adhesive composition, wherein the proportion of the structural unit derived from a carboxyl group-containing (meth)acrylate is 1.0 part by weight or less, relative to 100 parts by weight of all the structural units constituting the (meth)acrylic resin. The ratio of the structural unit derived from the hydroxy group-containing (meth)acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight based on 100 parts by weight of all the structural units constituting the (meth)acrylic resin. , and the pressure-sensitive adhesive composition according to claim 2 the amount of the structural unit hydroxy group-containing (meth) acrylates derived from the formula (a2) is 0.25 to 1.0 parts by weight. The (meth)acrylic resin is a constitutional unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0° C. and an alkyl acrylate (a3-2) having a glass transition temperature of 0° C. or higher. The pressure-sensitive adhesive composition according to claim 1 or 2, comprising a structural unit derived from an alkyl acrylate (a3) containing a unit. Ratio of the structural unit derived from the alkyl acrylate (a3-1) whose homopolymer glass transition temperature is lower than 0°C to the structural unit derived from the alkyl acrylate (a3-2) whose homopolymer glass transition temperature is 0°C or higher ( The weight ratio) is (a3-1)/(a3-2)=20/80 to 95/5. The pressure-sensitive adhesive composition according to claim 3 or 5 . Carboxyl group-containing (meth) the amount of the structural units derived from acrylate, (meth) relative to all the structural units 100 parts constituting the acrylic resin, according to claim 2 or 3 is 0.001 to 0.5 parts by weight The pressure-sensitive adhesive composition according to. (Meth) weight average molecular weight of the acrylic resin is based on polystyrene pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is ^{6.0 × 10 5 ~2.5 × 10 6} . Crosslinking agent (B), pressure-sensitive adhesive composition according to any one of claims 1 to 8, which is an adduct according to the polyhydric alcohol compound of an aromatic isocyanate compound and / or aromatic isocyanate compounds. The proportion of the crosslinking agent (B), (meth) relative to 100 parts by weight of the acrylic resin (A), the pressure-sensitive adhesive composition according to any one of claims 1 to 9, which is 0.01 to 10 parts by weight. The silane compound (C) has the following formula (c1)

(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH ₂ — may be substituted by —O— or —CO—, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each Independently, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
The pressure-sensitive adhesive composition according to any one of claims 1 to 10 which is in a silane compound represented by. B in the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently. The pressure-sensitive adhesive composition according to claim 11 , which is an alkoxy group having 1 to 5 carbon atoms. The proportion of the silane compound (C), (meth) relative to 100 parts by weight of the acrylic resin (A), the pressure-sensitive adhesive composition according to any one of claims 1 to 12, which is 0.01 to 10 parts by weight. Gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition, pressure-sensitive adhesive composition according to any one of claims 1 to 13 50 to 95%. A pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is attached to a glass substrate, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer after 24 hours at a temperature of 23° C. and a relative humidity of 50% has a peeling speed of 300 mm/min. in pressure sensitive adhesive composition according to any one of claims 1 to 14, which is a 0.5~10N / 25mm. Used to form the pressure-sensitive adhesive layer laminated on the optical film, the pressure-sensitive adhesive composition according to any one of claims 1 to 15.

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