JP2017110062A - Adhesive resin composition, cured product using the same, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive resin composition capable of forming an adhesive layer excellent in adhesive strength, transparency, and anticorrosion ability.SOLUTION: The adhesive resin composition contains (A) a (meth)acrylic acid derivative polymer, (B) a (meth)acrylic acid derivative monomer having a (meth)acryloyl group, (C) a crosslinking agent having a (meth)acryloyl group, (D) a photopolymerization initiator, and (E) a rust inhibitor. The (meth)acrylic acid derivative monomer having a (meth)acryloyl group (B) contains (B-1) a (meth)acrylic acid derivative monomer having an amide group.SELECTED DRAWING: None

Description

  The present invention relates to an adhesive resin composition, a cured product using the same, and an image display device.

  A liquid crystal display device is mentioned as an example of a typical image display device. Generally, a polarizing plate, a laminate of a polarizing plate and a retardation plate, and the like are attached to an optical component such as a liquid crystal cell in a liquid crystal display device. In recent years, the demand for liquid crystal display devices with a built-in touch panel has increased. A liquid crystal display device incorporating a touch panel includes, for example, a protective plate, a touch panel, a polarizing plate, and a liquid crystal cell. And in recent liquid crystal display devices, in order to prevent cracking of the liquid crystal display device, to relieve stress and impact, and to improve visibility, an adhesive layer for bonding a protective plate and a touch panel, and a touch panel and a polarizing plate, An adhesive layer is used to bond the two. Since such a liquid crystal display device has been used for various purposes such as in-vehicle use, outdoor instruments, mobile phones, personal computers, etc., the use environment has become very severe (for example, high temperature or high temperature and high humidity). . Under such severe conditions, the pressure-sensitive adhesive layer that bonds each member has a reduced adhesive force, and air bubbles and peeling may easily occur at the bonding interface.

  Therefore, there is a demand for a pressure-sensitive adhesive composition capable of forming a highly durable pressure-sensitive adhesive layer that does not decrease the adhesive force even under severe conditions and does not generate bubbles or peeling at the sticking interface. For example, a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive film that does not cause foaming, peeling, or the like at the bonding interface even when exposed to a high temperature or high temperature and high humidity for a long time after being bonded to an adherend has been proposed ( See Patent Document 1 below).

  Further, in the image display device, it is necessary to provide metal wiring for input / output at the peripheral portion of the information input unit (for example, touch panel) and the image display unit (for example, liquid crystal cell). In these image display devices, there is a problem that metal wiring corrodes when moisture, acid gas, or corrosive components enter from the outside environment. In recent years, corrosion of metal wiring has been regarded as a further problem with the trend toward larger and narrower image display devices. In addition, in metal wiring, instead of ITO having high resistance and low sensitivity, there are increasing examples of shift changing to Cu and Ag having low resistance and high sensitivity. However, Cu and Ag are known to be easily oxidized and corroded. Therefore, for the purpose of preventing oxidation and corrosion of metal wiring, a method of preventing moisture permeation and permeation of corrosive components by forming a rust preventive film on the metal wiring has been proposed (see Patent Document 2 below).

JP 2007-238853 A JP 2011-028594 A

  However, the formation of the rust-preventing film needs to be performed after the metal wiring is applied, which increases the number of steps and takes time, so that improvement of manufacturing yield and cost reduction are major issues. Moreover, when a rust preventive film is used, for example, when a rust preventive film is formed on a touch panel of an image display device in which a protective plate, an adhesive layer, and a touch panel are bonded together in this order, the adhesive strength between the adhesive layer and the touch panel, etc. Problems may arise in terms of ensuring the adhesion reliability of the adhesive and the transparency of the adhesive layer and the like. Furthermore, since the information input unit and the image display unit of the image display device require visibility in the display unit, the adhesive layer used in the information input unit and the image display unit has an adverse effect on the visibility. Therefore, it is required to have excellent appearance such as transparency.

  The present invention has been made in view of the above-described problems of the prior art, and is a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer excellent in adhesive strength, transparency, and corrosion resistance, and the pressure-sensitive adhesive resin composition. It aims at providing the hardened | cured material and image display apparatus which used the thing.

  As a result of intensive studies to solve the above problems, the present inventors form a pressure-sensitive adhesive layer that is excellent in adhesive strength, transparency, and corrosion resistance by using a pressure-sensitive resin composition containing a specific component. The present invention has been completed.

  That is, the present invention includes (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having (meth) acryloyl group, (C) a crosslinking agent having (meth) acryloyl group, (D) An adhesive resin composition containing a photopolymerization initiator and (E) a rust inhibitor, wherein the (B) (meth) acrylic acid-based derivative monomer having a (meth) acryloyl group is (B- 1) An adhesive resin composition comprising a (meth) acrylic acid derivative monomer having an amide group is provided.

  According to the pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive layer having excellent adhesive strength, transparency, and corrosion prevention ability can be formed. When the conventional adhesive resin composition contains a rust preventive agent directly, there is a tendency that the adhesive strength and transparency of the formed adhesive layer are deteriorated or the corrosion preventing ability by the rust preventive agent cannot be exhibited. is there. On the other hand, the pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer excellent in adhesive strength, transparency, and corrosion-preventing ability by directly containing a rust preventive agent in a specific base polymer constituting the pressure-sensitive adhesive layer. it can. Here, the specific base polymer is the above (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having (meth) acryloyl group, (C) (meth) acryloyl group And (D) a photopolymerization initiator. Moreover, since the adhesive resin composition of this invention can form the adhesion layer which is excellent in corrosion prevention ability, formation of a rust prevention film becomes unnecessary. Therefore, an image display device having excellent adhesive strength and transparency can be manufactured efficiently and at low cost.

  Moreover, in the adhesive resin composition of the present invention, the (B-1) (meth) acrylic acid derivative monomer having an amide group may contain acryloylmorpholine. According to such an adhesive resin composition, when the adhesive layer obtained is further improved in adhesion between the obtained adhesive layer and a substrate such as glass or plastic, and the adhesive layer is formed into a sheet shape, The handleability can be further improved.

  In the adhesive resin composition of the present invention, the (B) (meth) acrylic acid derivative monomer having a (meth) acryloyl group is (B-2) a (meth) acrylic acid derivative monomer having a hydroxyl group. Further, it may be included. According to such a pressure-sensitive adhesive resin composition, a pressure-sensitive adhesive layer that is more excellent in adhesive strength, transparency, and corrosion resistance can be formed.

  Furthermore, in the adhesive resin composition of the present invention, the (E) rust inhibitor may contain at least one selected from the group consisting of benzotriazole, imidazole, triazole, tetrazole and derivatives thereof. According to such a pressure-sensitive adhesive resin composition, a pressure-sensitive adhesive layer that is more excellent in adhesive strength, transparency, and corrosion resistance can be formed.

  The present invention also provides a cured product of the adhesive resin composition of the present invention. Since this hardened | cured material is hardened | cured using the adhesive resin composition of the said invention, it can form the adhesion layer excellent in adhesive strength, transparency, and corrosion prevention ability.

  Moreover, -10 degreeC-30 degreeC may be sufficient as the glass transition temperature of the said hardened | cured material. According to such a cured product, it is possible to form an adhesive layer that is superior in adhesive strength, transparency, and corrosion prevention ability.

  The present invention further provides an image display device comprising an adhesive layer containing a cured product of the above-mentioned adhesive resin composition of the present invention. Since the image display device includes the pressure-sensitive adhesive layer containing the cured product of the pressure-sensitive adhesive resin composition of the present invention, the image display device is excellent in adhesion reliability such as adhesion strength and anti-foaming peelability, transparency, and corrosion resistance. Can be provided.

  In the image display device of the present invention, the adhesive layer is formed between the protective plate and the image display panel, between the protective plate and the touch panel, or between the touch panel and the image display panel. Also good. According to such an image display device, it is possible to provide an image display device that is excellent in adhesive reliability such as adhesive strength and foaming peeling resistance, transparency, and corrosion prevention ability.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive resin composition which can form the adhesion layer excellent in adhesive strength, transparency, and corrosion prevention ability, and the hardened | cured material and image display apparatus using the same can be provided. Therefore, the adhesive resin composition of the present invention is useful for preventing cracking of an image display device, alleviating stress and impact, and improving visibility, and having excellent transparency, and improving display image fogging, flickering, and the like. In addition, for the formation of a pressure-sensitive adhesive layer in which the occurrence of reduced adhesive strength, bubbles, floats, peeling, etc. is suppressed, particularly under high temperature conditions (for example, 60 ° C. or higher) and high humidity conditions (for example, 90% RH or higher). Applied.

1 is a schematic cross-sectional view showing an embodiment of an image display device according to the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.

<Adhesive resin composition>
The adhesive resin composition according to the present embodiment comprises (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having (meth) acryloyl group, (C) (meth) acryloyl. A (meth) acrylic acid-based derivative having a (meth) acryloyl group, the adhesive resin composition comprising a cross-linking agent having a group, (D) a photopolymerization initiator, and (E) a rust inhibitor It is related with the adhesive resin composition in which a monomer contains the (B-1) (meth) acrylic-acid-type derivative monomer which has an amide group. Hereinafter, each component contained in the adhesive resin composition according to the present embodiment will be described.

[(A) (Meth) acrylic acid derivative polymer]
(A) (meth) acrylic acid derivative polymer (hereinafter also referred to as “component (A)”) is a homopolymer obtained by polymerizing one monomer having one (meth) acryloyl group in the molecule or 2 A copolymer obtained by copolymerizing a combination of two or more species. As long as the effect of the present invention is not impaired, a compound having two or more (meth) acryloyl groups in the molecule, a polymerizable compound having no (meth) acryloyl group (for example, acrylonitrile, styrene, acetic acid) A compound having one polymerizable unsaturated bond in the molecule such as vinyl, ethylene and propylene, a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene) and the like (meth) acryloyl group It may be a copolymer copolymerized with one monomer in the molecule.

  In the present specification, (meth) acrylic acid, (meth) acryloyl group, (meth) acrylate are methacrylic acid and corresponding acrylic acid, methacryloyl group and corresponding acryloyl group, methacrylate and corresponding acrylate. Means.

  Examples of the monomer constituting the (A) (meth) acrylic acid derivative polymer include (meth) acrylic acid; (meth) acrylic acid amide; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate, etc. 1 to 18 alkyl (meth) acrylates; (meth) acrylic acid esters having an aromatic ring such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate and butoxydiethylene glycol (Meth) acrylates having alkoxy groups such as meth) acrylate and methoxytriethylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylic acid ester having an alicyclic group or heterocyclic group such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (Meth) acrylic acid ester having a hydroxyl group: tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol mono Polyethylene glycol monomethyl ether (meth) acrylates such as tilether (meth) acrylate and nonaethylene glycol monomethyl ether (meth) acrylate; Polypropylene glycol monomethyl ether (meth) acrylates such as heptapropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol ethyl Examples include polyethylene glycol ethyl ether (meth) acrylate such as ether (meth) acrylate; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and octapropylene glycol mono (meth) acrylate.

  Among the above compounds, it is preferable to use (meth) acrylate having an alkyl group having 4 to 18 carbon atoms. When the copolymerized polymer of one molecule is 100% by mass, the proportion of the structural unit derived from the (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is preferably 5 to 95% by mass, More preferably, it is 10-90 mass%. If it is in this range, there exists a tendency for the adhesiveness of the adhesion layer obtained and transparent substrates, such as glass and a plastic, to improve. Such a copolymerization ratio can be generally obtained by copolymerizing each monomer with the same ratio as the above copolymerization ratio.

  The monomer copolymerized with the (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is not limited to the above-described monomers, but includes a hydroxyl group, a morpholino group, an amino group, a carboxyl group, a cyano group, a carbonyl group, a nitro group, and the like. A monomer having a polar group, that is, a (meth) acrylate having such a polar group is preferable because the adhesiveness between the obtained adhesive layer and a transparent substrate such as glass or plastic tends to be improved. Among these, (meth) acrylate having a hydroxyl group is more preferable.

  (A) The weight average molecular weight of the (meth) acrylic acid derivative polymer is a value converted using a standard polystyrene calibration curve by gel permeation chromatography, and is from 100,000 to 1,000,000. Preferably, it is 100,000-700,000, More preferably, it is 100,000-500,000. By making the weight average molecular weight 100,000 or more, the pressure-sensitive adhesive layer has an adhesive force that does not cause peeling on a transparent substrate or the like in a high temperature (for example, 80 ° C. or higher) and high humidity (for example, 90% RH or higher) environment. There is a tendency that can be obtained, and by making it 1,000,000 or less, the cohesiveness is improved and the workability tends to be good.

  As a polymerization method for the (A) (meth) acrylic acid derivative polymer, a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, or the like can be used.

  (A) When polymerizing the (meth) acrylic acid derivative polymer, a polymerization initiator may be used. As the polymerization initiator, a compound capable of generating radicals by heat can be used. Specifically, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide, di Organic peroxides such as propionyl peroxide, diacetyl peroxide, didodecyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1 ′ -Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis ( , 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis Azo compounds such as (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (imidazolin-2-yl) propane] Can be mentioned.

  The content of the (A) (meth) acrylic acid derivative polymer is preferably 10 to 90% by mass and more preferably 15 to 90% by mass with respect to the total amount of the adhesive resin composition. (A) When the content of the (meth) acrylic acid derivative polymer is 10 to 90% by mass, the viscosity of the adhesive resin composition falls within an appropriate viscosity range for producing an adhesive layer, and the processability is good. In addition, the obtained adhesive layer tends to have good adhesion to a transparent substrate such as glass or plastic.

[(B) (Meth) acrylic acid derivative monomer having (meth) acryloyl group]
The (B) (meth) acrylic acid derivative monomer (hereinafter also referred to as “component (B)”) is a monomer having a (meth) acryloyl group and (B-1) a (meth) acryl having an amide group. Includes acid-based derivative monomers. The component (B) may be a (meth) acrylic acid derivative monomer having one (meth) acryloyl group in the molecule. The component (B) may further include (B-1) a (meth) acrylic acid derivative monomer other than the (meth) acrylic acid derivative monomer having an amide group.

[(B-1) (Meth) acrylic acid derivative monomer having amide group]
(B-1) The (meth) acrylic acid derivative monomer having an amide group improves the adhesion between the obtained adhesive layer and a substrate such as glass or plastic, and when the adhesive layer is formed into a sheet, This is important for improving the handleability of the produced sheet adhesive layer. Such a monomer is not particularly limited as long as the monomer has an amide group, and a known material can be used. Specific examples thereof include N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, and N, N-diethyl (meth). Examples include acrylamide and N-hydroxyethyl (meth) acrylamide. Among these, (meth) acryloylmorpholine is particularly preferable, and acryloylmorpholine is more preferable.

  (B-1) The content of the (meth) acrylic acid derivative monomer having an amide group is preferably 0.1 to 30% by mass, and preferably 0.1 to 20% by mass with respect to the total amount of the adhesive resin composition. Is more preferable.

  Further, (B-1) (meth) acrylic acid derivative monomers other than (meth) acrylic acid derivative monomers having an amide group may be used in combination. Such a monomer is not particularly limited as long as it is a monomer having a (meth) acryloyl group, and a known material can be used. Specific examples thereof include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl ( C1-C18 alkyl (meth) acrylates of alkyl groups such as (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) ) (Meth) acrylic acid esters having an aromatic ring such as acrylate; (meth) acrylates such as butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate and methoxytriethylene glycol (meth) acrylate Acrylic acid ester; (meth) acrylic acid having an alicyclic group or a heterocyclic group such as cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Ester; (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; 2- (2-methacryloyloxyethyloxy) (Meth) acrylic acid ester having an isocyanate group such as ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate; tetraethylene glycol monomethyl ether (meth) acrylate, hexaethyleneglycol Polyethylene glycol monomethyl ether (meth) acrylates such as monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate and nonaethylene glycol methyl ether (meth) acrylate; polypropylene glycol such as heptapropylene glycol monomethyl ether (meth) acrylate Monomethyl ether (meth) acrylate; polyethylene glycol ethyl ether (meth) acrylate such as tetraethylene glycol ethyl ether (meth) acrylate; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono ( And (meth) acrylate.

Among these, in particular, a (meth) acrylic acid ester having a hydroxyl group (also referred to as “(B-2) a (meth) acrylic acid derivative monomer having a hydroxyl group”) and an alkyl group having 4 to 18 carbon atoms in the alkyl group. It is preferable to use (meth) acrylate together. (B-2) Examples of the (meth) acrylic acid derivative monomer having a hydroxyl group include a hydroxyl group-containing (meth) acrylate represented by the following general formula (g).
_{CH 2 = CXCOO (C p H} 2p O) q H ··· (g)

In general formula (g), X represents H or CH ₃ , p represents an integer of 2 to 4, and q represents an integer of 1 to 10.

  Examples of the alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group include n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, and n-octyl (meth) acrylate. , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc., but n-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate and n-octyl (meth) acrylate are preferable, and 2-ethylhexyl (meth) acrylate is particularly preferable. Also, acrylate is more preferable than methacrylate. These (meth) acrylates may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate represented by the general formula (g) include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Such as (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylate; polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate and triethylene glycol mono (meth) acrylate; dipropylene glycol mono (meth) acrylate And polypropylene glycol mono (meth) acrylates such as tripropylene glycol mono (meth) acrylate; polybutylene glycol mono (meth) acrylates such as dibutylene glycol mono (meth) acrylate and tributylene glycol mono (meth) acrylate 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 1-hydroxybutyl (meth) acrylate are preferred More preferably 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate is more preferable. Moreover, you may use these (meth) acrylates individually by 1 type or in combination of 2 or more types.

  (B) 4-80 mass% is preferable with respect to the whole quantity of an adhesive resin composition, and, as for content of a (meth) acrylic-acid type derivative monomer, 4-70 mass% is more preferable. (B) When the content of the (meth) acrylic acid derivative monomer is 4 to 80% by mass, the obtained adhesive layer is bonded between the glass substrate and the glass substrate, and then at a high temperature (for example, 60 ° C. or more). ) And after the reliability test under high humidity (for example, 90% RH or more), the occurrence of bubbles and peeling at the sticking interface tends to be favorably suppressed.

[Crosslinking agent having (C) (meth) acryloyl group]
(C) The crosslinking agent having a (meth) acryloyl group (hereinafter, also referred to as “component (C)”) may be any crosslinking agent having a (meth) acryloyl group in the molecule (the (A) component and ( B) component is not included), it is possible to use known materials. (C) As a component, the crosslinking agent which has 2 or more of (meth) acryloyl groups is preferable, and when using the crosslinking agent which has 3 or more of (meth) acryloyl groups, bridge | crosslinking which has two (meth) acryloyl groups It is more preferable because the amount used is smaller than that of the agent.

  Examples of the crosslinking agent having two (meth) acryloyl groups in the molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) a Relate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3 -Propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, Aliphatic (meth) acrylates such as ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate; cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, propoxylated cyclohexanedimethanol ( Meta Acrylate, ethoxylated propoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated Propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, Ethoxylated hydrogenated bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol F di (meth) Alicyclic (meth) acrylates such as acrylates; ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) ) Acrylate, propoxylated bisphenol F di (meth) acrylate, ethoxylated propoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) acrylate, ethoxylated fluorene type di (meth) acrylate, propoxylated fluorene type di (meth) acrylate, ethoxylated propoxylated fluorene Aromatic (meth) acrylates such as di (meth) acrylates; heterocyclic rings such as ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate Formula (meth) acrylates; these caprolactone modified products; aliphatic epoxy (meth) acrylates such as neopentyl glycol type epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) Acrylate, alicyclic epoxy (meth) acrylate such as hydrogenated bisphenol F type epoxy (meth) acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, Phenol F-type epoxy (meth) acrylate, bisphenol AF type epoxy (meth) acrylates, and aromatic epoxy (meth) acrylates such as fluorene epoxy (meth) acrylate.

  Examples of the cross-linking agent having three or more (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Ethoxylated propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol Aliphatic (meth) acrylates such as ethyl tetra (meth) acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate; ethoxylated isocyanuric acid tri (meth) acrylate Heterocyclic (meth) acrylates such as propoxylated isocyanuric acid tri (meth) acrylate and ethoxylated propoxylated isocyanuric acid tri (meth) acrylate; modified caprolactone thereof; phenol novolac type epoxy (meth) acrylate, cresol novolac type Aromatic epoxy (meth) acrylates such as epoxy (meth) acrylate are exemplified.

Preferred examples of the crosslinking agent having two (meth) acryloyl groups include those represented by the following formulas (a) to (f).

  Moreover, it is preferable that the crosslinking agent which has (C) (meth) acryloyl group further has a urethane bond. Examples of the crosslinking agent further having a urethane bond include (poly) urethane (meth) acrylate and (poly) urethane di (meth) acrylate.

  (C) The crosslinking agent having a (meth) acryloyl group is preferably a monomer or oligomer having a (meth) acryloyl group.

  (C) It is preferable that content of a crosslinking agent is 10 mass% or less with respect to the whole quantity of an adhesive resin composition, it is more preferable that it is 7 mass% or less, and it is 5 mass% or less. Further preferred. (C) When the content of the crosslinking agent is 10% by mass or less, the obtained adhesive layer for an image display device tends to have appropriate adhesive strength and flexibility, and the reliability and impact resistance of the image display device are improved. There is a tendency to be able to improve. In addition, although there is no restriction | limiting in particular about the minimum of content of this crosslinking agent, since it exists in the tendency which can improve the shape stability of the adhesion layer at the time of high temperature, it is preferable that it is 0.1 mass% or more.

[(D) Photopolymerization initiator]
(D) A photopolymerization initiator (hereinafter, also referred to as “component (D)”) promotes the curing reaction of the adhesive resin composition by irradiation with active energy rays. Here, active energy rays refer to ultraviolet rays, electron beams, α rays, β rays, γ rays and the like. The selection of the photopolymerization initiator is not particularly limited, and known materials such as benzophenone materials, anthraquinone materials, benzoyl materials, sulfonium salts, diazonium salts, onium salts, and the like can be used.

  Specifically, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone , Α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2-benzo Anthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane -One, aromatic ketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Benzoin ether compounds such as benzoin phenyl ether; benzyl, 2,2-diethoxyacetophenone, benzyldimethyl ketal, ester compounds of β- (acridin-9-yl) (meth) acrylic acid; 9-phenylacridine, 9-pyridylacridine Acridine compounds such as 1,7-diacridinoheptane, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) ) Imidazo Dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2-benzyl-2-dimethylamino-1- (4-mol Holinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, bis (2,4,6-trimethylben Yl) - phenyl phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like. A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  Further, from the viewpoint of easily suppressing coloring of the adhesive resin composition, examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1 [Alpha] -hydroxyalkylphenone compounds such as [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -Acylphosphine oxide compounds such as phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide Oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl Phenyl) propanone) and a combination thereof are preferred.

  Further, from the viewpoint of facilitating the production of a particularly thick adhesive layer, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos A photopolymerization initiator containing an acyl phosphine oxide compound such as fin oxide or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is preferred.

  Further, from the viewpoint of easily reducing the odor of the adhesive layer, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable as the photopolymerization initiator. A plurality of these photopolymerization initiators may be used in combination.

  (D) It is preferable that content of a photoinitiator is 0.1-5 mass% with respect to whole quantity of an adhesive resin composition. By setting it as 5 mass% or less, there exists a tendency for the transmittance | permeability of the obtained adhesion layer to become high, and there exists a tendency for the hue to be suppressed from becoming yellowish. From the above viewpoint, 3 mass% or less is more preferable.

[(E) Rust preventive]
(E) A rust inhibitor (hereinafter also referred to as “component (E)”) contains a compound that prevents corrosion such as rust of metal. Although it does not specifically limit as a rust preventive agent, For example, the compound, nitrites, etc. which consist of an amine compound, imidazole, triazole, tetrazole, benzotriazole, and those derivatives are mentioned. In addition, ammonium benzoate, ammonium phthalate, ammonium stearate, ammonium palmitate, ammonium oleate, ammonium carbonate, dicyclohexylamine benzoate, urea, urotropine, thiourea, phenyl carbamate, cyclohexylammonium-N-cyclohexyl And carbamate (CHC). In addition, a rust preventive agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the amine compound include hydroxyl-containing amine compounds such as 2-amino-2-methyl-1-propanol, monoethanolamine, monoisopropanolamine, diethylethanolamine, ammonia, and aqueous ammonia; cyclic amines such as morpholine; cyclohexyl And cyclic alkylamine compounds such as amines; and linear alkylamines such as 3-methoxypropylamine. Examples of the nitrites include dicyclohexylammonium nitrite (DICHAN), diisopropylammonium nitrite (DIPAN), sodium nitrite, potassium nitrite, and calcium nitrite.

  From the viewpoint of compatibility with the base polymer, transparency of the resulting adhesive layer, and from the viewpoint that it is difficult to inhibit the reaction of the base polymer after addition to the base polymer (for example, crosslinking reaction, polymerization reaction), It preferably contains at least one selected from the group consisting of benzotriazole, imidazole, triazole, tetrazole and derivatives thereof, and more preferably contains at least one selected from the group consisting of benzotriazole and derivatives thereof.

  Specifically, examples of the benzotriazole derivatives include 4-methylbenzotriazole, 5-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4- Isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, Lower alkylbenzotriazoles such as 4-hexylbenzotriazole and 5-hexylbenzotriazole, 5-methoxybenzotriazole, 1-hydroxybenzotriazo 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, carboxybenzotriazole, 2,3-dicarboxypropylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [Maleic acid] benzotriazole, 4- or 5-chlorobenzotriazole, 4- or 5-nitrobenzotriazole, benzotriazole monoethanolamine salt, benzotriazole diethylamine salt, benzotriazole cyclohexylamine salt, benzotriazole morpholine salt, benzotriazole Examples thereof include isopropylamine salt and methylbenzotriazole cyclohexylamine salt.

  Moreover, as a triazole derivative, 3-mercaptotriazole etc. are mentioned, for example.

  These (E) components may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.

  (E) Although content of a rust preventive agent is not specifically limited, It is preferable that it is 0.02-3 mass parts with respect to 100 mass parts of whole quantity of an adhesive resin composition, 0.02-2.5 It is more preferable that it is a mass part, and it is still more preferable that it is 0.02-2 mass part. (E) When the content of the rust inhibitor is within the above range, an adhesive layer having excellent corrosion prevention ability can be formed, and (E) the same as the adhesive resin composition not containing the rust inhibitor There is a tendency that an adhesive layer having characteristics and physical properties, in particular, adhesion reliability such as adhesive strength and anti-foaming peelability can be reliably ensured, and an increase in haze can be reliably prevented.

[Other additives]
In addition to the components (A), (B), (C), (D), and (E), various additives are added to the adhesive resin composition according to the present embodiment as necessary. May be included. As such various additives, for example, preservation of the adhesive resin composition obtained by blending the above component (A), component (B), component (C), component (D) and component (E). Polymerization inhibitors such as paramethoxyphenol for the purpose of enhancing stability, heat-resistant agents such as triphenylphosphine for the purpose of enhancing the heat resistance of the cured product obtained by curing the adhesive resin composition with light, light such as ultraviolet rays It is possible to contain a light stabilizer such as HALS (Hindered Amine Light Stabilizer) for the purpose of enhancing the resistance to silane, and a silane coupling agent for the purpose of enhancing the adhesion to glass or the like.

  In addition, when an adhesive layer is obtained using the adhesive resin composition of the present embodiment, when the adhesive layer is sandwiched between substrates such as a polyethylene terephthalate film, the peelability from the substrate such as the polyethylene terephthalate film is improved. In order to control, surfactants, such as polydimethylsiloxane type surfactant and fluorine type surfactant, can be blended.

  The said additive may be used individually by 1 type, and may be contained in combination of 2 or more type. The content of these other additives is usually small compared to the total content of the above-mentioned components (A), (B), (C), (D) and (E). The amount of the adhesive resin composition is about 0.01 to 5% by mass.

  The adhesive resin composition according to the present embodiment can be used as an adhesive in a liquid state as it is, but is preferably used as a sheet-like adhesive sheet for an image display device.

<Adhesive sheet for image display device>
Next, the pressure-sensitive adhesive sheet for an image display device according to this embodiment will be described. The pressure-sensitive adhesive sheet for an image display device according to the present embodiment includes a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive resin composition of the present embodiment. The cured product is obtained by irradiating the adhesive resin composition of the present embodiment with an active energy ray and curing it. Hereinafter, a method for producing the pressure-sensitive adhesive sheet for an image display device of the present embodiment will be exemplified.

  The pressure-sensitive adhesive sheet for an image display device according to the present embodiment is, for example, a method in which the pressure-sensitive adhesive resin composition according to the present embodiment is applied on a substrate in a sheet shape, and the adhesive resin composition is cured by irradiating the active energy rays. Can be obtained. That is, the pressure-sensitive adhesive sheet for an image display device according to the present embodiment includes a base and a pressure-sensitive adhesive layer formed on the base, and the pressure-sensitive adhesive layer includes a cured product of the pressure-sensitive adhesive resin composition according to the present embodiment. It may be. Moreover, the pressure-sensitive adhesive sheet for an image display device according to the present embodiment may further include another layer on the pressure-sensitive adhesive layer. Note that the pressure-sensitive adhesive sheet for an image display device of the present embodiment may be a single-layer pressure-sensitive adhesive sheet obtained by curing the pressure-sensitive adhesive resin composition of the present embodiment into a sheet shape. Although it does not restrict | limit especially as a base | substrate, For example, films, such as a polyethylene terephthalate, etc. are mentioned. The other layers may be the same as or different from the base material.

The light source of the active energy ray preferably has a light emission distribution at a wavelength of 400 nm or less. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a metal halide lamp, and a microwave. An excited mercury lamp can be used. Moreover, although irradiation energy is not specifically limited, Usually, it is about 500-5000 mJ / cm < ² >.

  Since the pressure-sensitive adhesive sheet for an image display device according to the present embodiment includes a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive resin composition according to the present embodiment, the pressure-sensitive adhesive sheet has appropriate adhesive strength and reworkability, and has a desired thickness. Therefore, it can be made to a thickness that does not contain bubbles and can exhibit excellent impact relaxation properties. The thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet for an image display device of the present embodiment is not particularly limited depending on the intended use and usage method, but a thickness of about 0.05 to 2 mm is preferable. When used in this range, for example, there is a tendency that a particularly excellent effect can be exhibited as a transparent adhesive sheet for laminating an optical member on an image display member.

  Moreover, it is preferable that it is -10 degreeC-30 degreeC, and, as for the glass transition temperature of the hardened | cured material of the adhesive resin composition which concerns on this embodiment, it is more preferable that it is -10 degreeC-10 degreeC. Examples of the glass transition temperature measuring method include a method using a wide-range dynamic viscoelasticity measuring device.

  The pressure-sensitive adhesive composition of the present embodiment and the pressure-sensitive adhesive sheet for an image display device of the present embodiment can be applied to various image display devices.

<Image display device>
Next, the image display apparatus of this embodiment using the adhesive resin composition of the present embodiment or the pressure-sensitive adhesive sheet for image display apparatus will be described. The image display device of the present embodiment includes an adhesive layer, and the adhesive layer is formed using the adhesive resin composition of the present embodiment or the adhesive sheet for an image display device of the present embodiment. .

  Examples of the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic EL display (OLED), and electronic paper (EP). The pressure-sensitive adhesive resin composition and the pressure-sensitive adhesive sheet for an image display device according to this embodiment are, for example, functional layers having functionality such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer of the image display device, Multi-layered products in which functional layers are formed or laminated on optical filter substrates such as polyethylene films and polyester films, transparent protective substrates such as glass, acrylic resin, polycarbonate, etc., or these transparent protective substrates have various functions A multilayered product obtained by forming or laminating functional layers having a functional layer can be used for combining and bonding. Moreover, it can also be used as an optical filter combined with such a multilayer product. When an adhesive layer is formed using the adhesive resin composition of the present embodiment, for example, the adhesive resin composition of the present embodiment is applied or filled on an adherend such as the above multilayered product. The adhesive layer can be formed by curing from. When forming the adhesive layer using the adhesive sheet for an image display device of the present embodiment, for example, the adhesive for the image display device of the present embodiment using a roll laminate, a vacuum bonding machine, a single wafer bonding machine, or the like. The pressure-sensitive adhesive layer can be formed by transferring and laminating the pressure-sensitive adhesive layer in the sheet onto an adherend such as the above multilayered product.

  The antireflection layer may be a layer having an antireflection property with a visible light reflectance of 5% or less, and is a layer treated by a known antireflection method on a transparent substrate such as a transparent plastic film. Can be used.

  The antifouling layer may be any layer that makes it difficult to get dirt on the surface, and a known layer can be used. In order to lower the surface tension, a layer made of fluorine resin or silicone resin can be used.

  The dye layer is used to increase color purity, and is used to reduce unnecessary light when the color purity of light emitted from an image display device such as a liquid crystal display device is low. The pigment layer can be obtained by dissolving a pigment that absorbs unnecessary portions of light in a resin, and forming or laminating the pigment film on a substrate film such as a polyethylene film or a polyester film.

  The hard coat layer is used to increase the surface hardness. As a hard-coat layer, what formed or laminated | stacked acrylic resins, such as urethane acrylate and epoxy acrylate, and epoxy resins, etc. on base films, such as a polyethylene film, can be used. Similarly, in order to increase the surface hardness, it is also possible to use a transparent protective substrate such as glass, acrylic resin or polycarbonate, or a substrate obtained by forming or laminating a hard coat layer on these substrates.

  The pressure-sensitive adhesive resin composition and the pressure-sensitive adhesive sheet for an image display device of the present embodiment can be used after being formed or laminated on a polarizing plate. In this case, a film can be formed or laminated on the viewing side of the polarizing plate, and a film can be formed or laminated on the opposite side.

  When an adhesive layer is provided on the viewing side of the polarizing plate, an antireflection layer, an antifouling layer, a hard coat layer, or the like may be further provided on the viewing side of the adhesive layer. When an adhesive layer is provided between the polarizing plate and the liquid crystal cell, a functional layer may be further provided on the viewing side of the polarizing plate.

  In the image display device according to the present embodiment, the position of the adhesive layer is not particularly limited as long as the adhesive layer can be applied due to the configuration of the image display device, but the image display panel and the viewing side of the image display device are not limited. It is preferably between the frontmost protective plate (front plate) and disposed at an appropriate position on the viewing side. Specifically, it is preferably disposed between the image display panel and the protective plate. Moreover, in the image display apparatus which combined the touch panel with the image display apparatus, it is preferable that the adhesive layer is disposed between the touch panel and the image display panel and / or between the touch panel and the protective plate. The image display panel includes a liquid crystal panel, an organic EL panel, and the like.

  FIG. 1 is a schematic cross-sectional view illustrating an example of the image display device of the present embodiment. A liquid crystal display device 10 having a built-in touch panel as shown in FIG. 1 includes a protective plate 1, a touch panel 2, a polarizing plate 3, and a liquid crystal cell 4, and an adhesive layer between the protective plate 1 and the touch panel 2. 5 is disposed, and an adhesive layer 6 is further disposed between the touch panel 2 and the polarizing plate 3. In addition, the said adhesion layer 5 and / or the adhesion layer 6 are formed using the adhesive resin composition of the said embodiment, or the adhesive sheet for image display apparatuses.

  As the protective plate of the image display device, a general optical transparent substrate can be used. Specific examples include a glass plate, an inorganic plate such as quartz, a plastic (organic) plate such as an acrylic resin plate, a polycarbonate plate and a polyethylene terephthalate plate, and a resin sheet such as a thick polyester sheet.

  When the image display device is a liquid crystal display device, a general liquid crystal cell can be used as the liquid crystal cell. The liquid crystal cell is classified into TN, STN, VA, IPS, and the like depending on a liquid crystal control method, but a liquid crystal cell using any control method can be used.

  Hereinafter, the present invention will be described by way of examples. The present invention is not limited to these examples.

[Production Example 1]
<Synthesis of (A) (meth) acrylic acid derivative polymer>
Into a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen inlet tube, 84.0 g of 2-ethylhexyl acrylate and 36.0 g of 2-hydroxyethyl acrylate as an initial monomer and 150.0 g of methyl ethyl ketone are taken. The sample was heated from room temperature (25 ° C.) to 70 ° C. for 15 minutes while replacing the nitrogen with an air flow of 100 mL / min.

  Thereafter, while maintaining at 70 ° C., 21.0 g of 2-ethylhexyl acrylate and 9.0 g of 2-hydroxyethyl acrylate were used as additional monomers, and a solution in which 1.0 g of lauroyl peroxide was dissolved in these additional monomers was prepared. This solution was added dropwise over 60 minutes. After completion of dropping, the reaction was further continued for 2 hours.

  Subsequently, methyl ethyl ketone was distilled off to obtain a copolymer (weight average molecular weight 150,000) of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (hereinafter, this copolymer was referred to as “acrylic acid derivative”). Polymer ”).

In addition, the measurement of the weight average molecular weight was performed using the gel permeation chromatography which used tetrahydrofuran (THF) as a solvent, and it determined using the calibration curve of a standard polystyrene using the following apparatus and measurement conditions.
Device: Hitachi, Ltd. RI Detector: L-3350
Solvent: THF
Column: Gelpac GL-R420 + R430 + R440 manufactured by Hitachi Chemical Co., Ltd.
Column temperature: 40 ° C
Flow rate: 2.0 mL / min

[Production Example 2]
<(C) Synthesis of a cross-linking agent having a bifunctional (meth) acryloyl group>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube, 223.12 g of polypropylene glycol (molecular weight 2,000), 76.29 g of lactone-modified hydroxyethyl acrylate, 99.68 g of 2-ethylhexyl acrylate Taking 0.12 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, raising the temperature to 75 ° C. while flowing air, and then stirring 49.35 g of isophorone diisocyanate for 2 hours while stirring at 75 ° C. The solution was uniformly dropped over the course of the reaction.

When the reaction was completed for 5 hours after the completion of the dropwise addition, 44.85 g of 2-hydroxyethyl acrylate was further added, and the reaction was performed for 1 hour. As a result of IR measurement (measurement wave number: 2270 cm ⁻¹ ), it was confirmed that the isocyanate had disappeared, the reaction was terminated, and the structural unit derived from polypropylene glycol and the structural unit derived from isophorone diisocyanate were used as repeating units. A polyurethane diacrylate having a polymerizable unsaturated bond at the terminal (weight average molecular weight 8,500) was obtained.

<Preparation of adhesive resin composition and production of adhesive sheet for image display device>
Example 1
88.75 parts by mass of the acrylic acid derivative polymer obtained in Production Example 1, 4.85 parts by mass of polyurethane diacrylate obtained in Production Example 2, 4.13 parts by mass of 2-ethylhexyl acrylate (2-EHA), hydroxy 1.36 parts by mass of ethyl acrylate (HEA), 0.41 parts by mass of acryloylmorpholine (ACMO), 0.5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (I-184) (Irgacure-184, manufactured by BASF Japan Ltd., product) Name) and 0.05 part by mass of 1,2,3-benzotriazole (trade name “VERZONE Crystal # 120”, manufactured by Daiwa Kasei Co., Ltd.) An adhesive resin composition was obtained.

The above-obtained adhesive resin composition was dropped onto a polyethylene terephthalate film, and a similar polyethylene terephthalate film was further covered thereon, and the adhesive resin composition was applied in a sheet form with a roller. Using an ultraviolet irradiation device (Igraphics Co., Ltd., idle fin 3000, high power metal halide lamp), ultraviolet rays were irradiated at ² J / cm ² to cure the adhesive resin composition, and the polyethylene terephthalate film was used as an adhesive resin composition. A transparent pressure-sensitive adhesive sheet for an image display device with a cured product (pressure-sensitive adhesive layer) sandwiched therebetween was obtained. The thickness of the adhesive layer was adjusted to 150 μm.

(Examples 2 to 7 and Comparative Example 1)
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the components shown in Table 1 were blended in the amounts shown in the same table. In Table 1, the unit of the numerical value representing the blending amount is part by mass.

<Evaluation>
The following (1)-(4) was evaluated about the adhesive sheet obtained by each Example and the comparative example.

(1) Peel strength The prepared pressure-sensitive adhesive sheet was cut into a size of 10 mm in width and 80 mm in length, the polyethylene terephthalate film on one side of the pressure-sensitive adhesive sheet was peeled off, and a hand roller was placed on white plate glass having a size of 25 mm in width and 100 mm in length. Using (pressure bonding temperature: 25 ° C., load: 500 gf), the pressure-sensitive adhesive sheet was bonded so that the pressure-sensitive adhesive layer was in contact with the white glass sheet. Next, the polyethylene terephthalate film on the other surface of the pressure-sensitive adhesive sheet is peeled off, and a polyethylene terephthalate film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) is cut into dimensions of 15 mm in width and 150 mm in length. Was bonded to the pressure-sensitive adhesive sheet so as to be in contact with the pressure-sensitive adhesive layer, and a sample in which the pressure-sensitive adhesive layer was sandwiched between white plate glass and polyethylene terephthalate film was prepared. Using a tensile tester (Orientec Co., Ltd., trade name RTC-1210), the polyethylene terephthalate film is peeled off from the sample at a peeling angle of 180 ° and a peeling speed of 300 mm / min. The strength was measured.

(2) Optical characteristics (A) Measurement of L *, a *, b * The prepared pressure-sensitive adhesive sheet was cut into dimensions of 40 mm in width and 100 mm in length, the polyethylene terephthalate film on one side of the pressure-sensitive adhesive sheet was peeled off, and the width 50 mm × Using a hand roller (crimping temperature: 25 ° C., load: 500 gf) on a glass substrate (white glass) having a length of 100 mm × thickness of 3 mm, an adhesive sheet was bonded so that the adhesive layer was in contact with the white plate glass. . Next, the polyethylene terephthalate film on the other surface of the pressure-sensitive adhesive sheet is peeled off, and L *, using a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., SQ-2000 [trade name]) with the pressure-sensitive adhesive layer surface as the light source side. The values of a * and b * were measured.

(B) Measurement of turbidity (haze) The produced pressure-sensitive adhesive sheet was cut into dimensions of 40 mm in width and 100 mm in length, and the polyethylene terephthalate film on one side of the pressure-sensitive adhesive sheet was peeled off, and the width 50 mm × length 100 mm × thickness 3 mm. A pressure-sensitive adhesive sheet was bonded to a glass substrate (white plate glass) having dimensions using a hand roller (pressure bonding temperature: 25 ° C., load: 500 gf) so that the pressure-sensitive adhesive layer was in contact with the white plate glass. Subsequently, the polyethylene terephthalate film on the other surface of the pressure-sensitive adhesive sheet is peeled off, and the pressure-sensitive adhesive layer surface is used as a light source side, using a turbidimeter (Nippon Denshoku Industries Co., Ltd., NDH-5000 [trade name]), JIS K 7136. The haze was measured according to the above.
Haze (%) = (Td / Tt) × 100
Td: diffuse transmittance Tt: total light transmittance

(3) Metal corrosion resistance (corrosion prevention)
A film (hereinafter sometimes referred to as “copper film”) in which a copper layer was provided on one surface of a polyethylene terephthalate base material (manufactured by Geomat Co., Ltd., thickness 100 μm) was prepared. The produced pressure-sensitive adhesive sheet was cut into dimensions of 12 mm in width and 110 mm in length, the polyethylene terephthalate film on one side of the pressure-sensitive adhesive sheet was peeled off, and using a hand roller (crimping temperature: 25 ° C., load: 500 gf), copper in the copper film The adhesive sheet was bonded to the copper film so that the adhesive layer was in contact with the layer. Then, the process by an autoclave (heating temperature: 30 degreeC, pressure: 0.3MPa) was performed for 10 minutes, and it was set as the evaluation sample.

As a device for measuring the sheet resistance value of the copper layer in the evaluation sample, a digital multimeter (trade name “U1152B”, manufactured by Keysight Technologies) was used. Under an environment of 25 ° C., the sheet resistance value (initial sheet resistance value: R ₀ ) of the evaluation sample was measured, and the color of copper was visually observed.

After the measurement, the evaluation sample was put in an environment of 85 ° C. and 85% RH for 240 hours. After taking out, leave it in an environment of 25 ° C. for 3 hours, and then measure the sheet resistance value (post-test sheet resistance value: R ₁ ) in an environment of 25 ° C., and visually check the color change of copper from the beginning. Observed.

From the initial sheet resistance value (R ₀ ) and the post-test sheet resistance value (R ₁ ), the rate of increase of the sheet resistance value is obtained by the following calculation formula, and metal corrosion resistance (rust prevention) according to the following evaluation criteria: Evaluated.
Resistance increase rate T (%) = (R ₁ −R ₀ ) / R ₀ × 100
(Evaluation criteria)
A: Resistance increase rate is less than 120% and Cu is not discolored (determined that Cu corrosion prevention ability is good).
B: Resistance increase rate is 120% or more and less than 150%, and there is no Cu discoloration (determined to have Cu corrosion prevention ability)
C: Resistance increase rate is 150% or more, or Cu discoloration (determined not having Cu corrosion prevention ability).

  By using the pressure-sensitive adhesive resin composition of the present invention and the pressure-sensitive adhesive sheet for an image display device of the present invention, an image display device having impact resistance and excellent adhesion reliability, transparency, and corrosion prevention effect is provided. Can do. In addition, according to the present invention, since the formation of the rust preventive film is unnecessary, the manufacturing process of the image display device is reduced. As a result, the cost can be reduced and the yield can be improved. Therefore, the pressure-sensitive adhesive resin composition and the pressure-sensitive adhesive sheet for image display device of the present invention are useful for image display devices such as liquid crystal displays (LCD), image display devices incorporating information input units such as touch panels, especially for touch panel applications. .

  DESCRIPTION OF SYMBOLS 1 ... Protective plate, 2 ... Touch panel, 3 ... Polarizing plate, 4 ... Liquid crystal cell, 5 ... Adhesive layer for bonding a protective plate and a touch panel, 6 ... Adhesive layer for bonding a touch panel and a polarizing plate, 10 ... Liquid crystal display device.

Claims (8)

(A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having (meth) acryloyl group, (C) cross-linking agent having (meth) acryloyl group, (D) photopolymerization initiation An adhesive resin composition containing an agent and (E) a rust inhibitor,
The adhesive resin composition in which the (meth) acrylic acid-based derivative monomer having the (B) (meth) acryloyl group includes a (B-1) (meth) acrylic acid-based derivative monomer having an amide group.   The adhesive resin composition according to claim 1, wherein the (B-1) amide group-containing (meth) acrylic acid derivative monomer contains acryloylmorpholine.   The pressure-sensitive adhesive according to claim 1 or 2, wherein the (B) (meth) acrylic acid derivative monomer having a (B) hydroxyl group further comprises the (B) (meth) acryloyl group. Resin composition.   The adhesive resin composition according to any one of claims 1 to 3, wherein the (E) rust inhibitor includes at least one selected from the group consisting of benzotriazole, imidazole, triazole, tetrazole, and derivatives thereof. object.   Hardened | cured material of the adhesive resin composition as described in any one of Claims 1-4.   The hardened | cured material of Claim 5 whose glass transition temperature is -10 degreeC-30 degreeC.   An image display apparatus provided with the adhesion layer containing the hardened | cured material of the adhesive resin composition as described in any one of Claims 1-4.   The image display device according to claim 7, wherein the adhesive layer is formed between the protection plate and the image display panel, between the protection plate and the touch panel, or between the touch panel and the image display panel. .