JP2024033911A - Adhesive compositions, adhesives and adhesive sheets - Google Patents

Abstract

An object of the present invention is to provide a pressure-sensitive adhesive composition that exhibits excellent adhesive properties in a low crosslinked state after primary curing, and provides excellent adhesive properties and reliability even after complete curing. [Solution] The acrylic resin (A) contains an acrylic resin (A) and a photopolymerization initiator (B), the acrylic resin (A) contains 5 to 25% by weight of structural units derived from a hydroxyl group-containing monomer (a1), and , an alkyl group containing two or more tertiary carbons as a structural unit derived from a branched alkyl (meth)acrylate (a2) having a glass transition temperature of less than 0 ° C. and having an alkyl group containing a branched structure when forming a homopolymer. 5 to 50% by weight of structural units derived from the hyperbranched structure-containing alkyl (meth)acrylate (a2-1), and a branched alkyl (meth) other than the hyperbranched structure-containing alkyl (meth)acrylate (a2-1). An adhesive composition containing a structural unit derived from acrylate (a2-2) and having an acrylic resin (A) having a glass transition temperature of -10°C or higher. [Selection diagram] None

Description

The present invention relates to an adhesive composition, an adhesive, and an adhesive sheet.

In recent years, touch panels that combine a display and a position input device have been widely used in mobile devices such as televisions, personal computer monitors, notebook computers, mobile phones, smartphones, and tablet terminals. Among these, capacitive touch panels are generally popular.
A touch panel is usually composed of a display made of organic EL or liquid crystal, a transparent conductive film substrate (ITO substrate), and a protective film (protective glass). Transparent adhesive sheets are used to bond these touch panel members together.

Displays made of flexible devices such as organic EL can be used for displays of various shapes, including flat, curved, foldable, and rollable displays due to their characteristics. In transparent adhesive sheets used to bond laminates made up of displays with complex shapes such as curved surfaces, it is necessary to bond members of various shapes together, so the adhesive used for transparent adhesive sheets is low-crosslinked before completely curing. Pasted in condition. Therefore, sufficient adhesive physical properties are required in the process of completely curing the adhesive layer in a low crosslinked state.
For example, when bonding to a complex-shaped member, poor bonding is likely to occur due to the transparent adhesive sheet sticking to a location other than the intended location. Therefore, there is a demand for a transparent adhesive sheet with low tackiness.
In addition, in order to fix complex-shaped members to each other, it is required to suppress peeling of the transparent adhesive sheet from the members under stress. Therefore, there is a demand for a transparent adhesive sheet that has a high constant load holding capacity even in a low crosslinked state.

In addition, the adhesive layer after being completely cured is required to have excellent performance not only in adhesive physical properties such as normal adhesive strength, but also in reliability when bonding various members such as polarizing plates and glass. For example, in order to obtain excellent durability after complete curing, the degree of crosslinking must be low until it is bonded to the adherend, and it is also necessary to efficiently increase the degree of crosslinking at the time of complete curing. It will be done.

Therefore, it is expected that sufficient adhesion to the adherend will be possible by laminating the adhesive to the adherend in a low crosslinked state. Furthermore, by completely curing the adhesive sheet in a state where it is bonded to an adherend in a low crosslinked state, the adhesive sheet becomes highly crosslinked, and it is expected that durability will be improved.
Generally, in primary curing, the material is crosslinked and cured by thermal crosslinking or by irradiation with active energy rays, and in complete curing, it is crosslinked and cured by irradiation with active energy rays. Examples of pressure-sensitive adhesive sheets using such multi-stage curable pressure-sensitive adhesives include the pressure-sensitive adhesive sheets described in Patent Documents 1 to 3.

Patent Document 1 discloses that by further using an organic solvent that easily volatizes under general drying conditions in a solvent-based adhesive made of an acrylic resin, and blending a specific proportion of an ethylenically unsaturated monomer that is resistant to volatilization, It is disclosed that thick coating is possible and that a beautiful adhesive layer on the surface of the coating film can be obtained.
Furthermore, in Patent Document 2, in order to form a three-dimensional network structure of a solvent-based acrylic ester pressure-sensitive adhesive without using a crosslinking agent, a hydrogen abstraction type photopolymerization initiator is used, and a photopolymerization initiator is used after the coating drying process. It is disclosed that the aging step can be omitted by irradiation.
Furthermore, Patent Document 3 discloses that by using an acrylic resin having a high glass transition temperature, an adhesive having high step followability and high blister resistance can be obtained.

Japanese Patent Application Publication No. 2012-111939 JP2017-210542A International Publication No. 2017/022770

However, in none of Patent Documents 1 to 3, the adhesive properties in a low crosslinked state during primary curing are not considered. Therefore, the adhesive properties in a low crosslinked state during primary curing may be insufficient, so there is room for improvement.

The present invention is an adhesive composition that can be used for multi-stage curing, which provides excellent adhesive properties in a low crosslinked state after primary curing, and has excellent adhesive properties and reliability even after complete curing. The object of the present invention is to provide a pressure-sensitive adhesive sheet having an obtained pressure-sensitive adhesive composition; a pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition; and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive.

In order to solve the above problems, as a result of intensive studies by the present inventors, the primary It has been found that excellent adhesive properties such as low tackiness and high constant load holding power can be achieved even in a low crosslinked state after curing, and excellent adhesive properties and reliability can also be achieved after complete curing.

That is, the present invention is an adhesive composition containing an acrylic resin (A) and a photopolymerization initiator (B),
The acrylic resin (A) has a structural unit derived from the hydroxyl group-containing monomer (a1), and a branched alkyl (meth) having a glass transition temperature of less than 0° C. when forming a homopolymer and an alkyl group containing a branched structure. Contains a structural unit derived from acrylate (a2),
The content of the structural unit derived from the hydroxyl group-containing monomer (a1) is 5 to 25% by weight of the entire acrylic resin (A),
The structural unit derived from the branched alkyl (meth)acrylate (a2) is a highly branched alkyl (meth)acrylate having a glass transition temperature of less than 0°C and having an alkyl group containing two or more tertiary carbons when forming a homopolymer. ) Structural units derived from acrylate (a2-1) and branched alkyls (excluding the multi-branched structure-containing alkyl (meth)acrylate (a2-1)) whose glass transition temperature is less than 0°C when forming a homopolymer. Contains a structural unit derived from meth)acrylate (a2-2),
The content of the structural unit derived from the hyperbranched structure-containing alkyl (meth)acrylate (a2-1) is 5 to 50% by weight of the entire acrylic resin (A),
The present invention relates to an adhesive composition characterized in that the acrylic resin (A) has a glass transition temperature based on dynamic viscoelasticity of -10°C or higher.

According to the present invention, there is provided an adhesive composition that can be used for multi-stage curing, which provides excellent adhesive properties in a low crosslinked state after primary curing, and has excellent adhesive properties and reliability even after complete curing. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition capable of obtaining properties; a pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition; and a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is provided.

Hereinafter, the present invention will be explained in detail, but these are examples of desirable embodiments.
Furthermore, the meanings of the following terms in this specification are shown below.
"(Meth)acrylic" means acrylic or methacrylic.
"(Meth)acryloyl" means acryloyl or methacryloyl.
"(Meth)acrylate" means acrylate or methacrylate.
"Acrylic resin" is a resin obtained by polymerizing a monomer component containing at least one (meth)acrylic monomer.
The term "sheet" conceptually includes sheets, films, and tapes.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.

<Adhesive composition>
The adhesive composition of the present invention contains an acrylic resin (A) and a photopolymerization initiator (B). The adhesive composition of the present invention contains, in addition to an acrylic resin (A) and a photopolymerization initiator (B), a crosslinking agent (C), a silane coupling agent (D), a carbodiimide compound (E), and other components. It may further contain optional components if necessary.
Each component will be explained in order below.

(Acrylic resin (A))
The acrylic resin (A) used in the present invention has a structural unit derived from the hydroxyl group-containing monomer (a1) and a branched structure having a glass transition temperature of less than 0°C when forming a homopolymer and an alkyl group containing a branched structure. It contains a structural unit derived from alkyl (meth)acrylate (a2), and may contain structural units derived from other copolymer components as necessary.
In addition, the acrylic resin (A) used in the present invention is composed of a hydroxyl group-containing monomer (a1) and a branched alkyl group (meth) having a glass transition temperature of less than 0°C when forming a homopolymer and having an alkyl group containing a branched structure. ) It is a polymerization product of acrylate (a2) and other copolymerization components used as necessary.
The copolymer component is a general term for monomer components having a polymerizable double bond. The copolymerization components do not include a polymerization initiator or a polymerization solvent.

[Hydroxy group-containing monomer (a1)]
The hydroxyl group-containing monomer (a1) used in the present invention contains one or more hydroxyl groups and an ethylenically unsaturated group.
Examples of the hydroxyl group-containing monomer (a1) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxy Hydroxyl group-containing alkyl (meth)acrylates such as octyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; Alkylene-modified monomers; other monomers containing primary hydroxyl groups such as 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth)acrylamide, and hydroxyethyl acrylamide; 2-hydroxypropyl (meth)acrylate, 2- Secondary hydroxyl group-containing monomers such as hydroxybutyl (meth)acrylate and 3-chloro 2-hydroxypropyl (meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate.
Among these, primary hydroxyl group-containing alkyl (meth)acrylates are preferred in that they can be efficiently cured during complete curing, and it is particularly preferred to use 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.

[Branched alkyl (meth)acrylate (a2)]
The glass transition temperature (hereinafter referred to as "Tg") when forming the homopolymer of the branched alkyl (meth)acrylate (a2) used in the present invention is less than 0°C. Branched alkyl (meth)acrylate (a2) does not have a hydroxyl group.
The Tg of the branched alkyl (meth)acrylate (a2) is preferably -80 to -20°C, more preferably -75 to -30°C, particularly preferably -70 to -40°C. When Tg is within this range, the effects of the present invention are likely to be obtained.
Note that, for the Tg when a homopolymer of branched alkyl (meth)acrylate (a2) is formed, a standard analytical value described in "POLYMER HANDBOOK" published by Wiley, etc. can be adopted.

The branched alkyl (meth)acrylate (a2) used in the present invention has a Tg of less than 0°C when a homopolymer is formed and a hyperbranched structure-containing alkyl group having an alkyl group containing two or more tertiary carbons as a branched structure ( meth)acrylate (a2-1) and a branched alkyl (meth)acrylate (a2-2) having a Tg of less than 0°C when a homopolymer is formed, excluding the multibranched structure-containing alkyl (meth)acrylate (a2-1) ).

Examples of the alkyl (meth)acrylate (a2-1) containing a multi-branched structure include isodecyl (meth)acrylate, isomyristyl (meth)acrylate, isotridecyl (meth)acrylate, isostearyl (meth)acrylate, and the like. can. Among these, isodecyl (meth)acrylate is preferred because it has excellent active energy ray curability upon complete curing.
One type selected from these may be used alone, or two or more types may be used in combination.

Examples of the branched alkyl (meth)acrylate (a2-2) include isobutyl acrylate, isoamyl acrylate, 2-ethylhexyl (meth)acrylate, and isononyl acrylate. Among them, 2-ethylhexyl acrylate is preferred from the viewpoint of adhesive properties.
One type selected from these may be used alone, or two or more types may be used in combination.

[Alkyl (meth)acrylate (a3) with a glass transition temperature of 0°C or higher]
The acrylic resin (A) used in the present invention may further contain a structural unit derived from an alkyl (meth)acrylate (a3) having a Tg of 0° C. or higher when a homopolymer is formed.
Examples of the alkyl (meth)acrylate (a3) include methyl acrylate (Tg=8°C), methyl methacrylate (Tg=105°C), ethyl methacrylate (Tg=65°C), n-butyl methacrylate (Tg=20°C) , cyclohexyl acrylate (Tg = 15°C), cyclohexyl methacrylate (Tg = 65°C), isobutyl methacrylate (Tg = 48°C), t-butyl acrylate (Tg = 14°C), t-butyl methacrylate (Tg = 107°C), Examples include isobornyl acrylate (Tg=94°C) and isobornyl methacrylate (Tg=180°C). One type selected from these may be used alone, or two or more types may be used in combination.
It is preferable to include a branched alkyl (meth)acrylate as the alkyl (meth)acrylate (a3) because it can be efficiently cured with active energy rays during complete curing and can reduce tackiness. Among them, isobutyl methacrylate is preferred.

[Ethylenically unsaturated monomer (a4)]
The acrylic resin (A) used in the present invention may optionally contain other copolymerizable monomers other than the hydroxyl group-containing monomer (a1), branched alkyl (meth)acrylate (a2), and alkyl (meth)acrylate (a3). It may further contain a structural unit derived from the ethylenically unsaturated monomer (a4).
Other copolymerizable ethylenically unsaturated monomers (a4) include linear alkyl (meth)acrylates such as ethyl acrylate, n-butyl acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, and lauryl acrylate. ; Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyldiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol-(meth)acrylate, ortho-phenyl phenoxy Aromatic ring-containing monomers such as ethyl (meth)acrylate, nonylphenol ethylene oxide adduct (meth)acrylate; alicyclic-containing monomers such as cyclohexyloxyalkyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl ( meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol ( meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate Ether chain-containing monomers such as meth)acrylate; (meth)acrylic acid, acrylic acid dimers such as β-carboxyethyl acrylate, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, N - Carboxy group-containing monomers such as glycolic acid and cinnamic acid; (meth)acrylamide, N-(n-butoxyalkyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth) Amide group-containing monomers such as acrylamide and N,N-dimethylaminoalkyl (meth)acrylamide; Benzophenone-containing monomers such as 4-(meth)acryloyloxybenzophenone; Others, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, acetic acid Vinyl, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, acrylic chloride, methyl vinyl ketone, N-acrylamide methyl trimethyl Examples include ammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, and the like.
The ethylenically unsaturated monomer (a4) may be used alone or in combination of two or more.

In addition, as ethylenically unsaturated monomers having two or more ethylenically unsaturated groups, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, divinylbenzene, etc. can also be used in combination.

[Composition of acrylic resin (A)]
The content of structural units derived from the hydroxyl group-containing monomer (a1) in the acrylic resin (A) is 5 to 25% by weight, particularly 10 to 23% by weight, based on the entire acrylic resin (A) (100% by weight). %, more preferably 13 to 20% by weight. If the content of the structural unit derived from the hydroxyl group-containing monomer (a1) is too small, the heat-and-moisture resistance after complete curing and the reliability at high temperatures tend to decrease. If the content of the structural unit derived from the hydroxyl group-containing monomer (a1) is too large, the viscosity tends to increase due to the influence of stronger hydrogen bonds, and processing suitability tends to decrease.

The content of the structural unit derived from branched alkyl (meth)acrylate (a2) in the acrylic resin (A) is preferably 20 to 70% by weight based on the entire acrylic resin (A) (100% by weight), More preferably 30 to 65% by weight, still more preferably 40 to 60% by weight. If the content is too small, active energy ray curability during complete curing tends to decrease, while if the content is too large, adhesive physical properties such as tackiness during primary curing tend to decrease.

The content of the structural unit derived from the hyperbranched structure-containing alkyl (meth)acrylate (a2-1) of the acrylic resin (A) is 5 to 50% by weight based on the entire acrylic resin (A) (100% by weight). The amount is preferably 7.5 to 45% by weight, more preferably 10 to 40% by weight. If the content is too low, it tends to peel off from the member under stress, and if the content is too high, the adhesive properties after complete curing tend to deteriorate.

The content of the structural unit derived from the branched alkyl (meth)acrylate (a2-2) in the acrylic resin (A) is preferably 5 to 60% by weight based on the entire acrylic resin (A) (100% by weight). The amount is preferably 10 to 55% by weight, and even more preferably 15 to 50% by weight. If the content is too small, the adhesive properties such as adhesive strength will tend to decrease, and if the content is too large, the adhesive properties such as tackiness during primary curing will tend to decrease.

Content ratio (a2-1) of the structural unit derived from the multi-branched structure-containing alkyl (meth)acrylate (a2-1) and the structural unit derived from the branched alkyl (meth)acrylate (a2-2) in the acrylic resin (A) :a2-2) is preferably 100:150 to 100:700, more preferably 100:200 to 100:450, and even more preferably 100:230 to 100:350 in weight ratio. If the content ratio is within this range, there is a tendency for an excellent balance between active energy ray curability and adhesive properties upon complete curing; if it is outside this range, active energy ray curability and adhesive properties tend to decrease. There is.

When the acrylic resin (A) contains a structural unit derived from alkyl (meth)acrylate (a3), the content of the structural unit derived from alkyl (meth)acrylate (a3) is based on the entire acrylic resin (A) (100% by weight %), preferably 5 to 50% by weight, more preferably 10 to 45% by weight, even more preferably 15 to 40% by weight. If this content is too small, adhesive physical properties such as tackiness during primary curing will tend to deteriorate, while if the content is too large, the glass transition temperature of the acrylic resin (A) will rise excessively, resulting in a decrease in primary curing. At times, the adhesion to the adherend tends to decrease.

When the acrylic resin (A) contains a structural unit derived from the ethylenically unsaturated monomer (a4), the content of the structural unit derived from the ethylenically unsaturated monomer (a4) is based on the entire acrylic resin (A) (100% by weight). %), preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less. If the content of the ethylenically unsaturated monomer (a4) is too large, the balance of adhesive properties tends to deteriorate.

[Physical properties of acrylic resin (A)]
The Tg based on the dynamic viscoelasticity of the acrylic resin (A), that is, the temperature at which the loss tangent of the dynamic viscoelasticity is maximum, is -10°C or higher, preferably -5 to 20°C, more preferably 0 to 20°C. The temperature is 15°C, particularly preferably 2 to 13°C.
If the temperature at which the loss tangent of the dynamic viscoelasticity of the acrylic resin (A) reaches its maximum is too high, the adhesive force tends to decrease as the pressure-sensitive adhesive layer's ability to follow steps and adhesion decreases. If the temperature at which the loss tangent of the dynamic viscoelasticity of the acrylic resin (A) reaches its maximum is too low, the adhesive properties tend to deteriorate in the low crosslinked state during primary curing.

Tg based on dynamic viscoelasticity is determined by the following measurement method.
By adding a suitable organic solvent, an acrylic resin solution containing only the acrylic resin (A) of the present invention and an organic solvent is prepared. After adjusting the concentration of the acrylic resin solution, it is coated onto a release sheet so that the thickness after drying is 50 μm. After that, the organic solvent is removed by drying by heat treatment at 90 to 105°C for 5 to 10 minutes, and then this is attached to a release sheet, and an acrylic resin containing 99% by weight or more of acrylic resin (A) is used. Create a resin sheet. Thereafter, a plurality of acrylic resin sheets are laminated to create an acrylic resin sheet with a thickness of approximately 800 μm.
The dynamic viscoelasticity of the prepared sheet was measured under the following conditions, and the temperature at which the loss tangent (loss modulus G''/storage modulus G' = tan δ) was the maximum was read, and the value was determined based on the dynamic viscoelasticity. This is the glass transition temperature of the acrylic resin (A).

(Dynamic viscoelasticity measurement conditions)
Measuring equipment: Dynamic viscoelasticity measuring device (product name: DVA-225, manufactured by IT Keizai Control Co., Ltd.)
Deformation mode: shear Strain: 0.1%
Measurement temperature: -100~60℃
Measurement frequency: 1Hz

On the other hand, the calculated glass transition temperature (calculated Tg) is calculated from the following Fox formula. In the present invention, "Tg based on the dynamic viscoelasticity of the acrylic resin (A)" is different from the calculated Tg.

Tg: Glass transition temperature (K) of copolymer
Tga: Glass transition temperature (K) of homopolymer of monomer A
Wa: Weight fraction of structural units derived from monomer A in the copolymer Tgb: Glass transition temperature (K) of homopolymer of monomer B
Wb: Weight fraction of structural units derived from monomer B in the copolymer Tgn: Glass transition temperature (K) of homopolymer of monomer N
Wn: Weight fraction of structural units derived from monomer N in the copolymer (Wa+Wb+...+Wn=1)

The weight average molecular weight (Mw) of the acrylic resin (A) is preferably 50,000 to 500,000, more preferably 100,000 to 400,000, even more preferably 150,000 to 350,000. If the weight average molecular weight of the acrylic resin (A) is too large, the viscosity will become too high and the coating properties and handling will tend to deteriorate. If the weight average molecular weight of the acrylic resin (A) is too small, the cohesive force tends to decrease, the adhesive properties decrease, and the durability after complete curing tends to decrease.
The weight average molecular weight of the acrylic resin (A) is the weight average molecular weight at the time of completion of production. The weight average molecular weight is measured for the acrylic resin (A) that has not been heated or the like after production.

The weight average molecular weight of the acrylic resin (A) is the weight average molecular weight in terms of standard polystyrene molecular weight. The weight average molecular weight was measured using a high-performance liquid chromatograph (Japan Waters Co., Ltd., "Waters 2695 (main body)" and "Waters 2414 (detector)"), column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation Range: 100 to 2×10 ⁷ , number of theoretical plates: 10,000 plates/piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm).It is measured by using three pieces in series.
Number average molecular weight can also be measured using a similar method. Further, the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the acrylic resin (A) is preferably 15 or less, more preferably 10 or less, still more preferably 7 or less, particularly preferably 5 or less. If the degree of dispersion of the acrylic resin (A) is too high, the durability of the pressure-sensitive adhesive layer decreases, and foaming etc. tend to occur more easily. If the degree of dispersion of the acrylic resin (A) is too low, handling properties tend to decrease. The lower limit of the degree of dispersion is usually 1.1 from the viewpoint of manufacturing limitations.

[Method for producing acrylic resin (A)]
The acrylic resin (A) includes the above-mentioned hydroxyl group-containing monomer (a1), branched alkyl (meth)acrylate (a2), and optionally used alkyl (meth)acrylate (a3) and ethylenically unsaturated monomer (a4). (Hereinafter, these are also collectively referred to as copolymer component (a).) It can be produced by polymerizing.

Examples of the polymerization method for the acrylic resin (A) include conventionally known polymerization methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Solution polymerization is preferred in terms of reaction safety and stability and the ability to produce the acrylic resin (A) with any monomer composition.
An example of a preferred method for producing the acrylic resin (A) will be shown below.

First, copolymerization component (a) and a polymerization initiator are mixed or dropped into an organic solvent to perform solution polymerization.
Examples of organic solvents used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane; esters such as methyl acetate, ethyl acetate, and butyl acetate; methyl alcohol; Aliphatic alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aliphatic ethers such as dimethyl ether and diethyl ether; Fats such as methylene chloride and ethylene chloride Group halogenated hydrocarbons; cyclic ethers such as tetrahydrofuran; and the like.
Among these organic solvents, esters and ketones are preferred, and ethyl acetate, acetone, and methyl ethyl ketone are particularly preferred.
One type of organic solvent may be used alone, or two or more types may be used in combination.

As the polymerization initiator used in the polymerization reaction, azo polymerization initiators, peroxide polymerization initiators, and the like, which are ordinary radical polymerization initiators, can be used.
Examples of the azo polymerization initiator include 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, (1-phenylethyl)azodiphenylmethane, 2,2' -Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. It will be done.
Examples of peroxide-based polymerization initiators include benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, and tert-hexyl. Examples include peroxyneodecanoate, diisopropyl peroxycarbonate, diisobutyryl peroxide, and the like.
Among them, azo polymerization initiators are preferred, and 2,2'-azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) are more preferred.
One type of polymerization initiator may be used alone, or two or more types may be used in combination.

The amount of the polymerization initiator used is usually 0.001 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of copolymerization component (a). parts, particularly preferably 1 to 4 parts by weight, more preferably 1.5 to 3 parts by weight, and most preferably 2 to 2.5 parts by weight. If the amount of the polymerization initiator used is too small, the polymerization rate of the acrylic resin (A) tends to decrease and the amount of residual monomer tends to increase. Moreover, the weight average molecular weight of the acrylic resin (A) tends to become high. If the amount of polymerization initiator used is too large, the acrylic resin (A) tends to gel.

The polymerization conditions for solution polymerization are not particularly limited, and polymerization can be performed according to conventionally known polymerization conditions. For example, the copolymerization component (a) and a polymerization initiator can be mixed or dropped into an organic solvent for polymerization.

The polymerization temperature in the polymerization reaction is usually 40 to 120°C, but in the present invention, it is preferably 50 to 90°C from the viewpoint of stable reaction. If the polymerization temperature is too high, the acrylic resin (A) tends to gel easily, and if it is too low, the activity of the polymerization initiator decreases, so the polymerization rate tends to decrease and the amount of residual monomer increases.
The polymerization time in the polymerization reaction is not particularly limited, but it is 0.5 hours or more, preferably 1 hour or more, more preferably 2 hours or more, particularly preferably 5 hours or more from the last addition of the polymerization initiator.
The polymerization reaction is preferably carried out while the solvent is refluxed because heat can be easily removed.

(Photopolymerization initiator (B))
The adhesive composition of the present invention contains a photopolymerization initiator (B) in addition to the acrylic resin (A).
The photopolymerization initiator (B) preferably contains an intramolecular hydrogen abstraction type photopolymerization initiator (b1) and an intermolecular hydrogen abstraction type photopolymerization initiator (b2).
The photopolymerization initiator (B) may be other than the intramolecular hydrogen abstraction type photopolymerization initiator (b1) and the intermolecular hydrogen abstraction type photopolymerization initiator (b2), as long as it does not impair the effects of the invention. It may further contain a photopolymerization initiator (b3).

[Intramolecular hydrogen abstraction type photopolymerization initiator (b1)]
The intramolecular hydrogen abstraction type photopolymerization initiator (b1) has a structure that can generate radicals by abstracting hydrogen from the photopolymerization initiator itself, and specifically has a phenylglyoxylate structure, etc. be.
Examples of the intramolecular hydrogen abstraction type photopolymerization initiator (b1) include oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester, methyl phenylglyoxylate, and the like.
Among these, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester, which has a plurality of crosslinking points in the molecule, is preferred in terms of crosslinking efficiency during complete curing.
Also, as a commercially available product, IGM RESINS B. V. Examples include "Omnirad MBF" and "Omnirad 754" manufactured by the company.
The intramolecular hydrogen abstraction type photopolymerization initiator (b1) may be used alone or in combination of two or more.

[Intermolecular hydrogen abstraction type photopolymerization initiator (b2)]
The intermolecular hydrogen abstraction type photopolymerization initiator (b2) has a structure that can generate radicals by abstracting hydrogen from sources other than the photopolymerization initiator itself, and specifically has a benzophenone structure, etc. .
For example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyloxybenzophenone, 4-[2- ((meth)acryloyloxy)ethoxy]benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, carboxymethoxymethoxybenzophenone-polyethylene glycol 250 diester, methyl 2-benzoylbenzoate, 4-(1,3-acryloyl -1,4,7,10,13-pentaoxotridecyl)benzophenone and the like.

Among these, 2,4,6-trimethylbenzophenone is preferred because it is a low viscosity liquid and is easy to handle. In addition, high crosslinking is possible, such as 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy)ethoxy]benzophenone, and 4-(meth)acryloyloxy-, which have multiple crosslinking points in the molecule. 4'-methoxybenzophenone and carboxymethoxymethoxybenzophenone-polyethylene glycol 250 diester are preferred.
In addition, commercially available products include "MBP" manufactured by Shinryosha, IGM RESINS B. V. Examples include "Omnirad BP", "Omnirad 4MBZ", "Esacure TZT", and "Omnipol BP" manufactured by the company.
The intermolecular hydrogen abstraction type photopolymerization initiator (b2) may be used alone or in combination of two or more.

[Other photopolymerization initiators (b3)]
Other photoinitiators (b3) include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-( 2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4 -Acetophenones such as morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoins such as isobutyl ether; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4, Examples include acyl phosphophone oxides such as 6-trimethylbenzoyl)-phenylphosphine oxide.
The other photopolymerization initiators (b3) may be used alone or in combination of two or more.

As an auxiliary agent for the photopolymerization initiator (B), triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4- It is also possible to use diisopropylthioxanthone or the like in combination.
One type of auxiliary agent for the photopolymerization initiator (B) may be used alone, or two or more types may be used in combination.

(Crosslinking agent (C))
It is preferable that the adhesive composition of the present invention further contains a crosslinking agent (C) in addition to the acrylic resin (A) and the photopolymerization initiator (B).
Examples of the crosslinking agent (C) include an active energy ray crosslinking agent (c1) and a thermal crosslinking agent (c2). The active energy ray crosslinking agent (c1) and the thermal crosslinking agent (c2) may be used alone or in combination of two or more.

When only the active energy ray crosslinking agent (c1) is contained as the crosslinking agent (C), multistage curing becomes possible only by controlling the active energy ray dose. Further, when the crosslinking agent (C) contains an active energy ray crosslinking agent (c1) and a thermal crosslinking agent (c2), multistage curing is also possible by using both thermal curing and active energy ray curing.
By controlling the crosslinking reaction in this manner, the cohesive force of the entire adhesive layer can be adjusted, and stable adhesive properties can be obtained after primary curing or after complete curing.

[Active energy ray crosslinking agent (c1)]
Examples of the active energy ray crosslinking agent (c1) include polyfunctional crosslinking agents containing two or more ethylenically unsaturated groups in one molecule.
For example, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, ) acrylate, (poly)butylene glycol mono(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, (poly) ) Pentamethylene glycol di(meth)acrylate, (poly)hexamethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, EO-modified glycerin tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate , isocyanuric acid ethylene oxide modified tri(meth)acrylate, polyfunctional urethane (meth)acrylate, and the like.
Among these, (meth)acrylates containing two ethylenically unsaturated groups are preferred in terms of the balance of adhesive properties after curing, and in particular, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol Di(meth)acrylate and (poly)tetramethylene glycol di(meth)acrylate are preferred.
One type of polyfunctional crosslinking agent may be used alone, or two or more types may be used in combination.

[Thermal crosslinking agent (c2)]
The thermal crosslinking agent (c2) can exhibit excellent adhesive strength by reacting with a functional group derived from a functional group-containing monomer that is a constituent monomer of the acrylic resin (A). For example, isocyanate crosslinking agent (c2-1), epoxy crosslinking agent (c2-2), aziridine crosslinking agent (c2-3), melamine crosslinking agent (c2-4), aldehyde crosslinking agent (c2-5) ), amine crosslinking agents (c2-6), and metal chelate crosslinking agents (c2-7). Among these, the isocyanate crosslinking agent (c2-1) is preferably used in terms of improving the adhesion to the base material and the reactivity with the acrylic resin (A).
The thermal crosslinking agent (c2) may be used alone or in combination of two or more.

Examples of the isocyanate crosslinking agent (c2-1) include tolylene diisocyanate compounds such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate. Xylylene diisocyanate compounds such as diisocyanate and tetramethylxylylene diisocyanate; aromatic isocyanate compounds such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. compounds and aliphatic isocyanate compounds such as lysine diisocyanate; alicyclic isocyanate compounds such as isophorone diisocyanate; and adducts of these isocyanate compounds and polyol compounds such as trimethylolpropane; bullets and isocyanate compounds of these isocyanate compounds. Nurate form; etc. are mentioned.
Among the isocyanate-based crosslinking agents (c2-1), aromatic isocyanate-based compounds are preferably used from the viewpoint of excellent reactivity, and tolylene diisocyanate-based compounds are particularly preferred. Further, from the viewpoint of suppressing yellowing, it is preferable to use an aliphatic isocyanate-based compound, and particularly preferably a hexamethylene diisocyanate-based compound.

Examples of the epoxy crosslinking agent (c2-2) include bisphenol A/epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexane. Examples include diol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, and the like.

Examples of the aziridine crosslinking agent (c2-3) include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N,N'-diphenylmethane -4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), and the like.

Examples of the melamine crosslinking agent (c2-4) include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexaptoxymethylmelamine, hexapentyloxymethylmelamine, hexahexyloxymethylmelamine, and melamine resins. etc.

Examples of the aldehyde crosslinking agent (c2-5) include glyoxal, malondialdehyde, succindialdehyde, maleic dialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, and benzaldehyde.

Examples of the amine crosslinking agent (c2-6) include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, polyamide, and the like.

Examples of the metal chelate crosslinking agent (c2-7) include acetylacetone and acetoacetyl ester combinations of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, and zirconium. Examples include positional compounds and the like.

(Silane coupling agent (D))
The adhesive composition of the present invention improves durability by further containing a silane coupling agent (D) as a compound other than the acrylic resin (A), the photopolymerization initiator (B), and the crosslinking agent (C). This is preferable in that it allows

The silane coupling agent (D) is an organosilicon compound containing one or more reactive functional groups and one or more alkoxy groups bonded to silicon atoms in its structure. The silane coupling agent (D) includes monomer type and oligomer type.
Examples of the reactive functional groups in the silane coupling agent (D) include epoxy groups, (meth)acryloyl groups, mercapto groups, hydroxyl groups, carboxy groups, amino groups, amide groups, and isocyanate groups. Among these, epoxy groups and mercapto groups are preferred because of their excellent durability and reworkability.

The content of the reactive functional group in the silane coupling agent (D) is preferably 3,000 g/mol or less, more preferably 1,500 g/mol or less, and even more preferably 1,000 g/mol or less. When the reactive functional group is within the above numerical range, the balance between durability and reworkability is improved. The lower limit of the content of reactive functional groups in the silane coupling agent (D) is 200 g/mol.

The alkoxy group bonded to the silicon atom in the silane coupling agent (D) is preferably an alkoxy group having 1 to 8 carbon atoms from the viewpoint of durability and storage stability. Among them, methoxy group and ethoxy group are more preferred.
The silane coupling agent (D) may have a reactive functional group and an organic functional group other than the alkoxy group bonded to a silicon atom, such as an alkyl group or a phenyl group.

Examples of the silane coupling agent (D) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, methyltri(glycidyl)silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-( Examples include 3,4-epoxycyclohexyl)ethyltrimethoxysilane. Among these, γ-glycidoxypropyltrimethoxysilane is preferred from the viewpoint of heat resistance.
The silane coupling agent (D) may be used alone or in combination of two or more.

(Carbodiimide compound (E))
The adhesive composition of the present invention further contains a carbodiimide compound (E) as a compound other than the acrylic resin (A), the photopolymerization initiator (B), the crosslinking agent (C), and the silane coupling agent (D). It is preferable to do so from the viewpoint of heat resistance.
Examples of the carbodiimide compound (E) include bis(2,6-diisopropylphenyl)carbodiimide, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t- Examples include monocarbodiimides such as butylcarbodiimide and didodecylcarbodiimide, polycarbodiimides containing a plurality of carbodiimides, and cyclic carbodiimides. Among these, from the viewpoint of heat resistance, monocarbodiimide compounds are preferred, and bis(2,6-diisopropylphenyl)carbodiimide is more preferred.
One type of carbodiimide compound (E) may be used alone, or two or more types may be used in combination.

(optional ingredient)
The adhesive composition of the present invention may contain an adhesive as another optional component, if necessary. The adhesive composition of the present invention may contain conventionally known additives such as a crosslinking accelerator, an antistatic agent, a tackifier, and a functional dye.

(Composition of adhesive composition)
The content of the acrylic resin (A) is preferably 80% by weight or more, more preferably 90 to 99.9% by weight, even more preferably 92 to 99.9% by weight, based on the entire pressure-sensitive adhesive composition. When the content of the acrylic resin (A) is within the above numerical range, excellent adhesive properties are likely to be obtained in a low crosslinked state after primary curing.

The content of the photopolymerization initiator (B) is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 4.0 parts by weight, and 1 to 100 parts by weight of the acrylic resin (A). More preferably .0 to 3.0 parts by weight. When the content of the photopolymerization initiator (B) is within the above numerical range, sufficient curability can be obtained during complete curing.

The content of the intramolecular hydrogen abstraction type photopolymerization initiator (b1) is preferably 0.1 to 5.0 parts by weight, and 0.5 to 3.0 parts by weight based on 100 parts by weight of the acrylic resin (A). is more preferable.
If the content of the intramolecular hydrogen abstraction type photopolymerization initiator (b1) is too large, there is a tendency for discoloration to occur after the wet heat durability test. If the content of the intramolecular hydrogen abstraction type photopolymerization initiator (b1) is too small, the degree of crosslinking does not increase, and the adhesive properties during primary curing and the durability after complete curing tend to deteriorate.

The content of the intermolecular hydrogen abstraction type photopolymerization initiator (b2) is preferably 0.1 to 3.0 parts by weight, and 0.5 to 2.0 parts by weight based on 100 parts by weight of the acrylic resin (A). is more preferable.
If the content of the intermolecular hydrogen abstraction type photopolymerization initiator (b2) is too large, durability tends to deteriorate due to bleed-out. If the content of the intermolecular hydrogen abstraction type photopolymerization initiator (b2) is too small, the degree of crosslinking will not increase, and the adhesive properties during primary curing and the durability after complete curing will tend to deteriorate.

When the photoinitiator (B) contains another photoinitiator (b3), the content of the photoinitiator (b3) is 2.0 parts by weight per 100 parts by weight of the acrylic resin (A). The amount is preferably at most 1.0 parts by weight, more preferably at most 1.0 parts by weight.

When the adhesive composition contains a crosslinking agent (C), the content of the crosslinking agent (C) is usually preferably 20 parts by weight or less, and 0.001 to 100 parts by weight, based on 100 parts by weight of the acrylic resin (A). It is more preferably 10 parts by weight, and even more preferably 0.1 to 7.5 parts by weight. If the content of the crosslinking agent (C) is too large, the adhesive strength tends to decrease. If the content of the crosslinking agent (C) is too low, durability tends to decrease.

When the adhesive composition contains an active energy ray crosslinking agent (c1), the content of the active energy ray crosslinking agent (c1) is usually 0.01 to 100 parts by weight per 100 parts by weight of the acrylic resin (A). It is preferably 20 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.5 to 7.5 parts by weight.
If the content of the active energy ray crosslinking agent (c1) is too small, the cohesive force will be insufficient and there will be a tendency that sufficient durability will not be obtained. If the content of the active energy ray crosslinking agent (c1) is too large, the adhesive properties during primary curing tend to deteriorate.

When the adhesive composition contains a thermal crosslinking agent (c2), the content of the thermal crosslinking agent (c2) is usually preferably 0.001 to 5 parts by weight per 100 parts by weight of the acrylic resin (A). , more preferably 0.02 to 1 part by weight, and even more preferably 0.05 to 0.5 part by weight.
If the content of the thermal crosslinking agent (c2) is too small, the cohesive force will be insufficient and the adhesive properties will tend to deteriorate during primary curing. If the content of the thermal crosslinking agent (c2) is too large, the adhesive strength tends to decrease upon complete curing.

When the adhesive composition contains a silane coupling agent (D), the content of the silane coupling agent (D) is preferably 0.001 to 3 parts by weight per 100 parts by weight of the acrylic resin (A). , more preferably 0.005 to 1 part by weight, even more preferably 0.01 to 0.5 part by weight, particularly preferably 0.015 to 0.3 part by weight.
If the content of the silane coupling agent (D) is too small, it tends to be difficult to obtain the effect of improving durability. If the content of the silane coupling agent (D) is too large, the adhesive strength tends to decrease due to the influence of bleed-out and the like.

When the adhesive composition contains a carbodiimide compound (E), the content of the carbodiimide compound (E) is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic resin (A), and 0. .1 to 5 parts by weight are more preferred, 0.2 to 2 parts by weight are even more preferred, and 0.3 to 1 parts by weight are particularly preferred.
If the content of the carbodiimide compound (E) is too low, the thermal stability of the acrylic resin (A) tends to decrease. If the content of the carbodiimide compound (E) is too high, durability tends to decrease due to bleed-out and the like.

When the adhesive composition contains other adhesives or additives, the content of the other adhesives or additives is preferably 10 parts by weight or less, and 5 parts by weight or less based on 100 parts by weight of the acrylic resin (A). Part or less is more preferable.

(Preparation of adhesive composition)
By mixing the acrylic resin (A), the photopolymerization initiator (B), if necessary, the crosslinking agent (C), the silane coupling agent (D), the carbodiimide compound (E), and other optional components. The adhesive composition of the present invention can be obtained. The mixing method is not particularly limited, and various methods may be employed, such as a method of mixing each component at once, or a method of mixing any component and then mixing the remaining components at once or sequentially. Can be done.

(Application)
The pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive for a multi-stage curable pressure-sensitive adhesive sheet that is cured in multiple stages. Excellent adhesive properties are obtained even in a low crosslinked state after primary curing, and after complete curing, not only ordinary adhesive properties such as adhesive strength but also various types and shapes of members such as polarizing plates and glass can be laminated. Excellent durability is achieved when
The adhesive composition of the present invention has excellent adhesive physical properties such as low tackiness and high constant load holding capacity even in a low crosslinked state after primary curing, and thus improves workability and reliability. Therefore, it can be particularly suitably applied to adhesives and adhesive sheets used in touch panels, image display devices, and the like.

<Adhesive>
The adhesive of the present invention is obtained by crosslinking the above-described adhesive composition of the present invention. When the pressure-sensitive adhesive composition of the present invention is crosslinked (cured), the acrylic resin (A) contained in the pressure-sensitive adhesive composition forms a crosslinked structure at least either within the molecule or between the molecules. As a result, the pressure-sensitive adhesive composition of the present invention is crosslinked and becomes a pressure-sensitive adhesive according to the present invention.
When the acrylic resin (A) has an active energy ray crosslinkable structural site, a crosslinked structure can be formed by irradiation with active energy rays.

The pressure-sensitive adhesive of the present invention exhibits multi-stage curability, allowing it to be cured in multiple stages. The adhesive of the present invention becomes a low crosslinked state by primary curing before complete curing. Complete curing and primary curing are not necessarily clearly distinguishable, but can be distinguished by differences in gel fraction and dynamic viscoelasticity.

The curing means in both the primary curing step and the complete curing step is not particularly limited, and may be heating or irradiation with active energy rays. Further, the primary curing step may be performed in multiple steps, or multi-stage curing may be performed to achieve a completely cured state.
Since the adhesive of the present invention has excellent adhesive properties after primary curing, it is suitably used for bonding optical members constituting touch panels, image display devices, and the like.

It can also be said that the adhesive of the present invention contains at least a crosslinked product of the acrylic resin (A) of the present invention. The crosslinked product may be a partially crosslinked product in which at least a portion of the acrylic resin (A) is partially crosslinked, or a completely crosslinked product in which all of the acrylic resin (A) is completely crosslinked. good. Moreover, the adhesive of the present invention may contain both a partially crosslinked product and a completely crosslinked product of the acrylic resin (A).

<Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of the present invention. The pressure-sensitive adhesive sheet of the present invention can exhibit multi-stage curability in which the pressure-sensitive adhesive layer is cured in multiple stages.
A pressure-sensitive adhesive sheet can be obtained by providing a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of the present invention on a base sheet. Further, by providing an adhesive layer on a release sheet, a double-sided adhesive sheet can be obtained. Furthermore, a double-sided pressure-sensitive adhesive sheet without a base material can also be produced by forming a pressure-sensitive adhesive layer on a release sheet instead of the base sheet, and bonding the release sheet to the opposite side of the pressure-sensitive adhesive layer. A thick adhesive layer may be further formed by further forming an adhesive layer on the formed adhesive layer.
The obtained pressure-sensitive adhesive sheet or double-sided pressure-sensitive adhesive sheet is used by peeling off the release sheet from the pressure-sensitive adhesive layer.

Examples of methods for producing the pressure-sensitive adhesive sheet include methods (i) and (ii) below.
(i) A method of dissolving the adhesive composition of the present invention in a solvent and coating it to form an adhesive sheet.
(ii) A method of melting the adhesive composition of the present invention by heating to form an adhesive sheet.

Method (i) will be explained.
When the adhesive composition of the present invention is dissolved in a solvent and applied to form an adhesive sheet, the concentration of the coating liquid containing the adhesive composition of the present invention is adjusted with an appropriate organic solvent, and Coat directly onto the sheet. Thereafter, it is dried by heat treatment, for example, at 80 to 105° C. for 0.5 to 10 minutes, and then it is attached to a base sheet or a release sheet. Thereafter, the pressure-sensitive adhesive composition is crosslinked (cured) by irradiation with active energy rays or aging to produce a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive.

As the organic solvent used for concentration adjustment, those mentioned as organic solvents used in the polymerization reaction of the acrylic resin (A) can be used. The concentration of the adhesive composition is usually 20 to 60% by weight, preferably 30 to 50% by weight as a solid content.

The method (ii) will be explained.
When the pressure-sensitive adhesive composition of the present invention is melted by heating to form a pressure-sensitive adhesive sheet, it may be coated on one or both sides of a base sheet in a molten state and then cooled, or it may be coated on the base sheet using a T-die or the like. An adhesive layer is formed on one or both sides of the base sheet to a desired thickness by extrusion lamination or the like. Then, if necessary, a release sheet is attached to the surface of the adhesive layer to produce a pressure-sensitive adhesive sheet.
In addition, after the adhesive layer is formed on the base sheet, the adhesive composition is cured (crosslinked) by performing active energy ray irradiation treatment if necessary and further aging. A sheet can be produced.
Furthermore, a double-sided pressure-sensitive adhesive sheet without a base material can also be produced by forming a pressure-sensitive adhesive layer on a release sheet and bonding the release sheet to the opposite side of the pressure-sensitive adhesive layer.
The obtained pressure-sensitive adhesive sheet or double-sided pressure-sensitive adhesive sheet is used by peeling off the release sheet from the pressure-sensitive adhesive layer.

Examples of the base sheet include polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalate copolymers; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride; Polyfluorinated ethylene resins such as polyvinylidene fluoride and polyethylene fluoride; polyamides such as nylon 6 and nylon 6,6; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl Vinyl polymers such as alcohol copolymers, polyvinyl alcohol, and vinylon; Cellulose resins such as cellulose triacetate and cellophane; Acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate. Polystyrene; Polycarbonate; Polyarylate; Synthetic resin sheets such as polyimide, metal foils such as aluminum, copper, iron, etc., papers such as high-quality paper and glassine paper, woven and non-woven fabrics made of glass fibers, natural fibers, synthetic fibers, etc. It will be done. These base sheets can be used as a single layer or as a multilayer in which two or more types are laminated. Among these, synthetic resin sheets are preferred from the viewpoint of weight reduction.

As the release sheet, for example, various types of synthetic resin sheets, paper, woven fabrics, nonwoven fabrics, etc. exemplified in the base sheet, which have been subjected to release treatment, can be used. As the release sheet, it is preferable to use, for example, a silicone release sheet.

The method for applying the adhesive composition is not particularly limited. Examples include methods such as roll coating, die coating, gravure coating, comma coating, slot coating, and screen printing.

As active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays; electromagnetic waves such as X-rays and γ rays; electron beams; proton rays; neutron rays and the like can be used. Curing with ultraviolet rays is preferred from the viewpoint of curing speed, availability of irradiation equipment, cost, etc.

The gel fraction of the adhesive layer of the adhesive sheet before complete curing is such that it can be easily attached regardless of the shape of the adherend, and that the adhesive layer can hold the adherend after attachment. From this point of view, it is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight, particularly preferably 5 to 45% by weight.

The gel fraction of the adhesive layer of the adhesive sheet after complete curing is preferably 60 to 90% by weight, more preferably 62 to 87% by weight, particularly preferably 65% by weight from the viewpoint of durability and adhesive strength. ~85% by weight. If the gel fraction is too low, the cohesive force decreases, which tends to decrease durability. Note that if the gel fraction is too high, the adhesive force tends to decrease due to an increase in cohesive force.

The gel fraction can be adjusted as appropriate, for example, by the following method.
・Adjust the dose of active energy rays.
- Adjusting the content of active energy ray crosslinkable structural moieties in the acrylic resin (A).
-Adjust the type and amount of the photopolymerization initiator (B) and crosslinking agent (C).

The gel fraction is a measure of the degree of crosslinking (degree of curing), and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (without a release sheet) formed by forming an adhesive layer on a polymer sheet (for example, polyethylene terephthalate (PET) film, etc.) serving as a base material is wrapped in a 200-mesh SUS wire mesh. , and immersed in toluene maintained at 23° C. for 24 hours, and the weight percentage of the undissolved adhesive component remaining in the wire gauze is defined as the gel fraction. However, the weight of the base material is calculated by subtracting it from the weight before and after dissolving in toluene.

The thickness of the adhesive layer of the adhesive sheet is usually preferably 50 to 3000 μm, more preferably 75 to 1000 μm, particularly preferably 100 to 350 μm. If the thickness of the adhesive layer is too thin, the impact absorption properties tend to decrease. If the adhesive layer is too thick, the overall thickness tends to increase when it is attached to an optical member, reducing its practicality.

The thickness of the adhesive layer in the present invention is determined by calculating the thickness of the constituent members other than the adhesive layer from the measured value of the entire thickness of the adhesive layer-containing laminate using "ID-C112B" manufactured by Mitutoyo. This is the value obtained by subtracting.

The adhesive layer of the adhesive sheet of the present invention preferably has a haze value of 2% or less, more preferably 0 to 1.5%, particularly preferably 0 to 1% when the thickness of the adhesive layer is 100 μm. If the haze value is too high, the adhesive layer tends to whiten and its transparency decreases.
The haze value is the value of the diffuse transmittance (DT) and total light transmittance (TT) obtained by measuring the diffuse transmittance and total light transmittance using HAZE MATER NDH4000 (manufactured by Nippon Denshoku Industries). is calculated by substituting it into the following [Formula 1]. This machine complies with JIS K7361-1.
Haze value (%) = (DT/TT) x 100 ... [Formula 1]

In the present invention, an optical member with an adhesive layer can be obtained by laminating an adhesive layer on an optical member. For example, an optical member with an adhesive layer can be obtained by pasting the adhesive layer surface of the adhesive sheet of the present invention, in which an adhesive layer is formed on a release sheet, on an optical member and then peeling off the release sheet. Can be done. Moreover, optical members can also be bonded together using the above-mentioned double-sided adhesive sheet.

Examples of the optical member include members constituting a touch panel and an image display device. Examples include displays (organic EL, liquid crystal), transparent conductive film substrates (ITO substrates), protective films (glass), transparent antennas (films), transparent wiring, and the like.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following description. In the examples, "part" and "%" mean on a weight basis. In addition, the weight average molecular weight, glass transition temperature based on dynamic viscoelasticity, thickness of the adhesive layer, and haze value (%) of the acrylic resin (A) were measured according to the method described in the above embodiment.

<Abbreviations, raw materials>
(Hydroxy group-containing monomer (a1))
・4HBA: 4-hydroxybutyl acrylate ・HEA: 2-hydroxyethyl acrylate

(Hyperbranched structure-containing alkyl (meth)acrylate (a2-1))
・IDMA: Isodecyl methacrylate (Tg of homopolymer: -41°C)
・IDA: Isodecyl acrylate (Tg of homopolymer: -62°C)

(Branched alkyl (meth)acrylate (a2-2))
・2EHA: 2-ethylhexyl acrylate (Tg of homopolymer: -70°C)

(Alkyl (meth)acrylate (a3))
・MMA: Methyl methacrylate (Tg of homopolymer: 105°C)
・EMA: Ethyl methacrylate (Tg of homopolymer: 65°C)
・IBMA: Isobutyl methacrylate (Tg of homopolymer: 48°C)

・ADVN: 2,2'-azobis(2,4-dimethylvaleronitrile) (10 hour half-life temperature 52°C)

(Photopolymerization initiator (B))
[Intramolecular hydrogen abstraction type photopolymerization initiator (b1)]
・Omnirad 754: IGM Resins B. V. [Intermolecular hydrogen abstraction type photopolymerization initiator (b2)]
・Esacure TZT: IGM Resins B. V. Products manufactured by Shinryosha, MBP: Products manufactured by Shinryosha

(Crosslinking agent (C))
・Polypropylene glycol #400 diacrylate (NK ester APG400, product manufactured by Shin-Nakamura Chemical Co., Ltd.)

(Silane coupling agent (D))
・KBM403 (product manufactured by Shin-Etsu Chemical Co., Ltd.)

<Production Example 1: Production of acrylic resin (A-1)>
In a 2L flask equipped with a condenser, ethyl acetate: 23.33 parts (boiling point 77°C) as a polymerization solvent, acetone: 6.67 parts (boiling point 56°C), ADVN: 0.01 part as a polymerization initiator, and 2EHA as a monomer. : 21 parts, IBMA: 10 parts, HEA: 7.5 parts, and IDMA: 6 parts, and after heating and refluxing in a flask, methyl ethyl ketone: 8.33 parts (boiling point 80°C), ADVN: 0.15 parts. , 2EHA: 14 parts, EMA: 7.5 parts, IBMA: 10 parts, HEA: 7.5 parts, and IDMA: 9 parts were added dropwise over 2 hours. Furthermore, after 30 minutes of dropping, a mixture of 6.67 parts of ethyl acetate, 0.17 parts of ADVN, and 7.5 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, ADVN: 0.05 part of the mixture was added and reacted to obtain a solution of acrylic resin (A-1). Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-1).

<Production Example 2: Production of acrylic resin (A-2)>
In a 2L flask equipped with a condenser, ethyl acetate: 23.33 parts (boiling point 77°C) as a polymerization solvent, acetone: 6.67 parts (boiling point 56°C), AIBN: 0.01 part as a polymerization initiator, and 2EHA as a monomer. : 24 parts, IBMA: 6 parts, HEA: 7.5 parts, IDMA: 6 parts, and heated to reflux in a flask, followed by ethyl acetate: 10 parts, ADVN: 0.15 parts, 2EHA: 16 parts, EMA: 7.5 parts, IBMA: 9 parts, HEA: 7.5 parts, and IDMA: 9 parts were added dropwise over 2 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 7.5 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, 7.5 parts of EMA, and 3.33 parts of ethyl acetate, ADVN: 0.05 part of the mixture was added and reacted, and further, after 30 minutes of dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 7.5 parts of EMA was added dropwise over 1 hour to react. , a solution of acrylic resin (A-2) was obtained. Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-2).

<Production Example 3: Production of acrylic resin (A-3)>
In a 2L flask equipped with a condenser, 30 parts of ethyl acetate (boiling point 77°C) as a polymerization solvent, 6.67 parts of acetone (boiling point 56°C), 0.01 part of AIBN as a polymerization initiator, and 22 parts of 2EHA as a monomer. .8 parts, IBMA: 6.8 parts, HEA: 7.5 parts, IDMA: 6 parts and heated to reflux in a flask, followed by 10 parts of ethyl acetate, 0.15 parts of ADVN, and 15 parts of 2EHA. .2 parts of EMA, 7.5 parts of IBMA, 10.2 parts of IBMA, 7.5 parts of HEA, and 9 parts of IDMA were added dropwise over 2 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 7.5 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, 7.5 parts of EMA, and 3.33 parts of ethyl acetate, ADVN: A solution of acrylic resin (A-3) was obtained by adding 0.05 part of the mixture and causing a reaction. Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-3).

<Production Example 4: Production of acrylic resin (A-4)>
In a 2L flask equipped with a condenser, ethyl acetate: 20 parts (boiling point 77°C) as a polymerization solvent, acetone: 6.67 parts (boiling point 56°C), ADVN: 0.01 part as a polymerization initiator, 2EHA: 15 as a monomer. After adding 10 parts of IBMA, 9 parts of 4HBA, and 8 parts of IDA and heating to reflux in a flask, 10 parts of methyl ethyl ketone (boiling point 80°C), 0.15 parts of ADVN, 15 parts of 2EHA, EMA: 12 parts, IBMA: 15 parts, 4HBA: 6 parts, and IDA: 2 parts were added dropwise over 2 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 8 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, 0. By adding 05 parts of the mixture and reacting, a solution of acrylic resin (A-4) was obtained. Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-4).

<Production Example 5: Production of acrylic resin (A-5)>
In a 2L flask equipped with a condenser, ethyl acetate: 20 parts (boiling point 77°C) as a polymerization solvent, acetone: 3.33 parts (boiling point 56°C), ADVN: 0.01 part as a polymerization initiator, 2EHA: 15 as a monomer. After adding 12 parts of IBMA, 7.5 parts of HEA, and 10.5 parts of IDA and heating to reflux in a flask, 10 parts of methyl ethyl ketone (boiling point 80°C), 0.15 parts of ADVN, and 2EHA were added. 15 parts of EMA, 2 parts of IBMA, 18 parts of IBMA, 7.5 parts of HEA, and 4.5 parts of IDA were added dropwise over 2 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 8 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, 0. A solution of acrylic resin (A-5) was obtained by adding 0.05 parts of the mixture and causing the reaction. Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-5).

<Production Example 6: Production of acrylic resin (A-6)>
In a 2L flask with a condenser, 20 parts of ethyl acetate (boiling point 77°C) as a polymerization solvent, 6.67 parts of acetone (boiling point 56°C), 0.01 part of ADVN as a polymerization initiator, and 17 parts of 2EHA as a monomer. .5 parts, IBMA: 10 parts, HEA: 7.5 parts, IDA: 10.5 parts, and after heating and refluxing in a flask, methyl ethyl ketone: 10 parts (boiling point 80 ° C.), ADVN: 0.15 parts. , 2EHA: 17.5 parts, EMA: 2 parts, IBMA: 15 parts, HEA: 7.5 parts, and IDA: 4.5 parts were added dropwise over 2 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate, 0.17 parts of ADVN, and 8 parts of EMA was added dropwise over 1 hour, and after 1 hour, 3.33 parts of ethyl acetate, 0. A solution of acrylic resin (A-6) was obtained by adding 0.05 parts of the mixture and causing a reaction. Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A-6).

<Comparative Production Example 1: Production of acrylic resin (A'-1)>
A monomer solution was prepared by mixing 66 parts of 2EHA, 27 parts of MMA, and 7 parts of HEA. In a 2L flask equipped with a condenser, put 33.33 parts of ethyl acetate (boiling point 77°C) as a polymerization solvent, 0.01 part of ADVN as a polymerization initiator, and 10% of 100 parts of the monomer solution prepared in advance. After heating to reflux in the flask, a mixed solution of 10 parts of acetone (boiling point 56°C) and 90% of the remaining monomer solution was added dropwise over 3 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate and 0.14 parts of ADVN was added dropwise over 1 hour to react, thereby obtaining a solution of acrylic resin (A'-1). Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A'-1).

<Comparative Production Example 2: Production of acrylic resin (A'-2)>
A monomer solution was prepared by mixing 55 parts of IDMA, 30 parts of IBMA, and 15 parts of 4HBA. In a 2L flask equipped with a condenser, 16.67 parts of ethyl acetate (boiling point 77°C) as a polymerization solvent, 16.67 parts of methyl ethyl ketone (boiling point 80°C), and 0.01 part of ADVN as a polymerization initiator were prepared in advance. After adding 10% of 100 parts of the monomer solution and heating under reflux in the flask, a mixed solution of 10 parts of ethyl acetate and 90% of the remaining monomer solution was added dropwise over 3 hours. Furthermore, 30 minutes after the dropwise addition, a mixture of 10 parts of ethyl acetate and 0.15 parts of ADVN was added dropwise over 1 hour to react, thereby obtaining a solution of acrylic resin (A'-2). Table 1 shows the measurement results of the glass transition temperature based on the weight average molecular weight (Mw), degree of dispersion (PDI), and dynamic viscoelasticity of the acrylic resin (A'-2).

<Example 1>
Omnirad 754: 2.0 parts (solid content equivalent), Esacure TZT: 1.0 part (solid content equivalent), polypropylene glycol # for 100 parts (solid content equivalent) of the solution of acrylic resin (A-1). 400 diacrylate: 3.0 parts (in terms of solid content) and KBM403: 0.1 part (in terms of solid content) were mixed to obtain an adhesive composition. The obtained adhesive composition was adjusted to a solid concentration of 45% with toluene, applied to a polyester release sheet so that the thickness after drying was approximately 50 μm, and dried at 100°C for 5 minutes to obtain an adhesive composition. A drug composition layer was formed.

Two polyester release sheets each having a pressure-sensitive adhesive composition layer formed thereon were prepared in this way, and the two pressure-sensitive adhesive composition layers were stacked facing each other. With both sides of the laminated adhesive composition layer sandwiched between polyester release sheets, it was exposed to a high-pressure mercury UV irradiation device at a peak illumination intensity of 150 mW/cm ² and a cumulative exposure amount of 1000 mJ/cm ² (1000 mJ/cm ^{2 )} . A pressure-sensitive adhesive layer was formed by irradiation with ultraviolet rays (primary curing), and a substrate-less double-sided pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer having a thickness of 100 μm was obtained.
Next, the release sheet on one side was peeled off from the adhesive layer of the obtained base material-less double-sided adhesive sheet, and the exposed adhesive layer side was pressed onto an easily bonded polyethylene terephthalate (PET) sheet (thickness 125 μm), A PET sheet with an adhesive layer having a thickness of 100 μm was obtained.

<Examples 2 to 5, Comparative Examples 1 and 2>
As shown in Table 2, adhesive compositions of each example were prepared in the same manner as in Example 1 except that the acrylic resin (A-1) was changed. Next, in the same manner as in Example 1, a substrate-less double-sided adhesive sheet with an adhesive layer having a thickness of 100 μm and a PET sheet with an adhesive layer were sequentially produced. Table 2 shows the composition of the adhesive composition of each example.

<Example 6>
As shown in Table 2, the adhesive compositions of each example were prepared in the same manner as in Example 1, except that the acrylic resin (A-1) and the intermolecular hydrogen abstraction type photoinitiator (b2) were changed. did. Next, in the same manner as in Example 1, a substrate-less double-sided adhesive sheet with an adhesive layer having a thickness of 100 μm and a PET sheet with an adhesive layer were sequentially produced. Table 2 shows the composition of the adhesive composition.

<Measurement method, evaluation method>
Measurement methods and evaluation methods for the adhesive compositions of Examples and Comparative Examples are shown below. The results are shown in Tables 3 to 5.

(Gel fraction: before complete curing (after primary curing))
The base material-less double-sided adhesive sheet of each example was cut into 40 mm x 40 mm, left to stand for 30 minutes at 23°C x 50% RH, then one release sheet was peeled off, and the exposed adhesive layer side was cut to 50 mm. It was bonded to a 100 mm x SUS mesh sheet (200 mesh). The remaining release sheet was peeled off, and the SUS mesh sheet was folded back from the center in the longitudinal direction to enclose the adhesive layer with the SUS mesh sheet. The gel fraction (%) was calculated from the weight change when this was immersed for 24 hours in a sealed container containing 250 g of toluene maintained at 23°C.

(Constant load holding capacity (40℃): Before complete curing (after primary curing))
The PET sheet with the adhesive layer of each example was cut into a size of 25 mm wide x 75 mm long (adhesive layer part width 25 mm x length 50 mm + non-adhesive layer part width 25 mm x length 25 mm), and released. The sheet was peeled off. The exposed adhesive layer side was attached to a stainless steel plate (SUS304) by applying pressure by moving a 2 kg roller back and forth (applied area: 25 mm x 50 mm), and left to stand in an atmosphere of 40° C. for 20 minutes. After that, a 50g weight was hung on the lengthwise end of the non-applied part (area 25mm x 25mm), a 50g load was applied in a direction 90° to the plane of the stainless steel plate, and the plate was left in that state for 60 minutes. , the distance over which the PET sheet was peeled was measured. The evaluation criteria are as follows.
◎...Peeling distance is less than 5 mm.
○...Peeling distance is 5 mm or more and less than 10 mm.
x: The peeling distance was 10 mm or more, or the PET sheet was completely peeled off and fell.

(Probe tack: before complete curing (after primary curing))
The PET sheet with the adhesive layer of each example was cut into a size of 12 mm width x 12 mm length, the release sheet was peeled off, and the PET sheet with the adhesive layer was cut using a probe tack tester (manufactured by Tester Sangyo Co., Ltd., Probe Tack Tester TE-6001). The probe tack (unit: N) was measured under the following conditions: a pressurization time of 1 second, a pasting pressure of 500 gf, a pushing speed of 120 mm/min, a pulling speed of 600 mm/min, and a probe diameter of 5.1 mm (diameter). The evaluation criteria are as follows.
◎ Probe tack (unit: N) is less than 5.
○...Probe tack (unit: N) is 5 or more and less than 7.5.
Δ...Probe tack (unit: N) is 7.5 or more and less than 10.
×...Probe tack (unit: N) is 10 or more.

(Gel fraction: after complete curing)
After irradiating the base material-less double-sided adhesive sheet of each example with ultraviolet rays using a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW/cm ² and a cumulative exposure amount of 4000 mJ/cm ² (1000 mJ/cm ² ×4 passes). It was cut into 40 mm x 40 mm and left to stand for 30 minutes at 23°C x 50% RH. Thereafter, one of the release sheets was peeled off, and the exposed adhesive layer side was bonded to a 50 mm x 100 mm SUS mesh sheet (200 mesh). The remaining release sheet was peeled off, and the SUS mesh sheet was folded back from the center in the longitudinal direction to enclose the adhesive layer with the SUS mesh sheet. The gel fraction (%) was calculated from the weight change when this was immersed for 24 hours in a sealed container containing 250 g of toluene maintained at 23°C.

(180 degree peel strength (23℃): after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 25 mm width x 100 mm length, and was irradiated with a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW/cm ² and an integrated exposure amount of 4000 mJ/cm ² (1000 mJ). After UV irradiation was performed at ^{a speed} of 4 passes), the release sheet was peeled off. The exposed adhesive layer side was applied to alkali-free glass ("Eagle It was left undisturbed for 30 minutes. Thereafter, the 180 degree peel strength (N/25 mm) was measured at room temperature (23° C.) at a peel rate of 300 mm/min.

The evaluation criteria for 180 degree peel strength are as follows.
○...Peel strength is 20 (N/25 mm) or more.
×... Peel strength is less than 20 (N/25 mm).

(Constant load holding capacity (80℃): after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 25 mm wide x 75 mm long (adhesive layer part width 25 mm x length 50 mm + non-adhesive layer part width 25 mm x length 25 mm), and After UV irradiation was performed using a UV irradiation device under the conditions of peak illuminance: 150 mW/cm ² and cumulative exposure amount: 4000 mJ/cm ² (1000 mJ/cm ² ×4 passes), the release sheet was peeled off. The exposed adhesive layer side was attached to a stainless steel plate (SUS304) under pressure by moving a 2 kg roller back and forth (applied area: 25 mm x 50 mm), and left to stand in an atmosphere of 80° C. for 20 minutes. After that, a 50g weight was hung on the lengthwise end of the non-applied part (area 25mm x 25mm), a 50g load was applied in a direction 90° to the plane of the stainless steel plate, and the plate was left in that state for 60 minutes. , the distance over which the PET sheet was peeled was measured. The evaluation criteria are as follows.
○...Peeling distance is less than 5 mm.
Δ...Peeling distance is 5 mm or more and less than 10 mm.
x: The peeling distance was 10 mm or more, or the PET sheet was completely peeled off and fell.

(Holding power (80℃): after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 25 mm x 50 mm, and exposed using a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW/cm ² and a cumulative exposure amount of 4000 mJ/cm ² (1000 mJ/cm ^{2 )} . After irradiating with ultraviolet rays (×4 passes), the release sheet was peeled off. A stainless steel plate (SUS304) was placed on the exposed adhesive layer side, and a 2 kg roller was moved back and forth to apply pressure and paste (applied area 25 mm x 25 mm), and a creep tester (manufactured by Tester Sangyo Co., Ltd., maintained with a constant humidity chamber) was applied. Using a force tester BE-501), the holding force was measured under an atmosphere of 80° C. for 24 hours under a load of 1 kg. The evaluation criteria are as follows.
◎...No deviation (N.C).
○...The deviation is less than 0.5 mm.
x: The deviation was 0.5 mm or more, or the PET sheet fell.

(Moisture heat resistance test: after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 30 mm x 50 mm, and was exposed to a high-pressure mercury UV irradiation device at a peak illumination intensity of 150 mW/cm ² and a cumulative exposure amount of 4000 mJ/cm ² (1000 mJ/cm ^{2 )} . After irradiation with ultraviolet rays (×4 passes), the release sheet was peeled off. The exposed adhesive layer side was bonded to alkali-free glass ("Eagle XG" manufactured by Corning, thickness 1.1 mm). Thereafter, autoclave treatment was performed at 50°C, 0.5 MPa, for 20 minutes, and the layer composition of "alkali-free glass/adhesive layer/PET" was changed by standing in an atmosphere of 23°C, 50% RH for 30 minutes. A test piece having the following properties was prepared.
Using the obtained test piece, a heat-and-moisture resistance test was conducted for 7 days (168 hours) in an atmosphere of 85° C. and 85% RH, and the haze values before and after the heat-and-moisture test were measured.
The haze value after the heat-and-moisture test was measured after being left in an atmosphere of 23° C. and 50% RH for 2 hours after the heat-and-moisture test.

The haze value is the value of the diffuse transmittance (DT) and total light transmittance (TT) obtained by measuring the diffuse transmittance and total light transmittance using HAZE MATER NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) It was calculated by substituting into the following formula 1. Furthermore, the rate of increase (%) in haze value was calculated from Formula 2 below. This machine complies with JIS K7361-1.
Haze value (%) = (DT/TT) x 100 ... [Formula 1]
Haze value difference (%) = Haze value after heat-and-moisture resistance test - Haze value before start of heat-and-moisture resistance test ... [Formula 2]

The evaluation criteria for the heat and humidity resistance test are as follows.
◎...Haze value difference is less than 2.0%.
Good: Haze value difference is 2.0% or more and less than 3.5%.
x: Haze value difference is 3.5% or more.

(Probe tack: after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 12 mm width x 12 mm length, and was irradiated with a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW/cm ² and an integrated exposure amount of 4000 mJ/cm ² (1000 mJ). / cm ² × 4 passes), peel off the release sheet, and use a probe tack tester (manufactured by Tester Sangyo Co., Ltd., Probe Tack Tester TE-6001) to apply pressure for 5 seconds and paste. Probe tack (unit: N) was measured under the conditions of a pressure of 1000 gf, a pushing speed of 120 mm/min, a pulling speed of 600 mm/min, and a probe diameter of 5.1 mm (diameter).

(Curved surface durability: after complete curing)
The PET sheet with the adhesive layer of each example was cut into a size of 40 mm x 120 mm, and the release sheet was peeled off. The exposed adhesive layer side is pressurized and bonded to one TAC film surface polarizing plate of a polarizing plate in which TAC films are laminated on both sides of a polarizer to form a "PET sheet/adhesive layer/polarizing plate" layer. A laminate of the following configuration was obtained.
Thereafter, the laminate was attached and fixed to an aluminum plate (width: 70 mm, length: 150 mm, thickness: 0.3 mm) with a tape so that the PET surface was the front surface, thereby producing an aluminum plate-fixed sample. The prepared sample was bent to a diameter of 5 mm using a mandrel testing machine, and after being fixed in that state, it was autoclaved (0.5 MPa x 50°C x 20 minutes), and the peak illuminance was measured using a high-pressure mercury UV irradiation device. The curved sample was irradiated with ultraviolet rays at: 150 mW/cm ² and cumulative exposure amount: 4000 mJ/cm ² (1000 mJ/cm ² ×4 passes) to prepare a sample for curved surface durability evaluation. The curved surface durability evaluation sample has a layer structure of PET/adhesive layer/polarizing plate/aluminum plate in order from the outside. There is an aluminum plate on the innermost side.
Using the obtained sample for curved surface durability evaluation, the curved portions and bent portions were removed after being exposed under the conditions of 80°C, Dry, 7 days, and 60°C, 90% RH, 7 days. The edges of the polarizing plate were observed and evaluated based on the following criteria.

(Evaluation criteria: bent part)
A: No lifting, foaming, or adhesive protrusion was observed.
B: Lifting, foaming, or adhesive protrusion is observed.

(Evaluation criteria: Polarizing plate edge)
A: No air bubbles were observed at the edges.
B: Floating of less than 0.5 mm or very few air bubbles are observed at the edge.
C: A float of 0.5 mm or more is observed at the edge or air bubbles are observed at a portion of the edge.
D: Bubbles were generated on the entire edge.

(Evaluation criteria: comprehensive evaluation)
◎...The evaluation of the bent part is A and the evaluation of the end of the polarizing plate is A.
〇...The evaluation of the bent part is A and the evaluation of the end of the polarizing plate is B.
×... The evaluation of the bent portion is A and the evaluation of the end of the polarizing plate is C or D, or the evaluation of the bent portion is B and the evaluation of the end of the polarizing plate is A to D.

(Polarizing plate durability: after complete curing)
The base material-less double-sided adhesive sheet of each example was cut into a size of 60 mm x 100 mm, and one of the release sheets was peeled off. The exposed adhesive layer side was bonded under pressure to one TAC-based film surface polarizing plate of a polarizing plate in which TAC-based films were laminated on both sides of a polarizer. Next, the other release sheet was peeled off, and the exposed adhesive layer side was bonded to alkali-free glass ("Eagle 20 minutes). After that, UV irradiation was performed from the alkali-free glass side using a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW/cm ² and an integrated exposure amount of 4000 mJ/cm ² (1000 mJ/cm ² × 4 passes) to improve the durability of the polarizing plate. A sample for evaluation was prepared.
After leaving the polarizing plate durability evaluation sample in an atmosphere of 23°C and 50% RH for 1 day, durability tests were conducted for 7 days (168 hours) in an atmosphere of 80°C and 60°C and 90% RH. and evaluated based on the following criteria.
〇: No lifting is observed at the end of the polarizing plate.
Δ...The lifting of the end portion of the polarizing plate is less than 0.5 mm.
x: The edge of the polarizing plate is lifted by 0.5 mm or more.

The pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition of the example exhibited excellent pressure-sensitive adhesive properties such as high constant load holding power and low tackiness even in a low crosslinked state before complete curing (after primary curing). Furthermore, even after complete curing, it exhibited excellent adhesive properties and durability.
On the other hand, in Comparative Example 1, in which the acrylic resin (A) does not contain a structural unit derived from a hyperbranched structure-containing alkyl (meth)acrylate (a2-1) containing two or more tertiary carbons, low crosslinking after primary curing The adhesive properties in the state and the adhesive properties after complete curing were poor.
In addition, in Comparative Example 2 in which the acrylic resin (A) contains more than a predetermined amount of structural units derived from a hyperbranched structure-containing alkyl (meth)acrylate (a2-1) containing two or more tertiary carbons, completely cured The subsequent adhesive physical properties were poor.

A pressure-sensitive adhesive using the pressure-sensitive adhesive composition of the present invention has excellent pressure-sensitive adhesive properties in a low crosslinked state after primary curing. A pressure-sensitive adhesive using the pressure-sensitive adhesive composition of the present invention is particularly useful as a pressure-sensitive adhesive used for bonding optical members constituting touch panels, image display devices, etc., sealing organic EL displays, and the like.

Claims (11)

An adhesive composition containing an acrylic resin (A) and a photopolymerization initiator (B),
The acrylic resin (A) has a structural unit derived from the hydroxyl group-containing monomer (a1), and a branched alkyl (meth) having a glass transition temperature of less than 0° C. when forming a homopolymer and an alkyl group containing a branched structure. Contains a structural unit derived from acrylate (a2),
The content of the structural unit derived from the hydroxyl group-containing monomer (a1) is 5 to 25% by weight of the entire acrylic resin (A),
The structural unit derived from the branched alkyl (meth)acrylate (a2) is a highly branched alkyl (meth)acrylate having a glass transition temperature of less than 0°C and having an alkyl group containing two or more tertiary carbons when forming a homopolymer. ) Structural units derived from acrylate (a2-1) and branched alkyls (excluding the multi-branched structure-containing alkyl (meth)acrylate (a2-1)) whose glass transition temperature is less than 0°C when forming a homopolymer. Contains a structural unit derived from meth)acrylate (a2-2),
The content of the structural unit derived from the hyperbranched structure-containing alkyl (meth)acrylate (a2-1) is 5 to 50% by weight of the entire acrylic resin (A),
A pressure-sensitive adhesive composition, wherein the acrylic resin (A) has a glass transition temperature of -10°C or higher. The adhesive composition according to claim 1, wherein the acrylic resin (A) further contains a structural unit derived from an alkyl (meth)acrylate (a3) having a glass transition temperature of 0 ° C. or higher when forming a homopolymer. thing. The adhesive composition according to claim 1, wherein the acrylic resin (A) has a weight average molecular weight of 50,000 to 500,000. The adhesive composition according to claim 1, wherein the photopolymerization initiator (B) contains an intramolecular hydrogen abstraction type photopolymerization initiator (b1) and an intermolecular hydrogen abstraction type photopolymerization initiator (b2). . The adhesive composition according to claim 1, further comprising a crosslinking agent (C). A pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition according to any one of claims 1 to 5. The adhesive according to claim 6, wherein crosslinking is performed by irradiation with active energy rays. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 6. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 7. The pressure-sensitive adhesive sheet according to claim 8, wherein the pressure-sensitive adhesive layer is multi-stage curable. The pressure-sensitive adhesive sheet according to claim 9, wherein the pressure-sensitive adhesive layer is multi-stage curable, curing in multiple stages.