CN106536653B - Active energy ray-curable adhesive composition, and adhesive sheet obtained using same - Google Patents

Active energy ray-curable adhesive composition, and adhesive sheet obtained using same Download PDF

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CN106536653B
CN106536653B CN201580039727.3A CN201580039727A CN106536653B CN 106536653 B CN106536653 B CN 106536653B CN 201580039727 A CN201580039727 A CN 201580039727A CN 106536653 B CN106536653 B CN 106536653B
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meth
acrylate
compound
active energy
energy ray
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CN106536653A (en
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谷口亮辅
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Mitsubishi Kasei Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesive Tapes (AREA)

Abstract

An active energy ray-curable adhesive composition which contains a urethane (meth) acrylate compound (A) obtained by reacting a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) and a polyol compound (a3) and which has a weight average molecular weight of 20000 to 120000, and an ethylenically unsaturated monomer (B) containing a heterocyclic monomer (B1) and a hydroxyl group-containing monomer (B2) in a content ratio (weight ratio) of the heterocyclic group-containing monomer (B1) to the hydroxyl group-containing monomer (B2) of (B1): (b2) 25: 75-80: 20.

Description

Active energy ray-curable adhesive composition, and adhesive sheet obtained using same
Technical Field
The present invention relates to an active energy ray-curable adhesive composition containing a urethane (meth) acrylate compound, and an adhesive sheet obtained using the same.
Background
There are various types in adhesives: a strongly adhesive pressure-sensitive adhesive for the purpose of firmly adhering an adherend for a long period of time; a pressure-sensitive adhesive suitable for various fields is designed and used, for example, as a release pressure-sensitive adhesive assuming that the pressure-sensitive adhesive is released from an adherend after being adhered.
Further, for example, adhesives used for optical devices such as touch panels and optical members such as optical recording media are required to exhibit excellent transparency, particularly under high-temperature and high-humidity conditions, in addition to adhesive force.
As an adhesive used for an optical member, for example, patent document 1 discloses that a resin composition for an ultraviolet-curable adhesive containing a urethane (meth) acrylate resin has an excellent balance between an adhesive force to a substrate and a holding force.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-136557
Disclosure of Invention
Problems to be solved by the invention
However, the adhesive force of the adhesive resin composition of patent document 1 is hardly said to be sufficient. In addition, although the resin composition for an adhesive achieves good resistance to thermal yellowing, the effect is achieved by adding additives such as a stabilizer and an antioxidant, and the properties such as resistance to moist heat cannot be improved by the resin composition for an adhesive itself.
Therefore, in the present invention, against such a background, it is an object to provide: an adhesive composition for obtaining an adhesive having a good balance between adhesion and wet heat resistance.
Means for solving the problems
However, the present inventors have made extensive studies in view of the above circumstances, and as a result, have found that: the present inventors have found that an adhesive having a good balance between adhesive strength and moist heat resistance can be obtained by using an active energy ray-curable adhesive composition containing a urethane (meth) acrylate compound having a relatively high molecular weight and an ethylenically unsaturated monomer, and an active energy ray-curable adhesive composition containing a heterocyclic ring-containing monomer (b1) and a hydroxyl group-containing monomer (b2) as ethylenically unsaturated monomers at a predetermined content ratio, and have completed the present invention.
That is, the present invention is directed to an active energy ray-curable adhesive composition containing a urethane (meth) acrylate compound (a) obtained by reacting a polyisocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) and a polyol compound (a3) and having a weight average molecular weight of 20000 to 120000, and an ethylenically unsaturated monomer (B) containing a heterocyclic monomer (B1) and a hydroxyl group-containing monomer (B2), wherein the content ratio (weight ratio) of the heterocyclic monomer (B1) to the hydroxyl group-containing monomer (B2) is (B1): (b2) 25: 75-80: 20.
further, the present invention provides an adhesive obtained by curing the active energy ray-curable adhesive composition, and an adhesive sheet comprising: and an adhesive layer obtained by curing the active energy ray-curable adhesive composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable adhesive composition of the present invention can provide an adhesive having a good balance between adhesive strength and moist heat resistance, that is, an adhesive which exhibits high adhesive strength and does not deteriorate in transparency even when exposed to moist heat, and is useful as an adhesive for optical members such as optical devices such as touch panels and optical recording media. The reason for obtaining the above-described effects is not clear, but it is considered that: by using the urethane (meth) acrylate compound (a) having a relatively high molecular weight, flexibility of the pressure-sensitive adhesive layer is increased, and thus the adhesive strength is improved. Further, it is considered that: by combining the heterocyclic monomer (B1) and the hydroxyl group-containing monomer (B2) as the ethylenically unsaturated monomer (B) in a specific ratio, the balance between the aggregating power and hydrophilicity can be controlled, and an adhesive having a good balance between the adhesive force and the moist heat resistance and excellent in adhesion can be obtained.
Detailed Description
The present invention will be described in detail below, which is an example of a desired embodiment.
In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylic acid group means acrylic acid group or methacrylic acid group, (meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate. The acrylic resin is a resin obtained by polymerizing a polymerization component containing at least 1 type of (meth) acrylate monomer.
The active energy ray-curable adhesive composition of the present invention contains a urethane (meth) acrylate compound (a) and an ethylenically unsaturated monomer (B).
[ urethane (meth) acrylate compound (A) ]
The urethane (meth) acrylate compound (a) used in the present invention is obtained by reacting a polyisocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a polyol compound (a 3).
Examples of the polyisocyanate compound (a1) include: aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate and the like; alicyclic polyisocyanates such as alicyclic diisocyanates (e.g., isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, etc.), and trimer compounds or polymer compounds of these polyisocyanates; allophanate type polyisocyanates, biuret type polyisocyanates, and the like.
These can be used alone in 1 or a combination of 2 or more.
Among them, aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like are preferably used from the viewpoint of reducing yellowing; alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate are particularly preferably used from the viewpoint of small curing shrinkage (particularly isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate), and hydrogenated xylylene diisocyanate and isophorone diisocyanate are more preferably used from the viewpoint of excellent reactivity and versatility.
Examples of the hydroxyl group-containing (meth) acrylate compound (a2) include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate; 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, propylene oxide-modified propylene oxide-, Dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, and the like.
These can be used alone in 1 or a combination of 2 or more.
Among them, from the viewpoint of excellent flexibility of the pressure-sensitive adhesive layer, a hydroxyl group-containing (meth) acrylate compound having 1 ethylenically unsaturated group is preferable, and hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate are more preferable, and from the viewpoint of excellent reactivity and versatility, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferably used.
Examples of the polyol compound (a3) include: polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.
Examples of the polyether polyol include: polyether polyols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyhexamethylene glycol, and random copolymers or block copolymers of these polyalkylene glycols.
Examples of the polyester polyol include: condensation polymers of polyhydric alcohols and polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reactants obtained from 3 components of polyhydric alcohols, polycarboxylic acids, and cyclic esters.
Examples of the polyol include: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1, 4-tetramethylene glycol, 1, 3-tetramethylene glycol, 2-methyl-1, 3-trimethylene glycol, 1, 5-pentamethylene glycol, neopentyl glycol, 1, 6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1, 4-cyclohexanediol and the like), bisphenols (bisphenol a and the like), sugar alcohols (xylitol, sorbitol and the like), and the like.
Examples of the polycarboxylic acid include: aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, p-phenylene dicarboxylic acid, and trimellitic acid.
Examples of the cyclic ester include propiolactone, β -methyl-valerolactone and caprolactone.
Examples of the polycarbonate polyol include: a reactant of a polyhydric alcohol and phosgene, a ring-opened polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.
Examples of the polyol include the polyols exemplified in the description of the polyester polyol, and examples of the alkylene carbonate include: ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.
The polycarbonate polyol may have an ester bond together with a carbonate bond as long as it has a carbonate bond in the molecule and a hydroxyl group at the end.
Examples of the polyolefin polyol include: polyolefin polyols having a saturated hydrocarbon skeleton of a homopolymer or copolymer of ethylene, propylene, butene, or the like and having a hydroxyl group at a molecular terminal thereof. Examples thereof include: polyisoprene polyol, polybutadiene polyol, nitrile polyol, styrene-butadiene polyol, and the like.
The polyolefin-based polyol may be a hydrogenated polyolefin-based polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof have been hydrogenated.
Examples of the (meth) acrylic polyol include: the (meth) acrylate ester may be, for example, a polyol having at least 2 hydroxyl groups in the molecule of a polymer or copolymer of the (meth) acrylate ester: and alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.
Examples of the polysiloxane polyol include: dimethylpolysiloxane polyols, methylphenylpolysiloxane polyols, and the like.
Among them, polyester polyols and polyether polyols are preferred, and polyester polyols are particularly preferred in view of versatility.
The number of hydroxyl groups contained in the polyol compound (a3) is preferably 2 to 5, particularly preferably 2 to 3, and further preferably 2. When the number of hydroxyl groups is too large, gelation tends to occur during the reaction.
In the present invention, the weight average molecular weight of the polyol compound (a3) is preferably 1000 to 20000, particularly preferably 2000 to 18000, and further preferably 3000 to 16000. When the weight average molecular weight is too small, the adhesive strength of the pressure-sensitive adhesive layer tends to be low, and when it is too large, the reactivity with the polyisocyanate compound (a1) tends to be low.
The weight average molecular weight is a weight average molecular weight in terms of a standard polystyrene molecular weight, and Shodex GPCKF-806L (exclusion limit molecular weight: 2 × 10) as a column used in high performance liquid chromatography ("Shorex GPC system-11" manufactured by Shorey and electrician Co., Ltd.) (exclusion limit molecular weight: 2 ×7The separation range is 100-2 × 107Theoretical plate number: 10000 grades/root, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) was used.
The hydroxyl value of the polyol compound (a3) is preferably 10 to 300mgKOH/g, particularly preferably 15 to 150mgKOH/g, and further preferably 20 to 120 mgKOH/g. When the hydroxyl value is too high, the urethane (meth) acrylate compound (a) tends to have a low molecular weight and a low adhesive strength, and when it is too low, the urethane (meth) acrylate compound (a) tends to have a high viscosity and a low workability.
In the present invention, the urethane (meth) acrylate compound (a) can be produced as follows.
Examples thereof include: (1) a method in which the polyisocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2), and the polyol compound (a3) are all or separately charged into a reactor and reacted; (2) a method in which a polyol compound (a3) is reacted with a polyisocyanate compound (a1) in advance, and the resulting reaction product is reacted with a hydroxyl group-containing (meth) acrylate compound (a 2); for example, the method (2) is preferred in view of stability of the reaction, reduction of by-products, and the like.
The reaction of the polyisocyanate compound (a1) and the polyol compound (a3) can be carried out by a known reaction method. In this case, for example, the isocyanate group in the polyisocyanate compound (a 1): the molar ratio of hydroxyl groups in the polyol-based compound (a3) is usually 2 n: (2n-2) (n is an integer of 2 or more), whereby an isocyanate group-remaining urethane (meth) acrylate compound containing a terminal isocyanate group can be obtained, and after obtaining this compound, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (a2) can be performed.
The addition reaction between the reaction product obtained by reacting the polyisocyanate compound (a1) with the polyol compound (a3) in advance and the hydroxyl group-containing (meth) acrylate compound (a2) can be carried out by a known reaction means.
In the case where the reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (a2) is, for example, 2 isocyanate groups of the polyisocyanate compound (a1) and 1 hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2), the reaction product: the hydroxyl group-containing (meth) acrylate compound (a2) is 1: about 2, when the isocyanate group of the polyisocyanate compound (a1) is 3 and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) is 1, the reaction product: the hydroxyl group-containing (meth) acrylate compound (a2) is 1: about 3.
The addition reaction of the reaction product with the hydroxyl group-containing (meth) acrylate compound (a2) is terminated when the residual isocyanate group content in the reaction system becomes 0.2 wt% or less, whereby the urethane (meth) acrylate compound (a) can be obtained.
In the reaction between the polyisocyanate compound (a1) and the polyol compound (a3) and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), it is preferable to use a catalyst for accelerating the reaction.
Examples of the catalyst include: organic metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris (acetylacetonate) ethylacetoacetate, and zirconium tetraacetylacetonate; metal salts such as tin octenoate, zinc caproate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, tin chloride, potassium acetate, etc.; amine catalysts such as triethylamine, triethylenediamine, benzyldiethylamine, 1, 4-diazabicyclo [2,2,2] octane, 1, 8-diazabicyclo [5,4,0] undecene, N, N, N ', N' -tetramethyl-1, 3-butanediamine, N-methylmorpholine and N-ethylmorpholine; bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, and the like; and bismuth-based catalysts such as organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth dineodecanoate (bismuth neodecanoate), bismuth disilicate, and bismuth digallate, and bismuth salts of organic acids such as bismuth digallate, and dibutyl tin dilaurate and 1, 8-diazabicyclo [5,4,0] undecene are suitable. These can be used alone in 1 or a combination of 2 or more.
In the reaction between the polyisocyanate compound (a1) and the polyol compound (a3) and the reaction product thereof with the hydroxyl group-containing (meth) acrylate compound (a2), an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene, may be used as needed.
In addition, the reaction temperature is usually 30 to 90 ℃, preferably 40 to 80 ℃, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
When the urethane (meth) acrylate compound (a) is produced by reacting the polyisocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2) and the polyol compound (a3), a mixture of the urethane (meth) acrylate compound (a) and the ethylenically unsaturated monomer (B) may be produced by allowing the ethylenically unsaturated monomer (B) described later to exist in the reaction system.
For example, in the method of producing the urethane (meth) acrylate compound (a) by reacting the polyisocyanate compound (a1) and the polyol compound (a3) in advance and reacting the resultant reaction product with the hydroxyl group-containing (meth) acrylate compound (a2), the ethylenically unsaturated monomer (B) may be present in the reaction system when the polyisocyanate compound (a1) and the polyol compound (a3) are reacted.
The weight-average molecular weight of the urethane (meth) acrylate compound (A) is 20000 to 120000, preferably 21000 to 100000, particularly preferably 22000 to 90000, and further preferably 25000 to 80000. When the weight average molecular weight is too low, the adhesive strength of the pressure-sensitive adhesive layer tends to be low, and when too high, the viscosity of the urethane (meth) acrylate compound (a) tends to be too high, and handling tends to be difficult.
The weight average molecular weight is a weight average molecular weight in terms of a standard polystyrene molecular weight, and Shodex GPCKF-806L (exclusion limit molecular weight: 2 × 10) as a column used in high performance liquid chromatography ("Shorex GPC system-11" manufactured by Shorey and electrician Co., Ltd.) (exclusion limit molecular weight: 2 ×7The separation range is 100-2 × 107Theoretical plate number: 10000 grades/root, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) was used.
The viscosity of the urethane (meth) acrylate compound (A) is preferably 1000 to 1000000 mPas, particularly preferably 2000 to 800000 mPas, and more preferably 3000 to 600000 mPas in a viscometer at 60 ℃. When the viscosity is too high, handling tends to be difficult, and when it is too low, control of the film thickness tends to be difficult in coating.
The viscosity was measured by an E-type viscometer.
[ ethylenically unsaturated monomer (B) ]
The active energy ray-curable adhesive composition of the present invention contains a heterocyclic ring-containing monomer (B1) and a hydroxyl group-containing monomer (B2) as an ethylenically unsaturated monomer (B) (excluding the urethane (meth) acrylate compound (a)) (hereinafter, sometimes referred to as an "ethylenically unsaturated monomer (B)").
Examples of the heterocyclic ring-containing monomer (b1) include: heterocyclic ring-containing monomers having a nitrogen atom such as (meth) acryloylmorpholine, tetramethylpiperidine (meth) acrylate, pentamethylpiperidine (meth) acrylate, maleimide (meth) acrylate, ethylene oxide-modified di (meth) acrylate isocyanurate, ethylene oxide-modified tri (meth) acrylate isocyanurate, N-vinylpyrrolidone and 2-vinylpyridine; heterocyclic ring-containing monomers having an oxygen atom such as glycidyl (meth) acrylate, 3-ethyl-3-oxetanyl methyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanospiro-2- (1, 3-dioxolan-4-yl) methyl (meth) acrylate, γ -butyrolactone (meth) acrylate, trimethylolpropane (formal) (meth) acrylate, and the like; heterocyclic ring-containing monomers having 2 or more kinds of hetero atoms such as oxazolidinone (meth) acrylate, and the like. Among them, from the viewpoint of excellent flexibility of the pressure-sensitive adhesive layer, the heterocyclic-ring-containing monomer (b1) having 1 ethylenically unsaturated group is preferable, the heterocyclic-ring-containing monomer having 1 ethylenically unsaturated group and having a nitrogen atom is more preferable, and from the viewpoint of excellent aggregating power of the pressure-sensitive adhesive layer, among them, (meth) acryloyl morpholine is particularly preferable.
Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
In order to obtain the active energy ray-curable adhesive composition of the present invention, the heterocyclic ring-containing monomer (b1) may be contained in the urethane (meth) acrylate compound (a) after synthesis, or may be used as a diluent in the synthesis reaction of the urethane (meth) acrylate compound (a). In order to suppress the increase in viscosity, the heterocyclic ring-containing monomer (b1) is preferably used as a diluent in the synthesis reaction of the urethane (meth) acrylate-based compound (a).
When the heterocyclic ring-containing monomer (b1) is used as a diluent in the synthesis reaction of the urethane (meth) acrylate compound (a), the monomer is usually (a): (b1) 50: 50-95: 5 (weight ratio), preferably (A): (b1) 60: 40-90: 10 (weight ratio), particularly preferably (a): (b1) 70: 30-90: 10 (weight ratio).
Examples of the hydroxyl group-containing monomer (b2) include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, propylene glycol mono (, Glycerol mono (meth) acrylate, glycerol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, N-methylol (meth) acrylamide, and the like.
Among them, a hydroxy ester-based (meth) acrylate compound having 1 ethylenically unsaturated group is preferable from the viewpoint of excellent flexibility of the pressure-sensitive adhesive layer, a hydroxy alkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate is more preferable from the viewpoint of excellent versatility, and 4-hydroxybutyl (meth) acrylate is particularly preferably used from the viewpoint of high adhesive force of the pressure-sensitive adhesive layer and low skin irritation.
Further, they may be used alone in 1 kind or in combination of 2 or more kinds.
In order to obtain the active energy ray-curable adhesive composition of the present invention, the hydroxyl group-containing monomer (b2) may be contained in the urethane (meth) acrylate compound (a) after synthesis, or may be used in the form of the hydroxyl group-containing (meth) acrylate (a3) as a diluent in the synthesis reaction of the urethane (meth) acrylate compound (a).
In the present invention, the content ratio (weight ratio) of the heterocyclic ring-containing monomer (b1) to the hydroxyl group-containing monomer (b2) is (b 1): (b2) 25: 75-80: 20. preferably (b 1): (b2) 25: 75-75: 25. particularly preferred is (b 1): (b2) 30: 70-70: 30. more preferably (b 1): (b2) 30: 70-60: 40.
when the ratio of the heterocyclic monomer (b1) to the hydroxyl group-containing monomer (b2) is too high, the coating film tends to be hardened and the adhesive force of the adhesive layer tends to be lowered, and when the ratio of the heterocyclic monomer (b1) to the hydroxyl group-containing monomer (b2) is too low, the adhesive force of the adhesive layer tends to be lowered due to insufficient cohesive force, and the viscosity during production tends to be too high, making production difficult.
As the ethylenically unsaturated monomer (B), in addition to the heterocyclic ring-containing monomer (B1) and the hydroxyl group-containing monomer (B2), there may be included: other monomers (b3) such as monofunctional monomers, 2-functional monomers, and 3-or more-functional monomers.
Examples of the monofunctional monomer include styrene monomers such as styrene, vinyltoluene, chlorostyrene, and α -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide-modified (n-2) (meth) acrylate, nonylphenol propylene oxide-modified (n-2.5) (meth) acrylate, acid ester of a phosphate derivative such as 2- (meth) acryloyloxyethyl acrylate, half-butyl (meth) acrylate, polyoxyethylene (sec-butoxyethyl (meth) acrylate, and polyoxyethylene (meth) acrylate.
Examples of the 2-functional monomer include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol a type di (meth) acrylate, propylene oxide-modified bisphenol a type di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, ethoxylated cyclohexane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and the like.
Examples of the above-mentioned 3-or more-functional monomer include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, and the like.
In addition, a michael adduct of acrylic acid or a 2-acryloyloxyethyl dicarboxylic acid monoester may be used in combination, and examples of the michael adduct of acrylic acid include: acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.
The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, and examples thereof include: 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Further, oligoester acrylates may be mentioned.
When the ethylenically unsaturated monomer (B) contains another monomer (B3) in addition to the heterocyclic ring-containing monomer (B1) and the hydroxyl group-containing monomer (B2), the proportion of the other monomer (B3) in the ethylenically unsaturated monomer (B) is not particularly limited, and is usually 30% by weight or less, preferably 25% by weight or less, and particularly preferably 20% by weight or less.
The content ratio (weight ratio) of the urethane (meth) acrylate compound (a) to the ethylenically unsaturated monomer (B) is usually (a): (B) 80: 20-20: 80. preferably (a): (B) 75: 25-30: 70. particularly preferred is (a): (B) 70: 30-40: 60. more preferably (a): (B) 65: 35-50: 50. when the amount of the ethylenically unsaturated monomer (B) is too large relative to the urethane (meth) acrylate compound (a), the viscosity of the adhesive composition tends to be too low and thick coating (imprasto) tends to be difficult, and when it is too small, the viscosity of the adhesive composition tends to be too high and handling tends to be difficult.
In this manner, the active energy ray-curable adhesive composition of the present invention can be obtained.
In the present invention, it is preferable that the active energy ray-curable adhesive composition further contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light, and examples thereof include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one Acetophenones such as ketone and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-propan-1-one; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzylammonium bromide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methylchloride; acylphosphine oxides such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; and the like. These photopolymerization initiators may be used alone or in combination of 2 or more.
Further, as the auxiliary agent for these photopolymerization initiators, for example, triethanolamine, triisopropanolamine, 4 ' -dimethylaminobenzophenone (Michler's ketone), 4 ' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (n-butoxy) 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like can be used in combination. These auxiliaries may also be used alone or in combination of 2 or more.
The content of the photopolymerization initiator is preferably 1 to 10 parts by weight, and particularly preferably 2 to 5 parts by weight, based on 100 parts by weight of the total of the urethane (meth) acrylate compound (a) and the ethylenically unsaturated monomer (B). When the content is too small, the curing rate tends to be low, and when the content is too large, the curability does not improve and the economical efficiency tends to be low.
The active energy ray-curable adhesive composition of the present invention may contain an antioxidant, a flame retardant, an antistatic agent, a filler, a leveling agent, a stabilizer, a reinforcing agent, a matting agent, and the like in addition to the urethane (meth) acrylate compound (a), the ethylenically unsaturated monomer (B), and the photopolymerization initiator. Further, as the crosslinking agent, a compound having an action of causing crosslinking by heat, specifically, an epoxy compound, an aziridine compound, a melamine compound, an isocyanate compound, a chelate compound, or the like may be used.
Further, the active energy ray-curable adhesive composition of the present invention may contain a polythiol compound in order to suppress unreacted components and improve adhesive strength.
The polythiol compound is not particularly limited, and compounds having 2 to 6 mercapto groups in the molecule are preferable, and examples thereof include aliphatic polythiols such as alkanedithiol having 2 to 20 carbon atoms, aromatic polythiols such as xylylenedithiol, polythiols obtained by substituting a halogen atom of a halohydrin adduct of an alcohol with a mercapto group, polythiols obtained by reacting a hydrogen sulfide of a polyepoxy compound, polythiols obtained by esterifying a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule with mercaptoacetic acid, β -mercaptopropionic acid, or β -mercaptobutyric acid, and 1 kind or more thereof may be used alone or in combination.
The content of the polythiol compound is preferably 0.01 to 10 parts by weight or less, and particularly preferably 0.1 to 5 parts by weight or less, based on 100 parts by weight of the total of the urethane (meth) acrylate compound (a) and the ethylenically unsaturated monomer (B).
In the active energy ray-curable adhesive composition of the present invention, in order to adjust the viscosity at the time of application, alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatic compounds such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; the diluent solvent such as diacetone alcohol is preferably substantially free of the solvent because the solvent may remain in the coating film and the cured component may volatilize during drying.
The term "substantially free of a solvent" means that the content is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less, based on the entire active energy ray-curable adhesive composition.
The active energy ray-curable adhesive composition of the present invention is generally applied to a substrate sheet or the like as an adhesive sheet (the adhesive sheet includes an adhesive film and an adhesive tape unless otherwise specified) for practical use, and after being applied to the substrate sheet, the adhesive composition is crosslinked by irradiation with active energy rays to become an adhesive, thereby exhibiting adhesiveness.
Examples of the substrate sheet include: polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymers, polycarbonate resins, polyurethane resins, acrylic resins, polystyrene resins, ethylene-vinyl acetate copolymers, resin sheets such as polyvinyl chloride, polybutylene, polybutadiene, polymethylpentene and acrylonitrile-butadiene-styrene copolymer (ABS), and glass sheets. Various base material sheets may be used, for example, those obtained by surface treatment such as anchor coating or corona treatment or plasma treatment.
The method for applying the active energy ray-curable adhesive composition is not particularly limited, and examples thereof include: and wet coating methods such as spray coating, shower, dipping, roll coating, spin coating, screen printing, inkjet printing, and dispensing.
When the solvent is contained, the coating may be dried after the coating, and the drying conditions may be set to a drying temperature and a drying time sufficient for volatilizing the solvent, and the drying temperature is usually 40 to 100 ℃, and particularly preferably 50 to 90 ℃. The drying time is a time that can completely volatilize the solvent in the coating film during drying, and is preferably 1 to 60 minutes in view of production suitability.
The active energy ray-curable adhesive composition of the present invention is applied to a substrate sheet and dried, and then irradiated with active energy rays to be cured (crosslinked) to form an adhesive, and further to form an adhesive sheet.
Further, a release film may be laminated on the surface of the pressure-sensitive adhesive in order to protect the pressure-sensitive adhesive from contamination until the pressure-sensitive adhesive sheet of the present invention is attached to an adherend (member). As the separator, the resin sheet and the release-treated substrate such as paper, cloth, or nonwoven fabric described above can be used.
When the adhesive composition is provided on the substrate sheet, the adhesive composition is usually prepared as a solution of an active energy ray-curable adhesive composition, and if necessary, the solution is adjusted to a viscosity suitable for coating with a solvent, and then the solution is coated on the substrate sheet and dried. Examples of the coating method include: a direct coating method of directly coating the active energy ray-curable adhesive composition in a solution state on a substrate sheet; a transfer coating method in which the active energy ray-curable adhesive composition in a solution state is applied to a separator and then is bonded to a substrate sheet.
In the direct coating method, there may be mentioned: a method in which an active energy ray-curable adhesive composition is applied to a substrate sheet, heated and dried, and then irradiated with active energy rays, followed by sticking a separator; a method in which an active energy ray-curable adhesive composition is applied to a substrate sheet, heated and dried, then a separator is attached, and then irradiated with active energy rays. The coating can be performed by a method such as roll coating, die coating, gravure coating, comma coating, screen printing, or print coating using dispensing.
On the other hand, in the transfer coating method, there are exemplified: a method of applying an active energy ray-curable adhesive composition to a separator, heating and drying the adhesive composition, irradiating the adhesive composition with active energy rays, and then attaching a substrate sheet; a method in which an active energy ray-curable adhesive composition is applied to a separator, heated and dried, then a substrate sheet is attached, and then irradiated with active energy rays. As the coating method, the same method as the direct coating can be used.
As the active energy ray, there can be used: electromagnetic waves such as far ultraviolet rays, near ultraviolet rays, infrared rays, etc., X rays, gamma rays, etc.; and electron beams, proton beams, neutron beams, and the like, curing by ultraviolet irradiation is advantageous in terms of curing speed, ease of obtaining an irradiation device, price, and the like. In the case of electron beam irradiation, curing can be performed without using a photopolymerization initiator.
As a method for curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, L ED, or the like, which emits light in a wavelength region of 150 to 450nm, may be used, and irradiation is performed at 30 to 3000mJ/cm2The method is suitable for the left and the right.
After the ultraviolet irradiation, the curing may be completed by heating as necessary.
The thickness of the pressure-sensitive adhesive layer formed on the substrate sheet after the irradiation with the active energy ray may be appropriately set according to the application, and is usually 5 to 300 μm, preferably 10 to 250 μm. When the thickness of the pressure-sensitive adhesive layer is too small, the pressure-sensitive adhesive properties tend to be difficult to stabilize, and when it is too thick, adhesive residue tends to be easily caused.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the examples, "part" and "%" are based on weight.
Urethane (meth) acrylate compounds (a-1) to (a-7) were produced as the urethane (meth) acrylate compound (a) as shown below.
< production of urethane (meth) acrylate Compound (A-1) >
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 12.2g (0.055 mol) of isophorone diisocyanate (a1), 85.2g (0.044 mol) of 2-functional polyester polyol (a3-1) (weight average molecular weight (Mw) 7000), and 0.02g of dibutyltin dilaurate as a reaction catalyst were charged, and reacted at 60 ℃ for 8 hours, 2.6g (0.022 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were charged, and reacted at 60 ℃ for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a urethane (meth) acrylate compound (A-1) (Mw; 34000) was obtained.
< production of urethane (meth) acrylate Compound (A-2)
In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blown inlet, 8.5g (0.038 mol) of isophorone diisocyanate (a1), 53.9g (0.027 mol) of 2-functional polyester polyol (a3-1) (Mw 7000), 15.7g (0.004 mol) of 2-functional polyester polyol (a3-2) (Mw 12000), 20.0g of acryloyl morpholine (b1-1), 0.02g of dibutyltin dilaurate as a reaction catalyst, and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were charged, reacted at 60 ℃ for 8 hours, then 1.8g (0.015 mol) of 2-hydroxyethyl acrylate (a2) was charged, and reacted at 60 ℃ for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a mixture of the urethane (meth) acrylate compound (A-2) (Mw; 35000) and acryloyl morpholine (b1-1) (urethane (meth) acrylate compound concentration: 80%) was obtained.
< production of urethane (meth) acrylate Compound (A-3)
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 7.8g (0.035 mol) of isophorone diisocyanate (a1), 42.0g (0.021 mol) of 2-functional polyester polyol (a3-1) (Mw 7000), 28.6g (0.007 mol) of 2-functional polyester polyol (a3-2) (Mw 12000), 20.0g of acryloyl morpholine (b1-1), and 0.02g of dibutyltin dilaurate as a reaction catalyst were put into the flask, and after the mixture was reacted at 60 ℃ for 8 hours, 1.7g (0.015 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were put into the flask, and the mixture was reacted at 60 ℃ for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a mixture of the urethane (meth) acrylate compound (A-3) (Mw; 36000) and acryloyl morpholine (b1-1) (urethane (meth) acrylate compound concentration: 80%) was obtained.
< production of urethane (meth) acrylate Compound (A-4)
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 26.4g (0.119 mol) of isophorone diisocyanate (a1), 51.4g (0.109 mol) of 2-functional polyester polyol (a3-3) (Mw 1300), 20.0g of acryloyl morpholine (b1-1), and 0.02g of dibutyltin dilaurate as a reaction catalyst were put into the flask, and after allowing the flask to react at 60 ℃ for 8 hours, 2.2g (0.019 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were put into the flask, and the mixture was allowed to react at 60 ℃ for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a mixture of the urethane (meth) acrylate compound (A-4) (Mw; 36000) and acryloyl morpholine (b1-1) (urethane (meth) acrylate compound concentration: 80%) was obtained.
< production of urethane (meth) acrylate Compound (A-5)
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet, 11.4g (0.051 mol) of isophorone diisocyanate (a1), 86.5g (0.044 mol) of 2-functional polyether polyol (a3-4) (Mw 7000) and 0.02g of dibutyltin dilaurate as a reaction catalyst were charged, and after allowing to react at 60 ℃ for 8 hours, 2.2g (0.019 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were charged and allowed to react at 60 ℃ for 6 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a urethane (meth) acrylate compound (A-5) (Mw; 38000) was obtained.
< production of urethane (meth) acrylate Compound (A-6)
14.0g (0.063 mol) of isophorone diisocyanate (a1), 81.0g (0.042 mol) of 2-functional polyester polyol (a3) (Mw 7000), and 0.02g of dibutyltin dilaurate as a reaction catalyst were put into a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blowing port, and reacted at 60 ℃ for 4 hours, 5.0g (0.043 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were put into the flask, and reacted at 60 ℃ for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a urethane (meth) acrylate compound (A-6) (Mw; 18000) was obtained.
< production of urethane (meth) acrylate Compound (A-7)
16.4g (0.074 mol) of isophorone diisocyanate (a1), 72.7g (0.037 mol) of a 2-functional polyether polyol (a3) (Mw 7000), and 0.02g of dibutyltin dilaurate as a reaction catalyst were put into a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blowing port, and reacted at 60 ℃ for 4 hours, then 10.9g (0.094 mol) of 2-hydroxyethyl acrylate (a2) and 0.04g of 2, 6-di-t-butylcresol as a polymerization inhibitor were put into the flask, and reacted at 60 ℃ for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, whereby a urethane (meth) acrylate compound (A-7) (Mw; 13000) was obtained.
< ethylenically unsaturated monomer (B) >
The following were prepared as the ethylenically unsaturated monomer (B).
(b 1-1): acryloyl morpholine
(b 2-1): acrylic acid 4-hydroxybutyl ester
(b 3-1): acrylic acid n-butyl ester
[ example 1]
The urethane (meth) acrylate resin (a-1) prepared in the above-described manner (55.2 parts), the ethylenically unsaturated monomer (b1-1)13.8 parts, and (b2-1)31 parts (containing (by weight ratio) 4 parts of (b 1-1): (b2-1) ═ 31: 69), and 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan corporation; "Irgacure 184") as a photopolymerization initiator were uniformly mixed to obtain an active energy ray-curable adhesive composition.
[ example 2]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the amount of the ethylenically unsaturated monomer (b1-1) was changed to 22.4 parts and (b2-1)22.4 parts (the content ratio (weight ratio) was changed to (b 1-1): 50).
[ example 3 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the content of the ethylenically unsaturated monomer (b1-1) was changed to 31.4 parts and (b2-1)13.4 parts (the content ratio (weight ratio) was changed to (b 1-1): and (b 2-1): 70: 30).
[ example 4 ]
The active energy ray-curable adhesive composition (the content ratio of the ethylenically unsaturated monomer (b 1-1): b 2-1): 31: 69) was obtained by uniformly mixing 69 parts of the mixture of the urethane (meth) acrylate resin (a-2) and the acryloylmorpholine (b1-1) (55.2 parts of the urethane (meth) acrylate compound (a-2), 13.8 parts of acryloylmorpholine (b1-1), 31 parts of the ethylenically unsaturated monomer (b2-1), and 4 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (basf japan; "Irgacure 184") as a photopolymerization initiator.
[ example 5 ]
The active energy ray-curable adhesive composition (content ratio of ethylenically unsaturated monomer (b 1-1): b 2-1): 31: 69) was obtained by uniformly mixing 69 parts of the mixture of the urethane (meth) acrylate resin (a-3) and acryloylmorpholine (b1-1) (55.2 parts of urethane (meth) acrylate compound (a-3), 13.8 parts of acryloylmorpholine (b1-1), 31 parts of ethylenically unsaturated monomer (b2-1), and 4 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (basf japan; "Irgacure 184") as a photopolymerization initiator.
[ example 6 ]
The active energy ray-curable adhesive composition (content ratio of ethylenically unsaturated monomer (b 1-1): b 2-1): 31: 69) was obtained by uniformly mixing 69 parts of the mixture of the urethane (meth) acrylate resin (a-4) and acryloylmorpholine (b1-1) (55.2 parts of urethane (meth) acrylate compound (a-4), 13.8 parts of acryloylmorpholine (b1-1), 31 parts of ethylenically unsaturated monomer (b2-1), and 1-hydroxy-cyclohexyl-phenyl-ketone (basf japan; "Irgacure 184") as a photopolymerization initiator.
[ example 7 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the urethane (meth) acrylate resin (a-1) was changed to the urethane (meth) acrylate resin (a-5).
[ comparative example 1]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the contents of the ethylenically unsaturated monomer (b1-1) and (b2-1) were changed to 2.2 parts and 42.6 parts (the content ratio (weight ratio) was (b 1-1): 5: 95) (b 2-1).
[ comparative example 2]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the contents of the ethylenically unsaturated monomer (b1-1) and (b2-1) were changed to 4.5 parts and 40.3 parts (the content ratio (weight ratio) was (b 1-1): (b 2-1): 10: 90).
[ comparative example 3 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the amount of the ethylenically unsaturated monomer (b1-1) was changed to 9 parts and (b2-1)35.9 parts (the content ratio (weight ratio) was changed to (b 1-1): 20: 80).
[ comparative example 4 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the content of the ethylenically unsaturated monomer (b1-1) was changed to 40.3 parts and (b2-1)4.5 parts (the content ratio (weight ratio) was changed to (b 1-1): and (b 2-1): 90: 10).
[ comparative example 5 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the urethane (meth) acrylate resin (a-1) was changed to the urethane (meth) acrylate resin (a-6).
[ comparative example 6 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the urethane (meth) acrylate resin (a-1) was changed to the urethane (meth) acrylate resin (a-7).
[ comparative example 7 ]
An active energy ray-curable adhesive composition was obtained in the same manner as in example 1 except that the ethylenically unsaturated monomer (b2-1) was changed to the ethylenically unsaturated monomer (b 3-1).
< production of adhesive sheet for measuring adhesive force >
The active energy ray-curable adhesive compositions obtained in examples 1 to 7 and comparative examples 1 to 7 were applied to an easily adhesive polyethylene terephthalate (PET) film (thickness: 125 μm) using an applicator so that the cured film thickness became 175 μm, and the resultant was irradiated with 80W/cm (high-pressure mercury lamp) × 18cmH × 2.04.04 m/min × 3Pass (cumulative 2400 mJ/cm/min) using a desk type UV irradiation apparatus (manufactured by Kazaki electric Co., Ltd., "conveyer type desk type irradiation apparatus") (high-pressure mercury lamp) at 80W/cm × cmH 3532.04 m/min × Pass)2) The pressure-sensitive adhesive sheet for measuring adhesive force was obtained by curing the sheet by irradiation with ultraviolet rays under the conditions of (1).
< test method >
The pressure-sensitive adhesive sheet for measuring adhesive force thus obtained was cut into 25mm × 100mm pieces, and then pressed against a glass plate as an adherend by reciprocating the pressure-sensitive adhesive sheet 2 times at 23 ℃ under an atmosphere of 50% relative humidity using a 2kg rubber roller to prepare a test piece, and after the test piece was left to stand in the same atmosphere for 30 minutes, a 180-degree peel test was carried out at a peel speed of 0.3 m/minute to measure the initial adhesive force (N/25mm), and the evaluation was carried out according to the following criteria.
(evaluation criteria)
○. 10N/25mm or more
×. smaller than 10N/25mm
< production of adhesive sheet for Damp-Heat test >
The active energy ray-curable adhesive compositions obtained in examples 1 to 7 and comparative examples 1 to 7 were cured using an applicator, and thenThe film thickness of (2) was coated on an easy adhesion-treated polyethylene terephthalate (PET) film (thickness: 125 μm) so as to be 175 μm, and the film was laminated on a release polyethylene terephthalate film (thickness: 50 μm), and then subjected to a UV irradiation apparatus (manufactured by Kawasaki electric Co., Ltd., "conveyor belt type desk type irradiation apparatus") under a pressure of 80W/cm (high pressure mercury lamp) of × 18cmH × 2.04.04 m/min × 3Pass (cumulative 2400 mJ/cm)2) The pressure-sensitive adhesive sheet for a wet heat resistance test was obtained by curing the pressure-sensitive adhesive sheet under the conditions of (1).
< test method >
The obtained pressure-sensitive adhesive sheet for a wet heat resistance test was cut to 25mm × 40mm, and then pressure-bonded to a glass plate as an adherend to prepare a test piece.
The obtained test piece was left to stand at 80 ℃ and 90% RH for 100 hours, and b ＊ immediately after the end of the test was measured by a color difference meter to evaluate the moist heat resistance (transparency of the adhesive layer) as follows.
(evaluation criteria)
○ · 3 or less
×. greater than 3
< preparation of sample for Shore E measurement >
The active energy ray-curable adhesive compositions obtained in examples 1 to 7 and comparative examples 1 to 7 were charged into a polyethylene container, and subjected to 80W/cm (high pressure mercury lamp) × 18cmH × 2.04.04 m/min × 5Pass (cumulative 4000 mJ/cm) using a desk type UV irradiation apparatus (manufactured by Kawasaki electric Co., Ltd. "conveyor desk type irradiation apparatus") (high pressure mercury lamp) to obtain an adhesive composition2) The ultraviolet ray was irradiated under the conditions of (1) and cured, thereby obtaining a shore E measurement sample having a thickness of about 8 mm.
< test method >
The flexibility of the pressure-sensitive adhesive layer obtained by curing the active energy ray-curable pressure-sensitive adhesive composition was evaluated by pressing a pressing surface of an Asker rubber durometer type C (manufactured by polymer instruments) against the surface of the obtained shore E measurement sample and measuring the value after the lapse of 15 seconds.
(evaluation criteria)
○ DEG.70 or less
△ DEG.greater than 70 and less than 90 DEG.
×. greater than 90
The content of the urethane (meth) acrylate resin (a), the weight average molecular weight (Mw) thereof, and the ethylenically unsaturated monomer (B) in examples 1 to 7 and comparative examples 1 to 7 are shown in table 1, and the evaluation results are shown in table 2. In the table, "-" means that no component is contained.
[ Table 1]
Figure BDA0001215142850000261
[ Table 2]
Figure BDA0001215142850000271
From the above evaluation results, it is clear that the adhesive sheets of examples 1 to 7 of the present invention have a good balance between adhesive strength and moist heat resistance and are excellent, and the adhesive layers obtained in examples 1 to 7 have excellent flexibility.
On the other hand, it is found that the moist heat resistance is good but the adhesive force is insufficient in comparative examples 1 to 4 in which the content ratio of the heterocyclic ring-containing monomer (b1) and the hydroxyl group-containing monomer (b2) is outside the range defined in the present invention. In addition, it is also seen that the adhesive layer obtained in comparative example 4 is poor in flexibility.
Further, it is found that comparative examples 5 and 6 using a urethane (meth) acrylate compound having a weight average molecular weight lower than the lower limit defined in the present invention have good moist heat resistance, but the adhesive strength of comparative example 5 is insufficient, and the adhesive strength of comparative example 6 is too low to be measured. In addition, it is found that the adhesive layer obtained in comparative example 6 is inferior in flexibility.
Further, it is found that the adhesive force and the moist heat resistance of comparative example 7 in which another ethylenically unsaturated monomer (b3) was used in place of the hydroxyl group-containing monomer (b2) were not sufficient.
Industrial applicability
The adhesive obtained by curing the active energy ray-curable adhesive composition of the present invention has a good balance between adhesive strength and moist heat resistance and is therefore useful as an adhesive for an electronic component fixing sheet (tape), an electronic component label sheet (tape), and an optical display or a touch sensor. For example, the adhesive can be used for bonding the optical display panel to the touch panel, bonding the optical display panel to the protective panel, bonding the touch panel to the protective panel, bonding the optical display panel to the optical display panel, and bonding the optical display panel to the parallax barrier.
In addition, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive of the present invention is excellent in flexibility, and therefore, excellent in level difference following property between members. Therefore, the pressure-sensitive adhesive layer can be suitably used for the application of adhering an optical member having a level difference by, for example, formation or printing of an ITO transparent electrode, and can be suitably used for a touch panel including such an optical member.
Furthermore, the adhesive sheet having an adhesive layer obtained by curing the active energy ray-curable adhesive composition of the present invention can be used in various fields in addition to the electronic components and optical members described above.
While the present invention is described in more detail with reference to the above embodiments, the above embodiments are merely illustrative and not to be construed as limiting. Various modifications and adaptations obvious to those skilled in the art are of course within the scope of the present invention.
[ related applications ]
The present application claims benefit based on priority of japanese patent application No. (japanese patent application 2014-.

Claims (7)

1. An active energy ray-curable adhesive composition characterized by containing a urethane (meth) acrylate compound (A) and an ethylenically unsaturated monomer (B),
the urethane (meth) acrylate compound (A) is obtained by reacting a polyisocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a polyol compound (a3), and has a weight-average molecular weight of 20000 to 120000,
the ethylenically unsaturated monomer (B) excludes the urethane (meth) acrylate-based compound (A),
the ethylenically unsaturated monomer (B) contains a heterocyclic ring-containing monomer (B1) and a hydroxyl group-containing monomer (B2), and the content ratio of the heterocyclic ring-containing monomer (B1) to the hydroxyl group-containing monomer (B2) is (B1) in terms of weight ratio: (b2) 30: 70-80: 20.
2. the active energy ray-curable adhesive composition according to claim 1, wherein the polyisocyanate compound (a1) is an alicyclic polyisocyanate.
3. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the number of unsaturated groups in the hydroxyl group-containing (meth) acrylate compound (a2) is 1.
4. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the polyol compound (a3) is a polyether polyol or a polyester polyol.
5. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the content ratio of the urethane (meth) acrylate compound (a) to the ethylenically unsaturated monomer (B) is (a): (B) 80: 20-20: 80.
6. an adhesive obtained by curing the active energy ray-curable adhesive composition according to any one of claims 1 to 5.
7. An adhesive sheet, characterized by comprising: an adhesive layer obtained by curing the active energy ray-curable adhesive composition according to any one of claims 1 to 5.
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