JP2018048274A - Active energy ray-curable composite resin composition, active energy ray-curable composite resin adhesive using the composition, and adhesive tape for bonding optical member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin composition curable by irradiation with active energy rays, which suppresses foaming associated with a volatilized material derived from plastics under high temperature or high temperature and high humidity conditions and which achieves water vapor barrier property and low dielectric property, an adhesive using the resin composition, and an adhesive tape for bonding optical members, which is cured by active energy rays.SOLUTION: A cured product having excellent foaming resistance, water vapor barrier property and low dielectric property, or an adhesive tape for bonding an optical member can be obtained by: compounding a urethane acrylate resin having less than 2 functional groups, a polyisobutylene resin having a number average molecular weight of 300 to 100,000, and a crosslinking agent to give a crosslinked point density of 0.03 to 0.15 mmol/g; and curing the obtained composite resin with active energy rays.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composite resin composition, an active energy ray-curable composite resin adhesive using the composition, and an adhesive tape for joining optical members.

  2. Description of the Related Art Conventionally, electronic devices in which an image display device such as a liquid crystal display and a touch panel are combined are widely used in applications such as notebook computers, electronic blackboards, electronic books, mobile phones, and car navigation systems. As an image recognition method of this touch panel, a capacitance type that recognizes by a difference in capacitance change is mainstream from the viewpoint of multi-touch property, high sensitivity, and high visibility.

  As a configuration of this capacitive touch panel, in addition to a cover glass and a liquid crystal display, a transparent electrode film in which an ITO electrode (Indium Tin Oxide) is formed on a transparent plastic substrate such as PET or PC is used as an adhesive tape or an adhesive. And a multi-layer structure is proposed (for example, Patent Documents 1 to 4).

  In recent years, with the shift to larger, flexible, wearable, and portable touch panels, it is possible to reduce resistance from conventional ITO electrode films, and next-generation transparent materials such as silver and copper that can be flexible. The use of electrode films is on the rise.

  This next-generation transparent electrode such as silver or copper has a lower visible light transmittance than the ITO electrode, so from the viewpoint of ensuring visibility, the electrode L / S (line and space: line width and line of the electrode) A method of increasing the aperture ratio by reducing the space between the two has been performed.

  However, by increasing the aperture ratio, next-generation transparent electrodes such as silver and copper are greatly affected by moisture such as water vapor, which may cause a short circuit between the electrodes due to ion migration. In such a background, as a technique for suppressing ion migration, a method of treating an electrode with an organic sulfur compound such as benzyltriazole compound, cyclohexylamine, phenol compound, or dialkylthiodipropionate, an adhesive tape, Techniques for adding to the adhesive are disclosed (for example, Patent Documents 5 to 9).

  In addition, with the enhancement of functions such as an increase in touch panel size, higher integration, and improvement in response speed, there is an increasing need for thinning the members to reduce the weight. In general, in the case of a capacitive touch panel, the capacitance that affects sensitivity changes depending on the relative dielectric constant and film thickness of the material being used. There was a risk of malfunction due to increased sensitivity. Therefore, in order to obtain a constant sensitivity, it has been strongly desired to reduce the dielectric constant of the member.

  However, acrylic tapes with low water vapor barrier properties are used for the adhesive tapes and adhesives used in conventional touch panels, and the following occurs due to the intrusion of water vapor from the end face side or laminated surface of the adhesive tape or adhesive. There was a concern about the generation of ion migration of the generation electrode. In addition, the entry of water vapor increases the relative dielectric constant of the cured adhesive and the adhesive tape, which may cause malfunction.

  Furthermore, the method of adding benzyltriazole compounds or cyclohexylamine to the pressure-sensitive adhesive tape or adhesive also has a concern of working in the direction of increasing the dielectric constant and coloring, and can solve such problems. The development of adhesive tapes and adhesives has been strongly desired.

  In addition, by changing the base material to polycarbonate or PET film as the touch panel becomes flexible, due to volatilization of moisture contained in the plastic base material, adhesive tapes and adhesives that have not been found on conventional glass base materials There was a problem that foaming and visibility were reduced.

  As efforts to solve this problem, combined use of oligomers with high glass transition temperature (Tg) such as alicyclic acrylic oligomers and carboxyl group-containing acrylic oligomers, (meth) acrylic acid alkoxyalkyl esters and (meth) acrylic A technique for suppressing foaming of a pressure-sensitive adhesive tape or an adhesive by improving the adhesiveness by using a nitrogen atom-containing acrylic monomer such as acid amide is disclosed (for example, Patent Documents 10 to 16).

  However, these conventional methods for suppressing foaming are difficult to achieve both water vapor barrier properties and low dielectric properties, and the development of pressure-sensitive adhesive tapes and adhesives that balance foam resistance is strongly desired. It was.

JP 2003-238915 A JP 2003-342542 A JP 2004-231723 A JP 2002-363530 A Japanese Unexamined Patent Publication No. 03-039320 Japanese Patent Application Laid-Open No. 10-279979 JP 2001-006769 A JP 2010-254951 A JP2012-077281 JP 2005-015524 A JP 2012-201877 A JP 2014-077096 A JP 2013-006892 A JP 2013-001769 A JP 2013-119604 A JP 2012-2333060 A

  The present invention has been made on the basis of the circumstances as described above, and is excellent in water vapor barrier properties, low dielectric properties, and foam resistance, and further, irradiation of active energy rays excellent in high adhesion even in the case of a thin film. It is to provide a composite resin composition curable by an active energy ray, an active energy ray-curable composite resin adhesive using the resin composition, and an adhesive tape obtained by curing the adhesive with an active energy ray. The “adhesive” in the present invention includes the concept of a pressure-sensitive adhesive that is pressure-sensitively bonded from an adhesive that does not have self-adhesiveness. In addition, the “adhesive tape” in the present invention includes a sheet-like concept.

  As a result of intensive studies, the present inventors have found that a urethane acrylate resin having a functional group number of less than 2, a polyisobutylene resin having a number average molecular weight of 300 to 100,000, and a crosslinking in an active energy ray-curable composite resin composition. An active energy ray-curable composite resin composition optimal for bonding and sealing of members such as electronic devices is obtained by combining a crosslinking agent so that the point concentration is 0.03 to 0.15 mmol / g. The present invention has been found.

  That is, the present invention includes the following embodiments (1) to (20).

(1) An active energy ray-curable composite resin composition containing a urethane acrylate resin composition (A), a polyisobutylene resin (B), and a crosslinking agent (C),
The urethane acrylate resin composition (A) comprises an olefin polymer (a1) having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3), and The number of functional groups of the (meth) acryloyl group derived from the (meth) acrylic acid hydroxy compound (a3) is less than 2,
The polyisobutylene resin (B) contains a structure derived from an isobutylene monomer represented by the following general formula (1), and the number average molecular weight of the polyisobutylene resin (B) is in the range of 300 to 100,000; And the crosslinking agent (C) is contained in the active energy ray-curable composite resin composition so that the functional group concentration of the crosslinking agent (C) is 0.03 to 0.15 mmol / g. An active energy ray-curable composite resin composition.

(2) The active energy ray-curable composite resin composition according to (1) above, wherein the distance between cross-linking points of the cross-linking agent (C) obtained by the following mathematical formula 1 is 500 to 10,000.
Distance between cross-linking points of cross-linking agent (C) =
(Number average molecular weight of crosslinking agent (C) / number of functional groups of crosslinking agent (C)) (Equation 1)
(3) The crosslinking agent (C) comprises an olefin polymer (a1) having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3) (meth). The active energy ray-curable composite resin composition according to the above (1) or (2), wherein the number of functional groups of the (meth) acryloyl group derived from the hydroxy acrylic compound (a3) is 2 or more.

  (4) The active energy ray-curable composite resin composition according to any one of (1) to (3) above, wherein the polyisobutylene resin (B) has a number average molecular weight of 300 to 5,000. .

  (5) The active energy ray according to any one of (1) to (4) above, wherein the active energy ray-curable composite resin composition contains 5 to 60% by mass of the polyisobutylene resin (B). A curable composite resin composition.

  (6) The active energy ray-curable composite resin composition according to any one of (1) to (5) above, which contains a tackifier (D).

(7) a tackifier (D) is contained an alicyclic structure, a number average molecular weight 300 to 10,000, and iodide above (6 iodine value is equal to or less than 50gI ₂ / 100g ) Active energy ray-curable composite resin composition.

  (8) The active energy ray-curable composite resin according to (6) or (7) above, wherein the active energy ray-curable composite resin composition contains 5 to 40% by mass of the tackifier (D). Composition.

  (9) The active energy ray curing according to any one of (1) to (8) above, which comprises (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester terminal. Mold composite resin composition.

  (10) The active energy ray-curable composite resin composition as described in (9) above, wherein the alkyl group of the (meth) acrylic acid ester (E) has a branched structure.

  (11) The activity described in (9) or (10) above, wherein the content of (meth) acrylic acid ester (E) in the active energy ray-curable composite resin composition is 70% by mass or less Energy ray curable composite resin composition.

  (12) An active energy ray-curable composite resin adhesive comprising the active energy ray-curable composite resin composition according to any one of (1) to (11) above.

  (13) An active energy ray-curable composite resin adhesive comprising 1 to 100% by mass of the active energy ray-curable composite resin composition according to any one of (1) to (11).

(14) In the cured adhesive with active energy rays of the active energy ray-curable composite resin adhesive according to (12) or (13) above, the water vapor permeability measured in accordance with JIS K7129 has a film thickness of 25 μm, An active energy ray-curable composite resin adhesive that is 100 g / (m ² · 24 h) or less under conditions of a temperature of 40 ° C. and a humidity of 90%.

  (15) In the adhesive cured product by active energy rays of the active energy ray-curable composite resin adhesive according to any one of (12) to (14) above, the relative dielectric constant is a frequency of 1 MHz, a temperature of 22 ° C., and An active energy ray-curable composite resin adhesive having a humidity of 3.5 or less under a humidity of 60% and a dielectric loss tangent of 0.1 or less.

  (16) In the cured adhesive obtained by the active energy ray of the active energy ray-curable composite resin adhesive according to any one of (12) to (15) above, the average transmittance at a wavelength of 400 to 800 nm has a film thickness of 100 μm. An active energy ray-curable composite resin adhesive characterized by being 90% or more under conditions.

  (17) An active energy ray-curable composite resin adhesive layer and an optical member-bonding pressure-sensitive adhesive tape comprising a separator layer, wherein the adhesive layer is any one of the above (12) to (16) An adhesive tape for joining optical members, comprising a curable composite resin adhesive.

(18) In the pressure-sensitive adhesive tape described in (17) above, the water vapor permeability measured according to JIS K7129 is 100 g / (m ² · 24 h) or less under conditions of a film thickness of 25 μm, a temperature of 40 ° C., and a humidity of 90%. An adhesive tape for joining optical members, wherein

  (19) The relative dielectric constant of the pressure-sensitive adhesive tape according to (17) or (18) is 3.5 or less at a frequency of 1 MHz, a temperature of 22 ° C., and a humidity of 60%, and the dielectric loss tangent is 0.1. An adhesive tape for joining optical members, wherein the pressure-sensitive adhesive tape is 1 or less.

  (20) The optical tape according to any one of (17) to (19), wherein an average transmittance at a wavelength of 400 to 800 nm is 90% or more under a film thickness of 100 μm. Adhesive tape.

  According to the present invention, a urethane acrylate resin having a functional group number of less than 2, a polyisobutylene resin having a number average molecular weight of 300 to 100,000, and a crosslinking point concentration in the active energy ray-curable composite resin composition is 0.03. By combining the cross-linking agent so as to be ˜0.15 mmol / g, it has excellent foam resistance under high temperature and high temperature and high humidity environment, and at the same time, has both water vapor barrier property, low dielectric property, and adhesiveness, A composite resin composition that can be cured by irradiation with an active energy ray can be provided.

  This active energy ray-curable composite resin composition, and adhesives and pressure-sensitive adhesive tapes obtained by curing the composition with active energy rays are used in applications that require water vapor barrier properties, low dielectric properties, and foam resistance, such as electronic devices. It is possible to apply.

  The active energy ray-curable composite resin composition of the present invention contains a urethane acrylate resin composition (A), a polyisobutylene resin (B), and a crosslinking agent (C), and the urethane acrylate resin composition (A) It is a reaction product of an olefin polymer (a1) having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3), and a (meth) acrylic acid hydroxy compound ( It is a resin composition in which the number of functional groups of the (meth) acryloyl group derived from a3) is less than 2.

  Here, as the olefin polymer (a1) having two or more active hydrogen groups used in the urethane acrylate resin composition (A), for example, a diene compound such as butadiene, isoprene, butene, isobutene, metallic lithium, Polyols obtained by polymerizing in the presence of an anionic polymerization catalyst such as metal potassium and metal sodium and then addition polymerization of alkylene oxide such as ethylene oxide and propylene oxide can be mentioned, and the number average molecular weight is 1,000- 8,000 is preferred. Moreover, the hydrogenated polyol which hydrogenated these can also be mentioned. Specifically, for example, polybutadiene polyol, polyisoprene polyol, polybutene polyol, polyisobutylene polyol, hydrogenated polybutadiene polyol obtained by hydrogenation of these, hydrogenated polyisoprene polyol, hydrogenated polybutene polyol, hydrogenated polyisobutylene polyol, and the like can be given. . Among these olefin polymers having two or more active hydrogen groups, hydrogenated polybutadiene polyols and hydrogenated polyisoprene polyols from the viewpoints of curability by active energy rays, water vapor barrier properties, low dielectric properties, and yellowing resistance. Hydrogenated polybutene polyol and hydrogenated polyisobutylene polyol are preferred.

  When the number of active hydrogen groups of the olefin polymer (a1) is less than 2, it is not preferable because the reaction with the isocyanate compound (a2) cannot be sufficiently performed and the cohesiveness and adhesiveness may be lowered. In addition, when the number average molecular weight is less than 1,000, the compatibility with the polyisobutylene resin (B) may be lowered, and the transparency may be deteriorated. When the number average molecular weight exceeds 8,000, it is sufficient. There is a possibility that it becomes difficult to impart good coatability by imparting cohesiveness or increasing the viscosity.

  In addition to the olefin polymer (a1), the urethane acrylate resin composition (A) of the present invention is not essential, but polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, silicone polyol, castor. Polymers having active hydrogen groups such as oil-based polyols, fluorine-based polyols, and polythiol compounds, and low-molecular polyols may be used in combination.

<Polyester polyol>
Specific examples of the polyester polyol include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid. , Sebacic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, etc. At least one kind of dicarboxylic acid having 36 carbon atoms obtained by dimerization of an unsaturated fatty acid having 18 carbon atoms such as acid, oleic acid or linoleic acid, or an anhydride thereof, ethylene glycol, 1,2- Propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol Heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl ) Those obtained from a polycondensation reaction with one or more low molecular weight polyols having a molecular weight of 500 or less, such as benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like. Also, lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone can be exemplified. Furthermore, a polyester-amide polyol obtained by replacing a part of the low molecular polyol with a low molecular polyamine such as hexamethylene diamine, isophorone diamine or monoethanolamine or a low molecular amino alcohol can also be used.

<Polyether polyol>
Specific examples of the polyether polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol , Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol Small molecules such as Initiates compounds having 2 or more, preferably 2-3 active hydrogen groups such as riols or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. As an agent, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., or alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether And polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran.

<Polycarbonate polyol>
Specific examples of the polycarbonate polyol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin The One or more kinds of low molecular polyols such as methylolpropane and pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, di Examples thereof include those obtained from dealcoholization reaction and dephenol reaction with diaryl carbonates such as phenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate. Moreover, the polyol obtained by transesterification of polycarbonate polyol, polyester polyol, and low molecular weight polyol can also be used.

<Acrylic polyol>
As the acrylic polyol, acrylic acid ester and / or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester), an acrylic acid hydroxy compound having at least one hydroxyl group in the molecule that can be a reaction point, and / or Mention may be made of a methacrylic acid hydroxy compound (hereinafter referred to as a (meth) acrylic acid hydroxy compound) and a polymerization initiator, which is obtained by copolymerizing an acrylic monomer using thermal energy or light energy such as ultraviolet rays or electron beams. it can.

<(Meth) acrylic acid ester>
Specific examples of (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth) acrylate esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. (Meth) such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Acrylic acid alkyl ester, cyclohexyl (meth) acrylate and other (meth) acrylic acid esters with alicyclic alcohols, (meth) acrylic acid phenyl and (meth) acrylic acid aryl esters such as benzyl (meth) acrylate Can be mentioned. Such (meth) acrylic acid esters can be used singly or in combination of two or more.

<(Meth) acrylic acid hydroxy compound>
Examples of the (meth) acrylic acid hydroxy compound include those having at least one hydroxyl group in the molecule that can be a reaction point with the isocyanate compound (a2). Specifically, for example, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid-4-hydroxybutyl, Di (meth) acrylic acid glycerin, methacrylic acid-2-hydroxy-3-acryloyloxypropyl, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, (meth) acrylic acid-2-hydroxy-3- Examples include phenoxypropyl and cyclohexanedimethanol (meth) acrylate.

<Silicone polyol>
Specific examples of the silicone polyol include a vinyl group-containing silicone compound obtained by polymerizing γ-methacryloxypropyltrimethoxysilane and the like, and α, ω-dihydroxypolydimethylsiloxane having at least one terminal hydroxyl group in the molecule, α, Examples thereof include polysiloxanes such as ω-dihydroxypolydiphenylsiloxane.

<Castor oil-based polyol>
Specific examples of the castor oil-based polyol include linear or branched polyester polyols obtained by the reaction of castor oil fatty acid and polyol. Dehydrated castor oil, partially dehydrated castor oil partially dehydrated, hydrogenated castor oil added with hydrogen, and the like can also be used.

<Fluorine-based polyol>
Specific examples of the fluorine-based polyol include linear or branched polyols obtained by a copolymerization reaction using a fluorine-containing monomer and a monomer having a hydroxy group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyl trifluoroethylene. Etc. Examples of the monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and vinyl hydroxyalkyl crotonates. Examples thereof include monomers having a hydroxyl group such as hydroxyl group-containing vinyl carboxylate or allyl ester.

<Polythiol compound>
Specific examples of the polythiol compound include, for example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6 -Hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1, 2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis-thiomalate ( 2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mecaptoethyl ester) Captoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3 -Mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ) Ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mer) Ptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane), 1,2 -Dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercapto) Methyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1 , 3-Bis (mercaptomethyleneoxy) benzene, 1,4-bi (Mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3- Trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) Benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mer Putmethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1, 3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1, 2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4 Tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1, , 4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5 -Tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (Mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1, 4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p -Methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 2,5 -Dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4, 6-tetrachloro-1,5-bis (mercaptomethyl) benzene, 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino 4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym -Triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thio Butyloxy-4,6-dithiol-sym-triazine, 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2- Bis (mercaptoethylthio) benzene 1,3-bis (mercaptoethylthio) ) Benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mermercaptomethylthio) benzene, 1,2,4-tris (mermercaptomethylthio) benzene, 1,3,5-tris (Mermercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1 , 2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3 4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethyl) Thio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis ( 2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ) Ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris ( Mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoe) Ruthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, Bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercapto) Ethyl) disulfide, bis (mercaptopropyl) disulfide, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate) ), Hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), Hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl Ether bis (3-mercaptopropionate), 1,4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thio Glycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester) ), Dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropion Acid bis (2,3-dimercaptopropyl ester), dithi Glycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 3,4-thiophenedithiol, 2,5-dimercapto-1,3,4-thiadiazole, etc. Can be mentioned.

<Low molecular polyol>
Examples of the low molecular weight polyol include polyols having a number average molecular weight of 500 or less, and specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol 3,3-dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A Bis (β-hydroxyethyl) Benzene, xylylene glycol, may be mentioned glycerin, trimethylolpropane, pentaerythritol and the like.

  Next, the isocyanate compound (a2) will be described.

  Examples of the isocyanate compound (a2) used in the urethane acrylate resin composition (A) include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, sulfur atom-containing diisocyanates, and their allophanate-modified polyisocyanates. Isocyanate, isocyanurate-modified polyisocyanate, uretdione-modified polyisocyanate, urethane-modified polyisocyanate, burette-modified polyisocyanate, uretoimine-modified polyisocyanate, acylurea-modified polyisocyanate, etc. can be used alone or in combination of two or more, polyisobutylene From the viewpoint of compatibility with the resin (B), water vapor barrier properties, and low dielectric properties, alicyclic diisocyanates are preferred.

<Aromatic diisocyanate>
Specific examples of the aromatic diisocyanate include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4′-diphenylmethane diisocyanate. 2,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate / 4,4′-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl -4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane Isocyanate, m- phenylene diisocyanate, p- phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, can be mentioned 3,3'-dimethoxy-4,4'-diisocyanate.

<Aromatic aliphatic diisocyanate>
Specific examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene or a mixture thereof. Examples thereof include a mixture, ω, ω′-diisocyanato-1,4-diethylbenzene, and the like.

<Aliphatic diisocyanate>
Specific examples of the aliphatic diisocyanate include, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, Ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4 -Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, bis (isocyanate ethyl) ) Carbonate, bis (isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'-diisocyanate, lysine diisocyanate methyl ester, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 2-isocyanatopropyl Examples include -2,6-diisocyanatohexanoate.

<Alicyclic diisocyanate>
Specific examples of the alicyclic diisocyanate include, for example, isophorone diisocyanate, cyclohexyl diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis (4 -Isocyanate-n-butylidene) pentaerythritol, hydrogenated hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2 .1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatepropyl)- 6-Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)- 5- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane, 2-iso Anatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane, 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] -Heptane, hydrogenated hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated hydrogenated tolylene diisocyanate, hydrogenated hydrogenated xylene diisocyanate, hydrogenated hydrogenated tetramethylxylene diisocyanate, etc. . In particular, from the viewpoints of flexibility and compatibility, isophorone diisocyanate or dicyclohexylmethane diisocyanate can be preferably used.

<Sulfur atom-containing diisocyanate>
Specific examples of the sulfur atom-containing diisocyanate include, for example, thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, diphenyl sulfide-2,4′-diisocyanate. , Diphenyl sulfide-4,4′-diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanate dibenzylthioether, bis (4-isocyanatomethylphenyl) sulfide, 4,4′-methoxyphenylthioethylene glycol-3 , 3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide 5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5, 5'-diisocyanate, 3,3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyl disulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone- 3,3′-diisocyanate, benzidine sulfone-4,4′-diisocyanate, diphenylmethanesulfone-4,4′-diisocyanate, 4-methyldiphenylsulfone-2,4′-diisocyanate, 4,4′-dimethoxydiphenylsulfone- 3,3'- Diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanate benzyldisulfone, 4,4′-dimethyldiphenylsulfone-3,3′-diisocyanate, 4,4′-di-tert-butyldiphenylsulfone-3,3 '-Diisocyanate, 4,4'-methoxyphenylethylenesulfone-3,3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4' -Isocyanate phenol ester, 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanate phenol ester, 4-methyl-3-isocyanatophenylsulfonylanilide-3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine- , 4′-diisocyanate, 4,4′-methoxyphenylsulfonyl-ethylenediamine-3,3′-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3′-isocyanate, thiophene-2,5 -Diisocyanate, 1,4-dithian-2,5-diisocyanate and the like can be mentioned.

<Polyisothiocyanate compound>
Specific examples of the polyisothiocyanate compound include 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, P-pheny. Range isopropylidene diisothiocyanate, cyclohexane diisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4-diisothiocyanate toluene, 2, 5-diisothiocyanate-m-xylene, 4,4-diisothiocyanate-1,1′-biphenyl, 1,1′-methylenebis (4-isothiocyanatebenzene), 1,1′-methylenebis (4-isothiocyanate) -2-methylbenzene), 1, '-Methylenebis (4-isothiocyanate-3-methylbenzene), 1,1'-(1,2-ethanediyl) bis (4-isothiocyanatebenzene), 4,4'-diisothiocyanate benzophenone, 4,4 '-Diisothiocyanate-3,3'-dimethylbenzophenone,benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4'-diisocyanate, 2,4,6- Triisothiocyanate-3,5-triazine, hexanedioil diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenecarbonyldiisothiocyanate, 1,4-benzenecarbonyldiisothiocyanate, (2 , 2'-bipyridi ) -4,4′-dicarbonyldiisothiocyanate, thiobis (3-isothiocyanate propane), thiobis (2-isothiocyanate ethane), dithiobis (2-isothiocyanate ethane), 1-isothiocyanate-4-[(2 -Isocyanate) sulfonyl] benzene, thiobis (4-isothiocyanate benzene), sulfonyl bis (4-isothiocyanate benzene), sulfinyl bis (4-isothiocyanate benzene), dithiobis (4-isothiocyanate benzene), 4-isothiocyanate- 1-[(4-Isocyanatophenyl) sulfonyl] -2-methoxy-benzene, 4-methyl-3-isothiocyanate benzenesulfonyl-4′-isocyanate phenyl ester, 4-methyl-3-isothiocyanate Nzensulfonylanilide-3′-methyl-4′-isocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithian-2,5-diisothiocyanate, 1-isocyanate-3-isothiocyanate propane, 1- Isocyanate-5-isothiocyanate pentane, 1-isocyanate-6-isothiocyanate hexane, isothiocyanate carbonyl isocyanate, 1-isocyanate-4-isothiocyanate cyclohexane, 1-isocyanate-4-isothiocyanate benzene, 4-methyl-3-iso Thiocyanate-1-isothiocyanate benzene, 2-isocyanate-4,6-diisothiocyanate-1,3,5-triazine, 4-isothiocyanate-4′-isothiocyanate diphenylsulfate I de, and 2-isothiocyanate-2'isothiocyanate diethyl disulfide and the like.

<(Meth) acrylic acid hydroxy compound (a3)>
Next, the (meth) acrylic acid hydroxy compound (a3) will be described.

  The (meth) acrylic acid hydroxy compound (a3) used for introducing the functional group of the (meth) acryloyl group of the urethane acrylate resin composition (A) has at least 1 in the molecule that can be a reaction point with the isocyanate compound (a2). Specifically, for example, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, ( (Meth) acrylic acid-4-hydroxybutyl, glycerin di (meth) acrylate, methacrylic acid-2-hydroxy-3-acryloyloxypropyl, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, (meth ) -2-hydroxy-3-phenoxypropyl acrylate, cyclohexane dimethacrylate (meth) acrylate Lumpur, and the like.

Further, from the viewpoint of enhancing the compatibility with the olefin polymer (a1) and the polyisobutylene resin (B), the hydroxy compound (meth) acrylate (a3) has a solubility parameter of 23.4 J ^1/2 cm ^{−3 / 2} or less (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid-4-hydroxybutyl, and (meth) acrylic acid cyclohexanedimethanol are preferred. 23.4J ^1/2 compatibility decreases transparency exceeds cm ^-3/2 When olefin polymer (a1) or polyisobutylene resin (B) may be deteriorated.

  The amount of the (meth) acrylic acid hydroxy compound (a3) to be introduced is adjusted so that the number of functional groups of (meth) acryloyl groups per molecule of the urethane acrylate resin composition (A) is less than 2. By adjusting the number of functional groups of the (meth) acryloyl group to be less than 2, the urethane resin skeleton of the urethane acrylate resin composition (A) is in a branch polymer state, so that it is compatible with the polyisobutylene resin (B). In addition to improving the water vapor barrier property, the water vapor barrier property can be enhanced. When the number of functional groups of the (meth) acryloyl group in the urethane acrylate resin composition (A) is 2 or more, the deterioration of transparency and the decrease in water vapor barrier properties accompanying the decrease in compatibility with the polyisobutylene resin (B) May occur.

  The number average molecular weight of the urethane acrylate resin composition (A) thus obtained is preferably in the range of 2,000 to 40,000, and more preferably in the range of 5,000 to 20,000. If it is less than the lower limit, there is a risk of causing a decrease in adhesiveness. If the upper limit is exceeded, coating due to a decrease in transparency or an increase in viscosity due to a decrease in compatibility with the polyisobutylene resin (B). May cause sexual deterioration.

  Moreover, as a urethane group density | concentration of a urethane acrylate resin composition (A), it is preferable that it is the range of 0.2-3.0 mmol / g, and it is further more preferable that it is the range of 0.2-0.7 mmol / g. preferable. If it is less than the lower limit, there is a risk of lowering the adhesiveness and heat resistance due to a decrease in cohesiveness. If the upper limit is exceeded, the transparency of the polyisobutylene resin (B) is reduced. May cause degradation.

  Next, the polyisobutylene resin (B) blended in the active energy ray-curable composite resin composition in the same manner as the urethane acrylate resin composition (A) will be described.

  The polyisobutylene resin (B) is a resin containing a structure derived from the isobutylene monomer represented by the general formula (1) having a number average molecular weight of 300 to 100,000. By blending the polyisobutylene resin (B) having a number average molecular weight of 300 to 100,000, the free volume voids of the polymer can be reduced, and excellent water vapor barrier properties can be imparted. The polyisobutylene resin (B) having a number average molecular weight in the range of 300 to 5,000 is particularly excellent in compatibility with the urethane acrylate resin composition (A), and has excellent water vapor barrier properties. Since transparency can be provided, it is more preferable. When the polyisobutylene resin (B) used has a number average molecular weight of less than 300, it causes a decrease in adhesiveness and a decrease in foaming resistance due to a decrease in cohesiveness. Compatibility with the composition (A) is greatly reduced, resulting in a decrease in water vapor barrier properties and a decrease in coating properties accompanying an increase in viscosity.

<Polyisobutylene resin (B)>
Specific examples of the polyisobutylene resin (B) used in the present invention include, for example, polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, and an isobutylene and butadiene. Examples thereof include copolymers and halogenated butyl rubber obtained by brominating or chlorinating these copolymers. These polyisobutylene resins (B) can be used alone or in combination of two or more. In addition, when polyisobutylene resin (B) is a copolymer, it is preferable that the structural unit which consists of isobutylene is contained most in all the structural units.

  Further, the polyisobutylene resin (B) may be a polyisobutylene resin having an unsaturated bond at the end of the resin and inside the molecule, but from the viewpoint of weather resistance and water vapor barrier properties, polymerization and hydrogenation reaction A resin containing a large number of structural units composed of isobutylene having no unsaturated bond in the main chain and side chain that can form a dense molecular structure due to the disappearance of the unsaturated bond is preferable, hydrogenated polyisobutylene, or water A copolymer of added isobutylene and n-butene is particularly preferred.

The unsaturated bond content of hydrogenated polyisobutylene or a copolymer of hydrogenated isobutylene and n-butene can be measured by the iodine value test method of chemical products of JIS K0070, and has water vapor barrier properties and weather resistance. from the viewpoint iodide it is preferably iodine value is not more than 50gI ₂ / 100g.

  Furthermore, the content of the polyisobutylene resin (B) in the active energy ray-curable composite resin composition is preferably 5 to 60% by mass, and more preferably 5 to 40% by mass. When the amount is less than 5% by mass, the water vapor barrier property may not be sufficiently obtained. When the amount exceeds 60% by mass, the compatibility is deteriorated, and the adhesiveness and foaming resistance associated with the decrease in transparency and cohesion are deteriorated. May cause degradation.

<Crosslinking agent (C)>
In addition to the urethane acrylate resin composition (A) and the polyisobutylene resin (B), the active energy ray-curable composite resin composition of the present invention maintains the performance balance of water vapor barrier properties, low dielectric properties, and adhesive properties. From the viewpoint of imparting foam resistance, the active energy ray-curable composite resin composition contains a crosslinking agent (C).

  The cross-linking agent (C) is not particularly limited as long as it is a compound that can react with at least one of the urethane acrylate resin composition (A) and the polyisobutylene (B), but from the viewpoint of reactivity and availability. Bifunctional or higher functional epoxy acrylate resins, urethane acrylate resins, polyester acrylate resins, polyether acrylate resins, (meth) acrylic acid esters, and epoxy resins, and the like. Among these crosslinking agents, water vapor barrier properties, A urethane acrylate resin is preferable from the viewpoint of a balance of low dielectric properties, adhesiveness, compatibility, and foam resistance. Moreover, these crosslinking agents can be used individually or in combination of 2 or more types.

<Bifunctional or higher epoxy acrylate resin>
Specific examples of the bifunctional or higher functional epoxy acrylate resins include epoxy acrylate resins obtained by reacting known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like with (meth) acrylic acid. Yes, bisphenol A EO adduct di (meth) acrylic acid, bisphenol A PO adduct di (meth) acrylic acid, and the like.

<Bifunctional or higher urethane acrylate resin>
A specific example of the bifunctional or higher urethane acrylate resin is, for example, a reaction product of a polyol having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3). And a urethane acrylate resin having 2 or more functional groups having a (meth) acryloyl group derived from the (meth) acrylic acid hydroxy compound (a3). Examples of the polyol having two or more active hydrogen groups include active hydrogen such as olefin polyol, polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, silicone polyol, castor oil polyol, fluorine polyol, and polythiol compound. Examples thereof include a polymer having a group and a low molecular polyol. Among these polyols, olefinic polyols are preferred from the viewpoint of a balance between water vapor barrier properties, low dielectric properties, and foam resistance.

<Bifunctional or higher polyester acrylate resin>
Specific examples of the bifunctional or higher functional polyester acrylate resin include a polyester acrylate resin obtained by reacting the polyester polyol with (meth) acrylic acid.

<Bifunctional or higher polyether acrylate resin>
Specific examples of the bifunctional or higher functional polyether acrylate resin include a polyether acrylate resin obtained by reacting the above polyether polyol with (meth) acrylic acid, for example.

<Bifunctional (meth) acrylic acid ester>
Specific examples of the bifunctional or higher functional (meth) acrylic acid ester include, for example, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di (meth) acrylic acid-1,4-butanediol, Di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) acrylic acid isononanediol, di (meth) ) Dioxane glycol acrylate, di (meth) acrylic acid-1,10-decanediol, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol di (meth) acrylate-tricyclo Decane, trimethylolpropane tri (meth) acrylate, 2, 2, 4, , 6,6-hexa [2- (methacryloyloxy) -ethoxy] -1,3,5-triaza-2,4,6-triphosphorine, di (meth) acrylic acid polytetramethylene glycol, di (meth) acrylic acid -3-methyl-1,5-pentanediol, trimethylolpropane acrylic acid benzoate, hydroxypivalic acid neopentyl glycol acrylic acid adduct, 2-hydroxy-3-acryloyloxypropyl methacrylate, tri (meth) acrylic acid Pentaerythritol, pentaerythritol tetra (meth) acrylate, dipetaerythritol hexa (meth) acrylate, dendrimer acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorenediacrylate, tris- (2- Acryloxyethyl Isocyanurate, di (meth) ethylene glycol acrylate, 2- (meth) may be mentioned ethyl acrylate acid phosphate and the like.

<Bifunctional or higher epoxy resin>
Specific examples of the bifunctional or higher functional epoxy resin include, for example, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl). Cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol poly Glycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane Li glycidyl ether, adipic acid diglycidyl ester, o- phthalic acid diglycidyl ester, triglycidyl - tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol -S- diglycidyl ether, and the like.

  Such a crosslinking agent (C) has a functional group concentration of the crosslinking agent (C) in the active energy ray-curable composite resin composition (in the present invention, this is the crosslinking point concentration) of 0.03 to 0.03. It is contained so as to be 0.15 mmol / g. The cross-linking agent (C) can react with at least one of the urethane acrylate resin composition (A) and the polyisobutylene (B). By mix | blending this crosslinking agent (C), the deformation | transformation of the adhesive agent by foaming can be suppressed and foaming resistance can be provided.

  The crosslinking agent (C) preferably has a distance between crosslinking points in the range of 500 to 10,000. If the distance between the cross-linking points is less than the lower limit, there is a risk of causing a decrease in water vapor barrier properties and adhesiveness. If the distance exceeds the upper limit, it is difficult to suppress deformation of the adhesive due to foaming, so foam resistance is prevented. It may cause a decline in sex.

  The “distance between crosslinking points” in the present invention is a quotient of the number average molecular weight and the number of functional groups of the crosslinking agent (C). Specifically, for example, the number average molecular weight is 10,000 and the tetrafunctional crosslinking agent. In this case, the distance between cross-linking points is 2,500.

<Tackifier (D)>
In addition to the urethane acrylate resin composition (A), the polyisobutylene resin (B), and the crosslinking agent (C), the active energy ray-curable composite resin composition of the present invention has improved adhesion, low dielectric constant, and From the viewpoint of further improving the water vapor barrier property, it is preferable to add a tackifier (D).

  As the tackifier (D), conventionally known ones can be used. For example, hydrogenated rosin or hydrogenated rosin derivatives of rosin derivatives, hydrogenated terpene resins, aromatic modified terpene resins, terpene phenols Hydrogenated terpene derivatives of resin, hydrogenated C5 petroleum resin obtained by copolymerizing C5 fraction, hydrogenated C9 petroleum resin obtained by copolymerizing C9 fraction, C5 fraction, Examples thereof include hydrogenated C5 / C9 petroleum resins obtained by copolymerizing C9 fractions, alicyclic (meth) acrylic acid ester oligomers, and the like.

<Hydrogenated rosin derivatives>
Specific examples of hydrogenated rosin derivatives include unmodified rosin resins such as gum rosin, wood rosin and tall oil rosin, rosin ester resins obtained by esterifying unmodified rosin resins with alcohols, unmodified rosin resins as phenol, m- Examples thereof include hydrogenated products of phenol-modified rosin resins modified with phenols such as cresol, 3,5-xylenol, p-alkylphenol and resorcin. These hydrogenated rosin derivatives can be used alone or in combination of two or more.

<Hydrogenated terpene derivatives>
Specific examples of hydrogenated terpene derivatives include, for example, unmodified terpene resins such as α-pinene polymers, β-pinene polymers, dipentene polymers, and aromatics obtained by modifying unmodified terpene resins with aromatic compounds such as styrene. Examples thereof include a hydrogenated product of a modified terpene resin, a hydrogenated product of a phenol-modified terpene resin obtained by modifying an unmodified terpene resin with a phenol compound such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcin. These hydrogenated terpene derivatives can be used alone or in combination of two or more.

<Hydrogenated C5 / C9 / C5 / C9 petroleum resin>
Specific examples of hydrogenated C5 petroleum resins include, for example, copolymerization of unsaturated hydrocarbons having 5 carbon atoms such as pentene, isoprene, piperine and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha. Examples thereof include hydrogenated products of C5-based petroleum resins such as dicyclopentadiene. Specific examples of hydrogenated products of C9 petroleum resins include, for example, indene, vinyltoluene, α-methylstyrene, β-methylstyrene, etc. produced by thermal decomposition of petroleum naphtha as in C5 petroleum resins. Examples thereof include hydrogenated products of C9 petroleum resins obtained by copolymerizing unsaturated hydrocarbons having 9 carbon atoms. Specific examples of hydrogenated products of C5 / C9 petroleum resins include hydrogenated products of C5 / C9 petroleum resins obtained by copolymerizing the C5 fraction and the C9 fraction. These hydrogenated products of petroleum resins can be used alone or in combination of two or more.

<Aliphatic (meth) acrylic acid ester oligomer>
Specific examples of the alicyclic (meth) acrylic acid ester oligomer include, for example, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate. , At least one alicyclic (meth) acrylic ester such as dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, and aliphatic Examples include alicyclic (meth) acrylate oligomers obtained by copolymerizing with (meth) acrylates.

  Among these tackifiers, C5 petroleum resin hydrogenated product, C9 petroleum resin hydrogenated product, or C5 / C9 based hydrogenated product from the viewpoints of improved adhesion, low dielectric property, water vapor barrier property, and compatibility. A hydrogenated product of petroleum resin is preferable, and a hydrogenated product of C9-based petroleum resin is particularly preferable because of excellent balance of properties and compatibility.

Further, the unsaturated bond content of this tackifier (D) can be measured by the iodine value test method of chemical products of JIS K0070, and the iodine value is 50 gI ₂ from the viewpoint of water vapor barrier properties and weather resistance. / 100 g or less is preferable.

  The softening point of these tackifiers (D) is preferably 80 to 140 ° C. from the viewpoint of adhesiveness and cohesiveness, and more preferably 90 to 120 ° C. from the viewpoint of adhesiveness. When the amount is less than the lower limit, sufficient cohesiveness cannot be obtained and deformation against foaming cannot be suppressed, and foam resistance may be reduced. Moreover, when exceeding an upper limit, there exists a possibility of producing a fall of a softness | flexibility and a fall of adhesiveness.

  The tackifier (D) preferably has a number average molecular weight of 300 to 10,000 having an alicyclic structure, and may be blended in the active energy ray-curable composite resin composition in the range of 5 to 40% by mass. More preferred. By blending the tackifier containing the alicyclic structure, the hydrophobicity of the resin composition is improved, which greatly contributes to the improvement of low dielectric properties and water vapor barrier properties. Moreover, blending the tackifier in the above range is preferable because the balance of transparency and adhesiveness is good. If the blending amount is less than the lower limit, the improvement in adhesion and water vapor barrier properties are not sufficient, and if the blending amount exceeds the upper limit, transparency and adhesion may be deteriorated.

<(Meth) acrylic acid ester (E)>
In addition to the urethane acrylate resin composition (A), the polyisobutylene resin (B), and the cross-linking agent (C), the active energy ray-curable composite resin composition of the present invention has a low viscosity and adhesiveness. From the viewpoint of improvement, (meth) acrylic acid ester (E) or (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester terminal has a number average molecular weight of 1,000 to 500,000. Those partially polymerized so as to be in the range can be used in combination. In the present invention, the (meth) acrylic acid ester (E) is also obtained by partially polymerizing the (meth) acrylic acid ester (E) so that the number average molecular weight is in the range of 1,000 to 500,000. Including.

  Specific examples of the (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester end include, for example, decyl (meth) acrylate (carbon number 10), undecyl (meth) acrylate (carbon number). 11), dodecyl (meth) acrylate [lauryl acrylate] (carbon number 12), tridecyl (meth) acrylate (carbon number 13), tetradecyl (meth) acrylate (carbon number 14), (meth) Pentadecyl acrylate (15 carbon atoms), hexadecyl (meth) acrylate (16 carbon atoms), heptadecyl (meth) acrylate (17 carbon atoms), octadecyl (meth) acrylate (18 carbon atoms), (meth) acrylic acid Nonadecyl (19 carbon atoms), eicosyl (meth) acrylate (20 carbon atoms), heneicosyl (meth) acrylate (2 carbon atoms) ), (Meth) acrylic acid ester having a linear alkyl group such as docosyl (meth) acrylate (22 carbon atoms) at the ester terminal, isomethyl (meth) acrylate (10 carbon atoms), (meth) acrylic Isomyristyl acid (carbon number 14), isostearyl (meth) acrylate (carbon number 18), (meth) acrylic acid-2-propylheptyl (carbon number 10), isoundecyl (meth) acrylate (carbon number 11), Isododecyl (meth) acrylate (12 carbon atoms), isotridecyl (meth) acrylate (13 carbon atoms), isopentadecyl (meth) acrylate (15 carbon atoms), isohexadecyl (meth) acrylate (16 carbon atoms) ), An alkyl group having a branched structure such as isoheptadecyl (meth) acrylate (carbon number 17) at the ester end (meta And acrylic acid esters. Among these (meth) acrylic acid esters, isostearyl (meth) acrylate having a tert-butyl group is particularly preferable because it contributes to low dielectric constant because the molar volume increases and the dipole moment decreases.

  Moreover, as long as the performance does not deteriorate, (meth) acrylic acid ester, alicyclic (meth) acrylic acid ester, aromatic (meth) acrylic acid ester having an alkyl group having 1 to 9 carbon atoms at the ester terminal, Cyclic ether-based (meth) acrylic acid esters, the aforementioned (meth) acrylic acid hydroxy compounds, other (meth) acrylic acid derivatives, or acrylamide derivatives can also be used in combination. Among these, it is preferable to use an alicyclic (meth) acrylic acid ester because the compatibility between the polyisobutylene resin (B) and the (meth) acrylic acid ester and the water vapor barrier property can be improved.

<C1-C9 (meth) acrylic acid ester>
Specific examples of the (meth) acrylic acid ester having an alkyl group having 1 to 9 carbon atoms at the ester terminal include, for example, methyl (meth) acrylate (carbon number 1), ethyl (meth) acrylate (carbon number 2), Propyl (meth) acrylate (3 carbon atoms), isopropyl (meth) acrylate (3 carbon atoms), butyl (meth) acrylate (4 carbon atoms), (meth) acrylic acid-tert-butyl (4 carbon atoms) , Isobutyl (meth) acrylate (4 carbon atoms), isoamyl (meth) acrylate (5 carbon atoms), pentyl (meth) acrylate (5 carbon atoms), hexyl (meth) acrylate (6 carbon atoms), ( 2-ethylhexyl (meth) acrylate (8 carbon atoms), octyl (meth) acrylate (8 carbon atoms), nonyl (meth) acrylate (9 carbon atoms), isononyl (meth) acrylate It can be mentioned the number 9), such as carbon.

<Aliphatic (meth) acrylic acid ester>
Specific examples of the alicyclic (meth) acrylic acid ester include, for example, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Mention may be made of dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate and the like.

<Aromatic (meth) acrylic acid ester>
Specific examples of the aromatic (meth) acrylic acid ester include, for example, benzyl (meth) acrylate (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid-o-phenylphenol, (meth) acrylic Examples include acid-p-cumylphenol ethyl, (meth) acrylic acid-3-phenoxybenzyl, (meth) acrylic acid phenoxyethylene glycol, and (meth) acrylic acid phenoxydiethylene glycol.

<Cyclic ether-based (meth) acrylic acid ester>
Specific examples of the cyclic ether (meth) acrylic acid ester include, for example, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and (meth) acrylic. Acid-4-hydroxybutyl glycidyl ether, (meth) acrylic acid-3-oxetanylmethyl, (meth) acrylic acid-3-methyloxetanylmethyl, (meth) acrylic acid-3-ethyloxetanylmethyl, (meth) acrylic acid- Examples thereof include 3-butyloxetanylmethyl, (meth) acrylic acid-3-hexyloxetanylmethyl, and the like.

<(Meth) acrylic acid derivatives and acrylamide derivatives>
Specific examples of other (meth) acrylic acid derivatives include carboxyl group-containing (meth) acrylic acid derivatives such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, (meth ) Alkyl carbitol group-containing (meth) acrylic acid derivatives such as ethyl carbitol acrylate, (meth) acrylic acid-2-ethylhexyl carbitol (meth) acrylate, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- Alkoxy group-containing (meth) acrylic acid derivatives such as (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane, (meth) acrylic Acid polyethylene glycol Glycol-based (meth) acrylic acid derivatives such as (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol, (meth) acrylic acid-2,2,2-trifluoro Ethyl, (meth) acrylic acid-2,2,3,3-tetrafluoropropyl, (meth) acrylic acid-1H, 1H, 5H-octafluoropentyl, (meth) acrylic acid-3,3,4,4, Fluorine-based (meth) acrylic acid derivatives such as 5,5,6,6,7,7,8,8,8-tridecafluorooctyl, or other derivatives such as (meth) acrylic acid oxyethyl hexahydrophthalimide And (meth) acrylic acid morpholine.

  Specific examples of acrylamide derivatives include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-sec. N-hydroxyalkyl such as butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, and N-hydroxyalkyl such as N-hydroxyethyl (meth) acrylamide (Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N , N-Di-n-propyl (Meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, or N, N-dialkyl (meth) acrylamide of N, N-dihexyl (meth) acrylamide, etc. Can be mentioned.

  By using the (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester terminal, it is easy to maintain a low dielectric property as compared with a general (meth) acrylic acid ester. Therefore, it is preferable. The content of the (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester terminal is preferably 70% by mass or less in the active energy ray-curable composite resin composition.

  If the content of (meth) acrylic acid ester (E) exceeds 70% by mass, the frequency dependence of the relative permittivity increases, and the relative permittivity may increase in the low frequency range and the water vapor barrier property may decrease. There is. Moreover, when the carbon number of the alkyl group of (meth) acrylic acid ester (E) is less than 10, there is a risk that the effect of low dielectric properties is reduced, and when the carbon number exceeds 22, the crystallinity is high, Transparency may be reduced.

  Moreover, Tg in the homopolymer of (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at the ester terminal used in combination with the active energy ray-curable composite resin composition is −80 to 10 ° C. It is preferable that it is preferably −60 to 0 ° C. If the Tg of the homopolymer is less than −80 ° C., the adhesiveness may decrease due to a decrease in cohesion, and if it exceeds 10 ° C., the adhesiveness may decrease due to an increase in elastic modulus. is there.

  Next, a specific method for producing the active energy ray-curable composite resin composition will be described.

As a manufacturing method of the active energy ray hardening-type composite resin composition of this invention, the urethane acrylate resin composition (A) manufactured previously, polyisobutylene resin (B), a crosslinking agent (C), and as needed , A tackifier (D), a method obtained by blending (meth) acrylic acid ester (E) (hereinafter referred to as a production method by a blend method), a polyisobutylene resin having no active hydrogen group (B), , A method of synthesizing the urethane acrylate resin composition (A) in the components of the crosslinking agent (C), if necessary, the tackifier (D), and the (meth) acrylic acid ester (E) (hereinafter referred to as a production method by a one-pot method) It is roughly divided into two manufacturing methods.
These production methods are not particularly limited, and are appropriately selected depending on the ease of adjustment of the number of functional groups of the acryloyl group and production stability.

<Representative examples of production methods by blending method>
First step: An isocyanate compound (a2), a hydroxy group-containing acrylate compound (a3), and a polymerization inhibitor are charged in an amount in which the isocyanate group becomes excessive with respect to the hydroxyl group, and 40 to 90 in a dry air stream. An acryloyl group-containing isocyanate compound is produced by urethanation at ° C.
Second step: The olefin polymer (a1) and the isocyanate compound (a2) are charged in an amount in which the active hydrogen groups are excessive with respect to the isocyanate groups, and the nitrogen gas or a dry air stream is used in a flow of 40 to 90. The active hydrogen group-terminated urethane prepolymer I is produced by urethanization reaction at ° C.
Third step: Under a dry air stream, the active hydrogen group-terminated urethane prepolymer I obtained in the second step is charged with the acryloyl group-containing isocyanate compound obtained in the first step, and the isocyanate group is substantially determined by IR analysis. The urethane acrylate resin composition (A) is produced by urethanation at 40 to 90 ° C. until it no longer exists.
Fourth step: The urethane acrylate resin composition (A) obtained in the third step is added to the polyisobutylene resin (B), the crosslinking agent (C), the tackifier (D), and the (meth) acrylic ester as required. (E) is charged and mixed at 20 to 90 ° C. to obtain an active energy ray-curable composite resin composition.

<Representative example of manufacturing method by one pot method>
First step: In the polyisobutylene resin (B), the crosslinking agent (C), if necessary, the tackifier (D), and the (meth) acrylic acid ester (E), the isocyanate compound (a2) and the hydroxy group An acryloyl group-containing isocyanate compound is prepared by charging an acrylate compound (a3) and a polymerization inhibitor in an amount of excess isocyanate groups with respect to hydroxyl groups, and urethanating at 40 to 90 ° C. in a dry air stream. A mixed solution containing is produced.
Second step: The mixed solution of the acrylolyl group-containing isocyanate compound obtained in the first step is charged with the olefin polymer (a1) and, if necessary, the isocyanate compound (a2), and the isocyanate group is substantially determined by IR analysis. The active energy ray-curable composite resin composition is synthesized by urethanation at 40 to 90 ° C. until it is no longer present.

  Here, the “amount of excess isocyanate group” means that the molar ratio of the isocyanate group of the isocyanate compound to the active hydrogen group of the olefin polymer exceeds 1 when R = isocyanate group / active hydrogen group when the raw materials are charged. And preferably 1.2 or more. When the amount is less than the lower limit, the obtained active energy ray-curable composite resin composition tends to be thickened or gelled, which may cause a decrease in compatibility or a decrease in adhesiveness.

  The “amount of excess active hydrogen group” means that the molar ratio of the isocyanate group of the isocyanate compound to the active hydrogen group of the olefin polymer is less than 1 when R = isocyanate group / active hydrogen group. It is to become. When it becomes more than the upper limit, the obtained active energy ray-curable composite resin composition is liable to be thickened or gelled, which may cause a decrease in compatibility or a decrease in adhesiveness.

  Moreover, as reaction temperature of the urethanation reaction at the time of synthesize | combining an acryloyl group containing isocyanate compound and a urethane acrylate resin composition (A), 40-90 degreeC is preferable and 40-60 degreeC is still more preferable. When the reaction temperature exceeds the upper limit, acryloyl group self-polymerization may occur.

  The reaction time for performing the urethanization reaction at the above temperature varies depending on the component to be polymerized and the temperature, but is generally adjusted within 10 hours, preferably 1 to 5 hours to complete the urethanization reaction. Is preferred. If it exceeds 10 hours, coloring or self-polymerization may occur.

  Furthermore, in order to adjust the reaction time of the urethanization reaction, a known urethanization catalyst can be used. Specific examples of the urethanization catalyst include organic metal compounds such as dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof. These catalysts can be used alone or in combination of two or more, and it is preferable to add 50 ppm to 5,000 ppm with respect to the resin composition.

<Polymerization inhibitor>
Further, a polymerization inhibitor can be used in combination in order to suppress the self-polymerization of the acryloyl group. Specific examples of the polymerization inhibitor include, for example, 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, 2,6-di-tert-butyl-p-cresol, 1,1-diphenyl-2 -Picrylhydrazyl free radical, hydroquinone, hydroquinone monomethyl ether, phenothiazine, ammonium-N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine aluminum salt and the like. These polymerization inhibitors can be used alone or in combination of two or more, and it is preferable to add 100 ppm to 5,000 ppm with respect to the resin composition.

  When the active energy ray-curable composite resin composition of the present invention is produced in the presence of an organic solvent, various organic solvents that can dissolve each component without affecting the reaction can be used as the solvent. Further, if necessary, after the active energy ray-curable composite resin composition is obtained, the organic solvent can be removed to make a solventless system.

<Organic solvent>
Specific examples of the organic solvent include aliphatic hydrocarbons such as hexane, octane, decane, nonane, undecane, and alicyclic groups such as cyclohexane, cyclooctane, cyclohexene, cycloheptane, cyclopentane, methylcyclohexane, and methylcyclopentane. Hydrocarbons, aromatic hydrocarbons such as toluene, styrene, ethylbenzene, cumene and anisole, ketones such as methyl isobutyl ketone and cyclohexanone, esters such as butyl acetate and isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl Glycol ether esters such as ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethers such as dioxane, methylene iodide, mono Halogenated hydrocarbons such as chlorobenzene, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. These solvents can be used alone or in combination of two or more.

  Moreover, the thermal stability at the time of reaction can be improved by synthesize | combining a urethane acrylate resin composition (A) or an active energy ray hardening-type composite resin composition in (meth) acrylic acid ester (E). Moreover, since the polyisobutylene resin (B) to be blended can be uniformly dispersed in the resin composition by adding (meth) acrylic acid ester (E), the water vapor barrier property and compatibility can be improved. it can.

  The active energy ray-curable composite resin composition of the present invention thus obtained has an acryloyl group contained in the composition reacted and cured, so that the active energy ray is an electron beam, an ultraviolet ray, or a visible ray. Light can be used. In addition, when curing with an electron beam, it is unnecessary, but when curing with ultraviolet rays, a photopolymerization initiator can be used from the viewpoint of shortening the polymerization time or reducing the monomer component.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it initiates photopolymerization, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, and aromatic sulfonyl chlorides. Photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, An acyl phosphine oxide photopolymerization initiator or the like can be used.

<Benzoin ether photopolymerization initiator>
Specific examples of the benzoin ether photopolymerization initiator include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (Trade name: Irgacure 651, manufactured by BASF), anisole methyl ether, and the like.

<Acetophenone photopolymerization initiator>
Specific examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4 -(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl- Propan-1-one (trade name: Irgacure 1173, manufactured by BASF), methoxyacetophenone and the like can be mentioned.

<Α-ketol photopolymerization initiator>
Specific examples of the α-ketol photopolymerization initiator include, for example, 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane- 1-one etc. are mentioned.

<Aromatic sulfonyl chloride photopolymerization initiator>
Specific examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like.

<Photoactive oxime-based photopolymerization initiator>
Specific examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.

<Benzoin-based photopolymerization initiator>
Specific examples of the benzoin photopolymerization initiator include benzoin and the like.

<Benzyl photopolymerization initiator>
Specific examples of the benzyl photopolymerization initiator include benzyl and the like.

<Benzophenone photopolymerization initiator>
Specific examples of the benzophenone photopolymerization initiator include, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio). ) Phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′- Examples thereof include bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4′-dimethylaminobenzophenone.

<Ketal photopolymerization initiator>
Specific examples of the ketal photopolymerization initiator include benzyldimethyl ketal.

<Thioxanthone photopolymerization initiator>
Specific examples of the thioxanthone photopolymerization initiator include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropyl Examples include thioxanthone, 2,4-diisopropylthioxanthone, dodecyl thioxanthone and the like.

<Acylphosphine photopolymerization initiator>
Specific examples of the acylphosphine photopolymerization initiator include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, Bis (2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-( 1-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) Octylphosphine oxide, bis ( -Methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2- Methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropane-1 -Yl) phosphine oxide, bis (2,4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine Oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, (2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2 , 6-Dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide Bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -2,3,5,6-tetramethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethoxyoxybenzoyl-2, 4,6-trimethylbenzoyl-n-butylphosphine Xoxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide, 1,10-bis [bis (2,4 , 6-trimethylbenzoyl) phosphine oxide] decane, tri (2-methylbenzoyl) phosphine oxide, and the like.

  Among these photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, which is an acetophenone-based photopolymerization initiator (especially with little absorption in the visible light region, hardly yellowing, has low oxygen inhibition and excellent surface curability) Trade name: Irgacure 184, manufactured by BASF) and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Irgacure 1173, manufactured by BASF) are preferable.

  The addition amount of the photopolymerization initiator is not particularly limited, but it is preferably added in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable composite resin composition. If it is less than the lower limit, there is a risk of damage to the member or the influence of the remaining monomer component due to irradiation with active energy rays for a long time. There is a risk that the performance is lowered, and further, the active energy ray does not reach the deep part, resulting in poor curing.

<Photosensitizer>
Moreover, in order to improve photopolymerizability, a photoinitiator and a photosensitizer can be used. The photosensitizer is not particularly limited and known ones can be used. Specific examples thereof include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Isoamyl dimethylaminobenzoate, 4, 4- dimethylamino benzophenone, 4, 4- diethylamino benzophenone etc. are mentioned.

  The active energy ray-curable composite resin composition of the present invention thus obtained can be used as needed with a tackifier, a silane coupling agent, a flame retardant, an antioxidant, a light stabilizer, a leveling agent, an increase agent. For adding adhesives such as adhesives, antistatic agents, surface lubricants, fluorescent brighteners, fillers and curing with active energy ray-curable composite resin adhesives or active energy rays to obtain adhesive tapes It can be an adhesive.

  The viscosity of the active energy ray-curable composite resin adhesive or the adhesive for curing with active energy rays to obtain a pressure-sensitive adhesive tape is not particularly limited as long as it does not affect the performance. If it is the range of -50,000 mPa * s, it can coat by methods, such as a well-known bar coat, roll coat, spin coat, dip coat, gravure coat, flow coat, or spray coat.

<Manufacturing method of adhesive tape>
Next, a method for obtaining a pressure-sensitive adhesive tape by curing an adhesive composed of the active energy ray-curable composite resin composition of the present invention with active energy rays by ultraviolet rays will be described.
First step: An adhesive comprising an active energy ray-curable composite resin composition prepared by adding a photopolymerization initiator in advance is applied to a release-treated sheet (separator), and adhesive / separator 2 A layer structure or a three-layer structure of separator / adhesive / separator coated with a separator is formed after coating.
2nd process: It hardens | cures by irradiating an ultraviolet-ray from the upper part of a separator, a lower part, or both.

  Here, the separator is not particularly limited as long as the cured pressure-sensitive adhesive tape can be peeled off from the separator, but in general, a plastic made of a silicone-based, fluorine-based, or long-chain alkyl-based release agent alone or in combination of two or more types. A separator treated with a film can be used. Among these, a separator treated with a silicone system can be particularly preferably used from the viewpoint of easy peeling.

  Examples of the plastic film used for the separator include polyethylene, polypropylene, polyethylene terephthalate, and polyester film having a thickness of about 5 to 200 μm, and polyethylene terephthalate is preferably used from the viewpoint of surface smoothness and strength.

  The film thickness of the adhesive is not particularly limited as long as the performance does not deteriorate, but it is preferably adjusted in the range of 5 to 500 μm from the viewpoint of adhesiveness and water vapor barrier properties. If it is less than the lower limit value, the adhesiveness may be insufficient, and there may be a problem that the adhesive peels off over time or the water vapor barrier property becomes insufficient. Moreover, when exceeding an upper limit, there exists a possibility that hardening to a deep part may become inadequate.

Examples of the apparatus that irradiates ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm. ² is preferred. This irradiation energy is also applied to the curing of the active energy ray-curable composite resin adhesive.

The water vapor permeability measured in accordance with JIS K7129 of the active energy ray-curable composite resin adhesive thus obtained and the pressure-sensitive adhesive tape was a film thickness of 25 μm, a temperature of 40 ° C., and a humidity. It is preferably 100 g / (m ² · 24 h) or less under 90% condition, and more preferably 60 g / (m ² · 24 h) or less. When the upper limit is exceeded, next-generation transparent electrodes such as silver and copper are greatly affected by moisture such as water vapor, and there is a risk of short circuit between the electrodes due to ion migration.

  Further, the dielectric constant of the adhesive cured product of the active energy ray-curable composite resin adhesive and the pressure-sensitive adhesive tape is preferably 3.5 or less under the conditions of a frequency of 1 MHz, a temperature of 22 ° C., and a humidity of 60%. 3.0 or less is more preferable. If the upper limit value is exceeded, there is a risk that it will be difficult to reduce the sensitivity due to the noise signal or to make it thinner.

  The dielectric loss tangent is preferably 0.1 or less, more preferably 0.05 or less, under the conditions of a frequency of 1 MHz, a temperature of 22 ° C., and a humidity of 60%. Exceeding the upper limit may cause damage to the member due to heat storage.

  The active energy ray-curable composite resin adhesive and the adhesive tape obtained from the active energy ray-curable composite resin composition of the present invention are suitably used for joining electronic devices that combine an image display device such as a liquid crystal display and a touch panel. Therefore, from the viewpoint of visibility, the average transmittance at a wavelength of 400 to 800 nm is preferably 90% or more under the condition of a film thickness of 100 μm. If it is less than the lower limit, the visibility may be reduced. In addition, the HAZE value at this time is preferably 1% or less. If the upper limit is exceeded, the visibility may be reduced.

  The active energy ray-curable composite resin adhesive and the adhesive tape obtained from the active energy ray-curable composite resin composition of the present invention are limited to the use of an electronic device in which an image display device such as a liquid crystal display is combined with a touch panel. Not a thing, organic EL display device, polarizing plate such as PDP, retardation plate, optical compensation film, brightness enhancement film, light guide plate, reflection film, antireflection film, transparent conductive film, design film, decorative film, surface protection film It can also be applied to bonding and sealing of prisms, lenses, color filters, transparent substrates, and members in which these are laminated.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Synthesis of urethane acrylate resin composition (A)>
<Synthesis Example 1>
In a reaction apparatus equipped with a stirrer, a thermometer, a heating device, and a distillation column, 369.3 g of 2-hydroxypropyl acrylate (hereinafter, 2-HPA) and 630 of isophorone diisocyanate (hereinafter, IPDI) are used. 0.7 g and 0.5 g of hydroquinone monomethyl ether (hereinafter referred to as MEHQ) were added, and the reaction was carried out at 60 ° C. for 168 hours with stirring in a dry air stream. Obtained. The isocyanate group content of the obtained acryloyl group-containing isocyanate compound was 11.9% by mass, and the reaction proceeded theoretically.

<Synthesis Example 2>
Stirrer, thermometer, a reactor equipped heating device, a distillation column, a polybutadiene polyol (GI-2000, manufactured by Nippon Soda Co., Ltd., an iodine _{value: 11.4gI} 2 / 100g) and 887.4g of urethane catalyst As a dioctyl tin dilaurate (hereinafter referred to as DOTDL) 0.1g and MEHQ 0.5g was charged and dissolved in a dry air stream at 60 ° C with stirring. 74.9 g of IPDI was added to this mixed solution, and a urethanization reaction was performed at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 37.7 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition The product UVA-1 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-1 was 9,400, and the number of functional groups of the acryloyl group was 1.1.

<GPC: Molecular weight measurement of urethane acrylate resin composition>
(1) Measuring instrument: HLC-8220 (manufactured by Tosoh Corporation)
(2) Column: TSKgel (manufactured by Tosoh Corporation)
・ G3000H-XL
・ G2500H-XL
・ G2000H-XL, G1000H-XL
(3) Carrier: THF (tetrahydrofuran)
(4) Detector: RI (refractive index) detector (5) Temperature: 40 ° C
(6) Flow rate: 1.000 ml / min
(7) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)
F-80 (molecular weight: 7.06 × 10 ⁵ , molecular weight distribution: 1.05)
F-20 (molecular weight: 1.90 × 10 ⁵ , molecular weight distribution: 1.05)
F-10 (molecular weight: 9.64 × 10 ⁴ , molecular weight distribution: 1.01)
F-2 (molecular weight: 1.81 × 10 ⁴ , molecular weight distribution: 1.01)
F-1 (molecular weight: 1.02 × 10 ⁴ , molecular weight distribution: 1.02)
A-5000 (molecular weight: 5.97 × 10 ³ , molecular weight distribution: 1.02)
A-2500 (molecular weight: 2.63 × 10 ³ , molecular weight distribution: 1.05)
A-500 (molecular weight: 5.0 × 10 ² , molecular weight distribution: 1.14)
(8) Sample solution concentration: 0.5% THF solution

<Synthesis Example 3>
Stirrer, thermometer, heating apparatus, the reactor having a distillation column, hydrogenated polyisoprene polyol (EPOL, manufactured by Idemitsu Kosan Co., Ltd., an iodine _{value: 6.2gI} 2 / 100g) and the 934.0G, the DOTDL 0.1 g and 0.5 g of MEHQ were charged and dissolved under stirring at 60 ° C. in a dry air stream. 25.5 g of IPDI was added to this mixed solution, and a urethanization reaction was performed at 80 ° C. for 3 hours while stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 40.5 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition The product UVA-2 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-2 was 8,700, and the number of functional groups of the acryloyl group was 1.0.

<Synthesis Example 4>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower was charged with 953.3 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ, while stirring at 60 ° C. in a dry air stream. Dissolved. This mixed solution was charged with 26.0 g of IPDI and subjected to a urethanization reaction at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 20.7 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high-viscosity liquid urethane acrylate resin composition A product UVA-3 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-3 was 8,500, and the number of functional groups of the acryloyl group was 0.5.

<Synthesis Example 5>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower is charged with 915.5 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. This mixed solution was charged with 25.0 g of IPDI and subjected to urethanization reaction at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 59.5 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition A product UVA-4 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-4 was 8,900, and the number of functional groups of the acryloyl group was 1.5.

<Synthesis Example 6>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower was charged with 920.2 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. The mixed solution was charged with 79.8 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to obtain a transparent high viscosity liquid urethane acrylate resin composition UVA-5. Obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-5 was 4,400, and the number of functional groups of the acryloyl group was 1.0.

<Synthesis Example 7>
A reactor equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 941.0 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. 38.6 g of IPDI was added to this mixed solution, and a urethanization reaction was performed at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 20.4 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition The product UVA-6 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-6 was 17,300, and the number of functional groups of the acryloyl group was 1.1.

<Synthesis Example 8>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower is charged with 806.8 g of polypropylene glycol (Sanix PP1000, manufactured by Sanyo Chemical Industries), 0.1 g of DOTDL, and 0.5 g of MEHQ. The solution was dissolved with stirring at 60 ° C. in a dry air stream. To this mixed solution, 155.6 g of IPDI was charged, and urethanization reaction was performed at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 37.6 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition The product UVA-7 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-7 was 9,400, and the number of functional groups of the acryloyl group was 0.9.

<Synthesis Example 9>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower is charged with 897.7 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. 24.5 g of IPDI was added to this mixed solution, and a urethanization reaction was performed at 80 ° C. for 3 hours while stirring to obtain a hydroxyl group-terminated urethane prepolymer. The resulting hydroxyl-terminated urethane prepolymer was charged with 77.8 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to form a transparent high viscosity liquid urethane acrylate resin composition The product UVA-8 was obtained. The number average molecular weight by GPC of this urethane acrylate resin composition UVA-8 was 9,100, and the number of functional groups of the acryloyl group was 2.2.

<Synthesis of cross-linking agent (C)>
<Synthesis Example 10>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower was charged with 792.7 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. 160.4 g of IPDI was added to this mixed solution, and urethanization reaction was performed at 80 ° C. for 3 hours with stirring to obtain an isocyanate group-terminated urethane prepolymer. The obtained isocyanate group-terminated urethane prepolymer was charged with 46.9 g of 2-HPA and reacted at 60 ° C. for 6 hours in a dry air stream to obtain a transparent high-viscosity liquid crosslinking agent UVC-1. The number average molecular weight of this crosslinking agent UVC-1 by GPC was 5,100, the number of functional groups of the acryloyl group was 3.7, the distance between crosslinking points was 1,390, and the concentration of crosslinking points was 0.726 mmol / g.

<Synthesis Example 11>
A reactor equipped with a stirrer, thermometer, heating device, and distillation tower was charged with 832.9 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. To this mixed solution, 22.8 g of IPDI was added, and a urethanization reaction was performed at 80 ° C. for 3 hours with stirring to obtain a hydroxyl group-terminated urethane prepolymer. The obtained hydroxyl-terminated urethane prepolymer was charged with 144.3 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream. 2 was obtained. The number average molecular weight of this crosslinking agent UVC-2 by GPC was 9,800, the number of functional groups of the acryloyl group was 4.0, the distance between crosslinking points was 2,440, and the concentration of crosslinking points was 0.408 mmol / g.

<Synthesis Example 12>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower is charged with 897.7 g of EPOL, 0.1 g of DOTDL, and 0.5 g of MEHQ while stirring at 60 ° C. in a dry air stream. Dissolved. 24.5 g of IPDI was added to this mixed solution, and a urethanization reaction was performed at 80 ° C. for 3 hours while stirring to obtain a hydroxyl group-terminated urethane prepolymer. The resulting hydroxyl-terminated urethane prepolymer was charged with 77.8 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to produce a transparent high viscosity liquid crosslinking agent UVC- 3 was obtained. The number average molecular weight of this crosslinking agent UVC-3 by GPC was 9,000, the number of functional groups of the acryloyl group was 2.2, the distance between crosslinking points was 4,530, and the concentration of crosslinking points was 0.244 mmol / g.

<Synthesis Example 13>
In a reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower, polyfunctional polypropylene glycol (Primepol FF-3500, number average molecular weight: 5,000, functional group number: 3.0, manufactured by Sanyo Chemical Industries, Ltd.) ), 855.5 g, DOTDL 0.1 g, and MEHQ 0.5 g, and dissolved under stirring at 60 ° C. in a dry air stream. This mixed solution was charged with 174.5 g of the acryloyl group-containing isocyanate compound synthesized in Synthesis Example 1 and reacted at 60 ° C. for 6 hours in a dry air stream to obtain a transparent high-viscosity liquid crosslinking agent UVC-4. The number average molecular weight by GPC of this crosslinking agent UVC-4 was 6,060, the number of functional groups of the acryloyl group was 3.0, the distance between crosslinking points was 2,020, and the concentration of crosslinking points was 0.495 mmol / g.

<Preparation of active energy ray-curable composite resin composition>
<Example 1>
In a reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower, 500 g of toluene, 458.3 g of urethane acrylate resin UVA-1 synthesized in Synthesis Example 2, and a polyisobutylene resin (trade name: Oppanol30SF, BASF Corp., number average molecular weight: 80,000, an iodine _{value: 0.3gI} 2 / 100g) and 5g, a crosslinking agent UVC-2 36.7 g were charged, under dry air stream, with stirring 80 ° C. 1 Time mixing was performed to prepare an active energy ray-curable composite resin composition. The viscosity of this active energy ray-curable composite resin composition was 500 mPa · s under 25 ° C. conditions.

  Other active energy ray-curable composite resin compositions were prepared in the same amounts as in Tables 1 to 3 using the urethane acrylate resin (A) and the crosslinking agent (C) synthesized in the same manner as in Example 1.

The abbreviations of the raw materials used in Tables 1 to 3 are as follows.
(1) Glissopal1000: polyisobutylene (BASF Corp., number average molecular weight: 1,000, an iodine _{value: 25.4gI} 2 / 100g)
(2) polybutene 30SH: hydrogenated isobutene / n-butene copolymer (manufactured by NOF Corporation, number average molecular weight: 1,900, an iodine _{value: 0.5gI} 2 / 100g)
(3) Polybutene 200 N: hydrogenated isobutene / n-butene copolymer (manufactured by NOF Corporation, number average molecular weight: 3,900, an iodine _{value: 0.2gI} 2 / 100g)
(4) Oppanol30SF: polyisobutylene (BASF Corporation, number-average molecular weight: 80,000, an iodine _{value: 0.3gI} 2 / 100g)
(5) Polybutene 0N: hydrogenated isobutene / n-butene copolymer (manufactured by NOF Corporation, number average molecular weight: 250, iodine _{value: 1.8gI} 2 / 100g)
(6) Oppanol100: polyisobutylene (BASF Corporation, number-average molecular weight: 300,000, an iodine _{value: 0.1gI} 2 / 100g)
(7) TMP: trimethylolpropane triacrylate (8) P-100: hydrogenated C9 resin (trade name: Alcon P-100, manufactured by Arakawa Chemical Industries, softening point: 100 ° C., iodine value: 9.5 gI ₂ / 100g)
(9) KE-311: ultra-pale rosin ester (manufactured by Arakawa Chemical Industries, Ltd., trade name: Pine Crystal KE-311, softening point: 100 ℃, an iodine _{value: 55.2gI} 2 / 100g)
(10) ISA: Isostearyl acrylate (11) 2-EHA: 2-ethylhexyl acrylate

<Preparation of active energy ray-curable composite resin adhesive and adhesive for adhesive tape for optical member joining>
3 parts by weight of a photopolymerization initiator (Irgacure 1173, manufactured by BASF) is mixed with 100 parts by weight of the solid content of Examples 1 to 10 and Comparative Examples 1 to 5, and dissolved uniformly. Thus, an active energy ray-curable composite resin adhesive and an adhesive for adhesive tape for joining optical members were obtained.

(1) Evaluation test 1:
<Water vapor barrier property>
An active energy ray-curable composite resin adhesive was applied to a 25 μm PET film with a coater so as to have a thickness of 25 μm after curing, and the other adhesive surface was covered with a 25 μm PET film. Thereafter, the irradiation energy irradiation intensity 80 mW / cm ² at 365nm was to produce a test piece cured by irradiation with UV light so as to 1,000 mJ / cm ^2. Further, the water vapor barrier property was measured in accordance with JIS K7129 method A (moisture sensitive sensor method) and the water vapor permeability was measured under the following conditions. The water vapor permeability of the adhesive was calculated based on the following (Equation 1), assuming that the water vapor permeability of a 25 μm PET film was 25.7 g / (m ² · 24 h).
<Calculation formula of water vapor permeability when the thickness of the adhesive layer is 25 μm>

A: Total thickness of the measured sample (μm, eg: PET film / adhesive layer / PET film total thickness)
B: Water vapor transmission rate of the measured sample (g / m 2 · day)
C: PET film thickness (when using two layers of 25 μm PET film, 50 μm)
D: Water vapor permeability of the PET film at a thickness of C (the water vapor permeability is 12.85 g / m 2 · day because the PET film has a thickness of 50 μm in the case of two layers)
<Measurement conditions>
Test apparatus: water vapor permeability meter (L80-5000, manufactured by Lyssy)
・ Measurement atmosphere: 40 ℃ × 90% RH
・ Measurement diameter: 80mm
<Evaluation criteria>
・ 60 g / (m ² · 24 h) or less: Evaluation: ○
61 to 100 g / (m ² · 24 h): Evaluation: Δ
・ 101 g / (m ² · 24 h) or more: Evaluation: ×

(2) Evaluation test 2:
<Specific dielectric and dielectric loss tangent>
An active energy ray-curable composite resin adhesive was applied to a peeled 50 μm PET film with a coater so that the thickness was 200 μm after curing, and the other adhesive surface was coated with a peeled 50 μm PET film. . Thereafter, the irradiation energy irradiation intensity 80 mW / cm ² at 365nm The laminate of release PET film / adhesive / release PET film was cured by irradiation with UV light so as to 1,000 mJ / cm ^2. Next, the peeled PET film on one side was peeled off and bonded to the following electrode to prepare a test piece for dielectric measurement. The relative dielectric constant and dielectric loss tangent were measured under the following conditions.
<Measurement conditions>
Test equipment: precision LCR meter HP4284A (manufactured by Agilent Technologies)
・ Measurement electrode: SE-70 (manufactured by Ando Electric Co., Ltd.)
-Test piece: 50 mm x 50 mm
-Electrode shape: Main electrode diameter 38 mm, counter electrode 60 mm x 60 mm
・ Electrode material: Main electrode Copper foil, Counter electrode Aluminum ・ Frequency: 1 MHz
・ Pretreatment: C-24h / 22 ± 1 ° C / 60 ± 5% RH
Measurement atmosphere: 22 ° C x 60% RH
<Evaluation criteria for relative permittivity>
-3.0 or less: Evaluation: ○
3.1-3.5: Evaluation: △
・ 3.6 or more: Evaluation: ×
<Evaluation criteria for dielectric loss tangent>
-0.04 or less: Evaluation: ○
0.05-0.10: Evaluation: △
・ 0.11 or more: Evaluation: ×

(3) Evaluation test 3:
<Foaming resistance>
A polycarbonate plate 2mm thick active energy ray-curable composite resin adhesive is applied by coater so as to 100μm thickness after curing, after coating a PET film of 25 [mu] m, the irradiation energy irradiation intensity 80 mW / cm ² at 365 nm 1 It was cured by irradiating with UV light so as to be 1,000 mJ / cm ² . Then, it processed so that an adhesion area might be 40 mm x 40 mm, and the presence or absence of foaming was evaluated on the following conditions.
<Measurement conditions>
・ Measurement atmosphere: 80 ℃ × 100h
-Adhesive area: 40mm x 40mm
<Evaluation criteria>
・ No foaming: Evaluation: ○
・ Slight foaming: Evaluation: △
-There is large foaming on the entire bonding surface: Evaluation:

(4) Evaluation test 4:
<Transmissivity>
An active energy ray-curable composite resin adhesive was applied to a peeled 50 μm PET film with a coater so as to have a thickness of 100 μm after curing, and the peeled 50 μm PET film was coated on the other adhesive surface. . Thereafter, the irradiation energy irradiation intensity 80 mW / cm ² at 365nm The laminate of release PET film / adhesive / release PET film was cured by irradiation with UV light so as to 1,000 mJ / cm ^2. Next, the peeled PET film on one side was peeled off and bonded to quartz glass, the other peeled PET film was peeled off, and measurement was performed under the following conditions.
<Measurement conditions>
Test apparatus: spectrophotometer U-3300 (manufactured by Hitachi High-Technologies Corporation)
-Wavelength: 400-800nm
・ Measurement atmosphere: 25 ℃ × 50% RH
<Evaluation criteria>
・ 90% or more: Evaluation: ○
-Less than 90%: Evaluation: △

(5) Evaluation test 5:
<HAZE>
An active energy ray-curable composite resin adhesive was applied to a peeled 50 μm PET film with a coater so as to have a thickness of 100 μm after curing, and the peeled 50 μm PET film was coated on the other adhesive surface. . Thereafter, the irradiation energy irradiation intensity 80 mW / cm ² at 365nm The laminate of release PET film / adhesive / release PET film was cured by irradiation with UV light so as to 1,000 mJ / cm ^2. Next, the peeled PET film on one side was peeled off and bonded to an acrylic plate having a thickness of 2 mm, the other peeled PET film was peeled off, and measurement was performed under the following conditions. The HAZE of the adhesive was obtained by removing the HAZE value of the acrylic plate from the measured value.
<Measurement conditions>
Test apparatus: Haze meter (MR-100, manufactured by Murakami Color Research Laboratory)
・ Measurement atmosphere: 25 ℃ × 50% RH
<Evaluation criteria>
・ 0.5 or less: Evaluation: ◎
・ 0.6-1.0: Evaluation: ○
・ 1.1 or higher: Evaluation: △

(6) Evaluation test 6:
Adhesion tests are conducted when the active energy ray-curable composite resin adhesive is applied directly to the adherend and when the active energy ray-curable composite resin composition is processed into an adhesive tape and then bonded to the adherend. The technique to do was done.
<Adhesiveness of adhesive>
A polycarbonate plate 2mm thick active energy ray-curable composite resin adhesive is applied by coater so as to 100μm thickness after curing, after coating a PET film of 25 [mu] m, the irradiation energy irradiation intensity 80 mW / cm ² at 365 nm 1 It was cured by irradiating with UV light so as to be 1,000 mJ / cm ² . Thereafter, the peel force was measured under the following conditions.
<Adhesiveness of adhesive tape>
An active energy ray-curable composite resin adhesive was applied to the peeled 50 μm PET film with a coater so as to have a thickness of 100 μm after curing, and the other adhesive surface was covered with a 25 μm PET film. Thereafter, the irradiation energy irradiation intensity 80 mW / cm ² at 365nm was to produce a test piece cured by irradiation with UV light so as to 1,000 mJ / cm ^2. Next, the peeled PET film was peeled off, bonded to a 2 mm thick polycarbonate plate, pressure-bonded with 2 kg, and measured under the following conditions after 20 minutes.
<Measurement conditions>
・ Measurement atmosphere: 25 ℃ × 50% RH
・ Tearing speed: 300 mm / min
Peeling mode: 180 ° peel Tables 4 to 6 show the characteristics of the active energy ray-curable composite resin adhesive and the pressure-sensitive adhesive tape.

  As shown in Tables 4 to 6, the active energy ray-curable composite resin adhesives and adhesive tapes prepared in Examples 1 to 10 are excellent in water vapor barrier properties, low dielectric properties, and foam resistance. It was. On the other hand, Comparative Examples 1 to 5 were inferior in these performances.

Claims (20)

An active energy ray-curable composite resin composition containing a urethane acrylate resin composition (A), a polyisobutylene resin (B), and a crosslinking agent (C),
The urethane acrylate resin composition (A) comprises an olefin polymer (a1) having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3), and The number of functional groups of the (meth) acryloyl group derived from the (meth) acrylic acid hydroxy compound (a3) is less than 2,
The polyisobutylene resin (B) contains a structure derived from an isobutylene monomer represented by the following general formula (1), and the number average molecular weight of the polyisobutylene resin (B) is in the range of 300 to 100,000; And the crosslinking agent (C) is contained in the active energy ray-curable composite resin composition so that the functional group concentration of the crosslinking agent (C) is 0.03 to 0.15 mmol / g. An active energy ray-curable composite resin composition.

2. The active energy ray-curable composite resin composition according to claim 1, wherein the distance between cross-linking points of the cross-linking agent (C) obtained by the following mathematical formula 1 is 500 to 10,000.

Distance between cross-linking points of cross-linking agent (C) =
(Number average molecular weight of crosslinking agent (C) / number of functional groups of crosslinking agent (C)) (Equation 1) The (meth) acrylic acid hydroxy group in which the cross-linking agent (C) comprises an olefin polymer (a1) having two or more active hydrogen groups, an isocyanate compound (a2), and a (meth) acrylic acid hydroxy compound (a3). The active energy ray-curable composite resin composition according to claim 1 or 2, wherein the number of functional groups of the (meth) acryloyl group derived from the compound (a3) is 2 or more. The active energy ray-curable composite resin composition according to any one of claims 1 to 3, wherein the polyisobutylene resin (B) has a number average molecular weight of 300 to 5,000. The active energy ray-curable composite resin composition according to any one of claims 1 to 4, wherein the active energy ray-curable composite resin composition contains 5 to 60% by mass of the polyisobutylene resin (B). . 6. The active energy ray-curable composite resin composition according to claim 1, further comprising a tackifier (D). Tackifier (D) is contained an alicyclic structure, a number average molecular weight 300 to 10,000, and, an iodine value is according to claim 6, characterized in that 50gI ₂ / 100g or less An active energy ray-curable composite resin composition. The active energy ray-curable composite resin composition according to claim 6 or 7, wherein the active energy ray-curable composite resin composition contains 5 to 40% by mass of a tackifier (D). The active energy ray-curable composite resin composition according to claim 1, comprising (meth) acrylic acid ester (E) having an alkyl group having 10 to 22 carbon atoms at an ester end. The alkyl group of (meth) acrylic acid ester (E) has a branched structure, The active energy ray hardening-type composite resin composition of Claim 9 characterized by the above-mentioned. The active energy ray-curable composite resin according to claim 9 or 10, wherein the content of (meth) acrylic acid ester (E) in the active energy ray-curable composite resin composition is 70% by mass or less. Composition. An active energy ray-curable composite resin adhesive comprising the active energy ray-curable composite resin composition according to any one of claims 1 to 11. An active energy ray-curable composite resin adhesive comprising 1 to 100% by mass of the active energy ray-curable composite resin composition according to any one of claims 1 to 11. In the adhesive cured material by the active energy ray of the active energy ray-curable composite resin adhesive according to claim 12 or 13, the water vapor permeability measured in accordance with JIS K7129 has a film thickness of 25 µm, a temperature of 40 ° C, and a humidity. An active energy ray-curable composite resin adhesive characterized by being 100 g / (m ² · 24 h) or less under 90% conditions. The adhesive cured product by active energy rays of the active energy ray-curable composite resin adhesive according to any one of claims 12 to 14, wherein the relative dielectric constant is a frequency of 1 MHz, a temperature of 22 ° C, and a humidity of 60%. An active energy ray-curable composite resin adhesive having a dielectric loss tangent of 3.5 or less and a dielectric loss tangent of 0.1 or less. The adhesive cured product by active energy rays of the active energy ray-curable composite resin adhesive according to any one of claims 12 to 15, wherein an average transmittance at a wavelength of 400 to 800 nm is 90% or more under the condition of a film thickness of 100 µm. An active energy ray-curable composite resin adhesive, characterized in that The active energy ray-curable composite resin adhesive layer according to any one of claims 12 to 16, wherein the adhesive layer is an adhesive tape for joining an optical member comprising an active energy ray-curable composite resin adhesive layer and a separator layer. An adhesive tape for joining optical members, comprising: 18. The pressure-sensitive adhesive tape according to claim 17, wherein the water vapor permeability measured in accordance with JIS K7129 is 100 g / (m ² · 24 h) or less under conditions of a film thickness of 25 μm, a temperature of 40 ° C., and a humidity of 90%. A pressure-sensitive adhesive tape for bonding optical members. The relative dielectric constant of the pressure-sensitive adhesive tape according to claim 17 or 18 is 3.5 or less at a frequency of 1 MHz, a temperature of 22 ° C, and a humidity of 60%, and a dielectric loss tangent is 0.1 or less. A pressure-sensitive adhesive tape for bonding optical members. The pressure-sensitive adhesive tape for joining optical members, wherein the pressure-sensitive adhesive tape according to any one of claims 17 to 19 has an average transmittance at a wavelength of 400 to 800 nm of 90% or more under a film thickness of 100 µm.