JP2007182557A - Impact resisting adhesive layer, method for producing the same and impact resisting adhesive laminated structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an impact resisting adhesive layer excellent in adhesion, transparency, radiation-curability, and shock absorbing property, to provide a method for producing the layer, and to provide an impact resisting adhesive laminated structure having the impact resisting adhesive layer. <P>SOLUTION: The method for producing the impact resisting adhesive layer serially comprises a deaerating step deaerating an acrylic radiation-curable liquid adhesive composition, a coating step coating on a substrate surface the acrylic radiation-curable liquid adhesive composition deaerated in the step, and a curing step curing the radiation curable liquid composition coated in the step. Wherein the impact resisting adhesive laminated structure A comprises an impact resisting adhesive layer 1 having a thickness of 50-2,000 μm, a 180° peel adhesion of 0.1-10 N/25mm, a tanδ peak value of ≥1 and a haze of ≤1 at 25°C, and another layer 2 such as a protective film set on the surface of the impact resisting adhesive layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an impact-resistant adhesive layer, a method for producing the same, and an impact-resistant adhesive laminated structure. More specifically, the present invention relates to an impact resistant adhesive layer excellent in adhesiveness, transparency, radiation curability and impact resistance, a method for producing the impact resistant adhesive layer, and an impact resistant adhesive laminated structure including the impact resistant adhesive layer.

  In recent years, flat display panels such as a liquid crystal display panel (LCD) and a plasma display panel (PDP) have been used as display panels. A flat display panel is usually a laminated structure in which a plurality of films are laminated. For example, in an LCD, an optical film such as a polarizing plate, a retardation plate, a viewing angle widening film, and a brightness improving film is usually laminated on the surface of a liquid crystal panel. And each layer which comprises a planar display panel is bonded together by the adhesive layer normally formed with various adhesives.

  Patent Document 1 below describes an optical film with a pressure-sensitive adhesive in which an optical film is laminated on a glass cracking-proof pressure-sensitive adhesive layer whose dynamic storage modulus at 20 ° C. is in a specific range. Patent Document 1 described below describes that acrylic, rubber-based, polyester-based, and silicone-based pressure-sensitive adhesives can be used as the pressure-sensitive adhesive that forms the glass cracking-preventing pressure-sensitive adhesive layer. Patent Document 1 below describes that the pressure-sensitive adhesive can be a heat-crosslinking pressure-sensitive adhesive and a photocrosslinking pressure-sensitive adhesive such as ultraviolet rays or electron beams.

  Patent Document 2 below contains an initial polymer (A) composed of a copolymer of a specific acrylate monomer and another vinyl monomer, and a (meth) acrylic monomer (B), and has a specific glass transition point. A range of acrylic syrup resin compositions are described. Patent Document 2 below describes that the composition is cured by irradiation with ultraviolet rays or electron beams, and can be used as various pressure-sensitive adhesive sheets.

JP 2004-271935 A JP 2005-240044 A

  It is known that a glass plate or the like constituting a flat display panel is not very viscoelastic and is easily damaged when pressed or hit. A laminate in which a glass plate or the like and another layer such as a polarizing plate are directly bonded together with an adhesive layer cannot be said to have sufficient strength. As a method for increasing the strength of the laminated body and preventing the laminated body from being damaged, a method of further providing a shock absorbing layer can be considered. However, the method of separately providing a shock absorbing layer requires a step of separately providing a shock absorbing layer. Therefore, it has been desired to develop a pressure-sensitive adhesive layer that is excellent in adhesiveness and impact resistance. It is also important that the flat display panel is excellent in transparency. Therefore, not only each layer which comprises a planar display panel but the adhesion layer which bonds each layer is calculated | required that it is excellent in transparency. Furthermore, when the adhesive layer is obtained by irradiation, if the gas derived from unreacted components aggregates to generate bubbles and floats, the visibility of the flat display panel is affected. Therefore, the adhesive layer is required to be excellent in radiation curability.

  The present invention has been made in view of the above circumstances, and is an impact-resistant adhesive layer excellent in adhesiveness, transparency, radiation curability and impact resistance, a method for producing the same, and an impact-resistant adhesive laminate provided with the impact-resistant adhesive layer. An object is to provide a structure.

The present invention is as follows.
(1) A deaeration process for degassing the radiation curable liquid adhesive composition, an application process for applying the radiation curable liquid adhesive composition degassed by the deaeration process to the surface of the base layer, and irradiation with radiation. And a curing step of curing the radiation-curable liquid adhesive composition applied in the application step, in order.
(2) The radiation curable liquid adhesive composition comprises (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane (meth) acrylate, and (E) photopolymerization initiator. The method for producing an impact-resistant adhesive layer according to the above (1), which is a radiation curable liquid adhesive composition comprising
(3) The method for producing an impact-resistant pressure-sensitive adhesive layer according to (1) or (2), wherein the dissolved oxygen content in the radiation-curable liquid pressure-sensitive adhesive composition after the deaeration step is 90% or less of the saturated oxygen content. .
(4) the radiation is ultraviolet light, in any one of (1) to (3) peak irradiance 50~1000mW / cm ^2, and integrated light quantity irradiating the UV under the condition of 100 to 2000 mJ / cm ² The manufacturing method of the impact-resistant adhesion layer of description.
(5) The method for producing an impact-resistant adhesive layer according to any one of (1) to (4), wherein the resulting impact-resistant adhesive layer has a thickness of 50 to 2000 μm.
(6) Impact-resistant adhesive layer having a thickness of 50 to 2000 μm, a 180 ° peel adhesive strength of 1 to 10 N / 25 mm, a peak value of tan δ of 1 or more, and a haze at 25 ° C. of 1 or less. .
(7) An impact-resistant adhesive layer obtained by the method according to any one of (1) to (5) above.
(8) The impact-resistant adhesive laminate structure comprising the impact-resistant adhesive layer described in (6) or (7) above and another layer provided on at least one surface of the impact-resistant adhesive layer. .

According to the method for producing an impact-resistant adhesive layer of the present invention, an impact-resistant adhesive layer excellent in adhesiveness, transparency, radiation curability and impact resistance (including impact absorption) can be obtained.
In the method for producing an impact-resistant adhesive layer of the present invention, the radiation curable liquid adhesive composition comprises (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane acrylate, and ( E) When it is a radiation curable liquid pressure-sensitive adhesive composition containing a photopolymerization initiator, an impact-resistant pressure-sensitive adhesive layer having excellent adhesion, transparency, radiation curable property, and impact resistance can be obtained.
In the method for producing an impact-resistant pressure-sensitive adhesive layer of the present invention, when the amount of dissolved oxygen contained in the radiation-curable liquid pressure-sensitive adhesive composition after the degassing step is 90% or less of the amount of saturated oxygen, the adhesiveness and transparency are further increased. In addition, an impact-resistant adhesive layer having excellent radiation curability and impact resistance can be obtained.
In the method of impact adhesive layer of the present invention, the radiation is ultraviolet light, the peak irradiance is 50~1000mW / cm ^2, and integrated light quantity irradiating the UV under the condition of 100 to 2000 mJ / cm ^2, further adhesive It is possible to obtain an impact-resistant pressure-sensitive adhesive layer having excellent properties, transparency, radiation curability and impact resistance.
In the method for producing an impact-resistant adhesive layer of the present invention, when the resulting impact-resistant adhesive layer has a thickness of 50 to 2000 μm, an impact-resistant adhesive layer further excellent in adhesiveness, transparency, radiation curability and impact resistance is obtained. Obtainable.
The impact-resistant adhesive layer of the present invention is excellent in adhesiveness, transparency, radiation curability and impact resistance. The impact-resistant adhesive laminate structure of the present invention includes an impact-resistant adhesive layer that is excellent in adhesiveness, transparency, radiation curability, and impact resistance. When the impact-resistant adhesive layer of the present invention and the impact-resistant adhesive laminate structure of the present invention are used, a laminate structure having excellent transparency and impact resistance can be obtained.

Hereinafter, the present invention will be described in detail.
(1) Method for Producing Impact-resistant Adhesive Layer The method for producing the impact-resistant adhesive layer of the present invention includes a degassing step for degassing the radiation-curable liquid adhesive composition, and the radiation curing degassed by the degassing step. Characterized in that it comprises a coating step of coating the surface of the mold liquid adhesive composition on the surface of the base layer and a curing step of curing the radiation-curable liquid adhesive composition applied by the coating step by irradiating with radiation. And

(A) Radiation-curable liquid pressure-sensitive adhesive composition The radiation-curable liquid pressure-sensitive adhesive composition is not particularly limited as long as the radiation-curable liquid pressure-sensitive adhesive composition is cured by irradiation with radiation and the cured product has a property of having adhesiveness. . Examples of the radiation curable liquid pressure-sensitive adhesive composition include acrylic, rubber-based, polyester-based, and silicone-based pressure-sensitive adhesive compositions. From the viewpoints of transparency and durability, an acrylic radiation-curable liquid adhesive composition is preferable as the radiation-curable liquid adhesive composition. The “liquid” includes not only liquid such as solution but also semi-solid such as gel.

  The acrylic radiation curable liquid pressure-sensitive adhesive composition is composed of (meth) acrylic acid alkyl ester as a main component, and is a composition that is polymerized by irradiation with radiation such as ultraviolet rays and exhibits adhesiveness. There is no particular limitation. Examples of the acrylic radiation curable liquid adhesive composition include (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane (meth) acrylate, and (E) light. Radiation curable liquid pressure-sensitive adhesive composition containing at least one polymerization initiator, in particular, (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane (meth) Examples include radiation curable liquid pressure-sensitive adhesive compositions containing acrylate and at least one of (E) a photopolymerization initiator. Specific examples of the acrylic radiation curable liquid adhesive composition include (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane (meth) acrylate, and ( E) Radiation curable liquid pressure-sensitive adhesive composition containing a photopolymerization initiator.

  The (A) acrylic syrup is a syrup-like composition containing an acrylic polymer obtained by polymerizing an acrylic monomer and, if necessary, another monomer. Examples of the acrylic monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid annealed ester, (meth) acrylic acid alkoxyalkyl, polyvalent acrylic acid ester, and alicyclic alcohol methacrylic acid ester. Can be mentioned. The acrylic monomers may be used alone or in combination of two or more. As said acrylic monomer, the acrylic monomer which has (meth) acrylic-acid alkylester or (meth) acrylic-acid alkylester as a main component is preferable.

  As the acrylic monomer, for example, one or more of monofunctional acrylate and polyfunctional acrylate can be used. Specific examples of the monofunctional acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, Ryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate , Phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol Examples include (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and 7-amino-3,7-dimethyloctyl (meth) acrylate. The monofunctional acrylate may be used alone or in combination of two or more.

  Specific examples of the polyfunctional acrylate include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, Triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Bisphenol A diglycidyl ether end (meth) acrylic acid addition, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri Di (meth) of diol which is an adduct of (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A ethylene oxide or propylene oxide Di (meth) acrylate of diol which is an adduct of acrylate, hydrogenated bisphenol A ethylene oxide or propylene oxide, diglycidyl ether of bisphenol A (meth) Epoxy obtained by adding acrylate (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, and cyclohexane dimethanol di (meth) acrylate. The said polyfunctional acrylate may be used individually by 1 type, and may use 2 or more types together.

  Examples of the other monomers include N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and hydroxybutyl vinyl ether. Lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and t-octyl (meth) acrylamide. One of these other monomers may be used alone, or two or more thereof may be used in combination.

  The viscosity of the (A) acrylic syrup is usually 1000 to 100000 cps, preferably 2000 to 95000 cps, more preferably 3000 to 90000 cps, and more preferably 10,000 to 90000 cps. This viscosity is a viscosity measured with a B-type viscometer at 25 ° C. The weight average molecular weight of the acrylic polymer contained in the acrylic syrup (A) is usually 500,000 to 3,000,000, preferably 500,000 to 2,500,000, more preferably 600,000 to 2,000,000, more preferably 700,000. ~ 1.8 million. It is preferable for the viscosity and the weight average molecular weight to be in the above ranges since application is easy and the tackiness and impact resistance of the resulting impact resistant adhesive layer can be improved.

  The (A) acrylic syrup may contain not only the acrylic polymer but also the (meth) acrylic acid alkyl ester as a monomer. When the (A) acrylic syrup contains the monomer, the viscosity of the (A) acrylic syrup can be adjusted to an appropriate range. As a result, the application and handling of the (A) acrylic syrup can be facilitated, which is preferable. There is no limitation in particular in the method of containing the said monomer. The (A) acrylic syrup containing the monomer is usually unreacted with the acrylic polymer by stopping the reaction before the reaction rate reaches 100% in the polymerization reaction for obtaining the acrylic polymer. It can be obtained as a mixture of the above monomers.

  As said (B) acrylate monomer, the said acrylic monomer is mentioned, for example. The (B) acrylate monomer may be used alone or in combination of two or more. The (B) acrylate monomer may be the same monomer as the acrylic monomer constituting the acrylic polymer contained in the (A) acrylic syrup, or may be a different monomer.

  Content of the said (B) acrylate monomer can be selected according to the kind of each said component, content, etc. The content of the (B) acrylate monomer is usually 1 to 80% by mass, preferably 3 to 75% by mass, when the total content of the (A) acrylic syrup and the (B) acrylate monomer is 100% by mass. %, More preferably 5 to 70% by mass, and more preferably 10 to 65% by mass.

  Moreover, when the said (B) acrylate monomer contains 2 or more types of acrylate monomers, content of each acrylate monomer can be made into various ranges as needed. When the (B) acrylate monomer contains two or more acrylate monomers, the acrylate monomer can be selected according to the type and content of each component. For example, when the total amount of the (B) acrylate monomer is 100% by mass, the content of the acrylate monomer as the main component (the component having the highest content) is usually 30 to 90% by mass, preferably 35 to 85% by mass. %, More preferably 40 to 80% by mass. More specifically, for example, the (B) acrylate monomer contains an alicyclic ether-containing acrylate such as tetrahydrofurfuryl acrylate, an alkyl acrylate such as 2-ethylhexyl acrylate, and a hydroxyl group-containing acrylate such as 4-hydroxybutyl acrylate. When it does, content of the acrylate monomer which is a main component can be made into the said range.

［式（１）において、Ｘはアクリロイル基、グリシジル基、メルカプト基又はハロゲン基であり、Ｒ^１は２価の有機基であり、Ｒ^２は炭化水素基である。］ As said (C) silane coupling agent, the compound represented by following formula (1) is mentioned, for example.

[In Formula (1), X is an acryloyl group, a glycidyl group, a mercapto group, or a halogen group, R ¹ is a divalent organic group, and R ² is a hydrocarbon group. ]

  X is a functional group selected from the group consisting of an acryloyl group, a glycidyl group, a mercapto group, or a halogen group. Among these, an acryloyl group and a mercapto group are particularly preferable in terms of expressing high adhesiveness.

If R ¹ is a divalent organic group, the structure is not limited. For example, the carbon number of R ¹ is usually 1 to 20, preferably 1 to 18, more preferably 2 to 15, and more preferably 3 to 12. R ¹ may have a linear structure or a branched structure. Further, R ¹ may be a saturated organic group (saturated alkyl group or the like), an unsaturated organic group (unsaturated alkyl group or the like), or an alicyclic or aromatic organic group. Specific examples of R ¹ include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a cyclohexyl group, and a benzyl group.

If R ² is a hydrocarbon group, the type and structure are not particularly limited. Usually, the carbon number of R ² is 1 to 10, preferably 1 to 8, more preferably 1 to 6, and more preferably 1 to 4. R ² may have a linear structure or a branched structure. Further, R ¹ may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an alicyclic or aromatic hydrocarbon group. In the above formula (1), R ² may be the same group or different groups.

  More specifically, examples of the hydrocarbon group include (1) methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. Group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group A linear or branched alkyl group such as a group, n-nonadecyl group, n-eicosyl group, i-propyl group, i-butyl group, sec-butyl group, t-butyl group, and t-dodecyl group, (2) cyclopentyl Group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, norbornyl group, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyl group Bridged alicyclic groups such as mantyl group, ethyladamantyl group, and butyladamantyl group, (3) alkenyl groups such as vinyl group and propenyl group, (4) phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group Aryl groups such as a group, mesityl group, naphthyl group, and anthryl group, and (5) heteroaryl groups such as a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidinyl group, and a pyrrolidinyl group. Among these, an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group, i-propyl group) is preferable.

In the formula (1), R ¹ and R ² may further have other functional groups or atoms in the structure. Examples of other functional groups include thiol groups, hydroxyl groups, ether groups, thioether groups, sulfinyl groups, sulfonyl groups, carbonyl groups, carboxyl groups, carboxylic anhydride groups, nitrile groups, and amide groups. Examples of the atoms include various heteroatoms (oxygen atoms, nitrogen atoms, sulfur atoms, etc.) and halogen atoms (fluorine atoms, chlorine atoms, iodine atoms, etc.). The above-mentioned other functional groups or atoms may be only one kind or may contain two or more kinds. The number of the other functional groups or atoms is not particularly limited, and may be one or may include two or more.

  Specific examples of the compound represented by the above formula (1) include 3- (meth) acryloxypropyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, vinyltrialkoxysilane, tetraalkoxysilane, 3 -Mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane and the like. In these, the silane coupling agent which has a C1-C2 alkoxysilyl group is preferable. In particular, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3-mercaptopropyltrialkoxysilane are preferable in terms of developing high adhesiveness.

  Content of the said (C) silane coupling agent can be selected according to the kind of each said component, content, etc. The content of the (C) silane coupling agent is usually 0.05 to 5 parts by mass, preferably 0 with respect to 100 parts by mass in total of the contents of the (A) acrylic syrup and the (B) acrylate monomer. 0.1 to 3 parts by mass, more preferably 0.2 to 2 parts by mass, and more preferably 0.3 to 1.5 parts by mass.

  The (D) urethane (meth) acrylate is preferably urethane (meth) acrylate obtained by reacting diisocyanate, hydroxyl group-containing (meth) acrylate, and diol. As this reaction, for example, (1) a method in which diol, diisocyanate and hydroxyl group-containing (meth) acrylate are charged together and reacted, (2) a method in which diol and diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted. , (3) a method of reacting diisocyanate and hydroxyl group-containing (meth) acrylate, and then reacting with diol, and (4) reacting diisocyanate and hydroxyl group-containing (meth) acrylate, then reacting with diol, and finally hydroxyl group-containing Examples include a method of reacting (meth) acrylate.

  The (D) urethane (meth) acrylate is a diol and a diisocyanate such that the diol is preferably contained in one molecule as a repeating unit of 2 or more molecules, more preferably 3 or more in one molecule. The reaction rate is adjusted to react. Specifically, for example, the molar ratio of the diisocyanate is adjusted to be 1.5 mol or less with respect to 1 mol of the diol. The ratio of the hydroxyl group-containing (meth) acrylate is preferably adjusted to 1.0 to 1.5 equivalents with respect to the excess isocyanate equivalent calculated from the molar ratio of the diol and the diisocyanate.

  Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and m-phenylene diisocyanate. P-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6- Hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) ) Fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis ( Isocyanatomethyl) -bicyclo [2.2.1] heptane and the like. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylene bis (4-cyclohexyl isocyanate), which are aliphatic compounds, are particularly preferable. By using an aliphatic compound for the diisocyanate component, yellowing during heating can be suppressed. When seeking better yellowing at the time of heating, it is preferable to use isophorone diisocyanate or methylene bis (4-cyclohexyl isocyanate). These diisocyanates can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) ) Acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol Mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate Examples thereof include compounds obtained by addition reaction of (meth) acrylic acid with glycidyl group-containing compounds such as acrylate, dipentaerythritol penta (meth) acrylate, alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate. it can. Of these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more.

  Examples of the diol include aliphatic polyether diol, cyclic polyether diol, polyester diol, polycarbonate diol, and polycaprolactone diol.

  Examples of the aliphatic polyether diol include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more ion-polymerizable cyclic compounds. Examples thereof include polyether diol obtained by polymerization. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, 1,2-butylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3- Methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, Cyclic agents such as butyl glycidyl ether and benzoic acid glycidyl ester Le acids and the like. Polyether diol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with cyclic imines such as ethyleneimine, cyclic lactone acids such as β-propiolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. Specific combinations of the two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 And terpolymers of -oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, ethylene oxide, and the like. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form. Among these, at least one diol selected from the group consisting of polypropylene glycol, polybutylene glycol, a copolymer of 1,2-butylene oxide and ethylene oxide and a copolymer of propylene oxide and ethylene oxide is used. Is preferred.

  Examples of commercially available products of the aliphatic polyether diol include PPG-400, PPG1000, PPG2000, PPG3000, EXCENOL720, 1020, 2020, PREMINOL PML S-X4001, PML S-4003, PML S-X4004, and PML S-X4008. , PML S-X4011, PML S-X4016, NPML-4002A (above, manufactured by Asahi Glass Urethane Co., Ltd.), EO / BO500, EO / BO1000, EOBO / 2000, EO / BO3000, EO / BO4000 (above, Daiichi Kogyo Pharmaceutical Co., Ltd.) Manufactured), PTMG650, PTMG1000, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation), PEG1000, Unisafe DC1100, DC1800 (above, manufactured by NOF Corporation), PPTG2000, PPT 1000, PTG400, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000A, PBG2000B (or, Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

  Examples of the cyclic polyether diol include bisphenol A alkylene oxide addition diol, bisphenol F alkylene oxide addition diol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A alkylene oxide addition diol, hydrogenated bisphenol. Alkylene oxide addition diol of F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide addition diol of anthrahydroquinone, 1,4-cyclohexanediol and its alkylene oxide addition diol, tricyclodecane diol, tricyclo Decanedimethanol, pentacyclopentadecanediol, pentacyclopentadecane dimethano Etc. The. Among these, alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol A, and tricyclodecane dimethanol are preferable. Examples of commercially available cyclic polyether polyols include Uniol DA400, DA700, DA1000, DB400 (manufactured by NOF Corporation), N1162 (Daiichi Kogyo Seiyaku Co., Ltd.), tricyclodecane dimethanol (Mitsubishi Chemical Corporation). Manufactured).

  Examples of the polyester diol include a polyester diol obtained by reacting a diol with a diacid base. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 3-methyl. -1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and the like. Examples of the dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. Examples of commercially available polyester diols include Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.) and the like.

  Examples of the polycarbonate diol include polytetrahydrofuran polycarbonate and 1,6-hexanediol polycarbonate. Commercially available products of the above polycarbonate diol include DN-980, 981, 982, 983 (manufactured by Nippon Polyurethane Co., Ltd.), PC-8000 (manufactured by PPG, USA), and PC-THF-CD (manufactured by BASF). Can be mentioned.

  Examples of the polycaprolactone diol include ε-caprolactone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, Examples thereof include polycaprolactone diols obtained by reacting diols such as neopentyl glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. As these diols, Plaxel 205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel) can be obtained as a commercial product.

  The number average molecular weight of the diol is preferably 300 to 15,000, more preferably 1000 to 12000, and particularly preferably 2000 to 12000.

  Many other diols other than those described above can also be used. Examples of such other diols include ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and dicyclopentadiene. Dimethylol compound, tricyclodecane dimethanol, β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated diol compound, polydimethylsiloxane carbitol-modified diol, etc. Is mentioned.

  The number average molecular weight of these other diol components is 300 to 5000, preferably 300 to 2000, and more preferably 300 to 1000.

  It is also possible to use a diamine together with the diol component. Examples of such diamines include ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, diamines such as 4,4'-diaminodiphenylmethane, diamines containing heteroatoms, and polyether diamines.

  In the (D) urethane (meth) acrylate, urethane (meth) acrylate obtained by reacting 2 mol of a hydroxyl group-containing (meth) acrylate compound with respect to 1 mol of diisocyanate can also be blended. As such urethane (meth) acrylate, for example, a reaction product of hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate, hydroxyethyl (meth) acrylate and 2,5 (or 6) -bis (isocyanate methyl)- Bicyclo [2.2.1] heptane reactant, hydroxyethyl (meth) acrylate and isophorone diisocyanate reactant, hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate reactant, hydroxypropyl (meth) acrylate And a reaction product of isophorone diisocyanate.

  Content of the said (D) urethane (meth) acrylate can be selected according to the kind of each said component, content, etc. The content of the (D) urethane (meth) acrylate is usually 0.1 to 20 parts by mass, preferably 100 parts by mass of the total content of the (A) acrylic syrup and the (B) acrylate monomer, preferably It is 0.2-18 mass parts, More preferably, it is 0.3-15 mass parts.

  Examples of the (E) photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, and 3-methyl. Acetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino - propan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like. Commercially available products of the above (E) photopolymerization initiator include, for example, Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61 (above, manufactured by Ciba Specialty Chemicals), Lucirin LR8728 (BASF), Darocur 1116, 1173 (Merck), Ubekrill P36 (UCB), and the like. The (E) photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

  The content of the (E) photopolymerization initiator can be selected according to the type and content of each component. The content of the (E) photopolymerization initiator is usually 0.1 to 15 parts by mass, preferably 0 with respect to 100 parts by mass in total of the contents of the (A) acrylic syrup and the (B) acrylate monomer. 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass.

  It is preferable to add a photosensitizer to the (E) photopolymerization initiator as necessary. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino. And isoamyl benzoate. As a commercial item of the said photosensitizer, Ubekrill P102, 103, 104, 105 (above, the product made from UCB) etc. are mentioned, for example.

  The radiation curable liquid pressure-sensitive adhesive composition may contain other components as necessary as long as the performance is not impaired. Examples of other components include pigments, dyes, lubricants, softeners, photosensitizers, antioxidants, antioxidants, stabilizers such as heat stabilizers, weathering agents, metal deactivators, UV absorbers, Stabilizers such as light stabilizers, copper damage inhibitors, antibacterial and antifungal agents, dispersants, plasticizers, crystal nucleating agents, flame retardants, tackifiers, foaming aids, crosslinking agents, co-crosslinking agents, vulcanization Agent, vulcanization aid, foaming agent, colorant such as titanium oxide and carbon black, metal powder such as ferrite, inorganic fiber such as glass fiber and metal fiber, organic fiber such as carbon fiber and aramid fiber, composite fiber, titanium Inorganic whiskers such as potassium oxide whiskers, glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo powder, Fillers such as Tutton flock, cork powder, barium sulfate, fluororesin, polymer beads or mixtures thereof, fillers such as polyolefin wax, cellulose powder, rubber powder, wood powder, low molecular weight polymer, silane coupling agent, and titanium cup A ring agent etc. are mentioned. These may be used alone or in combination of two or more.

Moreover, in order to suppress the yellowing by an ultraviolet-ray or a heating, the said radiation curable liquid adhesive composition can add the compound which has a phosphite ester represented by following formula (5), and a phenol group.
(R ⁹ O) _n P (OR ¹⁰ ) _3-n (5)
(In formula (5), n represents an integer of 1 to 3, R ⁹ represents an organic group having a phenolic hydroxyl group, and R ¹⁰ represents an organic group that may contain a phosphorus atom.)

R ⁹ and R ¹⁰ may have an element other than carbon. Examples of elements other than carbon include nitrogen, sulfur, oxygen, halogen and phosphorus. The R ⁹ and R ¹⁰ may be a cyclic organic group in which two or more of the R ⁹ and R ¹⁰ are connected.

Examples of R ⁹ include hydroxyphenyl, hydroxynaphthyl, and hydroxyphenylalkyl groups, which may be substituted with 1 to 3 alkyl groups, alkoxy groups, or halogen atoms on a benzene or naphthalene ring. As the above-mentioned R ^10, for example, an alkyl group, an aryl group, or an aralkyl group and the like. Here, examples of the aryl group include a phenyl or naphthyl group which may be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Examples of the arylalkyl group include a phenylalkyl group that may be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Moreover, as described above, the R ⁹ and the R ¹⁰ may be linked. In the case where R ¹⁰ contains a phosphorus atom, 2 to 4 phosphites having a phenolic hydroxyl group are bonded to a divalent to tetravalent alkane residue or a divalent to tetravalent aromatic hydrocarbon residue. There are cases. In the above formula (5), when R ⁹ is 2 or more, each R ⁹ may be the same group or different groups. Similarly, if a said R ¹⁰ is 2 or more, each R ¹⁰ together may be the same group or a different group.

  Specific examples of the compound having a phosphite group and a phenolic hydroxyl group represented by the above formula (5) include 2-methyl-4-hydroxyphenyl diethyl phosphite, 2-t-butyl-4-hydroxyphenyl diethyl. Phosphite, 2,5-di-t-butyl-4-hydroxyphenyl diethyl phosphite, bis (2,5-di-t-butyl-4-hydroxyphenyl) ethyl phosphite, tris (2,5-di- t-butyl-4-hydroxyphenyl) phosphite, tetrakis (2,5-di-t-butyl-4-hydroxyphenyl) -2,5-di-t-butyl-hydroxyquinonediyl-phosphite.

As the compound having a phosphite group represented by the above formula (5) and a phenolic hydroxyl group, a compound represented by the following formula (6) or (7) is particularly preferable. As a commercial item of the compound which has these phosphite group and phenolic hydroxyl group, "Sumilyzer GP" (made by Sumitomo Chemical Co., Ltd.) is mentioned, for example.

  The content of the compound having a phosphite group and a phenolic hydroxyl group represented by the above formula (5) is preferably 0.1 to 10% by mass with respect to the total amount of the radiation curable liquid adhesive composition, and further Preferably it is 0.1-5 mass%, Most preferably, it is 0.1-3 mass%.

  The radiation curable liquid pressure-sensitive adhesive composition can contain a dialkylaminobenzoic acid ester in order to reduce the tack after curing. Specific examples of the dialkylaminobenzoic acid ester include dialkylaminobenzoic acid alkyl esters such as methyl, ethyl, propyl, butyl or isoamyl esters of dialkylaminobenzoic acid. Here, as an alkyl group of a dialkylamino group, a C1-C6 thing is preferable. The ester residue is preferably an alkyl group having 1 to 6 carbon atoms. The dialkylamino group and the carboxyl group of the dialkylaminobenzoic acid are preferably bonded to the para position on the benzene ring. Of these, ethyl p-dimethylaminobenzoate is particularly preferred. Examples of commercially available dialkylaminobenzoic acid esters include Kayacure EPA and Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.). The content of the dialkylaminobenzoic acid ester is preferably 0.05 to 5% by mass with respect to the total amount of the radiation curable liquid pressure-sensitive adhesive composition, more preferably from the viewpoint of curability of the end face. It is 1-3 mass%, Most preferably, it is 0.2-1 mass%.

  The radiation-curable liquid pressure-sensitive adhesive composition can contain an aromatic thiol compound in order to improve the heat and moisture resistance. The aromatic thiol compound is preferably an aromatic heterocyclic compound having a mercapto group, and specific examples thereof include mercaptobenzoxazole, mercaptobenzothiazole, 1-phenyl-5-mercapto-1H-tetrazole and the like. Commercial products of the above aromatic thiol compounds include Noxeller M, Noxeller MP, Nocrack MB, Nocrack MMB (above, Ouchi Shinsei Chemical Co., Ltd.), Accel M, Antage MB (above, Kawaguchi Chemical Co., Ltd.), Sunseller M, Sunseller MG (manufactured by Sanshin Chemical Co., Ltd.), Soxinol M, Sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.), and the like. It is preferable that content of the said aromatic thiol compound is 0.01-5 mass% with respect to the whole quantity of the said radiation-curable liquid adhesive composition from a heat-and-moisture resistant point, More preferably, it is 0.05-4. % By mass.

  The radiation curable liquid pressure-sensitive adhesive composition may contain an antioxidant in order to improve thermal stability and color stability. Although there is no restriction | limiting in particular in the kind of said antioxidant, The hindered which has the structure where the methyl group and the C1-C8 hydrocarbon group couple | bonded with the carbon atom of the both sides of the carbon atom which the phenolic hydroxyl group couple | bonded. Phenol type antioxidants can be preferably used. Examples of the hindered phenol type antioxidant include benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxy, ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethyl Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol-bis {3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 2, 2-thio-diethylenebis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} and the like. As a commercial item of the said hindered phenol type antioxidant, Irganox 245,1035 (above, Ciba Specialty Chemicals company make), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd. make), etc. are mentioned, for example. The content of the hindered phenol-type antioxidant is preferably 0.01 to 3% by mass, more preferably based on the total amount of the radiation-curable liquid adhesive composition, from the viewpoint of thermal stability and color stability. It is 0.03-1 mass%, More preferably, it is 0.05-0.5 mass%.

(B) Manufacturing process The said deaeration process is a process of reducing the amount of dissolved oxygen from the said radiation-curable liquid adhesive composition. The method for producing an impact-resistant adhesive layer of the present invention comprises the degassing step, whereby when the radiation curable liquid adhesive composition is cured by radiation, the radiation irradiation side of the radiation curable liquid adhesive composition and its The opposite side can be cured with a good balance. The degassing method of the radiation curable liquid adhesive composition is not particularly limited as long as the amount of dissolved oxygen can be reduced from the radiation curable liquid adhesive composition. Examples of the degassing method include vacuum degassing by reducing the pressure of the reaction vessel containing the radiation curable liquid adhesive composition, and dissolving an inert gas such as nitrogen or helium in the radiation curable liquid adhesive composition. Inert gas bubbling by reducing the amount of dissolved oxygen, ultrasonic degassing by applying ultrasonic waves, the radiation curable liquid adhesive composition is brought into contact with a thin film such as a hollow fiber, and one space separated from the film And a thin film deaeration in which the gas concentration difference between the inside and outside of the thin film is degassed as a driving force. In the case of vacuum degassing, for example, degassing can be performed by reducing the pressure at room temperature (20 to 30 ° C.) and −0.09 MPaG for 1 hour while stirring the radiation curable liquid adhesive composition. .

      There is no particular limitation on the amount of dissolved oxygen contained in the radiation curable liquid adhesive composition after the degassing step. The amount of dissolved oxygen contained in the radiation curable liquid adhesive composition after the deaeration step is preferably 90% or less, more preferably 85% or less, more preferably 80% or less, particularly preferably 10 to 10% of the saturated oxygen amount. 75%. By setting the amount of dissolved oxygen in the above range, when the radiation curable liquid adhesive composition is cured by radiation, the radiation irradiation side of the radiation curable liquid adhesive composition and the opposite side can be cured in a balanced manner. it can. As a result, an impact resistant adhesive layer having an excellent balance between adhesiveness and impact resistance can be obtained, which is preferable.

  The application step is a step of applying the radiation curable liquid pressure-sensitive adhesive composition deaerated in the deaeration step to a base layer. There is no limitation in particular in the material of the said base layer, a kind, and a structure. As a member which comprises the said base layer, the glass plate of arbitrary materials, various resin (especially transparent resin), a functional member, etc. are mentioned, for example. These contents will be described later.

  The method for applying the radiation curable liquid adhesive composition to the base layer is not particularly limited. Examples of the application method include application by a roll coater, solvent casting method, spin coating method and the like. In addition, the application is not only a method of artificially applying the radiation curable liquid adhesive composition to the base layer, but the radiation curable liquid adhesive composition is dropped on the surface of the base layer, and then another member is attached. A method of spreading the radiation curable liquid pressure-sensitive adhesive composition over the entire surface of the base layer by disposing it on the surface of the base layer is also included.

  The said hardening process is a process of hardening the said radiation-curable liquid adhesive composition apply | coated by the said process by irradiating a radiation. The type of the radiation is not particularly limited as long as the radiation curable liquid adhesive composition can be cured. Examples of the radiation include active energy rays such as visible light, ultraviolet rays, electron beams, and X-rays. The radiation is preferably light (visible light or ultraviolet light). As the ultraviolet ray source, for example, a known irradiation device such as a mercury arc, a carbon arc, a low pressure mercury lamp, a medium / high pressure mercury lamp, a metal halide lamp, a chemical lamp, or a book light lamp can be used.

There is no particular limitation on the irradiation condition of the radiation. When ultraviolet rays are used as the radiation, the wavelength range of the ultraviolet rays is usually 150 to 500 nm, preferably 180 to 460 nm, and more preferably 200 to 400 nm. The peak irradiance of the ultraviolet, 50~1000mW / cm ^2, preferably 50 to 800 mW / cm ^2, more preferably 50~700mW / cm ^2, more preferably, to 50~600mW / cm ^2. Furthermore, the integrated light quantity of the ultraviolet light 100 to 2000 mJ / cm ^2, preferably 150~1500mJ / cm ^2, more preferably 200~1300mJ / cm ^2, more preferably, to 250~1000mJ / cm ^2.

In the method for producing an impact-resistant adhesive layer of the present invention, it is preferable that the ultraviolet irradiation condition is a low illuminance and a large integrated light quantity. That is, in the method for producing an impact-resistant adhesive layer of the present invention, it is preferable to irradiate ultraviolet rays with low illuminance for a long time. Specifically, for example, the conditions of the ultraviolet irradiation, the peak irradiance of the ultraviolet is 50~1000mW / cm ^2, and the accumulated light quantity of the ultraviolet light may be a condition of 100 to 2000 mJ / cm ^2. The preferable conditions for the ultraviolet irradiation can be the conditions in which the peak illuminance of the ultraviolet light is 50 to 800 mW / cm ² and the cumulative amount of the ultraviolet light is 150 to 1500 mJ / cm ² . More preferable conditions for the ultraviolet irradiation may be a condition in which the peak illuminance of the ultraviolet light is 50 to 700 mW / cm ² and the accumulated light amount of the ultraviolet light is 200 to 1300 mJ / cm ² . The preferable conditions for the ultraviolet irradiation may be a condition in which the peak illuminance of the ultraviolet light is 50 to 600 mW / cm ² and the accumulated light amount of the ultraviolet light is 250 to 1000 mJ / cm ² . By setting the peak illuminance and integrated light amount of the ultraviolet rays within the above ranges, the impact resistant adhesive layer has a good balance of transparency, adhesiveness and impact resistance, and the impact resistant radiation and radiation of the impact resistant adhesive layer are improved. Since curability can be improved, it is preferable.

  The irradiation with the radiation can be performed in an oxygen-free atmosphere substituted with an inert gas such as nitrogen gas. The irradiation with the radiation can also be performed in an air atmosphere. When irradiation with the radiation is performed in an air atmosphere, the adhesiveness of the impact-resistant adhesive layer on the radiation irradiation surface side can be increased.

  The thickness of the impact-resistant adhesive layer obtained by the production method of the present invention is not particularly limited, and can be set to various thicknesses depending on the application. The thickness of the impact-resistant adhesive layer obtained by the production method of the present invention is usually 2000 μm or less, preferably 100 to 1500 μm, more preferably 150 to 1000 μm, and more preferably 200 to 800 μm. It is preferable for the thickness to be within the above range since sufficient impact resistance can be maintained.

  The impact-resistant adhesive layer obtained by the production method of the present invention is excellent in transparency, adhesiveness and impact resistance. Specifically, the haze of the impact-resistant adhesive layer obtained by the production method of the present invention, the 180 ° peel adhesive strength, and the peak value of tan δ can be in the ranges described below.

(2) Impact resistant adhesive layer The impact resistant adhesive layer of the present invention has a thickness of 50 to 2000 μm, an adhesive strength of 0.1 to 10 N / 25 mm, a peak value of tan δ of 1 or more, and a haze of 1 or less. It is. The impact-resistant adhesive layer of the present invention is excellent in adhesive force and also in transparency, radiation curability and impact resistance. When the impact-resistant adhesive layer of the present invention is used, it is not necessary to separately provide an adhesive layer and an impact-resistant layer, and a laminated structure excellent in transparency, radiation curability and impact resistance can be easily obtained.

  As long as the impact-resistant adhesive layer of the present invention has the above thickness and physical properties, the material, shape, and structure are not particularly limited. The shock absorbing layer may have a single layer structure or a multilayer structure composed of two or more layers having the same or different materials and physical properties. Examples of the impact resistant adhesive layer having a multilayer structure include an impact resistant adhesive layer formed by laminating two or more layers having different tan δ peak values.

  The thickness of the impact-resistant adhesive layer of the present invention is 50 to 2000 μm, preferably 100 to 1500 μm, more preferably 150 to 1000 μm, and more preferably 200 to 800 μm. It is preferable for the thickness to be within the above range since sufficient impact resistance can be maintained.

  The 180 ° peel adhesive strength of the impact-resistant adhesive layer of the present invention is 0.1 N / 25 mm or more, preferably 0.3 N / 25 mm or more, more preferably 0.5 N / 25 mm or more, more preferably 0.8 N / 25 mm or more, Particularly preferably, it is 1 N / 25 mm or more and 10 N / 25 mm or less. The impact-resistant adhesive layer of the present invention has excellent adhesiveness because the 180 ° peel adhesive strength is in the above range. Moreover, the impact-resistant adhesive layer of this invention is excellent also in rework property by making 180 degree peeling adhesive force into the said range.

  The haze at 25 ° C. (especially 25 ° C., 0.5 mm thickness) of the impact-resistant adhesive layer of the present invention is 1 or less, preferably 0.5 or less, more preferably 0.3 or less. In addition, the measuring method of haze is a method as described in an Example. The impact-resistant adhesive layer of the present invention is excellent in transparency because the haze is in the above range.

  The peak value of tan δ of the impact-resistant adhesive layer of the present invention is 1.0 or more, preferably 1.1 or more, more preferably 1.2 or more, more preferably 1.3 or more. The method for measuring the peak value of tan δ is the method described in the examples. The impact-resistant adhesive layer of the present invention is excellent in impact resistance because the peak value of tan δ is in the above range.

  There is no limitation in particular in the method of obtaining the impact-resistant adhesion layer of this invention. The impact-resistant adhesive layer of the present invention can be usually obtained by the above-described method for producing an impact-resistant adhesive layer of the present invention.

  The radiation curable liquid pressure-sensitive adhesive composition may contain other components as necessary as long as the performance is not impaired. Examples of the other components are as described above.

(3) Impact-resistant adhesive laminate structure The impact-resistant adhesive laminate structure of the present invention includes the impact-resistant adhesive layer of the present invention and another layer provided on at least one surface of the impact-resistant adhesive layer.

  There are no particular limitations on the material, shape, and structure of the other layers. Examples of the other layers include a glass plate of any material, various resins (particularly transparent resin), and a functional member. Specific examples of the other layers include a protective film layer for protecting the impact-resistant adhesive layer of the present invention and various functional materials, and functional layers disposed in various display devices.

  Examples of the glass constituting the glass plate include borosilicate glass, aluminosilicate glass, and aluminoborosilicate glass, and low alkali glass and alkali-free glass in which the alkali metal content of these glasses is reduced. . In addition, silica glass, soda lime glass, or the like can be used.

  Specific examples of the resin include polycarbonate resins, acrylic resins such as polymethyl methacrylate, 1,2-polybutadiene resins, polyvinyl chloride resins, cyclic olefin copolymers, modified norbornene resins, norbornene. Resin, alicyclic acrylic resin, amorphous polyolefin such as polycyclohexylethylene, amorphous fluororesin, polystyrene resin, transparent ABS resin, polyethylene terephthalate, polyethylene naphthalate, amorphous copolyester, polyarylate, poly Methylpentene, polysulfone, polyethersulfone, polyetherimide, cellulose acetate, allyl diglycol carbonate resin, ethylene-vinyl acetate copolymer (EVA, usually containing 3% by mass or more vinyl acetate units), poly Styrene and polyolefin resins such as polypropylene, vinyl ester resins (excluding EVA.), Amorphous polyamide resins, urethane resins, epoxy resins, unsaturated polyester resins, and silicon resins. Of these, resins such as polycarbonate resins, acrylic resins, and polyester resins are preferable. In particular, these resins are preferably transparent.

  The protective film layer can be provided on at least one surface of the exposed surface of the impact-resistant adhesive layer of the present invention. For example, it can be provided on both exposed surfaces of the impact-resistant adhesive layer of the present invention. Further, it can be provided on one surface of the exposed surface of the impact-resistant adhesive layer of the present invention. The said protective film layer can be peeled from the impact-resistant adhesion layer of this invention. The impact-resistant adhesive laminate structure of the present invention can prevent the impact-resistant adhesive layer of the present invention from being damaged before use by having the protective film layer. Moreover, the impact-resistant adhesion laminated structure of this invention which has the said protective film layer can peel easily the said protective film layer at the time of use, and can obtain a laminated body easily by sticking on the other adherend surface.

  There are no particular limitations on the material, shape, and structure of the protective film layer. Specifically, as the material of the protective film layer, for example, polyester such as PET (polyethylene terephthalate), polyamide, polyimide, polyolefin, polycarbonate, acrylic resin, resin such as fluororesin, or resin is impregnated into paper. Resin-impregnated paper obtained by the above. In addition, the said protective film layer may be transparent and does not need to be transparent. The shape of the protective film layer may be a sheet or a film. Furthermore, the protective film layer may have a single layer structure or a laminate of two or more layers. In the impact-resistant adhesive laminate structure of the present invention, when there are two or more protective film layers, each protective film layer may be a protective film layer having the same material, shape, or structure, and the protective film having a different material, shape, or structure. You may use a layer together.

  Moreover, a peeling layer can be provided between the protective film layer and the impact-resistant adhesive layer. The impact-resistant pressure-sensitive adhesive laminated structure of the present invention can easily peel the protective film layer by having the release layer. The method for providing the release layer is not particularly limited. For example, the release layer can be provided by applying a release coating agent on the surface of the protective film layer. There is no particular limitation on the type of the release coating agent. Specific examples of the release coating agent include silicon coating agents, inorganic coating agents, fluorine coating agents, and organic-inorganic hybrid coating agents. The impact-resistant adhesive laminate structure of the present invention comprising the release layer is usually obtained by forming the impact-resistant adhesive layer of the present invention on the surface of the release layer after providing the release layer on the surface of the protective film layer. be able to.

  Examples of the functional layer include an ultraviolet cut plate, a polarizing plate (including various films constituting the polarizing plate), an array substrate, a color filter, a viewing angle widening film, an anti-reflection film, an anti-glare film, a transparent conductive film, and a layer. 1 type (s) or 2 or more types, such as a phase difference film, an electromagnetic wave absorption film, an infrared rays absorption film, and a film for touchscreens, are mentioned. Examples of various films constituting the polarizing plate include a polarizing film, a substrate film, and a protective film. If the other layer is a polarizing plate, an LCD can be produced by bonding the impact-resistant adhesive laminate structure of the present invention and the liquid crystal display panel via the impact-resistant adhesive layer.

  The impact-resistant adhesive laminate structure of the present invention only needs to include the impact-resistant adhesive layer of the present invention and another layer provided on at least one surface of the impact-resistant adhesive layer. Structure. The impact-resistant adhesive laminate structure of the present invention can be configured to have another layer on one exposed surface of the impact-resistant adhesive layer of the present invention (see FIG. 1). Moreover, the impact-resistant adhesive laminated structure of this invention can be set as the structure which has another layer in both the exposed surfaces of the impact-resistant adhesive layer of this invention (refer FIG. 2). Furthermore, the impact-resistant adhesive layer and the other layers may each be a single layer or a multilayer structure of two or more layers. When the impact-resistant adhesive layer has a multilayer structure of two or more layers, the configuration, thickness and physical properties of each impact-resistant adhesive layer may be the same or different. When the other layer has a multilayer structure of two or more layers, the type, configuration, thickness, and physical properties of each other layer may be the same or different.

  The impact-resistant adhesive laminated structure of this invention is illustrated in FIGS. FIG. 1 shows an impact-resistant adhesive laminate structure having another layer on one exposed surface of the impact-resistant adhesive layer of the present invention. The impact-resistant adhesive laminate structure A1 in FIG. 1 has a protective film layer 2 including the impact-resistant adhesive layer 1 and the release layer 21 of the present invention laminated. Moreover, FIG.2 and FIG.3 is an impact-resistant adhesion laminated structure provided with another layer on both the exposed surfaces of the impact-resistant adhesion layer of this invention. The impact-resistant adhesive laminate structure 2 in FIG. 2 is a structure having a protective film layer 2 having a release layer 21 on both surfaces of the impact-resistant adhesive layer 1 of the present invention. 3 has a protective film layer 2 having a release layer 21 on one surface of the impact-resistant adhesive layer 1 of the present invention, and a function such as a polarizing plate on the other surface. A structure having the layer 3.

  The impact-resistant adhesive laminate structure of the present invention can be produced by forming the impact-resistant adhesive layer of the present invention on at least one surface of the other layer. The impact-resistant adhesive laminate structure of the present invention can be usually produced by the method for producing an impact-resistant adhesive layer of the present invention, using the other layer as a base layer.

  Specific examples of the method for producing the impact-resistant adhesive laminate structure of the present invention using the above-mentioned other layers as the base layer and the impact-resistant adhesive layer production method of the present invention include the following methods. For example, in the impact-resistant adhesive laminate structure A1 of FIG. 1, the radiation-curable liquid adhesive composition is applied to the surface of the other layer (protective film layer 2), and then the radiation-curable liquid composition is irradiated by radiation. It can be obtained by curing the pressure-sensitive adhesive composition to form the impact-resistant pressure-sensitive adhesive layer 1 of the present invention. 2 is applied to the surface of the first other layer (protective film layer 2), and then the radiation-cured liquid adhesive composition is applied to the radiation-cured composition by radiation irradiation. The mold liquid pressure-sensitive adhesive composition can be cured, and then the second other layer (protective film layer 2 ′) can be bonded to the surface of the formed impact-resistant pressure-sensitive adhesive layer 1.

  2 is applied to the surface of the first other layer (protective film layer 2), and then the radiation-curable liquid composition applied. The second other layer (protective film layer 2 ′) is disposed so as to be in contact with the pressure-sensitive adhesive composition, and then the radiation-curable liquid pressure-sensitive adhesive composition is cured by irradiation with radiation. It can be obtained by forming the layer 1. Further, in the impact-resistant adhesive laminate structure of FIG. 2, the radiation-curable liquid adhesive composition is dropped on the surface of the first other layer (protective film layer 2), and then the first other layer ( By disposing the second other layer (protective film layer 2 ′) on the surface of the protective film layer 2), the radiation curable liquid adhesive composition is changed to the first other layer (protective film layer 2). ) And then curing the radiation-curable liquid pressure-sensitive adhesive composition by irradiation to form the impact-resistant pressure-sensitive adhesive layer 1 of the present invention.

  There is no limitation in particular in the use of the impact-resistant adhesion laminated structure of this invention. The impact-resistant adhesive layer constituting the impact-resistant adhesive laminate structure of the present invention is excellent in transparency, impact resistance and adhesiveness. Therefore, the impact-resistant adhesive laminate structure of the present invention can be used for display panels such as electronic and electric devices. The impact-resistant adhesive laminate structure of the present invention can be suitably used for, for example, an LCD panel, a plasma display panel (PDP), an organic EL display panel, a field emission display panel, an electronic paper display panel, and the like.

  Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not restrict | limited at all by these Examples. Further, “%” and “part” in the examples are based on mass unless otherwise specified.

(1) Preparation of radiation curable liquid adhesive composition The following materials were used as raw materials. And the radiation curable liquid adhesive composition (A1)-(A11) was prepared with the method as described below. Table 1 shows the compositions and ratios of the radiation curable liquid pressure-sensitive adhesive compositions (A1) to (A11).
(A) Acrylic syrup, trade name “BA-6” manufactured by Shinsetsu Kogyo Co., Ltd. (viscosity: 80000 cps, composition; acrylic acid / butyl acrylate = 6/94, polystyrene equivalent molecular weight of polymer in syrup; 1.7 million, molecular weight dispersion) (Mw / Mn: 3.1, solid content concentration: 16%)
Product name “2EHA-10” (viscosity: 60000 cps, composition: acrylic acid / 2-ethylhexyl acrylate = 10/90, polystyrene equivalent molecular weight of polymer in syrup; 1,200,000, molecular weight dispersion Mw / Mn 2.8, solid content concentration; 22%)
(B) Acrylate monomer Tetrahydrofurfuryl acrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, trimethylolpropane triacrylate, and isobornyl acrylate (C) silane coupling agent 3-methacryloxypropyltrimethoxysilane and 3-mercapto Propyltrimethoxysilane (D) urethane acrylate, manufactured by Daicel UC Corporation, trade name “Ebecryl 270”
(E) Photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

<Radiation curable liquid adhesive composition (A1)>
In a reaction vessel with an internal volume of 1 liter substituted with nitrogen, 350 g of acrylic syrup (manufactured by Shinsetsu Kogyo Co., Ltd., trade name “BA-6”), 350 g of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Industries), 70 g of urethane acrylate (Daicel Product name “Ebecryl 270” manufactured by UCB Co., Ltd.), 7 g of 3-methacryloxypropyltrimethoxysilane (trade name “KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.), 10.5 g of 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty) Chemicals, trade name “IRGACURE184”) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide 7 g (Asahi Denka Kogyo trade name “Optomer SP246”) were added. Next, the mixture was stirred at room temperature for 3 hours to obtain a radiation curable liquid pressure-sensitive adhesive composition (A1).

  Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring the radiation curable liquid adhesive composition (A1). The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A1) after 1 hour of vacuum degassing was 71% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A1) was 1%.

<Radiation curable liquid adhesive composition (A2)>
Instead of 350 g of the tetrahydrofurfuryl acrylate, 350 g of 2-ethylhexyl acrylate was used to obtain the radiation curable liquid pressure sensitive adhesive composition (A2) by the same method as the radiation curable liquid pressure sensitive adhesive composition (A1). Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A2) after 1 hour of vacuum degassing was 72% of the saturated oxygen content. Moreover, the weight reduction of the said radiation-curable liquid adhesive composition (A2) was 1%.

<Radiation curable liquid adhesive composition (A3)>
In place of 350 g of the tetrahydrofurfuryl acrylate, 175 g of the tetrahydrofurfuryl acrylate and 175 g of 2-ethylhexyl acrylate are used, and the radiation curable liquid pressure sensitive adhesive composition is prepared in the same manner as the radiation curable liquid pressure sensitive adhesive composition (A1). (A3) was obtained. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid adhesive composition (A3) after 1 hour of vacuum degassing was 72% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A3) was 1%.

<Radiation curable liquid adhesive composition (A4)>
In place of 350 g of the tetrahydrofurfuryl acrylate, 262.5 g of the tetrahydrofurfuryl acrylate and 87.5 g of 2-ethylhexyl acrylate are used, and the radiation curable type is obtained in the same manner as the radiation curable liquid adhesive composition (A1). A liquid adhesive composition (A4) was obtained. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A4) after 1 hour of vacuum degassing was 71% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A4) was 1%.

<Radiation curable liquid adhesive composition (A5)>
In place of 350 g of the tetrahydrofurfuryl acrylate, 350 g of the 4-hydroxybutyl acrylate is used, and the radiation curable liquid pressure sensitive adhesive composition (A5) is obtained by the same method as the radiation curable liquid pressure sensitive adhesive composition (A1). It was. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A5) after 1 hour of vacuum degassing was 73% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A5) was 1%.

<Radiation curable liquid adhesive composition (A6)>
Instead of 350 g of the tetrahydrofurfuryl acrylate, 175 g of the tetrahydrofurfuryl acrylate and 175 g of 4-hydroxybutyl acrylate are used, and the radiation curable liquid pressure sensitive adhesive composition is the same as the radiation curable liquid pressure sensitive adhesive composition (A1). A product (A6) was obtained. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A6) after 1 hour of vacuum degassing was 73% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A6) was 1%.

<Radiation curable liquid adhesive composition (A7)>
Instead of 350 g of the tetrahydrofurfuryl acrylate, 175 g of the tetrahydrofurfuryl acrylate and 175 g of trimethylolpropane triacrylate are used, and the radiation curable liquid pressure sensitive adhesive composition is the same as the radiation curable liquid pressure sensitive adhesive composition (A1). A product (A7) was obtained. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A7) after 1 hour of vacuum degassing was 70% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A7) was 1%.

<Radiation curable liquid adhesive composition (A8)>
The amount of 1-hydroxycyclohexyl phenyl ketone was 21 g, and instead of 7 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1.4 g of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( The radiation curable liquid adhesive composition (A8) was obtained in the same manner as the radiation curable liquid adhesive composition (A3) using a product name “IRGACURE819” manufactured by Ciba Specialty Chemicals. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid adhesive composition (A8) after 1 hour of vacuum degassing was 70% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A8) was 1%.

<Radiation curable liquid adhesive composition (A9)>
As the acrylic syrup, instead of the “BA-6”, the “2EHA-10” is used, and the radiation curable liquid adhesive composition (A9) is prepared in the same manner as the radiation curable liquid adhesive composition (A8). ) Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A9) after 1 hour of vacuum degassing was 71% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A9) was 1%.

<Radiation curable liquid adhesive composition (A10)>
Into a reaction vessel with an internal volume of 1 liter substituted with nitrogen, 350 g of acrylic syrup (trade name “2EHA-10”, manufactured by Shinseng Industries Co., Ltd.), 175 g of 2-ethylhexyl acrylate, 175 g of isobornyl acrylate, 70 g of urethane acrylate (Daicel UCB) Product name “Ebecryl 270”), 3-mercaptopropyltrimethoxysilane 7 g (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-503”), 1-hydroxycyclohexyl phenyl ketone 21 g (manufactured by Ciba Specialty Chemicals, Trade name “IRGACURE184”) and 1.4 g of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide were added. Subsequently, it stirred at room temperature for 3 hours and obtained the radiation-curable liquid adhesive composition (A10).

  Thereafter, the reaction vessel was depressurized, and vacuum deaeration was performed while stirring the radiation curable liquid adhesive composition (A10). The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A10) after 1 hour of vacuum degassing was 72% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A10) was 1%.

<Radiation curable liquid adhesive composition (A11)>
The above-mentioned radiation curable liquid adhesive composition (A11) using 525 g of “2EHA-10”, 35 g of 2-ethylhexyl acrylate, and 140 g of isobornyl acrylate, in the same manner as the above radiation curable liquid adhesive composition (A10). Got. Thereafter, the reaction vessel was depressurized and vacuum deaeration was performed while stirring. The dissolved oxygen content of the radiation curable liquid pressure-sensitive adhesive composition (A11) after 1 hour of vacuum degassing was 70% of the saturated oxygen content. The weight reduction of the radiation curable liquid pressure-sensitive adhesive composition (A11) was 1%.

In addition, the dissolved oxygen amount of the said radiation-curable liquid adhesive composition (A1)-(A11) was measured with the following method.
Into a reaction vessel having an internal volume of 1 liter substituted with dry air, 500 g of the radiation curable liquid pressure-sensitive adhesive composition is charged, then supplied with dry air, and stirred at room temperature for 1 hour, the radiation curable liquid pressure-sensitive adhesive composition. A saturated oxygen solution was prepared. The dry air was supplied while confirming with a pressure gauge so that the pressure in the reaction vessel was maintained at 1 atm. Then, using a DO meter for organic solvent (trade name “UC-12-SOL”, manufactured by Central Science Co., Ltd.), the saturated oxygen amount of the saturated oxygen solution of the radiation curable liquid adhesive composition (display value of the DO meter) ) Was measured. Next, using the DO meter, the amount of saturated oxygen (indicated value on the DO meter) of the radiation curable liquid adhesive composition that had been degassed in vacuum was measured. Based on these displayed values, the dissolved oxygen amount (%) was calculated from the following calculation formula.
Dissolved oxygen amount (%) = A / B
A: Display value of DO meter after vacuum deaeration B: Display value of DO meter of saturated oxygen solution

(2) Production of impact-resistant adhesive layer As a base layer, a polyester film with a release coat having a thickness of 100 μm (trade name “Purex A71” manufactured by Teijin DuPont) was used. And the said radiation-curable liquid adhesive composition (A1)-(A11) was apply | coated to the said peeling coat surface of the said base layer. The radiation curable liquid pressure-sensitive adhesive compositions (A1) to (A11) were applied by a bar coater. A metal halide lamp (manufactured by Eye Graphics) was used as an ultraviolet ray source. Then, the applied radiation curable liquid pressure-sensitive adhesive compositions (A1) to (A11) were irradiated with ultraviolet rays under conditions of a peak illuminance of 170 mW / cm ² and an integrated light amount of 500 mJ / cm ² . The radiation-curable liquid pressure-sensitive adhesive compositions (A1) to (A11) were cured by this ultraviolet irradiation to produce impact-resistant pressure-sensitive adhesive layers of Examples 1 to 9 and Comparative Examples 2 to 7. In addition, the thickness of the impact-resistant adhesive layer of Examples 1-9 and Comparative Examples 2-7 is shown in Table 2 and Table 3.

  The impact-resistant adhesive layer of Comparative Example 6 is an impact-resistant adhesive layer produced by the same method as in Example 1 except that vacuum degassing was not performed. The dissolved oxygen of the radiation-curable liquid adhesive composition used in Comparative Example 6 was 98% of the saturated oxygen amount.

(3) Evaluation The impact-resistant adhesive layers of Examples 1 to 9 and Comparative Examples 2 to 7 and a polarizing plate (trade name “Sumikaran SQ-1832A” manufactured by Sumitomo Chemical Co., Ltd.) to be a functional layer were bonded together. An impact-resistant adhesive laminate structure was obtained. The impact-resistant adhesive layer was bonded so that the ultraviolet irradiation surface was in contact with the polarizing plate. Subsequently, the polyester film with a release coat was peeled from the impact-resistant adhesive laminate structure. Then, the impact-resistant adhesive layers of Examples 1 to 9 and Comparative Examples 2 to 7 were bonded to a 4-inch square non-alkali glass plate (manufactured by Corning, trade name “# 1737”) with a thickness of 0.7 mm, Samples for evaluation comprising the impact-resistant adhesive layers of Examples 1 to 9 and Comparative Examples 2 to 7 were produced. In addition, a polarizing plate with a known pressure-sensitive adhesive (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikaran SQ-1832AP”) is used instead of the polarizing plate, and this and the base layer are bonded to form a laminated structure. A sample for evaluation of Comparative Example 1 was produced. Then, using these evaluation samples, transparency, tackiness, radiation curability and impact resistance were evaluated by the methods described below. The results are shown in Tables 2 and 3.

(A) Transparency About each said sample for evaluation, haze (%) in 25 degreeC was calculated | required using the model (BYSE-gardner Gmbh) make (haze-gard plus). Based on this haze, transparency was evaluated. When the haze is less than 1, the transparency is good, and when the haze value is 1 or more, the transparency is insufficient.
(B) Impact resistance [Test 1]
As a measuring device, a dynamic viscoelasticity measuring device (Rheometric Scientific FT, RSAII) was used. Using this apparatus, the temperature dispersion measurement from −70 ° C. to 150 ° C. was performed on the impact-resistant adhesive layers of Examples 1 to 9 and Comparative Examples 2 to 7, and the peak value of tan δ was measured. The measurement conditions are a frequency of 1 Hz and a tensile mode. When the peak value of tan δ is 1 or more, the impact resistance is good, and when the peak value of tan δ is less than 1, the impact resistance is insufficient.
[Test 2]
As shown in FIG. 4, a 1 mm thick acrylic plate 61 (manufactured by Nitto Resin Co., Ltd., “Clarex”) was placed on a base 62 made of marble or the like. The evaluation samples A of Examples 1 to 9 and Comparative Examples 1 to 7 were placed so that the alkali-free glass plate 4 was in contact with the acrylic plate 61. Subsequently, the iron ball 7 (diameter 5 cm, mass 550 g) was freely dropped from the predetermined height onto each of the evaluation samples A and collided. Then, the presence or absence of the glass crack of the said alkali free glass plate 4 was confirmed visually. And the lowest value was calculated | required as falling ball height (cm) in the height when the glass crack of the said alkali free glass plate 4 produced. The larger the falling ball height value, the better the impact resistance.
(C) Adhesiveness Each of the above impact-resistant adhesive laminate structures was cut with a width of 25 mm. Next, the polyester film with a release coat was peeled off from the impact-resistant adhesive laminate structure and bonded to a non-alkali glass subjected to a degreasing treatment. A 180 ° peel test was performed using the laminate bonded to the glass, and the peel strength (N / 25 mm) was measured. This peel strength was used as an index for tackiness. The 180 ° peel test was conducted using a tensile tester (manufactured by Shimadzu Corporation, trade name “AG2000”) under the conditions of 25 ° C. and a tensile speed of 300 mm / min.
(D) Radiation curable After producing the said impact-resistant adhesion laminated structure, it left still at room temperature for 1 week. Next, the occurrence of bubbles and floats was visually confirmed inside the impact-resistant adhesive layer and at the interface between the impact-resistant adhesive layer and the polarizing plate or the polyester film with release coat. Based on this result, radiation curability was judged by the following index. In addition, when radiation curability is not enough, the gas derived from an unreacted component aggregates and a bubble and a float generate | occur | produce.
○: No bubbles or floats are observed inside the shock-resistant adhesive layer or at the interface, and radiation curability is good.
X: Generation | occurrence | production of a bubble and a float are seen in the inside and interface of an impact-resistant adhesion layer, and it is inferior to radiation curability.

(Effect of Example)
Examples 1 to 9 having an impact-resistant adhesive layer of the present invention have a glass crack height of 30 to 110 cm, which is 6 times or more that of Comparative Example 1 having no impact-resistant adhesive layer. In Examples 1 to 9 having the impact-resistant adhesive layer of the present invention, the peak value of tan δ is 1.1 to 1.6. Therefore, it turns out that the impact-resistant adhesive layer of this invention is excellent in impact resistance. Moreover, Examples 1-9 which have an impact-resistant adhesion layer of this invention have a haze of 0.1, and it turns out that it is excellent in transparency.

  On the other hand, in Comparative Example 2, the thickness of the impact-resistant adhesive layer is outside the scope of the present invention. And it turns out that the comparative example 2 is inferior in impact resistance compared with Examples 1-9 whose glass crack height is 10 cm. Since Comparative Examples 3, 4 and 7 do not have the impact-resistant adhesive layer which is the transparency range of the present invention, the haze is 2.7 to 5.0 and is inferior in transparency. In Comparative Example 5, since the peak value of tan δ is as small as 0.6, the glass crack height is 20 cm, which is inferior in impact resistance. Moreover, the comparative example 6 has the impact-resistant adhesion layer obtained with the manufacturing method without a deaeration process. And in the comparative example 6, a bubble is seen in the interface of an impact-resistant adhesion layer and a polyester film with a peeling coat, and it turns out that it is inferior to radiation curability.

  Note that the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the present invention depending on the purpose and application.

  The impact-resistant adhesive layer and impact-resistant adhesive laminate structure of the present invention can be applied to various uses that require transparency, adhesiveness, and impact resistance. For example, the impact-resistant adhesive layer and impact-resistant adhesive laminate structure of the present invention can be applied to glass for automobiles, glass for building materials, bulletproof glass, etc., in addition to the above-described display devices such as electronic and electrical devices.

It is a schematic cross section for demonstrating an example of the shock absorption laminated structure of this invention. It is a schematic cross section for demonstrating an example of the shock absorption laminated structure of this invention. It is a schematic cross section for demonstrating an example of the shock absorption laminated structure of this invention. It is a schematic diagram for demonstrating the impact resistance test of a present Example.

Explanation of symbols

  A: Sample for evaluation, A1, A2, A3; Impact-resistant adhesive laminated structure, 1; Impact-resistant adhesive layer, 2, 2 '; Protective film layer, 21; Release layer, 3; Functional layer, 4; Board 61; acrylic board 62; base 7; iron ball.

Claims (8)

A degassing step of degassing the radiation curable liquid adhesive composition;
An application step of applying the radiation curable liquid adhesive composition degassed by the deaeration step to the surface of the base layer;
A curing step of curing the radiation-curable liquid adhesive composition applied by the application step by irradiating with radiation; and
The manufacturing method of the impact-resistant adhesion layer characterized by comprising sequentially.   The radiation curable liquid pressure-sensitive adhesive composition contains (A) acrylic syrup, (B) acrylate monomer, (C) silane coupling agent, (D) urethane (meth) acrylate, and (E) photopolymerization initiator. The method for producing an impact-resistant adhesive layer according to claim 1, which is a radiation curable liquid adhesive composition.   The method for producing an impact-resistant adhesive layer according to claim 1 or 2, wherein the amount of dissolved oxygen contained in the radiation-curable liquid adhesive composition after the degassing step is 90% or less of the saturated oxygen amount. The radiation is ultraviolet light, impact-adhesive layer according to any one of claims 1 to 3 peak irradiance 50~1000mW / cm ^2, and the accumulated amount of light irradiating the ultraviolet rays under the condition of 100 to 2000 mJ / cm ² Manufacturing method.   The method for producing an impact-resistant adhesive layer according to any one of claims 1 to 4, wherein the resulting impact-resistant adhesive layer has a thickness of 50 to 2000 µm.   An impact-resistant adhesive layer having a thickness of 50 to 2000 μm, a 180 ° peel adhesive strength of 1 to 10 N / 25 mm, a tan δ peak value of 1 or more, and a haze at 25 ° C. of 1 or less.   An impact-resistant adhesive layer obtained by the method according to any one of claims 1 to 5.   An impact-resistant adhesive laminate structure comprising: the impact-resistant adhesive layer according to claim 6 or 7; and another layer provided on at least one surface of the impact-resistant adhesive layer.

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