Polyisocyanate composition, resin composition, resin cured film, adhesive resin composition, adhesive resin sheet and laminated film

Abstract

To provide a polyisocyanate composition which enables production of an adhesive resin sheet that is excellent in hardness and transparency of a cured film, and is excellent in adhesive force, curability, transparency, bending resistance and workability.SOLUTION: A polyisocyanate composition contains a polyisocyanate composition (I) and a polyisocyanate composition (II), wherein a weight ratio of the polyisocyanate composition (I) to the polyisocyanate composition (II), which is represented by the following expression (P), is 4 or more and 15 or less, and the weight average molecular weight is 2,000 or more and 200,000 or less. Expression (P): [(II) / [(I)+(II)]]×100.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyisocyanate composition, a resin composition, a resin cured film, a pressure-sensitive adhesive resin composition, a pressure-sensitive adhesive resin sheet, and a laminated film.

Background Art

[0002] In recent years, plastic films and adhesives have been used in various fields because they have a wide range of functions. Under such circumstances, not only applications to flat parts but also applications to parts that have not been used much so far, such as curved surfaces, bent parts, and parts with stretching and shrinking movements, have been increasing. For example, applications such as flexible displays, foldable displays, bonding of automobile members, and bonding of those with large unevenness have been cited, and the demand has been rapidly expanding in recent years. Along with this, highly flexible films and adhesives that have good followability, flex resistance, stretchability, and toughness with respect to curved surfaces and bending are required. In addition, for optical applications, high transparency, specifically, a low haze value, for example, 3.0% or less, is also required at the same time. Furthermore, processability is also required for adhesives.

[0003] For example, Patent Document 1 discloses a method for producing a prepolymer for a stretchable polyurethane paint, which includes reacting an aliphatic diisocyanate or an alicyclic diisocyanate with a polycaprolactone diol and / or triol having a number average molecular weight of 500 or more and 1500 or less. In addition, Patent Document 2 discloses a mixture of a prepolymer obtained by reacting an aliphatic diisocyanate or an alicyclic diisocyanate with a polytetramethylene glycol having a number average molecular weight of 700 or more and 1500 or less, and a prepolymer obtained by reacting an aliphatic diisocyanate or an alicyclic diisocyanate with a polycaprolactone polyol having a number average molecular weight of 500 or more and 1500 or less.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 61-028518 [Patent Document 2] Japanese Patent Application Laid-Open No. 02-001718 [Summary of the Invention] [Problems to be Solved by the Invention]

[0005] However, in the conventional polyisocyanates modified with polyester polyols or polyether polyols described in Patent Document 1, Patent Document 2, etc., there is room for improvement in flexibility. Further, in these documents, the study has been limited to the use in paints, and the application to adhesives has not been specifically studied, and furthermore, the relationship between the structure of polyisocyanates and transparency has not been focused on at all. Also, a polyisocyanate necessary for obtaining an adhesive having good followability, flex resistance, stretchability, high adhesive strength, and good processability with respect to curved surfaces and bending has not been found so far.

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyisocyanate composition in which a cured film obtained by curing the polyisocyanate composition alone has good hardness and transparency. Furthermore, an object thereof is to provide a polyisocyanate composition capable of producing a coating film excellent in elongation rate and tensile breaking stress. Furthermore, an object thereof is to provide a polyisocyanate composition capable of producing a pressure-sensitive adhesive resin sheet excellent in adhesive strength, curability, transparency, flex resistance, and processability. [Means for Solving the Problems]

[0007] That is, the present invention includes the following aspects. A polyisocyanate composition comprising a polyisocyanate composition (I) and a polyisocyanate composition (II), wherein the polyisocyanate composition (I) is a derivative of a di(tri)isocyanate and a polyester polyol, the di(tri)isocyanate is at least one selected from the group consisting of an aliphatic di(tri)isocyanate and an alicyclic di(tri)isocyanate, the polyester polyol is either one or both of a bifunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more and 2200 or less, the molar ratio of the isocyanate groups of the di(tri)isocyanate to the hydroxyl groups of either one or both of the polyester polyol (A) and the polyester polyol (B) is 2.0 or more and 30.0 or less, the polyisocyanate composition (I) has a weight average molecular weight of 2500 or more and 200000 or less, the polyisocyanate composition (II) is a derivative of at least one diisocyanate selected from the group consisting of an aliphatic di(tri)isocyanate and an alicyclic di(tri)isocyanate, the polyisocyanate composition (II) has a weight average molecular weight of 500 or more and 6000 or less, an isocyanate group content of 12.0% by mass or more, and an average isocyanate functionality of 2.0 or more and 6.0 or less, and the weight ratio of the polyisocyanate composition (I) to the polyisocyanate composition (II) represented by the following (P) is 4 or more and 15 or less, and the weight average molecular weight is 2000 or more and 200000 or less. [(II) / 〔(I)+(II)〕]×100 ···(P) [2] The polyisocyanate composition according to [1], wherein the average isocyanate functionality is 2.2 or more and 6.0 or less. [3] The polyisocyanate composition according to [1] or [2], wherein the isocyanate group content is 3.0% by mass or more and 10.0% by mass or less. [4] The polyisocyanate composition (I) is the polyisocyanate composition according to any one of [1] to [3], wherein the content of the polyester polyol (A) is 0.1 part by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the diisocyanate, and the content of the polyester polyol (B) is 0.1 part by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the diisocyanate. [5] The polyisocyanate composition according to any one of [1] to [4], wherein the polyester polyol is a polycaprolactone polyol. [6] The polyisocyanate composition according to any one of [1] to [5], wherein the König hardness of the cured film cured under the following curing conditions is 15 or more and 90 or less. Curing conditions: The polyisocyanate composition is applied on glass, and a cured film with a film thickness of 40 μm formed after storage in an environment of 23 °C and 65% humidity for 168 hours is used as the measurement object, and the König hardness in an environment of 23 °C is measured. [7] The polyisocyanate composition according to any one of [1] to [6], wherein the haze value measured under the following conditions is 3.0% or less. Measurement conditions: The polyisocyanate composition is applied on glass, and a cured film with a film thickness of 40 μm formed after storage in an environment of 23 °C and 65% humidity for 168 hours is pasted on glass with a haze value of 0.1%, and measured with a haze meter. [8] A resin composition containing the polyisocyanate composition according to any one of [1] to [7] and a polyol, wherein the polyol has a glass transition temperature of 0 °C or more and 100 °C or less, a hydroxyl value of 10 mgKOH / g or more and 400 mgKOH / g or less, and a weight average molecular weight of 5.0×10 3 or more × 2.0×10 5 or less, and the molar ratio (NCO / OH) of the isocyanate group of the polyisocyanate composition to the hydroxyl group of the polyol is 0.01 or more and 50 or less. [9]The resin composition according to [8], wherein the blending amount of the polyisocyanate composition with respect to 100 parts by mass of the polyol is 0.01 part by mass or more and 200 parts by mass or less.

[10] A resin cured film obtained by curing the resin composition according to [8] or [9], wherein a test piece produced by curing under the following conditions has an elongation rate of 140% or more, a stress at an elongation rate of 140% of 30.0 MPa or less, and a tensile breaking stress of 1.2 times or more the stress at the elongation rate of 140%: a resin cured film. Conditions: A resin composition in which the molar ratio (NCO / OH) of the isocyanate group of the polyisocyanate composition to the hydroxyl group of the polyol is 1 is cured at 90°C for 30 minutes, and after storage for 168 hours in an environment of 23°C and 65% humidity, a test piece obtained by cutting a coating film with a thickness of 40 μm formed into a width of 10 mm and a length of 100 mm.

[11] An adhesive resin composition comprising the polyisocyanate composition according to any one of [1] to [7] and a crosslinkable functional group-containing polymer having a glass transition temperature of 0°C or lower.

[12] The adhesive resin composition according to

[11] , wherein the crosslinkable functional group-containing polymer is an acrylic polymer, a urethane polymer, or a rubber polymer.

[13] The crosslinkable functional group-containing polymer according to

[11] or

[12] , which is copolymerized from a polymerizable (meth)acrylic monomer having a crosslinkable functional group and a (meth)acrylic acid ester monomer having 1 to 18 carbon atoms at the ester group terminal, and has a glass transition temperature Tg of -75.0°C or higher and 0.0°C or lower: the adhesive resin composition.

[14] The weight average molecular weight of the crosslinkable functional group-containing polymer is 1.0×10 5 or more and 5.0×10 6 or less: the adhesive resin composition according to any one of

[11] to

[13] .

[15] The crosslinkable functional group contained in the crosslinkable functional group-containing polymer is one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, a vinyl group, an amino group, and an oxetane group: the adhesive resin composition according to any one of

[11] to

[14] .

[16] The content of the polyisocyanate composition with respect to 100 parts by mass of the crosslinkable functional group-containing polymer is 0.01 part by mass or more and 20.00 parts by mass or less, and the pressure-sensitive adhesive resin composition according to any one of

[11] to

[15] .

[17] A pressure-sensitive adhesive resin sheet obtained by curing the pressure-sensitive adhesive resin composition according to any one of

[11] to

[16] .

[18] The pressure-sensitive adhesive resin sheet according to

[17] , wherein the thickness of the pressure-sensitive adhesive resin sheet is 1 μm or more and 1000 μm or less.

[19] The pressure-sensitive adhesive resin sheet according to

[17] or

[18] , wherein the gel fraction of the pressure-sensitive adhesive resin sheet is 20.00% by mass or more and 99.99% by mass or less.

[20] A laminate comprising the pressure-sensitive adhesive resin sheet having a thickness of 50 μm, a width of 20 mm, and a length of 100 mm is attached to a SUS304BA plate as an adherend, pressure-bonded once back and forth with a 2 kg roller, cured at 23°C for 30 minutes, and the 180-degree peel adhesive force measured at a speed of 23°C and 300 mm / min is 0.01 N / 20 mm or more and 100 N / 20 mm or less. The pressure-sensitive adhesive resin sheet according to any one of

[17] to

[19] .

[21] The pressure-sensitive adhesive resin composition according to any one of

[11] to

[16] is coated on a peeled polyethylene terephthalate film having a thickness of 38 μm, dried at 135°C for 3 minutes and cured, then stored in an environment of 23°C and 50% RH for 7 days, peeled from the peeled polyethylene terephthalate film, and the obtained pressure-sensitive adhesive resin sheet having a thickness of 50 μm is attached to glass having a haze value of 0.1%, and the haze value measured with a haze meter is 2.0% or less. A pressure-sensitive adhesive resin sheet.

[22] A laminated film having a film on at least one side of the pressure-sensitive adhesive resin sheet according to any one of

[17] to

[21] , and these are laminated.

[23] The laminated film according to

[22] , wherein the film is selected from at least one of polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide, and triacetyl cellulose resins.

[24] The laminated film according to

[22] or

[23] , which is used for optical applications.

Advantages of the Invention

[0008] According to the present invention, a polyisocyanate composition can be provided in which the cured film obtained by curing the polyisocyanate composition alone has good hardness and transparency. Furthermore, a polyisocyanate composition can be provided that can produce a coating film excellent in elongation and tensile breaking stress. Furthermore, a polyisocyanate composition can be provided that can produce a pressure-sensitive adhesive resin sheet excellent in adhesive strength, curability, transparency, flex resistance, and processability.

[0009] In this specification, a cured product obtained by curing a polyisocyanate composition alone is referred to as a cured film. In this specification, a cured product obtained by curing a resin composition containing a polyisocyanate composition is referred to as a resin cured film. In this specification, a cured product obtained by curing a pressure-sensitive adhesive resin composition containing a polyisocyanate composition is referred to as a pressure-sensitive adhesive resin sheet.

Embodiments for Carrying Out the Invention

[0010] <Polyisocyanate Composition> The polyisocyanate composition of this embodiment includes a polyisocyanate composition (I) and a polyisocyanate composition (II). Detailed descriptions of the polyisocyanate composition (I) and the polyisocyanate composition (II) will be given later. The polyisocyanate composition (I) is a component that imparts flexibility and strength to a cured product obtained by curing the polyisocyanate composition alone or to a cured product of a composition containing the polyisocyanate composition. The polyisocyanate composition (II) is a component that imparts hardness to a cured product of the polyisocyanate composition or to a cured product of a composition containing the polyisocyanate composition.

[0011] The polyisocyanate composition of the present embodiment is represented by the following (P), and the weight ratio of the polyisocyanate composition (I) to the polyisocyanate composition (II) is 4 or more and 15 or less, preferably 4.5 or more and 14 or less, and more preferably 4.8 or more and 13 or less.

[0012] For the calculation of the following (P), the weight when the solid content of the polyisocyanate composition (I) is 100% is used as the value of the polyisocyanate composition (I), and the weight when the solid content of the polyisocyanate composition (II) is 100% is used as the value of the polyisocyanate composition (II).

[0013] [(II) / 〔(I)+(II)〕]×100 ···(P)

[0014] When a polyisocyanate composition in which the value of (P) satisfies the above range is used, a cured film having good flexibility, hardness, strength and transparency, a resin cured film excellent in elongation and tensile breaking stress, and an adhesive resin sheet excellent in adhesiveness, curability, transparency, flex resistance and processability can be obtained.

[0015] The weight average molecular weight of the polyisocyanate composition of the present embodiment is 2000 or more, preferably 2100 or more, more preferably 2200 or more, further preferably 2300 or more, and particularly preferably 2400 or more. The upper limit of the weight-average molecular weight of the polyisocyanate composition of the present embodiment is 200,000, preferably 180,000, more preferably 150,000, still more preferably 120,000, still more preferably 100,000, still more preferably 80,000, still more preferably 70,000, and most preferably 50,000.

[0016] The weight-average molecular weight of the polyisocyanate composition of the present embodiment can be measured, for example, by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC").

[0017] The isocyanate group content (NCO group content) of the polyisocyanate composition of the present embodiment is preferably 3.0% by mass or more and 10.0% by mass or less, more preferably 3.5% by mass or more and 9.8% by mass or less, still more preferably 4.0% by mass or more and 9.6% by mass or less, and particularly preferably 5.0% by mass or more and 9.5% by mass or less, based on the total mass of the polyisocyanate composition in a state substantially free of solvents and diisocyanates.

[0018] The NCO group content can be determined, for example, by reacting the isocyanate groups of the polyisocyanate composition with an excess of an amine (such as dibutylamine) and back-titrating the remaining amine with an acid such as hydrochloric acid.

[0019] The average isocyanate functionality of the polyisocyanate composition of the present embodiment is more preferably 2.2 or more and 6.0 or less from the viewpoint of enhancing the curability and flexibility of the pressure-sensitive adhesive resin composition. The average isocyanate functionality of the polyisocyanate composition of the present embodiment can be measured using the method described in the examples below.

[0020] The polyisocyanate composition of the present embodiment is preferably liquid at 23°C from the viewpoint of handling properties such as compounding when diluted with a solvent such as butyl acetate or ethyl acetate.

[0021] By having the above configuration, the polyisocyanate composition of this embodiment has a cured film obtained by curing the polyisocyanate composition alone with a hardness that is lower than before and not too low, and good flexibility and transparency. Further, by using the polyisocyanate composition of this embodiment, a resin cured film can be obtained with a stress at an elongation rate of 140% that is lower than before, an elongation rate higher than that of conventional products, and a high tensile breaking stress. Furthermore, by using the polyisocyanate composition of this embodiment, an adhesive resin sheet excellent in adhesiveness, curability, transparency, flex resistance, and processability can be obtained. Next, each constituent of the polyisocyanate composition of this embodiment will be described in detail below.

[0022] ≪Polyisocyanate Composition (I)≫ The polyisocyanate composition (I) is a derivative of di(tri)isocyanate and polyester polyol. The di(tri)isocyanate is at least one selected from the group consisting of aliphatic di(tri)isocyanates and alicyclic di(tri)isocyanates.

[0023] The polyisocyanate composition (I) has a weight average molecular weight of 2500 or more and 200000 or less, preferably 3000 or more and 150000 or less, and more preferably 3500 or more and 100000 or less.

[0024] When the weight average molecular weight of the polyisocyanate composition (I) is within the above range, it is preferable from the viewpoints of flexibility and high elongation rate.

[0025] The polyester polyol is either one or both of a bifunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more and 2200 or less.

[0026] In the polyisocyanate composition of the present embodiment, the molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of either one or both of the polyester polyol (A) and the polyester polyol (B) (molar ratio of isocyanate groups / hydroxyl groups) is 2.0 or more and 30.0 or less, preferably 2.0 or more and 25.0 or less, more preferably 2.1 or more and 23.0 or less, still more preferably 2.2 or more and 20.0 or less, yet more preferably 2.3 or more and 20.0 or less, yet more preferably 2.4 or more and 20.0 or less, yet more preferably 2.5 or more and 20.0 or less, and most preferably 2.52 or more and 20.0 or less.

[0027] The molar ratio of isocyanate groups / hydroxyl groups can be calculated, for example, using the molar amounts of the hydroxyl groups of the polyester polyol (A) and the polyester polyol (B) used in the production of the polyisocyanate composition and the molar amount of the isocyanate groups of the diisocyanate.

[0028] The polyisocyanate composition (I) has a structural unit derived from a diisocyanate and one or more of the above polyester polyols in one molecule. When the polyisocyanate composition (I) is derived from a diisocyanate and either one or both of the polyester polyol (A) and the polyester polyol (B), it may be a polyisocyanate having all the structural units derived from the diisocyanate and either one or both of the polyester polyol (A) and the polyester polyol (B) in one molecule, or a mixture of a polyisocyanate having a structural unit derived from the diisocyanate and the polyester polyol (A) in one molecule and a polyisocyanate having a structural unit derived from the diisocyanate and the polyester polyol (B) in one molecule.

[0029] The polyisocyanate composition (I) can have at least one or more structures selected from the group consisting of allophanate structure, uretdione structure, iminooxadiazinedione structure, isocyanurate structure, urea structure, urethane structure, and biuret structure. Among them, it preferably has at least one structure selected from the group consisting of urethane structure, allophanate structure, biuret structure, urea structure, uretdione structure, and isocyanurate structure, more preferably has at least one structure selected from the group consisting of urethane structure, allophanate structure, biuret structure, urea structure, and uretdione structure, still more preferably has at least one structure selected from the group consisting of urethane structure, allophanate structure, urea structure, and uretdione structure, even more preferably has at least one structure selected from the group consisting of urethane structure, allophanate structure, and uretdione structure, still even more preferably has at least one structure selected from the group consisting of urethane structure and allophanate structure, and most preferably has a urethane structure.

[0030] [Diisocyanate] The diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

[0031] Examples of the aliphatic diisocyanate include, but are not limited to, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato) hexanoate, 1,6-diisocyanatohexane (hereinafter sometimes abbreviated as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, etc. These aliphatic diisocyanates may be used alone or in combination of two or more.

[0032] Examples of alicyclic diisocyanates include, but are not limited to, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter may be abbreviated as "hydrogenated XDI"), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl-1-isocyanato-3-(isocyanatomethyl)cyclohexane (hereinafter may be abbreviated as "IPDI"), 4,4'-diisocyanato-dicyclohexylmethane (hereinafter may be abbreviated as "hydrogenated MDI"), 2,5- or 2,6-diisocyanatomethylnorbornane, and the like. These alicyclic diisocyanates may be used alone or in combination of two or more.

[0033] These aliphatic diisocyanates and alicyclic diisocyanates may be used alone or in combination of two or more of the aliphatic diisocyanate and the alicyclic diisocyanate. Also, from the viewpoint of flexibility, the mass ratio of the alicyclic polyisocyanate to the aliphatic diisocyanate is preferably 0 / 100 or more and 30 / 70 or less.

[0034] Among them, as the diisocyanate, 1,4-diisocyanatobutane, HDI, PDI (1,5-pentamethylene diisocyanate), 1,7-diisocyanatoheptane, 1,8-diisocyanatooctane, IPDI, hydrogenated XDI, or hydrogenated MDI is preferable, HDI, PDI or IPDI is more preferable, and HDI, PDI is even more preferable.

[0035] In the production of the polyisocyanate, in addition to the diisocyanates described above, isocyanate monomers as shown below may be further used. Aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), 4-isocyanatomethyl-1,8-octamethylene diisocyanate (hereinafter may be referred to as "NTI"), bis(2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter may be referred to as "GTI").

[0036] [Triisocyanate] As the triisocyanate, triisocyanates such as 1,3,6-hexamethylene triisocyanate (hereinafter may be referred to as "HTI"), lysine triisocyanate (hereinafter may be referred to as "LTI") can be used.

[0037] [Polyester polyol (A) and polyester polyol (B)] The polyester polyol constituting the polyisocyanate composition (I) is either one or both of polyester polyol (A) and polyester polyol (B). Polyester polyol (A) has a number average molecular weight of 500 or more and is a bifunctional polyester polyol (diol). Polyester polyol (B) has a number average molecular weight of 500 or more and 2200 or less and is a trifunctional or higher polyester polyol.

[0038] The number average molecular weight of polyester polyol (A) is 500 or more, preferably 800 or more, more preferably 1500 or more, and still more preferably 1800 or more. When the number average molecular weight of polyester polyol (A) is at least the above lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.

[0039] On the other hand, the upper limit value of the number average molecular weight of the polyester polyol (A) is not particularly limited, but for example, it can be 7000, preferably 6000, more preferably 5000, and even more preferably 4500.

[0040] The number average molecular weight Mn of the polyester polyol (A) is, for example, the number average molecular weight based on polystyrene by GPC measurement. When two or more kinds of polyester polyols (A) are mixed and used, the number average molecular weight of the mixture is calculated.

[0041] The number average molecular weight of the polyester polyol (B) is 500 or more and 2200 or less, preferably 800 or more and 2200 or less, and more preferably 800 or more and 1600 or less. The number average molecular weight Mn of the polyester polyol (B) is, for example, the number average molecular weight based on polystyrene by GPC measurement. When two or more kinds of polyester polyols (B) are mixed and used, the number average molecular weight of the mixture is calculated.

[0042] Examples of the polyester polyol (A) include, for example, the polyester polyol of any one of the following (1) or (2). (1) A polyester polyol obtained by a condensation reaction of a dibasic acid alone or a mixture of two or more kinds and a dihydric alcohol alone or a mixture of two or more kinds. (2) A polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with a dihydric alcohol. Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol. Among them, as the polyester polyol (A), a bifunctional polycaprolactone polyol is preferable.

[0043] Examples of commercially available bifunctional polycaprolactone polyols include, for example, "Placcel 210" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH / g, acid value 0.09 mgKOH / g), "Placcel 210CP" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH / g, acid value 0.16 mgKOH / g), trade name "Placcel 212" (number average molecular weight 1250, hydroxyl value 90.8 mgKOH / g, acid value 0.09 mgKOH / g), trade name "Placcel 212CP" (number average molecular weight 1250, hydroxyl value 90.2 mgKOH / g, acid value 0.14 mgKOH / g), "Placcel 220" (number average molecular weight 2000, hydroxyl value 56.7 mgKOH / g, acid value 0.06 mgKOH / g), "Placcel 220CPB" (number average molecular weight 2000, hydroxyl value 57.2 mgKOH / g, acid value 0.16 mgKOH / g), "Placcel 220CPT" (number average molecular weight 2000, hydroxyl value 56.6 mgKOH / g, acid value 0.02 mgKOH / g), "Placcel 230" (number average molecular weight 3000, hydroxyl value 37.6 mgKOH / g, acid value 0.07 mgKOH / g), "Placcel 240 (number average molecular weight 4000, hydroxyl value 28.5 mgKOH / g, acid value 0.07 mgKOH / g), etc. As the bifunctional polycaprolactone polyol, from the viewpoints of hydrolysis resistance and reaction stability during polyisocyanate synthesis, it is preferable to use one with a lower acid value.

[0044] As the polyester polyol (B), any polyester polyol having 3 or more functional groups may be used, and a polyester polyol having 3 to 10 functional groups is preferable, a polyester polyol having 3 to 7 functional groups is more preferable, a polyester polyol having 3 to 5 functional groups is further preferable, a polyester polyol having 3 to 4 functional groups is particularly preferable, and a trifunctional polyester polyol (triol) is most preferable.

[0045] Examples of the trifunctional polyester polyol (B) include, for example, the following polyester polyols (1) or (2). (1) A polyester polyol obtained by a condensation reaction of a dibasic acid alone or a mixture of two or more kinds thereof and a trivalent alcohol alone or a mixture of two or more kinds thereof. (2) A polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with a trivalent alcohol. Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the trivalent alcohol include trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane, and the like. Among them, as the trifunctional polyester polyol (B), a trifunctional polycaprolactone polyol is preferable.

[0046] Examples of commercially available trifunctional polycaprolactone polyols include, for example, "Placcel 305" (number average molecular weight 550, hydroxyl value 305.6 mgKOH / g, acid value 0.50 mgKOH / g), "Placcel 308" (number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g), "Placcel 309" (number average molecular weight 900, hydroxyl value 187.3 mgKOH / g, acid value 0.20 mgKOH / g), "Placcel 312" (number average molecular weight 1250, hydroxyl value 136.1 mgKOH / g, acid value 0.38 mgKOH / g), "Placcel 320" (number average molecular weight 2000, hydroxyl value 85.4 mgKOH / g, acid value 0.29 mgKOH / g) manufactured by Daicel Corporation; "Polyolite OD-X-2735" (number average molecular weight 500), "Polyolite OD-X-2542C" (number average molecular weight 850), "Polyolite OD-X-2588" (number average molecular weight 1250) manufactured by DIC Corporation, and the like.

[0047] In the polyisocyanate composition (I), the content (charged amount) of the polyester polyol (A) with respect to 100 parts by mass of the diisocyanate is preferably 0.1 part by mass or more and 900 parts by mass or less, more preferably 0.5 part by mass or more and 850 parts by mass or less, still more preferably 1 part by mass or more and 800 parts by mass or less, and particularly more preferably 1 part by mass or more and 750 parts by mass or less.

[0048] When the content of the polyester polyol (A) is at least the above lower limit value, the hardness of the cured film obtained by curing the polyisocyanate composition alone is low and the flexibility is better. In addition, an adhesive resin sheet excellent in adhesiveness and curability can be obtained. On the other hand, when the content of the polyester polyol (A) is at most the above upper limit value, the polyisocyanate composition can maintain a liquid state without gelling during production, and has a high elongation rate and breaking strength, and better flexibility when made into an adhesive resin sheet.

[0049] The content of the polyester polyol (A) can be calculated, for example, from the blending amounts of the diisocyanate and the polyester polyol (A) during the production of the polyisocyanate composition and the yield of the obtained polyisocyanate composition.

[0050] In the polyisocyanate composition (I), the content (charged amount) of the polyester polyol (B) with respect to 100 parts by mass of the diisocyanate is preferably 0.1 part by mass or more and 900 parts by mass or less, more preferably 0.5 part by mass or more and 850 parts by mass or less, still more preferably 1 part by mass or more and 800 parts by mass or less, and particularly more preferably 1 part by mass or more and 750 parts by mass or less.

[0051] When the content of the polyester polyol (B) is at least the above lower limit value, the hardness of the cured film obtained by curing the polyisocyanate composition alone is low and the flexibility is better. Moreover, a pressure-sensitive adhesive resin sheet excellent in adhesiveness and curability can be obtained. On the other hand, when the content of the polyester polyol (B) is not more than the above upper limit value, the liquid state can be maintained without gelation during the production of the polyisocyanate composition, and the flexibility when the pressure-sensitive adhesive resin sheet is obtained is better.

[0052] The content of the polyester polyol (B) can be calculated, for example, from the blending amounts of the diisocyanate and the polyester polyol (B) during the production of the polyisocyanate composition, and the yield of the obtained polyisocyanate composition.

[0053] [Method for Producing Polyisocyanate Composition (I)] The polyisocyanate composition (I) is obtained by reacting the above diisocyanate with one or more polyester polyols selected from the group consisting of the polyester polyol (A) and the polyester polyol (B). Hereinafter, the polyester polyol (A) and the polyester polyol (B) may be simply referred to as polyester polyol.

[0054] When the polyester polyol (A) and the polyester polyol (B) are used in combination, the polyester polyol (A) and the polyester polyol (B) can be used alone or as a mixture. When used as a mixture, they may be mixed before reacting with the diisocyanate, or each polyester polyol may be reacted with the diisocyanate alone to form a polyisocyanate and then mixed.

[0055] That is, as a method for producing a polyisocyanate composition, for example, a method of simultaneously reacting a diisocyanate, a polyester polyol (A), and a polyester polyol (B) to obtain a polyisocyanate composition; a method of reacting a diisocyanate with a polyester polyol (A), reacting a diisocyanate with a polyester polyol (B), and mixing the two reaction products to obtain a polyisocyanate composition; a method of reacting a diisocyanate with a polyester polyol (A) or a polyester polyol (B), and then further reacting the remaining polyester polyol to obtain a polyisocyanate composition, etc. can be mentioned.

[0056] The reaction between the polyester polyol and the diisocyanate is carried out as follows. The reaction temperature is usually from room temperature (about 23°C) to 200°C, preferably from 60°C to 180°C, more preferably from 60°C to 170°C. If the reaction temperature is at or above the lower limit value, the reaction time will be shorter. On the other hand, if it is at or below the upper limit value, an increase in the viscosity of the polyisocyanate and gelation due to undesirable side reactions can be more effectively avoided, and coloring of the produced polyisocyanate can also be more effectively avoided.

[0057] The reaction may be carried out without a solvent, or may be carried out using an arbitrary solvent that is inert to isocyanate groups. Further, if necessary, a known catalyst may be used to promote the reaction between the isocyanate group and the hydroxyl group.

[0058] ≪Polyisocyanate Composition (II)≫ The polyisocyanate composition (II) is a derivative of at least one diisocyanate selected from the group consisting of aliphatic di(tri)isocyanates and alicyclic di(tri)isocyanates. The description of at least one diisocyanate selected from the group consisting of aliphatic di(tri)isocyanates and alicyclic di(tri)isocyanates that constitute the polyisocyanate composition (II) is the same as the description in the above ≪Polyisocyanate Composition (I)≫.

[0059] The polyisocyanate composition (II) has a weight average molecular weight of 500 or more and 6000 or less, preferably 550 or more and 5000 or less, and more preferably 600 or more and 4000 or less. When the weight average molecular weight of the polyisocyanate composition (II) is within the above range, it is preferable from the viewpoints of hardness and viscosity.

[0060] The polyisocyanate composition (II) has an isocyanate group content of 12.0% by mass or more, preferably 15% by mass or more, and more preferably 17% by mass or more. When the isocyanate group content of the polyisocyanate composition (II) is at least the above lower limit value, it is preferable from the viewpoints of hardness and curability.

[0061] The isocyanate group content of the polyisocyanate composition (II) is, for example, 40% by mass or less, 30% by mass or less, 28% by mass or less, or 25% by mass or less.

[0062] The polyisocyanate composition (II) has an average isocyanate functionality of 2.0 or more and 6.0 or less, preferably 2.5 or more and 5.0 or less, and more preferably 2.7 or more and 4.5 or less. When the average isocyanate functionality of the polyisocyanate composition (II) is within the above range, it is preferable from the viewpoints of curability, hardness, and viscosity.

[0063] ≪Cured film≫ One aspect of the present invention is a cured film obtained by curing the polyisocyanate composition of the above embodiment alone. The cured film of one aspect of the present invention has low hardness and good flexibility and transparency.

[0064] The cured film of one aspect of the present invention can be produced, for example, by diluting or dissolving the above-described polyisocyanate composition of the present embodiment with a solvent as necessary, coating it on a adherend using a coater or the like, drying it as necessary, and curing it by heat.

[0065] The cured film of one aspect of the present invention has a König hardness of 90 or less, preferably 85 or less, and more preferably 80 or less, in a 23°C environment after curing under the following curing conditions. When the König hardness is equal to or less than the above upper limit value, the hardness is low and the flexibility is excellent. On the other hand, the lower limit value of the König hardness of the cured film is 15, preferably 16 or more, and more preferably 17 or more.

[0066] Curing conditions: Only the polyisocyanate composition of this embodiment is applied on glass, and after storing for 168 hours in an environment of 23°C and 65% humidity, a cured film with a film thickness of 40 μm formed by the reaction of moisture in the air and the polyisocyanate composition is used as the measurement target, and the König hardness in a 23°C environment is measured.

[0067] The cured film of one aspect of the present invention preferably has a haze value measured under the following conditions of 3.0% or less, more preferably 2.9% or less, and even more preferably 2.8% or less. When the haze value of the cured film is equal to or less than the above upper limit value, the transparency is excellent. On the other hand, the lower limit value of the haze value of the cured film is not particularly limited, and the closer it is to 0.0%, the more preferable it is. For example, it can be 0.0%, and it can be 0.01%.

[0068] Measurement conditions: Only the polyisocyanate composition of this embodiment is applied on glass, and after storing for 168 hours in an environment of 23°C and 65% humidity, a cured film with a film thickness of 40 μm formed by the reaction of moisture in the air and the polyisocyanate composition is pasted on glass with a haze value of 0.1% and measured with a haze meter.

[0069] <Paint composition> The polyisocyanate composition of the above-described embodiment can also be used as a curing agent component of a paint composition. That is, one aspect of the present invention is a paint composition containing the polyisocyanate composition of the above-described embodiment and a polyol.

[0070] The polyol contained in the coating composition is preferably an acrylic polyol, having a glass transition temperature of 0 °C or higher and 100 °C or lower, a hydroxyl value of 10 mgKOH / g or higher and 400 mgKOH / g or lower, and a weight average molecular weight of 5.0×10 3 or more × 2.0×10 5 or less.

[0071] (Glass transition temperature of the polyol) The glass transition temperature (Tg) of the polyol is 0 °C or higher and 100 °C or lower, preferably 5 °C or higher and 60 °C or lower. When using a polyol with a glass transition temperature within the above range, the breaking strength of the resulting coating film can be enhanced. The glass transition temperature can be determined by known thermal analysis methods such as differential scanning calorimetry (DSC).

[0072] (Hydroxyl value of the polyol) The hydroxyl value per resin of the polyol is 10 mgKOH / resin g or higher and 400 mgKOH / resin g or lower. When the hydroxyl value per resin is within the above range, the mechanical properties of the resulting coating film tend to be further improved. Note that the hydroxyl value of the polyol can be measured in accordance with JIS K1557.

[0073] (Weight average molecular weight of the polyol) The weight average molecular weight of the polyol is 5.0×10 3 or more × 2.0×10 5 or less, preferably 6.0×10 3 or more × 1.0×10 5 or less.

[0074] In the coating composition, the molar ratio (NCO / OH) of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol is 0.01 or higher and 50 or lower.

[0075] In the above coating composition, the content of the above polyisocyanate composition with respect to 100 parts by mass of the polyol is preferably 0.01 part by mass or more and 200 parts by mass or less, more preferably 0.05 part by mass or more and 190 parts by mass or less, and even more preferably 0.10 part by mass or more and 180 parts by mass or less.

[0076] The resin cured film obtained by curing the above coating composition, for the test piece produced by curing under the following conditions, the elongation rate is preferably 140% or more, the stress at an elongation rate of 140% is preferably 25.0 MPa or less, and the tensile fracture stress is preferably 1.2 times or more the stress at an elongation rate of 140%. Conditions: A resin composition with a molar ratio (NCO / OH) of isocyanate groups in the polyisocyanate composition to the hydroxyl groups of the polyol being 1 is cured at 90 °C for 30 minutes, and after storage for 168 hours in an environment of 23 °C and 65% humidity, a test piece is cut from the coating film with a thickness of 40 μm formed into a width of 10 mm and a length of 100 mm.

[0077] The above test piece is set on a tensile testing machine so that the distance between the gripping tools is 20 mm, and a tensile test is performed at a speed of 20 mm / min to measure the elongation rate and the tensile fracture stress.

[0078] Also, the elongation rate of the test piece of the resin cured film is preferably 140% or more, more preferably 145% or more, even more preferably 150% or more, particularly preferably 155% or more, and most preferably 160% or more. On the other hand, the upper limit of the elongation rate can be, for example, 5000%.

[0079] Also, the stress at an elongation rate of 140% of the test piece of the resin cured film is preferably 30.0 MPa or less, more preferably 29.0 MPa or less, even more preferably 28.0 MPa or less, and still more preferably 27.0 MPa or less. On the other hand, the lower limit of the stress at an elongation rate of 140% can be, for example, 0.01 MPa.

[0080] Further, the tensile breaking stress of the test piece of the resin cured film is preferably 1.2 times or more, more preferably 1.3 times or more, even more preferably 1.4 times or more, still more preferably 1.5 times or more, and particularly preferably 1.6 times the stress at the elongation rate of 140%. On the other hand, the upper limit of the ratio of the tensile breaking stress to the stress at the elongation rate of 140% can be, for example, 30 times. When the elongation rate is equal to or higher than the above lower limit value, the stress at the elongation rate of 140% is equal to or lower than the above upper limit value, and the ratio of the tensile breaking stress to the stress at the elongation rate of 140% is equal to or higher than the above lower limit value, the followability, flexibility, flex resistance, impact resistance, and durability of the coating film and the adhesive to the adherend are more excellent.

[0081] <Adhesive resin composition> One aspect of the present invention is an adhesive resin composition comprising the polyisocyanate composition of the above-described embodiment and a crosslinkable functional group-containing polymer having a glass transition temperature of 0.0 °C or lower.

[0082] By including the polyisocyanate composition described above, the adhesive resin composition of the present embodiment can form an adhesive layer having higher flexibility than before, and an adhesive resin sheet excellent in adhesive strength, holding power, curability, transparency, flex resistance, step followability, impact resistance, and durability can be obtained.

[0083] ≪Crosslinkable functional group-containing polymer≫ The glass transition temperature of the crosslinkable functional group-containing polymer is 0.0 °C or lower, preferably -75.0 °C or higher and 0.0 °C or lower, more preferably -75.0 °C or higher and -5.0 °C or lower, even more preferably -75.0 °C or higher and -7.0 °C or lower, and particularly preferably -75.0 °C or higher and -10.0 °C or lower.

[0084] When the glass transition temperature Tg of the polymer containing a crosslinkable functional group is within the above range, the adhesive strength of the cured product of the pressure-sensitive adhesive resin composition tends to be more excellent. The glass transition temperature of the polymer containing a crosslinkable functional group can be measured, for example, by removing the organic solvent and water in the solution in which the polymer containing a crosslinkable functional group is dissolved or dispersed under reduced pressure and then vacuum-drying it, and using a differential scanning calorimetry (DSC) measuring apparatus, and using the value measured under the condition of a heating rate of 5 °C / min as the glass transition temperature.

[0085] The weight average molecular weight Mw of the polymer containing a crosslinkable functional group is preferably 1.0×10 5 or more and 5.0×10 6 or less, more preferably 1.2×10 5 or more and 4.0×10 6 or less, still more preferably 1.5×10 5 or more and 3.0×10 6 or less, particularly preferably 2.0×10 5 or more and 2.5×10 6 or less. When the weight average molecular weight of the polymer containing a crosslinkable functional group is within the above range, the adhesive strength, holding power, flexibility, flex resistance, step followability, impact resistance, and durability of the cured product of the pressure-sensitive adhesive resin composition tend to be more excellent. The weight average molecular weight Mw of the polyol can be measured, for example, by using the method described in the examples below.

[0086] The polymer containing a crosslinkable functional group may be any polymer containing a crosslinkable functional group that can react with the isocyanate group of the above polyisocyanate composition. Examples of the crosslinkable functional group include a hydroxyl group, a thiol group, an amino group, an epoxy group, a carboxy group, a vinyl group, an amino group oxetane group, etc. Among them, a hydroxyl group, an epoxy group, a carboxy group, or a vinyl group, an amino group is preferable, a hydroxyl group, an epoxy group, or a carboxy group, an amino group is more preferable, a hydroxyl group, or a carboxy group, an amino group is still more preferable, and a hydroxyl group is particularly preferable. That is, a polyol is preferable as the polymer containing a crosslinkable functional group.

[0087] Specific examples of the polymer containing a crosslinkable functional group include, for example, aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, acrylic polymers, urethane polymers, rubber polymers, and the like. Among them, the polymer containing a crosslinkable functional group is preferably an acrylic polymer, a urethane polymer, or a rubber polymer.

[0088] [Aliphatic hydrocarbon polyol] Examples of the aliphatic hydrocarbon polyol include end-hydroxylated polybutadiene and its hydrogenated products.

[0089] [Polyether polyol] Examples of the polyether polyol include those obtained by any of the following methods (1) to (3). (1) Polyether polyols or polytetramethylene ether glycols obtained by adding a single or a mixture of alkylene oxides to a single or a mixture of polyhydric alcohols. (2) Polyether polyols obtained by reacting a polyfunctional compound with an alkylene oxide. (3) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyol obtained in (1) or (2) as a medium. Examples of the polyhydric alcohol include glycerin and propylene glycol. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Examples of the polyfunctional compound include ethylenediamine and ethanolamine.

[0090] [Polyester polyol] Examples of the polyester polyol include any of the following (1) or (2) polyester polyols. (1) A polyester polyol resin obtained by a condensation reaction of a dibasic acid alone or a mixture of two or more kinds thereof with a polyhydric alcohol alone or a mixture of two or more kinds thereof. (2) A polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with a polyhydric alcohol. Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, etc. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane, etc.

[0091] [Epoxy resin] Examples of the epoxy resin include novolak type epoxy resins, β-methyl epichlorohydrin type epoxy resins, cyclic oxirane type epoxy resins, glycidyl ether type epoxy resins, glycol ether type epoxy resins, epoxy type aliphatic unsaturated compounds, epoxidized fatty acid esters, ester type polycarboxylic acids, aminoglycidyl type epoxy resins, halogenated type epoxy resins, resorcin type epoxy resins, etc., and resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, etc.

[0092] [Fluorine-containing polyol] Examples of the fluorine-containing polyol include copolymers such as fluoroolefins, cyclohexyl vinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid vinyl ester, etc. disclosed in Reference 1 (Japanese Patent Laid-Open No. 57-34107), Reference 2 (Japanese Patent Laid-Open No. 61-275311), etc.

[0093] [Acrylic polymer] The acrylic polymer contains at least one kind of polymerizable (meth)acrylic monomer unit having a crosslinkable functional group. As the crosslinkable functional group, it preferably contains a hydroxyl group, a carboxy group, an epoxy group, or a vinyl group, more preferably contains a hydroxyl group or a carboxy group, and even more preferably contains a hydroxyl group.

[0094] The acrylic polymer may contain a crosslinkable functional group alone or may contain a combination of two or more different kinds of crosslinkable functional groups. That is, the acrylic polymer may be obtained by polymerizing a polymerizable (meth)acrylic monomer having a crosslinkable functional group alone, or may be obtained by copolymerizing two or more kinds of polymerizable (meth)acrylic monomers having different kinds of crosslinkable functional groups.

[0095] In addition to the polymerizable (meth)acrylic monomer unit having a crosslinkable functional group, the acrylic polymer can contain at least one kind of polymerizable acrylic monomer unit having no crosslinkable functional group. That is, the acrylic polymer is obtained by polymerizing a polymerizable (meth)acrylic monomer having at least one kind of crosslinkable functional group, or by copolymerizing a polymerizable (meth)acrylic monomer having at least one kind of crosslinkable functional group and a polymerizable (meth)acrylic monomer having no crosslinkable functional group.

[0096] In addition to the polymerizable (meth)acrylic monomer unit having a crosslinkable functional group, the acrylic polymer preferably contains at least one kind of (meth)acrylic acid ester monomer unit in which the number of carbon atoms at the ester group terminal is 1 or more and 18 or less. That is, the acrylic polymer may be obtained by copolymerizing a polymerizable (meth)acrylic monomer having at least one kind of crosslinkable functional group and a (meth)acrylic acid ester monomer in which the number of carbon atoms at the ester group terminal is 1 or more and 18 or less. The (meth)acrylic acid ester monomer may or may not have a crosslinkable functional group, but preferably does not have a crosslinkable functional group. The number of carbon atoms at the ester group terminal of the (meth)acrylic acid ester monomer is preferably 1 or more and 18 or less.

[0097] The acrylic polymer is obtained by copolymerizing a polymerizable (meth)acrylic monomer having a crosslinkable functional group and a (meth)acrylic acid ester monomer having 1 to 18 carbon atoms at the ester group terminal, and preferably has a glass transition temperature Tg of -75.0°C or higher and 0.0°C or lower.

[0098] Examples of the polymerizable (meth)acrylic monomer having a crosslinkable functional group include those shown in the following (i) to (v). These may be used alone or in combination of two or more. (i) Acrylic esters having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxylbutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyl octyl acrylate. (ii) Methacrylic esters having a hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxylbutyl methacrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyl octyl methacrylate. (iii) (Meth)acrylic esters having a polyhydroxy group such as acrylic acid monoester or methacrylic acid monoester of glycerin, acrylic acid monoester or methacrylic acid monoester of trimethylolpropane. (iv) Unsaturated carboxylic acids such as acrylic acid and methacrylic acid. (v) (Meth)acrylic esters having an epoxy group such as glycidyl methacrylate.

[0099] Examples of the (meth)acrylic acid ester monomer having 1 to 18 carbon atoms at the ester group terminal include (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid - n - butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid - sec - butyl, (meth)acrylic acid - tert - butyl, (meth)acrylic acid pentyl, (meth)acrylic acid isopentyl, (meth)acrylic acid hexyl, (meth)acrylic acid - 2 - ethylhexyl, (meth)acrylic acid heptyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid decyl, (meth)acrylic acid isodecyl, (meth)acrylic acid undecyl, (meth)acrylic acid dodecyl ((meth)acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl, (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl, (meth)acrylic acid heptadecyl, (meth)acrylic acid stearyl, (meth)acrylic acid isostearyl, (meth)acrylic acid nonadecyl, (meth)acrylic acid eicosyl, (meth)acrylic acid benzyl, (meth)acrylic acid cyclohexyl and other (meth)acrylic acid esters. These may be used alone or in combination of two or more.

[0100] In addition to the polymerizable (meth)acrylic monomer unit having a crosslinkable functional group, the acrylic polymer may further contain other monomer units other than the above (meth)acrylic acid ester monomer. That is, the acrylic polymer can be obtained by polymerizing a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups, or by copolymerizing a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups and one or more other monomers. The other monomers may or may not have a crosslinkable functional group, but it is preferable that they do not have a crosslinkable functional group.

[0101] Examples of other monomers include those shown in the following (i) to (ii) etc. These may be used alone or in combination of two or more. (i) Unsaturated amides such as (meth)acrylamide, N-methylolacrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide, etc. (ii) Styrene, vinyltoluene, vinyl acetate, (meth)acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate.

[0102] Furthermore, as other monomers copolymerizable with the polymerizable (meth)acrylic monomer having the crosslinkable functional group, polymerizable ultraviolet stability monomers disclosed in JP-A-1-261409 (Reference 3), JP-A-3-006273 (Reference 4), etc. may be used.

[0103] Specific examples of the polymerizable ultraviolet stability monomer include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, etc.

[0104] For example, an acrylic polymer can be obtained by solution polymerizing the above monomer components in the presence of a radical polymerization initiator such as a known peroxide or azo compound, and diluting with an organic solvent etc. as necessary.

[0105] When obtaining an aqueous-based acrylic polymer, it can be produced by known methods such as solution polymerization of an olefinically unsaturated compound and conversion to an aqueous layer, or emulsion polymerization. In that case, water solubility or water dispersibility can be imparted by neutralizing acidic moieties such as carboxylic acid-containing monomers like acrylic acid and methacrylic acid, or sulfonic acid-containing monomers with amines or ammonia.

[0106] [Content ratio with the curing agent component] In the pressure-sensitive adhesive resin composition of this embodiment, the content of the above-described polyisocyanate composition with respect to 100 parts by mass of the crosslinkable functional group-containing polymer is preferably 0.01 part by mass or more and 20.00 parts by mass or less, more preferably 0.03 part by mass or more and 15.00 parts by mass or less, and even more preferably 0.05 part by mass or more and 13.0 parts by mass or less.

[0107] (Other components) The pressure-sensitive adhesive resin composition of this embodiment may further contain other additives. Examples of other additives include curing agents other than polyisocyanate compositions that can react with the crosslinkable functional group-containing polymer, curing catalysts, solvents, pigments (extender pigments, coloring pigments, metallic pigments, etc.), tackifier resins, photoinitiators, ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface modifiers, flow regulators, pigment dispersants, defoamers, thickeners, film-forming aids, and the like.

[0108] Examples of the curing agent include melamine resins, urea resins, epoxy group-containing compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane group-containing compounds or resins, hydrazide compounds, and the like.

[0109] The curing catalyst may be a basic compound or a Lewis acidic compound. Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetinates, hydroxides of onium salts, onium carboxylates, halides of onium salts, metal salts of active methylene compounds, onium salts of active methylene compounds, aminosilanes, amines, phosphines, and the like. As the onium salt, an ammonium salt, a phosphonium salt, or a sulfonium salt is preferable. Examples of the Lewis acidic compound include organic tin compounds, organic zinc compounds, organic titanium compounds, organic zirconium compounds, and the like.

[0110] Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, tert-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, and the like. These solvents may be used alone or in combination of two or more.

[0111] In addition, as the pigments (extender pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents for suppressing coloring during the baking process, coating surface conditioners, flow conditioners, pigment dispersants, defoaming agents, thickeners, and film-forming aids, known ones can be appropriately selected and used.

[0112] ≪Method for Producing Pressure-Sensitive Adhesive Resin Composition≫ The pressure-sensitive adhesive resin composition can be produced by a conventionally known method. For example, a melt-kneading method using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a kneader, a multi-screw extruder, etc., a method in which each component is dissolved or dispersion-mixed and then coated on a cheesecloth film by a coater or the like, and then the solvent is removed by heating, etc. are used.

[0113] The pressure-sensitive adhesive resin composition of the present embodiment may be foamed in order to achieve the effects of weight reduction, softening, and improvement of adhesion. As the foaming method, there are a chemical method, a physical method, the use of a heat-expandable microballoon, etc. By adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent or a physical foaming agent, or by adding a heat-expandable microballoon, etc., air bubbles can be distributed inside the material.

[0114] In addition, by adding a hollow filler (already expanded balloon), weight reduction, softening, and improvement of adhesion may be achieved.

[0115] The pressure-sensitive adhesive resin composition of the present embodiment may be added with a tackifier resin for adjusting the tackiness. Examples of the tackifier resin include rosin-based tackifier resins, terpene-based tackifier resins, petroleum-based tackifier resins, styrene-based tackifier resins, etc. These tackifier resins may be used alone or in combination of two or more. In addition, the softening point of the tackifier resin is preferably 90°C or higher and 160°C or lower.

[0116] <Pressure-Sensitive Adhesive Resin Sheet> One aspect of the present invention is a pressure-sensitive adhesive resin sheet obtained by curing the pressure-sensitive adhesive resin composition of the above-described present embodiment. The pressure-sensitive adhesive resin sheet is preferably formed by curing the pressure-sensitive adhesive resin composition of the present embodiment by heat or light. The pressure-sensitive adhesive resin sheet of the present embodiment is excellent in pressure sensitivity, flex resistance, holding power, curability, flex resistance, step followability, impact resistance, durability, and transparency.

[0117] In the pressure-sensitive adhesive resin sheet of the present embodiment, the thickness of the adhesive layer can be appropriately determined according to the intended use, but it is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 900 μm or less, still more preferably 3 μm or more and 800 μm or less, and particularly preferably 5 μm or more and 700 μm or less.

[0118] The pressure-sensitive adhesive resin sheet of the present embodiment can be produced, for example, by coating a pressure-sensitive adhesive resin composition on a substrate, drying it if necessary, and then curing it. Examples of the method for coating the pressure-sensitive adhesive resin composition on the substrate include methods of coating using an applicator, a roll coater, a knife coater, a gravure coater, etc. When drying is performed after the coating, for example, a heat drying method of putting the obtained laminate into a dryer or the like and drying it at a temperature of 50°C or more and 150°C or less for 1 minute or more and 30 minutes or less can be mentioned. Alternatively, other drying methods include, for example, natural drying, hot air drying, infrared drying, etc.

[0119] The substrate is not particularly limited, and examples include papers such as high-quality paper, coated paper, cast-coated paper, thermal paper, and inkjet paper; cloths such as woven cloth and non-woven cloth; resin films such as polyvinyl chloride, synthetic paper, polyethylene terephthalate (PET), polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polystyrene, polycarbonate, nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and polyimide; porous resin films such as porous polypropylene films; vapor deposition films obtained by vapor depositing aluminum or the like on PET, polyolefin, etc.; and metal foils. The substrate may have a release treatment on its surface.

[0120] The heating temperature during curing can be 70°C or higher and 160°C or lower, can be 75°C or higher and 155°C or lower, and can be 80°C or higher and 150°C or lower.

[0121] The adhesive resin sheet of this embodiment preferably has a gel fraction of 20.00% by mass or more and 99.99% by mass or less, more preferably 25.0% by mass or more and 99.99% by mass or less, still more preferably 30.0% by mass or more and 99.99% by mass or less, particularly preferably 32.0% by mass or more and 99.9% by mass or less, and most preferably 35.0% by mass or more and 99.99% by mass or less. When the gel fraction is at or above the above lower limit value, it is more excellent in adhesive strength, holding power, durability, flex resistance, and curability. The gel fraction of the adhesive resin sheet is measured by the following method.

[0122] First, the above adhesive resin composition is coated on a polyethylene terephthalate film subjected to a peeling treatment with a thickness of 38 μm, dried and cured at 135°C for 3 minutes, and then a laminate comprising an adhesive resin sheet with a thickness of 50 μm stored for 7 days in an environment of 23°C and 50% RH is obtained. From the obtained laminate, the peeled polyethylene terephthalate film is peeled off to obtain an adhesive resin sheet. The obtained adhesive resin sheet is wrapped in a mesh sheet after being stored in an environment of 23°C and 50% RH for 7 days, immersed in ethyl acetate at 23°C for 1 week, taken out, and then dried at 120°C for 2 hours to calculate the gel fraction. Note that the gel fraction referred to here is the percentage of the mass of the adhesive resin sheet dried after immersion in ethyl acetate with respect to the mass of the adhesive resin sheet before immersion in ethyl acetate.

[0123] The adhesive resin sheet of the present embodiment preferably has a 180-degree peel adhesion measured by the following method of 0.01 N / 20 mm or more and 100 N / 20 mm or less, more preferably 0.01 N / 20 mm or more and 80 N / 20 mm or less, still more preferably 0.01 N / 20 mm or more and 60 N / 20 mm or less, particularly preferably 0.01 N / 20 mm or more and 40 N / 20 mm or less, and most preferably 0.01 N / 20 mm or more and 30 N / 20 mm or less. By having the 180-degree peel adhesion equal to or higher than the above lower limit value, the adhesive strength is excellent.

[0124] First, the above adhesive resin composition is coated on a polyethylene terephthalate film with a thickness of 25 μm, dried and cured at 135 °C for 3 minutes, and then stored in an environment of 23 °C and 50% RH for 7 days. A laminate comprising an adhesive resin sheet with a thickness of 50 μm, a width of 20 mm, and a length of 100 mm is attached to a SUS304BA plate as an adherend, pressure-bonded once back and forth with a 2 kg roller, cured at 23 °C for 30 minutes, and then measured at a speed of 23 °C and 300 mm / min.

[0125] The adhesive resin sheet of the present embodiment preferably has a haze value measured by the following method of 2.0% or less, more preferably 1.8% or less, still more preferably 1.6% or less, particularly preferably 1.3% or less, and most preferably 1.0% or less. By having the haze value equal to or lower than the above upper limit value, the transparency is excellent. On the other hand, the lower limit value of the haze value of the adhesive resin sheet is not particularly limited, and the closer it is to 0.0%, the more preferable it is. For example, it can be 0.0%, and it can be 0.01%.

[0126] First, the above adhesive resin composition is coated on a peeled polyethylene terephthalate film with a thickness of 38 μm, dried and cured at 135 °C for 3 minutes, then stored in an environment of 23 °C and 50% RH for 7 days, peeled from the peeled polyethylene terephthalate film, and a 50-μm-thick adhesive resin sheet is bonded to glass with a haze value of 0.1% and measured with a haze meter.

[0127] <Laminated film> One aspect of the present invention is a laminated film having a film on at least one side of the pressure-sensitive adhesive resin sheet of the above-described embodiment, and these being laminated.

[0128] The film constituting the laminated film is preferably a film composed of a material selected from at least one of polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide, and triacetyl cellulose resin.

[0129] The pressure-sensitive adhesive resin sheet and laminated film of the present invention are preferably applied to optical members, and are particularly preferably used for applications such as attaching to metal thin films and metal electrodes in optical applications. Examples of the metal thin film include, but are not particularly limited to, thin films composed of metals, metal oxides, and mixtures thereof, such as thin films of ITO (indium tin oxide), ZnO, SnO, and CTO (cadmium tin oxide). The thickness of the metal thin film is not particularly limited, but is about 10 to 200 nm. Usually, a metal thin film such as ITO is provided on a transparent plastic film substrate such as a polyethylene terephthalate film (especially a PET film) and used as a transparent conductive film. When attaching the above-described pressure-sensitive adhesive sheet of the present invention to a metal thin film, it is preferably used such that the surface on the pressure-sensitive adhesive layer side becomes the pressure-sensitive adhesive surface on the side to be attached to the metal thin film.

[0130] Also, the above-described metal electrode may be an electrode composed of a metal, a metal oxide, or a mixture thereof, and is not particularly limited. Examples thereof include electrodes of ITO, silver, copper, and CNT (carbon nanotube).

[0131] As an example of a specific use of the pressure-sensitive adhesive sheet of the present invention, a pressure-sensitive adhesive sheet for a touch panel used in the production of a touch panel can be mentioned. The pressure-sensitive adhesive sheet for a touch panel is used, for example, in the production of a capacitive touch panel to bond a transparent conductive film provided with a metal thin film such as ITO to a polymethyl methacrylate resin (PMMA) plate, a hard coat film, a glass lens, etc. The touch panel is not particularly limited, but is used, for example, in mobile phones, tablet computers, portable information terminals, etc.

[0132] Further, an optical member can be used as the support of the pressure-sensitive adhesive sheet of the present invention. The pressure-sensitive adhesive layer can be formed on the optical member by directly applying the pressure-sensitive adhesive layer to the optical member and drying and removing a polymerization solvent or the like. Further, the pressure-sensitive adhesive layer formed on the peeled separator can be appropriately transferred to the optical member to form a pressure-sensitive adhesive type optical member.

[0133] In addition, the peeled sheet used in the production of the above pressure-sensitive adhesive type optical member can be used as it is as the separator of the pressure-sensitive adhesive type optical member, and the process can be simplified.

[0134] Further, in the pressure-sensitive adhesive type optical member, when forming the pressure-sensitive adhesive layer, an anchor layer can be formed on the surface of the optical member, or various adhesion promotion treatments such as corona treatment and plasma treatment can be performed, and then the pressure-sensitive adhesive layer can be formed. Further, an adhesion promotion treatment may be performed on the surface of the pressure-sensitive adhesive layer.

[0135] The pressure-sensitive adhesive type optical member of the present invention can be used as a transparent conductive film with an adhesive layer using a transparent conductive film as an optical member. The transparent conductive film has a transparent conductive thin film serving as a metal thin film such as ITO on one surface of a transparent plastic film substrate. The other surface of the transparent plastic film substrate has the adhesive layer of the present invention. A transparent conductive thin film can be provided on the transparent plastic film substrate via an undercoat layer. Note that a plurality of undercoat layers can be provided. An oligomer migration prevention layer can be provided between the transparent plastic film substrate and the adhesive layer.

[0136] The transparent plastic film substrate is not particularly limited, but various plastic films having transparency are used. The plastic film is formed of a single layer of film. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins and the like can be mentioned. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable. The thickness of the film substrate is preferably 15 to 200 μm.

[0137] The film substrate may be subjected to an etching treatment or an undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. in advance on the surface to improve the adhesion of the transparent conductive thin film or the undercoat layer provided thereon to the film substrate. Further, before providing the transparent conductive thin film or the undercoat layer, dust removal and cleaning may be performed by solvent cleaning or ultrasonic cleaning as necessary.

[0138] The constituent materials and thickness of the transparent conductive thin film are not particularly limited and are as exemplified for the above metal thin film. The undercoat layer can be formed of an inorganic substance, an organic substance, or a mixture of an inorganic substance and an organic substance. For example, as the inorganic substance, inorganic substances such as NaF(1.3), Na3AlF6(1.35), LiF(1.36), MgF2(1.38), CaF2(1.4), BaF2(1.3), SiO2(1.46), LaF3(1.55), CeF3(1.63), Al2O3(1.63) etc. [the numerical values in the parentheses of the above respective materials are the refractive indices of light] can be mentioned. Among these, SiO2, MgF2, A12O3 etc. are preferably used. In particular, SiO2 is suitable. In addition to the above, a composite oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide with respect to indium oxide can be used. Examples of the organic substance include acrylic resin, urethane resin, melamine resin, alkyd resin, siloxane-based polymer, organic silane condensate etc. At least one of these organic substances is used. In particular, as the organic substance, it is desirable to use a thermosetting resin composed of a mixture of melamine resin, alkyd resin, and organic silane condensate.

[0139] The thickness of the undercoat layer is not particularly limited, but is usually about 1 to 300 nm, preferably 5 to 300 nm, from the viewpoints of optical design and the effect of preventing oligomer generation from the film base material.

[0140] The transparent conductive film with the above adhesive layer is used in the formation of various devices such as touch panels and liquid crystal displays. In particular, it can be preferably used as an electrode plate for a touch panel. The touch panel is suitably used for various detection methods (for example, resistive film method, capacitance method, etc.).

[0141] A capacitance type touch panel usually has a transparent conductive film provided with a transparent conductive thin film having a predetermined pattern shape formed on the entire surface of the display display portion. The transparent conductive film with the above adhesive layer is appropriately laminated so that the adhesive layer and the patterned transparent conductive thin film face each other.

[0142] In addition, the pressure-sensitive adhesive type optical member of the present invention can be used as an optical film with an adhesive layer using an optical film for an image display device as the optical member.

[0143] As the optical film, those used for forming an image display device such as a liquid crystal display device or an organic EL display device are used, and the type thereof is not particularly limited. For example, a polarizing plate can be mentioned as the optical film. As the polarizing plate, those having a transparent protective film on one or both sides of the polarizer are generally used.

Example

[0144] Hereinafter, the present embodiment will be described in more detail based on examples and comparative examples, but the present embodiment is not limited by the following examples at all.

[0145] <Test items> Regarding the polyisocyanate compositions produced in the examples and comparative examples, the measurement of each physical property and each evaluation were performed according to the methods shown below.

[0146] [Physical property 1] (Isocyanate group content) First, 2 g or more and 3 g or less of the measurement sample was precisely weighed into a flask (W g). Next, 20 mL of toluene was added to dissolve the measurement sample. Next, 20 mL of a toluene solution of 2N di-n-butylamine was added, and after mixing, it was left at room temperature for 15 minutes. Next, 70 mL of isopropyl alcohol was added and mixed. Next, this solution was titrated with a 1N hydrochloric acid solution (factor F) using an indicator. The obtained titration value was taken as V2 mL. Next, without the polyisocyanate sample, the obtained titration value was taken as V1 mL. Next, the isocyanate group content (NCO%) (mass%) of the polyisocyanate composition was calculated from the following formula. Note that the value of NCO% calculated in a state not containing a solvent was adopted.

[0147] Isocyanate group content (mass%) = [(V1 - V2) × F × 42 / (W × 1000)] × 100

[0148] [Physical Property 2] (Number-average molecular weight and weight-average molecular weight) The number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight based on polystyrene by gel permeation chromatography (GPC) measurement using the following apparatus.

[0149] (Measurement conditions) Apparatus: HLC-802A manufactured by Tosoh Corporation Column: One G1000HXL manufactured by Tosoh Corporation One G2000HXL One G3000HXL Carrier: Tetrahydrofuran Detection method: Differential refractometer

[0150] [Physical Property 3] (Average isocyanate functionality number) The average isocyanate functionality number (average NCO number) of the polyisocyanate composition was determined by the following formula. In the formula, "Mn" means the number-average molecular weight, and the value measured in the above "Physical Property 2" was used. "NCO%" was the value calculated in the above "Physical Property 1". Average isocyanate functionality number = (Mn × NCO% × 0.01) / 42

[0151] [Physical Property 4] (Glass transition temperature Tg) The glass transition temperature of the polyol for paint preparation and the polymer containing crosslinkable functional groups was measured using a differential scanning calorimetry (DSC) measuring apparatus under the condition of a heating rate of 5 °C / min after removing the organic solvent and water in the acrylic polyol solution or the polymer solution containing crosslinkable functional groups under reduced pressure and then vacuum drying, and the measured value was used as the glass transition temperature.

[0152] [Preparation of cured film consisting of polyisocyanate composition alone] For each polyisocyanate composition, it was coated on a release film using an applicator, and after storing for 168 hours in an environment of 23 °C and 65% humidity, a cured film with a film thickness of 40 μm was obtained.

[0153] [Evaluation 1] (Flexibility of the cured film) For the cured film, the König hardness (number of swings) at 23°C was measured using a König hardness tester (Pendulum hardness tester by BYK Gardner). Those with a König hardness of 90 swings or less were evaluated as having low hardness and good flexibility. Also, those with 15 swings or more were considered to have good processability.

[0154] Furthermore, the haze value of the cured film was measured by the method described in [Evaluation 5] below.

[0155] [Preparation of the coating film] Each polyisocyanate composition and the polyol for preparing the resin composition were mixed at a ratio such that the molar ratio NCO / OH of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol for preparing the resin composition was 1, to obtain a resin composition. Each obtained coating composition was applied onto a polypropylene (PP) plate using an applicator, cured at 90°C for 30 minutes, and stored in an environment of 23°C and 65% humidity for 168 hours to obtain a resin cured film with a film thickness of 40 μm.

[0156] [Evaluation 2] (Stress at 140% elongation, elongation, and tensile breaking stress) For the obtained coating film, a test piece with a width of 10 mm and a length of 100 mm was set on a tensile testing machine with a grip distance of 20 mm, and a tensile test was conducted at a speed of 20 mm / min to measure the stress at 140% elongation, elongation, and tensile breaking stress. Those with a stress at 140% elongation of 30.0 MPa or less, an elongation of 140% or more, and a tensile breaking stress of 1.2 times or more the stress at 140% elongation were evaluated as having good stress at 140% elongation, elongation, and ratio of tensile breaking stress to stress at 140% elongation, respectively. Also, those with a large elongation, a low stress at 140% elongation, and a tensile breaking stress of 1.2 times or more the stress at 140% elongation were evaluated as having better flex resistance.

[0157] [Preparation of Adhesive Resin Composition X] To 100 parts by mass of the solid content of the crosslinkable functional group-containing polymer (acrylic polymer) OH1, 1.0 part by mass (solid content amount) of each polyisocyanate composition and ethyl acetate were added to prepare an adhesive resin composition X having a solid content of 25% by mass.

[0158] [Preparation of Adhesive Resin Sheet 1] (Preparation of Adhesive Resin Sheet for 180° Peel Adhesion Measurement) The adhesive resin composition X was applied onto a 25-μm-thick polyethylene terephthalate (PET) film with an applicator so that the thickness after drying would be 50 μm, and dried at 135°C for 3 minutes. Then, it was stored in an environment of 23°C and 50% RH for 7 days to obtain an adhesive resin sheet for 180° peel adhesion measurement.

[0159] [Evaluation 3] [Adhesion] A laminate comprising an adhesive resin sheet having an adhesive thickness of 50 μm, a width of 20 mm and a length of 100 mm obtained in the above-mentioned "Preparation of Adhesive Resin Sheet 1" was attached to a SUS304BA plate as the adherend, pressure-bonded once back and forth with a 2-kg roller, cured at 23°C for 30 minutes, and then the 180° peel adhesion was measured at a speed of 300 mm / min and 23°C using a tensile testing machine. Those with a value of 0.01 N / 20 mm or more were evaluated as having good adhesion.

[0160] [Preparation of Adhesive Resin Sheet 2] (Preparation of Adhesive Resin Sheet for Gel Fraction Measurement) The adhesive resin composition X was applied onto a PET film having been subjected to a peeling treatment with a thickness of 38 μm with an applicator so that the thickness after drying would be 50 μm, and dried at 135°C for 3 minutes. Then, it was stored in an environment of 23°C and 50% RH for 7 days to obtain an adhesive resin sheet for gel fraction measurement.

[0161] [Evaluation 4] [Curing Property] About 0.1 g or more and 0.2 g or less of the pressure-sensitive adhesive resin sheet obtained in the above "Production 2 of Pressure-Sensitive Adhesive Resin Sheet" was taken, wrapped with a mesh sheet, immersed in ethyl acetate for one week, and then dried at 120 °C for 2 hours. Subsequently, the gel fraction (mass %) was calculated using the following formula. Those with a gel fraction of 20.0 mass % or more were evaluated to have good curability.

[0162] (Gel fraction) = [(Mass of sample after drying) / (Mass of sample before ethyl acetate addition)] × 100

[0163] [Production 3 of Pressure-Sensitive Adhesive Resin Sheet] [Production of Laminate Comprising Pressure-Sensitive Adhesive Resin Sheet for Haze Value Measurement] The pressure-sensitive adhesive resin composition X or the pressure-sensitive adhesive resin composition Y was coated on a polyethylene terephthalate film having a thickness of 38 μm and subjected to peeling treatment, dried and cured at 135 °C for 3 minutes, stored in an environment of 23 °C and 50% RH for 7 days, and then peeled from the peeled polyethylene terephthalate film. A pressure-sensitive adhesive resin sheet having a thickness of 50 μm thus obtained was bonded to glass having a haze value of 0.1% to obtain a laminate comprising a pressure-sensitive adhesive resin sheet for haze value measurement.

[0164] [Evaluation 5] (Transparency) Regarding the laminate obtained by bonding the cured film obtained in the above "Production of Cured Film of Polyisocyanate Composition" to glass having a haze value of 0.1% and the laminate obtained in the above "Production 3 of Pressure-Sensitive Adhesive Resin Sheet", using a haze meter (HM-65N) manufactured by Murakami Color Technology Research Institute, on the light source side, of the two surfaces of each laminate, the surface opposite to the glass (that is, the surface coated with the polyisocyanate composition or the pressure-sensitive adhesive resin composition) was arranged, and the haze was measured. Those with a haze value of 3.0% or less were evaluated to have good transparency.

[0165] >[Production of Polyol for Resin Composition Preparation]< [Synthesis Example 1-1] >[Production of Polyol for Resin Composition Preparation]< 29 parts by mass of butyl acetate was charged into a four-necked flask equipped with a stirring device, a thermometer, a cooling pipe, and a nitrogen gas inlet, and the temperature was raised to 112 °C under nitrogen gas ventilation. After reaching 112 °C, the ventilation of nitrogen gas was stopped, and a mixture consisting of 22.3 parts by mass of 2-hydroxyethyl methacrylate, 8.0 parts by mass of methyl methacrylate, 26.1 parts by mass of butyl acrylate, 42.3 parts by mass of styrene, 1.3 parts by mass of acrylic acid, and 2.1 parts by mass of 2,2'-azobis(isobutyronitrile) was added dropwise over 5 hours. Next, after stirring for 3 hours while flowing nitrogen gas at 115 °C, it was cooled to 60 °C, and a butyl acetate solution was added to obtain a solution of a polyol for producing a resin composition having a solid content of 60% by mass. The polyol for producing the resin composition had a glass transition temperature Tg of 29.3 °C, a hydroxyl value of 139 mgKOH / g based on the resin solid content, and a weight average molecular weight Mw of 2.65×10 4 It was.

[0166] <Synthesis of crosslinkable functional group-containing polymer> [Synthesis Example 2-1] (Synthesis of crosslinkable functional group-containing polymer (acrylic polymer) OH1) 97 parts by mass of 2-ethylhexyl acrylate (2EHA) and 3 parts by mass of 4-hydroxybutyl acrylate (4-HBA) were charged into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a cooling tube, and 145 parts by mass of ethyl acetate was charged as a solvent. Next, while stirring under a nitrogen gas atmosphere, 0.14 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the reaction was carried out at 63 °C for 9 hours. After the reaction, it was cooled to obtain an acrylic polymer OH1 having a solid content concentration of 42.2% by mass. The glass transition temperature measured excluding the solvent of the acrylic polymer OH1 was -69.0 °C, and the weight average molecular weight was 8.7×10 5 It was.

[0167] <Production of polyisocyanate composition> [Synthesis Example 1] (Production of polyisocyanate composition PA-a1-(I)) Into a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream, and 37.5 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g) (the amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol B1 is 9.1) was stirred while maintaining the temperature inside the reactor at 100°C. The reaction was stopped when the yield reached 41.5% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin-film distillation apparatus to obtain a polyisocyanate composition PA-a1-(I). The obtained polyisocyanate composition PA-a1-(I) was analyzed by H-NMR and C-NMR, and the presence of urethane groups and allophanate groups was confirmed. Among these groups, the molar ratio of urethane groups was the highest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was a liquid at 23°C.

[0168] [Synthesis Example 2] (Production of Polyisocyanate Composition PA-a2-(I)) Into a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream, and 38.8 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g) (the amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol B1 is 8.8) was stirred while maintaining the temperature inside the reactor at 100°C. The reaction was stopped when the yield reached 41.8% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin-film distillation apparatus to obtain a polyisocyanate composition PA-a2-(I). The obtained polyisocyanate composition PA-a2-(I) was analyzed by 1H-NMR and 13C-NMR to confirm the presence of urethane groups and allophanate groups, and among these groups, the molar ratio of urethane groups was the highest. Subsequently, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was liquid at 23°C.

[0169] [Synthesis Example 3] (Production of Polyisocyanate Composition PA-a3-(I)) Into a four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream, and 3-functional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g): 40.0 parts by mass (an amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol B1 is 8.5) was stirred while maintaining the temperature inside the reactor at 100°C. The reaction was stopped when the yield reached 42.2% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin-film distillation apparatus to obtain a polyisocyanate composition PA-a3-(I). The obtained polyisocyanate composition PA-a3-(I) was analyzed by 1H-NMR and 13C-NMR to confirm the presence of urethane groups and allophanate groups, and among these groups, the molar ratio of urethane groups was the highest. Subsequently, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was liquid at 23°C.

[0170] [Synthesis Example 4] (Production of Polyisocyanate Composition PA-a4-(I)) Into a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream. While stirring, 45.0 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 312", number average molecular weight 1250, hydroxyl value 136.1 mgKOH / g, acid value 0.38 mgKOH / g) (the amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol B2 is 10.9) was added, and the temperature inside the reactor was maintained at 100°C. The reaction was stopped when the yield reached 40.6% by mass. After filtering the reaction solution, unreacted HDI was removed using a thin-film distillation apparatus to obtain a polyisocyanate composition PA-a4-(I). The obtained polyisocyanate composition PA-a4-(I) was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and among these groups, the molar ratio of urethane groups was the highest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was a liquid at 23°C.

[0171] [Synthesis Example 5] (Production of Polyisocyanate Composition PA-a5-(I)) In a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream. While stirring, 45.0 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 312", number average molecular weight 1250, hydroxyl value 136.1 mgKOH / g, acid value 0.38 mgKOH / g) (an amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyols A1 and B2 is 10.4) was added, and the temperature inside the reactor was maintained at 100 °C. The reaction was stopped when the yield reached 40.9% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin-film distillation apparatus to obtain a polyisocyanate composition PA-a5-(I). The obtained polyisocyanate composition PA-a5-(I) was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and among these groups, the molar ratio of urethane groups was the highest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was a liquid at 23 °C.

[0172] [Synthesis Example 6] (Production of Polyisocyanate Composition C1) The inside of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was purged with nitrogen, 1000 g of HDI was charged, and 0.1 g of tetramethylammonium caprylate and 0.05 g of isobutanol were added as catalysts while stirring at 66 °C. After 4 hours, the reaction end point set by measuring the refractive index of the reaction solution was confirmed, and 0.2 g of phosphoric acid was added to stop the reaction. Thereafter, after filtering the reaction solution, unreacted HDI monomer was removed by a thin-film distillation apparatus to obtain a polyisocyanate C1 having an isocyanurate structure. The isocyanate group content of the obtained polyisocyanate B-2 was 23.1% by mass, the average number of isocyanate functional groups was 3.2, and the weight average molecular weight was 760.

[0173] [Synthesis Example 7] (Production of Polyisocyanate Composition PA-a7-(I)) Into a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream. While stirring, 34.0 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g) (an amount such that the molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol B1 is 10.1) was added, and the temperature inside the reactor was maintained at 100 °C. The reaction was stopped when the yield reached 41.0% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin-film distillation apparatus to obtain a polyisocyanate composition. Into a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser, under a nitrogen stream, to 100 parts by mass of the obtained polyisocyanate composition, further 8.0 parts by mass of a trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1") (manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g) was added, and 0.01 part by weight of 2-ethylhexyl acid phosphate (JP-508T, manufactured by Johoku Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 95 °C for 3.0 hours to obtain a polyisocyanate composition PA-a7-(I). The obtained polyisocyanate composition PA-a7-(I) was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and among these groups, the molar ratio of urethane groups was the highest. Thereafter, ethyl acetate was added to the obtained polyisocyanate composition and diluted to a solid content of 70% by mass, and the resulting state was a liquid at 23 °C.

[0174] [Examples 1 to 6, Comparative Examples 1 to 3] (Production of Polyisocyanate Compositions PA-a1 to PA-a5, PA-a7, PB-b1 to PB-b3) At the ratios shown in Table 1 for the solid content ratio formulation, PA-a1-(I) to PA-a7-(I) obtained in Synthesis Examples 1 to 7 as the polyisocyanate composition (I) and the polyisocyanate composition C1 obtained in Synthesis Example 6 as the polyisocyanate composition (II) were mixed, ethyl acetate was added, and the mixture was diluted to a solid content of 70% by mass to obtain a polyisocyanate composition.

[0175] (Polyester polyol (A)) A1: A bifunctional polycaprolactone polyol, manufactured by Daicel Corporation, trade name "Placcel 220CPT", number average molecular weight 2000, hydroxyl value 56.6 mgKOH / g, acid value 0.02 mgKOH / g (Polyester polyol (B)) B1: A trifunctional polycaprolactone polyol, manufactured by Daicel Corporation, trade name "Placcel 308", number average molecular weight 850, hydroxyl value 195.3 mgKOH / g, acid value 0.38 mgKOH / g B2: A trifunctional polycaprolactone polyol, manufactured by Daicel Corporation, trade name "Placcel 312", number average molecular weight 1250, hydroxyl value 136.1 mgKOH / g, acid value 0.38 mgKOH / g

[0176]

Table 1

[0177]

Table 2

[0178] As shown in Table 1, when the polyisocyanate composition was used in this embodiment, a cured film with good flexibility, hardness, and transparency was obtained. Furthermore, when the polyisocyanate composition was used in this embodiment, a pressure-sensitive adhesive resin sheet excellent in adhesion, curability, transparency, flex resistance, and processability could be manufactured.

Claims

1. A polyisocyanate composition comprising a polyisocyanate composition (I) and a polyisocyanate composition (II), wherein the polyisocyanate composition (I) is a derivative of a di(tri)isocyanate and a polyester polyol, the di(tri)isocyanate is at least one selected from the group consisting of an aliphatic di(tri)isocyanate and an alicyclic di(tri)isocyanate, the polyester polyol is either one or both of a bifunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more and 2200 or less, the molar ratio of the isocyanate groups of the di(tri)isocyanate to the hydroxyl groups of either one or both of the polyester polyol (A) and the polyester polyol (B) is 2.0 or more and 30.0 or less, the polyisocyanate composition (I) has a weight average molecular weight of 2500 or more and 200000 or less, the polyisocyanate composition (II) is a derivative of at least one diisocyanate selected from the group consisting of an aliphatic di(tri)isocyanate and an alicyclic di(tri)isocyanate, the polyisocyanate composition (II) has a weight average molecular weight of 500 or more and 6000 or less, an isocyanate group content of 12.0% by mass or more, and an average isocyanate functionality of 2.0 or more and 6.0 or less, A polyisocyanate composition, wherein the weight ratio of the polyisocyanate composition (I) to the polyisocyanate composition (II) represented by the following (P) is 4 or more and 15 or less, and the weight average molecular weight is 2000 or more and 200000 or less. [(II) / [(I)+(II)]]×100...(P)

2. The polyisocyanate composition according to claim 1, wherein the average isocyanate functionality is 2.2 or more and 6.0 or less.

3. The polyisocyanate composition according to claim 1 or 2, wherein the isocyanate group content is 3.0% by mass or more and 10.0% by mass or less.

4. The polyisocyanate composition (I) is such that the content of the polyester polyol (A) relative to 100 parts by mass of the di(tri)isocyanate is 0.1 part by mass or more and 900 parts by mass or less. The polyisocyanate composition according to claim 1 or 2, wherein the content of the polyester polyol (B) is 0.1 part by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the di(tri)isocyanate.

5. The polyisocyanate composition according to claim 1 or 2, wherein the polyester polyol is a polycaprolactone polyol.

6. The polyisocyanate composition according to claim 1 or 2, wherein the König hardness of the cured film cured under the following curing conditions is 15 or more and 90 or less. Curing conditions: The polyisocyanate composition is applied on glass, and a cured film with a film thickness of 40 μm formed after storage for 168 hours in an environment of 23°C and 65% humidity is used as the measurement object, and the König hardness in an environment of 23°C is measured.

7. The polyisocyanate composition according to claim 1 or 2, wherein the haze value measured under the following conditions is 3.0% or less. Measurement conditions: The polyisocyanate composition is applied on glass, and a cured film with a film thickness of 40 μm formed after storage for 168 hours in an environment of 23°C and 65% humidity is pasted on glass with a haze value of 0.1%, and the haze value is measured with a haze meter.

8. A resin composition comprising the polyisocyanate composition according to claim 1 or 2 and a polyol, The polyol has a glass transition temperature of 0°C or higher and 100°C or lower, a hydroxyl value of 10 mg KOH / g or higher and 400 mg KOH / g or lower, and a weight average molecular weight of 5.0×10 ３ or more × 2.0×10 ５ or less, wherein the molar ratio (NCO / OH) of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol is 0.01 or more and 50 or less.

9. The resin composition according to claim 8, wherein the blending amount of the polyisocyanate composition is 0.01 part by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyol.

10. A resin cured film obtained by curing the resin composition according to claim 8, wherein a test piece manufactured by curing under the following conditions has an elongation rate of 140% or more, a stress at an elongation rate of 140% of 25.0 MPa or less, and a tensile breaking stress of 1.2 times or more the stress at the elongation rate of 140%. Conditions: A resin composition in which the molar ratio (NCO / OH) of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol is 1 is cured at 90°C for 30 minutes, and a coating film with a film thickness of 40 μm formed after storage for 168 hours in an environment of 23°C and 65% humidity is cut into test pieces with a width of 10 mm and a length of 100 mm.

11. An adhesive resin composition comprising the polyisocyanate composition according to claim 1 or 2 and a crosslinkable functional group-containing polymer having a glass transition temperature of 0°C or lower.

12. The adhesive resin composition according to claim 11, wherein the crosslinkable functional group-containing polymer is an acrylic polymer, a urethane polymer, or a rubber polymer.

13. The crosslinkable functional group-containing polymer is copolymerized from a polymerizable (meth)acrylic monomer having a crosslinkable functional group and a (meth)acrylic acid ester monomer having 1 to 18 carbon atoms at the ester group terminus, and the glass transition temperature Tg is -75.0°C or higher and 0.0°C or lower. The adhesive resin composition according to claim 11.

14. The weight average molecular weight of the crosslinkable functional group-containing polymer is 1.0×10 ５ or more and 5.0×10 ６ or less, and the pressure-sensitive adhesive resin composition according to claim 11.

15. The crosslinkable functional group contained in the crosslinkable functional group-containing polymer is at least one selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, and a vinyl group, an amino group, and an oxetane group. The adhesive resin composition according to claim 11.

16. The content of the polyisocyanate composition with respect to 100 parts by mass of the crosslinkable functional group-containing polymer is 0.01 part by mass or more and 20.00 parts by mass or less. The adhesive resin composition according to claim 11.

17. An adhesive resin sheet obtained by curing the adhesive resin composition according to claim 11.

18. The adhesive resin sheet according to claim 17, wherein the thickness of the adhesive resin sheet is 1 μm or more and 1000 μm or less.

19. The adhesive resin sheet according to claim 17, wherein the gel fraction of the adhesive resin sheet is 20.00% by mass or more and 99.99% by mass or less.

20. A laminate comprising the adhesive resin sheet having a thickness of 50 μm, a width of 20 mm, and a length of 100 mm is attached to a SUS304BA plate as an adherend, pressure-bonded once back and forth with a 2 kg roller, cured at 23°C for 30 minutes, and then measured at 23°C and a speed of 300 mm / min. The 180-degree peel adhesive strength is 0.05 N / 20 mm or more and 100 N / 20 mm or less. The adhesive resin sheet according to claim 17.

21. The pressure-sensitive adhesive resin composition according to claim 11 was coated on a peeled polyethylene terephthalate film with a thickness of 38 μm, dried and cured at 135° C. for 3 minutes, then stored in an environment of 23° C. and 50% RH for 7 days, and peeled from the peeled polyethylene terephthalate film. The obtained pressure-sensitive adhesive resin sheet with a thickness of 50 μm was pasted on glass with a haze value of 0.1%, and the haze value measured with a haze meter was 2.0% or less. A pressure-sensitive adhesive resin sheet.

22. A laminated film having a film on at least one side of the pressure-sensitive adhesive resin sheet according to claim 17, and the two being laminated.

23. The laminated film according to claim 22, wherein the film is selected from at least one of polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide, and triacetyl cellulose resins.

24. The laminated film according to claim 22, which is used for optical applications.

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