KR102035955B1 - Stress distributing film, optical member, and electronic member - Google Patents

Abstract

It provides a stress dispersion film having excellent stress dispersibility. Moreover, the optical member and electronic member provided with such a stress dispersion film are provided. The stress-dispersion film of this invention is a stress-dispersion film containing the laminated body of a plastic film and an adhesive layer, and the indentation energy at the time of applying the load in the perpendicular direction with the said laminated body from the plastic film side of the said laminated body is 260 microJ or more. .

Description

STRESS DISTRIBUTING FILM, OPTICAL MEMBER, AND ELECTRONIC MEMBER}

The present invention relates to a stress dispersion film, an optical member and an electronic member provided with the stress dispersion film.

In order to provide rigidity or impact resistance, optical films, such as a touch panel using LCD, a lens part of a camera, and an electronic device, an adhesive film may be adhere | attached on the exposed surface side (for example, a patent document One). Such an adhesive film has a base material layer and an adhesive layer normally.

The optical member and the electronic member as described above may be subjected to a load due to a pressing force in various situations such as assembly, processing, transportation, and use, and the optical member and the electronic member are damaged by such a load. Causes a problem.

Japanese Patent Publication No. 2014-234460

An object of the present invention is to provide a stress dispersing film having excellent stress dispersibility. Moreover, it is providing the optical member and electronic member provided with such a stress dispersion film.

The stress dispersing film of the present invention,

It is a stress dispersion film containing the laminated body of a plastic film and an adhesive layer,

The indentation energy when the load is applied in the direction perpendicular to the laminate from the plastic film side of the laminate is 260 µJ or more.

In one embodiment, the thickness of the said plastic film is 4 micrometers-500 micrometers.

In one embodiment, the thickness of the said adhesive layer is 1 micrometer-300 micrometers.

In one embodiment, the said adhesive layer is formed from an adhesive composition, and this adhesive composition has OH in the monomeric unit (I) derived from (meth) acrylic-acid alkylester which has a C1-C20 alkyl group as an alkylester part, and a molecule | numerator Polymer (A) which has monomeric unit (II) derived from the (meth) acrylic acid ester which has group and / or COOH group.

In one embodiment, the molar content rate of the NCO group in the said adhesive composition is set to [NCO], the molar content rate of the epoxy group in the said adhesive composition is set to [epoxy], and the molar content rate of the OH group in this adhesive composition is made into It is ([NCO] + [epoxy]) / ([OH] + [COOH]) <0.05, when it is set as [OH] and the molar content rate of the COOH group in this adhesive composition is [COOH].

In one embodiment, the said adhesive composition contains a bifunctional or more organic polyisocyanate type crosslinking agent and / or an epoxy type crosslinking agent.

In one embodiment, the said adhesive composition contains the polymer (B) whose weight average molecular weights which have a monomeric unit derived from an alicyclic structure containing (meth) acrylic acid ester represented by General formula (1) are 1000 or more and less than 30000.

CH ₂ = C (R ¹ ) COOR ² ... (One)

(In Formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having an alicyclic structure.)

In one embodiment, the loss tangent tan-delta in the whole temperature range of -40 degreeC-150 degreeC of the said adhesive layer is 0.10 or more.

The optical member of the present invention includes the stress dispersion film.

The electronic member of this invention is equipped with the said stress dispersion film.

According to the present invention, it is possible to provide a stress dispersing film having excellent stress dispersibility. Moreover, the optical member or electronic member provided with such a stress dispersion film can be provided.

1 is a schematic cross-sectional view of a stress dispersion film according to one embodiment of the present invention.
2 is a schematic cross-sectional view of a stress dispersing film according to another embodiment of the present invention.

In this specification, when there exists an expression of "(meth) acryl", it means "acryl and / or methacryl", and when there is an expression of "(meth) acrylate", it is "acrylate and / or methacryl" Rate ”. In addition, when there is an expression "weight" in this specification, you may replace with the "mass" commonly used as SI type unit which shows weight.

In this specification, when there exists the expression "(a) monomeric unit (A)", monomeric unit (A) is a structural unit in which the unsaturated double bond which monomer (a) has cleaved by superposition | polymerization, and is formed. In addition, the structural unit in which an unsaturated double bond cleaves by superposition | polymerization is formed and unsaturated double of the structure of "RpRqC = CRrRs" (Rp, Rq, Rr, Rs is arbitrary appropriate group couple | bonded with a carbon atom by a single bond) Bond "C = C" is a structural unit of "-RpRqC-CRrRs-" formed by cleavage by superposition | polymerization.

In this specification, the content rate of the monomeric unit in a polymer can be known, for example by various structural analysis (for example, NMR etc.) of the said polymer. Moreover, even if it does not perform the above various structural analysis, you may make content rate of the monomeric unit derived from the said various monomer calculated based on the usage-amount of the various monomers used when manufacturing a polymer as a content rate of the monomeric unit in a polymer. That is, you may handle the content rate of any monomer (m) in the all monomer components used when manufacturing a polymer as content rate of the monomeric unit derived from the monomer (m) in the said polymer.

≪≪A. Stress Dispersion Film≫≫

The stress dispersion film of this invention contains the laminated body of a plastic film and an adhesive layer. One layer may be sufficient as a plastic film, and two or more layers may be sufficient as it. One layer may be sufficient as an adhesive layer, and two or more layers may be sufficient as it.

1 is a schematic cross-sectional view of a stress dispersing film according to one embodiment of the present invention. In FIG. 1, the stress dispersion film 100 of this invention consists of a laminated body of the plastic film 10 and the adhesive layer 20. As shown in FIG. Although not shown in FIG. 1, any suitable steel adhesive layer may be provided on the surface of the pressure-sensitive adhesive layer 20.

2 is a schematic cross-sectional view of a stress dispersing film according to another embodiment of the present invention. In FIG. 2, the stress dispersion film 100 of this invention consists of an adhesive layer 20, the plastic film 10, and the adhesive layer 20, and the adhesive layer 20, the plastic film 10, and the adhesive layer Have (20) in this order. That is, in FIG. 2, the stress dispersion film 100 of this invention consists of a laminated body of the adhesive layer 20, the plastic film 10, and the adhesive layer 20. As shown in FIG. Although not shown in FIG. 2, any suitable steel adhesive layer may be provided on the surface of the pressure-sensitive adhesive layer 20 on one side or both sides.

In the case of the form which an adhesive layer exposes as an outermost layer, you may provide arbitrary appropriate separators (peel sheet) on the said exposure surface side.

In the stress dispersion film of the present invention, the indentation energy when a load is applied in the direction perpendicular to the laminate from the plastic film side of the laminate of the plastic film and the pressure-sensitive adhesive layer is 260 µJ or more. The measuring method of the said indentation energy is mentioned later. The indentation energy is preferably 260 µJ to 10000 µJ, more preferably 270 µJ to 9000 µJ, still more preferably 280 µJ to 8000 µJ, and particularly preferably 290 µJ to 7000 µJ. By the indentation energy being in the above range, it is possible to provide a stress dispersion film having excellent stress dispersibility.

The thickness of the plastic film is preferably 4 µm to 500 µm, more preferably 10 µm to 400 µm, still more preferably 15 µm to 350 µm, and particularly preferably 20 µm to 300 µm. By the thickness of a plastic film being in the said range, the stress dispersing film which has more excellent stress dispersibility can be provided.

The thickness of an adhesive layer becomes like this. Preferably it is 1 micrometer-300 micrometers, More preferably, it is 2 micrometers-250 micrometers, More preferably, it is 4 micrometers-200 micrometers, Especially preferably, it is 5 micrometers-150 micrometers. By the thickness of an adhesive layer being in the said range, the stress dispersion film which has more excellent stress dispersibility can be provided.

As a plastic film, arbitrary appropriate plastic films can be employ | adopted in the range which does not impair the effect of this invention. These plastic films are, for example, its compressive strength in ASTM D695, preferably 100Kg / cm ² to about 3000Kg / cm ^2, preferably in the 200Kg / cm ² to about 2900Kg / cm ² more, and more preferably 300 Kg / cm ² to 2800 Kg / cm ² , particularly preferably 400 Kg / cm ² to 2700 Kg / cm ² . Specific examples of such plastic films include polyester resins, polyolefin resins, polyamide resins, polyimide resins, and the like. Examples of the polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. As polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specifically as polyolefin resin, For example, Homo polypropylene; Propylene copolymers such as block-based, random-based, and graft-based copolymers having an ethylene component as a copolymerization component; Reactor TPO; Ethylene polymers such as low density, high density, linear low density and ultra low density; Ethylene propylene copolymer, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene methacrylic acid copolymer, ethylene methyl methacrylate copolymer Ethylenic copolymers such as these; Etc. can be mentioned.

The plastic film may contain any suitable additive as needed. As an additive which may be contained in a plastic film, antioxidant, a ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The kind, number, and amount of additives that may be contained in the plastic film may be appropriately set according to the purpose.

As an adhesive layer, arbitrary appropriate adhesive layers can be employ | adopted in the range which does not impair the effect of this invention. As such an adhesive layer, the adhesive layer formed from an acrylic adhesive, the adhesive layer formed from a rubber adhesive, the adhesive layer formed from a silicone adhesive, the adhesive layer formed from a urethane type adhesive, etc. are mentioned, for example.

The pressure-sensitive adhesive layer is preferably formed of a pressure-sensitive adhesive composition.

An adhesive layer apply | coats an adhesive composition on arbitrary suitable base materials, for example, it dries as needed, and forms an adhesive layer on a base material. Then, when a base material is peeled off, an adhesive layer is obtained. In addition, for example, the pressure-sensitive adhesive layer and the plastic film are stressed by applying the pressure-sensitive adhesive composition on any suitable plastic film, drying as necessary to form the pressure-sensitive adhesive layer on the plastic film, and leaving the plastic film as it is. A dispersion film is obtained. Moreover, an adhesive layer and a plastics are apply | coated, for example by apply | coating an adhesive composition on arbitrary appropriate base materials, drying as needed, forming an adhesive layer on a base material, and loading the adhesive layer obtained by peeling a base material to a plastic film. A stress dispersing film comprising a film is obtained. Further, for example, the pressure-sensitive adhesive composition and the plastic film are applied by applying the pressure-sensitive adhesive composition on any suitable substrate, drying as necessary to form an adhesive layer on the substrate, and transferring the pressure-sensitive adhesive layer formed on the substrate to the plastic film. The stress-dispersing film containing is obtained.

As a coating method of an adhesive composition, the extrusion coat by a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coating method, a die coater, etc. are mentioned, for example.

Such a pressure-sensitive adhesive composition is preferably derived from a (meth) acrylic acid ester having a monomer unit (I) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as an alkyl ester portion and an OH group and / or a COOH group in a molecule thereof. The polymer (A) which has a monomeric unit (II) of is included.

The content rate of the said polymer (A) in an adhesive composition becomes like this. Preferably it is 80 weight%-100 weight%, More preferably, it is 85 weight%-100 weight%, More preferably, it is 90 weight%-100 weight% Especially preferably, they are 92.5 weight%-100 weight%, Most preferably, they are 95 weight%-100 weight%. When the content rate of the said polymer (A) in an adhesive composition exists in the said range, the stress dispersion film which has more excellent stress dispersibility can be provided.

The polymer (A) has a monomer unit (I) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety. 1 type may be sufficient as the monomer unit (I) derived from the (meth) acrylic-acid alkylester which has a C1-C20 alkyl group as an alkyl ester part in a polymer (A), and may be 2 or more types.

The content rate of the monomer unit (I) derived from the (meth) acrylic-acid alkylester which has a C1-C20 alkyl group as an alkyl ester part in a polymer (A) becomes like this. Preferably it is 90 to 99.5 weight%, More preferably, it is more preferable. Preferably it is 91 to 99 weight%, More preferably, it is 92 to 98.5 weight%, Especially preferably, it is 93 to 98.2 weight%, Most preferably, it is 94 to 98 weight%. Stress dispersion | distribution which has more excellent stress dispersibility by the content rate of the monomeric unit (I) derived from the (meth) acrylic-acid alkylester which has a C1-C20 alkyl group as an alkyl ester part in a polymer (A) exists in the said range. Films may be provided.

As a (meth) acrylic-acid alkylester which has a C1-C20 alkyl group as an alkyl ester part, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl ( Meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. are mentioned.

Polymer (A) has monomeric unit (II) derived from (meth) acrylic acid ester which has OH group and / or COOH group in a molecule | numerator. 1 type of monomeric units (II) derived from the (meth) acrylic acid ester which has an OH group and / or a COOH group in a molecule | numerator in a polymer (A) may be sufficient, and 2 or more types may be sufficient as it. When the polymer (A) has a monomer unit (II) derived from (meth) acrylic acid ester having an OH group and / or a COOH group in a molecule, a stress dispersion film having more excellent stress dispersibility can be provided.

The content ratio of the monomer unit (II) derived from the (meth) acrylic acid ester having an OH group and / or a COOH group in the molecule in the polymer (A) is preferably 0.5% by weight to 10% by weight, more preferably 1 It is weight%-9 weight%, More preferably, it is 1.5 weight%-8 weight%, Especially preferably, it is 1.8 weight%-7 weight%, Most preferably, they are 2 weight%-6 weight%. Since the content rate of the monomeric unit (II) derived from the (meth) acrylic acid ester which has OH group and / or COOH group in a molecule | numerator in a polymer (A) exists in the said range, the stress dispersion film which has more excellent stress dispersibility is provided. can do.

As a (meth) acrylic acid ester which has an OH group in a molecule | numerator, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclo Hexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. are mentioned.

As a (meth) acrylic acid ester which has a COOH group in a molecule | numerator, it is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, for example. Etc. can be mentioned.

The polymer (A) may have a monomer unit (III) derived from another monomer. 1 type of monomeric units (III) derived from another monomer in a polymer (A) may be sufficient, and 2 or more types may be sufficient as it.

As another monomer, a cyano group containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, an amide group containing monomer, an imide group containing monomer, an amino group containing monomer, an epoxy group containing monomer, a vinyl ether monomer, N-acryloyl morpholine , Sulfo group-containing monomers, phosphoric acid group-containing monomers, acid anhydride group-containing monomers, and the like.

The pressure sensitive adhesive composition has a molar content ratio of NCO groups in the pressure sensitive adhesive composition as [NCO], a molar content ratio of epoxy groups in the pressure sensitive adhesive composition as [epoxy], and a molar content rate of OH groups in the pressure sensitive adhesive composition as [OH]. ], And it is ([NCO] + [epoxy]) / ([OH] + [COOH]) <0.05, when the molar content rate of COOH group in this adhesive composition is [COOH]. When ([NCO] + [epoxy]) / ([OH] + [COOH]) is in the above range, a stress dispersing film having more excellent stress dispersibility can be provided. In addition, when there is no NCO group in an adhesive composition, [NCO] = 0, and when there is no epoxy group in an adhesive composition, [epoxy] = 0. In other words, the lower limit of ([NCO] + [epoxy]) / ([OH] + [COOH]) is zero.

The pressure-sensitive adhesive composition preferably contains a bifunctional or higher organic polyisocyanate crosslinking agent and / or an epoxy crosslinking agent. 1 type may be sufficient as 2 or more types of organic polyisocyanate type crosslinking agents and / or epoxy type crosslinking agents which may be contained in the adhesive composition of this invention, and may be 2 or more types.

The total content of the bifunctional or higher organic polyisocyanate crosslinking agent and the epoxy crosslinking agent in the pressure sensitive adhesive composition is preferably 0.001 part by weight to 0.4 part by weight, more preferably 0.0025 part by weight based on 100 parts by weight of the polymer (A). To 0.3 part by weight, more preferably 0.005 to 0.2 part by weight, particularly preferably 0.0075 to 0.15 part by weight, most preferably 0.01 to 0.1 part by weight. Since the total content ratio of the said bifunctional or more organic polyisocyanate type crosslinking agent and the epoxy type crosslinking agent in the adhesive composition of this invention exists in the said range with respect to 100 weight part of polymers (A), the stress dispersion film which has more excellent stress dispersibility is obtained. Can provide.

As a bifunctional or more organic polyisocyanate type crosslinking agent, For example, Lower aliphatic polyisocyanates, such as butylene diisocyanate and hexamethylene diisocyanate; Alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate; Trimethylolpropane / tolylene diisocyanate trimer adduct (for example, Nippon Polyurethane Co., Ltd. make, brand name "coronate L"), trimethylolpropane / hexamethylene diisocyanate trimer adduct (for example, Nippon Poly Isocyanate adducts, such as the urethane high school company make, brand names "coronate HL", and the isocyanurate body of hexamethylene diisocyanate (for example, the Nippon Polyurethane high school company make, brand name "coronate HX"); Etc. can be mentioned.

As an epoxy type crosslinking agent, for example, bisphenol A, an epoxy resin of an epichlorohydrin type, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1, 6-hexanediolglycidyl ether, trimethylolpropanetriglycidyl ether, diglycidyl aniline, diamineglycidylamine, N, N, N ', N'-tetraglycidyl-m-xylenediamine (e.g. For example, Mitsubishi Gas Chemical Co., Ltd. brand name "TETRAD-X", 1, 3-bis (N, N- diglycidyl aminomethyl) cyclohexane (for example, Mitsubishi Gas Chemical Co., Ltd. make, brand name) "TETRAD-C") etc. are mentioned.

The adhesive composition may contain the polymer (B) whose weight average molecular weight which has a monomeric unit derived from an alicyclic structure containing (meth) acrylic acid ester represented by General formula (1) is 1000 or more and less than 30000.

CH ₂ = C (R ¹ ) COOR ² ... (One)

(In Formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having an alicyclic structure.)

1 type of polymers (B) may be sufficient, and 2 or more types may be sufficient as it.

The weight average molecular weight of the polymer (B) is preferably 1000 to 30000, more preferably 1250 to 25000, still more preferably 1500 to 20000, particularly preferably 1750 to 15000, most preferably 2000 To 10000. When the weight average molecular weight of a polymer (B) exists in the said range, even if the amount of a crosslinking agent is increased, the stress dispersion film which has more excellent stress dispersibility can be provided.

The content ratio of the polymer (B) in the pressure-sensitive adhesive composition is preferably 0.5 parts by weight to 50 parts by weight, more preferably 1 part by weight to 45 parts by weight, and more preferably 100 parts by weight of the polymer (A). 2 to 40 parts by weight, particularly preferably 3 to 35 parts by weight, most preferably 4 to 30 parts by weight. By the content rate of the polymer (B) in an adhesive composition being in the said range with respect to 100 weight part of polymers (A), even if the amount of a crosslinking agent is increased, the stress dispersion film which has more excellent stress dispersibility can be provided.

The content rate of the monomeric unit derived from an alicyclic structure containing (meth) acrylic acid ester represented by General formula (1) in a polymer (B) becomes like this. Preferably it is 40 to 99.5 weight%, More preferably, it is 42.5 weight% To 99% by weight, more preferably 45% to 98.5% by weight, particularly preferably 47.5% to 98% by weight, most preferably 50% to 97.5% by weight. Since the content rate of the monomeric unit derived from an alicyclic structure containing (meth) acrylic acid ester represented by General formula (1) in a polymer (B) exists in the said range, even if the quantity of a crosslinking agent is increased, it has more excellent stress dispersibility. A stress dispersion film can be provided.

As an alicyclic structure containing (meth) acrylic acid ester represented by the said General formula (1), for example, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl methacrylate, dicyclo Fentanyloxyethyl acrylate, tricyclopentanyl methacrylate, tricyclopentanyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2 -Methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, and the like.

The polymer (B) may have a monomer unit (IV) derived from another monomer. 1 type of monomeric units (IV) derived from another monomer in a polymer (B) may be sufficient, and 2 or more types may be sufficient as it.

As another monomer which can be contained in a polymer (B), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n Nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) Acrylate, n-tetradecyl (meth) acrylate, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.

A polymer (A) and a polymer (B) can be manufactured by arbitrary appropriate methods in the range which does not impair the effect of this invention. As such a manufacturing method, solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), etc. are mentioned, for example. Among these manufacturing methods, from the viewpoint of cost and productivity, solution polymerization is preferable. The polymer (A) obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like. The polymer (B) obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

As a method of solution polymerization, the method of melt | dissolving a monomer component, a polymerization initiator, etc. in a solvent, heating and superposing | polymerizing, and obtaining a polymer solution etc. are mentioned, for example.

As heating temperature at the time of heating and superposing | polymerizing in solution polymerization, 50 degreeC-90 degreeC is mentioned, for example. As heating time in solution polymerization, 1 hour-24 hours are mentioned, for example.

As a solvent used for solution polymerization, arbitrary appropriate solvent can be used in the range which does not impair the effect of this invention. As such a solvent, For example, aromatic hydrocarbons, such as toluene, benzene, and xylene; Esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Organic solvents, such as these, are mentioned. 1 type of solvents may be sufficient as it, and 2 or more types may be sufficient as it.

In manufacture of a polymer (A) and a polymer (B), a polymerization initiator can be used. 1 type may be sufficient as such a polymerization initiator, and 2 or more types may be sufficient as it. As such a polymerization initiator, for example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2-amidinopropane) dihydrochloride, 2,2'- azobis [2- (5 -Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) sulfate, 2,2'-azobis (N, N'- Azo initiators such as dimethylene isobutyl amidine) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (available from Wako Pure Chemical Industries, Ltd., VA-057); Persulfates such as potassium persulfate and ammonium persulfate; Di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, di (4-methylbenzoyl) peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane, t-butylhydroperoxide, hydrogen peroxide, etc. Peroxide initiators; Redox-based initiators in combination with a peroxide and a reducing agent such as a combination of persulfate and sodium bisulfite, and a combination of peroxide and sodium ascorbate; Etc. can be mentioned.

Any appropriate amount of the polymerization initiator can be employed as long as the effect of the present invention is not impaired. As such a usage-amount, it is 0.01 weight part-5 weight part preferably with respect to 100 weight part of monomer components, for example.

In manufacture of a polymer (A) and a polymer (B), a chain transfer agent can be used. 1 type of these chain transfer agents may be sufficient, and 2 or more types may be sufficient as it. As such a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, 2-ethylhexyl 2-thiohexyl, 2,3-dimer Capto-1-propanol etc. are mentioned.

The amount of chain transfer agent used may be any appropriate amount used within the scope of not impairing the effects of the present invention. As such a usage-amount, it is 0.01 weight part-5 weight part preferably with respect to 100 weight part of monomer components, for example.

In the production of the polymer (A) and the polymer (B), generally any other suitable additive that can be used for the polymerization reaction can be used.

The adhesive composition of this invention may contain the crosslinking catalyst. As a crosslinking catalyst, arbitrary appropriate crosslinking catalysts can be employ | adopted in the range which does not impair the effect of this invention. Examples of such a crosslinking catalyst include metal-based crosslinking catalysts (especially tin-based crosslinking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, nase ferric iron, butyltin oxide and dioctyltin dilaurate. Can be mentioned. 1 type of crosslinking catalysts may be sufficient, and 2 or more types may be sufficient as it.

The amount of the crosslinking catalyst used may be any appropriate amount used within the range that does not impair the effects of the present invention. As such an amount used, for example, it is preferably 0.001 part by weight to 0.05 part by weight based on 100 parts by weight of the monomer component.

The pressure-sensitive adhesive composition may contain any appropriate other additives within a range that does not impair the effects of the present invention. As such other additives, for example, a silane coupling agent, a crosslinking retardant, an emulsifier, a coloring agent, a powder such as a pigment, a dye, a surfactant, a plasticizer, a tackifier, a surface lubricant, a leveling agent, a softener, an antioxidant, and an antioxidant , Light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic fillers, organic fillers, metal powders, particulates, thin substances and the like. 1 type may be sufficient as such another additive, and 2 or more types may be sufficient as it.

The loss tangent tan-delta in the whole temperature range of -40 degreeC-150 degreeC of an adhesive layer becomes like this. Preferably it is 0.10 or more. When the said loss tangent tan-delta in the whole temperature range of -40 degreeC-150 degreeC of an adhesive layer is 0.10 or more, a stress dispersion film which has more excellent stress dispersibility can be provided. In addition, the measuring method of the said loss tangent tan-delta is mentioned later.

The upper limit of the loss tangent tan δ in the entire temperature range of -40 ° C to 150 ° C of the pressure-sensitive adhesive layer is preferably 2.40 or less, more preferably 2.20 or less, still more preferably 2.00 or less, particularly preferably 1.80 or less. When the upper limit of the said loss tangent tan-delta exists in the said range, the stress dispersion film which has more excellent stress dispersibility can be provided.

The lower limit of the loss tangent tan δ in the entire temperature range of −40 ° C. to 150 ° C. of the pressure sensitive adhesive layer is preferably 0.12 or more, more preferably 0.14 or more, still more preferably 0.16 or more, and particularly preferably 0.18 or more. When the lower limit of the loss tangent tan δ is in the above range, a stress dispersing film having more excellent stress dispersibility can be provided.

≪≪C. Optical member, electronic member≫≫

The stress dispersing film of the present invention has excellent stress dispersibility. For this reason, it can use suitably as a protective material for the purpose of protecting an optical member or an electronic member from the impact from the exterior. That is, the optical member of this invention is equipped with the stress dispersion film of this invention. Moreover, the electronic member of this invention is equipped with the stress dispersion film of this invention.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when it describes as "part", unless there is a special matter, it means "weight part", and when it describes as "%", it means "weight%" unless there is a special matter.

<Measurement of weight average molecular weight>

The weight average molecular weight (Mw) of the polymer was measured using the Tosoh Corporation GPC apparatus (HLC-8220GPC). In addition, the weight average molecular weight (Mw) was calculated | required in polystyrene conversion value.

Measurement conditions are as follows.

Sample concentration: 0.2 wt% (THF solution)

Sample injection volume: 10 μl eluent

THF flow rate: 0.6ml / min

Measuring temperature: 40 ℃

Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)

Reference column: TSKgel SuperH-RC (x1)

Detector: Differential Refractometer (RI)

<Production of Adhesive Sheet (A)>

(Examples 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 26, Comparative Examples 1, 3, 5, 7)

The obtained adhesive composition is apply | coated to the base material "lumirror S10" (thickness 50 micrometers, Toray Corporation) which consists of a polyester resin so that thickness after drying may be set to 10um, and it is cured on condition of drying temperature 130 degreeC, and drying time 30 second. Dried. In this way, an adhesive layer was produced on the substrate. Subsequently, the siliconized surface of the base material which consists of a polyester resin with a thickness of 25 micrometers which performed siliconization on one surface was bonded to the surface of an adhesive layer, and the adhesive sheet (A) was obtained.

(Examples 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, Comparative Examples 2, 4, 6, 8)

The obtained adhesive composition is apply | coated to the base material "lumirror S10" (thickness 38um, Toray Corporation) which consists of a polyester resin so that thickness after drying may be 22 micrometers, and it is cured on condition of drying temperature of 130 degreeC, and drying time of 30 seconds. Dried. In this way, an adhesive layer was produced on the substrate. Subsequently, the siliconized surface of the base material which consists of a polyester resin with a thickness of 25 micrometers which performed siliconization on one surface was bonded to the surface of an adhesive layer, and the adhesive sheet (A) was obtained.

<Measurement of indentation energy>

The indentation energy was computed according to the following procedure using the "SAICAS DN-20 type | mold by the Daipla Wintes company" at measurement temperature: 25 degreeC and indentation rate: 5 micrometers / sec.

(Step 1)

When the pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive sheet (A) is attached to a flat indenter (load detection side), the base material side of the pressure-sensitive adhesive sheet (A) attached to the flat indenter is pressed into a spherical indenter, and a load of 20 N is detected. Indentation depth (μm) was calculated.

(Step 2)

The pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive sheet (A) was attached to the slide glass, press-fitted into the spherical indenter from the base material side (load detection side) of the pressure-sensitive adhesive sheet (A) attached to the slide glass, and press-fitted to the indentation depth determined in Step 1. It was.

When the vertical load y = f (x) (x: indentation depth) applied to a spherical indenter is set, the indentation energy W (μJ) until 20 N is applied to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet A is expressed by the following equation. It calculated (r is the indentation depth when the load of 20N is applied to the adhesive layer side of the adhesive sheet (A)).

<Production of Adhesive Sheet (B)>

Applying the obtained pressure-sensitive adhesive composition to a peeling treatment surface of a 38-micrometer-thick polyester film (trade name: MRF, manufactured by Mitsubishi Chemical Co., Ltd.), in which one side was peeled off with silicon so as to have a thickness of 50 µm after drying with a fountain roll. And it cured on the conditions of drying temperature 130 degreeC, and drying time 3 minutes, and dried. In this way, an adhesive layer was produced on the substrate. Subsequently, a 38-micrometer-thick polyester film (brand name: MRF, Mitsubishi Chemical Co., Ltd. product) which peeled one side | surface with the silicone on the surface of an adhesive layer, and the peeling process surface of the said film has an adhesive layer side The coating was made as possible. In this way, an adhesive sheet (B) was produced.

<Measurement of glass transition temperature (Tg), storage modulus, loss modulus, and tanδ (loss tangent)>

It calculated | required by the following method using the dynamic-viscoelasticity measuring apparatus (ARES made from Leometrics company).

Only the adhesive layer was taken out from the obtained adhesive sheet (B), it was laminated | stacked, it was made into thickness of about 2 mm, it punched at phi 7.9 mm, the cylindrical pellet was produced, and it was set as the sample for a measurement. The measurement sample was fixed to a jig of a φ7.9 mm parallel plate, and the temperature dependence of storage modulus (G ') and loss modulus (G ") was measured by the dynamic viscoelasticity measuring device, and tan δ = G ″ / G' As a calculation, tnaδ was calculated. In addition, the temperature which the obtained tan-delta curve becomes the maximum was made into glass transition temperature (Tg) (degreeC).

Measurement conditions are as follows.

Measurement: shear mode,

Temperature range: -70 ° C to 150 ° C

Temperature rise rate: 5 ℃ / min

Frequency: 1 Hz

Production Example 1 (meth) acrylic polymer (1)

2-ethylhexyl acrylate (made by Nippon Shokubai Co., Ltd.): 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler. : 4 parts by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight and ethyl acetate: 156 parts by weight, nitrogen gas was introduced with gentle stirring The polymerization was carried out for 6 hours while maintaining the liquid temperature in the flask at around 65 ° C to prepare a solution (40% by weight) of the (meth) acrylic polymer (1) having a weight average molecular weight of 550,000.

Production Example 2 (meth) acrylic polymer (2)

2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 4-hydroxybutyl acrylate (Osaka Yuki) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. Teacher manufacture): 10 weight part, acrylic acid (made by Toagosei Co., Ltd.): 0.02 weight part, 2,2'- azobisisobutyronitrile (made by Wako Pure Chemical Industries Ltd.): 0.2 weight part, ethyl acetate as a polymerization initiator: 156 parts by weight was added thereto, nitrogen gas was introduced with gentle stirring, the liquid temperature in the flask was maintained at around 65 ° C, and the polymerization reaction was carried out for 6 hours to give a solution of the (meth) acrylic polymer (2) having a weight average molecular weight of 540,000 (40). Wt%) was prepared.

[Manufacture example 3]: (meth) acrylic-type polymer (3)

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 99 parts by weight, 4-hydroxybutyl acrylate (manufactured by Osaka Yuki Chemical Co., Ltd.) : 1 part by weight and 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 1 part by weight and ethyl acetate: 156 parts by weight, nitrogen gas was introduced while gently stirring The liquid temperature in the flask was maintained at around 60 ° C to carry out a polymerization reaction for 7 hours to prepare a solution (39% by weight) of the (meth) acrylic polymer (3) having a weight average molecular weight of 1.6 million.

[Manufacture example 4]: (meth) acrylic-type polymer (4)

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 92 parts by weight, and N-acryloyl morpholine (manufactured by Goujin Co., Ltd.): 5 parts by weight Acrylic acid (manufactured by Toagosei Co., Ltd.): 2.9 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 part by weight and 200 parts by weight of ethyl acetate were added slowly. Nitrogen gas was introduce | transduced with stirring, the liquid temperature in the flask was maintained at 55 degreeC, and polymerization reaction was performed for 8 hours, and the solution (33 weight%) of the (meth) acrylic-type polymer (4) of the weight average molecular weight 1.8 million was manufactured.

[Manufacture example 5]: (meth) acrylic-type polymer (5)

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 95 parts by weight, acrylic acid (manufactured by Toagosei Co., Ltd.): 5 parts by weight, 2 as a polymerization initiator. , 2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was about 63 ° C. The polymerization reaction was carried out for 10 hours to prepare a solution (40% by weight) of the (meth) acrylic polymer (5) having a weight average molecular weight of 700,000.

[Manufacture example 6]: Alicyclic structure containing (meth) acrylic-type polymer (6)

Cyclohexyl methacrylate [glass transition temperature of single polymer (cyclohexyl polymethacrylate): 66 degreeC] as a monomer component: 95 weight part, acrylic acid: 5 weight part, 2-mercaptoethanol as a chain transfer agent: 3 weight part 0.2 part by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator and 103.2 part by weight of toluene as a polymerization solvent were charged into a separable flask and stirred for 1 hour while introducing nitrogen gas. Thus, after removing oxygen in a polymerization system, it heated up at 70 degreeC, made it react for 3 hours, and made it react at 75 degreeC for 2 hours, and the solution (50 weight weight) of the (meth) acrylic-type polymer (6) of the weight average molecular weight 4000 %) Was obtained.

[Manufacture example 6]: Alicyclic structure containing (meth) acrylic-type polymer (7)

Toluene: 100 parts by weight, dicyclopentanyl methacrylate (DCPMA) (brand name: FA-513M, manufactured by Hitachi Kasei Kogyo Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. : 60 parts by weight, methyl methacrylate (MMA): 40 parts by weight and methyl thioglycolate: 3.5 parts by weight as a chain transfer agent. After stirring for 1 hour at 70 ° C. under a nitrogen atmosphere, 0.2 part by weight of 2,2′-azobisisobutyronitrile was added as a polymerization initiator, followed by reaction at 70 ° C. for 2 hours, and then at 80 ° C. for 4 hours. After making it react, it was made to react at 90 degreeC for 1 hour, and the solution (51 weight%) of the (meth) acrylic-type polymer (7) of weight average molecular weight 4000 was obtained.

[Examples 1 and 2]

To 100 parts by weight of the solids of the solution of the (meth) acrylic polymer (1) to the solution of the (meth) acrylic polymer (1), the total solids were diluted with ethyl acetate and stirred with a disper And the adhesive composition (1) containing acrylic resin were obtained. The results are shown in Table 1.

[Examples 3 and 4]

0.01 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) to the solution of the (meth) acrylic-type polymer (1) in solid content conversion. As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. The adhesive composition (2) containing was obtained. The results are shown in Table 1.

[Examples 5 and 6]

0.1 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) to the solution of the (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. The adhesive composition (3) containing was obtained. The results are shown in Table 1.

[Examples 7, 8]

0.05 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) in the solution of the (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) was added in terms of solid content. It diluted with ethyl acetate so that it might be% and stirred with the disper, and obtained the adhesive composition (4) containing acrylic resin. The results are shown in Table 1.

[Examples 9 and 10]

0.1 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) to the solution of the (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) was added in terms of solid content. It diluted with ethyl acetate so that it might be% and stirred with the disper, and obtained the adhesive composition (5) containing acrylic resin. The results are shown in Table 1.

[Examples 11 and 12]

0.3 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of (meth) acrylic-type polymer (1) to the solution of (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) was added in terms of solid content. It diluted with ethyl acetate so that it might be% and stirred with the disper, and obtained the adhesive composition (6) containing acrylic resin. The results are shown in Table 1.

[Examples 13 and 14]

0.1 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) to the solution of the (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nihon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (7) was added in terms of solid content. It diluted with ethyl acetate so that it might become% and stirred with the disper, and obtained the adhesive composition (7) containing acrylic resin. The results are shown in Table 1.

[Examples 15 and 16]

0.3 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of (meth) acrylic-type polymer (1) to the solution of (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nihon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (7) was added in terms of solid content. It diluted with ethyl acetate so that it might be% and stirred with the disper, and obtained the adhesive composition (8) containing acrylic resin. The results are shown in Table 1.

[Examples 17 and 18]

To 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2) in the solution of the (meth) acrylic polymer (2), the total solid content was diluted with ethyl acetate and stirred with a disper And the adhesive composition (9) containing acrylic resin were obtained. The results are shown in Table 2.

[Examples 19 and 20]

0.1 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (2) to the solution of the (meth) acrylic-type polymer (2) , 0.05 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in terms of solids content, 0.005 parts by weight of fermented Nasemite (manufactured by Nihon Kagaku Sangyo Co., Ltd.) as a crosslinking catalyst, and a total solid content of 25 It diluted with ethyl acetate so that it might become weight%, it stirred with the disper, and obtained the adhesive composition (10) containing acrylic resin. The results are shown in Table 2.

[Examples 21 and 22]

0.02 part by weight of coronate L (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (3) in the solution of the (meth) acrylic polymer (3) As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. The adhesive composition 11 containing was obtained. The results are shown in Table 2.

[Examples 23 and 24]

To the solution of the (meth) acrylic polymer (5), 0.075 part by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a solid content relative to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (5) As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. The adhesive composition 12 containing was obtained. The results are shown in Table 2.

EXAMPLE 25

To 100 parts by weight of Hibra 5125 (Kuraray Co., Ltd.), the total solid content was diluted with toluene so as to obtain a pressure-sensitive adhesive composition (13) containing a rubber-based resin. The results are shown in Table 2.

EXAMPLE 26

To 100 parts by weight of Hibra 5127 (manufactured by Kuraray), the total solid content was diluted with toluene so that the total solid content was 25% by weight to obtain an adhesive composition (14) containing a rubber-based resin. The results are shown in Table 2.

[Comparative Examples 1 and 2]

0.5 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (1) to the solution of the (meth) acrylic-type polymer (1) As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. An adhesive composition (C1) was obtained. The results are shown in Table 2.

[Comparative Examples 3 and 4]

0.45 parts by weight of coronate L (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2) in the solution of the (meth) acrylic polymer (2) 0.3 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in terms of solids content, 0.005 parts by weight of fermented Nasemite (manufactured by Nihon Kagaku Sangyo Co., Ltd.) as a crosslinking catalyst, and the total solids was 25 It diluted with ethyl acetate so that it might become weight%, it stirred with the disper, and obtained the adhesive composition (C2) containing acrylic resin. The results are shown in Table 2.

(Comparative Examples 5 and 6)

0.3 weight part of coronate L (made by Nippon Polyurethane Co., Ltd.) in solid content conversion as a crosslinking agent with respect to 100 weight part of solids of the solution of the (meth) acrylic-type polymer (4) to the solution of the (meth) acrylic-type polymer (4). As a crosslinking catalyst, 0.005 parts by weight of ferrous Nasemite (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disper to prepare an acrylic resin. An adhesive composition (C3) was obtained. The results are shown in Table 2.

(Comparative Examples 7, 8)

To the solution of the (meth) acrylic polymer (5), 0.075 part by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a solid content relative to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (5) As a crosslinking catalyst, 0.005 parts by weight of Nasem ferric iron (manufactured by Nihon Kagaku Sangyo Co., Ltd.) was added in terms of solid content, and 20 parts by weight of a solution of the (meth) acrylic polymer (6) was added in terms of solid content, and the total solid content was 25 weight parts. It diluted with ethyl acetate so that it might be% and stirred with the disper, and obtained the adhesive composition (C4) containing acrylic resin. The results are shown in Table 2.

[Example 27]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (1) obtained in Examples 1 and 2, the polyester film is peeled off from one side, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

EXAMPLE 28

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (2) obtained in Examples 3 and 4, the polyester film is peeled off from one side, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

EXAMPLE 29

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (4) obtained in Example 7, 8, the polyester film is peeled from one side, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

EXAMPLE 30

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (7) obtained in Examples 13 and 14, the polyester film is peeled off from one side, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

[Example 31]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 9 obtained in Examples 17 and 18, a polyester film is peeled off from one surface, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

[Example 32]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 10 obtained in Examples 19 and 20, a polyester film is peeled off from one surface, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

[Example 33]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 11 obtained in Examples 21 and 22, the polyester film is peeled off from one side, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

EXAMPLE 34

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 12 obtained in Examples 23 and 24, a polyester film is peeled off from one surface, and it is a polarizing plate (Nitto Denko Corporation make) which is an optical member. And the brand name "TEG1465DUHC"), and the optical member to which the adhesive sheet was bonded was obtained.

EXAMPLE 35

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 13 obtained in Example 25, the polyester film is peeled off from one side, and it is a polarizing plate (Nitto Denko Co., Ltd. make, brand name) which is an optical member. It bonded to "TEG1465DUHC", and obtained the optical member to which the adhesive sheet was bonded.

[Example 36]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 14 obtained in Example 26, a polyester film is peeled from one side, and it is a polarizing plate (Nitto Denko Corporation make, brand name) which is an optical member It bonded to "TEG1465DUHC", and obtained the optical member to which the adhesive sheet was bonded.

[Example 37]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (1) obtained in Examples 1 and 2, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Co., Ltd.) which is an electronic member And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

EXAMPLE 38

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (2) obtained in Examples 3 and 4, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Co., Ltd. which is an electronic member) And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

EXAMPLE 39

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition (4) obtained in Examples 7 and 8, a polyester film is peeled off from one side, and an electroconductive film (Nitto Denko Co., Ltd. which is an electronic member) And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

[Example 40]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 7 obtained in Examples 13 and 14, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Co., Ltd. which is an electronic member) And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

[Example 41]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 9 obtained in Examples 17 and 18, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Corporation) which is an electronic member And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

EXAMPLE 42

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 10 obtained in Examples 19 and 20, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Co., Ltd. which is an electronic member) And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

EXAMPLE 43

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 11 obtained in Examples 21 and 22, a polyester film is peeled off from one side, and an electrically conductive film (Nitto Denko Co., Ltd. which is an electronic member) And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

EXAMPLE 44

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 12 obtained in Examples 23 and 24, a polyester film is peeled off from one side, and the electrically conductive film (Nitto Denko Corporation) which is an electronic member And an electronic member to which the pressure-sensitive adhesive sheet was adhered.

[Example 45]

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 13 obtained in Example 25, the polyester film is peeled off from one side, and the electrically conductive film (Nitto Denko Co., Ltd. product) which is an electronic member, It adhere | attached on brand name "Elecrister V270L-TFMP", and the electronic member to which the adhesive sheet was bonded was obtained.

EXAMPLE 46

About each of the adhesive sheet (A) and the adhesive sheet (B) obtained from the adhesive composition 14 obtained in Example 26, a polyester film is peeled off from one side, and an electroconductive film (Nitto Denko Corporation make) which is an electronic member, It adhere | attached on brand name "Elecrister V270L-TFMP", and the electronic member to which the adhesive sheet was bonded was obtained.

The stress dispersion film of this invention can be used suitably as a protective material for the purpose of protecting an optical member or an electronic member from the impact from the outside, for example.

10: plastic film
20: adhesive layer
100: stress dispersion film

Claims (8)

It is a stress dispersion film which consists of a laminated body of a plastic film and an adhesive layer,
The thickness of this plastic film is 15 micrometers-300 micrometers,
The thickness of this adhesive layer is 1 micrometer-300 micrometers,
The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition has a monomer unit (I) derived from (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as an alkyl ester portion, and an OH group and / or a COOH group in a molecule. It includes the polymer (A) or rubber type resin which has a monomeric unit (II) derived from (meth) acrylic acid ester to have,
The pressure-sensitive adhesive composition comprises a bifunctional or higher organic polyisocyanate crosslinking agent and / or an epoxy crosslinking agent,
The stress-dispersion film whose indentation energy when the load is applied to the said laminated body in the perpendicular direction from the plastic film side of this laminated body is 280 microJ or more and 7000 microJ or less.
However, the said indentation energy is measured as follows.
Using "SAICAS DN-20 type" manufactured by Dipla Wintes Co., Ltd., the indentation energy is calculated according to the following procedure at a measurement temperature of 25 ° C and a indentation rate of 5 µm / sec.
(Step 1)
Indentation depth when the pressure-sensitive adhesive layer side of the laminate is attached to a flat indenter (load detection side), the plastic film side of the laminate attached to the flat indenter is pressed into a spherical indenter, and a 20 N load is detected. ) Is calculated.
(Step 2)
The pressure-sensitive adhesive layer side of the laminate is attached to the slide glass, press-fitted with a spherical indenter from the plastic film side (load detection side) of the laminate attached to the slide glass, and press-fits to the press-fitting depth determined in Step 1.
When the vertical load y = f (x) (x: indentation depth) applied to the spherical indenter is calculated, the indentation energy W (μJ) until 20 N is applied to the pressure-sensitive adhesive layer side of the laminate is calculated by the following equation. (r is the indentation depth when a load of 20 N is applied to the pressure-sensitive adhesive layer side of the laminate).

The stress dispersing film of claim 1, wherein the plastic film has a thickness of 20 μm to 300 μm. The stress distribution film of Claim 1 or 2 whose thickness of the said adhesive layer is 1 micrometer-150 micrometers. The molar content ratio of NCO groups in the pressure-sensitive adhesive composition is set to [NCO], the molar content ratio of epoxy groups in the pressure-sensitive adhesive composition is set to [epoxy], and the OH group in the pressure-sensitive adhesive composition according to claim 1 or 2. When the molar content ratio is [OH] and the molar content ratio of COOH groups in the pressure-sensitive adhesive composition is [COOH], 0 ≦ ([NCO] + [epoxy]) / ([OH] + [COOH]) < Stress dispersion film, which is 0.05. delete The stress dispersion film according to claim 1 or 2, wherein the loss tangent tan δ in the entire temperature range of −40 ° C. to 150 ° C. of the pressure-sensitive adhesive layer is 0.10 or more and 2.40 or less. The optical member provided with the stress-dispersion film of Claim 1 or 2. The electronic member provided with the stress-dispersion film of Claim 1 or 2.

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