TWI638872B - Pressure-sensitive adhesive composition, pressure-sensitive adhesive tape or sheet - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition which can secure an adhesive force (adhesive force) without performing a hardening treatment and can form an adhesive layer having excellent moisture resistance.

The adhesive composition of the present invention is characterized in that it contains an acrylic monomer mixture or a partial polymer thereof, and an isobutylene polymer, and the moisture permeability of the adhesive layer formed by the adhesive composition is 100g / m ² . less than day.

Description

Adhesive composition, adhesive tape or sheet

The present invention relates to an adhesive composition, and an adhesive tape or sheet.

Conventionally, a composition containing an epoxy resin has been known as an adhesive or an adhesive for preventing moisture (for example, refer to Patent Documents 1, 2, and 3). However, after the composition containing the epoxy resin is adhered to the adherend, it is necessary to perform a hardening treatment such as heat treatment or ultraviolet treatment (UV treatment) to ensure the adhesion, and it is not easy to use the adherend or the substrate which is not heat resistant or ultraviolet. . In addition, it is difficult to relax the curing conditions or to secure the adhesion without performing a curing treatment.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-126699

[Patent Document 2] Japanese Patent Laid-Open No. 2012-151109

[Patent Document 3] Japanese Patent Laid-Open No. 2007-112956

Therefore, an object of the present invention is to provide an adhesive composition capable of ensuring an adhesive force (adhesive force) without performing a hardening treatment and forming an adhesive layer having excellent moisture resistance.

Furthermore, another object of the present invention is to provide an adhesive tape or sheet having a pressure-sensitive adhesive layer having excellent moisture resistance without the need for a hardening treatment after bonding.

The present inventors conducted intensive studies, and as a result, found that an adhesive composition containing an acrylic monomer mixture or a part of the polymer thereof and an isobutylene polymer was formed by the adhesive composition. The adhesive layer can ensure an adhesive force (adhesive force) without performing a hardening treatment, and can form an adhesive layer having excellent moisture resistance, thereby completing the present invention.

That is, the present invention provides an adhesive composition, which is characterized in that it contains an acrylic monomer mixture or a partial polymer thereof, and an isobutylene polymer, and is an adhesive layer formed by the above adhesive composition The permeability measured by the following method was 100 g / m ² . less than day.

Method for measuring water vapor transmission rate: An adhesive layer (thickness: 50 μm) formed from the above-mentioned adhesive composition is bonded to a triethyl cellulose film (thickness: 25 μm) to obtain a measurement sample. The obtained measurement sample is used according to JIS The test method for moisture permeability of Z 0208 is to measure the moisture permeability under the following conditions.

Measurement temperature: 40 ° C

Relative humidity: 90%

Measurement time: 24 hours

The adhesive force of the adhesive layer formed by the above-mentioned adhesive composition is preferably 1.0 N / 25 mm or more.

The content of the isobutylene-based polymer is preferably 15 parts by weight or more with respect to 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof.

The adhesive layer formed by the above-mentioned adhesive composition preferably has a crosslinked structure.

The gel fraction of the adhesive layer formed by the above-mentioned adhesive composition is preferably 20% by weight or more.

Furthermore, the present invention provides an adhesive tape or sheet, which is characterized by having an adhesive layer formed of the above-mentioned adhesive composition.

Since the adhesive composition of the present invention has the above-mentioned structure, it is possible to secure an adhesive force (adhesive force) without performing a hardening treatment, and to form an adhesive layer having excellent moisture resistance.

In addition, since the adhesive tape or sheet of the present invention has an adhesive layer formed by the above-mentioned adhesive composition, the adhesive force (adhesive force) can be secured without performing a hardening treatment after bonding, and the moisture resistance is excellent.

[Adhesive composition]

The adhesive composition of the present invention contains at least an acrylic monomer mixture or a partial polymer thereof, and an isobutylene polymer. In the adhesive composition of the present invention, the isobutylene-based polymer is dissolved or dispersed in the acrylic monomer mixture or a part of the polymer thereof. The adhesive composition of the present invention is preferably an acrylic adhesive composition containing an acrylic monomer mixture or a partial polymer thereof. The adhesive layer formed from the adhesive composition of the present invention is preferably an acrylic adhesive layer formed from an acrylic adhesive composition.

In the present specification, the "acrylic monomer mixture" refers to a mixture (or a single substance) containing only monomer components, and means a mixture (or a single substance) containing at least one type of acrylic monomer as a monomer component. The "partial polymer of an acrylic monomer mixture" refers to a composition in which one or two or more monomer components among the monomer components contained in the acrylic monomer mixture are partially polymerized. The partial polymer of the acrylic monomer mixture also includes a partial polymer obtained by partially polymerizing one or more monomer components of the monomer component and the monomer component contained in the acrylic monomer mixture. mixture.

In addition, in this specification, an adhesive composition means the composition for formation of an adhesive layer, and includes the meaning of the composition for formation of an adhesive.

The adhesive composition of the present invention is not particularly limited, and may be a composition containing at least an acrylic monomer mixture and an isobutylene polymer, or a composition containing at least an acrylic monomer mixture and an isobutylene polymer. combination. In particular, the adhesive composition of the present invention preferably contains at least the acrylic monomer mixture and the isobutylene polymer from the viewpoint of uniformly dissolving or dispersing the isobutylene polymer in the acrylic monomer mixture or a part of the polymer thereof. Polymer composition.

The adhesive composition of the present invention may contain an optional component such as the following photopolymerization initiator in addition to the acrylic monomer mixture or a partial polymer thereof, and the isobutylene polymer. For example, when the adhesive composition of the present invention is a composition containing at least an acrylic monomer mixture and an isobutylene polymer, the adhesive composition of the present invention includes an acrylic monomer mixture and an isobutylene polymer. It may also contain a photopolymerization initiator. When the adhesive composition of the present invention is a composition containing at least a part of the polymer of the acrylic monomer mixture and the isobutylene polymer, the part of the polymer containing the acrylic monomer mixture and the isobutylene polymer is excluded. In addition, it may contain a photopolymerization initiator.

In the adhesive composition of the present invention, the ratio of the acrylic monomer mixture or a part of the polymer thereof to the total amount (total weight, 100% by weight) of the adhesive composition of the present invention is not particularly limited. From the viewpoint of sufficient adherence of the adherend, it is preferably 30% by weight or more, and more preferably 50% by weight or more.

(Acrylic monomer mixture or partial polymer thereof)

The acrylic monomer mixture is a mixture (single) of one or more monomer components, and includes at least one acrylic monomer. The said acrylic monomer mixture may contain only an acrylic monomer, and may contain monomers other than an acrylic monomer and an acrylic monomer. The monomer other than the acrylic monomer is not particularly limited, and examples thereof include a polar group-containing monomer or a polyfunctional monomer described below. In addition, monomers other than the following (meth) acrylic acid alkyl esters, polar group-containing monomers, and polyfunctional monomers (in some cases, referred to as "other copolymerizable monomers") can also be mentioned. For example, the acrylic monomer mixture may also be A mixture of an acrylic monomer, a polar group-containing monomer, and a polyfunctional monomer.

Although it does not specifically limit in the said acrylic monomer mixture, For example, it is preferable to contain an alkyl (meth) acrylate. The said (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.

The "(meth) acrylic acid" means "acrylic acid" and / or "methacrylic acid" (one or both of "acrylic acid" and "methacrylic acid"), and the same shall apply hereinafter.

In addition, unless otherwise stated, "alkyl" means a linear or branched alkyl group.

The alkyl (meth) acrylate is not particularly limited, and examples thereof include an alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms (C _1-24 alkyl (meth) acrylate) Ester).

The C _1-24 alkyl (meth) acrylate is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (methyl) Base) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, (meth) acrylic acid Amyl ester, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (formyl) (Isyl) isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) Tetradecyl acrylate, pentadecyl (meth) acrylate, isopentadecyl (meth) acrylate, cetyl (meth) acrylate, isohexadecane (meth) acrylate Esters and the like.

The content of the (meth) acrylic acid alkyl ester in the acrylic monomer mixture is not particularly limited. For example, it is preferably 10% by weight or more with respect to the total amount (100% by weight) of the acrylic monomer mixture ( For example, 10 to 100% by weight), more preferably 20% by weight or more, and even more preferably 30% by weight or more. When the acrylic monomer mixture contains two or more kinds of (meth) acrylic acid alkyl esters, the content of the so-called (meth) acrylic acid alkyl ester refers to the acrylic monomer mixture. All (Meth) C Total content of alkyl enoate.

As described above, from the viewpoint of obtaining moderate cohesion in the adhesive layer and the viewpoint of obtaining appropriate adhesiveness in the adhesive layer, the acrylic monomer mixture may contain a polar group-containing monomer. Although it does not specifically limit as said polar group containing monomer, For example, (meth) acrylic acid, a methylene succinic acid, a maleic acid, fumaric acid, a butyric acid, a methacrylic acid, etc. are mentioned. Carboxyl-containing monomers (also includes monomers containing anhydride groups such as maleic anhydride); 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 4 -Hydroxybutyl (meth) acrylates such as hydroxybutyl ester, 6-hydroxyhexyl (meth) acrylate, vinyl alcohol, allyl alcohol and other hydroxyl-containing monomers; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, and other monomers containing ammonium groups; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate Amine-containing monomers such as esters, tert-butylaminoethyl (meth) acrylate; epoxy-containing monomers such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate ; Cyano-containing monomers such as acrylonitrile or methacrylonitrile N- vinyl-2-pyrrolidone, (meth) Bing Xixi group Also included: vinylpyridine, N-vinylpiperidone, vinylpyrimidine, N-vinylpiperidine , N-vinyl pyrrole, N-vinylimidazole, vinyl Heterocyclic vinyl monomers such as azoles; monomers containing sulfonic acid groups, such as sodium vinyl sulfonate; phosphate-containing monomers, such as 2-hydroxyethylpropenyl phosphate; cyclohexyl cis-butene difluorene Monoimide group-containing monomers such as imines, isopropyl cis-butene difluorene imine, and isocyanate group-containing monomers such as 2-methacryloxyethyl isocyanate. The above polar group-containing monomers can be used alone or in combination of two or more.

Among them, from the viewpoint of the adhesive properties of glass, the polar group-containing monomer is preferably a carboxyl group-containing monomer or a hydroxyl group-containing monomer, and more preferably acrylic acid (AA) or 2-hydroxyethyl acrylate ( HEA), 4-hydroxybutyl acrylate (4HBA).

The content of the polar group-containing monomer in the acrylic monomer mixture is not It is particularly limited. For example, it is preferably 0 to 75% by weight, and more preferably 0 to 50% by weight based on the total amount (100% by weight) of the acrylic monomer mixture. When two or more polar group-containing monomers are contained in the acrylic monomer mixture, the content of the so-called polar group-containing monomer refers to all of the monomers contained in the acrylic monomer mixture. The total content of the polar group-containing monomer.

Further, as described above, from the viewpoint that the gel fraction of the adhesive layer can be easily adjusted by cross-linking, and from the viewpoint that the adhesive layer cannot be easily flowed by cross-linking, the acrylic acid is described above. The polyfunctional monomer mixture may be contained in the monomer mixture. The above-mentioned polyfunctional monomer refers to a monomer having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group is not particularly limited, and examples thereof include radical polymerization such as vinyl, propenyl, isopropenyl, vinyl ether (vinyloxy), and allyl ether (allyloxy) groups. Sexual functional group. Furthermore, the aforementioned (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxyalkyl ester, a polar group-containing monomer, and other copolymerizable monomers have only one ethylenically unsaturated group in one molecule. Monomer (monofunctional monomer).

The polyfunctional monomer is not particularly limited, and examples thereof include hexanediol di (meth) acrylate (1,6-hexanediol di (meth) acrylate) and butanediol di (meth) ) Acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, (meth) Allyl acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Among them, trimethylolpropane triacrylate is preferred. Moreover, the said polyfunctional monomer can be used individually or in combination of 2 or more types.

The content of the above-mentioned polyfunctional monomer is not particularly limited. For example, it is preferably 0.0001 to 5% by weight, more preferably 0.001 to 3% by weight relative to the total amount (100% by weight) of the acrylic monomer mixture, It is preferably 0.005 to 1% by weight. Moreover, in the above acrylic acid When two or more kinds of polyfunctional monomers are contained in the monomer mixture, the above-mentioned so-called polyfunctional monomer content refers to the total amount of the contents of all polyfunctional monomers contained in the acrylic monomer mixture.

As described above, the acrylic monomer mixture may contain other copolymerizable monomers (the (meth) acrylic acid alkyl ester, the polar group-containing monomer, and a monomer other than the polyfunctional monomer) as the monomers. Monomer composition. Examples of the other copolymerizable monomers include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and methoxytriethylene glycol (meth) acrylate. Ester, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxy (meth) acrylate Alkoxyalkyl (meth) acrylates such as butyl butyl; epoxy-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; sodium vinyl sulfonate, etc. Monomers containing sulfonic acid groups; Monomers containing phosphate groups; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isomethacrylate (Meth) acrylates having alicyclic hydrocarbon groups such as esters; phenyl (meth) acrylates, phenoxyethyl (meth) acrylates, and benzyl (meth) acrylates (meth) having aromatic hydrocarbon groups ) Acrylic esters; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins or diene such as ethylene, propylene, butadiene, isoprene, isobutylene, etc. Types; vinyl ethers such as vinyl alkyl ethers; vinyl chloride and the like. Moreover, other copolymerizable monomers can be used individually or in combination of 2 or more types.

The acrylic monomer mixture is not particularly limited, and can be prepared, for example, by mixing the monomer components (preferably, uniformly mixing them).

Part of the polymer of the acrylic monomer mixture can be obtained by polymerizing the acrylic monomer mixture. The polymerization method is not particularly limited, and examples thereof include polymerization by active energy ray irradiation. In addition, from the viewpoint of suppressing polymerization inhibition by oxygen, polymerization is preferably performed in order to avoid contact with oxygen. For example, it is preferred to perform polymerization in a nitrogen atmosphere, or to perform polymerization by blocking oxygen with a release liner. Together.

Examples of the active energy ray irradiated during the above-mentioned active energy ray polymerization (photopolymerization) include alpha rays, beta rays, gamma rays, neutron rays, electron beams and other free radiation or ultraviolet rays, and particularly preferred is ultraviolet rays. The irradiation energy, irradiation time, and irradiation method of the active energy ray are not particularly limited, as long as the photopolymerization initiator can be activated to generate a polymerization reaction of the monomer.

In the above-mentioned active energy ray polymerization (photopolymerization), a polymerization initiator such as a photopolymerization initiator (photoinitiator) may be used. These polymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α-keto alcohol-based photopolymerization initiator, and aromatic sulfonic acid.醯 Chlorine-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, diphenylethylenedione-based photopolymerization initiator, benzophenone-based photopolymerization initiator Ketal photopolymerization initiator, 9-oxysulfur Photopolymerization initiators.

Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-di Phenylethane-1-one, anisole and methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexyl Phenylketone, 4-phenoxydichloroacetophenone, 4- (thirdbutyl) dichloroacetophenone, and the like. Examples of the α-keto alcohol-based photopolymerization initiator include 2-methyl-2-hydroxyphenylacetone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropane- 1-keto and the like. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime. Examples of the benzoin-based photopolymerization initiator include benzoin. Examples of the diphenylethylenedione-based photopolymerization initiator include diphenylethylenedione and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzophenacylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and polyethylene. Benzophenone, α-hydroxycyclohexylphenyl ketone and the like. Examples of the ketal-based photopolymerization initiator include benzophenone dimethyl ketal and the like. As the above 9-oxysulfur Examples of photopolymerization initiators include 9-oxysulfur , 2-chloro9-oxysulfur 2-methyl 9-oxysulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxysulfur 2,4-diisopropyl 9-oxysulfur Dodecyl 9-oxysulfur Wait.

The use amount of the photopolymerization initiator is not particularly limited, but is preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the total amount of the monomer components.

The polymerization rate of a part of the polymers of the acrylic monomer mixture is not particularly limited. For example, it is preferably 20% by weight or less, and more preferably 15% by weight or less.

The polymerization rate of a part of the polymers of the acrylic monomer mixture was determined in the following manner.

A portion of a portion of the polymer was sampled and set as a sample. This sample is accurately weighed to determine its weight, and is set to "the weight of the polymer before drying". Next, the sample was dried at 130 ° C. for 2 hours, and the dried sample was accurately weighed to determine its weight, and was set to “the weight of a part of the polymer after drying”. Then, based on the "weight of some polymers before drying" and "weight of some polymers after drying", determine the weight of the sample reduced by drying at 130 ° C for 2 hours, and set it as the "weight reduction amount" "(Volatiles, unreacted monomer weight).

Based on the obtained "weight of the partial polymer before drying" and "weight reduction", the polymerization rate (% by weight) of the partial polymer was obtained according to the following formula.

Polymerization rate of part of polymer of monomer component (% by weight) = [1- (weight reduction) / (weight of some polymer before drying)] × 100

(Isobutylene polymer)

The adhesive composition of this invention contains the said acrylic monomer mixture or its partial polymer, and an isobutylene polymer. Therefore, formed by the adhesive composition of the present invention The moisture permeability of the adhesive layer is small. It is speculated that the reason is that the isobutylene polymer itself is not easily permeated by water vapor, and the isobutylene polymer in the adhesive layer blocks the path of water vapor or makes the water vapor when the water vapor wants to pass through the adhesive layer. The path grows or narrows, and water vapor is prevented from passing through the adhesive layer.

The isobutylene-based polymer (polyisobutylene) is a polymer including at least a monomer constituent unit derived from isobutene. That is, the isobutylene-based polymer is a polymer obtained by polymerizing a monomer component containing isobutylene. The isobutylene-based polymer is a polymer having at least a polyisobutylene skeleton in a main chain or a side chain. These isobutylene-based polymers may be used alone or in combination of two or more.

The isobutylene-based polymer may be a homopolymer of isobutylene, or a copolymer (isobutylene copolymer) of isobutylene and other monomers. In the above isobutylene copolymer, the other monomers copolymerized with isobutylene are not particularly limited, and examples thereof include monomers having an ethylenic double bond. Examples of the monomer having an ethylenic double bond include, for example, α-olefins (e.g., ethylene, propylene, etc.) having 2 to 20 carbon atoms, and aromatic vinyl compounds (e.g., styrenes such as styrene and methylstyrene). Compounds, etc.), 1,3-butadiene-based compounds (for example, 1,3-butadiene, isoprene, etc.) and the like. Among these, a styrene-based compound is preferred from the viewpoint of the ease of obtaining cohesion. The monomer components constituting the isobutylene-based polymer may be used alone or in combination of two or more.

The isobutylene polymer is not particularly limited, and examples thereof include butyl rubber (a polymer of isobutylene and isoprene), a random copolymer of isobutylene and n-butene, a polymer block of isobutylene, and others A block copolymer of a monomer polymer block (for example, a styrene polymer block of a styrene compound, an isoprene polymer block, etc.). Among them, a styrene-isobutylene block copolymer (SIB (Styrene Isobutylene) block copolymer) having styrene-based polymer blocks as hard segments and an isobutylene polymer block as soft segments, and benzene are preferred. Ethylene-isobutylene-styrene block copolymer (SIBS (Styrene Isobutylene Styrene) block copolymer).

The above-mentioned SIBS block copolymer may be a commercially available product, and examples thereof include a trade name "SIBSTAR-062M" (manufactured by Kaneka Co., Ltd.), a trade name "SIBSTAR-062T" (manufactured by Kaneka Co., Ltd.), and a trade name "SIBSTAR -072T "(manufactured by Kaneka Corporation).

The ratio of isobutylene in the monomers constituting the isobutylene-based polymer is not particularly limited, and from the viewpoint of moisture resistance of the adhesive layer, it is relative to the total amount of all monomer components (100 weights) constituting the isobutylene-based polymer. %), Preferably 30% by weight or more (for example, 30 to 100% by weight), and more preferably 50% by weight or more (for example, 50 to 100% by weight).

The content of the isobutylene polymer in the adhesive composition of the present invention is not particularly limited, and it is preferably 15 parts by weight or more (for example, 15 to 100) with respect to 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof. Parts by weight). When the content of the isobutylene-based polymer is 15 parts by weight or more, in the adhesive layer formed by the adhesive composition, it is easy to obtain more excellent moisture resistance. In addition, if the content of the isobutylene-based polymer is 100 parts by weight or less, the adhesive layer formed from the adhesive composition has sufficient adhesiveness, and excellent cohesion is easily obtained even at high temperatures. In addition, it is effective because it can effectively suppress the flow of the adhesive layer.

(Adhesion imparting resin)

The adhesive composition of the present invention may further contain an adhesive-imparting resin from the viewpoint of further improving the adhesiveness in the adhesive layer formed by the adhesive composition. The adhesion-imparting resin is not particularly limited, and examples thereof include alicyclic saturated hydrocarbon resins, petroleum resins, terpene resins, coumarone-indene resins, styrene resins, turpentine resins, Based phenol resin, xylene resin, etc. The adhesion-imparting resin may be a hydrogenated adhesion-imparting resin (for example, an alicyclic saturated hydrocarbon resin, a turpentine resin, a petroleum resin, a terpene resin, a coumarone-indene resin, a styrene resin, Derivatives obtained by hydrogenating adhesion-imparting resins such as alkylphenol resins and xylene resins (hydrogenated turpentine resin, hydrogenated petroleum resin, hydrogenated terpene resin) Wait). The said adhesion-imparting resin can be used individually or in combination of 2 or more types.

The content of the adhesion-imparting resin in the adhesive composition of the present invention is not particularly limited, and is preferably 1 to 50 parts by weight, and more preferably 1.5 to 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof. ~ 40 parts by weight, more preferably 2 to 30 parts by weight. If the content of the above-mentioned adhesion-imparting resin is 1 part by weight or more, it is preferable to obtain excellent adhesiveness in the adhesive layer formed by the adhesive composition. In addition, if the content of the adhesion-imparting resin is 50 parts by weight or less, it is preferable that the cohesive force is not easily reduced in the adhesive layer formed by the adhesive composition.

As long as the effect of the present invention is not impaired, the adhesive composition of the present invention may further contain an acrylic oligomer. Since the acrylic oligomer system functions as an adhesion-imparting component, it is possible to improve adhesion. These acrylic oligomers can be used alone or in combination of two or more.

As long as the effect of the present invention is not impaired, the adhesive composition of the present invention may further contain a silane coupling agent. If the adhesive composition of the present invention contains a silane coupling agent, the adhesiveness (especially the adhesiveness in a high-temperature and high-humidity environment and the high-temperature and high-humidity environment) in an adhesive layer formed by the adhesive composition Adhesion to glass) is further improved. These silane coupling agents can be used alone or in combination of two or more.

The silane coupling agent is not particularly limited, and preferred examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-aminopropyl Trimethoxysilane, N-phenyl-aminopropyltrimethoxysilane, and the like.

The content of the silane coupling agent in the adhesive composition of the present invention is not particularly limited, and is preferably 0.01 to 1 part by weight, and more preferably 0.03 to 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof. ~ 0.5 parts by weight.

In the adhesive composition of the present invention, from the viewpoint of adjusting the gel fraction of the adhesive layer formed by the adhesive composition within a moderate range, the adhesive layer formed by the adhesive composition is adjusted. From the viewpoint of making it difficult to flow and facilitating handling, a crosslinking agent may be further contained. The crosslinking agent is not particularly limited, and examples thereof include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent, and a metal alkane. Oxide-based crosslinking agent, metal chelate-based crosslinking agent, metal salt-based crosslinking agent, carbodiimide-based crosslinking agent, An oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, an amine-based crosslinking agent, and the like. Among these, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are preferred. These crosslinking agents can be used alone or in combination of two or more.

Examples of the isocyanate-based cross-linking agent (polyfunctional isocyanate compound) include 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate. Lower aliphatic polyisocyanates such as diisocyanate; cycloaliphatic diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates Isocyanates; aromatic polyisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. : Trimethylolpropane / toluene diisocyanate adduct [manufactured by Japan Polyurethane Industry Co., Ltd., trade name “Coronate L”], trimethylolpropane / hexamethylene diisocyanate adduct [Japan Polyurethane Industry Co., Ltd. Co., Ltd., trade name "Coronate HL"].

Examples of the epoxy-based crosslinking agent (multifunctional epoxy compound) include N, N, N ', N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol Anhydride polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris (2-hydroxyethyl) isocyanurate triglycidyl, m Resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule can also be cited. Furthermore, Commercial products such as the brand name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) are listed.

The content of the above-mentioned crosslinking agent in the adhesive composition of the present invention is not particularly limited, and from the viewpoint of controlling the gel fraction of the adhesive layer formed by the adhesive composition within a moderate range, relative It is preferably 0.001 to 30 parts by weight, more preferably 0.005 to 25 parts by weight, and still more preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof.

To the extent that the effects of the present invention are not impaired, the adhesive composition of the present invention may contain additives. Examples of the additives include cross-linking accelerators, anti-aging agents, fillers, colorants (such as pigments and dyes), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, and surfactants. , Antistatic agent, etc. These additives may be used alone or in combination of two or more.

The method for preparing the adhesive composition of the present invention is not particularly limited, and examples thereof include the above-mentioned acrylic monomer mixture or a part of the polymer thereof, an isobutylene polymer, and any optional components (for example, the above-mentioned photopolymerization) The initiator, the adhesion-imparting resin, the acrylic oligomer, the silane coupling agent, the cross-linking agent, the additive, and the like) are mixed.

For example, in the case where the adhesive composition of the present invention includes a composition of an acrylic monomer mixture and an isobutylene polymer, and further includes a photopolymerization initiator, such a composition can be obtained by mixing the acrylic monomer mixture , An isobutylene polymer and a photopolymerization initiator are prepared by mixing.

In addition, in the case where the adhesive composition of the present invention is a composition containing a part of an acrylic monomer mixture and an isobutylene polymer, and further a photopolymerization initiator, such a composition can be obtained by applying acrylic acid A part of the polymer of the monomer mixture, the isobutylene polymer, and the photopolymerization initiator are mixed and prepared. As described above, the partial polymer of the acrylic monomer mixture is formed by partially polymerizing the acrylic monomer mixture. For example, a composition containing a part of the polymer of the acrylic monomer mixture, an isobutylene polymer, and further a photopolymerization initiator can be prepared by the following method: First, the acrylic monomer mixture is polymerized with at least photopolymerization. After the composition of the initiator is partially polymerized, a photopolymerization initiator is further added. Furthermore, a composition containing at least a part of the polymer of the acrylic monomer mixture and the isobutylene polymer can be prepared by the following method: First, after the acrylic monomer mixture is partially polymerized, an acrylic monomer or polystyrene is added. Functional monomers, etc.

The viscosity of the adhesive composition of the present invention is not particularly limited. From the viewpoint of making the operation of the adhesive composition easier and further improving the coating property, it is preferably 0.1 to 100 Pa. s, more preferably 0.5 ~ 50Pa. s.

Moreover, in this specification, the so-called viscosity refers to a viscosity measured using a BH viscometer as a viscometer and a rotor: No. 5 rotor, a rotation speed: 10 rpm, and a measurement temperature: 30 ° C.

In addition, since the viscosity of the acrylic monomer mixture is low, there is a tendency that a composition containing the acrylic monomer mixture as a main component is difficult to apply to a substrate, a support, or the like. However, the adhesive composition of the present invention contains an isobutylene polymer in addition to the acrylic monomer mixture or a part of the polymer thereof, and thus the viscosity can be easily maintained within the above range.

Regarding the adhesive composition of the present invention, since the isobutylene polymer is easily dissolved in the acrylic monomer mixture or a part of the polymer, the viscosity can be maintained within the above range without adding a solvent. That is, the adhesive composition of the present invention may be solvent-free. In the case where the adhesive layer of the present invention does not contain a solvent, the heating and drying after coating is not required, and the formation of the adhesive layer becomes easier. It is also excellent in environmental aspects and safety.

In addition, the viscosity of the adhesive composition of the present invention can be adjusted by, for example, blending various polymer components such as acrylic rubber and tackifier additives.

Isobutylene-based polymers generally do not have a cross-linking point, so a cross-linked structure cannot be constructed, and if they are heated at high temperatures, they tend to flow, and they may have poor durability at high temperatures. Moreover, in many cases, the isobutylene-based polymer has poor adhesion and tackiness. However, since the adhesive composition of the present invention contains an acrylic monomer mixture or a partial polymer thereof and an isobutylene-based polymer, an adhesive layer having excellent moisture resistance and adhesion can be formed. In addition, when the adhesive layer has a crosslinked structure, durability at high temperatures can be particularly improved.

With regard to the adhesive composition of the present invention, the moisture permeability of the adhesive layer formed by the adhesive composition measured by the following method was 100 g / m ² . Less than day, preferably 80g / m ² . Less than day, more preferably 60g / m ² . less than day.

Method for measuring moisture permeability: An adhesive layer (thickness: 50 μm) formed from an adhesive composition is bonded to a triethyl cellulose film (thickness: 25 μm) to obtain a sample for measurement, and the obtained sample for measurement is used in accordance with JIS Z The moisture permeability test method of 0208 measures the moisture permeability under the following conditions.

Measurement temperature: 40 ° C

Relative humidity: 90%

Measurement time: 24 hours

In addition, in this specification, the "permeability of the adhesive layer formed by the adhesive composition and measured by the above-mentioned method" in the adhesive composition is only referred to as the "permeability of the present invention" situation.

The moisture permeability of the adhesive composition of the present invention is 100 g / m ² . Less than day, so it has excellent moisture resistance.

[Adhesive tape or sheet]

The adhesive tape or sheet of the present invention has an adhesive layer formed from the adhesive composition of the present invention. That is, the adhesive tape or sheet of the present invention is preferably an acrylic adhesive tape or sheet having an acrylic adhesive layer formed of an acrylic adhesive composition. In this specification, the adhesive tape or sheet of the present invention may be referred to simply as "adhesive tape of the present invention" shape. Moreover, the adhesive layer formed from the adhesive composition of this invention may be called "adhesive layer of this invention."

The adhesive tape of the present invention may be a single-sided adhesive tape with only one side being the surface of the adhesive layer (adhesive side), or a double-sided adhesive tape with both sides being the surface of the adhesive layer. The adhesive tape of the present invention is not particularly limited, and a double-sided adhesive tape is preferred from the viewpoint of bonding the adherends to each other.

The adhesive tape of the present invention may be an adhesive tape without a substrate (base material layer), a so-called "substrate-free type" adhesive tape (there is a case called a "substrate-free adhesive tape"), and may also be a substrate Adhesive tape (there is a case called "adhesive tape with substrate"). Examples of the substrateless adhesive tape include a double-sided adhesive tape including only the adhesive layer of the present invention (adhesive layer formed from the adhesive composition of the present invention), or an adhesive layer including the adhesive layer of the present invention and the present invention. Double-sided adhesive tapes, etc. of an adhesive layer other than the adhesive layer of the invention (there may be a case called "other adhesive layer"). Examples of the adhesive tape having a substrate include a single-sided adhesive tape having the adhesive layer of the present invention on one side of the substrate, or a pair of adhesive tapes having the adhesive layer of the present invention on both sides of the substrate. A surface adhesive tape, or a double-sided adhesive tape having the adhesive layer of the present invention on one side of one substrate and another adhesive layer on the other side.

It should be noted that when the above-mentioned "base material (base material layer)" is used (adhered to) an adherend (optical member or the like) of the adhesive tape of the present invention, it is attached together with the adhesive layer. The part of the adherend does not include a release liner (release film) that is peeled off when the adhesive tape is used (attached).

Among them, the adhesive tape of the present invention can correspond to various forms when used, and is not limited to the form used, and from the viewpoint of increasing the options of the use method, the adhesive tape without a substrate is preferred, and more preferably A double-sided adhesive tape without a substrate (a substrate-free double-sided adhesive tape) containing only the adhesive layer of the present invention.

(Adhesive layer of the present invention)

The adhesive layer of the present invention is formed from the adhesive composition of the present invention. The invention The method for forming the adhesive layer is not particularly limited, and examples thereof include coating (applying) the adhesive composition of the present invention on an appropriate support such as a substrate or a release liner, and irradiating active energy rays. Moreover, if necessary, it may be heat-dried after coating.

Moreover, in the said coating (coating), a well-known coating method can also be used. For example, a conventional coater, specifically, a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, a blade coater, or the like can be used. , Sprayer, corner wheel coater, direct coater, etc.

When the active energy ray is irradiated after applying the adhesive composition of the present invention, examples of the radiated active energy ray include alpha rays, beta rays, gamma rays, neutron rays, electron beams, and other free radiation or ultraviolet rays. Especially preferred is ultraviolet light. The irradiation energy, irradiation time, and irradiation method of the active energy ray are not particularly limited.

The adhesive layer of the present invention contains at least a base polymer (that is, an acrylic polymer as a base polymer) derived from an acrylic monomer mixture or a partial polymer thereof, and an isobutylene polymer. The adhesive layer of the present invention is not particularly limited. For example, the adhesive layer may have a uniform composition as a whole, and may also include a structure having a portion in which the adhesive layer contains a large portion of an isobutylene-based polymer (for example, 60 to 80% by weight of an isobutylene polymer (in some cases referred to as "isobutylene polymer portion"), and a large amount of the above-mentioned polymer derived from an acrylic monomer mixture or a part of the polymer is used as a base polymerization Part of an acrylic polymer (such as a part containing 60 to 80% by weight or more of the base polymer) (there is a case where it is referred to as an "acrylic polymer part").

Generally, the adhesive layer includes a uniform structure as a whole, and in many cases has a uniform feature as a whole. The adhesive layer of the present invention (adhesive layer formed from the adhesive composition of the present invention) preferably has a large portion of the isobutylene polymer (for example, the above-mentioned isobutylene polymer portion) and an acrylic polymer as a base polymer. A structure in which a large portion of the polymer (for example, the above-mentioned acrylic polymer portion) is dispersed with a minute distribution. That is, the adhesive layer of the present invention preferably has a separation structure (phase) of an acrylic polymer and an isobutylene polymer. Separated structure) as the phase structure. If the adhesive layer of the present invention has such a structure, various characteristics such as moisture resistance, cohesion (especially cohesion at high temperature), and adhesiveness can be obtained at a higher level than in the case of uniformity. In other words, as a whole adhesive layer, moisture resistance, adhesion, and cohesion at high temperatures can be achieved at a higher level. The reason is that the isobutylene polymer has low moisture permeability, especially excellent moisture resistance. On the other hand, the acrylic polymer has high moisture permeability and poor moisture resistance, but has excellent cohesion, especially at high temperatures. , Excellent adhesion. In addition, when the adhesive composition of the present invention contains an adhesion-imparting resin, and when the adhesive layer of the present invention has such a structure, the adhesion-imparting resin is moderately distributed in the portion where the isobutylene-based polymer is large and the acrylic polymer is Many of the two. Therefore, if the adhesive layer of the present invention contains an adhesion-imparting resin, the entire adhesive layer will not reduce the moisture resistance, and the adhesion will be further improved. Examples of the adhesion-imparting resin capable of easily obtaining such characteristics include a saturated hydrocarbon resin.

Regarding the ratio of the portion where the isobutylene polymer is large (for example, the isobutylene polymer portion) and the portion where the acrylic polymer is large (for example, the acrylic polymer portion), for example, the ratio of The polymerization rate of a part of the polymer, the content of the acrylic monomer mixture or a part of the polymer in the adhesive composition, the content of the isobutylene polymer in the adhesive composition, the illuminance of the active energy ray, etc. Adjustment.

The thickness of the adhesive layer of the present invention is not particularly limited. From the viewpoint of obtaining excellent adhesiveness and the viewpoint of suppressing the flow of the adhesive layer, it is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

The adhesive layer of the present invention preferably has a crosslinked structure. That is, the adhesive layer formed by the adhesive composition of the present invention preferably has a crosslinked structure. If it has a crosslinked structure, the thermal stability of the adhesive layer is further improved. For example, even in a high-temperature environment (for example, a temperature environment of 80 to 100 ° C), problems such as flow and peeling of the adhesive layer are not easy to occur. The crosslinked structure can be obtained, for example, by using a polyfunctional monomer or a crosslinking agent.

The gel fraction of the adhesive layer of the present invention (adhesive formed from the adhesive composition of the present invention) is not particularly limited. From the viewpoint of thermal stability and the viewpoint of suppressing the flow of the adhesive layer at high temperature, It is preferably 20% by weight or more (for example, 20 to 99.9% by weight), more preferably 30% by weight or more (for example, 30 to 99.9% by weight), and still more preferably 50% by weight or more (for example, 50 to 99.9% by weight). It is more preferably 60% by weight or more (for example, 60 to 99.9% by weight).

The above-mentioned gel fraction (solvent-insoluble component) was determined as follows.

(Measurement of gel fraction)

Adhesive layer: Take about 0.1g and wrap it in a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nitto Denko Corporation) with an average pore diameter of 0.2 μm, and then bundle it with a kite thread. Weight, and let this weight be the weight before immersion. The weight before immersion is the total weight of the acrylic adhesive layer (taken from the above), the tetrafluoroethylene sheet, and the kite string. The total weight of the tetrafluoroethylene sheet and the kite string was also measured in advance, and this weight was set to the weight of the packaging bag.

Then, a person who wrapped the adhesive layer with a tetrafluoroethylene sheet and bundled it with a kite string (referred to as a "sample") was placed in a 50 ml container filled with ethyl acetate, and left at 23 ° C for 7 days. After that, the sample was taken out of the container (after ethyl acetate treatment), transferred to an aluminum cup, and dried at 130 ° C for 2 hours in a dryer to remove ethyl acetate. Then, the weight was measured, and the weight was set to Is the weight after immersion.

Then, the gel fraction was calculated according to the following formula.

Gel fraction (% by weight) = (a-b) / (c-b) × 100

(In the above formula, a is the weight after dipping, b is the weight of the packaging bag, and c is the weight before dipping)

In addition, the adhesive layer of the present invention has a moisture permeability of 100 g / m ² obtained by the following measurement method from the viewpoint of obtaining excellent moisture resistance. Day or less (preferably 85 g / m ² .day or less, more preferably 70 g / m ² .day or less).

Measuring method of water vapor transmission rate: An adhesive layer (thickness: 50 μm) is bonded to a triethyl cellulose film (thickness: 25 μm) to obtain a measurement sample. The obtained measurement sample is used according to According to the JIS Z 0208 moisture permeability test method (cup method), the moisture permeability was measured under the following conditions. More specifically, the measurement can be performed by the method described in "(Method for Measuring Moisture Permeability)" in (Evaluation) below.

Measurement temperature: 40 ° C

Relative humidity: 90%

Measurement time: 24 hours

Furthermore, the adhesive force of the adhesive layer of the present invention (measurement temperature: 23 ° C, relative humidity: 50% RH, tensile speed: 300mm / min, peeling angle: 180 °, peeling condition for glass plate) is not particularly limited It is preferably 1.0N / 25mm or more, more preferably 3.0N / 25mm or more, and even more preferably 5.0N / 25mm or more. When the adhesive force is within the above range, the acrylic adhesive layer has excellent adhesiveness without being subjected to a hardening treatment.

The adhesive force of the said acrylic adhesive layer can be measured more specifically by the method described in "(measurement of an adhesive force)" of the following (evaluation).

(Base material)

As described above, the adhesive tape of the present invention may also be a substrate-attached adhesive tape having at least the adhesive layer and the substrate layer of the present invention. The substrate is not particularly limited, and examples thereof include a plastic substrate (polymer substrate). The substrate may be a substrate (single-layer substrate) including one layer, or may have a multilayer structure (layered substrate) of two or more layers.

The material constituting the plastic substrate is not particularly limited, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate. Polyesters such as esters; Polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymers; Polyvinyl alcohol; Polyvinylidene chloride; Polyvinyl chloride; Vinyl chloride-vinyl acetate copolymers; Polyvinyl acetate; Polyfluorene Amines; polyimide; celluloses such as triethylammonium cellulose and diethylammonium cellulose; fluorine-based resins; polyethers; polyetheramines; polyetheretherketones; polyphenylene sulfide; polystyrene and other polymers Styrenic resins; polycarbonates; polyethers; acrylic resins such as polymethyl methacrylate. Furthermore, the above materials can be used alone or in combination of two or more use.

Among them, as a material constituting the above-mentioned plastic base material, in terms of a good degree of balance of strength, handling (handling property), cost, dimensional stability, and gripping force, polyester or cellulose, acrylic acid is preferred. Based on resins, more preferred are polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA). That is, the substrate is preferably a polyethylene terephthalate substrate, a triethyl cellulose substrate, or a polymethyl methacrylate substrate.

The said base material can also be surface-treated as needed. Examples of the surface treatment include treatments using chemical or physical methods such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, and ionizing radiation treatment. Further, an undercoating treatment for improving the adhesion with the adhesive layer may be performed.

In addition, from the viewpoint of improving the scratch resistance (friction resistance) of the surface, the substrate may be subjected to a hard coating treatment. When the surface of the substrate is subjected to a hard coating treatment, the substrate surface protection (the property that the surface of the substrate is less likely to be injured) is improved. From the viewpoint of suppressing the generation of static electricity, the substrate may be subjected to an antistatic treatment.

The base material may be, for example, a base material that is subjected to an undercoating treatment to improve the adhesion to the adhesive layer on one surface and a hard coating treatment to the other surface.

(Other layers)

In addition to the adhesive layer and the substrate of the present invention, the adhesive tape of the present invention may have other layers (such as an intermediate layer, an undercoat layer, etc.) within a range that does not impair the effects of the invention.

(Release liner)

As described above, in the adhesive tape of the present invention, the adhesive surface may be protected by a release liner. The release liner is not particularly limited, and a known or commonly-used release liner is preferably used. Specifically, preferred examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. (PBT, Polybutylece Terephthalate) and other polyester resins; polyethylene (PE, Polyethylene), polypropylene (PP, Polypropylene), polymethylpentene (PMP, Polymethylpentene), ethylene-propylene copolymer, ethylene-vinyl acetate Ethylene Vinyl Acetate Copolymer (EVA) and other olefin-based resins as monomers; olefin-based resins; PVC (Polyvinyl Chloride); vinyl acetate-based resins; polycarbonate (PC); Phenyl sulfide (PPS, Polyphenylene Sulfide); Polyamines (nylon), fully aromatic polyamines (aromatic polyamines) and other fluorene-based resins; polyfluorene-based resins; polyetheretherketone (PEEK, Polyetheretherketone); olefin resins such as polyethylene (PE), polypropylene (PP); including polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer Fluorine-based resins such as vinyl chloride, vinylidene fluoride copolymers, etc.

Further, examples of the release liner include a release liner having a release layer (release treatment layer) on at least one surface of a release liner substrate, a release adhesive containing a fluorine-based polymer with low adhesion, Non-polar polymer release liner with low adhesion. In addition, a release liner substrate (that is, the release liner substrate itself) which does not have a release layer may be mentioned. The fluorine-based polymer is not particularly limited, and examples thereof include polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl fluoride, polyvinylidene fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene. -Vinylidene fluoride copolymers, etc. The non-polar polymer is not particularly limited, and examples thereof include olefin resins such as polyethylene (PE) and polypropylene (PP). Among them, a release liner having a release layer on at least one surface of the release liner substrate, and a release liner substrate without a release layer (that is, the release liner substrate itself) are preferably used.

The release liner substrate is not particularly limited, and examples thereof include a plastic film. Examples of such a plastic film include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); Olefin resins with α-olefins such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) as monomer components ; Polyvinyl chloride (PVC); Vinyl acetate resin; Polycarbonate (PC); Polyphenylene sulfide (PPS); Polyamines (nylon), fully aromatic polyamines (aromatic polyamines) and other amine-based resins Polyimide resin; plastic film containing polyetheretherketone (PEEK). Among these, from the viewpoints of processability, availability, workability, dust resistance, and cost, a plastic film made of a polyester resin is preferable, and a PET film is more preferable.

The release treatment agent constituting the release layer is not particularly limited, and examples thereof include a release treatment agent such as a polysiloxane-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl-based release treatment agent, and molybdenum sulfide. Among these, from the viewpoints of peeling control and stability over time, a polysiloxane-based peeling treatment agent is preferred. Moreover, a peeling processing agent can be used individually or in combination of 2 or more types.

The said release liner can be manufactured by a well-known and usual method. The thickness of the release liner is not particularly limited.

(Production method)

The manufacturing method of the adhesive tape of this invention is not specifically limited, A well-known formation method can be used. For example, in the case where the adhesive tape of the present invention is an adhesive tape with a substrate, it can be produced by forming the adhesive layer of the present invention from the adhesive composition of the present invention on at least one side of the substrate. In addition, when the adhesive tape of the present invention is a substrate-free adhesive tape including the adhesive layer of the present invention, the adhesive layer of the present invention can be formed on the release liner by the adhesive composition of the present invention. While making.

(Physical properties)

The adhesive tape of the present invention is not particularly limited, and from the viewpoint of obtaining excellent moisture resistance, the moisture permeability determined by the following measurement method is preferably 100 g / m ² . Less than day, more preferably 80g / m ² . Less than day, and more preferably 60 g / m ² . less than day.

Measuring method of water vapor transmission rate: An adhesive tape was adhered to a triethylammonium cellulose film (thickness: 25 μm) to obtain a measurement sample. The obtained measurement measurement sample was used according to the JIS Z 0208 water vapor transmission test method under the following conditions: The moisture permeability was measured.

Measurement temperature: 40 ° C

Relative humidity: 90%

Measurement time: 24 hours

The adhesive force of the adhesive tape of the present invention (measurement temperature: 23 ° C, relative humidity: 50% RH, tensile speed: 300mm / min, peeling angle: 180 °, peeling condition for glass plate) is not particularly limited, and is preferably It is 1.0N / 25mm or more, more preferably 3.0N / 25mm or more, and even more preferably 5.0N / 25mm or more. When the adhesive force is within the above range, the adhesive tape of the present invention has excellent adhesiveness without being subjected to a hardening treatment.

More specifically, the adhesive force of the adhesive tape of the present invention can be measured by the method described in "(Measurement of Adhesive Force)" (Evaluation) below.

The thickness of the adhesive tape of the present invention is not particularly limited, but is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

Since the adhesive tape of the present invention has the adhesive layer of the present invention, it is not subjected to a hardening treatment after bonding, exhibits sufficient adhesion to the adherend, and has excellent moisture resistance. In addition, the adherend can be protected from moisture.

Since the adhesive tape of the present invention exhibits sufficient adhesion to the adherend without hardening treatment, and has excellent moisture resistance, it can be used for protection of adherends that are not resistant to humidity. For example, the adhesive tape of the present invention can be used as a protective film.

Since the adhesive tape of the present invention has the above-mentioned characteristics, it can be used, for example, in electric or electronic equipment (for example, electric or electronic equipment that is not heat-resistant, humidity, or ultraviolet rays). In particular, it can be preferably used for surface protection use in the manufacture of electrical or electronic equipment, surface protection use in the use of electrical or electronic equipment, and the like. Moreover, it can be used suitably for optical use (For example, the surface protection use at the time of manufacture of an optical product or an optical member, the surface protection use at the time of use of an optical product, or an optical member, etc.).

The electrical equipment is not particularly limited, and examples thereof include home appliances such as televisions, refrigerators, washing machines, and vacuum cleaners, and outdoor units such as air conditioners. Moreover, as the electron The device is not particularly limited, and examples thereof include image display devices such as a liquid crystal display and a plasma display, a mobile phone, a smart phone, a tablet PC (Personal Computer) (tablet computer), a notebook personal computer, Personal digital assistant (PDA, Personal Digital Assistance), Walkman, portable game console, mobile TV and other mobile devices.

The above-mentioned optical products refer to the use of optical properties (such as polarizing properties, light refraction properties, light scattering properties, light reflection properties, light transmission properties, light absorption properties, light diffraction properties, optical rotation properties, visibility, etc.) in the products. ). Examples of the optical products include a liquid crystal display device, a display device such as a plasma display panel (PDP), an electronic paper, or an input device such as a touch panel, or an appropriate combination of the display device and the input device. The resulting device, etc.

The above-mentioned optical member refers to a member having the above-mentioned optical characteristics. Examples of the optical member include members constituting the device (optical device) such as the display device (image display device) and the input device, or members used in the devices, and examples thereof include polarizing plates and wavelength plates. , Retardation plate, optical compensation film, brightness enhancement film, light guide plate, reflective film, anti-reflection film, transparent conductive film (ITO (Indium Tin Oxide) film), design film, decorative film, surface protection board,稜鏡, a lens, a color filter, a transparent substrate, or a member in which these are laminated (these are collectively referred to as "optical film") and the like. In addition, as for the "plate" and "film" mentioned above, those that include a plate shape, a film shape, and a sheet shape, for example, include a "polarizing plate" and a "polarizing sheet". Furthermore, in the "optical member" in the present invention, as described above, a member (design film) that protects the visibility or excellent appearance of the display part in the display device or the input device and also performs the function of decoration or protection is also included. , Decorative film or surface protective film, etc.).

More specifically, the adhesive tape of the present invention can be preferably used for thin-layer display members (for example, touch panels using LCDs, etc.), thin-layer display devices (for example, LCDs or color filters used therefor), and images. Identification members, thin-layer optical films (e.g., polarizing plates, etc.), electronic devices (especially Thin-layer electronic equipment) and other surface protection applications.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited in any way.

(Example 1)

80 parts by weight of butyl acrylate (BA) and 0.8 parts by weight of acrylic acid (AA) were mixed to obtain an acrylic monomer mixture.

To 80 parts by weight of the acrylic monomer mixture, a styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062M", manufactured by Kaneka Corporation, weight average molecular weight 48000, and styrene content rate 20%) was added. : 20 parts by weight, TMPTA (Trihydroxymethyl propane triacrylate, polyfunctional monomer): 0.08 parts by weight, alicyclic saturated hydrocarbon resin (trade name "Arkon P125", Arakawa Chemical Industries, Ltd.) Co., Ltd.): 6 parts by weight, 1-hydroxy-cyclohexyl-phenyl-one (photopolymerization initiator, trade name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, and 2,2- Dimethoxy-1,2-diphenylethane-1-one (photopolymerization initiator, trade name "Irgacure 651", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, uniformly mixed, and An acrylic adhesive composition was obtained.

The acryl-based adhesive composition was applied on the release-treated surface of a release liner (trade name "MRF # 38", manufactured by Mitsubishi Resin Co., Ltd.) so that the thickness of the formed adhesive layer was 50 µm. To form an acrylic adhesive composition layer. Then, a release liner ("MRE # 38", manufactured by Mitsubishi Resin Co., Ltd.) was attached to the surface of the acrylic adhesive composition layer. Then, a black light (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays with an illuminance of 5 mW / cm ² for 360 seconds to light-harden the acrylic adhesive composition layer to form an acrylic adhesive layer.

In addition, the illuminance of ultraviolet rays uses an industrial UV detector (trade name "UVR-T1", manufactured by Topcon Technohouse Co., Ltd.) and has a maximum wavelength of about 350 nm. High sensitivity).

Then, an acrylic pressure-sensitive adhesive tape (a substrate-free type double-sided pressure-sensitive adhesive tape with both sides of the adhesive layer protected by a release liner) was produced.

(Example 2)

38 parts by weight of butyl acrylate (BA), 38 parts by weight of 2-ethylhexyl acrylate (2EHA), and 4 parts by weight of acrylic acid (AA) were mixed to obtain an acrylic monomer mixture.

To 80 parts by weight of the acrylic monomer mixture, a styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062M", manufactured by Kaneka Corporation, weight average molecular weight 48000, and styrene content rate 20%) was added. : 20 parts by weight, trimethylolpropane triacrylate (TMPTA, polyfunctional monomer): 0.08 parts by weight, alicyclic saturated hydrocarbon resin (trade name "Arkon P115", manufactured by Arakawa Chemical Industry Co., Ltd.): 18 parts by weight, 1-hydroxy-cyclohexyl-phenyl-one (photopolymerization initiator, trade name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, and 2,2-dimethoxy -1,2-diphenylethane-1-one (photopolymerization initiator, trade name "Irgacure 651", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, uniformly mixed to obtain acrylic adhesive剂 组合 物。 Composition.

The acryl-based adhesive composition was applied on the release-treated surface of a release liner (trade name "MRF # 38", manufactured by Mitsubishi Resin Co., Ltd.) so that the thickness of the formed adhesive layer was 50 µm. To form an acrylic adhesive composition layer. Then, a release liner ("MRE # 38", manufactured by Mitsubishi Resin Co., Ltd.) was attached to the surface of the acrylic adhesive composition layer. Then, a black light (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays with an illuminance of 5 mW / cm ² for 360 seconds, and the acrylic adhesive composition layer was photo-cured to form an acrylic adhesive layer.

In addition, the illuminance of ultraviolet rays was adjusted using an industrial UV detector (trade name "UVR-T1", manufactured by Topcon Technohouse Co., Ltd., having maximum sensitivity at about 350 nm).

Then, an acrylic pressure-sensitive adhesive tape (a substrate-free type double-sided pressure-sensitive adhesive tape with both sides of the adhesive layer protected by a release liner) was produced.

(Example 3)

59.1 parts by weight of 2-ethylhexyl acrylate (2EHA) and 5.9 parts by weight of acrylic acid (AA) were mixed to obtain an acrylic monomer mixture.

To 80 parts by weight of the acrylic monomer mixture, a styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062T", manufactured by Kaneka Co., Ltd., having a weight average molecular weight of 60,000 and a styrene content of 20% was added. ): 35 parts by weight, trimethylolpropane triacrylate (TMPTA, polyfunctional monomer): 0.3 parts by weight, alicyclic saturated hydrocarbon resin (trade name "Arkon P125", manufactured by Arakawa Chemical Industry Co., Ltd.) : 10.5 parts by weight, 1-hydroxy-cyclohexyl-phenyl-one (photopolymerization initiator, trade name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, and 2,2-dimethoxy -1,2-diphenylethane-1-one (photopolymerization initiator, trade name "Irgacure 651", manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight was added and uniformly mixed to obtain acrylic acid Tie adhesive composition.

The acryl-based adhesive composition was coated on the release-treated surface of a release liner (trade name "MRF # 38", manufactured by Mitsubishi Resin Co., Ltd.) so that the thickness of the formed adhesive layer was 75 μm. To form an acrylic adhesive composition layer. Then, a release liner ("MRE # 38", manufactured by Mitsubishi Resin Co., Ltd.) was attached to the surface of the adhesive composition layer. Then, a black light (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays with an illuminance of 5 mW / cm ² for 360 seconds, and the acrylic adhesive composition layer was photo-cured to form an acrylic adhesive layer.

In addition, the illuminance of ultraviolet rays was adjusted using an industrial UV detector (trade name "UVR-T1", manufactured by Topcon Technohouse Co., Ltd., having maximum sensitivity at about 350 nm).

Then, an acrylic pressure-sensitive adhesive tape (a substrate-free type double-sided pressure-sensitive adhesive tape with both sides of the adhesive layer protected by a release liner) was produced.

(Comparative example 1)

85 parts by weight of 2-ethylhexyl acrylate (2EHA) and 5 parts by weight of acrylic acid (AA) were mixed to obtain an acrylic monomer mixture.

This acrylic monomer mixture was put into a 4-necked flask. Next, 0.05 parts by weight of 1-hydroxy-cyclohexyl-phenyl-one (photopolymerization initiator, trade name "Irgacure 184", manufactured by BASF Japan Co., Ltd.) and 2,2-dimethoxy-1 were added. 0.05 parts by weight of 2-diphenylethane-1-one (photopolymerization initiator, trade name "Irgacure 651", manufactured by BASF Japan Co., Ltd.), and nitrogen was injected into a 4-necked flask. Then, in a nitrogen atmosphere, ultraviolet rays were irradiated to generate photopolymerization, and a viscosity (BH-type viscometer, No. 5 rotor, 10 rpm, temperature 30 ° C.) was about 15 Pa. Partially polymerized monomer slurry of s (partial polymer of acrylic monomer mixture).

To 80 parts by weight of the partially polymerized monomer slurry, a styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062T", manufactured by Kaneka Co., Ltd.) was added. The weight average molecular weight was 60,000, and the styrene content was 20% ): 10 parts by weight, trimethylolpropane triacrylate (TMPTA, polyfunctional monomer): 0.3 parts by weight, 1-hydroxy-cyclohexyl-phenyl-one (photopolymerization initiator, trade name "Irgacure 184 ", Manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight and 2,2-dimethoxy-1,2-diphenylethane-1-one (photopolymerization initiator, trade name" Irgacure 651 " , Manufactured by BASF Japan Co., Ltd.): 0.05 parts by weight, uniformly mixed to obtain an acrylic adhesive composition.

On the release-treated surface of a release liner (trade name "MRF # 38", manufactured by Mitsubishi Resin Co., Ltd.), the above-mentioned acrylic adhesive composition was applied so that the thickness of the formed adhesive layer became 45 μm. To form an acrylic adhesive composition layer. Then, a release liner ("MRE # 38", manufactured by Mitsubishi Resin Co., Ltd.) was attached to the surface of the adhesive composition layer. Then, a black light (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays with an illuminance of 5 mW / cm ² for 360 seconds, and the acrylic adhesive composition layer was photo-cured to form an acrylic adhesive layer.

In addition, the illuminance of ultraviolet rays was adjusted using an industrial UV detector (trade name "UVR-T1", manufactured by Topcon Technohouse Co., Ltd., having maximum sensitivity at about 350 nm).

Then, an acrylic pressure-sensitive adhesive tape (a substrate-free type double-sided pressure-sensitive adhesive tape with both sides of the adhesive layer protected by a release liner) was produced.

(Measurement method of moisture permeability of the adhesive composition)

An adhesive composition was applied on the release-treated surface of a release liner (trade name "MRF # 38", manufactured by Mitsubishi Resin Co., Ltd.) so that the thickness of the formed adhesive layer became 50 μm to form Adhesive composition layer. Then, a release liner ("MRE # 38", manufactured by Mitsubishi Resin Co., Ltd.) was attached to the surface of the adhesive composition layer. Then, a black light lamp (manufactured by Toshiba Corporation) was irradiated with ultraviolet rays having an illuminance of 5 mW / cm ² for 360 seconds to harden the adhesive composition layer to form an adhesive layer. Then, a double-sided sheet protected by a release liner of the adhesive layer was obtained.

In addition, the illuminance of ultraviolet rays was adjusted using an industrial UV detector (trade name "UVR-T1", manufactured by Topcon Technohouse Co., Ltd., having maximum sensitivity at about 350 nm).

Next, the release liner on one side of the sheet was peeled off to expose the adhesive surface, and it was bonded to a triethyl cellulose film (TAC film, thickness 25 μm, manufactured by Konica Minolta Co., Ltd.), and sequentially laminated Release the adhesive tape of the liner, adhesive layer, and TAC film. Then, the release liner was peeled from this adhesive tape, and the measurement sample was obtained.

Then, using this sample for measurement, a moisture permeability test was performed under the following conditions. Method (cup method, based on JIS Z 0208) to measure the moisture permeability (water vapor transmission rate).

Measurement temperature: 40 ° C

Relative humidity: 90%

Measurement time: 24 hours

In the measurement, a constant temperature and humidity tank was used.

(Evaluation)

About the adhesive tape obtained in the said Example and the comparative example, the adhesive force etc. were measured. The measurement results are shown in Table 1.

(Measurement of subsequent force)

An adhesive tape with a length of 100 mm and a width of 25 mm was obtained from the adhesive tape. Then, the release liner on one side of the tape sheet was peeled off to expose the adhesive surface, and the adhesive surface of the tape sheet was adhered to a PET film (thickness: 25 μm), and a release liner, an adhesive layer, and PET were sequentially laminated. Single-sided adhesive tape (length 100mm, width 25mm) with base material attached to the film. The release liner was peeled from the single-sided adhesive tape with a base material to obtain a sample for measurement.

Next, a glass plate ("soda-lime glass # 0050", manufactured by Songlang Glass Industry Co., Ltd.) was bonded to the exposed adhesive surface (measurement surface) of the measurement sample in an atmosphere of 23 ° C and 50% RH, and the weight was 2 kg. The rollers are reciprocated once, thereby pressing. Then, it was left in an atmosphere of 23 ° C. and 50% RH for 30 minutes.

After being left to stand, a 180 ° peel test for a sample for measurement of peeling from a glass plate was carried out using a tensile tester (trade name "TCM-1kNB", manufactured by Minebea), and the 180 ° peeling adhesion to the glass plate (180 ° Peeling Adhesion) (N / 25mm). The measurement was performed under the conditions of 23 ° C. and 50% RH under conditions of a peeling angle of 180 ° and a stretching speed of 300 mm / min.

(Measurement of gel fraction)

The gel fraction of the adhesive layer was measured by the method described above.

[Table 1]

In the above Table 1, the “separation structure” in the column structure of the phase of the acrylic adhesive layer refers to the acrylic adhesive layer. The acrylic polymer and the isobutylene polymer as a whole are not one phase. Phase separation occurs between the polymer and the isobutylene polymer.

In the above Table 1, the following expressions have the following meanings.

BA: Butyl acrylate

2EHA: 2-ethylhexyl acrylate

AA: Acrylic

TMPTA: Trimethylolpropane triacrylate

SIBSTAR-062M: styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062M", manufactured by Kaneka Corporation, weight average molecular weight 48000, styrene content 20%)

SIBSTAR-062T: styrene-isobutylene-styrene copolymer (trade name "SIBSTAR-062T", manufactured by Kaneka Corporation, weight average molecular weight 60,000, styrene content rate 20%)

Arkon P115: alicyclic saturated hydrocarbon resin (trade name "Arkon P115", manufactured by Arakawa Chemical Industries, Ltd.)

Arkon P125: alicyclic saturated hydrocarbon resin (trade name "Arkon P125", manufactured by Arakawa Chemical Industries, Ltd.)

Claims (6)

An adhesive composition, characterized in that it comprises an acrylic monomer mixture or a part of a polymer thereof, and an isobutylene polymer, and the isobutylene polymer is a styrene-isobutylene-styrene block copolymer, The content of the styrene-isobutylene-styrene block copolymer in the adhesive composition is 15 parts by weight or more based on 100 parts by weight of the acrylic monomer mixture or a part of the polymer thereof, and relative to the acrylic monomer. 80 parts by weight of the polymer mixture or its partial polymer is 35 parts by weight or less, and the moisture permeability of the adhesive layer formed by the above-mentioned adhesive composition measured by the following method is 100 g / m ² . Day or less; Method for measuring moisture permeability: A pressure-sensitive adhesive layer (thickness: 50 μm) formed from the above-mentioned pressure-sensitive adhesive composition is bonded to a triethyl cellulose film (thickness: 25 μm) to obtain a measurement sample, and the obtained measurement sample is used According to the JIS Z 0208 moisture permeability test method, the moisture permeability is measured under the following conditions: measuring temperature: 40 ° C relative humidity: 90% measuring time: 24 hours. The adhesive composition according to claim 1, wherein the adhesive force of the adhesive layer formed by the above adhesive composition is 1.0 N / 25 mm or more. The adhesive composition according to claim 1 or 2, wherein the adhesive layer formed by the above adhesive composition has a crosslinked structure. The adhesive composition according to claim 1 or 2, wherein the gel fraction of the adhesive layer formed by the adhesive composition is 20% by weight or more. The adhesive composition according to claim 3, wherein the gel fraction of the adhesive layer formed by the adhesive composition is 20% by weight or more. An adhesive tape or sheet comprising an adhesive layer formed from the adhesive composition according to any one of claims 1 to 5.