TW201439246A - Flame-retardant adhesive composition - Google Patents

Abstract

The purpose of this invention is to provide an adhesive composition with the excellent flame-retardancy and the excellent adhesion property. The flame-retardant adhesive composition of this invention is characterized by containing the acrylic acid-based polymer and metal hydroxide with average particle size of 10 micron or less and/or the hydrated metal compound with average particle size of 10 micron or less. Given that the 180 DEG tensile adhesion strength for the adhesive layer formed by the composition obtained by removing the metal hydroxide and the hydrated metal compound from the flame-retardant adhesive composition is A, and that the 180 DEG tensile adhesion strength for the adhesive layer formed by the flame-retardant adhesive composition is B, the adhesion strength B/adhesion strength A is 0.8 or above, and the adhesive layer formed by the flame-retardant adhesive composition has the flame-retardancy of VTM-0 or VTM-1 under the flame retardancy test complying with the UL94 Standard.

Description

Flame retardant adhesive composition

This invention relates to a flame retardant adhesive composition.

In recent years, the miniaturization of mobile devices, home appliances, and the like has been progressing, and the adhesive sheets used therein have been being thinned. Since the heat accumulated in the interior of the machine has a fire, excellent flame retardancy (non-combustible properties) is required for the adhesive sheets.

In the past, an adhesive sheet containing a halogen-based flame retardant (Patent Document 1) or an adhesive sheet containing a phosphoric acid-based flame retardant (Patent Documents 2 to 4) is known as an adhesive sheet having flame retardancy. However, halogen-based flame retardants have problems in terms of environmental safety, and phosphoric acid-based flame retardants have problems such as contact troubles in electrical and electronic equipment. Therefore, the use of a flame retardant other than a halogen type or a phosphoric acid type is being studied.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-173657

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-1669

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-323268

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-189753

In order to obtain sufficient flame retardancy using a flame retardant other than a halogen-based or phosphoric acid-based flame retardant, it is necessary to increase the blending amount of the flame retardant to the adhesive layer. However, if the amount of the flame retardant is increased, there is a case where the adhesion is lowered. That is, an adhesive which is excellent in flame retardancy and excellent in adhesion is not known.

Therefore, an object of the present invention is to provide an adhesive composition which forms an adhesive layer which is excellent in flame retardancy and excellent in adhesion.

Therefore, the inventors of the present invention conducted diligent research and found that if an acrylic polymer and a metal hydroxide having a small average particle diameter and/or a hydrated metal compound having a small average particle diameter are used, adhesion can be achieved. The flame retardant adhesive composition having a specific range of strength or flame retardancy can form an adhesive layer which is excellent in flame retardancy and excellent in adhesion, and has completed the present invention.

In other words, the present invention is characterized in that it comprises an acrylic polymer and a flame retardant adhesive composition of a metal hydroxide having an average particle diameter of 10 μm or less and/or a hydrated metal compound having an average particle diameter of 10 μm or less. And a 180° tensile adhesion of the adhesive layer formed by removing the composition of the metal hydroxide and the hydrated metal compound from the flame-retardant adhesive composition (23° C., 50% RH, stretching) The peeling condition of the speed of 300 mm/min and the peeling angle of 180°, the adhesion force A to the SUS304 steel sheet), and the 180° tensile adhesion of the adhesive layer formed of the flame-retardant adhesive composition (23° C., 50%) When the RH, the stretching speed is 300 mm/min, the peeling angle is 180°, and the SUS304 steel sheet is the adhesive force B, the adhesive force B/adhesive force A is adhered to the flame-retardant adhesive composition. The 180° tensile adhesion of the agent layer/the 180° tensile adhesion of the adhesive layer formed by the above composition is 0.8 or more, and the adhesive layer formed of the above flame-retardant adhesive composition is blocked by the UL94 standard. Resistance to VTM-0 or VTM-1 in the flammability test Sex.

The average particle diameter is 10 μm or less based on 100 parts by weight of the acrylic polymer. The content of the metal hydroxide and/or the hydrated metal compound having an average particle diameter of 10 μm or less is preferably 40 to 300 parts by weight.

Further, the present invention provides an adhesive tape having an adhesive layer formed of the above flame-retardant adhesive composition.

Since the flame-retardant adhesive composition of the present invention has the above-described configuration, it is possible to form an adhesive layer which is excellent in flame retardancy and excellent in adhesion.

[Flame Retardant Adhesive Composition]

The flame-retardant adhesive composition of the present invention contains at least an acrylic polymer and a hydrated metal compound having an average particle diameter of 10 μm or less and/or a metal hydroxide having an average particle diameter of 10 μm or less. The adhesive composition of the present invention may contain a dispersant, a fluorine-based surfactant, a crosslinking agent, a tackifier resin, an acrylic oligomer, a decane coupling agent, or the like, as needed.

(acrylic polymer)

The acrylic polymer is not particularly limited, and for example, an acrylic polymer composed (formed) of a monomer component containing a (meth)acrylic acid alkyl ester as a main component is preferable. The monomer component may further contain a polar group-containing monomer, a polyfunctional monomer, or the like.

These acrylic polymers may be used alone or in combination of two or more.

Further, "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid" (one or both of "acrylic acid" and "methacrylic acid"), and the same applies hereinafter. Further, the "alkyl group" means a linear or branched alkyl group unless otherwise specified.

In the present specification, the polar group-containing monomer means a polar group-containing monomer other than the carboxyl group-containing monomer unless otherwise specified (having a carboxyl group in the molecule) Monomers other than polar groups).

The (meth)acrylic acid alkyl ester constituting the acrylic polymer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) Ethyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, eleven (meth)acrylate Alkyl ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (a) Base) cetyl acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, pentadecyl (meth) acrylate, eicosyl (meth) acrylate Ester ester Carbon atoms of an alkyl group of 1 to 20 (meth) acrylate. Among them, from the viewpoint of easily obtaining the balance of the adhesive properties, an alkyl (meth)acrylate having an alkyl group having 2 to 12 carbon atoms is preferred, and an alkane having a carbon number of 4 to 9 is more preferred. Alkyl (meth) acrylate.

The above alkyl (meth)acrylate may be used alone or in combination of two or more.

The blending ratio (content) of the alkyl (meth)acrylate in the monomer component constituting the acrylic polymer is not particularly limited, and is, for example, the total amount of the monomer component (100 wt%) constituting the acrylic polymer. %) is preferably 60% by weight or more (for example, 60 to 99% by weight), more preferably 80% by weight or more (for example, 80 to 98% by weight).

The monomer component constituting the acrylic polymer is not particularly limited, and when the material of the adherend is a metal or the like, it is preferable that the adherend is less likely to corrode (corrosion resistance). It does not substantially contain a carboxyl group-containing monomer. Here, the "carboxyl group-containing monomer" is a monomer containing one or more carboxyl groups (which may be in the form of an acid anhydride) in one molecule, and examples thereof include (meth)acrylic acid and methylene succinic acid. Maleic acid, Fumaric acid, crotonic acid, methacrylic acid, maleic anhydride, methylene succinic anhydride, and the like.

In addition, the term "substantially does not contain" means that it is inevitably mixed rather than actively blended, and specifically means that the above-mentioned acrylic polymerization is constituted with respect to the total amount of the monomer components (100% by weight). The content of the carboxyl group-containing monomer in the monomer component is preferably 0.1% by weight or less, more preferably less than 0.05% by weight, still more preferably less than 0.01% by weight.

When a monomer containing a carboxyl group is contained in the monomer component constituting the acrylic polymer, the fluidity of the flame-retardant adhesive composition of the present invention is lowered (viscosity is increased), and it becomes difficult to form an adhesive layer. . Further, in the flame-retardant adhesive composition of the present invention, even when a monomer having a carboxyl group is added, the effect of improving the adhesion is not easily obtained. The reason for these is not clear, but it can be considered that the reason is that a functional group (for example, a hydroxyl group) contained in the metal hydroxide and/or the hydrated metal compound reacts with a carboxyl group of the carboxyl group-containing monomer to become an acrylic polymer. In a state of being bonded to a metal hydroxide or the like, the fluidity of the flame-retardant adhesive composition is lowered, and the wettability is lowered. Further, it is considered that the adhesion improving effect obtained by the carboxyl group of the carboxyl group-containing monomer is also hard to be exhibited, so that the adhesive property is lowered.

The monomer component constituting the acrylic polymer may further contain a polar group-containing monomer from the viewpoint of obtaining an appropriate adhesive strength. Examples of the polar group-containing monomer include a nitrogen-containing monomer, a hydroxyl group-containing monomer, a sulfonic acid group-containing monomer, and a phosphate group-containing monomer. Among them, a nitrogen-containing monomer or a hydroxyl group-containing monomer is preferred from the viewpoint of obtaining high adhesion and holding power.

The above polar group-containing monomers may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate (4HBA/4HBM). 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, A (4-hydroxymethylcyclohexyl)methyl acrylate or the like. Among them, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of improving the wettability of the adherend.

Examples of the nitrogen-containing monomer include N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(1- Hydroxypropyl) (meth) acrylamide, N-(3-hydroxypropyl) (meth) acrylamide, N-(2-hydroxybutyl) (meth) acrylamide, N-(3 -hydroxybutyl)N-hydroxyalkyl(meth)acrylamide such as (meth)acrylamide or N-(4-hydroxybutyl)(meth)acrylamide; N-(methyl) propylene Base Cyclic (meth) acrylamide such as hydroxy (ACMO/MCMO), N-propylene decyl pyrrolidine; (meth) acrylamide, N-substituted (meth) acrylamide (N-ethyl (A) N-alkyl (meth) acrylamide such as acrylamide or N-n-butyl (meth) acrylamide; N,N-dimethyl(methyl) decylamine, N,N- Diethyl(meth)acrylamide (DEAA/DEMA), N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N -N (N-N-dialkyl (meth) acrylamide) such as di(n-butyl)(meth)acrylamide or N,N-di(t-butyl)(meth)acrylamide Acyclic (meth) acrylamide; N-vinyl-2-pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-3- Linoleone, N-vinyl-2-caprolactam, N-vinyl-1,3- 2-ketone, N-vinyl-3,5- N-vinyl cyclic guanamine such as oxadione; aminoethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, N, N-(meth) acrylate a monomer having an amine group such as dimethylaminopropyl ester; a monomer having a maleimide skeleton such as N-cyclohexylmethyleneimine or N-phenylmethylene iminoimide N-methylmethylenebutaneimine, N-ethylmethylenebutylimine, N-butylmethylenebutaneimine, N-2-ethylhexylmethylene A methylene butylimine monomer such as butyl quinone imine, N-lauryl methylene butyl quinone imine or N-cyclohexyl methylene dimethyl sulfoxide. Among them, N-vinyl-2-pyrrolidone, N-hydroxyethyl(meth)acrylamide, and N-(A) are preferred from the viewpoint of adhesion at the initial stage and subsequent reliability. Acrylate Porphyrin, N,N-diethyl(meth)acrylamide.

Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, and (meth)acrylamide. Propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid, and the like.

Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acrylonitrile phosphate.

The compounding ratio of the polar group-containing monomer in the monomer component constituting the acrylic polymer is not particularly limited, and is preferably, for example, preferably the total amount of the monomer component (100% by weight) constituting the acrylic polymer. It is 0.1% by weight or more, more preferably 0.5% by weight or more, further preferably 1% by weight or more, further preferably 2% by weight or more, further preferably 3% by weight or more, and particularly preferably 5% by weight or more. Further, the blending ratio of the polar group-containing monomer is not particularly limited, and is, for example, preferably 40% by weight or less, more preferably 40% by weight or less, based on the total amount of the monomer components (100% by weight) constituting the acrylic polymer. 30% by weight or less, further preferably 25% by weight or less, and particularly preferably 20% by weight or less. The ratio of the polar group-containing monomer in the monomer component is not particularly limited, and is, for example, preferably 0.1 to 40% by weight based on the total amount of the monomer component (100% by weight) constituting the acrylic polymer. . If the above blending ratio does not reach the above lower limit, the cohesive force of the adhesive layer is lowered, and a high holding force cannot be obtained. On the other hand, when the compounding ratio of the monomer containing a polar group exceeds the above upper limit, the cohesive force of the adhesive layer may become too high, and the adhesive force may be lowered.

When a polyfunctional monomer is contained in the monomer component constituting the acrylic polymer, a crosslinked structure can be introduced into the acrylic polymer, and a cohesive force necessary as an adhesive layer can be obtained.

The polyfunctional monomer is not particularly limited, and examples thereof include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(methyl). Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri Methyl) acrylate, tetramethylol methane tri(meth) acrylate, (a) Allyl acrylate, vinyl (meth) acrylate, divinyl benzene, epoxy acrylate, polyester acrylate, urethane acrylate, butanediol di(meth) acrylate, and the like.

These polyfunctional monomers may be used alone or in combination of two or more.

The compounding ratio of the above-mentioned polyfunctional monomer in the monomer component constituting the acrylic polymer is not particularly limited, and is preferably 2, for example, based on the total amount of the monomer component (100% by weight) constituting the acrylic polymer. The weight % or less (for example, 0.01 to 2% by weight), more preferably 0.02 to 1% by weight. When the blending ratio exceeds 2% by weight, the cohesive force of the adhesive layer may become too high and the adhesive strength may be lowered. Further, when the blending ratio is less than 0.01% by weight, the cohesive force of the adhesive layer may be lowered.

The monomer component may further contain a monomer (other monomer) other than the (meth)acrylic acid alkyl ester, the polar group-containing monomer, and the polyfunctional monomer. By using the above other monomers, various characteristics of the adhesive, the structure of the acrylic polymer, and the like can be more appropriately controlled.

The other monomer is not particularly limited, and examples thereof include a monomer having an epoxy group such as glycidyl (meth)acrylate or allyl glycidyl ether; and 2-methoxy B (meth)acrylate. Alkoxy group-containing monomer such as ester, 3-methoxypropyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate; acrylonitrile a monomer having a cyano group such as methacrylonitrile; a styrene monomer such as styrene or α-methylstyrene; an α-olefin such as ethylene, propylene, isoprene, butadiene or isobutylene; - a monomer having an isocyanate group such as isocyanatoethyl ester or 2-isocyanatoethyl methacrylate; a vinyl ester monomer such as vinyl acetate or vinyl propionate; and a vinyl ether monomer such as vinyl ether (meth) acrylate having a hetero ring such as tetrahydrofurfuryl (meth) acrylate; a monomer having a halogen atom such as fluorine (meth) acrylate; 3-methylpropenyl oxypropyl trimethyl a monomer having an alkoxyalkylene group such as decane or vinyltrimethoxydecane; an anthracene (meth) acrylate having a decane bond Monomer; alkyl (meth)acrylate having an alkyl group having 21 or more carbon atoms; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Ester, (meth)acrylic acid (meth) acrylate having an alicyclic hydrocarbon group such as ester; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy (meth) acrylate A (meth) acrylate having an aromatic hydrocarbon group such as diethylene glycol ester. Among them, from the viewpoint of improving the wettability of the flame-retardant adhesive layer, a monomer having an alkoxy group (particularly 2-methoxyethyl acrylate) is preferred.

The above other monomers may be used alone or in combination of two or more.

The compounding ratio of the other monomer constituting the monomer component of the acrylic polymer is not particularly limited, and for example, it is preferably 30% by weight based on the total amount of the monomer component (100% by weight) constituting the acrylic polymer. % or less, more preferably 20% by weight or less. In the case of using a monomer having an alkoxy group, it is not particularly limited. For example, the compounding ratio is preferably 5% by weight based on the total amount of the monomer component (100% by weight) constituting the acrylic polymer. The above (for example, 5 to 20% by weight) is more preferably 8% by weight or more (for example, 8 to 15% by weight).

In the acrylic polymer, for example, a monomer component or a partial polymer of the monomer component (a mixture of the monomer component and a partial polymer of the monomer component) may be polymerized by a known polymerization method. preparation. The polymerization method is not particularly limited, and examples thereof include a polymerization method using thermal or active energy ray irradiation using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) (thermal polymerization) Method, active energy ray polymerization method, and the like. Among them, from the viewpoint of shortening the polymerization time, etc., photopolymerization by ultraviolet irradiation using a photopolymerization initiator is preferred. The above polymerization method is not particularly limited, and it is preferred to carry out polymerization by avoiding contact with oxygen (for example, in a nitrogen atmosphere).

The polymerization initiator is not particularly limited, and examples thereof include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-keto alcohol photopolymerization initiator, and an aromatic sulfonamide. Chlorine photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, ketal system Photopolymerization initiator, 9-oxosulfur A photopolymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.

The above polymerization initiators may be used alone or in combination of two or more.

Examples of the benzoin ether 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 the like. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexyl. Phenyl ketone, 4-phenoxydichloroacetophenone, 4-(t-butyl)dichloroacetophenone, and the like. The α-keto alcohol-based photopolymerization initiator may, for example, be 2-methyl-2-hydroxypropiophenone or 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane- 1-ketone and the like. Examples of the aromatic sulfonium chloride-based photopolymerization initiator include 2-naphthalenesulfonium chloride and the like. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-ruthenium. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzhydrylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and polyethylene. A benzophenone, an α-hydroxycyclohexyl phenyl ketone or the like. Examples of the ketal-based photopolymerization initiator include benzoin dimethyl ketal and the like. As the above 9-oxygen sulfur A photopolymerization initiator, for example, 9-oxosulfur 2-chloro-9-oxosulfur 2-methyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur Isopropyl-9-oxosulfur 2,4-diisopropyl-9-oxosulfur Dodecyl-9-oxosulfur Wait.

The amount (content) of the photopolymerization initiator to be used is not particularly limited, and is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 5 parts by weight, based on the total amount of the monomer components (100 parts by weight) constituting the acrylic polymer. 0.05 to 3 parts by weight.

Irradiation energy and irradiation time of active energy rays (such as ultraviolet rays) during photopolymerization The content is not particularly limited. It suffices that the photopolymerization initiator can be activated to cause a reaction of the monomer component.

Examples of the above thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azobis (2). -methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisopramonitrile, 2,2'-azobis(2-amidinopropane) diphosphate Acid salt, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropane)脒)disulfate, 2,2'-azobis(N,N'-dimethylisobutylphosphonium) hydrochloride, 2,2'-azobis[N-(2-carboxyethyl) An azo polymerization initiator such as -2-methylpropionamidine hydrate; benzamidine peroxide, tert-butyl peroxymaleate, tert-butyl hydroperoxide, hydrogen peroxide, etc. A peroxide-based polymerization initiator; a persulfate such as potassium persulfate or ammonium persulfate; a combination of a persulfate and a sodium hydrogen sulfite; a redox polymerization initiator such as a combination of a peroxide and sodium ascorbate; and the like.

The amount of the above thermal polymerization initiator to be used is not particularly limited and can be selected from the range previously usable as a polymerization initiator. The polymerization by the thermal polymerization method can be carried out by dissolving a monomer component, a thermal polymerization initiator or the like in a suitable solvent (for example, toluene or ethyl acetate) at, for example, 20 to 100 ° C (typically 40 to 80 ° C). It is heated by heating at the polymerization temperature of the left and right.

The glass transition temperature (Tg) of the acrylic polymer is not particularly limited, and is, for example, preferably -10 ° C or lower (for example, -70 ° C to -10 ° C), more preferably -20 ° C or lower (for example, -70 ° C to - 20 ° C). In other words, it is preferable that the monomer component has a composition and a blending amount so that the Tg of the acrylic polymer is within the range.

Here, the Tg of the acrylic polymer means a value obtained from the Tg of the homopolymer of each monomer constituting the monomer component and the weight fraction (copolymerization ratio) of the monomer according to the formula of Fox. The Tg value of the homopolymer can be obtained by various publicly known materials ("Adhesive Technology Manual" of Nikkan Kogyo Shimbun Co., Ltd.).

(metal hydroxide, hydrated metal compound)

The metal hydroxide and the hydrated metal compound are not particularly limited, and examples thereof include aluminum hydroxide [Al ₂ O ₃ . 3H ₂ O; or Al(OH) ₃ ], bauxite [Al ₂ O ₃ . H ₂ O; or AlOOH], magnesium hydroxide [MgO. H ₂ O; or Mg(OH) ₂ ], calcium hydroxide [CaO. H ₂ O; or Ca(OH) ₂ ], zinc hydroxide [Zn(OH) ₂ ], decanoic acid [H ₄ SiO ₄ ; or H ₂ SiO ₃ ; or H ₂ Si ₂ O ₅ ], iron hydroxide [ Fe ₂ O ₃ . H ₂ O or 2FeO(OH)], copper hydroxide [Cu(OH) ₂ ], barium hydroxide [BaO. H ₂ O; or BaO. 9H ₂ O], zirconia hydrate [ZrO. nH ₂ O], tin oxide hydrate [SnO. H ₂ O], basic magnesium carbonate [3MgCO ₃ . Mg(OH) ₂ . 3H ₂ O], magnesium aluminum carbonate [6MgO. Al ₂ O ₃ . H ₂ O], dawsonite [Na ₂ CO ₃ . Al ₂ O ₃ . nH ₂ O], borax [Na ₂ O. B ₂ O ₅ . 5H ₂ O], zinc borate [2ZnO. 3B ₂ O ₅ . 3.5H ₂ O] and so on. Among them, from the viewpoint of obtaining excellent flame retardancy, aluminum hydroxide or magnesium hydroxide is preferred.

The hydrated metal compound and the above metal hydroxide may be used singly or in combination of two or more.

The shape of the metal hydroxide and the hydrated metal compound is not particularly limited, and may be in the form of a block, a needle, a plate or a layer. The block shape includes, for example, a spherical shape, a rectangular parallelepiped shape, a crushed shape, or the like shape.

It is known that when a metal hydroxide or a hydrated metal compound is contained in an adhesive layer normally, flame retardance improves. However, it is also known that as the ratio of the metal hydroxide and the hydrated metal compound contained in the adhesive layer is increased, the flame retardancy is improved, but compared to the adhesive layer containing no metal hydroxide or hydrated metal compound. The adhesion is reduced. On the other hand, when the ratio of the metal hydroxide and the hydrated metal compound contained in the adhesive layer is small, the effect of flame retardancy cannot be obtained. That is, it is recognized that it is difficult to combine flame retardancy and adhesion with a metal hydroxide or a hydrated metal compound.

The present inventors have found that when the average particle diameter of the metal hydroxide and/or the hydrated metal compound contained in the adhesive composition is small (for example, in the case of 0.1 to 10 μm), the flame retardancy is improved. And the adhesion is less reduced (for example, the adhesion B/adhesion A is 0.8 or more, etc.). Wherein, if the average particle diameter is 10 μm or less (especially When it is 8 μm or less, the adhesive force of the adhesive layer formed of the flame-retardant adhesive composition of the present invention and the combination of the metal hydroxide and the hydrated metal compound removed from the flame-retardant adhesive composition of the present invention The adhesive layer formed by the substance has substantially the same adhesive force or becomes high (for example, the adhesive force B/adhesive force A described below is 0.9 or more, 1.0 or more, 1.2 or more, 1.5 or more, 1.8 or more, etc.). In other words, when a metal hydroxide and/or a hydrated metal compound having an average particle diameter of 10 μm or less (especially 8 μm or less) is used, it is formed from a composition containing no metal hydroxide and a hydrated metal compound. The adhesive layer is more excellent in flame retardancy and adhesion.

The average particle diameter of the metal hydroxide and the hydrated metal compound is 10 μm or less (for example, 0.1 to 10 μm) from the viewpoint of obtaining an adhesive layer excellent in flame retardancy and adhesion. Among them, even if a metal hydroxide and/or a hydrated metal compound is added, the adhesion is less likely to be lowered, and the adhesion is compared to the adhesive layer formed of the adhesive composition containing no metal hydroxide or hydrated metal compound. From the viewpoint of increasing the height, it is preferably 10 μm or less (for example, 0.1 to 10 μm), and more preferably 8 μm or less (for example, 0.1 to 8 μm).

Further, the average particle diameter is a value of a volume basis determined by a particle size distribution measurement method by a laser scattering method. Specifically, the average particle diameter is determined by measuring the D50 value by a laser scattering type particle size distribution system.

The metal hydroxide having an average particle diameter of 10 μm or less and/or the content (total content) of the hydrated metal compound having an average particle diameter of 10 μm or less are not particularly limited, and for example, the flame-retardant adhesive composition of the present invention is used. The amount of the acrylic polymer is preferably 40 parts by weight or more, more preferably 45 parts by weight or more, and still more preferably 50 parts by weight or more. In addition, the content is preferably 300 parts by weight or less, more preferably 250 parts by weight or less, and still more preferably 200 parts by weight or less based on 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition. The above metal hydroxide having an average particle diameter of 10 μm or less with respect to 100 parts by weight of the above acrylic polymer in the flame-retardant adhesive composition The content (total content) of the hydrated metal compound having a compound and/or an average particle diameter of 10 μm or less is, for example, preferably 40 to 300 parts by weight. The flame retardancy can be obtained by the above content of 40 parts by weight or more. Adhesiveness can be obtained by the above content of 300 parts by weight or less.

The metal hydroxide and/or the hydrated metal compound described above are more excellent in flame retardancy and are obtained to have substantially the same or higher adhesive layer than the composition containing no metal hydroxide and hydrated metal compound. From the viewpoint of the adhesive layer of the adhesive, it is preferably contained in an amount of 40 to 300 parts by weight (preferably 45 to 250) per 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention. The metal hydroxide and/or the average particle diameter of the average particle diameter of 10 μm or less (preferably 8 μm or less, more preferably 5 μm or less) in an amount of 50 to 200 parts by weight, more preferably 10 μm or less. The hydrated metal compound is 8 μm or less, and more preferably 5 μm or less.

The metal hydroxide and the hydrated metal compound may be used in combination of two or more kinds of the above metal hydroxides and/or the hydrated metal compounds having different average particle diameters. When two or more kinds of the above metal hydroxides and/or the hydrated metal compound having different average particle diameters are used in combination, for example, particles having an average particle diameter of 5 μm or more and particles having an average particle diameter of less than 5 μm are preferably combined. use. By using the above metal hydroxide and/or the hydrated metal compound having different average particle diameters in this manner, the metal hydroxide and the hydrated metal compound can be more finely filled in the flame-retardant adhesive composition (adhesive) Within the layer). In order to obtain such an effect, for example, the mixing ratio (weight ratio) of particles having an average particle diameter of 5 μm or more and particles having an average particle diameter of less than 5 μm is preferably 1:10 to 10:1, more preferably 1:5 to 5: 1, further preferably 1:2 to 2:1.

For the metal hydroxide and the hydrated metal compound, for example, a metal hydroxide having an average particle diameter of 10 μm or less and/or a hydrated metal compound having an average particle diameter of 10 μm or less and an average particle diameter of more than 10 μm (for example, larger than A metal hydroxide of 10 μm or less and 100 μm or less) and/or a hydrated metal compound having an average particle diameter of more than 10 μm (for example, more than 10 μm and 100 μm or less) are used in combination. The average particle size is 10 μm or less. Adhesive composition when a metal hydroxide and/or a hydrated metal compound having an average particle diameter of 10 μm or less, a metal hydroxide having an average particle diameter of more than 10 μm, and/or a hydrated metal compound having an average particle diameter of more than 10 μm are used in combination It becomes easy to obtain a finer filling structure. The adhesive composition having a fine-filled structure has a high fluidity and a low viscosity, and thus the adhesion to the adherend is further improved (the adhesive force is further increased). Therefore, with respect to the total amount (100% by weight) of the metal hydroxide and the hydrated metal compound contained in the flame-retardant adhesive composition of the present invention, the metal hydroxide having an average particle diameter of 10 μm or less and the average particle diameter are The ratio of the hydrated metal compound of 10 μm or less is preferably 50% by weight or more (for example, 50 to 100% by weight), more preferably 70% by weight or more (for example, 70 to 100% by weight), still more preferably 90% by weight or more (for example, 90~100% by weight).

The metal hydroxide having an average particle diameter of 10 μm or less and the hydrated metal compound having an average particle diameter of 10 μm or less can be usually used as a commercially available product. For example, aluminum hydroxide can be used, and the product name "Higilite H-32" can be used (average The particle size is 8 μm (manufactured by Showa Denko Co., Ltd.), the product name is "Higilite H-42" (average particle size: 1 μm) (manufactured by Showa Denko Co., Ltd.), and the product name is "Higilite H-43M" (average particle size: 0.8 μm) (Showa Denko) Manufactured by the company, the product name "B103ST" (average particle size: 8 μm) (manufactured by Nippon Light Metal Co., Ltd.), and the product name "KISUMA 5A" (average particle size: 1 μm) (manufactured by Kyowa Chemical Industry Co., Ltd.), The product name is "ECOMAG Z-10" (average particle diameter: 1.4 μm) (manufactured by Tateho Chemical Industry Co., Ltd.).

(other flame retardants)

In order to further improve the flame retardancy, the flame-retardant adhesive composition of the present invention may further contain a flame retardant other than the above metal hydroxide and the hydrated metal compound insofar as it does not adversely affect the adhesion ( Other flame retardants). Examples of the other flame retardant include metal carbonates such as magnesium carbonate-calcium, calcium carbonate, barium carbonate, and dolomite; barium metaborate; magnesium oxide; zinc borate; tin compounds; carbon black; Agents, etc.

The above other flame retardants may be used alone or in combination of two or more.

The content of the other flame retardant is not particularly limited. For example, it is preferably 100 parts by weight or less (for example, 1 to 100 parts by weight per 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention). More preferably, it is 50 parts by weight or less. If the content of the other flame retardant exceeds 100 parts by weight, the adhesion may be remarkably lowered due to the bleeding of the monomer.

In the case of using the above-mentioned metal hydroxide and/or the above hydrated metal compound and the above other flame retardant in combination with the above-mentioned metal hydroxide and the above-mentioned other flame retardant, the above-mentioned metal hydroxide, the above-mentioned hydrated metal compound The total content of the other flame retardants is not particularly limited. For example, it is preferably 41 to 400 parts by weight, more preferably 50%, based on 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition. It is 350 parts by weight, and more preferably 60 to 300 parts by weight. As long as the above total amount is 41 to 400 parts by weight, high flame retardancy can be obtained. On the other hand, when the total amount exceeds 400 parts by weight, the flexibility may be lowered, and the adhesive force or the holding force may be lowered. Moreover, when the total amount is less than 41 parts by weight, sufficient flame retardancy may not be obtained.

Further, when the metal hydroxide and/or the hydrated metal compound and the other flame retardant are used in combination, the metal hydroxide having an average particle diameter of 10 μm or less and/or the hydration having an average particle diameter of 10 μm or less The ratio of the metal compound is not particularly limited as long as it does not adversely affect the adhesion, and for example, the total amount (100% by weight) of the metal hydroxide, the hydrated metal compound, and the other flame retardant is 50% by weight or more (or 60% by weight or more, or 70% by weight or more) may be mentioned.

(Dispersant)

The flame-retardant adhesive composition of the present invention may further contain a dispersing agent in such a manner that the metal hydroxide and/or the hydrated metal compound are not aggregated and stably dispersed, without impairing the effects of the present invention.

The dispersing agent is not particularly limited, and for example, a phosphate ester can be preferably used. As the phosphate ester, there are polyoxyethylene ethyl (or alkyl allyl) ether or polyoxyethylene ethyl aryl ether, polyoxyethylene ethyl ether or polyoxyethylene A phosphodiester, a phosphate triester, or a derivative thereof of the alkylalkyl aryl ether. Among them, a phosphoric acid monoester or a phosphodiester of polyoxyethylene ethyl ether or polyoxyalkylene aryl ether is preferably used.

The above dispersing agents may be used alone or in combination of two or more.

The content of the dispersing agent is not particularly limited, and is, for example, preferably 0.01 to 10 parts by weight, more preferably 0.05 part by weight, per 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention. 5 parts by weight, more preferably 0.1 parts by weight to 3 parts by weight.

For the above-mentioned dispersing agent, a commercially available product can be used. For example, the product name "Plysurf A212E" (manufactured by Daiichi Kogyo Co., Ltd.), the trade name "Plysurf A210G" (manufactured by Daiichi Kogyo Co., Ltd.), and the trade name "Plysurf A212C" are mentioned. (produced by Daiichi Chemical Co., Ltd.), trade name "Plysurf A215C" (manufactured by Daiichi Pharmaceutical Co., Ltd.), trade name "Phosphanol RE610" (manufactured by Toho Chemical Co., Ltd.), and trade name "Phosphanol RS710" (made by Toho Chemical Co., Ltd.) The product name is "Phosphanol RS610" (manufactured by Toho Chemical Co., Ltd.).

(fluorine-based surfactant)

The flame-retardant adhesive composition of the present invention may further contain a fluorine-based surfactant. By using the fluorine-based surfactant, the adhesion or frictional resistance between the acrylic polymer and the metal hydroxide and/or the hydrated metal compound is reduced, and the stress dispersion property is improved. Therefore, there is a case where the adhesive layer formed of the flame-retardant adhesive composition of the present invention can obtain higher adhesion.

The fluorine-based surfactant is not particularly limited, and for example, a fluorine-based surfactant having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group in the molecule is preferable. In view of the dispersibility of the acrylic polymer, the fluorine-based surfactant is preferably a fluorine-based nonionic surfactant having an oxy C _2-3 alkyl group and a fluorinated hydrocarbon group in the molecule. Agent.

Further, the above-mentioned fluorine-based surfactants may be used alone or in combination of two or more.

The fluorinated hydrocarbon group is not particularly limited, and for example, a perfluoro group is preferred. The above perfluoro group may be monovalent or may be a divalent or higher multivalent. Further, the fluorinated hydrocarbon group may have a double bond or a triple bond, and may have a linear, branched or cyclic structure. The number of carbon atoms of the above-mentioned fluorinated hydrocarbon group is not particularly limited, and is, for example, preferably 1 or 2 or more, more preferably 3 to 30, still more preferably 4 to 20. When the fluorinated hydrocarbon group is contained, when the flame-retardant adhesive composition of the present invention contains bubbles, the effect of improving the bubble mixing property and the bubble stability can be obtained.

The above-mentioned fluorinated hydrocarbon may be introduced into one type of the fluorine-based surfactant molecule, or two or more types may be introduced.

The above oxy C _2-3 alkylene group is represented by the formula: -RO- (R is a linear or branched alkyl group having 2 or 3 carbon atoms). The oxy C _2-3 alkylene group is not particularly limited, and examples thereof include an oxyethyl group (-CH ₂ CH ₂ O-) and an oxy-propyl group [-CH ₂ CH(CH ₃ )O-]. The oxy C _2-3 alkylene group may be in the form of an alcohol having a hydrogen atom bonded to an oxygen atom at the terminal, an ether bonded to another hydrocarbon group, or an ester bonded to another hydrocarbon group via a carbonyl group. Further, the cyclic ether or the lactone may be in a form having such a structure in one of the ring structures.

The oxy C _2-3 alkylene group may be introduced into one type of the fluorine-based surfactant molecule, or two or more types may be introduced.

The fluorine-based surfactant is not particularly limited, and examples thereof include a copolymer obtained by polymerizing a monomer component containing a monomer having an oxy C _2-3 alkyl group and a monomer having a fluorinated hydrocarbon group. When the fluorine-based surfactant is a copolymer, for example, a block copolymer, a graft copolymer or the like may be used.

The block copolymer (copolymer having an oxy C _2-3 alkyl group and a fluorinated hydrocarbon group in the main chain) is not particularly limited, and examples thereof include polyoxyethylidene perfluoroalkyl ether. Polyoxyalkylene perfluoroalkylate, polyoxyl-propyl perfluoroalkyl ether, polyoxy-extension isopropyl perfluoroalkyl ether, polyoxyethylene ethyl sorbitan perfluoroalkylate, polyoxygen Polyoxyalkylene propyl block copolymer perfluoroalkylate, polyoxyethylene glycol perfluoroalkylate, and the like.

The graft copolymer (copolymer having an oxy C _2-3 alkyl group and a fluorinated hydrocarbon group in the side chain) is not particularly limited, and examples thereof include ethylene having at least a polyoxyalkylene group. A copolymer obtained by polymerizing a monomer component of a compound and a vinyl compound having a fluorinated hydrocarbon group is preferably an acrylic copolymer. Examples of the above-mentioned vinyl compound having a polyoxyalkylene group include polyoxyethylene ethyl (meth) acrylate, polyoxypropyl propyl (meth) acrylate, and polyoxyethylene ethoxy propylene. A polyoxyalkylene (meth) acrylate such as a (meth) acrylate. Examples of the vinyl compound having a fluorinated hydrocarbon group include perfluorobutyl (meth)acrylate, perfluoroisobutyl (meth)acrylate, and perfluoropentyl (meth)acrylate (methyl). A (meth) acrylate containing a fluorinated hydrocarbon such as a perfluoroalkyl acrylate.

The fluorine-based surfactant may have an alicyclic hydrocarbon group or an aromatic hydrocarbon group in the molecule, in addition to the oxy C _2-3 alkylene group and the fluorinated hydrocarbon group, without hindering the dispersibility to the acrylic polymer. Various functional groups such as a carboxyl group, a sulfonic acid group, a cyano group, a decylamino group, and an amine group. For example, when the fluorine-based surfactant is an ethylene-based copolymer, a monomer component copolymerizable with a vinyl compound having a polyoxyalkylene group and a vinyl compound having a fluorinated hydrocarbon group may be used as a monomer. ingredient.

Such copolymerizable monomers may be used alone or in combination of two or more.

As the monomer component which can be copolymerized, for example, (meth)acrylic acid C _1-20 alkyl group such as undecyl (meth)acrylate or dodecyl (meth)acrylate can be preferably used. (meth)acrylate having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate; (meth)acrylate having an aromatic hydrocarbon group such as phenyl (meth)acrylate. Further, examples thereof include a carboxyl group-containing monomer such as maleic acid or crotonic acid; a sulfonic acid group-containing monomer such as sodium vinylsulfonate; an aromatic vinyl compound such as styrene or vinyl toluene; and ethylene; An olefin or a diene such as butadiene; a vinyl ether such as a vinyl alkyl ether; a guanamine-containing monomer such as acrylamide; or a (meth) acrylonitrile group An amino group-containing monomer such as a phenyl group; a glycidyl group-containing monomer such as methyl glycidyl (meth)acrylate; an isocyanate group-containing monomer such as isocyanate-2-methylpropenyloxyethyl; A polyfunctional copolymerizable monomer (polyfunctional monomer) such as pentaerythritol hexa(meth)acrylate or divinylbenzene.

The weight average molecular weight of the fluorine-based surfactant is not particularly limited. For example, if it is less than 20,000 (for example, 500 or more and less than 20,000), the acrylic polymer is reduced to the above metal hydroxide and/or the above hydration. The effect of adhesion or frictional resistance between metal compounds is high. Further, when a fluorine-based surfactant having a weight average molecular weight of 20,000 or more (for example, 20,000 to 100,000, preferably 22,000 to 80,000, more preferably 24,000 to 60,000) is used in combination, the mixing property of the bubbles or the stability of the mixed bubbles is used. Sexual improvement.

The amount of the fluorine-based surfactant to be used (solid content) is not particularly limited. For example, it is preferably 0.01 to 5 parts by weight based on 100 parts by weight of all the monomer components for forming the acrylic polymer. More preferably, it is selected from the range of 0.02 to 3 parts by weight, more preferably 0.03 part by weight to 2 parts by weight. When the amount used is less than 0.01 part by weight, the stability of the bubbles is not easily obtained, and if it exceeds 5 parts by weight, the adhesion performance may be lowered.

In the flame-retardant adhesive composition of the present invention, the metal hydroxide and/or the hydrated metal compound are not aggregated and stabilized in a smaller amount than in the case where the above-mentioned dispersant or the above-mentioned fluorine-based surfactant is used alone. In the presence of the flame-retardant adhesive layer, the stress dispersibility is improved, and from the viewpoint of higher adhesion, the above-mentioned dispersant and the above-mentioned fluorine-based surfactant may be used in combination. When the dispersing agent and the fluorine-based surfactant are used in combination, the mixing ratio is not particularly limited, and the ratio (weight ratio) of the dispersing agent to the fluorine-based surfactant is preferably 1:20 to 20:0.01. More preferably, it is 1:10 to 10:0.01, and further preferably 1:5 to 5:0.01.

Specific examples of the fluorine-based surfactant having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of less than 20,000 include a product name "FTERGENT 251" (manufactured by NEOS Co., Ltd.), and a product. "FTX-218" (manufactured by NEOS Co., Ltd.), trade name "MEGAFAC F-477" (manufactured by DIC Corporation), trade name "MEGAFAC F-470" (manufactured by DIC Corporation), and trade name "Surflon S-381" (manufactured by AGC Seimi Chemical Co., Ltd.), trade name "Surflon S-383" (manufactured by AGC Seimi Chemical Co., Ltd.), trade name "Surflon S-393" (manufactured by AGC Seimi Chemical Co., Ltd.), trade name "Surflon KH-20" (AGC) Seimi Chemical Co., Ltd., trade name "Surflon KH-40" (manufactured by AGC Seimi Chemical Co., Ltd.), and the like. Specific examples of the fluorine-based surfactant having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of 20,000 or more include the trade name "Eftop EF-352" (the electronic formation of Mitsubishi Materials) The company's product name is "Eftop EF-801" (manufactured by Mitsubishi Materials Corporation) and the product name "UNIDYNE TG-656" (manufactured by Daikin Industries Co., Ltd.).

(crosslinking agent)

The flame-retardant adhesive composition of the present invention may further contain a crosslinking agent from the viewpoint of adjusting the cohesive force of the flame-retardant adhesive layer. As the crosslinking agent, a known and customary crosslinking agent can be used, and examples thereof include an epoxy crosslinking agent, an isocyanate crosslinking agent, and an anthrone crosslinking agent. An oxazoline crosslinking agent, an aziridine crosslinking agent, a decane crosslinking agent, an alkyl etherified melamine crosslinking agent, a metal chelate crosslinking agent, and the like. Among them, an isocyanate crosslinking agent and an epoxy crosslinking agent are preferred.

Examples of the isocyanate crosslinking agent include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, hydrogenated dimethyl diisocyanate, and diphenylmethane. Isocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl dimethyl diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and such trimethylolpropane An adduct of a polyol or the like. Further, a compound having at least one or more isocyanate groups and one or more unsaturated bonds in one molecule may be used. Specifically, 2-isocyanatoethyl (meth)acrylate or the like may be used.

Examples of the epoxy-based crosslinking agent include bisphenol A and epichlorohydrin type epoxy. Resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, Diglycidyl aniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N'-diamine glycidol Amine methyl) cyclohexane or the like.

The content of the above-mentioned crosslinking agent is not particularly limited. For example, it is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention. The parts by weight are further preferably 0.01 to 2 parts by weight. When the content is more than 5 parts by weight, flexibility may not be obtained, and if it is less than 0.01 part by weight, cohesiveness may not be obtained.

(tackifying resin)

The flame-retardant adhesive composition of the present invention may further contain a tackifying resin from the viewpoint of further improving the adhesion. The tackifier resin is not particularly limited, and when the monomer component is copolymerized by polymerization using ultraviolet rays to obtain an acrylic polymer, it is preferred to use hydrogenation for the reason that polymerization is not easily hindered even when used in combination. Type of tackifying resin. Examples of the hydrogenated tackifier resin include tackifying a petroleum resin, a terpene resin, a benzofuran-quinone resin, a styrene resin, a rosin resin, an alkylphenol resin, and a xylene resin. A derivative obtained by hydrogenating a resin (hydrogenated petroleum resin, hydrogenated terpene resin, or the like). Among them, a hydrogenated petroleum resin and a hydrogenated terpene resin are preferable. The hydrogenated petroleum resin can be selected, for example, from an aromatic system, a dicyclopentadiene system, an aliphatic system, an aromatic-dicyclopentadiene copolymerization system, or the like. Further, the hydrogenated terpene resin can be selected, for example, from a terpene phenol resin or an aromatic terpene resin.

The softening point of the tackifying resin is not particularly limited, and is, for example, preferably from 80 to 200 ° C, more preferably from 100 to 200 ° C. By setting the softening point of the tackifying resin to this range, the cohesive force is further improved.

The content of the above-mentioned tackifying resin is not particularly limited, and is preferably from 1 to 50 parts by weight, more preferably from 2 to 40 parts by weight based on 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention. Further, it is preferably 3 to 30 parts by weight. When the content exceeds 50 parts by weight, the cohesive force may be lowered. If it is less than 1 part by weight, the effect of improving the adhesion may not be obtained.

(acrylic oligomer)

The flame-retardant adhesive composition of the present invention may further contain an acrylic oligomer from the viewpoint of further improving the adhesion. The acrylic oligomer has a higher glass transition temperature (Tg) and a smaller weight average molecular weight than the acrylic polymer, and functions as a tackifying resin and is difficult to polymerize when using ultraviolet rays. The advantage of hindering polymerization.

(decane coupling agent)

In the flame-retardant adhesive composition of the present invention, the adhesion and durability are further improved, or the affinity between the hydrated metal compound and/or the metal hydroxide and the acrylic polymer is further improved. In other words, it may further contain a decane coupling agent.

As the decane coupling agent, a known one can be suitably used, and examples thereof include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropane. An epoxy group-containing decane coupling agent such as methyl methyl diethoxy decane or 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane; 3-aminopropyltrimethoxy decane, N- 2-(Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, etc. Amino-based decane coupling agent; (meth)acrylic-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane; An isocyanate group-containing decane coupling agent such as isocyanatopropyltriethoxysilane or the like.

The above decane coupling agents may be used singly or in combination of two or more.

The content of the decane coupling agent is not particularly limited. For example, it is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight based on 100 parts by weight of the acrylic polymer in the flame-retardant adhesive composition of the present invention. The part by weight is further preferably 0.05 to 2 parts by weight. By using the above decane coupling agent within the above range, the cohesive force or durability is further improved. When the content is less than 0.01 parts by weight, the surface of the hydrated metal compound and/or the metal hydroxide contained in the flame-retardant adhesive layer may not be coated, and the affinity may not be improved.

(bubble)

The foam-containing adhesive layer can also be formed from the flame-retardant adhesive composition of the present invention by containing bubbles in the flame-retardant adhesive composition of the present invention (referred to as "bubble-containing flame-retardant adhesive layer" "The situation". The bubble-containing flame-retardant adhesive layer can provide a thickness and a cushioning property to the adhesive layer, and can improve the performance of the unevenness on the surface of the adherend, that is, the unevenness absorbability (concave-convex followability).

(other additives)

The flame-retardant adhesive composition of the present invention comprises the acrylic polymer, the hydrated metal compound and/or the metal hydroxide, the dispersant, the other flame retardant, the fluorine-based surfactant, and the crosslinking described above. In addition to the agent, the tackifying resin, the acrylic oligomer, and the decane coupling agent, other additives may be contained depending on the use of the flame-retardant adhesive composition. Examples of the other additives include a plasticizer, a filler, an anti-aging agent, a colorant (pigment or dye), and the like.

The flame-retardant adhesive composition of the present invention is not particularly limited, and for example, the acrylic polymer as an essential component, the metal hydroxide and/or the hydrated metal compound, and the above-mentioned dispersant may be added as needed. Prepared by mixing. Specifically, for example, a monomer component for forming the acrylic polymer, a polymerization initiator (for example, a photopolymerization initiator, a thermal polymerization initiator, etc.), and a suitable solvent (such as toluene or ethyl acetate). a monomer solution prepared by mixing, and the monomer solution is mixed with a polymerization initiator a polymer solution containing an acrylic polymer obtained by copolymerizing a monomer component, and then compounding the metal hydroxide and/or the hydrated metal compound in the polymer solution, if necessary, The above dispersant or the like is formulated to prepare a flame-retardant adhesive composition having a viscosity suitable for coating. Further, when the adhesive composition is cured by ultraviolet rays, a monomer mixture for forming an acrylic polymer, a photopolymerization initiator, or the like may be mixed to prepare a monomer mixture, and the monomer mixture may be subjected to ultraviolet rays. After the preparation of the composition (slurry) containing a part of the polymer obtained by polymerizing only a part of the monomer components, the metal hydroxide and/or the hydrated metal compound are blended in the slurry, and the dispersant or the like is optionally formulated. A flame retardant adhesive composition having a viscosity suitable for coating is prepared.

The flame-retardant adhesive composition of the present invention preferably has an appropriate viscosity from the viewpoint of excellent coatability. The viscosity of the flame-retardant adhesive composition of the present invention is, for example, preferably 5 to 50 Pa. s, more preferably 10~40Pa. s. If the above viscosity exceeds 50Pa. s, when the flame-retardant adhesive layer is formed, the viscosity is too high, and it is difficult to apply the flame-retardant adhesive composition.

In addition, the viscosity in this specification means the viscosity measured by the BH viscosity meter as a viscosity meter in the rotor: No. 5 rotor, rotation speed: 10 rpm, and measurement temperature: 30 degreeC.

The viscosity of the flame-retardant adhesive composition of the present invention can be prepared, for example, by a method of blending various polymer components such as an acrylic rubber and a viscosity-increasing additive; and using a monomer component to form an acrylic polymer (for example) A method of forming a partial polymer by partially polymerizing a monomer component such as a (meth) acrylate which forms an acrylic polymer.

[tape]

The flame-retardant adhesive composition of the present invention can be used to form an adhesive layer having a flame-retardant adhesive composition of the present invention (referred to as a "flame-retardant adhesive layer"). Tape) (in the case of "flame-resistant tape"). That is, the flame-retardant tape has at least one layer of a flame-retardant adhesive layer. The flame-retardant tape may have a base material, an adhesive layer other than the flame-retardant adhesive layer, a release liner, and other layers (for example, an intermediate layer, an undercoat layer, etc.) in addition to the flame-retardant adhesive layer. . The layer other than the flame-retardant adhesive layer may be designed in one layer or two or more layers.

In addition, in this specification, "adhesive sheet" also includes the meaning of "adhesive sheet". That is, in the present specification, the tape may be a tape having a sheet-like form.

The flame-retardant tape may be a single-sided tape having a surface on one side of the adhesive layer (adhesive surface) (ie, the surface of the flame-retardant adhesive layer), or a surface of the adhesive layer on both sides of the tape (adhesive) Double-sided tape. The flame-retardant tape is not particularly limited, and is preferably a double-sided tape from the viewpoint of bonding the articles (adhered bodies) to each other, and more preferably, the both surfaces are the surface of the flame-retardant adhesive layer. double-sided tape.

The flame-retardant tape may be a tape having a substrate (a flame-retardant tape with a substrate attached thereto) or a tape having no substrate (a substrate-free flame-retardant tape). Examples of the flame-retardant tape include (1) a flame-retardant tape composed of only an adhesive layer containing the flame-retardant adhesive layer and having no base material (for example, only a flame-retardant adhesive layer) (2) a flame-retardant tape having the flame-retardant adhesive layer on at least one surface side (both sides or one-side side) of the substrate (with a substrate) Flame retardant tape). Among them, the flame-retardant tape is preferably a substrate-free flame-retardant tape composed only of a flame-retardant adhesive layer from the viewpoint of ease of production and flame retardancy.

Further, the above-mentioned "substrate" does not include a release liner (separator) which is peeled off when the flame-retardant tape is used.

In the case where the flame-retardant tape is a flame-retardant tape with a base material, the flame-retardant adhesive layer may be provided on at least one surface side of the base material. An adhesive layer (other adhesive layer) other than the flame-retardant adhesive layer may be provided on the side opposite to the side on which the flame-retardant adhesive layer is provided on the substrate.

(flame retardant adhesive layer)

The above flame-retardant adhesive layer is an adhesive layer formed of the flame-retardant adhesive composition of the present invention. The flame-retardant adhesive layer may have any one of a single layer and a plurality of layers.

The thickness of the flame-retardant adhesive layer is not particularly limited, and is, for example, preferably 10 to 250 μm, more preferably 20 to 200 μm, still more preferably 30 to 150 μm. If the thickness is thinner than 10 μm, sufficient adhesion and holding force cannot be obtained.

Further, when the thickness is less than 10 μm, the flame retardancy may be insufficient.

180° tensile adhesion (180° peeling adhesion) of the above flame-retardant adhesive layer (23°C, 50% RH, tensile speed 300mm/min, peeling angle 180° peeling conditions, for SUS304 steel sheet) It is not particularly limited, and is, for example, preferably 3 N/20 mm or more (for example, 3 to 20 N/20 mm), more preferably 4 N/20 mm or more (for example, 4 to 20 N/20 mm), and still more preferably 5 N/20 mm or more (for example, 5 to 15 N). /20mm). In the case where the thickness of the flame-retardant adhesive layer is 120 μm or more, the 180° tensile adhesion is preferably 6 N/20 mm or more, and when the thickness of the flame-retardant adhesive layer is 30 μm or more. The above 180° tensile adhesion is 3N/20mm or more.

The above 180° tensile adhesion can be measured, for example, by the method described in "(1) 180° tensile adhesion" (Evaluation) below.

With respect to the above-mentioned flame-retardant adhesive layer, the 180° tensile adhesion (23° C., 50% RH, tensile speed) of the adhesive layer (flame-resistant adhesive layer) formed of the flame-retardant adhesive composition of the present invention 300 mm/min, peeling angle of 180° peeling conditions, for SUS304 steel sheet) (the case of "adhesive force B"), the average particle diameter is 10 μm or less with respect to the flame-retardant adhesive composition of the present invention. 180° tensile adhesion of the adhesive layer formed by the above metal hydroxide and the composition obtained by the above hydrated metal compound having an average particle diameter of 10 μm or less (23° C., 50% RH, tensile speed 300 mm/min, peeling) Peeling condition of 180° angle, for SUS304 steel plate) (in the case of "adhesion A") [Adhesive force B / Adhesion A (180 of the adhesive layer formed of the flame-retardant adhesive composition of the present invention) ° tensile adhesion The 180° tensile adhesion of the adhesive layer formed of the above composition is 0.8 or more, preferably 0.9 or more, more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 1.5 or more. Good is 1.8 or more. The reason for this is not certain, but the adhesive layer formed of the above composition obtained by removing the above metal hydroxide having an average particle diameter of 10 μm or less and the above hydrated metal compound having an average particle diameter of 10 μm or less is used. Adhesion of a flame-retardant adhesive layer formed of the flame-retardant adhesive composition of the present invention containing the above metal hydroxide having an average particle diameter of 10 μm or less and/or the above-described hydrated metal compound having an average particle diameter of 10 μm or less The force becomes higher.

a composition for forming an adhesive layer when the adhesive force A is measured (the above metal hydroxide having an average particle diameter of 10 μm or less and an average particle diameter of 10 μm or less are removed from the flame-retardant adhesive composition of the present invention) The composition obtained by hydrating a metal compound is set to use the following composition: the above-mentioned metal hydroxide having an average particle diameter of 10 μm or less and a composition other than the above-described hydrated metal compound having an average particle diameter of 10 μm or less and formation of the above-mentioned adhesive force B. The same composition of the flame-retardant adhesive composition of the present invention at the time of the adhesive layer (flame-resistant adhesive layer). Further, the adhesive layer at the time of measuring the adhesive force A and the flame-retardant adhesive layer at the time of measuring the adhesive force B are set to have the same thickness of the adhesive layer, and can be selected, for example, from 10 to 250 μm. The measurement of the adhesive force A and the adhesive force B was carried out under the same conditions using a flame-retardant adhesive layer having the same size and thickness.

The above flame-retardant adhesive layer has a flame retardancy of VTM-0 or VTM-1 in the flame retardancy test of the UL94 standard. The flame retardancy can be evaluated, for example, by the method described in "(2) Flame retardancy" below (evaluation).

(substrate)

The substrate is not particularly limited, and examples thereof include a polyester resin such as polyethylene terephthalate (PET), an acrylic resin such as polymethyl methacrylate, polycarbonate, and triethyl hydrazine. Plastics of raw materials such as cellulose, polyfluorene, polyarylate, polyimine, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer membrane.

The raw material of the plastic film may be one type or two or more types.

The thickness of the substrate is not particularly limited, and is, for example, preferably 1 to 40 μm. Further, the substrate may have any one of a single layer and a plurality of layers. The thickness of the substrate is not particularly limited, and is preferably, for example, 20% or less with respect to the thickness (total thickness) of the flame-retardant tape from the viewpoint of flame retardancy. Further, a known conventional surface treatment such as a physical treatment such as a corona discharge treatment or a plasma treatment, or a chemical treatment such as a primer treatment may be suitably applied to the surface of the substrate.

(Adhesive layer other than the flame-retardant adhesive layer)

The adhesive layer (other adhesive layer) other than the flame-retardant adhesive layer is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include an urethane-based adhesive and acrylic acid. An adhesive, a rubber-based adhesive, an anthrone-based adhesive, a polyester-based adhesive, a polyamide-based adhesive, an epoxy-based adhesive, a vinyl alkyl ether-based adhesive, a fluorine-based adhesive, and the like are known. A well-known adhesive layer formed of an adhesive.

The adhesive forming the other adhesive layer described above may be used alone or in combination of two or more.

(release liner)

The surface (adhesive surface) of the adhesive layer of the above flame-retardant tape can also be protected by a release liner before use. Furthermore, in the case where the flame-retardant tape is a double-sided tape, each of the adhesive faces may be separately protected by two separators, or may be wound into a roll by a separator having two sides as a peeling surface. Form and protect. The release liner is used as a protective material for the adhesive layer and is peeled off when the tape is attached to the adherend. Further, the release liner also functions as a support for the adhesive layer. Further, a release liner may not necessarily be provided.

As the release liner, a conventional release paper or the like can be used. Specifically, for example, in addition to a substrate having a release treatment layer obtained by a release treatment agent on at least one surface, a fluorine-containing polymer can be used (for example, Polytetrafluoroethylene, polychlorotrifluoroethylene, poly a low-adhesive substrate of vinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, fluorovinyl chloride-vinylidene fluoride copolymer, etc., or a non-polar polymer (eg polyethylene, poly A low-adhesive substrate such as an olefin-based resin such as propylene or the like.

As the release liner, for example, a release liner having a release treatment layer formed on at least one surface of the release liner substrate can be preferably used. As such a base material for a release liner, a polyester film (such as a polyethylene terephthalate film), an olefin resin film (such as a polyethylene film or a polypropylene film), a polyvinyl chloride film, or a polysiloxane film are used. A plastic substrate film (synthetic resin film) such as an amine film, a polyamide film (nylon film) or a ruthenium film, or a paper (Dawlin paper, Japanese paper, kraft paper, cellophane, synthetic paper, topcoat paper, etc.) In addition, a plurality of layers (two or three layers of composites) obtained by lamination, coextrusion, or the like can be used.

The release treatment agent constituting the release treatment layer is not particularly limited, and for example, an anthrone-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl release treatment agent, or the like can be used. The release treatment agents may be used alone or in combination of two or more. Further, the thickness of the release liner, the method of forming the film, and the like are not particularly limited.

The method for producing the flame-retardant tape is different depending on the composition of the flame-retardant adhesive composition of the present invention, and the like, and a known formation method can be used, and examples thereof include the following (1) to (3). And other methods.

(1) a partial polymer containing a monomer component forming the acrylic polymer, the metal hydroxide having an average particle diameter of 10 μm or less, and/or the hydrated metal compound having an average particle diameter of 10 μm or less, if necessary The flame-retardant adhesive composition of the present invention such as the above dispersing agent is coated (coated) on a substrate or a separator to form a layer of an adhesive composition to harden the layer of the adhesive composition (for example, heat hardening or utilizing) A method of producing a tape by forming a flame-retardant adhesive layer by curing by irradiation with an active energy ray such as ultraviolet rays.

(2) The acrylic polymer, the metal hydroxide having an average particle diameter of 10 μm or less, and/or the hydrated metal compound having an average particle diameter of 10 μm or less, and optionally the dispersant, etc., are dissolved in a solvent. Adhesive composition (solution) coating (coating) A method of producing a tape by drying and/or hardening on a substrate or a separator to form a flame-retardant adhesive layer.

(3) A method of further drying the tape produced in the above (1).

The hardening method of the above (1) to (3) is preferably a method of hardening by an active energy ray (especially a method of curing by ultraviolet rays) from the viewpoint of excellent productivity. Further, since the curing by the active energy ray is hindered by the oxygen in the air, it is preferable to block the oxygen by, for example, bonding the separator to the adhesive layer and hardening it in a nitrogen atmosphere.

When the bubble-containing flame-retardant adhesive layer is obtained, the bubble-containing flame retardant obtained by mixing bubbles (bubble forming gas) into the flame-retardant adhesive composition of the present invention can be obtained. After the adhesive composition is applied to a specific surface, it is irradiated with ultraviolet rays to be hardened, thereby forming a bubble-containing flame-retardant adhesive layer.

As a method of applying (coating) the flame-retardant adhesive composition of the present invention to a specific surface, a known coating method can be employed, and is not particularly limited, and examples thereof include roll coating and contact roll. Coating, gravure coating, reverse coating, roll brushing, spray coating, dip coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, utilization An extrusion coating method such as a die coater or the like.

The thickness (total thickness) of the flame-retardant tape is not particularly limited, and is, for example, preferably 10 to 1000 μm, more preferably 50 to 500 μm, still more preferably 100 to 300 μm. When the thickness is 10 μm or more, it becomes easy to follow the step portion, and the step absorbability is improved. Further, the thickness (total thickness) of the flame-retardant tape is a thickness from one adhesive face to the other adhesive face, and does not include the thickness of the release liner.

180° tensile adhesion (180° peeling adhesion) of the above flame-retardant tape (23°C, 50% RH, tensile speed 300mm/min, peeling angle 180° peeling conditions, no special for SUS304 steel) The limit is, for example, preferably 3 N/20 mm or more (for example, 3 to 20 N/20 mm), more preferably 4 N/20 mm or more (for example, 4 to 20 N/20 mm), and further preferably 5N/20mm or more (for example, 5~15N/20mm). In the case where the flame-retardant tape is a double-sided tape, it is preferred that the 180° tensile adhesion of at least one of the adhesive faces satisfies the above range.

The above 180° tensile adhesion can be measured, for example, by the method described in "(1) 180 ° tensile adhesion" (Evaluation) below.

With respect to the above flame-retardant tape, the 180° tensile adhesion of the flame-retardant tape having the flame-retardant adhesive layer formed of the flame-retardant adhesive composition of the present invention (23° C., 50% RH, tensile speed 300 mm) /min, peeling angle of 180°, and SUS304 steel sheet) having the above-mentioned metal hydroxide having an average particle diameter of 10 μm or less and having an average particle diameter of 10 μm from the flame-retardant adhesive composition of the present invention 180° tensile adhesion of the adhesive layer formed by the composition obtained by the above hydrated metal compound (23° C., 50% RH, tensile speed 300 mm/min, peeling angle 180° peeling conditions, for SUS304 steel sheet) [180° tensile adhesion of a flame-retardant tape having a flame-retardant adhesive layer formed of the flame-retardant adhesive composition of the present invention / tape having an adhesive layer formed by the above composition 180 The tensile bond strength is, for example, preferably 0.8 or more, more preferably 0.9 or more, still more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 1.5 or more, and still more preferably 1.8 or more. The reason for this is not certain, but there is a case where the adhesive is formed as compared with the above composition obtained by removing the above-mentioned metal hydroxide having an average particle diameter of 10 μm or less and the above-mentioned hydrated metal compound having an average particle diameter of 10 μm or less. The tape of the layer has a flame-retardant adhesive layer formed of the flame-retardant adhesive composition of the present invention containing the metal hydroxide having an average particle diameter of 10 μm or less and/or the hydrated metal compound having an average particle diameter of 10 μm or less. The adhesion of the flame retardant tape of the agent layer becomes high. In the case where the flame-retardant tape is a double-sided tape, it is preferred that at least one of the adhesive faces satisfies the above range.

An adhesive layer formed of a composition obtained by removing the above metal hydroxide having an average particle diameter of 10 μm or less and the above hydrated metal compound having an average particle diameter of 10 μm or less from the flame-retardant adhesive composition of the present invention The above adhesive when the adhesive force of the tape The tape is set to use the following tape: a metal hydroxide having an average particle diameter of 10 μm or less, a composition other than the above-described hydrated metal compound having an average particle diameter of 10 μm or less, and a flame-retardant tape having a flame-retardant adhesive layer. The same tape as the tape when bonding. Further, the measurement of the above-mentioned adhesive force was carried out under the same conditions using a tape having the same size and thickness.

The above flame-retardant tape has a flame retardancy of VTM-0 or VTM-1 in the flame retardancy test of the UL94 standard. The flame retardancy can be evaluated, for example, by the method described in "(2) Flame retardancy" below (evaluation).

The flame-retardant tape is excellent in flame retardancy and adhesion, and thus can be preferably used for mobile devices, home electric appliances, hard disks, LED (Light-Emitting Diode) illumination, lithium ion batteries, and tablet PCs. (Personal Computer, computer), rail vehicle interior parts, aircraft interior parts, etc.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The invention is not limited by these.

(Example 1)

82 parts by weight of 2-ethylhexyl acrylate as a monomer component, 12 parts by weight of 2-methoxyethyl acrylate, 5 parts by weight of N-vinyl-2-pyrrolidone (NVP), and hydroxyethyl In the monomer mixture obtained by mixing 1 part by weight of acrylamide (HEAA), the product name "Irgacure 651" (2,2-dimethoxy-1,2-diphenylethyl) is used as a photopolymerization initiator. 0.05 parts by weight of an alkyl-1-one (manufactured by BASF Jpan Co., Ltd.) and 0.05 parts by weight of a product name "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Jpan Co., Ltd.), followed by irradiation with ultraviolet rays until viscosity (BH viscosity meter No) .5 rotor, 10 rpm, measuring temperature 30 ° C) to reach about 20 Pa. To the s, a composition in which one of the monomer components is partially polymerized (partial polymer of the monomer mixture, slurry) is produced.

Adding dipentaerythritol hexapropyl as a polyfunctional monomer to 100 parts by weight of the above slurry 0.05 parts by weight of the enoate (trade name "KAYARAD DPHA-40H", manufactured by Nippon Kayaku Co., Ltd.) and 1 part by weight of the product name "Plysurf A212E" (manufactured by Daiichi Kogyo Co., Ltd.) as a dispersing agent. Furthermore, as a metal hydroxide, 50 parts by weight of a product name "Higilite H-43M" (shape: crushed shape, average particle diameter: 0.8 μm, manufactured by Showa Denko Co., Ltd.) was added as an aluminum hydroxide powder to obtain an adhesive composition (resistance). Flammable adhesive composition). Further, the weight of the acrylic polymer contained in the adhesive composition corresponds to the total amount of the above slurry and the polyfunctional monomer.

The above-mentioned peeling treatment surface of two pieces of release liner (trade name "DIAFOIL MRF38" (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) manufactured by polyethylene terephthalate which has been subjected to a release treatment on one side is coated with the above The adhesive composition is provided with an adhesive composition layer (flame retardant adhesive composition layer).

Next, the ultraviolet ray having an illuminance of about 5 mW/cm ² was irradiated on both sides of the laminate for 3 minutes to harden the adhesive composition layer to form an adhesive layer (flame-resistant adhesive layer) having a thickness of 120 μm to obtain a release liner/ A laminate of the adhesive layer/release liner. Further, the glass transition temperature of the acrylic polymer was -62.8 °C.

The release liner of the single-sided adhesive layer was peeled off and bonded to both sides of a polyethylene terephthalate film (trade name "Lumirror S-10", manufactured by Toray Industries, Inc.) having a thickness of 12 μm. A tape (flame retardant tape) having a release liner/adhesive layer/polyethylene terephthalate film/adhesive layer/release liner. The total thickness of the tape (the thickness of the release liner removed) was 252 μm.

(Example 2)

In the same manner as in Example 1, except that 50 parts by weight of the product name "Higilite H-32" (shape: crushed shape, average particle diameter: 8 μm, manufactured by Showa Denko) was used as the metal hydroxide. In a manner, a laminate or a tape (flame retardant tape) is obtained.

(Example 3)

In the same manner as in Example 1, except that 100 parts by weight of the product name "Higilite H-42" (shape: crushed shape, average particle diameter: 1 μm, manufactured by Showa Denko Co., Ltd.) was used as the metal hydroxide. In a manner, a laminate or a tape (flame retardant tape) is obtained.

(Example 4)

In the same manner as in Example 1, except that 150 parts by weight of a product name "Higilite H-43M" (shape: crushed shape, average particle diameter: 0.8 μm, manufactured by Showa Denko) was used as the metal hydroxide. In this way, a laminate or a tape (flame retardant tape) is obtained.

(Example 5)

In the same manner as in Example 1, except that 250 parts by weight of the product name "Higilite H-42" (shape: crushed shape, average particle diameter: 1 μm, manufactured by Showa Denko) was used as the metal hydroxide. In a manner, a laminate or a tape (flame retardant tape) is obtained.

(Comparative Example 1)

An adhesive composition was obtained in the same manner as in Example 1 except that the aluminum hydroxide powder was not added, and a laminate or tape was obtained using the adhesive composition.

(Comparative Example 2)

In the same manner as in Example 1, except that 25 parts by weight of the product name "Higilite H-43M" (shape: crushed shape, average particle diameter: 0.8 μm, manufactured by Showa Denko) was used as the metal hydroxide. In this manner, an adhesive composition was obtained, and a laminate or tape was obtained using the adhesive composition.

(Comparative Example 3)

In the same manner as in Example 1, except that 25 parts by weight of the product name "Higilite H-32" (shape: crushed shape, average particle diameter: 8 μm, manufactured by Showa Denko) was used as the metal hydroxide. Way to obtain an adhesive composition, using the adhesive The composition was obtained as a laminate or tape.

(Comparative Example 4)

In the same manner as in Example 1, except that 35 parts by weight of a product name "Higilite H-42" (shape: crushed shape, average particle diameter: 1 μm, manufactured by Showa Denko Co., Ltd.) was used as the metal hydroxide. In the manner of obtaining an adhesive composition, a laminate or tape was obtained using the adhesive composition.

(Comparative Example 5)

In the same manner as in Example 1, except that 150 parts by weight of the product name "Higilite H-21" (shape: crushed shape, average particle diameter: 26 μm, manufactured by Showa Denko) was used as the metal hydroxide. In the manner of obtaining an adhesive composition, a laminate or tape was obtained using the adhesive composition.

(Comparative Example 6)

In the same manner as in Example 1, except that 300 parts by weight of the product name "Higilite H-21" (shape: crushed shape, average particle diameter: 26 μm, manufactured by Showa Denko) was used as the metal hydroxide. In the manner of obtaining an adhesive composition, a laminate or tape was obtained using the adhesive composition.

(Comparative Example 7)

300 parts by weight of a product name "Higilite H-21" (shape: crushed shape, average particle diameter: 26 μm, manufactured by Showa Denko) as an aluminum hydroxide powder was used as a metal hydroxide, and an adhesive layer (flame retardant) was used. The thickness of the adhesive layer was 101 μm, and a polyethylene terephthalate film (trade name "Lumirror S-10", manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as a substrate, and In the same manner as in Example 1, a laminate or a tape was obtained.

(Example 6)

It is used as the aluminum hydroxide powder under the trade name "Higilite H-42" (shape: broken shape, average particle diameter: 1 μm, manufactured by Showa Denko) 35 parts by weight, and as a hydroxide In the same manner as in Example 1, except that the aluminum powder was used as a metal hydroxide in a product name of "Higilite H-10" (shape: crushed shape, average particle diameter: 55 μm, manufactured by Showa Denko Co., Ltd.). The method is to obtain a laminate and tape.

Further, the ratio of the aluminum hydroxide powder having an average particle diameter of 10 μm or less was 70% by weight based on the total amount of the aluminum hydroxide powder.

(Example 7)

The product name "Higilite H-42" (shape: broken shape, average particle diameter: 1 μm, manufactured by Showa Denko) 45 parts by weight of the aluminum hydroxide powder, and the trade name "Higilite H-10" as the aluminum hydroxide powder. In the same manner as in Example 1, a laminate or a tape (flame retardant property) was obtained in the same manner as in Example 1 except that the product was used as a metal hydroxide in an amount of 5 parts by weight (a shape: a crushed shape, an average particle diameter: 55 μm, manufactured by Showa Denko Co., Ltd.). tape).

Further, the ratio of the aluminum hydroxide powder having an average particle diameter of 10 μm or less was 90% by weight based on the total amount of the aluminum hydroxide powder.

(Evaluation)

The laminate or tape obtained in the examples and the comparative examples was subjected to the following measurement or evaluation. Moreover, the results are shown in Table 1.

(1) 180° tensile adhesion

A release liner was peeled off from the tape obtained in the above Examples and Comparative Examples, and a total thickness of the PET film substrate having a thickness of 25 μm was attached to the adhesive surface (the opposite surface to the measurement surface) by a thickness of 53 μm. Tape for lining (trade name "No. 31B", manufactured by Nitto Denko Corporation), cut out a length of 150 mm, a width of 20 mm, and a thickness (total thickness of the tape for removing the release liner and the tape for lining) 305 μm (150 mm) ×20 mm × 305 μm tape), and a strip of strips was produced.

Next, another release liner was peeled from the strip of the short strip, and the other adhesive surface (measurement surface) was crimped to the SUS304 steel sheet by reciprocating the 2 kg roller once at 23 ° C in a 50% RH atmosphere. On, make a measurement sample.

The test sample was allowed to stand in an environment of 23° C. and 50% RH for 30 minutes, and then subjected to a 180° peel test using a tensile tester (trade name “TCM-1kNB”, manufactured by Minebea Co., Ltd.) to measure 180° of the SUS304 steel plate. Tensile adhesion (180° peeling adhesion) (N/20mm). The measurement was carried out under the conditions of 23 ° C, 50% RH, a peeling angle of 180 °, and a stretching speed of 300 mm/min (mm/min).

(2) Flame retardancy

The following flame retardancy test was carried out in accordance with the flame retardancy test standard UL94.

The laminate obtained in the above examples and comparative examples was cut into a length of 200 mm and a width of 50 mm, and the release liners on both sides were peeled off to obtain five test pieces each composed of only an adhesive layer having a thickness of 120 μm. One end of the above test piece was vertically suspended. Thereafter, the burner was used, and the other end was ignited for 3 seconds, and the state of the test piece which was temporarily ignited after leaving the flame for 3 seconds was confirmed, and the case where the following reference X was satisfied was regarded as "VTM-0". The case where the following standard Y is satisfied is regarded as "VTM-1", and the case where the reference X and the reference Y are not satisfied is regarded as "poor", and the flame retardancy is evaluated.

Benchmark X: All of the following (1) to (5) are satisfied.

(1) The fire burning time (the total of the burning time after the initial ignition and the burning time after the second ignition) of each test piece was within 10 seconds.

(2) The total time of the fire burning time of the five test pieces was within 50 seconds.

(3) The total time between the fire burning time and the non-fire burning time of each test piece after the second ignition is within 30 seconds.

(4) In the five test pieces, there was no test piece in which the burning drip was dropped from the test piece and placed under the cotton fire.

(5) All the test pieces were not burned until the suspended portion (upper end portion).

Reference Y: All of the following (1') to (5') are satisfied.

(1') The fire burning time (the total of the burning time after the initial ignition and the burning time after the second ignition) of each test piece was within 30 seconds.

(2') The total time of the fire burning time of the five test pieces was within 250 seconds.

(3') The total time between the fire burning time and the non-fire burning time of each test piece after the second ignition is within 60 seconds.

(4') In the five test pieces, there was no test piece in which the burning drip was dropped from the test piece and placed under the cotton fire.

(5') All the test pieces were not burned until the suspended portion (upper end portion).

Claims (3)

A flame-retardant adhesive composition comprising an acrylic polymer and a metal hydroxide having an average particle diameter of 10 μm or less and/or a hydrated metal compound having an average particle diameter of 10 μm or less, and 180° tensile adhesion of the adhesive layer formed of the composition obtained by removing the above metal hydroxide and the above hydrated metal compound from the above flame-retardant adhesive composition (23° C., 50% RH, tensile speed 300 mm) /min, peeling angle of 180° peeling condition, adhesion force A to SUS304 steel sheet), 180° tensile adhesion of the adhesive layer formed of the flame-retardant adhesive composition (23° C., 50% RH, When the stretching speed is 300 mm/min, the peeling angle is 180°, and the SUS304 steel sheet is the adhesive force B, the adhesive force B/adhesive force A [adhesive layer formed of the above flame-retardant adhesive composition) The 180° tensile adhesion/180° tensile adhesion of the adhesive layer formed from the above composition is 0.8 or more, and the adhesive layer formed of the above flame-retardant adhesive composition is flame-retardant of UL94 standard. Flame retardancy of VTM-0 or VTM-1 in the test The flame-retardant adhesive composition according to claim 1, wherein the metal hydroxide having an average particle diameter of 10 μm or less and/or the hydrated metal having an average particle diameter of 10 μm or less or less based on 100 parts by weight of the acrylic polymer The content of the compound is 40 to 300 parts by weight. An adhesive tape having an adhesive layer formed of the flame-retardant adhesive composition of claim 1 or 2.