JP5266028B2 - Flame-retardant resin composition, pressure-sensitive adhesive sheet using the same, and method for producing the same - Google Patents

Description

  The present invention relates to a flame retardant resin composition, an adhesive sheet using the same, and a method for producing the same.

  In recent years, electronic parts used in the electric / electronic parts industry are required to have high flame retardancy. Conventionally, in order to realize this high flame retardancy, it has been carried out by a method of adding only a halogen flame retardant, a method of using a halogen flame retardant and antimony oxide together, a method of introducing a halogen group as a functional group into a base polymer, It is known that

  However, when halogenated flame retardants and antimony oxide are used, it is known that highly toxic gases such as hydrogen halide and antimony halide are generated during combustion. From the viewpoint of environmental protection, in RoHS, WEEE, etc. There are laws and regulations concerning halogen compounds. For this reason, development of a flame-retardant adhesive resin composition called so-called non-halogenated or non-antimonized and an adhesive sheet using the same has been actively conducted.

  Under such circumstances, a flame-retardant adhesive resin composition using a phosphorus-based flame retardant and an adhesive sheet using the same are known (see Patent Document 1).

  In general, the phosphorus-based flame retardant needs to be blended in a larger amount than the halogen-based flame retardant in order to obtain the same level of flame retardancy as the halogen-based flame retardant. However, if the phosphorus flame retardant content is increased, the phosphorus flame retardant precipitates on the surface of the adhesive layer, so the adhesive properties and mechanical properties are impaired, and the adhesion layer surface becomes cloudy due to the deposition of the phosphorus flame retardant. Problems such as deterioration in appearance occur.

  In the conventional development, the following method is taken as a method for preventing the flame retardant from precipitating on the surface of the adhesive layer so as not to particularly affect the adhesive property among the above problems.

  As a first method, a method of reducing the blending amount of the flame retardant itself, and as a second method, a method of adding a compatible material to both the main agent and the flame retardant has been studied. As a second method, a method of improving the miscibility of the pressure-sensitive adhesive base polymer and the phosphate ester flame retardant by adding an aromatic tackifier resin (see Patent Document 2) can be mentioned.

  However, in the first method, it is possible to suppress the flame retardant from precipitating on the surface of the adhesive layer, but the intended flame retardancy cannot be obtained, and in the second method, the amount of aromatic tackifying resin is increased. Since it affects the low-temperature properties of the adhesive, aromatic tackifying resins can only be used within the range that does not affect the low-temperature properties, and a large amount of phosphorus-based flame retardant is added to increase flame retardancy As a result, the compatibility between the phosphorus-based flame retardant and the pressure-sensitive adhesive is insufficient, and as a result, precipitation of a phosphorus compound occurs, resulting in a problem that the pressure-sensitive adhesive properties are deteriorated. There has not yet been proposed a material that satisfies both the adhesive properties and the flame retardant properties at the same time.

  Among methods for preventing the deterioration of the mechanical properties of the resin, for example, a method of adding a phenol aralkyl resin which is a kind of aromatic tackifying resin for the purpose of maintaining heat resistance is known (Patent Document 3). reference).

  Even in this method, since the amount of the phosphorus-based flame retardant added is small, the flame retardancy is still not sufficient.

  In recent years, in the fields of home appliances, electrical / electronic parts, aircraft, marine vehicles, etc. The industry demands high flame retardancy, high adhesion, and high reliability. Among these, regarding the high flame retardancy, the development of pressure-sensitive adhesive sheets that meet the UL94VTM-0 standard, which exceeds the standard UL510 standard as a flame retardant standard for electrical insulation pressure-sensitive adhesive sheets, has been strongly developed by the industry. It was desired.

JP-A-7-101021 JP 2006-219565 A JP-A-8-188717

  Therefore, the subject of the present invention is UL94VTM-0 while maintaining the adhesive properties and mechanical properties when processed into a sheet without using a halogen-based flame retardant or antimony oxide from the viewpoint of environmental protection. An object of the present invention is to provide a flame retardant resin composition having high flame retardancy that meets the standards, a pressure-sensitive adhesive sheet using the same, and a method for producing the same.

  In order to pass the UL94VTM-0 standard for evaluating flame retardancy, the present inventors have conducted extensive studies in order to solve such problems, and the flame retardant resin layer applied to the base material is organic phosphorus. In the flame-retardant resin composition comprising a system flame retardant, a base polymer and an aromatic-containing tackifying resin, the inventors have found that this is achieved by blending these three components at a specific ratio, and have completed the present invention.

  That is, this invention provides the adhesive sheet using this flame retardant resin composition, and its manufacturing method in addition to the following flame retardant resin compositions.

[1] A flame retardant resin composition comprising (A) an organophosphorous flame retardant, (B) a base polymer for an adhesive , and (C) an aromatic-containing tackifying resin. In the total amount of the component (B) and the component (C) of 100 parts by mass, the compounding amount of the component (A) is 15 to 30 parts by mass, the compounding amount of the component (B) is 5 parts by mass or more and the component (A) ) range of amounts +10 parts by component, the (with the amount of C) component is 30 to 80% by weight, said (C) is liquid at 20 to 80 mass% in component 25 ° C., the The component (A) is composed of at least one of aromatic-containing phosphazene and aromatic-containing condensed phosphate ester, and the component (C) is a xylene novolak resin, xylenephenol novolak resin, phenol novolac resin, bisphenol. One or more selected from the group consisting of: A (BPA) novolak resin, cresol novolak resin, phenol / hydroxybenzaldehyde resin, phenol-biphenylene resin, xylylene type phenol novolak resin, terpene phenol copolymer, rosin phenol copolymer A flame retardant resin composition.
[2] The aromatic-containing phosphazenes include SPS-100 (manufactured by Otsuka Chemical), SP-100 (manufactured by Otsuka Chemical), SPH-100 (manufactured by Otsuka Chemical), SPR-100 (manufactured by Otsuka Chemical), It consists of one or more selected from the group consisting of SA-100 (manufactured by Otsuka Chemical Co., Ltd.), Ravitor FP-100 (manufactured by Fushimi Pharmaceutical Co., Ltd.), and Ravitor FP-110 (manufactured by Fushimi Pharmaceutical Co., Ltd.), and contains the aromatic The condensed phosphoric acid ester is the flame retardant resin composition according to the above [1], comprising PX-200 (manufactured by Daihachi Chemical Co., Ltd.).

[ 3 ] A flame-retardant pressure-sensitive adhesive sheet in which a flame-retardant resin layer comprising the flame-retardant resin composition according to [1] or [2] is provided on at least one surface of a flame-retardant substrate.

[4] A method for producing a flame retardant pressure-sensitive adhesive sheet according to [3], on at least one surface of the flame-retardant substrate coated with the flame-retardant resin composition, the flame retardant resin layer A method for producing a flame-retardant pressure-sensitive adhesive sheet.

  According to the present invention, an organophosphorus flame retardant deposits on the surface of the resin layer even though a halogen flame retardant and antimony oxide are not used and a phosphorus flame retardant is used from the viewpoint of environmental protection. When processed into a sheet without any problem, a flame-retardant resin composition having high flame retardancy that passes the UL94VTM-0 standard and a pressure-sensitive adhesive sheet using the flame-retardant resin composition can be provided.

  Hereinafter, embodiments of the flame retardant resin composition of the present invention and an adhesive sheet using the same will be specifically described, but the present invention is not limited to the following embodiments, and departs from the spirit of the present invention. It is within the scope of the present invention to appropriately modify or improve these embodiments based on the ordinary knowledge of those skilled in the art.

[1] Flame retardant resin composition:
The flame retardant resin composition of the present invention contains an organic phosphorus flame retardant, a base polymer, and an aromatic-containing tackifying resin as essential components.

[1-1] (A) Organophosphorus flame retardant:
Examples of the (A) organophosphorous flame retardant used in the flame retardant resin composition of the present invention include phosphoric ester compounds such as phosphate esters and condensed phosphate esters, phosphazene compounds, phosphinates, and phosphones. Tertiary phosphines such as acid salt, phosphate ester amide, phosphorus-containing polymer, phosphine oxide, phosphine sulfide, triarylphosphine, trialkylphosphine, bis (diarylphosphino) benzene, tris (diarylphosphino) benzene, etc. Can be mentioned. These can be used alone or in combination of two or more.

  In the present invention, it is more preferable to use a phosphazene compound from the viewpoint of flame retardancy and hydrolysis resistance.

  As the phosphazene compound, conventionally known compounds can be used, but those containing halogen in the functional group are not preferable in consideration of the environment. Specifically, SPS-100, SP-100, SPH-100, SPR-100, SA-100 (all manufactured by Otsuka Chemical Co., Ltd.), Ravitor FP-100, Ravitor FP-110 (all manufactured by Fushimi Pharmaceutical Co., Ltd.) ) Etc. can be used.

  In this invention, the compounding quantity of (A) organophosphorus flame retardant made 100 mass parts the total amount of (A) organophosphorus flame retardant, (B) base polymer, and (C) aromatic containing tackifying resin. In some cases, the content is preferably 15 to 30 parts by mass, and more preferably 18 to 25 parts by mass. (A) If the blending amount of the organophosphorus flame retardant is less than 15% by mass, the flame retardancy satisfying the UL94VTM-0 standard will not be exhibited, and if it exceeds 30% by mass, the phase with each component The solubility is lowered and the flame retardant is precipitated, which results in the physical properties of the resin layer surface, for example, adhesive properties and poor appearance, which is not preferable.

  In the present invention, conventionally known flame retardants such as non-halogen and non-antimony, flame retardant aids and the like can be used in combination as long as the effects of the present invention can be achieved. Specifically, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide and calcium aluminate, metal oxides such as copper oxide, iron oxide, zinc oxide and magnesium oxide, boric acid and zinc borate compounds And boron-containing compounds such as melamine sulfate, melamine nitrate, melamine borate, melamine phthalate, melamine sulfamate, and melamine cyanurate.

[1-2] (B) Base polymer:
Examples of the base polymer (B) used in the flame-retardant resin composition of the present invention include acrylic resins, urethane resins, rubber-like elastic bodies, polystyrene resins, ABS resins, polycarbonate resins, and polyester resins (PBT). , PET), (modified) polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polyphenylene ether, polyether imide, polyamide resin, polyacetal, polymethyl methacrylate, and the like. When manufacturing the adhesive sheet of this invention mentioned later, it is preferable to use an acrylic resin, a urethane resin, and a rubber-like elastic body among these base polymers.

  As said acrylic resin, what can react with a crosslinking agent is preferable. This is because when used as the main agent of the pressure-sensitive adhesive, reaction with the crosslinking agent makes it possible to prevent fluidization of the resin composition at high temperatures and to adjust the pressure-sensitive adhesive properties such as tack and cohesive force. The acrylic resin includes a copolymer of an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester and a monomer having a functional group capable of reacting with a crosslinking agent. Examples of the "alkyl ester" of acrylic acid alkyl ester and methacrylic acid alkyl ester include, for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester. Hexyl ester, heptyl ester, octyl ester, isooctyl ester, 2-ethylhexyl ester, isodecyl ester, dodecyl ester, tridecyl ester, pentadecyl ester, octadecyl ester, nonadecyl ester, eicosyl ester, etc. . Examples of the functional group capable of reacting with the crosslinking agent include a carboxyl group, a hydroxyl group, an amide group, and an amino group.

  Examples of the monomer whose functional group capable of reacting with the crosslinking agent is a carboxyl group include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. Can do. Examples of the monomer whose functional group is a hydroxyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and hydroxyacrylate. Examples include hexyl, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxydecyl methacrylate, hydroxylauryl acrylate, and hydroxylauryl methacrylate. Examples of the amide group include amide groups such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, and diacetone (meth) acrylamide. Or a substituted amide group containing monomer can be mentioned. Examples of amino groups include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate , Diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and the like. Furthermore, these can be used individually by 1 type or in combination of 2 or more types.

  If desired, other monomers other than the (meth) acrylic acid alkyl ester and the monomer having a functional group capable of reacting with the crosslinking agent may be used in combination. Examples of other monomers include styrene, vinyl acetate, acrylonitrile, polyethylene glycol acrylate, N-vinyl pyrrolidone, and tetrafurfuryl acrylate.

  The acrylic resin can be obtained by radical copolymerization of monomer components. As the copolymerization method in this case, a conventionally known method can be used, and examples thereof include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method.

  Moreover, it is preferable that the glass transition temperature of an acrylic resin is -60--10 degreeC. By using an acrylic resin having a glass transition temperature in this range, the adhesion between the adherend and the resin layer (adhesive layer) is improved. On the other hand, if the glass transition temperature is higher than -10 ° C, the adhesive strength between the adherend and the pressure-sensitive adhesive layer tends to decrease. If the glass transition temperature is lower than -60 ° C, the cohesive force is insufficient and the heat resistance is insufficient. This is not preferable because the property tends to decrease. Thus, it is preferable that the glass transition temperature of an acrylic resin is the range of -55 degreeC--25 degreeC from the surface of the adhesiveness and heat resistance of a to-be-adhered body and a resin layer (adhesion layer).

  The urethane resin is composed of polyisocyanates and polyols. The urethane resin of the present invention can be obtained by dissolving the urethane resin as it is, in a solvent, or by dispersing in water.

  Examples of polyisocyanates used for the urethane resin include polyisocyanates conventionally used for urethane resins, such as aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like. Can do. These burette modified products, trimethylolpropane modified products, oligomerization reaction products such as dimers or trimers, and the like can also be used. These can be used alone or in combination of two or more. In the present invention, “aliphatic” means a linear or branched chain and does not contain an alicyclic group.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Examples thereof include range isocyanate, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, and the like.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene. A diisocyanate etc. can be mentioned.

  Examples of the polyols used in the urethane resin include conventionally used polyether polyols, polyester polyols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, And neopentyl glycol.

  Specific examples of the rubber-like elastic body include natural rubber, polyisoprene, butyl rubber, styrene / butadiene rubber, and liquid polyisoprene rubber.

  The blending amount of (B) base polymer is 5 parts by mass or more when the total amount of (A) organophosphorous flame retardant, (B) base polymer and (C) aromatic-containing tackifying resin is 100 parts by mass. And (A) It is necessary to mix | blend in the range of the compounding quantity +10 mass part or less of an organophosphorus flame retardant. When the blending amount of the (B) base polymer is less than 5 parts by mass, the cohesive force is reduced because the blending amount of the aromatic tackifying resin (C) is large, and the adhesive property cannot be satisfied. In addition, when the blending amount of (B) the base polymer exceeds (A) the blending amount of the organophosphorus flame retardant +10 parts by mass, the blending amount of the (C) aromatic tackifying resin is relatively decreased. Thereby, compatibility falls. As a result, the organophosphorus flame retardant deposits on the surface of the resin layer, which is not preferable. Further, even when the flame retardant does not precipitate, it is not preferable because the flame retardancy satisfying the UL94VTM-0 standard is not exhibited.

[1-3] (C) Aromatic-containing tackifying resin:
Examples of the aromatic-containing tackifying resin (C) used in the flame retardant resin composition of the present invention include, for example, styrene resins, xylene resins, terpene resins, aromatic petroleum resins, aliphatic aromatic petroleum oils. Resin phenol-type resin etc. are mentioned. However, it is not specifically limited to these, What is necessary is just to contain an aromatic in a chemical structure. In addition, these aromatic-containing tackifying resins can be used alone or in combination of two or more.

  The blending amount of (C) aromatic-containing tackifying resin depends on the blending amount of (A) the organophosphorus flame retardant and the base polymer, and is blended in the range of 30 to 80 Wt%. (A) Even if the blending amount of organophosphorus flame retardant is as low as 15 Wt%, (C) By blending 80 Wt% of aromatic tackifier resin, it conforms to UL94VTM-0 standard when processed into a sheet shape A flame retardant resin composition can be obtained.

  In the present invention, among these (C) aromatic-containing tackifying resins, it is preferable to use a xylene-based resin and a phenol-based resin. This is because the flame retardancy can be improved by a combination with an organic phosphorus flame retardant.

  Examples of the xylene-based resin include a xylene novolac resin and a xylene phenol novolac resin.

  Examples of phenolic resins include phenol novolac resins, bisphenol A (BPA) novolac resins, cresol novolac resins, phenol / hydroxybenzaldehyde resins, phenol-biphenylene resins, xylylene type phenol novolac resins, terpene phenol copolymers, and rosin phenol copolymers. A polymer etc. can be mentioned.

  Moreover, it is preferable to contain 20-80 mass parts of resin which is liquid at 25 degreeC among these xylene-type resin and phenol-type resin in 100 mass parts of (C) aromatic tackifying resin. This is because (B) the base polymer and (A) the organophosphorus flame retardant are allowed to exhibit adhesiveness at room temperature. On the other hand, if the content of the resin that is liquid at 25 ° C. is less than 20% by mass, it becomes difficult to realize adhesiveness at room temperature, and if it exceeds 80% by mass, the cohesive force decreases. This is not preferable because the holding power at high temperatures may be insufficient. Specifically, Nikanol G, Nikanol L, Nikanol H (all manufactured by Fudou Co., Ltd.), MEH-8000H (manufactured by Meiwa Kasei Co., Ltd.) and the like can be used as commercially available products.

  Here, as the resin that is “liquid” at 25 ° C., specifically, a resin having a viscosity at 25 ° C. of 1 to 3,000 Pa · s is preferably used. This is because the adhesiveness at room temperature can be expressed by using a resin having a viscosity in the desired range as described above at 25 ° C. Therefore, not only can the high flame retardancy satisfying the UL94VTM-0 standard be maintained, but also the destabilization of the resin composition such that (A) the organophosphorus flame retardant crystallizes over time and precipitates on the surface of the resin layer can be suppressed. And the effect of this application that the adhesiveness under room temperature expresses can be show | played synergistically.

  When the base polymer is an acrylic resin, an isocyanate crosslinking agent, a metal chelate crosslinking agent, or an epoxy crosslinking agent is known as a crosslinking agent. In the present invention, an isocyanate crosslinking agent is preferably used. Can do.

  As the isocyanate-based crosslinking agent, conventionally known isocyanate-based crosslinking agents such as polyvalent isocyanate compounds, oligomers and prepolymers thereof can be suitably used. Examples of the polyvalent isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, and diphenylmethane. Examples include -2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate. Among these, a trimethylolpropane adduct product of tolylene diisocyanate can be suitably used. This cross-linking agent is preferable in that it has an effect of imparting excellent flame retardancy and adhesiveness. In addition, a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

[2] Adhesive sheet:
The pressure-sensitive adhesive sheet of the present invention is provided with a film-like or sheet-like base material, and the flame-retardant resin composition of the present invention is provided as a resin layer on at least one surface thereof. It indicates a sheet having adhesiveness at room temperature or in a working environment.

  The pressure-sensitive adhesive sheet of the present invention includes a base material and a resin layer as its constituent elements. Hereinafter, each component will be described.

[2-1] Substrate:
The base material referred to in the present invention is a member for supporting the adhesive layer, and exhibits a film shape or a sheet shape. In the present specification, the term “film shape or sheet shape” means a thin film shape or a thin plate shape, and a film having a thickness of 4 to 250 μm is usually used.

  The constituent material of the substrate is not particularly limited, and can be appropriately selected from materials conventionally used as a substrate for an adhesive / adhesive sheet according to the use of the sheet. Specifically, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, triacetyl cellulose, cellophane, polyimide, polyamide, polyamideimide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, Alternatively, it can be selected from synthetic resins such as polysulfone, non-woven fabric, woven fabric, paper, glass, metal, or ceramic. The base material may be transparent or colored. Coloring can be performed by a method of blending various pigments or dyes into the constituent material of the substrate. Further, the surface of the base material is not limited to a smooth surface, and the surface thereof may be processed into a mat shape, primer-treated, or flame-retardant treated.

  Even if a base material contains the conventionally well-known additive in the constituent material, specifically, a heat stabilizer, an oxidation stabilizer, a weather stabilizer, a ultraviolet absorber, an antistatic agent, etc. Good. Moreover, it is preferable to use what gave surface treatment for the purpose of improving adhesiveness with the resin layer mentioned later. Examples of surface treatment include discharge treatment such as corona discharge treatment and glow discharge treatment, plasma treatment, flame treatment, ozone treatment, ionizing active ray treatment such as ultraviolet treatment, electron beam treatment, and radiation treatment, sand mat treatment, anchor treatment, Examples thereof include a roughening process such as a hairline process and an embossing process, a chemical process, and an easy adhesion layer coating process.

[2-2] Resin layer (adhesive layer):
The resin layer referred to in the present invention refers to a layer formed so as to cover at least one surface of a substrate, and among them, an adhesive layer refers to a layer that exhibits adhesiveness to an adherend. Is.

  By using the flame retardant resin composition of the present invention described above as the resin layer, both high flame retardance conforming to the UL94VTM-0 standard and good resin characteristics without flame retardant precipitation are achieved. It can be set as the adhesive sheet which has an advantageous effect compared with the conventional thing.

  The thickness of the resin layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 60 μm, and particularly preferably 10 to 50 μm. When the thickness of the resin layer is less than 2 μm, it is not preferable in that a sufficient adhesive force to the adherend may not be obtained even when the resin layer has adhesiveness. When exceeding 100 micrometers, it is not preferable at the point which may become a drying defect.

  The resin layer is prepared by, for example, dissolving or dispersing the above-described raw material composition in an appropriate solvent to obtain a resin layer forming coating solution having a solid concentration of about 20 to 50% by mass. Can be obtained by a method in which at least one surface of a substrate is coated according to a conventional method and dried.

  At this time, various conventionally used additives such as a crosslinking accelerator, an antioxidant, a stabilizer, a viscosity modifier, or an organic or inorganic filler are added to the resin layer forming coating solution. Also good. As the antioxidant, a phenolic antioxidant or the like is preferably used. As the organic filler, acrylic or urethane spherical fine particles are preferably used. As the inorganic filler, silica, calcium carbonate, alumina or the like is preferably used. it can.

  There are no particular restrictions on the application method, and conventionally known applications using wire bars, applicators, brushes, sprays, rollers, gravure coaters, die coaters, lip coaters, comma coaters, knife coaters, reverse coaters, spin coaters, etc. The method can be used. In forming the resin layer, the coating liquid may be directly applied to the substrate, or may be transferred to a substrate after being applied to a film having releasability. In addition, the surface of a base material or a film having releasability (hereinafter referred to as “base material or the like” as appropriate) may be subjected to a surface treatment in advance as necessary.

  There is no restriction | limiting in particular also about a drying method, Conventionally well-known drying methods, such as hot air drying and reduced pressure drying, can be utilized. About drying conditions, what is necessary is just to set suitably according to the kind of base polymer, the kind of solvent used with coating liquid, the film thickness of a resin layer, etc., but it is common to dry at the temperature of about 60-180 ° C. Is. In the case where the raw material composition has a crosslinkable composition, the raw material composition can be crosslinked by this heating.

  Depending on the amount of volatile matter remaining in the resin layer (hereinafter referred to as “residual volatile matter amount”), the adhesiveness between the resin layer and the substrate or the peelability after cooling may be adversely affected. Accordingly, the residual volatile content in the resin layer is preferably 4% by mass or less, and more preferably 2% by mass or less. In addition, what is necessary is just to adjust the quantity of the solvent for preparing resin layer formation coating liquid, the drying time after coating, etc. in order to set it as the desired residual volatile matter amount.

  Hereinafter, the flame-retardant resin composition of the present invention and the pressure-sensitive adhesive sheet using the same will be specifically described with reference to examples, but the flame-retardant resin composition of the present invention and the pressure-sensitive adhesive sheet using the same are described below. It is not limited at all by the examples. In addition, the adhesive sheet of an Example and a comparative example was evaluated by the flame retardance, adhesiveness A, adhesiveness B, and compatibility.

[1] Flame retardancy:
Based on UL94 flame retardancy standard, the flame retardance of the adhesive sheet of an Example and a comparative example was evaluated with the following references | standards.
○: When flame retardancy satisfying the UL94VTM-0 standard is shown,
×: When the UL94VTM-0 standard was not satisfied.

[2-1] Tackiness:
(Adhesion A)
After the production, the adhesiveness of the adhesive sheets of Examples and Comparative Examples cured for 1 month under a temperature condition of 40 ° C. was evaluated by measuring the ball tack value at an inclination angle of 30 ° according to JIS Z0237. In addition, what has description of "-" in a table | surface shows that the stable measurement result is not obtained, since precipitation of the organophosphorus flame retardant was seen in the compatibility evaluation mentioned later.

[2-2] Adhesiveness:
(Adhesive B)
After production, the tackiness of the pressure-sensitive adhesive sheets of Examples and Comparative Examples cured for one month under a temperature condition of 40 ° C. was evaluated by measuring the probe tack value in accordance with JIS Z0237 at a contact time of 60 seconds. In addition, what has description of "-" in a table | surface shows that the stable measurement result is not obtained, since precipitation of the organophosphorus flame retardant was seen in the compatibility evaluation mentioned later.

[3] Compatibility:
After the production, the conditions of the pressure-sensitive adhesive sheets of Examples and Comparative Examples cured for one month under a temperature condition of 40 ° C. were visually evaluated according to the following criteria.
(Evaluation criteria)
○: No precipitation of organophosphorus flame retardant observed
X: An organic phosphorus flame retardant is observed to be deposited.

Example 1
As shown in Table 1, acrylic resin A (a copolymer consisting of 84 parts by mass of n-butyl acrylate, 10 parts by mass of 2-ethylhexyl acrylate, and 6 parts by mass of acrylic acid, glass transition temperature -51 ° C., molecular weight (Mw)) 550,000) 30 parts by mass, 30 parts by mass of xylene phenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) as an aromatic tackifier resin, xylene novolac resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) 40 parts by mass, 30 parts by mass of phosphazene (trade name: SPS-100, manufactured by Otsuka Chemical Co., Ltd.) as an organophosphorus flame retardant, and isocyanate-based crosslinker (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) 0 part by mass, toluene / methyl ethyl ketone = 1/1 solution as diluent solvent, solid content 30% by mass And so that added, stirred and mixed to obtain a flame retardant resin composition.

  Next, this resin composition is applied to the surface of a 25 μm-thick polyimide film (trade name: Kapton 100V, manufactured by Toray DuPont) as a base material with a baker type applicator so that the film thickness after drying is 30 μm. This was heated and dried at 130 ° C. for 2 minutes to form a resin layer. The silicone-treated surface of a single-sided silicone-treated PET (trade name: MRF, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) film having a thickness of 50 μm was adhered to the surface of this resin layer as a release liner, The adhesive sheet was obtained by curing for months. The physical properties of this product are shown in Table 3.

(Example 2)
As shown in Table 1, the blending amount of acrylic resin A is 20 parts by mass, and as an aromatic tackifier resin, 30 parts by mass of xylene phenol novolac resin (trade name: Nikanol HP-150, manufactured by Fudou Co., Ltd.), xylene A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the novolac resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) was changed to 50 parts by mass. The physical properties of this product are shown in Table 3.

(Example 3)
As shown in Table 1, 30 parts by mass of phenol novolak resin (trade name: Tamano 759, Arakawa Chemical Co., Ltd.) as an aromatic tackifier resin, xylene novolac resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that 40 parts by mass and the compounding amount of the organic phosphorus flame retardant were changed to 20 parts by mass. The physical properties of this product are shown in Table 3.

Example 4
As shown in Table 1, 30 parts by mass of phenol novolac resin (trade name: MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.) as an aromatic tackifier resin, terpene phenol resin (trade name: Mighty Ace G-150, Yasuhara Chemical) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the product was changed to 40 parts by mass. The physical properties of this product are shown in Table 3.

(Example 5)
As shown in Table 1, 40 parts by mass of xylene novolac resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) and rosin phenol resin (trade name: Neotol 125P, manufactured by Harima Kasei Co., Ltd.) as an aromatic tackifying resin. 30 parts by mass, 40 parts by mass of the organophosphorus flame retardant, and the epoxy crosslinking agent (trade name: Tetrad X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as the crosslinking agent was changed to 1.0 part by mass. A pressure-sensitive adhesive sheet was obtained in the same manner as Example 1. The physical properties of this product are shown in Table 3.

(Example 6)
As shown in Table 1, 60 parts by mass of xylenephenol novolac resin (trade name: Nikanol HP-150, manufactured by Fudou Co., Ltd.) as an aromatic tackifier resin, xylene novolac resin (trade name: Nikanol G, Fudou Co., Ltd.) The pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the product was changed to 10 parts by mass. The physical properties of this product are shown in Table 3.

(Example 7)
As shown in Table 1, the acrylic resin A was changed to an acrylic resin B (copolymer composed of 54 parts by mass of n-butyl acrylate, 40 parts by mass of ethyl acrylate, 4 parts by mass of acrylamide and 2 parts by mass of 2-hydroxyethyl acrylate). A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the temperature was changed to -37 ° C and the molecular weight (Mw) was 500,000. The physical properties of this product are shown in Table 3.

(Example 8)
As shown in Table 1, 10 parts by mass of the acrylic resin A is blended, and 40 parts by mass of xylene phenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) is used as the aromatic tackifier resin. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 50 parts by mass of novolak resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) and 20 parts by mass of the flame retardant were changed. The physical properties of this product are shown in Table 3.

Example 9
As shown in Table 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 8 except that the blending amount of the flame retardant was changed to 40 parts by mass. The physical properties of this product are shown in Table 3.

(Example 10)
As shown in Table 1, 50 parts by mass of the acrylic resin A is blended, and 20 parts by mass of xylene phenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) is used as the aromatic tackifier resin. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that novolac resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) was changed to 30 parts by mass and the blending amount of the flame retardant was changed to 40 parts by mass. The physical properties of this product are shown in Table 3.

(Example 11)
As shown in Table 1, 100 parts by mass of the acrylic resin A is blended, and 30 parts by mass of xylene phenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) is used as the aromatic tackifier resin. Example 1 except that novolak resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) was changed to 45 parts by mass, the flame retardant compounding amount was changed to 75 parts by mass, and the crosslinking agent compounding amount was changed to 1.8 parts by mass. Thus, an adhesive sheet was obtained. The physical properties of this product are shown in Table 3.

(Example 12)
As shown in Table 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 11 except that the type of flame retardant was changed to an aromatic condensed phosphate ester (trade name: PX-200, manufactured by Daihachi Chemical Co., Ltd.). . The physical properties of this product are shown in Table 3.

(Example 13)
As shown in Table 1, an adhesive sheet was used in the same manner as in Example 1 except that the acrylic resin A was changed to 30 parts by mass of a rubber-like elastic body (trade name: liquid polyisoprene rubber LIR-410, manufactured by Kuraray Co., Ltd.). Got. The physical properties of this product are shown in Table 3.

(Example 14)
As shown in Table 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that acrylic resin A was changed to 30 parts by mass of urethane resin (trade name: U-250, manufactured by one company). The physical properties of this product are shown in Table 3.

(Comparative Example 1)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the amount of the flame retardant was changed to 10 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 2)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the blending amount of the flame retardant was changed to 50 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 3)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 8 except that the blending amount of the flame retardant was changed to 50 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 4)
As shown in Table 2, the blending amount of the acrylic resin A is 60 parts by mass, and 20 parts by mass of xylene phenol novolac resin (trade name: Nikanol HP-150, manufactured by Fudou Co., Ltd.) is used as the aromatic tackifier resin. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the resin (trade name: Nikanol G, manufactured by Fudou Co., Ltd.) was changed to 20 parts by mass and the blending amount of the flame retardant was changed to 40 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 5)
As shown in Table 2, the blending amount of acrylic resin A is 50 parts by mass, and 20 parts by mass of xylene phenol novolac resin (trade name: Nikanol HP-150, manufactured by Fudou Co., Ltd.) as an aromatic tackifier resin, xylene novolac resin. (Product name: Nikanol G, manufactured by Fudou Co., Ltd.) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the content was changed to 30 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 6)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2 except that the amount of the flame retardant was changed to 50 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 7)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 8 except that the amount of the flame retardant was changed to 10 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 8)
As shown in Table 2, 15 parts by mass of xylenephenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) as an aromatic tackifying resin, and aromatic condensed phosphate ester as an organic phosphorus flame retardant A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 30 parts by mass (trade name: PX-200, manufactured by Daihachi Chemical Co., Ltd.) and the blending amount of the crosslinking agent were changed to 0.5 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 9)
As shown in Table 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 8 except that the amount of the organophosphorus flame retardant was changed to 90 parts by mass. The physical properties of this product are shown in Table 4.

(Comparative Example 10)
As shown in Table 2, the blending amount of the acrylic resin A is 100 parts by mass, and 20 parts by mass of xylene phenol novolac resin (trade name: Nicanol HP-150, manufactured by Fudou Co., Ltd.) is used as the aromatic tackifier resin. 30 parts by weight of resin (liquid) (trade name: Nikanol G, manufactured by Fudou Co., Ltd.), 75 parts by weight of aromatic condensed phosphate ester (trade name: PX-200, manufactured by Daihachi Chemical Co., Ltd.) as an organic phosphorus flame retardant A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the blending amount of the parts and the crosslinking agent was changed to 1.5 parts by mass. The physical properties of this product are shown in Table 4.

  FIG. 1 shows a graph plotting the compounding amount of the organic phosphorus flame retardant with the horizontal axis and the base polymer as the vertical axis for Examples 1 to 14 and Comparative Examples 1 to 10. From the graph of FIG. 1, when the content ratio of the organic phosphorus flame retardant is 15 to 30 parts by mass, the content ratio of the base polymer is 5 parts by mass or more, and the compounding amount of the organic phosphorus flame retardant is 10 parts by mass or less. It can be seen that only the material satisfies the UL94VTM-0 standard, does not precipitate the flame retardant (good compatibility), and exhibits desired tackiness at room temperature. From this, the blending ratio of the three components of the organophosphorus flame retardant, the base polymer and the aromatic-containing tackifying resin in the present invention is extremely critical for satisfying a good balance of flame retardancy, compatibility and tackiness. It can be said that.

  Moreover, it turns out that it is more preferable from an adhesive viewpoint when 20-80 mass% uses what is liquid at 25 degreeC among aromatic containing tackifying resin from the comparison with Example 1 and Example 6. FIG. .

  The flame retardant resin composition of the present invention and the pressure-sensitive adhesive sheet using the flame retardant resin composition conform to UL94VTM-0 standard although they do not use a halogen flame retardant or antimony oxide. It can be suitably used for parts that require high flame resistance in the field of parts, aircraft, marine vehicles, and the like.

About Examples 1-14 and Comparative Examples 1-10, in the graph which plotted the compounding quantity of the organophosphorus flame retardant as the horizontal axis and the base polymer as the vertical axis, the range surrounded by the solid line shows the range of the present invention Yes.

Claims (4)

In a flame retardant resin composition comprising (A) an organophosphorus flame retardant, (B) a base polymer for an adhesive , and (C) an aromatic-containing tackifying resin,
In a total amount of 100 parts by mass of the component (A), the component (B), and the component (C),
The blending amount of the component (A) is 15 to 30 parts by mass,
The blending amount of the component (B) is 5 parts by mass or more and the blending amount of the component (A) +10 parts by mass or less,
The blending amount of the component (C) is 30 to 80% by mass,
20-80 mass% in the said (C) component is liquid at 25 degreeC,
The component (A) consists of at least one of aromatic-containing phosphazene and aromatic-containing condensed phosphate ester,
The component (C) is xylene novolak resin, xylene phenol novolak resin, phenol novolak resin, bisphenol A (BPA) novolak resin, cresol novolak resin, phenol / hydroxybenzaldehyde resin, phenol-biphenylene resin, xylylene type phenol novolak resin, terpene. A flame retardant resin composition comprising at least one selected from the group consisting of a phenol copolymer and a rosin phenol copolymer. The aromatic-containing phosphazenes include SPS-100 (Otsuka Chemical Co., Ltd.), SP-100 (Otsuka Chemical Co., Ltd.), SPH-100 (Otsuka Chemical Co., Ltd.), SPR-100 (Otsuka Chemical Co., Ltd.), and SA-100. (Otsuka Chemical Co., Ltd.), Ravitor (registered trademark) FP-100 (Fushimi Pharmaceutical Co., Ltd.), and Ravitor (registered trademark) FP-110 (Fushimi Pharmaceutical Co., Ltd.). ,
The flame-retardant resin composition according to claim 1, wherein the aromatic-containing condensed phosphate ester is PX-200 (manufactured by Daihachi Chemical Co., Ltd.). The adhesive sheet which has provided the flame-retardant resin layer which consists of a flame-retardant resin composition of Claim 1 or 2 in the at least single side | surface of a flame-retardant base material. A method for producing the flame-retardant pressure-sensitive adhesive sheet according to claim 3 ,
The manufacturing method of the adhesive sheet which apply | coats the said flame-retardant resin composition to the at least single side | surface of the said flame-retardant base material, and forms a flame-retardant resin layer.

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