CN112930379A - Flame-retardant adhesive and flame-retardant adhesive tape - Google Patents
Flame-retardant adhesive and flame-retardant adhesive tape Download PDFInfo
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- CN112930379A CN112930379A CN201980071661.4A CN201980071661A CN112930379A CN 112930379 A CN112930379 A CN 112930379A CN 201980071661 A CN201980071661 A CN 201980071661A CN 112930379 A CN112930379 A CN 112930379A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明的目的在于提供在用于使粘合剂层薄膜化的阻燃性粘合带的情况下，也能够以高水平兼顾其粘合性和阻燃性的阻燃性粘合剂，以及，即使薄壁化也能够以高水平兼顾其粘合性和阻燃性的阻燃性粘合带。本发明的阻燃性粘合剂的特征在于，含有粘合成分100质量份和聚磷酸铵65质量份以上，上述聚磷酸铵的相当于从累积粒度分布的小径侧起累积95％的粒子的粒径D95为20.0μm以下，在上述聚磷酸铵的X射线衍射测定中，衍射角2θ＝15.5±0.2°的峰强度值除以衍射角2θ＝14.6±0.2°的峰强度值而得到的值为1.4以上。另外，本发明的阻燃性粘合带的特征在于，基材的至少一面具有由上述阻燃性粘合剂形成的粘合剂层。An object of the present invention is to provide a flame-retardant adhesive tape that can achieve both adhesiveness and flame retardancy at a high level even in the case of a flame-retardant adhesive tape for thinning an adhesive layer, and , a flame-retardant adhesive tape that can balance both its adhesiveness and flame retardancy at a high level even if it is thinned. The flame-retardant adhesive of the present invention is characterized by containing 100 parts by mass of an adhesive component and 65 parts by mass or more of ammonium polyphosphate, wherein the ammonium polyphosphate is equal to 95% of the particles accumulated from the small diameter side of the cumulative particle size distribution. The particle diameter D95 is 20.0 μm or less, and in the X-ray diffraction measurement of ammonium polyphosphate, the value obtained by dividing the peak intensity value of the diffraction angle 2θ=15.5±0.2° by the peak intensity value of the diffraction angle 2θ=14.6±0.2° is 1.4 or more. Moreover, the flame-retardant adhesive tape of this invention is characterized in that at least one surface of a base material has an adhesive layer which consists of the said flame-retardant adhesive.
Description
Technical Field
The present invention relates to a flame-retardant adhesive and a flame-retardant adhesive tape.
Background
Due to remarkable progress in electronic technology, electric, electronic, and OA equipment have been highly integrated and have high performance, and an adhesive tape used for the equipment is also required to have high flame retardancy in order to reduce the risk of ignition due to high temperature and heat accumulation inside the equipment or to prevent ignition. In addition, in various fields such as home appliances, vehicles, and building materials, various studies have been made on flame retardancy of plastic materials, and high flame retardancy is also required for pressure-sensitive adhesive tapes used for fixing them.
As the adhesive tape, an adhesive containing ammonium polyphosphate has been proposed (for example, patent document 1), and thereby high flame retardancy can be exhibited.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-1669
Disclosure of Invention
In recent years, for example, in the above-mentioned applications, further high integration and weight reduction have been carried out, and the pressure-sensitive adhesive tape is required to be thin in addition to high flame retardancy at the level of UL94 VTM-0. In order to make the adhesive tape thin, it is necessary to thin not only the base material of the adhesive tape but also the adhesive layer. However, the pressure-sensitive adhesive tape has a trade-off relationship between the adhesiveness and the flame retardancy when the pressure-sensitive adhesive layer is made thin, and it is difficult to achieve a balance between these properties in the above-mentioned conventional techniques.
Accordingly, an object of the present invention is to provide a flame-retardant adhesive tape which can achieve both adhesion and flame retardancy at high levels even when used for making an adhesive layer thin, and a flame-retardant adhesive tape which can achieve both adhesion and flame retardancy at high levels even when made thin.
The present inventors have made intensive studies to solve the above problems of the prior art, and as a result, have found the present invention based on the following findings. That is, in the pressure-sensitive adhesive layer formed into a film, in order to secure flame retardancy, it is preferable to use type II ammonium polyphosphate among various flame retardants, but actually, if type II ammonium polyphosphate is contained in the pressure-sensitive adhesive layer formed into a film, sufficient adhesiveness cannot be obtained due to large particles existing in the particles, and it is difficult to industrially produce the pressure-sensitive adhesive layer so that large particles are not generated in the particles of type II ammonium polyphosphate. The present inventors have also found that: when the type II ammonium polyphosphate is used for a binder, if particles thereof are, for example, pulverized and thinned, sufficient flame retardancy may not be secured even if the adhesive property is obtained, and in the above case, the type I ammonium polyphosphate having a low effect of improving flame retardancy is generated in the type II ammonium polyphosphate. Further, the inventors obtained the following findings: even if the form I ammonium polyphosphate is generated in the form II ammonium polyphosphate, it has an allowable content in terms of flame retardancy. Based on the above findings, the present inventors have also conceived that the content of type I ammonium polyphosphate in a permissible amount in type II ammonium polyphosphate is limited by X-ray diffraction measurement in order to ensure flame retardancy on the premise that type II ammonium polyphosphate having relatively fine particles is used for forming a thin adhesive tape, and have completed the present invention.
Namely, the invention of the present application is as follows.
[ 1 ] A flame-retardant adhesive characterized by comprising 100 parts by mass of an adhesive component and 65 parts by mass or more of ammonium polyphosphate, wherein the particle diameter D95 of the ammonium polyphosphate corresponding to 95% cumulative particle size from the smaller diameter side of the cumulative particle size distribution is 20.0 μm or less,
in the X-ray diffraction measurement of the ammonium polyphosphate, a value obtained by dividing a peak intensity value at a diffraction angle 2 θ of 15.5 ± 0.2 ° by a peak intensity value at a diffraction angle 2 θ of 14.6 ± 0.2 ° is 1.4 or more.
[ 2 ] the flame-retardant adhesive according to the above [ 1 ], wherein the ammonium polyphosphate is classified.
[ 3 ] A flame-retardant adhesive according to the above [ 1 ] or [ 2 ], which contains a metal hydroxide.
The flame-retardant adhesive according to any one of [ 1 ] to [ 3 ] above, which comprises an aliphatic polyhydric alcohol and/or an ester of a rosin compound and an aliphatic polyhydric alcohol.
A flame-retardant adhesive tape characterized in that at least one surface of a substrate has an adhesive layer formed of the flame-retardant adhesive of any one of [ 1 ] to [ 4 ].
According to the present invention, it is possible to provide a flame-retardant adhesive agent which can achieve both the adhesiveness and the flame retardancy at a high level even in the case of a flame-retardant adhesive tape for thinning an adhesive layer, and a flame-retardant adhesive tape which can achieve both the adhesiveness and the flame retardancy at a high level even in the case of thinning.
Detailed Description
Hereinafter, embodiments of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited to the embodiments.
Flame retardant adhesive
The flame-retardant adhesive of the present embodiment is characterized by comprising 100 parts by mass of an adhesive component and 65 parts by mass or more of ammonium polyphosphate, wherein the particle diameter D95 of the ammonium polyphosphate corresponding to 95% cumulative particles from the smaller diameter side of the cumulative particle size distribution is 20.0 μm or less,
in the X-ray diffraction measurement of the ammonium polyphosphate, a value obtained by dividing a peak intensity value at a diffraction angle 2 θ of 15.5 ± 0.2 ° by a peak intensity value at a diffraction angle 2 θ of 14.6 ± 0.2 ° is 1.4 or more.
Accordingly, even when a flame-retardant adhesive (hereinafter, also simply referred to as "adhesive") is used as an adhesive layer of a flame-retardant adhesive tape (hereinafter, also simply referred to as "adhesive tape") having a reduced thickness, both the adhesiveness and the flame retardancy can be achieved at a high level.
Binding component
The adhesive component of the present embodiment is not particularly limited, and examples thereof include an acrylic adhesive component, a urethane adhesive component, a synthetic rubber adhesive component, a natural rubber adhesive component, and a silicone adhesive component. In the present embodiment, an acrylic pressure-sensitive adhesive component is preferable from the viewpoint of easily obtaining a strong adhesive force.
The acrylic pressure-sensitive adhesive component is not particularly limited, and includes, for example, at least 1 acrylic polymer containing an alkyl (meth) acrylate monomer as a monomer unit. Examples of the alkyl (meth) acrylate monomer include, but are not particularly limited to, alkyl (meth) acrylates having 2 to 14 carbon atoms in the alkyl group, and examples thereof include ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, octyl acrylate, isononyl acrylate, isodecyl acrylate, butyl methacrylate, hexyl methacrylate, isodecyl methacrylate, and lauryl methacrylate.
In the present specification, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate.
The acrylic polymer may be copolymerized with a monomer having a carboxyl group, a hydroxyl group, or the like, such as acrylic acid, maleic anhydride, or 2-hydroxyethyl (meth) acrylate. Thus, the structural units derived from the monomer serve as crosslinking points in the acrylic polymer, and the hardness of the adhesive component can be adjusted to exhibit a desired adhesive force.
The acrylic polymer is not particularly limited, and for example, vinyl acetate, acrylonitrile, acrylamide, styrene, and the like may be copolymerized to adjust the cohesive force of the acrylic polymer.
The acrylic polymer is not particularly limited, and polymerization can be carried out by a radical polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, and the like. As the polymerization initiator, organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, and azo polymerization initiators such as 2,2 '-azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), dimethyl-2, 2-azobis (2-methylpropionate), 4 '-azobis (4-cyanovaleric acid), dimethyl 2, 2' -azobis (2-methylpropionate), and azobis (2, 4-dimethylvaleronitrile) (AVN) can be used.
The acrylic polymer contains a crosslinkable crosslinking agent to be crosslinkable. Examples of the crosslinking agent include epoxy crosslinking agents and polyisocyanate compounds such as aliphatic diisocyanates, aromatic diisocyanates and aromatic triisocyanates. In addition, a crosslinking accelerator containing an organic metal compound or the like may be added to the acrylic polymer having a slow crosslinking reaction. The cohesive force can be increased by crosslinking the acrylic polymer.
Ammonium polyphosphate-
The flame-retardant adhesive of the present embodiment contains a specific ammonium polyphosphate. Thus, even in the pressure-sensitive adhesive tape obtained by thinning the pressure-sensitive adhesive layer, flame retardancy can be secured.
The content of ammonium polyphosphate is 65 parts by mass or more, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more, per 100 parts by mass of the binder component. By setting the content to 65 parts by mass or more, desired flame retardancy can be secured. The upper limit of the content is not particularly limited from the viewpoint of flame retardancy, and if the content is excessively increased relative to the adhesive component, the particles may be exposed on the surface of the adhesive layer when the adhesive tape is produced, and the adhesive strength may be lowered, and therefore, the content is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less.
In the present specification, the reference of the content of each component (for example, a binder component) is based on a nonvolatile component (solid component).
The particle diameter D95 of the ammonium polyphosphate, which corresponds to 95% of particles accumulated from the smaller diameter side of the cumulative particle size distribution, is 20.0 μm or less, preferably 19.0 μm or less, and more preferably 15.0 μm or less. By setting the particle diameter D95 to 20.0 μm or less, the number of particles having a large particle diameter is reduced, and therefore, the spacer effect caused by the large particles is suppressed, and the pressure-sensitive adhesive tape obtained by thinning the pressure-sensitive adhesive layer can secure the pressure-sensitive adhesive property.
The lower limit of the particle diameter D95 is not particularly limited from the viewpoint of securing adhesiveness, but if the particle diameter D95 is too low, the specific surface area increases after formation of fine powder, and thus poor dispersion and poor application due to thickening of the adhesive may occur, and therefore, the particle diameter is preferably 0.1 μm or more, more preferably 1.0 μm or more, and still more preferably 3.0 μm or more.
The particle diameter D50 of the ammonium polyphosphate, which corresponds to 50% cumulative particle size from the smaller diameter side of the cumulative particle size distribution, is preferably 10.0 μm or less, more preferably 8.0 μm or less, and still more preferably 7.5 μm or less. By setting the particle diameter D50 to 10.0 μm or less, sufficient adhesiveness can be ensured even in a pressure-sensitive adhesive tape in which the pressure-sensitive adhesive layer is made thin.
The particle diameter (D95, D50, etc.) corresponding to a predetermined cumulative proportion of particles from the smaller diameter side of the cumulative particle size distribution can be measured by the method described in the examples described later.
In the present embodiment, from the viewpoint of further securing the adhesiveness, the ammonium polyphosphate particles having a particle diameter of 20 μm or more are preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably not contained in the nonvolatile component of the flame retardant adhesive.
In the X-ray diffraction measurement of ammonium polyphosphate, the value obtained by dividing the peak intensity value at a diffraction angle 2 θ of 15.5 ± 0.2 ° by the peak intensity value at a diffraction angle 2 θ of 14.6 ± 0.2 ° is 1.4 or more. The peak appearing at a diffraction angle 2 θ of ammonium polyphosphate of 15.5 ± 0.2 ° is a peak observed characteristically in type II ammonium polyphosphate, and the peak appearing at a diffraction angle 2 θ of 14.6 ± 0.2 ° is a peak observed characteristically in type I and type II ammonium polyphosphates. That is, in the present invention, by defining the relationship between the respective peak intensity values, it is premised that form II ammonium polyphosphate is contained in ammonium polyphosphate, and the content of form I ammonium polyphosphate that is low in the allowable contribution to flame retardancy is defined therein. Therefore, in the present embodiment, by setting the ratio of the respective peaks to the above relationship, the content of the type I ammonium polyphosphate present in the type II ammonium polyphosphate can be suppressed, and therefore flame retardancy can be secured even in a pressure-sensitive adhesive tape obtained by forming a pressure-sensitive adhesive layer into a thin film.
In the present embodiment, from the same viewpoint, the value obtained by dividing the peak intensity value at the diffraction angle 2 θ of 15.5 ± 0.2 ° by the peak intensity value at the diffraction angle 2 θ of 14.6 ± 0.2 ° is preferably 1.5 or more, more preferably 1.6 or more, and still more preferably 2.0 or more.
In the present embodiment, from the above-described viewpoint, the larger the value obtained by dividing the peak intensity value at the diffraction angle 2 θ of 15.5 ± 0.2 ° by the peak intensity value at the diffraction angle 2 θ of 14.6 ± 0.2 °, the better, and the upper limit value thereof is not particularly limited, and the value may be 2.8 or less. As described above, in industrial production, the particles of the type II ammonium polyphosphate may include particles having a large particle size, but in this production process, the particle size of the type II ammonium polyphosphate is large, and crystals are likely to grow, in other words, the content of the type II ammonium polyphosphate in the large particles is likely to increase. In addition, in the process of satisfying the above-described limited range of the particle diameter D95, the large particles tend to decrease, and in the case of decreasing, the value obtained by dividing the peak intensity value at the diffraction angle 2 θ of 15.5 ± 0.2 ° by the peak intensity value at the diffraction angle 2 θ of 14.6 ± 0.2 ° tends to be 2.8 or less.
The measurement of the peak intensity value at the diffraction angle 2 θ defined in the X-ray diffraction measurement can be performed by the method described in the examples below.
The ammonium polyphosphate of the present embodiment is not particularly limited as long as it satisfies the above-mentioned particle size and the above-mentioned limited ratio of diffraction angle in X-ray diffraction measurement, and for example, it can be used in the form of a powder which is easily flowable and hardly water-soluble and whose surface is coated with a melamine/formaldehyde resin or the like, and which has a polymerization degree of phosphoric acid of 500 to 2000.
Here, in the present embodiment, when the ammonium polyphosphate satisfies the relationship between the limited particle diameter and the peak intensity value in the X-ray diffraction measurement, the ammonium polyphosphate form II produced by a known method can be obtained by pulverizing and classifying the ammonium polyphosphate form II particles. Specifically, the method of pulverization is not particularly limited, and a media type disperser/pulverizer such as a bead mill, a ball mill, an attritor, a planetary mill, a vibration mill, a mortar mill, and a non-media type disperser/pulverizer typified by a jet mill can be used. As the pulverization method, both wet and dry pulverization methods can be used, but wet pulverization is preferable in terms of easiness of dispersion after pulverization, and good recovery and handling of the pulverized material. When a media disperser/pulverizer is used, the material of the media is not particularly limited, and steel, glass, alumina, zirconia, silicon nitride, or the like can be used. The diameter of the medium is not particularly limited, and from the viewpoint of suppressing the decrease in form II ammonium polyphosphate due to excessive crushing and efficiently carrying out micronization, the diameter of the medium to be used is preferably 5mm or less, more preferably 3mm or less, and still more preferably 1mm or less. The pulverization is preferably carried out under stable conditions such as a shortened pulverization time or pulverization while cooling.
The method of classification is not particularly limited, and examples thereof include a classification method using gravity, centrifugal force, inertial force, and the like, and a classification method using a sieve. In addition, from the viewpoint of fine control of the classification point, in the case of dry classification, a forced vortex Classifier (manufactured by Aerofine Classifier, Nisshin Engineering, Inc.; manufactured by Micron separator, Hosokawa Micron, Inc.; Turboflex, manufactured by Hosokawa Micron, Inc.; etc.) or an inertial force field Classifier using the coanda effect (manufactured by Elbo jet mill, Nissan industries, Inc.; Cliffis, manufactured by Hosokawa Micron, Inc.) may be used.
In the classification, a flame retardant other than ammonium polyphosphate, a flame retardant aid, and the like may be contained, or after dispersing them in an arbitrary dispersion medium, the dispersion may be subjected to wet classification.
In the present embodiment, ammonium polyphosphate can suitably satisfy a specific relationship between a specific particle diameter and a peak intensity value in X-ray diffraction measurement, and thus it is preferable to use ammonium polyphosphate obtained by classification.
Metal hydroxide-
The flame retardant adhesive of the present embodiment may contain a metal hydroxide. This can further improve flame retardancy.
The content of the metal hydroxide is preferably 0.1 part by mass or more, more preferably 25 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more, based on 100 parts by mass of the binder component. By setting the content to 0.1 part by mass or more, the flame retardancy can be further improved.
From the viewpoint of improving flame retardancy, the content is not particularly limited, but if the content is excessively increased relative to the adhesive component, the particles may be exposed on the surface of the adhesive layer when the adhesive tape is produced, and the adhesive strength may be lowered, and therefore, the content is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 150 parts by mass or less, and particularly preferably 100 parts by mass.
The metal hydroxide is not particularly limited, and examples thereof include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. Among them, aluminum hydroxide is preferable because it can separate water at a relatively low temperature to exhibit high flame retardancy.
The metal hydroxide may be used in 1 kind or 2 or more kinds.
The metal hydroxide may be subjected to a surface treatment such as a coupling treatment or a stearic acid treatment in order to improve the dispersibility in the binder component. The particle diameter D95 of the component that can be present in solid form in the binder such as the metal hydroxide and the aliphatic polyol described later is preferably 20.0 μm or less. Examples of the shape of the metal hydroxide include a spherical shape, a needle shape, and a sheet shape.
Aliphatic polyols-
The flame retardant adhesive of the present embodiment may contain an aliphatic polyol. Thus, the flame retardant effect of ammonium polyphosphate, and even the flame retardancy of the adhesive, can be improved.
The content of the aliphatic polyol is preferably 5.0 parts by mass or more, more preferably 10.0 parts by mass or more, further preferably 15.0 parts by mass or more, and particularly preferably 16.0 parts by mass or more, based on 100 parts by mass of the binder component. By setting the content to 5.0 parts by mass or more, the flame retardancy can be further improved.
From the viewpoint of improving flame retardancy, the content is not particularly limited. However, since the aliphatic polyol exhibits improved flame retardancy in the presence of ammonium polyphosphate and the excessive component may become a flammable component, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of ammonium polyphosphate.
The aliphatic polyhydric alcohol is not particularly limited, and specific examples thereof include ethylene glycol, glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerin), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Among these, dipentaerythritol is preferable because it has high resistance to water bleed and can form a carbonized layer efficiently together with ammonium polyphosphate.
The aliphatic polyol may be used in 1 kind or 2 or more kinds.
Esters of rosin-based compounds with aliphatic polyols
The flame-retardant adhesive of the present embodiment may contain an ester of a rosin compound and an aliphatic polyol. Thereby, adhesiveness can be further imparted, and the flame-retardant effect by ammonium polyphosphate, even the flame retardancy of the adhesive can also be improved.
The content of the ester of the rosin-based compound and the aliphatic polyol is preferably 0.1 part by mass or more, more preferably 10.0 parts by mass or more, and still more preferably 20.0 parts by mass or more, based on 100 parts by mass of the binder component. By setting the content to 0.1 part by mass or more, the flame retardancy can be further improved.
From the viewpoint of improving flame retardancy, the content is not particularly limited, but is preferably 100 parts by mass or less, more preferably 70.0 parts by mass or less, and still more preferably 50.0 parts by mass or less.
Examples of the rosin-based compound which is an ester of a rosin-based compound and an aliphatic polyhydric alcohol include a rosin monomer, a disproportionated rosin, a polymerized rosin, a hydrogenated rosin, and a partially disproportionated rosin. The aliphatic polyol includes the above-mentioned aliphatic polyols, and among them, diethylene glycol, glycerin, pentaerythritol and the like are preferable, and pentaerythritol is more preferable. The rosin compound and the aliphatic polyol may be used in 1 or 2 or more species.
Other ingredients-
The flame-retardant adhesive of the present embodiment may contain a melamine derivative such as melamine cyanurate in an amount that does not impair the adhesive performance, and thus may further improve the flame retardancy or reduce the content of ammonium polyphosphate.
In addition, a tackifier resin may be contained within a range not reducing the required flame retardancy, and the adhesion to a non-polar adherend may be improved. Examples of the resin include terpene-based resins, terpene-phenolic resins, rosin-based resins, petroleum-based resins, coumarone-indene resins, and phenolic resins. The form may be a solid or viscous liquid at ordinary temperature, and the compound species may be used alone or in combination of 2 or more.
Physical Properties of flame retardant Adhesives
The flame-retardant adhesive of the present embodiment is used to provide flame retardancy, preferably, of UL94VTM-0 or more, as measured by the VTM test described in the UL94 standard, to any of a test piece having a substrate (12.5 μm thick, and a polyimide film (Kapton 50H, manufactured by tokyo corporation) on one side of which an adhesive layer having a thickness of 20 μm is formed and a test piece having a substrate (16 μm thick, and a rayon nonwoven fabric (DT-6, paplila manufactured by japan paper corporation) on both sides of which an adhesive layer having a thickness of 20 μm is formed.
The flame-retardant adhesive of the present embodiment preferably has a thickness of 16 μm and a 180 DEG peel adhesion of 5N or more when an adhesive layer having a thickness of 20 μm is formed on both surfaces of a rayon nonwoven fabric (manufactured by DT-6 PAPYLIA Japan paper-making Co., Ltd.). The peel adhesion can be performed by the method described in the examples described later.
The viscosity of the flame-retardant adhesive of the present embodiment measured with a B-type viscometer at 23 ℃ with respect to a solution prepared by dilution with ethyl acetate so that the solid content fraction becomes 30% is preferably 2000mPa · s or less.
Method for producing flame-retardant adhesive
The flame-retardant adhesive of the present embodiment is not particularly limited, and can be produced by, for example, adding a specific ammonium polyphosphate to an adhesive component, optionally adding a metal hydroxide, and stirring and dispersing the mixture by a high-speed disperser.
Flame-retardant adhesive tape
The flame-retardant pressure-sensitive adhesive tape of the present embodiment is characterized by having a pressure-sensitive adhesive layer formed of the flame-retardant pressure-sensitive adhesive according to the embodiment of the present invention on at least one surface of a substrate. Thus, even when the pressure-sensitive adhesive layer is made thin, both the pressure-sensitive adhesive property and the flame retardancy can be achieved at a high level.
The substrate of the flame-retardant pressure-sensitive adhesive tape of the present embodiment is not particularly limited, and examples thereof include a resin sheet, a nonwoven fabric, paper, a metal foil, a woven fabric, a rubber sheet, a foamed sheet, and a laminate thereof (particularly a laminate including a resin sheet). Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), Polyethylene (PE), polypropylene (PP), an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), wholly aromatic polyamide (aramid), Polyimide (PI), polyvinyl chloride (PVC), Polyphenylene Sulfide (PPs), a fluorine-based resin, and polyether ether ketone (PEEK). Examples of the nonwoven fabric include nonwoven fabrics of natural fibers (cellulose fibers); nonwoven fabrics of synthetic resin fibers such as polypropylene resin fibers, polyethylene resin fibers, and polyester resin fibers. Examples of the metal foil include copper foil, stainless steel foil, and aluminum foil. Examples of the paper include japanese paper and kraft paper.
As these substrates, those treated to be nonflammable, self-extinguishing, etc. may be used.
The flame-retardant pressure-sensitive adhesive tape of the present embodiment is formed with a pressure-sensitive adhesive layer comprising the above-mentioned flame-retardant pressure-sensitive adhesive, and the pressure-sensitive adhesive layer of the flame-retardant pressure-sensitive adhesive tape may have a thickness of 20.0 μm or less, preferably 18.0 μm or less, and more preferably 13.0 μm or less. In the case of the pressure-sensitive adhesive layer having the above thickness, it is not preferable because it is difficult to achieve both the pressure-sensitive adhesive property and the flame retardancy in the pressure-sensitive adhesive tape using the conventional pressure-sensitive adhesive, but the flame-retardant pressure-sensitive adhesive tape of the present embodiment can be suitably produced even if the thickness is set to the above thickness.
When the flame-retardant pressure-sensitive adhesive tape of the present embodiment has a pressure-sensitive adhesive layer on one surface of a substrate, the total thickness of the substrate and the pressure-sensitive adhesive layer may be 30.0 μm or less, preferably 25.0 μm or less, and more preferably 20.0 μm or less. When the pressure-sensitive adhesive layers are provided on both surfaces of the base material, the total thickness of the base material and the pressure-sensitive adhesive layer may be 50.0 μm or less, preferably 40.0 μm or less, and more preferably 30.0 μm or less.
In order to protect the pressure-sensitive adhesive layer, the flame-retardant pressure-sensitive adhesive tape of the present embodiment may be laminated with a release film. The release film is not particularly limited, and for example, a release film obtained by subjecting at least one surface or both surfaces of a substrate such as a synthetic resin film of polyethylene, polypropylene, polyester film or the like, paper, nonwoven fabric, cloth, foamed sheet, metal foil, or a laminate thereof to a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment for improving releasability from an adhesive can be used.
Method for producing flame-retardant adhesive tape
The flame-retardant adhesive tape of the present embodiment is not particularly limited, and can be produced by a known method, for example. Specifically, an adhesive tape having an adhesive layer formed on one surface thereof is formed by applying a flame-retardant adhesive to the surface of a release film and drying the same. Next, a substrate is attached to the surface of the adhesive layer, whereby the adhesive sheet can be manufactured. The adhesive tape having adhesive layers formed on both surfaces thereof can be produced by the following method: the adhesive tape is brought into contact with an adhesive tape having a 1 st adhesive layer formed on one surface thereof, a flame-retardant adhesive is applied to the surface of a release film, and the release film is dried to form a 2 nd adhesive layer, a substrate is bonded to the surface of the 2 nd adhesive layer, and the 1 st adhesive layer is bonded to the substrate.
[ examples ] A method for producing a compound
The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
First, the measurement method and the evaluation method used in examples and comparative examples will be described.
(1) Cumulative particle size distribution of ammonium polyphosphate (D95, D50)
The cumulative particle size distribution was measured by using a laser diffraction/scattering particle size distribution measuring apparatus (available from Nikkiso Co., Ltd.) Microtrac MT3300EX-II, both in water and organic solvent, and the particle size was measured to be 0.02 to 2000. mu.m). Ethyl acetate was circulated in a standard sample circulator SDC, and an ammonium polyphosphate dispersion (obtained by a production example described later) was charged to measure the particle size distribution. When the viscosity of the ammonium polyphosphate dispersion is high, the ammonium polyphosphate dispersion is diluted with ethyl acetate as appropriate and then charged.
Measuring parameters
Number of measurements: AVG/2
Measurement time (sec): 30
Distribution display: volume of
Particle permeability: through the use of
Particle refractive index: 1.81
Particle shape: non-spherical shape
Solvent name/refractive index: ethyl Acetate/1.37
(2) X-ray diffraction measurement of ammonium polyphosphate
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape thus obtained was fixed to a glass plate in an upward direction, and a wide-angle X-ray diffraction pattern was measured at arbitrary 3 positions on the surface of the pressure-sensitive adhesive layer using a SmartLab (manufactured by Rigaku) X-ray diffraction apparatus. The graphs obtained by measurement at the respective positions were obtained by dividing the peak intensity value at the diffraction angle 2 θ of 15.5 ± 0.2 ° by the peak intensity value at the diffraction angle 2 θ of 14.6 ± 0.2 °, and arithmetic-averaging the values to obtain the X-ray diffraction peak intensity ratio.
The measurement conditions were as follows: 2 theta/theta method 2 theta is 1 to 70deg.
step＝0.02deg.
speed＝20deg./min.
Analysis software: PDXL
(3) Thickness of adhesive layer
The obtained adhesive tape was immersed in liquid nitrogen for 1 minute, and then bent in liquid nitrogen using a forceps to cut the tape, thereby producing a section for observing the cut surface. After the cut piece was returned to normal temperature in a desiccator, the cut piece was fixed on a sample stage so that an electron beam was incident perpendicularly to the cut surface, and the cut surface was observed using an electron microscope (Miniscope (registered trademark) TM3030Plus, manufactured by Hitachi High-Technologies). The distance from an arbitrary point on the surface of the pressure-sensitive adhesive layer (the surface in contact with the release film) in the observation field to the surface of the base material in the vertical direction was measured for 10 positions, and the arithmetic average thereof was taken as the thickness of the pressure-sensitive adhesive layer.
In the case of a double-sided tape, the thickness of the pressure-sensitive adhesive layer is determined on both sides of the tape, and the smaller value is used as the thickness of the pressure-sensitive adhesive layer.
(4) Thickness of adhesive tape
The thickness of the obtained pressure-sensitive adhesive tape (in a state of having a release film) was measured at random at 10 positions using a constant-pressure thickness meter (stester industrial co., ltd.). Next, the thickness of the release film was subtracted from the measured thickness, and the arithmetic average was performed to obtain a value as the thickness of the adhesive tape.
(5) UL94VTM Combustion test
The determination was made by the combustion test in the VTM test described in the UL Standard (UL94 "method for testing combustion of Plastic Material for parts of Equipment"). The flame retardancy of the one-sided tape was determined as a result of a flame test performed on the one-sided tape under two conditions, i.e., the case where the adhesive surface was on the outside and the case where the adhesive surface was on the inside.
(6)180 degree peel adhesion (double side tape)
One adhesive surface of the adhesive tape was backed with a polyester film of 25 μm, and the size thereof was 20mm × 100mm, to obtain a tape sample. A stainless steel plate was placed on the other adhesive surface of the tape sample, and the tape sample was applied to the adhesive surface 1 time with a 2kg roller and then left at room temperature for 1 hour. Then, the film was peeled at a peeling speed of 300mm/min in a 180 ℃ direction, and the adhesion (N) at this time was measured.
(7)180 degree peel adhesion (Single side tape)
A stainless steel plate was placed on the adhesive surface of a tape sample having a size of 25mm X100 mm, and the tape sample was applied to the adhesive surface by reciprocal pressing 1 time using a 2kg roller, followed by standing at room temperature for 1 hour. Then, the film was peeled at a peeling speed of 300mm/min in a 180 ℃ direction, and the adhesion (N) at this time was measured.
Next, the respective components used in examples and comparative examples will be described.
(1) Binding composition
As the adhesive component, an acrylate copolymer obtained by the following method was used.
In a reaction vessel equipped with a condenser, stirrer, thermometer and dropping funnel, 50 parts of 2-ethylhexyl acrylate, 46 parts of n-butyl acrylate, 3.5 parts of acrylic acid, 0.5 part of 2-hydroxyethyl acrylate and 0.2 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator were dissolved in 100 parts of ethyl acetate, nitrogen substitution was performed, and then polymerization was performed at 80 ℃ for 8 hours. The resulting acrylic copolymer solution had a solid content of 50% and a weight average molecular weight of 40 ten thousand.
(2) Ammonium polyphosphate (APP)
(APP-1)
Ammonium polyphosphate (manufactured by CBC corporation, TERRAJU _ C-30) was used.
(APP-2)
The ammonium polyphosphate (APP-1) was classified by using an elbow jet classifier (EJ-15, manufactured by Nippon iron mining Co., Ltd.) under an injection pressure of 0.5MPa, with classification edge positions set so that the coarse particle removal rate became 30% and the fine particle removal rate became 0%.
(APP-3)
The ammonium polyphosphate (APP-1) was classified by using an elbow jet classifier (EJ-15, manufactured by Nippon iron mining Co., Ltd.) under an injection pressure of 0.5MPa, with classification edge positions set so that the coarse particle removal rate became 90% and the fine particle removal rate became 0%.
As described in the following production examples, the ammonium polyphosphate was used for the production of a binder after the ammonium polyphosphate dispersion was produced, and was subjected to a pulverization treatment in the production examples.
(3) Metal hydroxides
Aluminum hydroxide (BE 033, manufactured by Nippon light Metal Co., Ltd.) having an average particle size of 3 μm was used as the metal hydroxide.
(4) Aliphatic polyols
Dipentaerythritol (manufactured by Perstorp corporation, CharmerDP40) was used as the aliphatic polyol.
(5) Esters of rosin-based compounds and aliphatic polyhydric alcohols
·(E-1)
A polymerized rosin pentaerythritol ester (manufactured by Harima chemical Co., Ltd., Haritac PCJ) was used.
·(E-2)
Hydrogenated rosin methyl ester (M-HDR, manufactured by Takayasu oil chemical Co., Ltd.) was used.
(6) Base material
·(S-1)
Using a thickness of 16 μm, 6g/m2The nonwoven fabric of rayon fiber (PAPYLIA, manufactured by PAPYLIA JAPONICA K.K., DT-6).
·(S-2)
A polyimide film (Kapton 50H, manufactured by DuPont, Torilis) having a thickness of 12.5 μm was used.
(7) Curing agent
Epoxy crosslinking agent (E-2 XM, 2% solid, available from Sokka chemical Co., Ltd.)
(8) Diluting solvent
Ethyl acetate (manufactured by Showa Denko K.K.) was used.
Next, a method for producing each ammonium polyphosphate dispersion, and a method for producing each of the examples and comparative examples will be described.
Production example 1
To 100 parts by mass of the solid content of the acrylate copolymer, 150 parts by mass of APP-1 was added, and the mixture was sufficiently stirred to be uniformly dispersed, thereby obtaining an ammonium polyphosphate dispersion. The D95 determined on the basis of the particle size distribution was 23.0. mu.m, and D50 was 10.8. mu.m.
Production example 2
An ammonium polyphosphate dispersion was obtained in the same manner as in production example 1, except that APP-1 was changed to APP-2. D95 was 14.5 μm and D50 was 7.4 μm, determined on the basis of the particle size distribution.
(production example 3)
An ammonium polyphosphate dispersion was obtained in the same manner as in production example 1, except that APP-1 was changed to APP-3. D95 was 7.7 μm and D50 was 3.8 μm, determined on the basis of the particle size distribution.
Production example 4
100 parts by mass of APP-1 and 200 parts by mass of ethyl acetate were added to 100 parts by mass of the solid content of the acrylate copolymer, and after sufficiently stirring and dispersing, the mixture was passed through a horizontal 20L bead mill (Nanomill, manufactured by Haizhiki Kaisha, using beads made of zirconia having a particle diameter of 1mm, having a bead filling rate of 70%, a rotation speed of 1200rpm, and a discharge flow rate of 3 kg/min) for 5 times to obtain an ammonium polyphosphate dispersion. D95 was 12.3 μm and D50 was 7.1 μm, determined on the basis of the particle size distribution.
Production example 5
An ammonium polyphosphate dispersion was obtained in the same manner as in production example 4, except that the slurry was passed through a horizontal 20L bead mill 10 times. The D95 determined on the basis of the particle size distribution was 8.4 μm and the D50 was 4.2. mu.m.
(examples 1 to 3, 5 and 6 and comparative examples 1 to 4 and 6)
To the ammonium polyphosphate dispersions of production examples 1 to 5, an acrylate copolymer, aluminum hydroxide, dipentaerythritol, polymerized rosin pentaerythritol ester, hydrogenated rosin methyl ester, and an epoxy crosslinking agent were added so as to have the compositions shown in table 1, and the mixture was sufficiently stirred until uniform to obtain flame retardant adhesives.
Ethyl acetate was added to the obtained flame-retardant adhesive to prepare a mixture so that the solid content became 30%, and the mixture was applied to a polyester release film using an applicator having a coating thickness of 65 μm, and dried by heating at 85 ℃ for 3 minutes to obtain a flame-retardant adhesive layer. The flame-retardant adhesive layer thus obtained was bonded to both surfaces of the substrate S-1 using a desk laminator (manufactured by TESTER INDUSTRIAL CO., LTD.) at a conveying speed of 2.0m/S and a pressure of 0.25MPa, and then cured at 40 ℃ for 48 hours to obtain a flame-retardant adhesive tape having adhesive layers on both surfaces.
The results of evaluation of the obtained flame-retardant adhesive and flame-retardant adhesive tape by the above-described methods are shown in table 1.
The flame-retardant pressure-sensitive adhesive tape of comparative example 1 was judged to have low adhesiveness because no substrate was attached to the pressure-sensitive adhesive layer of the 1 st layer. In comparative examples 2, 3, 4 and 6, UL94VTM burning tests using the adhesive tapes were performed, and the test pieces burned to the marked lines due to ignition were found to be out of the UL94VTM rating.
(example 4, comparative example 5)
To the ammonium polyphosphate dispersions of production examples 1 and 2, an acrylic acid ester copolymer, aluminum hydroxide, dipentaerythritol, polymerized rosin pentaerythritol ester, hydrogenated rosin methyl ester, and an epoxy crosslinking agent were added so as to have the compositions shown in table 1, and the mixture was sufficiently stirred until uniform to obtain flame retardant adhesives.
Ethyl acetate was added to the obtained flame-retardant adhesive to prepare a mixture so that the solid content became 30%, and the mixture was applied to a polyester release film using an applicator having a coating thickness of 70 μm, and dried by heating at 85 ℃ for 3 minutes to obtain a flame-retardant adhesive layer. The flame-retardant adhesive layer thus obtained was bonded to one surface of the substrate S-2 using a desk laminator (manufactured by TESTER industries, ltd.) at a conveying speed of 2.0m/S and a pressure of 0.25MPa, and then cured at 40 ℃ for 48 hours, thereby obtaining a flame-retardant adhesive tape having an adhesive layer on one surface. The results of evaluating the obtained adhesive tape by the above-described method are shown in table 1.
The flame-retardant pressure-sensitive adhesive tape of comparative example 5 was judged to have low adhesiveness because no substrate was attached to the pressure-sensitive adhesive layer of the 1 st layer.
[ TABLE 1 ]
Industrial applicability
According to the present invention, there can be provided a flame-retardant adhesive which can achieve both the adhesiveness and the flame retardancy at a high level even when used for an adhesive layer obtained by thinning an adhesive tape, and a flame-retardant adhesive tape which can achieve both the adhesiveness and the flame retardancy at a high level even when thinned.
Claims (5)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018241816 | 2018-12-25 | ||
| JP2018-241816 | 2018-12-25 | ||
| PCT/JP2019/048655 WO2020137573A1 (en) | 2018-12-25 | 2019-12-12 | Flame-retardant adhesive agent and flame-retardant adhesive tape |
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| Publication Number | Publication Date |
|---|---|
| CN112930379A true CN112930379A (en) | 2021-06-08 |
| CN112930379B CN112930379B (en) | 2023-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201980071661.4A Active CN112930379B (en) | 2018-12-25 | 2019-12-12 | Flame retardant adhesives and flame retardant adhesive tapes |
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| Country | Link |
|---|---|
| JP (1) | JP6743999B1 (en) |
| KR (1) | KR102668134B1 (en) |
| CN (1) | CN112930379B (en) |
| WO (1) | WO2020137573A1 (en) |
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| TW202239700A (en) * | 2021-02-15 | 2022-10-16 | 瑞士商克萊瑞特國際股份有限公司 | Compositions comprising ammonium polyphosphates |
| KR102757738B1 (en) | 2022-10-21 | 2025-01-23 | 이노에프앤씨(주) | Flame retardant tape containing phosphoric acid-based monomer and solid phosphoric acid-based flame retardant, manufacturing method thereof, flame retardant adhesive resin containing phosphoric acid-based monomer for the same, and flame retardant adhesive composition comprising phosphoric acid-based monomer and solid phosphoric acid-based flame retardant |
| KR20250176368A (en) | 2024-06-12 | 2025-12-19 | 이은수 | Flame-retarding tape |
| KR102810476B1 (en) | 2024-12-03 | 2025-05-21 | 주식회사 엑스씨엠 | Adhesive tape with excellent flame retardancy and insulation performance |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07315817A (en) * | 1994-05-23 | 1995-12-05 | Chisso Corp | Production of ii type polyphosphoric acid ammonium fine particle |
| JPH111669A (en) * | 1997-06-16 | 1999-01-06 | Nitto Denko Corp | Flame retardant adhesive tape |
| JP2000230162A (en) * | 1999-02-10 | 2000-08-22 | Dainippon Ink & Chem Inc | Flame retardant pressure sensitive adhesive and flame retardant pressure sensitive adhesive tape |
| JP2012031422A (en) * | 2011-09-30 | 2012-02-16 | Dic Corp | Flame-retarding pressure-sensitive adhesive, and flame-retarding pressure-sensitive adhesive tape |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4180844B2 (en) | 2002-06-06 | 2008-11-12 | 昭和電工株式会社 | Curable flame retardant composition, cured product thereof and production method thereof |
| US20080157915A1 (en) * | 2007-01-03 | 2008-07-03 | Ethan Lin | Flame retardant, electrically-conductive pressure sensitive adhesive materials and methods of making the same |
| CN104937063B (en) | 2013-01-31 | 2017-06-16 | 株式会社寺冈制作所 | Anti-flammability adhesive composition, flame-retarded heat-conducting adhesive composition and bonding sheet |
| JP6838800B2 (en) * | 2015-03-04 | 2021-03-03 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet and pressure-sensitive adhesive composition suitable for it |
| EP3561011A4 (en) * | 2016-12-22 | 2019-12-25 | Mitsubishi Chemical Corporation | Double-sided adhesive tape |
-
2019
- 2019-12-12 KR KR1020217014468A patent/KR102668134B1/en active Active
- 2019-12-12 WO PCT/JP2019/048655 patent/WO2020137573A1/en not_active Ceased
- 2019-12-12 CN CN201980071661.4A patent/CN112930379B/en active Active
- 2019-12-12 JP JP2020518826A patent/JP6743999B1/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07315817A (en) * | 1994-05-23 | 1995-12-05 | Chisso Corp | Production of ii type polyphosphoric acid ammonium fine particle |
| JPH111669A (en) * | 1997-06-16 | 1999-01-06 | Nitto Denko Corp | Flame retardant adhesive tape |
| JP2000230162A (en) * | 1999-02-10 | 2000-08-22 | Dainippon Ink & Chem Inc | Flame retardant pressure sensitive adhesive and flame retardant pressure sensitive adhesive tape |
| JP2012031422A (en) * | 2011-09-30 | 2012-02-16 | Dic Corp | Flame-retarding pressure-sensitive adhesive, and flame-retarding pressure-sensitive adhesive tape |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102668134B1 (en) | 2024-05-22 |
| CN112930379B (en) | 2023-10-27 |
| KR20210106414A (en) | 2021-08-30 |
| JP6743999B1 (en) | 2020-08-19 |
| JPWO2020137573A1 (en) | 2021-02-18 |
| WO2020137573A1 (en) | 2020-07-02 |
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