Classifications

• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
  • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
• • 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
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J11/08—Macromolecular additives
• • 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
  • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
  • C09J125/02—Homopolymers or copolymers of hydrocarbons
  • C09J125/04—Homopolymers or copolymers of styrene
  • C09J125/08—Copolymers of styrene
  • C09J125/10—Copolymers of styrene with conjugated dienes
• • 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
  • C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • 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
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S45/00—Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
  • F21S45/50—Waterproofing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • C09J2205/102—
• • C09J2205/114—
• • 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
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
• • 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
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
• • 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
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • 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
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/20—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by refractors, transparent cover plates, light guides or filters
  • F21S41/28—Cover glass
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/20—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by refractors, transparent cover plates, light guides or filters
  • F21S41/2805—Cover glass
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/20—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by refractors, transparent cover plates, light guides or filters
  • F21S41/29—Attachment thereof
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S8/00—Lighting devices intended for fixed installation
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
  • F21V31/00—Gas-tight or water-tight arrangements
  • F21V31/04—Provision of filling media

Definitions

• the present invention relates to a hot melt composition, particularly to the hot melt composition which can prevent deformation of the adhesive at a high temperature and can be easily removed when a lighting appliance is disassembled.
• a hot melt adhesive is used as a sealant for an automotive lighting appliance.
• the hot melt adhesive is required to have high sealing property to the automotive lighting appliance and to be removable from the lighting appliance in consideration of disassembly when the lighting appliance is repaired.
• moisture-curable hot melt adhesives have been used as sealing agents for a lighting appliance, it has been difficult to disassemble a lens and a housing part of the lighting appliance using these moisture-curable hot melt adhesives and thus they have not been suitable for recent LED type lighting appliance that requires internal repairs.
• a hot melt adhesive containing a styrene-based block copolymer has been used as a sealing agent for a lighting appliance in some cases.
• Patent Literature 1 discloses a hot melt adhesive composition containing a styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS) and a styrene-ethylene/propylene-styrene block copolymer (SEPS) as thermoplastic block copolymers.
• Patent Literature 2 discloses a hot melt composition comprising a styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS) and a styrene-ethylene/butylene-styrene block copolymer (SEBS).
• SEEPS styrene-ethylene-ethylene/propylene-styrene block copolymer
• SEBS styrene-ethylene/butylene-styrene block copolymer
• Patent Literature 1 Japanese Patent Laid-Open No. 2011-190287
• Patent Literature 2 Japanese Patent Laid-Open No. 2008-127473
• the hot melt adhesive composition described in Patent Literature 1 can not completely prevent deformation of the adhesive at a high temperature.
• the hot melt composition described in Patent Literature 2 has low disassembly property after aging test and failed to completely prevent deformation of the adhesive at a high temperature.
• a hot melt composition comprising a specific thermoplastic block copolymer and a hydrocarbon-based liquid softening agent having an aniline point of a high temperature is hard to deform at a high temperature, has sufficient adhesive strength to a lighting appliance or the like, and is easy to be removed, and thus they have completed the present invention.
• a hot melt composition comprising:
• A2 a styrene-ethylene/propylene block copolymer (SEP).
• thermoplastic composition according to any one of the above items 1 to 3, further comprising (C) a tackifier resin.
• the tackifier resin (C) comprises (C1) a tackifier resin having a softening point of 120° C. or more.
• thermoplastic composition according to any one of the above items 1 to 5, further comprising a carbonate component.
• thermoplastic composition according to any one of the above items 1 to 6, further comprising an acrylic component.
• a lighting appliance in which a lens part and a housing part are joined with the hot melt composition according to any one of the above items 1 to 7.
• a vehicle comprising the lighting appliance according to the above item 8.
• the hot melt composition of the present invention deformation hardly occurs and form maintaining property is high at a high temperature, and adhesion to a substrate is excellent. Moreover, it is possible to disassemble the lighting appliance and the like using the hot melt composition of the present invention.
• form maintaining property is defined as difficulty to deform a hot melt composition at a high temperature. That is, the hot melt composition with less deformation at a high temperature is more excellent in form maintaining property.
• the present invention relates to a hot melt composition
• a hot melt composition comprising (A) a thermoplastic block copolymer which is a copolymer of a vinyl-based aromatic hydrocarbon and a conjugated diene compound and (B) a hydrocarbon-based liquid softening agent.
• the thermoplastic block copolymer (A) which is a copolymer of a vinyl-based aromatic hydrocarbon and a conjugated diene compound comprises (A1) a styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS), and the hydrocarbon-based liquid softening agent (B) comprises (B1) a hydrocarbon-based oil having an aniline point of 135° C. or more.
• SEEPS styrene-ethylene-ethylene/propylene-styrene block copolymer
• B comprises (B1) a hydrocarbon-based oil having an aniline point of 135° C. or more.
• thermoplastic block copolymer (A) which is a copolymer of a vinyl-based aromatic hydrocarbon and a conjugated diene compound (hereinafter, simply described as “a thermoplastic block copolymer (A)” or “component (A)”) is a copolymer obtained by block copolmerization of a vinyl-based aromatic hydrocarbon and a conjugated diene compound (including copolymers in which the copolymers are further copolymerized).
• thermoplastic block copolymer (A) may be a block copolymer having a vinyl-based aromatic hydrocarbon block and a conjugated diene compound block (non-hydrogenated block copolymer), or a hydrogenated block copolymer in which the block copolymers are hydrogenated.
• the thermoplastic block copolymer (A) may be used alone or in combination of two or more.
• the “vinyl-based aromatic hydrocarbon” means an aromatic hydrocarbon compound having a vinyl group, and specific examples thereof include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene and vinylanthracene. Particularly, styrene is preferred. These vinyl-based aromatic hydrocarbons may be used alone or in combination of two or more.
• the “conjugated diene compound” means a diolefin compound having at least a pair of conjugated double bonds.
• Specific examples of the “conjugated diene compound” include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferred.
• These conjugated diene compounds may be used alone or in combination of two of more.
• non-hydrogenated block copolymer specific examples include those in which blocks based on the conjugated diene compounds are not hydrogenated.
• hydrogenated block copolymer specific examples include block copolymers in which all or a part of the blocks based on the conjugated diene compounds are hydrogenated.
• the hydrogenated ratio of the “hydrogenated block copolymer” is represented by the “hydrogenation ratio”.
• “Hydrogenation ratio” of the “hydrogenated block copolymer” refers to a ratio of double bonds converted to saturated hydrocarbon bonds by hydrogenation based on the total aliphatic double bonds contained in the blocks based on the conjugated diene compounds.
• the “hydrogenation ratio” may be measured by an infrared spectrophotometer, a nuclear magnetic resonance device and the like.
• the hydrogenation ratio of the styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS) is preferably 80% or more, and more preferably 90% or more.
• the weight average molecular weight (Mw) of the thermoplastic block copolymer (A) is not particularly limited, but it is preferably from 50,000 to 500,000, and more preferably 150,000 to 400,000. When the weight average molecular weight of the thermoplastic block copolymer (A) is within the above range, it is excellent in form maintaining property, shear adhesive strength and disassembly property. In the present specification, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC) using a calibration curve using monodisperse molecular weight polystyrene as a standard substance to convert molecular weight.
• GPC gel permeation chromatography
• a styrene content of the thermoplastic block copolymer (A) is not particularly limited, but it is preferably 5 to 50 wt %, and more preferably 10 to 40 wt %.
• the styrene content refers to the ratio of styrene block contained in the thermoplastic block copolymer (A).
• the hot melt composition is excellent in heat resistance.
• the thermoplastic block copolymer (A) comprises “(A1) a styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS)”, which is a hydrogenated block copolymer.
• SEEPS styrene-ethylene-ethylene/propylene-styrene block copolymer
• SEEPS styrene-ethylene-ethylene/propylene-styrene block copolymer
• A1 is a hydrogenated product of a block copolymer composed of a styrene-butadiene-isoprene-styrene.
• the SEEPS (A1) is swollen with a liquid softening agent such as process oil, imparts rubber elasticity to the hot melt composition, and can exhibit high heat-resistance, adhesion and strength as a sealing agent. During application of the hot melt composition, SEEPS exhibits fluidity as a thermoplastic resin by heating. Examples of commercial products of SEEPS include SEPTON 4033, SEPTON 4044, SEPTON 4055, SEPTON 4077 and SEPTON 4099 manufactured by Kuraray Co., Ltd.
• thermoplastic block copolymer (A) preferably comprises, in addition to the SEEPS (A1), “(A2) a styrene-ethylene/propylene block copolymer (SEP)” which is another hydrogenated block copolymer.
• the styrene-ethylene/propylene block copolymer (SEP) (A2) is a hydrogenated product of a block copolymer composed of styrene-isoprene. Since SEP is an A-B type hydrogenated block copolymer, the styrene block is present only at one terminal end and the conjugated diene compound is present at the other terminal end. The presence of the conjugated diene compound at the terminal end improves compatibility with a paraffinic process oil and makes it possible to impart a tack to the hot melt composition.
• styrene-ethylene/propylene block copolymer (SEP)(A2)
• SEP styrene-ethylene/propylene block copolymer
• PC polycarbonate
• ethylene/propylene block which is a block part of conjugated diene compounds
• PP polypropylene
• the SEP (A2) can contribute particularly to the stabilization of the adhesion strength between two plastic adherends having different polarities.
• examples of the commercial products of SEP include KRATON G1701, G1702HU manufactured by KRATON corporation and SEPTON 1001, SEPTON 1020 and the like manufactured by Kuraray Co., Ltd.
• the content of the SEEPS (A1) to the total amount of 100 parts by weight of the thermoplastic block copolymer (A) is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, further preferably 50 parts by weight or more, still further preferably 60 parts by weight or more and may be 100 parts by weight.
• the content of the component (A1) in the total amount of the hot melt composition is preferably about 3 to 20 wt %.
• thermoplastic block copolymer (A) comprises (A1) a styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS) and (A2) a styrene-ethylene/propylene block copolymer (SEP),
• SEEPS styrene-ethylene-ethylene/propylene-styrene block copolymer
• SEP styrene-ethylene/propylene block copolymer
• the blending amount of SEP (A2) is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, further preferably 30 to 70 parts by weight, based on 100 parts by weight of the SEEPS (A1).
• the hot melt composition is hard to deform at a high temperature, excellent in adhesion to the lighting appliance, and easy to be removed, furthermore, fogging resistance is improved and the lens can be prevented from being fogged.
• thermoplastic block copolymer (A) may contain other block copolymers (A3) within a range not adversely affecting the present invention.
• block copolymers (A3) include hydrogenated block copolymers other than (A1) SEEPS and (A2) SEP and non-hydrogenated block copolymers.
• thermoplastic block copolymer examples include a styrene-ethylene/propylene-styrene block copolymer (also referred to as “SEPS”) in which a styrene-isoprene-styrene block copolymer is hydrogenated, a styrene-ethylene/butylene-styrene copolymer (also referred to as “SEBS”) in which a styrene-butadiene-styrene block copolymer is hydrogenated.
• SEPS styrene-ethylene/propylene-styrene block copolymer
• SEBS styrene-ethylene/butylene-styrene copolymer
• non-hydrogenated block copolymer examples include styrene-isoprene-styrene block copolymer (also referred to as “SIS”) and styrene-butadiene-styrene block copolymer (also referred to as “SBS”).
• SIS styrene-isoprene-styrene block copolymer
• SBS styrene-butadiene-styrene block copolymer
• the content of the thermoplastic block copolymer (A) based on the total amount of the hot melt composition is preferably 3 wt % or more, more preferably from 4 wt % to 20 wt %, and further preferably from 4 wt % to 10 wt %.
• the hot melt composition is excellent in heat resistance, adhesion and strength.
• the shear adhesive strength of the hot melt composition does not become excessively high and disassembly is easy.
• a hydrocarbon-based liquid softening agent (also referred to simply as “component (B)”) is blended for the purpose of adjusting the melt viscosity of the hot melt composition, imparting flexibility and improving wettability to the adherend.
• the hydrocarbon-based liquid softening agent is mainly composed of carbon and hydrogen, and is in a liquid state at a room temperature (about 20° C.).
• the hydrocarbon-based liquid softening agent may have hetero atoms such as an oxygen atom, a nitrogen atom and a sulfur atom.
• hydrocarbon-based liquid softening agent examples include paraffinic, naphthenic or aromatic-based process oil, liquid resins such as liquid polybutene, liquid polybutadiene and liquid polyisoprene, liquid paraffin and olefin process oil.
• process oil examples include Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd.
• the hydrocarbon-based liquid softening agent (B) comprises “(B1) a hydrocarbon-based oil having an aniline point of 135° C. or more” (also simply referred to as “component (B1)”). Since the aniline point of the component (B1) is higher than aniline points of the oils generally used in ordinary hot melt compositions, the melt viscosity of the hot melt composition is increased. As a result, the hot melt composition of the present invention can maintain its form at a high temperature, deformation is suppressed, and excellent form maintaining property can be achieved.
• the upper limit of the aniline point of the hydrocarbon-based oil of component (B1) is not particularly limited, but it is preferably 170° C. or less.
• the aniline point is defined as the lowest temperature at which equal volumes of aniline and a sample are uniformly present as a solution thereof, which is determined by a test method such as a test tube method, a U-tube method, a thin film method, as described in JIS 2256, K 2520.
• the temperature is increased while the mixture of aniline and the sample are stirred to form a uniform and transparent solution.
• the temperature is lowered and then, the temperature at which turbidity begins is measured.
• the aniline point is related to the rubber swellability of lubricating oil and process oil. The lower the aniline point of an oil is, the higher the solubility of the oil is.
• the hydrocarbon-based oil of the component (B1) of the present invention has a high aniline point of 135° C. or more and a high molecular weight, it's volatility is low and affinity with a midblock part of the thermoplastic block copolymer (a block part based on a conjugated diene compound) is high.
• the lighting appliance sealed with a conventional hot melt adhesive When the lighting appliance sealed with a conventional hot melt adhesive is used for a long time, there has been a problem that an adhesion strength has become high due to volatilization of the oil in the composition and the like and thus disassembly property deteriorates.
• the adhesive strength of the hot melt composition since the component (B1) continues to permeate into the midblock part of the thermoplastic block copolymer (A), the adhesive strength of the hot melt composition does not continue to increase with time and thus stable disassembly property can be maintained even when used for a long time.
• the hot melt composition of the present invention comprising the thermoplastic block copolymer (A) and the oil (B1) having an aniline point of 135° C. or more, since the component (B1) has a high molecular weight, the viscosity of the hot melt composition can be increased and form maintaining property can be enhanced.
• the hot melt composition of the present invention comprises the hydrocarbon-based oil (B1) having an aniline point of 135° C. or more, it is particularly suitable for sealing materials for a lighting appliance of an automobile and the like and it is excellent in disassembly property when the lighting appliance is repaired. Further, it is possible to achieve long-term stable physical properties, and to achieve both of coating property and high form maintaining property. Thus, excellent performance can be exhibited.
• hydrocarbon-based oil (B1) having an aniline point of 135° C. or more examples include a process oil such as a paraffin oil derived from a paraffinic crude oil, an aromatic oil and a naphthene oil derived from a naphthenic crude oil, which have aniline points of 135° C. or more.
• a process oil such as a paraffin oil derived from a paraffinic crude oil, an aromatic oil and a naphthene oil derived from a naphthenic crude oil, which have aniline points of 135° C. or more.
• Commercial products thereof include Diana Process Oil PW-380.
• the component (B1) one type may be used alone or two or more types may be used in combination.
• the hydrocarbon-based liquid softening agent (B) may comprise (B2) other hydrocarbon-based liquid softening agents (also referred to as “component (B2)”) in addition to the hydrocarbon-based oil (B1) having an aniline point of 135° C. or more.
• the content of the component (B1) based on 100 parts by weight of the component (B) is preferably 30 parts by weight or more, more preferably 50 parts by weight or more, further preferably 60 parts by weight or more, and may be 100 parts by weight.
• the content of the component (B1) in the total amount of the hot melt composition is preferably about from 10 wt % to 70 wt %.
• the aniline point of other hydrocarbon-based liquid softening agents (B2) is preferably less than 135° C., more preferably 130° C. or less, and the lower limit is not particularly limited but is preferably 100° C. or more. Further, component (B2) is preferably a hydrocarbon-based oil.
• the hot melt composition comprises both of the component (B1) and the component (B2) because the composition having a relatively low viscosity and high coating property can be obtained.
• the content of the hydrocarbon-based liquid softening agent (B) in the total amount of the hot melt composition is preferably 30 wt % or more, more preferably 40 to 80 wt %, and further preferably 40 to 70 wt %.
• the hot melt composition is excellent in form maintaining property at a high temperature and disassembly property is excellent even after long-term use.
• the content is 80 wt % or less, suitable form maintaining property of the hot melt composition can be obtained.
• One embodiment of the hot melt composition of the present invention preferably further comprises (C) a tackifier resin (also referred to as “component (C)”).
• Component (C) preferably comprises “(C1) a tackifier resin having a softening point of 120° C. or more”.
• the softening point is a value measured by an automatic softening point apparatus (ring and ball type) according to the petroleum asphalt test based on JIS K 2207.
• the softening point of the tackifier resin is within the above range, the fluidity of the polymer composition of the present invention is stabilized.
• the content of the tackifier resin (C1) having a softening point of 120° C. or more based on 100 parts by weight of the component (C) is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, and may be 100 parts by weight.
• the hot melt composition of the present invention comprises the tackifier resin (C1) having a softening point of 120° C. or more, higher form maintaining property can be kept.
• the tackifier resin is not particularly limited, but examples thereof include a rosin resin, a terpene resin, a terpene phenol resin, an aromatic hydrocarbon modified terpene resin, a petroleum resin, a phenolic resin, an acrylic resin, a styrene-acrylic copolymer resin. From the viewpoint of adhesion, it is preferable that styrene-based tackifier resin is basically used with aromatic hydrocarbon-based terpene resin. Examples of commercial product thereof include Easttack series and Endex series manufactured by Eastman Corporation.
• the tackifier resin (C) may be used alone or in combination of two or more.
• the content of the tackifyier resin (C) based on the total amount of the hot melt composition may be 0 wt %, but it is preferably 20 wt % or more, more preferably 30 to 50 wt %, further preferably 30 to 40 wt %.
• the content of the component (C) is 20 wt % or more, the adhesive strength of the hot melt composition is increased.
• the content is 50 wt % or less, excellent disassembly property of the hot melt composition can be easily obtained.
• One embodiment of the hot melt composition of the present invention preferably further comprises a polycarbonate component.
• the adherend is a polycarbonate substrate
• adhesiveness to the lens part of the lighting appliance is enhanced by chemical affinity between the polycarbonate component and the adherend. That is, when the hot melt composition comprises the polycarbonate component, high adhesion to the polycarbonate can be obtained.
• the hot melt composition when adhesion to a polycarbonate substrate is high, the hot melt composition can be remained on the lens (polycarbonate) side when the light appliance is disassembled.
• the polycarbonate component may be any polymer containing a polycarbonate structure.
• the polycarbonate component may have a terminal OH group, and may be a polycarbonate diol having OH groups at both terminals. From the viewpoint of compatibility with the hot melt composition, a polycarbonate diol is preferred.
• the number average molecular weight (Mn) of the polycarbonate component is not particularly limited, but is preferably from 300 to 50,000, more preferably from 500 to 40,000, further preferably from 1,000 to 35,000.
• a polycarbonate diol having a relatively small molecular weight (for example, Mn is 5000 or less) as a liquid component is used, the wettability to the polycarbonate (PC) is improved and a higher adhesion effect can be obtained at the interface with the polycarbonate substrate.
• Examples of commercially available products of the polycarbonate component include DURANOL T4672, T5650J and T5652 manufactured by Asahi Kasei Chemicals Corporation, NIPPOLAN 982R manufactured by Nippon Polyurethane Industry Co., Ltd. and recycling PC manufactured by Kansai Chemicals Co., Ltd.
• the content of the polycarbonate component to the total amount of the hot melt composition may be 0 wt %, but it is preferably 3 to 15 wt %, and more preferably 4 to 10 wt %.
• One embodiment of the hot melt composition of the present invention preferably further comprises an acrylic component. Since the solubility parameter of the acrylic component is close to that of the polycarbonate which is a component of the lens of the lighting appliance, the adhesion of the hot melt composition to the polycarbonate is enhanced by the chemical affinity between the acrylic component and the polycarbonate.
• acrylic component examples include acrylic resins which are homopolymers or copolymers of one or more compounds selected from ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, isononyl acrylate, methyl methacrylate, n-butyl methacrylate, methyl acrylate, acrylic acid, acrylamide, acrylonitrile, glycidyl methacrylate and the like.
• the acrylic copolymer may further comprise a monomer unit based on styrene, vinyl acetate or the like.
• the acrylic component may have a low glass transition point or a high glass transition point.
• an acrylic resin in bead form having sharp molecular weight distribution are preferred because the hot melt composition containing this has excellent adhesion to the polycarbonate resin and has excellent form maintaining property at a high temperature due to the acrylic resin having a high glass transition temperature.
• Examples of commercially available products of the acrylic component include Dianal series manufactured by Mitsubishi Rayon Corporation.
• the content of the acrylic component to the total amount of the hot melt composition may be 0 wt %, preferably 3 to 20 wt % and more preferably 4 to 15 wt %.
• the hot melt composition of the present invention may comprise additives commonly used in hot melt compositions, and they are not particularly limited as long as the hot melt composition targeted by the present invention can be obtained.
• an additive for example, an antioxidant, a plasticizer, an ultraviolet absorber, a pigment, a rheology control agent, wax and the like may be added.
• antioxidant examples include phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants and amine-based antioxidant.
• plasticizer examples include a phthalate ester-based plasticizer, an alkylsulfonic acid-based plasticizer, an adipate ester-based plasticizer, an acetate-based plasticizer, a phosphate ester-based plasticizer and the like.
• Examples of the “ultraviolet absorber” include benzotriazole, hindered amine, benzoate, benzotriazole and the like.
• pigment examples include carbon black, titanium oxide and the like.
• rheology control agent examples include fatty acid amide, fumed silica and the like.
• examples of commercial products of the fatty acid amide include A-S-A T-1700, A-S-A T-1800 and the like manufactured by Itoh Oil Chemicals Co., Ltd.
• waxes such as paraffin wax and microcrystalline wax.
• the hot melt composition of the present invention is produced by blending the above-mentioned components in a predetermined ratio, blending various additives as necessary, and mixing with heating and melting. Specifically, the above components were charged into a melt-mixing pot equipped with a stirrer and were mixed with heating to prepare the product.
• the method of using the hot melt composition of the present invention is not particularly limited.
• the hot melt composition of the present invention is melted by heating to 180 to 215° C. and is applied to an adherend (for example, a first member and/or a second member).
• the material of the second member may be the same as or different from that of the first member.
• a method may be exemplified in which the first member and the second member are joined to form a joined body when the hot melt composition is in a molten state, and then it is allowed to solidify under room temperature (about 20° C. to 25° C.) condition.
• various applicators may be used.
• adherend to which the composition of the present invention may be applied examples include plastics (for example, polyolefin such as polypropylene; polycarbonate; acrylic resin; PET resin), wood, rubber, glass and metal. It is exemplified as a preferred embodiment to use for adhesion of polycarbonate resins or acrylic resins; or adhesion between polycarbonate resin or acrylic resin and polypropylene.
• plastics for example, polyolefin such as polypropylene; polycarbonate; acrylic resin; PET resin), wood, rubber, glass and metal. It is exemplified as a preferred embodiment to use for adhesion of polycarbonate resins or acrylic resins; or adhesion between polycarbonate resin or acrylic resin and polypropylene.
• the hot melt composition of the present invention is also suitable for joining two plastics of different polarity such as joining PP (polypropylene) and PC (polycarbonate).
• the hot melt composition according to the present invention may be used as industrial sealing agents such as for sealing electronic and electric components, automobile components, vehicle components and the like, and it is preferably used for a lighting appliance.
• One embodiment of the present invention relates to a lighting appliance produced by using the above hot melt composition.
• the lighting appliance include lighting appliance for automotive lamps (for example, headlamps, rear combination lamps and the like) and lighting appliance for two-wheeled vehicles (motorbikes and the like).
• the composition of the present invention may be used for sealing (bonding) the lens and the housing of the automotive lighting appliance.
• the materials of the lens and the housing are not particularly limited.
• the material of the lens include a transparent resin such as polycarbonate, acrylic resin (PMMA: polymethyl methacrylate resin) and PET, glass, or the like.
• the material of the housing include polyolefin such as polypropylene. Since the lighting appliance of the present invention is manufactured by using the above hot melt composition, for example, the inspection time after the lens and the housing of the automotive lighting appliance are adhered is shortened and the lens is not fogged.
• hot melt composition of the present invention may be used for joining waterproof packing parts of household appliances such as washing machines, dryers and refrigerators.
• the present invention also relates to a vehicle having a lighting appliance manufactured by using the above hot melt composition. Since the vehicle of the present invention has a lighting appliance manufactured by using the hot melt composition, the lighting appliance is not peeled off by heat or impact and the lens is not fogged, thereby allowing for safer travelling.
• the vehicle according to the present invention is not particularly limited as long as it has the above lighting appliance. Specific examples of the vehicle include vehicles according to the Road Traffic Law such as railroad vehicles such as an electric railcar, a railroad car and a train, military vehicles such as a tank and an armored car, motor vehicles, motor bicycles (motorcycles), buses, and streetcars.
• a hot melt composition was poured into a polypropylene groove having a depth of 12 mm, a width of 7 mm and a length of 14 mm and left to stand in a dryer at 130° C. for 24 hours at an angle of 70°, and the moving distance of the lower tip of the hot melt composition (i.e. the distance flowed out from the state immediately after being applied) was measured.
• the evaluation criteria based on the moving distance are shown below.
• melt viscosity For the melt viscosity, hot melt compositions were heated and melted, and viscosities in a molten state were measured at 210° C., 200° C., 190° C. and 180° C. respectively at a rotation speed of 1 rpm using a rotational viscometer manufactured by Brookfield Corporation. The spindle was attached to the viscometer, the spindle was rotated, and the lowest value after 30 minutes from the start of heating was measured. Rotor No. 27 was used as the spindle.
• the shear test piece was set on a tensile tester (Tensilon® 250 type) and subjected to a tensile test at a tension speed of 50 mm/min at a temperature of 23° C. (room temperature), and the maximum load was measured.
• the maximum load (N) was defined as shear adhesion strength. When the maximum load was 2.0 N or more and 6.0 N or less, it was judged that both PC adhesion and disassembly were obtained, and when it was smaller than 2.0 N, it was judged that adhesion was insufficient.
• the initial disassembly property was determined by failure mode in a shear test.
• failure mode of the hot melt composition on the polycarbonate plate was an interface failure (also referred to as adhesion failure/“AF”), no material remained on the adhesion surface and it was judged that disassembly was OK.
• failure mode of the adhesive on the polycarbonate plate was cohesive failure even partially (also referred to as cohesive failure/“CF”), it was judged that there was a problem with disassembly because the adhesive remains on the polycarbonate at the time of being disassembled.
• the evaluation criteria are shown in Table 2.
• the shear test piece was taken out from the heat-resistant cycle oven.
• the shear test piece was set on a tensile tester (Tensilon® 250 type) and subjected to a tensile test at a tension speed of 50 mm/min to measure the maximum load.
• the maximum load (N) was defined as shear adhesion.
• the strength change ratio was calculated from the initial shear adhesion strength and the shear adhesion strength after the heat-resistant cycle test by the following formula.
• Strength change ratio (%) 100 ⁇ (Shear adhesion after heat-resistant cycle test ⁇ Initial shear adhesion strength)/Initial shear adhesion strength
• Disassembly property after heat-resistant cycle test was determined by failure mode in a shear test in the same way as the initial evaluation.
• failure mode of the hot melt composition on the polycarbonate plate was an interface failure (adhesion failure/AF)
• no material remained on the adhesion surface and it was judged that disassembly was OK.
• failure mode was AF and the strength change ratio was 20% or less, it was judged that it can be disassembled after a heat-resistant cycle test or after a long-term test expected in actual vehicle use.
• the hot melt composition melted at 190° C. was placed in a cartridge and applied to a release paper in a 2 mm bead shape using a hot melt gun (Heat Gun TR80 model manufactured by REKA Klebetechnik GmbH & Co. KG).
• the above adhesive was cut and 1 g of it was put into a 110 ml glass bottle (screw bottle No. 8 manufactured by AS ONE Co., Ltd. having a height of 120 mm, a diameter of 21 mm, a center part outside diameter of 40 mm), covered with a polycarbonate plate and a weight was placed thereon.
• the glass bottle containing the adhesive, the polycarbonate plate and the weight were placed in an oil bath (Heating Bath B-491 manufactured by BUCHI Co., Ltd.).
• the silicone oil in the oil bath was heated, it was confirmed that the temperature reached 90° C., and heating was carried out for 24 hours. After heating for 24 hours, the glass bottle, the polycarbonate plate and the weight were taken out from the oil bath and left to stand until room temperature was reached. Thereafter, the weight was removed, and the deposit on the polycarbonate plate was observed.
• Evaluation criteria for fogging resistance test are as follows.
• the hot melt compositions of the Examples strength change ratio was small even after the heat-resistant cycle test and stable disassembly was obtained. Accordingly, if the hot melt composition of the present invention is used for a lighting appliance, stable disassembly can be obtained after long-term use. Furthermore, the hot-melt compositions of the Examples had high fogging resistance and no fogging of the lens due to heating occurred.
• the present invention provides a hot melt composition used for bonding a lens and a housing for automotive lighting appliance.
• a sealing part can be easily disassembled for replacement or maintenance of electrical components in a lighting appliance represented by a light emitting diode.
• the hot melt composition according to the present invention can satisfy high adhesion to a polycarbonate resin which is required for sealing applications, high disassemble property required for repair and maintenance, and removing requirement from polycarbonate which is demand on workability at disassembling after even long-term use.

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