WO2024095878A1 - Modificateur pour résine thermoplastique, composition de résine, application associée à une résine hydrocarbonée aromatique hydrogénée, agent poisseux, et composition de colle ou adhésif - Google Patents

Modificateur pour résine thermoplastique, composition de résine, application associée à une résine hydrocarbonée aromatique hydrogénée, agent poisseux, et composition de colle ou adhésif Download PDF

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WO2024095878A1
WO2024095878A1 PCT/JP2023/038644 JP2023038644W WO2024095878A1 WO 2024095878 A1 WO2024095878 A1 WO 2024095878A1 JP 2023038644 W JP2023038644 W JP 2023038644W WO 2024095878 A1 WO2024095878 A1 WO 2024095878A1
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mass
parts
resin
aromatic hydrocarbon
hydrogenated aromatic
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PCT/JP2023/038644
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English (en)
Japanese (ja)
Inventor
尚樹 釜谷
雄吾 佐俣
陽水 山口
幸泰 西岡
徹也 柏原
慶輝 張
翼 伊藤
昭寛 川端
功基 柴地
隆 中谷
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荒川化学工業株式会社
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Publication of WO2024095878A1 publication Critical patent/WO2024095878A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a modifier for thermoplastic resins, a resin composition, the use of hydrogenated aromatic hydrocarbon resins, a tackifier, and a pressure-sensitive adhesive composition.
  • Hydrogenated aromatic hydrocarbon resins such as aromatic petroleum resins and pure monomer resins (hydrogenated aromatic hydrocarbon resins) are widely used as modifiers for thermoplastic resins such as polyolefin resins and engineering plastics, tackifiers for adhesives such as hot melts and pressure-sensitive adhesives, and binder resins for paints and inks.
  • thermoplastic resins are used in various industrial fields, and among them, engineering plastics and super engineering plastics are widely used as automobile materials, electrical and electronic equipment materials, and housing and building materials due to their excellent balance of heat resistance and strength.
  • the above thermoplastic resins, particularly engineering plastics and super engineering plastics often have high molding temperatures and poor melt fluidity, so additives such as lubricants are usually added to the thermoplastic resins to reduce the apparent flow viscosity during melting and improve molding processability (Patent Documents 1 and 2).
  • the above-mentioned adhesives and pressure-sensitive adhesives are primarily composed of base polymers such as acrylic polymers, rubber-based elastomers (natural rubber, synthetic rubber), and ethylene-vinyl acetate copolymers.
  • base polymers such as acrylic polymers, rubber-based elastomers (natural rubber, synthetic rubber), and ethylene-vinyl acetate copolymers.
  • these adhesives are used as compositions containing tackifiers such as rosin esters, various petroleum resins, and terpene resins (Patent Document 3).
  • thermoplastic resins particularly engineering plastics and super engineering plastics, have high melting points of approximately 200°C or higher, and are melted at high temperatures (250°C or higher).
  • the addition of conventional lubricants can cause smoke during melting.
  • adhesives and pressure-sensitive adhesives do not have sufficient adhesive strength even when conventional tackifiers are used. Furthermore, adhesives and pressure-sensitive adhesives that use conventional tackifiers may emit an odor during production and use.
  • the present invention aims to provide a novel modifier for thermoplastic resins that can suppress smoke generation during melting of the thermoplastic resin and improve the molding processability of the thermoplastic resin.
  • the present invention also aims to provide a novel tackifier that can suppress odors in adhesives and provide high adhesive strength to adhesives and adhesives.
  • thermoplastic resins that contains a hydrogenated aromatic hydrocarbon resin that has a high mass retention rate after heating at 300°C for two hours and a specific mixed methylcyclohexaneaniline cloud point (MMAP).
  • MMAP mixed methylcyclohexaneaniline cloud point
  • the inventors have also discovered that the above problem can be solved by using a tackifier that contains a hydrogenated aromatic hydrocarbon resin that has a high mass retention rate after heating at 300°C for two hours and a specific mixed methylcyclohexaneaniline cloud point (MMAP).
  • MMAP mixed methylcyclohexaneaniline cloud point
  • the present invention has been made to solve at least some of the problems described above, and can be realized in the following aspects or application examples.
  • (Item 2) A resin composition comprising the modifier according to item 1 and a thermoplastic resin.
  • the mass retention rate after heating at 300° C. for 2 hours is 64% by mass or more
  • the mixed methylcyclohexaneaniline cloud point (MMAP) is 5° C. or more and less than 40° C. Hydrogenated aromatic hydrocarbon resins, Tackifier.
  • a pressure-sensitive adhesive composition comprising the tackifier according to item 5 and a base polymer.
  • the range of the values of each physical property, content, etc. may be set as appropriate (for example, by selecting from the values described in each item below).
  • the range of the value ⁇ may be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A
  • Modifier for thermoplastic resin The present disclosure relates to a modifier for thermoplastic resins (hereinafter also referred to as modifier), which contains a hydrogenated aromatic hydrocarbon resin (hereinafter also referred to as hydrogenated aromatic hydrocarbon resin) having a mass retention rate (hereinafter also referred to as mass retention rate) of 64 mass% or more after heating at 300°C for 2 hours and a mixed methylcyclohexaneaniline cloud point (MMAP) (hereinafter also referred to as MMAP) of 5°C or more and less than 40°C.
  • a hydrogenated aromatic hydrocarbon resin hereinafter also referred to as hydrogenated aromatic hydrocarbon resin having a mass retention rate (hereinafter also referred to as mass retention rate) of 64 mass% or more after heating at 300°C for 2 hours and a mixed methylcyclohexaneaniline cloud point (MMAP) (hereinafter also referred to as MMAP) of 5°C or more and less than 40°C.
  • MMAP mixed methylcyclohexaneaniline
  • the above modifiers function to improve the fluidity of the thermoplastic resin when melted (fluidity improvers).
  • the hydrogenated aromatic hydrocarbon resin is not particularly limited as long as it is a hydrogenated aromatic hydrocarbon resin having a mass residual ratio and MMAP within the above range, and various known hydrogenated aromatic hydrocarbon resins can be used.
  • the hydrogenated aromatic hydrocarbon resins may be used alone or in combination of two or more.
  • aromatic hydrocarbon resin examples include aromatic petroleum resins and pure monomer resins.
  • the aromatic hydrocarbon resins may be used alone or in combination of two or more.
  • the aromatic petroleum resins include, for example, C9 petroleum resins obtained from C9 petroleum fractions of naphtha, and copolymers obtained by polymerizing the C9 petroleum resins alone or in combination.
  • C9 petroleum fractions include aromatic compounds with 8 carbon atoms such as styrene; aromatic compounds with 9 carbon atoms such as ⁇ -methylstyrene, ⁇ -methylstyrene, vinyltoluene, and indene; aromatic compounds with 10 carbon atoms such as 2-isopropenyltoluene, 4-isopropenyltoluene, 1-methylindene, 2-methylindene, and 3-methylindene; aromatic compounds with 11 carbon atoms such as 2,3-dimethylindene and 2,5-dimethylindene; and mixtures of these.
  • the pure monomer resins mentioned above include, for example, resins obtained by polymerizing polymerizable monomers (styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene, indene) obtained by refining the above C9 petroleum fraction through cationic polymerization, radical polymerization, etc.
  • polymerizable monomers styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene, indene
  • the method for producing the aromatic hydrocarbon resin is not particularly limited, but examples include a method in which raw materials such as petroleum fractions and polymerizable monomers are cationic polymerized in the presence of a Friedel-Crafts catalyst such as aluminum chloride or boron trifluoride.
  • a Friedel-Crafts catalyst such as aluminum chloride or boron trifluoride.
  • the hydrogenated aromatic hydrocarbon resin is preferably a hydrogenated aromatic petroleum resin.
  • Examples of the mass residual rate of the hydrogenated aromatic hydrocarbon resin include 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 78 mass%, 77 mass%, 76 mass%, 75 mass%, 74 mass%, 73 mass%, 72 mass%, 71 mass%, 70 mass%, 69 mass%, 68 mass%, 67 mass%, 66 mass%, 65 mass%, and 64 mass%, etc.
  • the mass residual ratio of the hydrogenated aromatic hydrocarbon resin is preferably 64% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass, from the viewpoint of suppressing smoke generation during melting of the thermoplastic resin.
  • the mass retention rate is measured by the method described in the Examples below.
  • thermoplastic resins particularly engineering plastics and super engineering plastics
  • the molding temperature of thermoplastic resins is often 250°C or higher.
  • the present inventors have hypothesized that when hydrogenated aromatic hydrocarbon resins are used as thermoplastic resins and emit smoke when melted, the hydrogenated aromatic hydrocarbon resins have many components that can volatilize and structures that can thermally decompose at the molding temperature, and therefore the smoke is generated by the volatile components and thermal decomposition products.
  • the present inventors have evaluated the mass retention rate of hydrogenated aromatic hydrocarbon resins under harsh conditions of heating at a temperature (300°C) equal to or higher than the molding temperature for a long period of time (2 hours), and have found that those with a mass retention rate of 64% or more have few such components and structures, and therefore suppress smoke generation even when used in the molding of thermoplastic resins.
  • the inventors since it is difficult to specify the details of hydrogenated aromatic hydrocarbon resins, such as the components that may volatilize at molding processing temperatures and the structures that may thermally decompose, the inventors have specified hydrogenated aromatic hydrocarbon resins that can suppress smoke generation when the thermoplastic resin is melted by defining the hydrogenated aromatic hydrocarbon resins based on the above mass residual ratio.
  • the heating conditions are mild, making it difficult to properly evaluate the tendency of hydrogenated aromatic hydrocarbon resins to emit smoke when the thermoplastic resin is melted.
  • the thermoplastic resin emits smoke when melted, the smoke causes equipment and mold contamination, but when the heating time is shorter than 2 hours, it is difficult to properly evaluate the degree of contamination because it is not possible to reflect the equipment and mold contamination that occurs in actual molding processing.
  • the mass residual ratio of the hydrogenated aromatic hydrocarbon resin is less than 64 mass%, when it is used in a thermoplastic resin, it tends to emit a lot of smoke when melted.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin may be, for example, 39°C, 38°C, 37°C, 36°C, 35°C, 34°C, 33°C, 32°C, 31°C, 30°C, 29°C, 28°C, 27°C, 26°C, 25°C, 24°C, 23°C, 22°C, 21°C, 20°C, 19°C, 18°C, 17°C, 16°C, 15°C, 14°C, 13°C, 12°C, 11°C, 10°C, 9°C, 8°C, 7°C, 6°C, or 5°C.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin is preferably 5°C or more and less than 40°C, more preferably 5°C to 35°C, and even more preferably 5°C to 20°C, in order to improve the fluidity of the thermoplastic resin when melted.
  • MMAP is measured by the method described in the Examples below.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin indicates the aromatic characteristics of the hydrogenated aromatic hydrocarbon resin. If the proportion of aromatic parts in the hydrogenated aromatic hydrocarbon resin is high, the MMAP tends to be low, and if the proportion of aromatic parts is low, the MMAP tends to be high.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin is less than 5°C, or if the MMAP is 40°C or higher, the flowability of the thermoplastic resin when melted tends to decrease.
  • the hydrogenated aromatic hydrocarbon resin is not particularly limited in terms of physical properties other than the mass residual rate and MMAP.
  • Examples of the color tone of the hydrogenated aromatic hydrocarbon resin include 400 Hazen, 350 Hazen, 300 Hazen, 250 Hazen, 200 Hazen, 150 Hazen, 100 Hazen, 95 Hazen, 90 Hazen, 85 Hazen, 80 Hazen, 75 Hazen, 70 Hazen, 65 Hazen, 60 Hazen, 55 Hazen, 50 Hazen, 45 Hazen, 40 Hazen, 35 Hazen, 30 Hazen, 25 Hazen, 20 Hazen, 15 Hazen, 10 Hazen, and 5 Hazen.
  • the color tone of the hydrogenated aromatic hydrocarbon resin is preferably about 10 to 400 Hazen, more preferably about 10 to 200 Hazen, in terms of suppressing coloration. In this disclosure, color tone is measured in Hazen units according to JIS K 0071-1, and in Gardner units according to JIS K 0071-2.
  • the weight average molecular weight of the above hydrogenated aromatic hydrocarbon resin may be, for example, 4,000, 3,900, 3,800, 3,700, 3,600, 3,500, 3,400, 3,300, 3,200, 3,100, 3,000, 2,900, 2,800, 2,700, 2,600, 2,500, 2,400, 2,300, 2,200, 2,100, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 900, etc.
  • the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is preferably 900 or more, more preferably 1,000 or more, from the viewpoint of further suppressing smoke generation when the thermoplastic resin is melted.
  • the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is preferably about 900 to 4,000, more preferably about 1,000 to 3,000, and even more preferably about 1,000 to 2,100, from the viewpoint of further suppressing smoke generation when the thermoplastic resin is melted and further improving the fluidity of the thermoplastic resin when melted.
  • the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the aromatic hydrogen content of the hydrogenated aromatic hydrocarbon resin may be, for example, 39%, 38%, 37%, 36%, 35%, 34%, 33%, 32%, 31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, etc.
  • the aromatic hydrogen content is preferably less than 40%, more preferably 37% or less, in order to further suppress smoke generation during melting of the thermoplastic resin.
  • the content of the aromatic hydrogen is preferably 10% or more and less than 40%, more preferably about 10 to 37%, and even more preferably 16 to 37%, from the viewpoint of further suppressing smoke generation when the thermoplastic resin is melted and further improving the fluidity of the thermoplastic resin when it is melted.
  • the aromatic hydrogen refers to a hydrogen atom covalently bonded to an aromatic ring in the hydrogenated aromatic hydrocarbon resin.
  • the aromatic hydrogen content is determined by NMR measurement and calculated based on the total H-spectrum area of 1H -NMR in the hydrogenated aromatic hydrocarbon resin and the H-spectrum area derived from the aromatic ring appearing at about 7 ppm in the 1H -NMR, according to the following formula (1):
  • Aromatic hydrogen content (H-spectrum area originating from aromatic ring appearing at about 7 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100(%) (1)
  • the olefin content of the hydrogenated aromatic hydrocarbon resin may be, for example, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0%.
  • the olefin content is preferably about 0 to 1.0%, more preferably about 0 to 0.5%, and even more preferably 0%, in order to further suppress coloration of the thermoplastic resin when melted.
  • olefin refers to the olefinic double bonds contained in the hydrogenated aromatic hydrocarbon resin, and does not include carbon-carbon double bonds in the aromatic ring.
  • the olefin content is determined by an NMR measurement method, and is calculated based on the total H-spectrum area of 1H -NMR in the hydrogenated aromatic hydrocarbon resin and the H-spectrum area derived from an olefinic double bond appearing at 5 to 6 ppm in the 1H -NMR, according to the following formula (2).
  • Olefin content (H-spectrum area derived from olefinic double bonds appearing at 4 to 6 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100(%) (2)
  • the hydrogenated aromatic hydrocarbon resin can be obtained by any of various known means. Specifically, for example, the hydrogenated aromatic hydrocarbon resin can be obtained by hydrogenating any of various known aromatic hydrocarbon resins under known hydrogenation conditions.
  • aromatic hydrocarbon resin examples include the aromatic petroleum resin and the pure monomer resin.
  • the hydrogenation conditions include, for example, a method in which the aromatic hydrocarbon resin is heated to about 200 to 350°C in the presence of a hydrogenation catalyst at a hydrogen partial pressure of about 0.2 to 30 MPa.
  • a hydrogenation catalyst include metals such as nickel, palladium, cobalt, ruthenium, platinum, and rhodium, and oxides of these metals.
  • the amount of the hydrogenation catalyst used is preferably about 0.01 to 10 parts by mass per 100 parts by mass of the raw material resin.
  • the above hydrogenation is carried out with the aromatic hydrocarbon resin melted or dissolved in a solvent.
  • the solvent for dissolving the petroleum resin is not particularly limited, but any solvent that is inert to the reaction and easily dissolves the raw materials and products may be used.
  • cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. can be used alone or in combination of two or more.
  • the amount of solvent used is usually 10% by mass or more of solids relative to the petroleum resin, and preferably 10 to 70% by mass. Note that the above hydrogenation conditions are described for a batch-type reaction format, but a flow-type reaction format (fixed bed type, fluidized bed type, etc.) can also be used.
  • the content of aromatic hydrogen in the hydrogenated aromatic hydrocarbon resin can be appropriately set by adjusting the hydrogenation rate of the aromatic rings of the aromatic hydrocarbon resin. Specifically, the higher the hydrogenation rate of the aromatic rings, the lower the content of aromatic hydrogen, and the lower the hydrogenation rate of the aromatic rings, the higher the content of aromatic hydrogen.
  • the weight average molecular weight of the above aromatic hydrocarbon resins may be, for example, 4,000, 3,900, 3,800, 3,700, 3,600, 3,500, 3,400, 3,300, 3,200, 3,100, 3,000, 2,900, 2,800, 2,700, 2,600, 2,500, 2,400, 2,300, 2,200, 2,100, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 900, etc.
  • the weight average molecular weight of the aromatic hydrocarbon resin is preferably 900 or more, more preferably 1,000 or more, because the mass residual rate of the hydrogenated aromatic hydrocarbon resin is high.
  • the weight average molecular weight of the aromatic hydrocarbon resin is preferably about 900 to 4,000, more preferably about 1,000 to 3,000, and even more preferably about 1,000 to 2,500, because the mass residual rate of the hydrogenated aromatic hydrocarbon resin is high.
  • the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the hydrogenated aromatic hydrocarbon resin may contain any of various known additives, provided that the effects of the present invention are not impaired.
  • additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers.
  • the additives may be used alone or in combination of two or more.
  • the modifier may contain any of various known additives as long as the effects of the present invention are not impaired.
  • additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers.
  • the additives may be used alone or in combination of two or more.
  • the content of the additive is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the hydrogenated aromatic hydrocarbon resin.
  • thermoplastic resins (Use of modifiers for thermoplastic resins)
  • the above-mentioned modifier can be used for various known thermoplastic resins.
  • the thermoplastic resin may be used alone or in combination of two or more. Examples of the thermoplastic resin include those described below.
  • the above modifier is preferably used for a thermoplastic resin containing at least one selected from the group consisting of polyester, polycarbonate, and polyphenylene ether, and more preferably used for a thermoplastic resin containing at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and modified polyphenylene ether resin, in order to further improve the fluidity during melting.
  • the modifier contains the hydrogenated aromatic hydrocarbon resin, and is therefore preferably used for thermoplastic resins with high molding temperatures, particularly preferably for engineering plastics and super engineering plastics.
  • the amount of the modifier used is not particularly limited.
  • the amount of the modifier used may be 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the amount of the modifier used is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted and to suppress the generation of smoke when the thermoplastic resin is melted.
  • the amount of the modifier used is preferably about 0.1 to 20 parts by mass, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 8 parts by mass in order to improve the fluidity of the thermoplastic resin when melted and to suppress the generation of smoke when the thermoplastic resin is melted.
  • the amount of the modifier used may be, for example, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, 0.9 parts by weight, 0.8 parts by weight, 0.7 parts by weight, 0.6 parts by weight, 0.5 parts by weight, 0.4 parts by weight, 0.3 parts by weight, 0.2 parts by weight, 0.1 parts by weight, etc., per 100 parts by weight of the thermoplastic resin.
  • the amount of the modifier used is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when the thermoplastic resin is melted.
  • the amount of the modifier used is preferably about 0.1 to 20 parts by mass in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when the thermoplastic resin is melted, and is more preferably about 0.5 to 15 parts by mass, and even more preferably about 5 to 10 parts by mass.
  • the method of using the modifier is not particularly limited.
  • the modifier is added to a mixer together with a thermoplastic resin, and melt-kneaded in the mixer.
  • the mixer include a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc.
  • the temperature of the melt-kneading is not particularly limited, but is usually in the range of the melting point of the thermoplastic resin -30°C to the melting point +30°C.
  • the present disclosure relates to a resin composition
  • a resin composition comprising the above-mentioned modifier (or the above-mentioned hydrogenated aromatic hydrocarbon resin) and a thermoplastic resin.
  • thermoplastic resin is not particularly limited, and various known thermoplastic resins can be used.
  • the thermoplastic resins may be used alone or in combination of two or more.
  • thermoplastic resin examples include polyolefin resins, styrene resins, ABS resins, polyamides, polyesters, polycarbonates, polyacetals, phenoxy resins, polymethyl methacrylate resins, polyphenylene ethers, polyphenylene sulfides, polyamide-imides, polyimides, polyether-imides, liquid crystal polymers, polyether-ether ketones, polyether-sulfones, polysulfones, polyarylates, and fluororesins.
  • the polyolefin resin is not particularly limited, and various known polyolefin resins can be used.
  • the polyolefin resins may be used alone or in combination of two or more.
  • the polyolefin resins include, for example, homopolymers of ⁇ -olefins having about 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene; binary or ternary (co)polymers of the above-mentioned ⁇ -olefins; binary or ternary (co)polymers of the above-mentioned ⁇ -olefins with ⁇ -olefins having about 9 to 18 carbon atoms, conjugated dienes, non-conjugated dienes, unsaturated carboxylic acids, (meth)acrylic acid esters, vinyl acetate, and the like.
  • Examples of the ⁇ -olefins having about 2 to 18 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and 1-octadecene.
  • Examples of the conjugated dienes and non-conjugated dienes include butadiene, isoprene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene.
  • unsaturated carboxylic acids examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride.
  • the unsaturated carboxylic acids may be neutralized with a base or the like.
  • Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, etc. Two or more of these ⁇ -olefins, conjugated dienes, non-conjugated dienes, unsaturated carboxylic acids, and (meth)acrylic acid esters may be used.
  • the polyolefin resins include, for example, ethylene resins such as polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, and ethylene-1-octene copolymer; propylene resins such as polypropylene, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-4-methyl-1-pentene copolymer, and propylene-ethylene-1-hexene copolymer; 1-butene resins such as 1-butene homopolymer, 1-butene-ethylene copolymer, and 1-butene-propylene copolymer; and 4-methyl-1-pentene resins such as 4-methyl-1-pentene homopolymer and
  • the styrene-based resin is not particularly limited, and various known styrene-based resins can be used.
  • the styrene-based resins may be used alone or in combination of two or more.
  • styrene resin examples include resins obtained by polymerizing a styrene compound and, if necessary, other compounds copolymerizable therewith in the presence or absence of a rubber polymer.
  • styrene compound examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, and the like.
  • Examples of other compounds copolymerizable with the styrene compound include vinyl cyanide compounds, acrylic acid esters, methacrylic acid esters, epoxy group-containing methacrylic acid esters, maleimide compounds, ⁇ , ⁇ -unsaturated carboxylic acids and their anhydrides, and the like.
  • Examples of the rubber polymer include polybutadiene, polyisoprene, diene copolymers, copolymers of ethylene and ⁇ -olefins, copolymers of ethylene and unsaturated carboxylic acid esters, ethylene, propylene, and non-conjugated diene terpolymers, and acrylic rubbers.
  • the styrene-based compound, the other compound copolymerizable with the styrene-based compound, and the rubber polymer may be used alone or in combination of two or more.
  • the styrene-based resin is preferably polystyrene.
  • polyamide The polyamide is not particularly limited, and various known polyamides can be used. The polyamides may be used alone or in combination of two or more.
  • the polyamide is a resin made of a polymer having an amide bond, and is made from amino acids, lactams, or diamines and dicarboxylic acids as the main raw materials.
  • the polyamide may be a polyamide homopolymer or copolymer derived from these raw materials, either alone or in the form of a mixture. Two or more of these raw materials may also be used in combination.
  • amino acids examples include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid.
  • lactams examples include ⁇ -caprolactam and ⁇ -laurolactam.
  • diamines examples include aliphatic diamines, aromatic diamines, alicyclic diamines, etc.
  • examples of the aliphatic diamines include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-/2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, etc.
  • aromatic diamines examples include metaxylylene diamine, paraxylylene diamine, etc.
  • alicyclic diamines examples include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine.
  • Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
  • Examples of the aliphatic dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid.
  • Examples of the alicyclic dicarboxylic acids include hexahydroterephthalic acid and hexahydroisophthalic acid.
  • polyamide resins include, for example, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polyhexamethylene dodecamide (polyamide 612), and polyundecane amide (polyamide 11).
  • polycaproamide polyamide 6
  • polyhexamethylene adipamide polyamide 66
  • polypentamethylene adipamide polyamide 56
  • polytetramethylene adipamide polyamide 46
  • polyhexamethylene sebacamide polyamide 610
  • polypentamethylene sebacamide polyamide 510
  • polyhexamethylene dodecamide polyamide 612
  • polyundecane amide polyamide 11
  • polydodecanamide polyamide 12
  • polynonane terephthalamide polyamide 9T
  • polycaproamide/polyhexamethylene terephthalamide copolymer polyamide 6/6T
  • polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer polyamide 66/6T
  • polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer polyamide 6T/6I
  • polyhexamethylene terephthalamide/polydodecanamide copolymer polyamide 6T/12
  • polyhexamethylene adipamide/polyhexamethylene terephthalamide/polydodecanamide copolymer polyamide 6T/12
  • the polyamide is preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 9T, polyamide 6/66 copolymer, or polyamide 6/12 copolymer, and from the same viewpoint, more preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, or polyamide 9T.
  • polyester The polyester is not particularly limited, and various known polyesters can be used. The polyesters may be used alone or in combination of two or more.
  • the polyester may be a polymer or copolymer obtained by a condensation reaction of a polycarboxylic acid (or an ester-forming derivative thereof) and a polyhydric alcohol (or an ester-forming derivative thereof) as the main components, or a mixture thereof.
  • a polycarboxylic acid or an ester-forming derivative thereof
  • a polyhydric alcohol or an ester-forming derivative thereof
  • two or more types of polycarboxylic acids and polyhydric alcohols may be used in combination.
  • the polycarboxylic acids include, for example, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, tricarboxylic acids, and ester-forming derivatives thereof.
  • aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and 5-sodium sulfoisophthalic acid.
  • Examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid.
  • Examples of alicyclic dicarboxylic acids include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
  • Examples of tricarboxylic acids include trimellitic acid.
  • the polyhydric alcohols include, for example, aliphatic glycols, alicyclic diols, aromatic diols, trimethylolpropane, pentaerythritol, glycerol, and ester-forming derivatives thereof.
  • the aliphatic glycols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol.
  • the alicyclic diols include, for example, cyclopentanediol, cyclohexanediol, and hydrogenated bisphenol A.
  • the aromatic diols include, for example, bisphenol A ethylene oxide (1 mol to 100 mol) adducts, bisphenol A propylene oxide (1 mol to 100 mol) adducts, and xylene glycol.
  • polyesters examples include polybutylene terephthalate, polybutylene (terephthalate/isophthalate), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/5-sodium sulfoisophthalate), polybutylene (terephthalate/5-sodium sulfoisophthalate), polyethylene naphthalate, and polycyclohexanedimethylene terephthalate.
  • the polyester is preferably polybutylene terephthalate, polybutylene (terephthalate/adipate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/adipate), polyethylene naphthalate, or polycyclohexanedimethylene terephthalate, more preferably polyethylene terephthalate or polybutylene terephthalate.
  • the polycarbonate is not particularly limited, and various known polycarbonates can be used.
  • the polycarbonates may be used alone or in combination of two or more.
  • the polycarbonate may be, for example, one obtained by reacting an aromatic dihydroxy compound with a carbonate precursor.
  • the polycarbonate may be linear or may have a branched structure.
  • the aromatic dihydroxy compounds include, for example, bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxydiaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, hydroquinones, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, etc.
  • the aromatic dihydroxy compounds may be used alone or in combination of two or more.
  • bis(hydroxyaryl)alkanes examples include 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), tetrabromobisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)dec ...
  • Examples of the bis(hydroxyaryl)cycloalkane include 1,1-bis(4-hydroxyphenyl)cyclohexane (also known as bisphenol Z), 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclooctane, and 9,9-bis(4-hydroxyphenyl)fluorene.
  • 1,1-bis(4-hydroxyphenyl)cyclohexane also known as bisphenol Z
  • 1,1-bis(4-hydroxyphenyl)cyclopentane 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
  • 1,1-bis(4-hydroxyphenyl)cyclohexane 1,1-bis(4-hydroxyphenyl)cyclooctane
  • the dihydroxydiaryl ethers include, for example, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, etc.
  • the dihydroxydiaryl sulfides include, for example, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc.
  • the dihydroxydiaryl sulfoxides include, for example, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, etc.
  • the dihydroxydiaryl sulfones include, for example, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc.
  • the carbonate precursor may be, for example, a carbonyl halide, a carbonic acid diester, etc.
  • One type of carbonate precursor may be used alone, or two or more types may be used in combination.
  • the carbonyl halides include, for example, phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds.
  • the carbonyl halides may be used alone or in combination of two or more.
  • the above carbonic acid diesters include, for example, diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, and dinaphthyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, di-tert-butyl carbonate, and dicyclohexyl carbonate; biscarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.
  • One type of carbonic acid ester may be used alone, or two or more types may be used in combination.
  • polycarbonates can be produced, for example, by interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.
  • the polycarbonate may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), or a polyester carbonate resin copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Two or more of these polycarbonates may be used.
  • the polyphenylene ether is not particularly limited, and various known polyphenylene ethers can be used.
  • the polyphenylene ethers may be used alone or in combination of two or more.
  • the polyphenylene ether may be, for example, a homopolymer or copolymer consisting of a repeating unit represented by the following general formula (1):
  • R1, R2, R3, and R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group, or an aryl group which may have a substituent, and n represents the number of repetitions.
  • Examples of the homopolymer represented by the above general formula (1) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, etc.
  • copolymers examples include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol.
  • the method for producing the polyphenylene ether is not particularly limited, and can be obtained by using various known means. Specific examples include the production methods described in U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, JP-B-52-17880, and JP-B-63-152628, etc.
  • the polyphenylene ether may contain various other phenylene ether units as partial structures within the scope of the present invention.
  • the phenylene ether units include 2-(dialkylaminomethyl)-6-methylphenylene ether units and 2-(N-alkyl-N-phenylaminomethyl)-6-methylphenylene ether units.
  • a small amount of diphenoquinone or the like may be bonded to the main chain of the polyphenylene ether resin.
  • it may be a polyphenylene ether resin modified with maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, anhydrides thereof, or unsaturated dicarboxylic acids in which one or two of the two carboxyl groups are esterified, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, epoxidized natural fats and oils, unsaturated alcohols of the general formula CnH2n-3OH (n is a positive integer) such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadiene-3-ol, or unsaturated alcohols of the general formula CnH2n-5OH, CnH2n-7OH (n is a positive integer).
  • modified polyphenylene ether resins may be used alone or in combination of two or more.
  • the melting point of the modified polyphenylene ether resin is defined as the peak top temperature of the peak observed in a temperature-heat flow graph obtained when the temperature is raised at 20°C/min in measurement with a differential scanning calorimeter (DSC), and if there are multiple peak top temperatures, it is defined as the highest temperature among them.
  • the polyphenylene ether may contain resin components other than polyphenylene ether, such as aromatic vinyl polymers and polyamides.
  • aromatic vinyl polymers include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, and acrylonitrile-styrene copolymers.
  • the content of polyphenylene ether is typically 70% by mass or more, preferably 80% by mass or more, based on the total amount of polyphenylene ether and polystyrene.
  • modified polyphenylene ether resins include, for example, "Iupiace” (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, "NORYL” (registered trademark) manufactured by SABIC Corporation, and "Zylon” (registered trademark) manufactured by Asahi Kasei Corporation.
  • the polyphenylene sulfide is not particularly limited, and various known polyphenylene sulfides can be used.
  • the polycarbonate may be used alone or in combination of two or more kinds.
  • the polyphenylene sulfide can be obtained, for example, by reacting a polyhalogenated aromatic compound with a sulfidizing agent in a polar organic solvent.
  • polyhalogenated aromatic compound examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, and 1-methoxy-2,5-dichlorobenzene, with p-dichlorobenzene being preferred. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but it is preferred to use a p-dihalogenated aromatic compound as the main component.
  • Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.
  • Examples of the alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred.
  • Examples of the alkali metal hydrosulfides include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these, with sodium hydrosulfide being preferred.
  • These alkali metal sulfides and hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.
  • the sulfidizing agents may be used alone or in combination of two or more.
  • the sulfidizing agent may also be an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide; or an alkali metal sulfide prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide.
  • the alkali metal hydroxide is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, or a mixture of two or more of these
  • the alkaline earth metal hydroxide is, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, etc., and preferably sodium hydroxide.
  • the polyphenylene sulfide can be produced in high yields by recovering and post-treating. Specifically, it can be produced by the method of obtaining a polymer with a relatively small molecular weight described in JP-B-45-3368, or the method of obtaining a polymer with a relatively large molecular weight described in JP-B-52-12240 and JP-A-61-7332.
  • the polyphenylene sulfide resin obtained by the above method can be used after various treatments such as crosslinking/polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution, or activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, or a functional group-containing disulfide compound.
  • polyphenylene sulfide products include, for example, “TORELINA” (registered trademark) manufactured by Toray Industries, Inc., “DIC.PPS” (registered trademark) manufactured by DIC Corporation, and “DURAFIDE” (registered trademark) manufactured by Polyplastics Co., Ltd.
  • the liquid crystal polymer is not particularly limited, and various known liquid crystal polymers can be used.
  • the liquid crystal polymer may be used alone or in combination of two or more kinds.
  • the liquid crystal polymer may be, for example, a liquid crystal polyester or a liquid crystal polyester amide.
  • the liquid crystal polyester may be, but is not limited to, an aromatic polyester.
  • the liquid crystal polyester may be, for example, a fully aromatic polyester made using only aromatic compounds as raw material monomers.
  • the liquid crystal polyester amide may be, but is not limited to, an aromatic polyester amide.
  • the liquid crystal polyester amide may be, for example, a fully aromatic polyester amide made using only aromatic compounds as raw material monomers.
  • the liquid crystal polymer may be, for example, a polyester partially containing aromatic polyester or aromatic polyester amide in the same molecular chain.
  • the aromatic polyester is not particularly limited, but may be, for example, (1) Polyesters consisting essentially of one or more aromatic hydroxycarboxylic acids and their derivatives; (2) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) a polyester composed of one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof; (3) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (c) Polyesters composed of one or more of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.
  • the aromatic polyester amide is not particularly limited, but may be, for example, (1) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more of aromatic hydroxyamines, aromatic diamines, and derivatives thereof; (c) a polyesteramide comprising one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof; (2) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more of aromatic hydroxyamines, aromatic diamines, and derivatives thereof; (c) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (d) polyesteramides composed of one or more of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. Furthermore, a molecular weight modifier may be used in combination with the above-mentioned components, if necessary.
  • the aromatic hydroxycarboxylic acid may be, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, or 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, or
  • aromatic hydroxycarboxylic acids include alkyl, alkoxy, or halogen-substituted derivatives of aromatic hydroxycarboxylic acids such as 2-naphthoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxy
  • aromatic diols include, for example, aromatic diols such as 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxyterphenyl, hydroquinone, resorcinol, 2,6-naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)methane, as well as alkyl, alkoxy, or halogen-substituted aromatic diols such as chlorohydroquinone, methylhydroquinone, tert-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4-
  • aromatic dicarboxylic acids include, for example, aromatic dicarboxylic acids such as terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, and 1,6-naphthalenedicarboxylic acid, and alkyl, alk
  • aromatic hydroxyamine examples include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxybiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, and 4-amino-4'-hydroxydiphenyl sulfide.
  • aromatic diamine examples include 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N,N'-dimethyl-1,4-phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminodiphenyl sulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), and 4,4'-diaminodiphenyl ether (oxydianiline).
  • the aromatic polyester is more preferably an aromatic polyester having the aromatic hydroxycarboxylic acid as a constituent component. In one embodiment, the aromatic polyester amide is more preferably an aromatic polyester amide having the aromatic hydroxycarboxylic acid as a constituent component.
  • the method for producing the liquid crystal polymer is not particularly limited, and can be obtained by using various known means.
  • the liquid crystal polymer can be produced by known methods such as direct polymerization or transesterification using the above-mentioned raw material monomer compound (or a mixture of raw material monomers).
  • melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used.
  • a compound capable of forming an ester it may be used in the polymerization in its original form, or it may be modified from a precursor to a derivative capable of forming an ester using an acylating agent or the like in a stage prior to polymerization.
  • the acylating agent include carboxylic anhydrides such as acetic anhydride.
  • catalysts may be used in the polymerization.
  • the catalyst include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine.
  • the amount of catalyst used is usually about 0.001 to 1% by mass, and preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers.
  • the liquid crystal polymer is preferably a liquid crystal polyester, which provides a resin composition with excellent heat resistance and high strength, and more preferably a wholly aromatic polyester, which provides the same.
  • the thermoplastic resin in the resin composition preferably includes at least one selected from the group consisting of polyester, polycarbonate, and polyphenylene ether, and more preferably includes at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and modified polyphenylene ether resin, in view of excellent fluidity when the resin composition is melted.
  • the resin composition contains the above-mentioned modifier, which suppresses smoke generation during melting and provides excellent fluidity during melting, even when the molding temperature is high, for example, when engineering plastics or super engineering plastics are used as the thermoplastic resin.
  • the resin composition may optionally contain a filler.
  • the filler is not particularly limited, and various known fillers can be used.
  • the filler may be used alone or in combination of two or more.
  • the filler may be, for example, spherical, needle-like, fibrous, or plate-like.
  • the above-mentioned fillers include, for example, fibers, crystalline silica, fused silica, calcium silicate, silica sand, talc, kaolin, mica, clay, bentonite, sericite, calcium carbonate, magnesium carbonate, glass beads, glass flakes, glass microballoons, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes, metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes, etc.
  • Specific examples of metals constituting metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.
  • the fibers are not particularly limited and various known fibers can be used.
  • the fibers include glass fibers, alumina fibers, polyester fibers, polyamide fibers, polyimide fibers, polyvinyl alcohol modified fibers, polyvinyl chloride fibers, polyolefin (polyethylene, polypropylene) fibers, fluororesin fibers, polybenzimidazole fibers, acrylic fibers, phenolic fibers, polyamide fibers, aramid fibers, cellulose (nano) fibers, liquid crystal polymer (liquid crystal polyester, liquid crystal polyester amide) fibers, polyether ketone fibers, polyether sulfone fibers, polyphenylene ether fibers, polyphenylene sulfide fibers, and other organic fibers; and metal fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel.
  • the fibers may be used alone or in combination of two or more.
  • the fibers preferably include at least one type selected from the group consisting of glass fibers and organic fibers.
  • the filler preferably contains at least one selected from the group consisting of glass fiber and carbon powder, in order to provide the resin composition with excellent impact resistance.
  • the melt viscosity of the resin composition was very high due to the filler, which sometimes resulted in extremely poor moldability.
  • the resin composition of the present disclosure uses the above-mentioned modifier, which reduces the melt viscosity even when the resin composition contains the above-mentioned filler, resulting in excellent moldability.
  • the resin composition may contain any additives as long as the effects of the present invention are not impaired.
  • the additives include flame retardants, conductive agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration dampers, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, release agents, antistatic agents, plasticizers, colorants, dyes, foaming agents, foam inhibitors, coupling agents, inorganic pigments, organic pigments, flow improvers other than the hydrogenated aromatic hydrocarbon resins, and light stabilizers.
  • the content of the modifier in the resin composition is not particularly limited.
  • the content of the modifier in the resin composition is, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the content of the modifier in the resin composition is preferably 0.1 parts by mass or more relative to 100 parts by mass of the thermoplastic resin from the viewpoint of excellent fluidity when the resin composition is melted, and is preferably 20 parts by mass or less relative to 100 parts by mass of the thermoplastic resin from the viewpoint of excellent fluidity when the resin composition is melted and smoke generation when the resin composition is melted is more suppressed.
  • the content of the modifier in the resin composition is preferably about 0.1 to 20 parts by mass from the viewpoint of excellent fluidity when the resin composition is melted and smoke generation when the resin composition is melted is more suppressed, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 8 parts by mass.
  • the content of the modifier in the resin composition is not particularly limited.
  • the content of the modifier in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the content of the modifier in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted.
  • the content of the modifier in the resin composition is preferably about 0.1 to 20 parts by mass in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted, and is more preferably about 0.5 to 15 parts by mass, and even more preferably about 5 to 10 parts by mass.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is not particularly limited.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is preferably about 0.1 to 20 parts by mass in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted, and is more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 8 parts by mass.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is not particularly limited.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted.
  • the content of the hydrogenated aromatic hydrocarbon resin in the resin composition is preferably about 0.1 to 20 parts by mass, more preferably about 0.5 to 15 parts by mass, and even more preferably about 5 to 10 parts by mass in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted.
  • the content of the filler in the resin composition is not particularly limited.
  • the content of the filler in the resin composition may be, for example, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, 0 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin.
  • the content of the filler in the resin composition is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of thermoplastic resin, in view of superior fluidity when the resin composition is melted.
  • the content of the additive in the resin composition is not particularly limited.
  • the content of the additive in the resin composition may be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, 0.005 parts by mass, 0.001 parts by mass, etc., relative to 100 parts by mass of the resin composition.
  • the content of the additive in the resin composition is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the resin composition. In one embodiment, the content of the additive in the resin composition is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the resin composition.
  • the method for producing the resin composition is not particularly limited, and various known methods can be adopted.
  • the method for producing the resin composition includes, for example, a method in which the modifier (or the hydrogenated aromatic hydrocarbon resin), the thermoplastic resin, and, if necessary, the filler and the additives are mixed in advance using various mixers such as a tumbler mixer or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader.
  • the temperature of the melt-kneading is not particularly limited, but is usually in the range of the melting point of the thermoplastic resin -30 ° C to the melting point +30 ° C.
  • the use of the modifier or the hydrogenated aromatic hydrocarbon resin increases the fluidity of the resin composition when melt-kneaded, resulting in excellent productivity. Furthermore, in conventional resin compositions containing fillers, the filler makes the resin composition have a very high melt viscosity, which significantly reduces the fluidity when melt-kneaded. However, when the modifier or the hydrogenated aromatic hydrocarbon resin is used, the fluidity when melt-kneaded is increased, even in the production of a resin composition containing a filler.
  • the molded article of the present disclosure can be obtained by molding the resin composition by various known molding methods.
  • the shape of the molded article is not particularly limited and can be appropriately selected according to the use and purpose of the molded article, and examples thereof include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, polygonal, irregular, hollow, frame-like, box-like, and panel-like shapes.
  • the method for molding the molded body is not particularly limited, and any conventionally known molding method can be used. Specific examples include injection molding, injection compression molding, extrusion molding, stretch film molding, inflation molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), press molding, rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. Of these, it is preferable that molding is performed by injection molding. Examples of injection molding machines include well-known injection molding machines such as ultra-high speed injection molding machines and injection compression molding machines.
  • the above molded products can be used for a variety of purposes, including automobile parts, electrical and electronic parts, building materials, various containers, daily necessities, household goods, and sanitary products.
  • the hydrogenated aromatic hydrocarbon resin can be used as a modifier for a thermoplastic resin.
  • the flowability of the thermoplastic resin is improved when the thermoplastic resin is melted.
  • the thermoplastic resin is not particularly limited, and examples thereof include those mentioned above.
  • the hydrogenated aromatic hydrocarbon resin is preferably used as a modifier for a thermoplastic resin containing at least one selected from the group consisting of polyester, polycarbonate, and polyphenylene ether, from the viewpoint of further improving the fluidity during melting, and more preferably used as a modifier for a thermoplastic resin containing at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and modified polyphenylene ether resin.
  • the hydrogenated aromatic hydrocarbon resin is preferably used as a modifier for thermoplastic resins having high molding temperatures, particularly preferably for engineering plastics and super engineering plastics.
  • the amount of the hydrogenated aromatic hydrocarbon resin used as a modifier for the thermoplastic resin is not particularly limited. Examples of the amount of the hydrogenated aromatic hydrocarbon resin used include the amount of the modifier used described above.
  • the present disclosure relates to a tackifier comprising the hydrogenated aromatic hydrocarbon resin.
  • the tackifier is used in a pressure-sensitive adhesive (including a pressure-sensitive adhesive composition described below) to improve the adhesive strength of the pressure-sensitive adhesive.
  • the hydrogenated aromatic hydrocarbon resin in the tackifier is preferably a hydrogenated aromatic petroleum resin.
  • Examples of the mass residual rate of the hydrogenated aromatic hydrocarbon resin include 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 78 mass%, 77 mass%, 76 mass%, 75 mass%, 74 mass%, 73 mass%, 72 mass%, 71 mass%, 70 mass%, 69 mass%, 68 mass%, 67 mass%, 66 mass%, 65 mass%, and 64 mass%, etc.
  • the mass residual rate of the hydrogenated aromatic hydrocarbon resin is preferably 64 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass% from the viewpoint of suppressing odor in the pressure-sensitive adhesive or adhesive.
  • the mass retention rate is measured by the method described in the Examples below.
  • the inventors have found that when an odor is generated during the production and/or use of an adhesive, it is the tackifier used in the adhesive that emits such an odor, and have surprisingly found that the use of a hydrogenated aromatic hydrocarbon resin having a mass residual rate of 64% or more in the adhesive can suppress odor during the production and/or use of the adhesive. Although the details of how odor is suppressed in the adhesive are unclear, it is presumed that this is because hydrogenated aromatic hydrocarbon resins having a mass residual rate of 64% or more contain less volatile components that cause odor and/or decomposition products that are generated when heated during the production and use of the adhesive.
  • the heating temperature is lower than 300°C and/or the heating time is shorter than 2 hours at the above mass retention rate, the heating conditions are mild, making it difficult to properly evaluate the odor tendency in the manufacture and/or use of the adhesive for hydrogenated aromatic hydrocarbon resins.
  • the mass residual rate of the hydrogenated aromatic hydrocarbon resin is less than 64 mass%, when it is used in a pressure-sensitive adhesive, it tends to emit an odor during its production and/or use.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin may be, for example, 39°C, 38°C, 37°C, 36°C, 35°C, 34°C, 33°C, 32°C, 31°C, 30°C, 29°C, 28°C, 27°C, 26°C, 25°C, 24°C, 23°C, 22°C, 21°C, 20°C, 19°C, 18°C, 17°C, 16°C, 15°C, 14°C, 13°C, 12°C, 11°C, 10°C, 9°C, 8°C, 7°C, 6°C, or 5°C.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin is preferably 5°C or more and less than 40°C, more preferably 5°C to 35°C, and even more preferably 5°C to 20°C, in order to improve the adhesive strength of the adhesive.
  • MMAP is measured by the method described in the Examples below.
  • the MMAP of the hydrogenated aromatic hydrocarbon resin indicates the aromatic characteristics of the hydrogenated aromatic hydrocarbon resin. If the proportion of aromatic parts in the hydrogenated aromatic hydrocarbon resin is high, the MMAP tends to be low, and if the proportion of aromatic parts is low, the MMAP tends to be high.
  • the adhesive strength of the pressure-sensitive adhesive tends to decrease.
  • the hydrogenated aromatic hydrocarbon resin is not particularly limited in terms of physical properties other than the mass residual rate and MMAP.
  • Examples of the color tone of the hydrogenated aromatic hydrocarbon resin include 400 Hazen, 350 Hazen, 300 Hazen, 250 Hazen, 200 Hazen, 150 Hazen, 100 Hazen, 95 Hazen, 90 Hazen, 85 Hazen, 80 Hazen, 75 Hazen, 70 Hazen, 65 Hazen, 60 Hazen, 55 Hazen, 50 Hazen, 45 Hazen, 40 Hazen, 35 Hazen, 30 Hazen, 25 Hazen, 20 Hazen, 15 Hazen, 10 Hazen, and 5 Hazen.
  • the color tone of the hydrogenated aromatic hydrocarbon resin is preferably about 10 to 400 Hazen, more preferably about 10 to 200 Hazen, in terms of suppressing coloration.
  • color tones are measured in Hazen units according to JIS K 0071-1 and in Gardner units according to JIS K 0071-2.
  • the weight average molecular weight of the above hydrogenated aromatic hydrocarbon resin may be, for example, 4,000, 3,900, 3,800, 3,700, 3,600, 3,500, 3,400, 3,300, 3,200, 3,100, 3,000, 2,900, 2,800, 2,700, 2,600, 2,500, 2,400, 2,300, 2,200, 2,100, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 900, etc.
  • the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is preferably 900 or more, more preferably 1,000 or more, from the viewpoint of further suppressing odor in the adhesive/tackifier.
  • the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is preferably about 900 to 4,000, more preferably about 1,000 to 3,000, and even more preferably about 1,000 to 2,100, from the viewpoint of further suppressing odor in the adhesive/tackifier and further improving adhesive strength in the adhesive/tackifier.
  • the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the aromatic hydrogen content of the hydrogenated aromatic hydrocarbon resin may be, for example, 39%, 38%, 37%, 36%, 35%, 34%, 33%, 32%, 31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, etc.
  • the aromatic hydrogen content is preferably less than 40%, more preferably 37% or less, from the viewpoint of further suppressing the odor of the adhesive/adhesive and further improving the adhesive strength of the adhesive/adhesive.
  • the aromatic hydrogen content is preferably 10% or more and less than 40%, more preferably about 10 to 37%, and even more preferably 16 to 37%.
  • the aromatic hydrogen refers to a hydrogen atom that is covalently bonded to an aromatic ring in the hydrogenated aromatic hydrocarbon resin.
  • the aromatic hydrogen content is determined by NMR measurement and calculated based on the total H-spectrum area of 1H -NMR in the hydrogenated aromatic hydrocarbon resin and the H-spectrum area derived from the aromatic ring appearing at about 7 ppm in the 1H -NMR, according to the following formula (1):
  • Aromatic hydrogen content (H-spectrum area originating from aromatic ring appearing at about 7 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100(%) (1)
  • the olefin content of the hydrogenated aromatic hydrocarbon resin may be, for example, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0%.
  • the olefin content is preferably about 0 to 1.0%, more preferably about 0 to 0.5%, and even more preferably 0%, in order to further suppress coloration in the adhesive.
  • olefin refers to the olefinic double bond contained in the hydrogenated aromatic hydrocarbon resin, and does not include the carbon-carbon double bond in the aromatic ring.
  • the olefin content is determined by an NMR measurement method, and is calculated based on the total H-spectrum area of 1H -NMR in the hydrogenated aromatic hydrocarbon resin and the H-spectrum area derived from an olefinic double bond appearing at 5 to 6 ppm in the 1H -NMR, according to the following formula (2).
  • Olefin content (H-spectrum area derived from olefinic double bonds appearing at 4 to 6 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100(%) (2)
  • the tackifier may contain any of various known additives as long as the effects of the present invention are not impaired.
  • additives include crosslinkers, dehydrating agents, crystal nucleating agents, plasticizers, flow improvers, weathering agents, antioxidants, UV absorbers, heat stabilizers, light stabilizers, and tackifiers other than the hydrogenated aromatic hydrocarbon resin.
  • the additives may be used alone or in combination of two or more.
  • the content of the additive is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the hydrogenated aromatic hydrocarbon resin.
  • the tackifier can be used for various known adhesives and pressure-sensitive adhesives.
  • the adhesives and pressure-sensitive adhesives may be used alone or in combination of two or more. Examples of the adhesives and pressure-sensitive adhesives include those described below.
  • the tackifier is preferably used in a pressure-sensitive adhesive that contains an acrylic polymer as the base polymer (acrylic pressure-sensitive adhesive) in order to further improve the adhesive strength of the pressure-sensitive adhesive.
  • the amount of the tackifier used in the acrylic pressure-sensitive adhesive is not particularly limited.
  • the amount of the tackifier used in the acrylic pressure-sensitive adhesive is, for example, 70 parts by weight, 69 parts by weight, 68 parts by weight, 67 parts by weight, 66 parts by weight, 65 parts by weight, 64 parts by weight, 63 parts by weight, 62 parts by weight, 61 parts by weight, 60 parts by weight, 59 parts by weight, 58 parts by weight, 57 parts by weight, 56 parts by weight, 55 parts by weight, 54 parts by weight, 53 parts by weight, 52 parts by weight, 51 parts by weight, 50 parts by weight, 49 parts by weight, 48 parts by weight, 47 parts by weight, 46 parts by weight, 45 parts by weight, 44 parts by weight, 43 parts by weight, 42 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 4 ...
  • the amount of the tackifier used in the acrylic pressure-sensitive adhesive is preferably about 2 to 70 parts by mass, more preferably about 5 to 70 parts by mass, and even more preferably about 20 to 70 parts by mass, per 100 parts by mass of the acrylic polymer, in terms of solid content, from the viewpoints that the effect of modification by the tackifier can be fully exerted and the decrease in heat resistance retention, tackiness, etc. can be further suppressed.
  • the method of using the tackifier is not particularly limited.
  • Examples of the method of using the tackifier include a method of mixing the tackifier with various known base polymers used in pressure-sensitive adhesives and adhesives, and, if necessary, various known organic solvents and additives. There are no particular limitations on the mixing method, and various known methods can be used. Examples of base polymers used in pressure-sensitive adhesives and adhesives include those described below.
  • the present disclosure relates to a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising the above tackifier (or the above hydrogenated aromatic hydrocarbon resin) and a base polymer.
  • the pressure-sensitive adhesive composition can be used as a pressure-sensitive adhesive.
  • the term "pressure-sensitive adhesive” clearly includes either or both of a pressure-sensitive adhesive and an adhesive.
  • the base polymer examples include acrylic polymers, synthetic rubber elastomers, and olefin polymers.
  • the base polymer may be used alone or in combination of two or more. If necessary, the base polymer may further contain a crosslinking agent, a filler, a release adjuster, a plasticizer, a softener, a colorant (pigment, dye, etc.), a surfactant, an antistatic agent, an antiaging agent, an ultraviolet absorber, an antioxidant, a light stabilizer, etc.
  • the acrylic polymer may be one generally used in various acrylic adhesives, such as a polymer of a monomer component containing alkyl (meth)acrylate.
  • the acrylic polymer may be produced by any of various known polymerization methods, such as a method of radically polymerizing the monomer component in the presence of a polymerization initiator.
  • the polymerization method may be, for example, solution polymerization, suspension polymerization, bulk polymerization, etc.
  • the acrylic polymer may be used alone or in combination of two or more.
  • (meth)acrylic means “at least one selected from the group consisting of acrylic and methacrylic.”
  • (meth)acrylate means “at least one selected from the group consisting of acrylate and methacrylate”
  • (meth)acryloyl group means “at least one selected from the group consisting of acryloyl group and methacryloyl group.”
  • alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, Examples of alkyl (meth)acrylate include acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth
  • the monomer components in the acrylic polymer may further include other monomers that are copolymerizable with the alkyl (meth)acrylate.
  • monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, keto group-containing monomers, monomers having a nitrogen atom-containing ring, alkoxysilyl group-containing monomers, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic structure, polyfunctional monomers, etc.
  • carboxyl group-containing monomers include, for example, ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), and crotonic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and citraconic acid, and their anhydrides (maleic anhydride, itaconic anhydride, etc.).
  • ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), and crotonic acid
  • ethylenically unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and citraconic acid, and their anhydrides (maleic anhydride, itaconic anhydride, etc.).
  • hydroxyl group-containing monomer examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate
  • unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • amide group-containing monomer examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.
  • amino group-containing monomer examples include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.
  • Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether.
  • Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
  • Examples of the keto group-containing monomer include diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, and vinyl acetoacetate.
  • Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, and N-(meth)acryloylmorpholine.
  • alkoxysilyl group-containing monomer examples include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane.
  • Examples of the (meth)acrylate having an alicyclic structure include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.
  • Examples of the (meth)acrylate having the aromatic structure include aryl (meth)acrylate (e.g., phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g., phenoxyethyl (meth)acrylate), and arylalkyl (meth)acrylate (e.g., benzyl (meth)acrylate).
  • aryl (meth)acrylate e.g., phenyl (meth)acrylate
  • aryloxyalkyl (meth)acrylate e.g., phenoxyethyl (meth)acrylate
  • arylalkyl (meth)acrylate e.g., benzyl (meth)acrylate
  • polyfunctional monomer examples include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin di(
  • the content of other monomers copolymerizable with the alkyl (meth)acrylate in the monomer component is preferably about 40% by mass or less relative to 100% by mass of the monomer component.
  • the monomer components may further include vinyl ester monomers such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrenes (such as ⁇ -methylstyrene) and vinyl toluene; olefin monomers such as ethylene, propylene, isoprene, butadiene and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether. In one embodiment, the content of these monomers is about 10% by mass or less relative to 100% by mass of the monomer components.
  • the polymerization initiator is not particularly limited, and examples thereof include azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride; 1,1-bis(t-hexylperoxy)-3,3,5-tetrahydrofuran;
  • the polymerization initiator include peroxide initiators such as trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxy
  • the weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, but is usually in the range of about 100,000 to 5,000,000. In one embodiment, the weight average molecular weight (Mw) of the acrylic polymer is preferably 1,500,000 or less, more preferably 1,000,000 or less, from the viewpoint of improving adhesive properties, and is preferably 200,000 or more, more preferably 300,000 or more, from the viewpoint of cohesiveness, etc. In this disclosure, the weight average molecular weight refers to a polystyrene equivalent value in the gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • the content of the tackifier in the adhesive composition is not particularly limited.
  • the content of the tackifier in the adhesive composition is, for example, 70 parts by mass, 69 parts by mass, 68 parts by mass, 67 parts by mass, 66 parts by mass, 65 parts by mass, 64 parts by mass, 63 parts by mass, 62 parts by mass, 61 parts by mass, 60 parts by mass, 59 parts by mass, 58 parts by mass, 57 parts by mass, 56 parts by mass, 55 parts by mass, 54 parts by mass, 53 parts by mass, 52 parts by mass, 51 parts by mass, 50 parts by mass, 49 parts by mass, 48 parts by mass, 47 parts by mass, 46 parts by mass, 45 parts by mass, 44 parts by mass, 43 parts by mass, 42 parts by mass, 41 parts by mass, or the like, based on 100 parts by mass of the acrylic polymer, in terms of solid content.
  • the content of the tackifier in the pressure-sensitive adhesive composition is, in terms of solid content, preferably about 2 to 70 parts by mass, more preferably about 5 to 70 parts by mass, and even more preferably about 20 to 70 parts by mass, per 100 parts by mass of the acrylic polymer, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is not particularly limited.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is, for example, 70 parts by mass, 69 parts by mass, 68 parts by mass, 67 parts by mass, 66 parts by mass, 65 parts by mass, 64 parts by mass, 63 parts by mass, 62 parts by mass, 61 parts by mass, 60 parts by mass, 59 parts by mass, 58 parts by mass, 57 parts by mass, 56 parts by mass, 55 parts by mass, 54 parts by mass, 53 parts by mass, 52 parts by mass, 51 parts by mass, 50 parts by mass, 49 parts by mass, 48 parts by mass, 47 parts by mass, 46 parts by mass, 45 parts by mass, 44 parts by mass, 43 parts by mass, 42 parts by mass,
  • Examples of the compound include 41 parts by mass, 40 parts by mass, 39 parts by mass, 38 parts by mass, 37 parts by mass, 36 parts by mass, 35 parts by mass, 34 parts by mass, 33 parts by mass, 32
  • the content of the hydrogenated aromatic hydrocarbon resin in the pressure-sensitive adhesive composition is, in terms of solid content, preferably about 2 to 70 parts by mass, more preferably about 5 to 70 parts by mass, and even more preferably about 20 to 70 parts by mass, per 100 parts by mass of the acrylic polymer, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • Synthetic rubber elastomer As the synthetic rubber elastomer, various known synthetic rubber elastomers used in pressure-sensitive adhesive compositions can be used. The synthetic rubber elastomers may be used alone or in combination of two or more.
  • Examples of the synthetic rubber elastomers include polyisoprene, styrene-butadiene rubber (SBR), styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, reclaimed rubber, butyl rubber, polyisobutylene, styrene-butadiene-vinylpyridine rubber, polybutadiene, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene
  • the content of the tackifier in the adhesive composition is not particularly limited.
  • the content of the tackifier in the adhesive composition is, for example, 210 parts by mass, 205 parts by mass, 200 parts by mass, 195 parts by mass, 190 parts by mass, 185 parts by mass, 180 parts by mass, 175 parts by mass, 170 parts by mass, 165 parts by mass, 160 parts by mass, 155 parts by mass, 150 parts by mass, 145 parts by mass, 140 parts by mass
  • Examples of the tackifier include 135 parts by mass, 130 parts by mass, 125 parts by mass, 120 parts by mass, 115 parts by mass, 110 parts by mass, 105 parts by mass, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts
  • the content of the tackifier in the pressure-sensitive adhesive composition is preferably about 15 to 210 parts by mass, in terms of solid content, per 100 parts by mass of the synthetic rubber-based elastomer, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is not particularly limited.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is, for example, 210 parts by mass, 205 parts by mass, 200 parts by mass, 195 parts by mass, 190 parts by mass, 185 parts by mass, 180 parts by mass, 175 parts by mass, 170 parts by mass, 165 parts by mass, 160 parts by mass, 155 parts by mass, 150 parts by mass, 145 parts by mass, 140 parts by mass, 15 ...
  • parts by mass 135 parts by mass, 130 parts by mass, 125 parts by mass, 120 parts by mass, 115 parts by mass, 110 parts by mass, 105 parts by mass, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, etc.
  • the content of the hydrogenated aromatic hydrocarbon resin in the pressure-sensitive adhesive composition is preferably about 15 to 210 parts by mass, in terms of solid content, relative to 100 parts by mass of the synthetic rubber-based elastomer, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • the olefin-based polymer is not particularly limited as long as it is a polymer of a monomer component containing various olefins, and various known polymers can be used.
  • the olefin-based polymer include an olefin-based homopolymer, which is a homopolymer of various olefins, and an olefin-based copolymer, which is a copolymer of various olefins and a copolymerizable monomer.
  • the olefin-based polymer may be used alone or in combination of two or more kinds.
  • the above olefins include, for example, ethylene, propylene, butene, butylene, isoprene, pentene, pentadiene, octene, isooctene, various isomers of hexene and hexadiene, various isomers of heptene and heptadiene; various alpha-olefins; and cyclic olefins such as cyclopentene, cyclohexene, norbornene, and dicyclopentadienyl.
  • the above olefins may be used alone or in combination of two or more.
  • Examples of the monomers copolymerizable with the olefins include vinyl acetate and the (meth)acrylic acid esters.
  • the copolymerizable monomer is preferably vinyl acetate.
  • the copolymerizable monomers may be used alone or in combination of two or more.
  • the amount of the copolymerizable monomer used in the olefin-based copolymer is preferably about 20 to 45% by mass relative to 100% by mass of the olefin-based copolymer.
  • the above-mentioned olefin-based homopolymers include, for example, polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, amorphous atactic polypropylene, etc.
  • the above-mentioned olefin-based copolymers include, for example, ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA), ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), ethylene methyl acrylate copolymer (EMA), ethylene methyl methacrylate copolymer (EMMA), etc.
  • EAA ethylene acrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EVA ethylene vinyl acetate copolymer
  • EAA ethylene ethyl acrylate copolymer
  • EMA ethylene methyl acrylate copolymer
  • EMMA methyl
  • the content of the tackifier in the adhesive composition is not particularly limited.
  • the content of the tackifier in the adhesive composition is, for example, 150 parts by mass, 145 parts by mass, 140 parts by mass, 135 parts by mass, 130 parts by mass, 125 parts by mass, 120 parts by mass, 115 parts by mass, 110 parts by mass, 105 parts by mass, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, etc., based on the solid content.
  • the content of the tackifier in the adhesive composition is preferably about 50 to 150 parts by mass based on the solid content, based on 100 parts by mass of the olefin-based polymer, in order to increase the adhesive strength of the adhesive.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is not particularly limited.
  • the content of the hydrogenated aromatic hydrocarbon resin in the adhesive composition is, for example, 150 parts by mass, 145 parts by mass, 140 parts by mass, 135 parts by mass, 130 parts by mass, 125 parts by mass, 120 parts by mass, 115 parts by mass, 110 parts by mass, 105 parts by mass, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, etc., based on 100 parts by mass of the olefin polymer, in terms of solid content.
  • the content of the hydrogenated aromatic hydrocarbon resin in the pressure-sensitive adhesive composition is preferably about 50 to 150 parts by mass, in terms of solid content, per 100 parts by mass of the olefin polymer, since this increases the adhesive strength of the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition is preferably an acrylic pressure-sensitive adhesive composition containing the acrylic polymer as the base polymer, because of the high effect of modification by the tackifier (or the hydrogenated aromatic hydrocarbon resin).
  • the above pressure-sensitive adhesive composition can be used in either a varnish type or hot melt type.
  • the organic solvent is not particularly limited, but specific examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, ethyl acetate, cyclohexane, methylcyclohexane, methanol, ethanol, propanol, isopropanol, and hexylene glycol.
  • the amount of the organic solvent used is not particularly limited, but is usually about 100 to 500 parts by mass per 100 parts by mass of the base polymer.
  • the organic solvent that can be used in the varnish type is not particularly required.
  • the pressure-sensitive adhesive composition may optionally contain various additives such as a crosslinking agent, oil, wax, a tackifier other than the hydrogenated aromatic hydrocarbon resin, an antifoaming agent, a viscosity modifier, a filler, an antioxidant, a water-resistant agent, a film-forming assistant, a preservative, a pH adjuster such as ammonia water or sodium bicarbonate, a leveling agent, a release adjuster, a plasticizer, a softener, a colorant (pigment, dye, etc.), a surfactant, an antistatic agent, an antiaging agent, an ultraviolet absorber, an antioxidant, and a light stabilizer, so long as the desired properties are not impaired.
  • additives such as a crosslinking agent, oil, wax, a tackifier other than the hydrogenated aromatic hydrocarbon resin, an antifoaming agent, a viscosity modifier, a filler, an antioxidant, a water-resistant agent, a film-forming assistant, a pre
  • crosslinking agent examples include isocyanate-based crosslinking agents and epoxy-based crosslinking agents.
  • content of the crosslinking agent is typically 10 parts by mass or less per 100 parts by mass of the base polymer, and preferably about 0.01 to 1.0 part by mass.
  • the above-mentioned isocyanate-based crosslinking agents include, for example, lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate; and biuret, isocyanurate, allophanate, and adduct forms thereof, as well as complexes obtained by reacting two or more selected from the group consisting of biuret, isocyanurate,
  • the above-mentioned epoxy crosslinking agents include, for example, compounds having two or more epoxy groups in the molecule, such as bisphenol A epichlorohydrin type epoxy resins, ethylene diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N'-diamine glycidylaminomethyl)cyclohexane.
  • bisphenol A epichlorohydrin type epoxy resins ethylene diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidy
  • the oil may be, for example, a naphthenic oil, a paraffinic oil, or a plasticizing oil such as an aromatic oil.
  • the oil may preferably be a naphthenic process oil, a paraffinic process oil, or a liquid polybutene.
  • the content of the oil is preferably about 4 to 200 parts by mass per 100 parts by mass of the base polymer.
  • the above waxes include, for example, animal-derived waxes such as beeswax, spermaceti, and shellac wax, vegetable-derived waxes such as carnauba wax, Japan wax, rice bran wax, and candelilla wax, petroleum-derived waxes such as paraffin wax and microcrystalline wax, synthetic waxes such as Fischer-Tropsch wax and low molecular weight polyethylene wax, and mineral-derived waxes such as montan wax and ozokerite.
  • animal-derived waxes such as beeswax, spermaceti, and shellac wax
  • vegetable-derived waxes such as carnauba wax, Japan wax, rice bran wax, and candelilla wax
  • petroleum-derived waxes such as paraffin wax and microcrystalline wax
  • synthetic waxes such as Fischer-Tropsch wax and low molecular weight polyethylene wax
  • mineral-derived waxes such as montan wax and ozokerite.
  • the above waxes may be used alone or in
  • the wax content is preferably about 10 to 100 parts by mass per 100 parts by mass of the base polymer.
  • the pressure-sensitive adhesive composition is obtained by mixing the tackifier (or the hydrogenated aromatic hydrocarbon resin) and the base polymer, and, if necessary, the organic solvent and the additives. There are no particular limitations on the mixing method, and various known methods can be used.
  • the present disclosure relates to an active energy ray-curable acrylic pressure-sensitive adhesive composition
  • an active energy ray-curable acrylic pressure-sensitive adhesive composition comprising the tackifier (or the hydrogenated aromatic hydrocarbon resin), an acrylic monomer, an acrylic oligomer, and a photopolymerization initiator.
  • the acrylic monomer may be, for example, the monomer component that is the raw material for the acrylic polymer.
  • the acrylic oligomer is a polymerizable polymer (macromonomer) containing a (meth)acryloyl group
  • any known raw material can be used without particular limitation as long as it is a raw material that synthesizes a polymer by a curing reaction in a relatively low polymerization degree of about 2 to 20.
  • Specific examples include polyacryl (meth)acrylate, polyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc.
  • photopolymerization initiator various known ones can be used without any particular limitation as long as they can be decomposed by active energy rays to generate radicals and initiate polymerization.
  • Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 4-methylbenzophenone.
  • the content of each component in the active energy ray-curable acrylic pressure-sensitive adhesive composition is not particularly limited.
  • the content of the tackifier in the active energy ray-curable acrylic pressure-sensitive adhesive composition may be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, etc., relative to 100 parts by mass of the total of the acrylic monomer and acrylic oligomer, calculated as solid content.
  • the content of the tackifier in the active energy ray-curable acrylic pressure-sensitive adhesive composition is preferably about 1 to 100 parts by mass, calculated as solid content, per 100 parts by mass of the acrylic monomer and acrylic oligomer combined, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • the content of the hydrogenated aromatic hydrocarbon resin in the active energy ray-curable acrylic adhesive/tackifier composition may be, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, etc., relative to 100 parts by mass of the total of the acrylic monomer and acrylic oligomer, calculated on a solid content basis.
  • the content of the hydrogenated aromatic hydrocarbon resin in the active energy ray-curable acrylic pressure-sensitive adhesive composition is preferably about 1 to 100 parts by mass per 100 parts by mass of the acrylic monomer and acrylic oligomer in total, in terms of solid content, in order to increase the adhesive strength of the pressure-sensitive adhesive.
  • the content of the photopolymerization initiator in the active energy ray curable acrylic adhesive composition is, for example, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., based on 100 parts by mass of the acrylic monomer and acrylic oligomer in total, calculated as solid content.
  • the content of the photopolymerization initiator in the active energy ray curable acrylic adhesive composition is, for example, about 0.1 to 100 parts by mass based on 100 parts by mass of the acrylic monomer and acrylic oligomer in total, calculated as solid content.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition may contain various additives as long as the desired properties are not impaired.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition may contain additives such as the above-mentioned crosslinking agent, surface conditioner, surfactant, ultraviolet absorber, antioxidant, light stabilizer, tackifier other than the above-mentioned tackifier resin, plasticizer, inorganic filler, silane coupling agent, colloidal silica, defoamer, wetting agent, and rust inhibitor.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition is obtained by mixing the tackifier (or the hydrogenated aromatic hydrocarbon resin), the acrylic monomer, the acrylic oligomer, and the photopolymerization initiator, and, if necessary, the additives.
  • the mixing method There are no particular limitations on the mixing method, and various known methods can be used.
  • the hydrogenated aromatic hydrocarbon resin can be used as a tackifier for adhesives.
  • the adhesive strength of the adhesive is improved.
  • the adhesive is not particularly limited, and examples thereof include those mentioned above.
  • the hydrogenated aromatic hydrocarbon resin is preferably used as a tackifier in an acrylic pressure-sensitive adhesive composition in order to further improve the adhesive strength of the pressure-sensitive adhesive.
  • the amount of the hydrogenated aromatic hydrocarbon resin used as a tackifier in the acrylic adhesive composition is not particularly limited.
  • the amount of the hydrogenated aromatic hydrocarbon resin used include the amount of the tackifier used described above.
  • some conventional tackifiers when used in active energy ray-curable acrylic pressure-sensitive adhesive compositions, absorb active energy rays such as ultraviolet rays and inhibit the polymerization reaction of acrylic monomers and acrylic oligomers (hereinafter also referred to as polymerization inhibition), which causes a problem of a decrease in the adhesive strength of the pressure-sensitive adhesive composition.
  • the hydrogenated aromatic hydrocarbon resin has a low or zero olefin content and can suppress the polymerization inhibition of acrylic monomers and acrylic oligomers, and is therefore preferably used as a tackifier for use in active energy ray-curable acrylic pressure-sensitive adhesive compositions.
  • the amount of the hydrogenated aromatic hydrocarbon resin used as a tackifier in the active energy ray-curable acrylic pressure-sensitive adhesive composition is not particularly limited.
  • Examples of the amount of the hydrogenated aromatic hydrocarbon resin used include the content of the hydrogenated aromatic hydrocarbon resin in the active energy ray-curable acrylic pressure-sensitive adhesive composition.
  • the present disclosure provides the following: (Item A1) The mass retention rate after heating at 300° C. for 2 hours is 64% by mass or more, The mixed methylcyclohexaneaniline cloud point (MMAP) is 5° C. or more and less than 40° C. Hydrogenated aromatic hydrocarbon resins, Modifier for thermoplastic resins. (Item A2) The thermoplastic resin modifier according to the above item, wherein the hydrogenated aromatic hydrocarbon resin is a hydrogenated aromatic petroleum resin. (Item A3) The modifier for thermoplastic resin according to any of the preceding items, wherein the hydrogenated aromatic hydrocarbon resin has a mixed methylcyclohexaneaniline cloud point (MMAP) of 5°C to 35°C.
  • MMAP mixed methylcyclohexaneaniline cloud point
  • thermoplastic resins according to any of the preceding items wherein the color tone of the hydrogenated aromatic hydrocarbon resin is 10 to 200 Hazen.
  • the modifier for thermoplastic resins according to any of the preceding items, wherein the hydrogenated aromatic hydrocarbon resin has a weight average molecular weight of 900 to 4,000.
  • the modifier for thermoplastic resins according to any of the preceding items, wherein the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is 1,000 to 3,000.
  • the weight average molecular weight of the hydrogenated aromatic hydrocarbon resin is 1,000 to 2,100.
  • thermoplastic resin according to any of the preceding items, wherein the aromatic hydrogen content of the hydrogenated aromatic hydrocarbon resin is 10 to 37%.
  • a resin composition comprising the modifier of any of the preceding items and a thermoplastic resin.
  • thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate and modified polyphenylene ether resin.
  • thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate and modified polyphenylene ether resin.
  • the thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate and modified polyphenylene ether resin.
  • the content of the modifier is 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic resin.
  • the content of the modifier is 0.5 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, and the content of the filler is 70 parts by mass or less per 100 parts by mass of the thermoplastic resin.
  • (Item A16) A molded article obtained by molding any one of the resin compositions described above.
  • (Item A17) 2. Use of the hydrogenated aromatic hydrocarbon resin according to any of the preceding items as a modifier for thermoplastic resins.
  • (Item A18) The use of the hydrogenated aromatic hydrocarbon resin according to item A17, wherein the thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate and modified polyphenylene ether resin.
  • (Item A19) The use of the hydrogenated aromatic hydrocarbon resin according to the above item A17 or A18, wherein the amount of the hydrogenated aromatic hydrocarbon resin used is 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic resin.
  • thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and modified polyphenylene ether resin.
  • thermoplastic resin comprises at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polycarbonate, and modified polyphenylene ether resin.
  • MMAP mixed methylcyclohexaneaniline cloud point
  • (Item A31) The tackifier of any of the preceding items, wherein the hydrogenated aromatic hydrocarbon resin has an olefin content of 0 to 0.5%.
  • (Item A32) A pressure-sensitive adhesive composition comprising any one of the tackifiers described above and a base polymer.
  • (Item A33) The pressure-sensitive adhesive composition according to the above item, wherein the base polymer comprises an acrylic polymer.
  • An active energy ray-curable acrylic pressure-sensitive adhesive composition comprising the tackifier according to any one of the above items, an acrylic monomer, an acrylic oligomer, and a photopolymerization initiator.
  • An active energy ray-curable acrylic pressure-sensitive adhesive composition comprising the tackifier according to any one of the above items, an acrylic monomer, an acrylic oligomer, and a photopolymerization initiator.
  • (Item A37) Use of the hydrogenated aromatic hydrocarbon resin according to item A36, in which the amount of the precursor hydrogenated aromatic hydrocarbon resin used is 2 to 70 parts by mass per 100 parts by mass of the acrylic polymer.
  • the modifier for thermoplastic resins provided in this disclosure can be used in thermoplastic resins to improve their fluidity when melted, thereby improving their moldability.
  • the modifier when used in thermoplastic resins, can also suppress smoke generation when melted.
  • the tackifier provided in this disclosure can improve the adhesive strength of adhesives and pressure-sensitive adhesives by using it in those adhesives and pressure-sensitive adhesives.
  • the tackifier can suppress odors during the production and/or use of adhesives and pressure-sensitive adhesives when used in those adhesives and pressure-sensitive adhesives.
  • Example 1 100 parts of C9 petroleum resin (Gardner color tone 10, weight average molecular weight 1,381) and 2 parts of a palladium-alumina catalyst (palladium content 3% by mass) supported on an alumina carrier (diameter 1.2 mm, specific surface area 200 m 2 /g) were subjected to a hydrogenation reaction in a shaking autoclave under conditions of a hydrogen partial pressure of 19.6 MPa, a reaction temperature of 285°C, and a reaction time of 1 hour. After completion of the reaction, the resulting resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 200°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,210, an aromatic hydrogen content of 36%, and an olefin content of 0%.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 200°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,290, an aromatic hydrogen content of 26%, and an olefin content of 0%.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 200°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,300, an aromatic hydrogen content of 19%, and an olefin content of 0%.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 200°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,340, an aromatic hydrogen content of 35%, and an olefin content of 0%.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 220°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 2,060, an aromatic hydrogen content of 37%, and an olefin content of 0%.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 220 ° C and 2.7 kPa to remove the solvent, and a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,230, an aromatic hydrogen content of 21%, and an olefin content of 0% was obtained.
  • Comparative Production Example 1 100 parts of C9 petroleum resin (color tone 9 Gardner, weight average molecular weight 1,303) and 3.5 parts of palladium-alumina catalyst (palladium content 3 mass%) supported on an alumina carrier (diameter 1.2 mm, specific surface area 200 m 2 /g) were subjected to a hydrogenation reaction in a shaking autoclave under conditions of hydrogen partial pressure 19.6 MPa, reaction temperature 250 ° C, and reaction time 4.5 hours. After completion of the reaction, the obtained resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature was gradually increased and reduced to 220 ° C and 2.7 kPa to remove the solvent, and a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,230, an aromatic hydrogen content of 15%, and an olefin content of 0% was obtained.
  • Comparative Production Example 2 100 parts of C9 petroleum resin (Gardner color tone 10, weight average molecular weight 1,381) and 7.7 parts of palladium-alumina catalyst (palladium content 3% by mass) supported on an alumina carrier (diameter 1.2 mm, specific surface area 200 m2/g) were subjected to a hydrogenation reaction in a shaking autoclave under the conditions of a hydrogen partial pressure of 19.6 MPa, a reaction temperature of 275°C, and a reaction time of 5 hours. After the reaction was completed, the resulting resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration.
  • the filtrate was then placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 200°C and 2.7 kPa to remove the solvent, resulting in a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,060, an aromatic hydrogen content of 2%, and an olefin content of 0%.
  • Comparative Production Example 3 100 parts of C9 petroleum resin (color tone 9 Gardner, weight average molecular weight 1,303) and 1.5 parts of palladium-alumina catalyst (palladium content 3% by mass) supported on an alumina carrier (diameter 1.2 mm, specific surface area 200 m 2 /g) were subjected to a hydrogenation reaction in a shaking autoclave under conditions of hydrogen partial pressure 19.6 MPa, reaction temperature 250°C, and reaction time 4.5 hours. After completion of the reaction, the obtained resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 220°C and 2.7 kPa to remove the solvent, thereby obtaining a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,130, an aromatic hydrogen content of 59%, and an olefin content of 0%.
  • Comparative Example 4 100 parts of C9 petroleum resin (color tone 9 Gardner, weight average molecular weight 1,303) and 2.0 parts of palladium-alumina catalyst (palladium content 3 mass%) supported on an alumina carrier (diameter 1.2 mm, specific surface area 200 m 2 /g) were subjected to a hydrogenation reaction in a shaking autoclave under conditions of hydrogen partial pressure 19.6 MPa, reaction temperature 280 ° C, and reaction time 4.5 hours. After completion of the reaction, the obtained resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration.
  • the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature regulator, and a pressure indicator, and the temperature and pressure were gradually increased and reduced to 220 ° C and 2.7 kPa to remove the solvent, and a hydrogenated C9 petroleum resin with a weight average molecular weight of 1,240, an aromatic hydrogen content of 35%, and an olefin content of 0% was obtained.
  • Aromatic hydrogen content (H-spectrum area derived from aromatic ring appearing at about 7 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100(%)
  • Olefin content (H-spectrum area derived from olefinic double bonds appearing at 4 to 6 ppm in 1 H-NMR/total H-spectrum area in 1 H-NMR) ⁇ 100 (%)
  • Example 1 100 parts of modified polyphenylene ether resin (manufactured by Global Polyacetal Co., Ltd., product name "Iupiace AH40") and 5 parts of hydrogenated aromatic petroleum resin of Production Example 1 as a modifier were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100”) and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 250 ° C.
  • a roller mixer type kneading device manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100
  • the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 250 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm with a cutter to obtain pellets.
  • Example 2 to 3 and 5 to 7 The same preparation as in Example 1 was carried out, except that in Example 1, the hydrogenated aromatic petroleum resin of Production Example 1 was used as the modifier, and the hydrogenated aromatic petroleum resin of Production Examples 2 to 6 was used, to obtain pellets.
  • Example 4 In Example 1, except that 8 parts of the hydrogenated aromatic petroleum resin of Production Example 3 was used as the modifier instead of the hydrogenated aromatic petroleum resin of Production Example 1, the same preparation as in Example 1 was performed to obtain pellets.
  • Comparative Example 1 100 parts of modified polyphenylene ether resin (manufactured by Global Polyacetal Corporation, product name "Iupiace AH40") was put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100”) and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 250° C.
  • a roller mixer type kneading device manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100
  • the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 250° C., and molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.
  • Example 6 instead of the hydrogenated aromatic petroleum resin of Production Example 1, 5 parts of a C9 petroleum resin having a weight average molecular weight of 2,380, an aromatic hydrogen content of 40%, an olefin content of 1.3%, a mass residual rate after heating at 300°C for 2 hours of 61%, and an MMAP of 12°C were used as a modifier. Preparation was performed in the same manner as in Example 1 to obtain pellets.
  • the rate of increase in MFR of the pellets of Examples 1 to 7 and Comparative Examples 2 to 6 relative to the MFR of Comparative Example 1 (blank) was evaluated according to the following criteria. The results are shown in Table 2. The greater the rate of increase in MFR, the better the moldability. ⁇ : The increase in MFR compared to blank is 30% or more. ⁇ : The increase in MFR compared to blank is 10% or more but less than 30%. ⁇ : The increase in MFR compared to blank is less than 10%.
  • Table 2 The blending amounts in Table 2 are values in parts by mass. The abbreviations and notes in Table 2 are as follows. *Since there was a lot of smoke and it was not possible to prepare pellets, the MFR was not measured. mPPE: modified polyphenylene ether resin, product name "Iupiace AH40", manufactured by Global Polyacetal Co., Ltd.
  • Example 8 80 parts (solid content equivalent) of an acrylic polymer (manufactured by Soken Chemical & Engineering Co., Ltd., product name "SK Dyne 1451", solid content 30%) and 20 parts of the hydrogenated aromatic petroleum resin of Production Example 1 as a tackifier were thoroughly kneaded, and then 0.3 parts of an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name "Coronate L”) was added to obtain an acrylic pressure-sensitive adhesive composition.
  • an acrylic polymer manufactured by Soken Chemical & Engineering Co., Ltd., product name "SK Dyne 1451", solid content 30%
  • an isocyanate crosslinking agent manufactured by Nippon Polyurethane Co., Ltd., product name "Coronate L
  • Example 8 Except that the hydrogenated aromatic petroleum resin of Production Example 1 was changed to the hydrogenated aromatic petroleum resin of Production Examples 2 to 6 as a tackifier, the same preparation as in Example 8 was performed to obtain an acrylic pressure-sensitive adhesive composition.
  • Example 14 An acrylic pressure-sensitive adhesive composition was obtained in the same manner as in Example 8, except that 5 parts of the hydrogenated aromatic petroleum resin of Production Example 1 was used as a tackifier.
  • Example 15 An acrylic pressure-sensitive adhesive composition was obtained in the same manner as in Example 8, except that 40 parts of the hydrogenated aromatic petroleum resin of Production Example 1 was used as a tackifier.
  • Comparative Example 7 An acrylic pressure-sensitive adhesive composition was obtained by adding 0.3 parts of an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name "Coronate L”) to 100 parts (solid content equivalent) of an acrylic polymer (manufactured by Soken Chemical & Engineering Co., Ltd., product name "SK Dyne 1451", solid content 30%).
  • Example 8 except that the hydrogenated aromatic petroleum resin of Production Example 1 was used as the tackifier in place of the hydrogenated aromatic petroleum resins of Comparative Production Examples 1 and 4, preparation was performed in the same manner as in Example 8 to obtain an acrylic pressure-sensitive adhesive composition.
  • the above sample tape was cut to a width of 25 mm, and was laminated to a polyethylene plate (PE plate) by rolling it back and forth once with a 2 kg roller, and was left to stand for one day. Then, a 180-degree peel test was performed under conditions of a pulling speed of 300 mm/min and a measurement temperature of 40° C., and the adhesive strength (N/25 mm) was measured. The results are shown in Table 3.

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Abstract

L'invention concerne un modificateur pour résine thermoplastique qui contient une résine hydrocarbonée aromatique hydrogénée présentant un taux résiduel en masse après chauffage pendant deux heures à 300°C supérieur ou égal à 64% en masse, et un point de trouble dans un méthylcyclohexane et une aniline mélangés (MMAP) supérieur ou égal à 5°C et inférieur à 40°C.
PCT/JP2023/038644 2022-11-01 2023-10-26 Modificateur pour résine thermoplastique, composition de résine, application associée à une résine hydrocarbonée aromatique hydrogénée, agent poisseux, et composition de colle ou adhésif WO2024095878A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09328524A (ja) * 1996-03-06 1997-12-22 Hercules Inc 石油に基づく脂肪族樹脂、該樹脂の軟化点及び分子量を制御する方法、及び該樹脂を含む感圧性ホットメルト接着剤
JP2002503737A (ja) * 1998-02-12 2002-02-05 ハーキュリーズ・インコーポレーテッド 芳香族化合物で変性した脂肪族炭化水素樹脂
JP2003530471A (ja) * 2000-04-07 2003-10-14 イーストマン・ケミカル・レジンズ・インコーポレーテッド ローカラー芳香族変性ｃ５炭化水素樹脂
WO2017171025A1 (fr) * 2016-03-31 2017-10-05 日本ゼオン株式会社 Résine hydrocarbonée modifiée et composition adhésive thermofusible
WO2020066791A1 (fr) * 2018-09-27 2020-04-02 日本ゼオン株式会社 Composition adhésive thermofusible
JP2022173091A (ja) * 2021-05-06 2022-11-17 荒川化学工業株式会社 樹脂組成物、成形体及び低誘電性樹脂用の流動性向上剤

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09328524A (ja) * 1996-03-06 1997-12-22 Hercules Inc 石油に基づく脂肪族樹脂、該樹脂の軟化点及び分子量を制御する方法、及び該樹脂を含む感圧性ホットメルト接着剤
JP2002503737A (ja) * 1998-02-12 2002-02-05 ハーキュリーズ・インコーポレーテッド 芳香族化合物で変性した脂肪族炭化水素樹脂
JP2003530471A (ja) * 2000-04-07 2003-10-14 イーストマン・ケミカル・レジンズ・インコーポレーテッド ローカラー芳香族変性ｃ５炭化水素樹脂
WO2017171025A1 (fr) * 2016-03-31 2017-10-05 日本ゼオン株式会社 Résine hydrocarbonée modifiée et composition adhésive thermofusible
WO2020066791A1 (fr) * 2018-09-27 2020-04-02 日本ゼオン株式会社 Composition adhésive thermofusible
JP2022173091A (ja) * 2021-05-06 2022-11-17 荒川化学工業株式会社 樹脂組成物、成形体及び低誘電性樹脂用の流動性向上剤

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