TW200925210A - Granular polyurethane resin composition, method for producing the same, and molded article of the same - Google Patents

Granular polyurethane resin composition, method for producing the same, and molded article of the same Download PDF

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TW200925210A
TW200925210A TW97138844A TW97138844A TW200925210A TW 200925210 A TW200925210 A TW 200925210A TW 97138844 A TW97138844 A TW 97138844A TW 97138844 A TW97138844 A TW 97138844A TW 200925210 A TW200925210 A TW 200925210A
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mass
parts
particulate
resin composition
polymerization
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TW97138844A
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Chinese (zh)
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Hideaki Ogata
Hirokazu Morita
Hiroyuki Shiraki
Yukio Tominaga
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Mitsui Chemicals Polyurethanes
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/122Pulverisation by spraying
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Disclosed is a granular polyurethane resin composition containing a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymerized material, a thermally crosslinkable monomer, and 0.1-6 parts by mass of a polymerization inhibitor per 100 parts by mass of the thermally crosslinkable monomer.

Description

200925210 六、發明說明: 【發明所屬之技術領域】 . 树明侧於粒子狀聚胺基甲_樹脂組成物、其製造方 法及成形品,誶言之,係關於頗適於遞鎮(si咖成形的粒 子狀聚胺基甲酸g旨樹脂組成物、其製造方法、及*該粒子狀 聚胺基甲酸酯樹脂組成物成形的成形品。 【先前技術】 ❿ 麟成卵材輕易成形為複雜形狀品、可使壁厚呈 均勻、材料良率佳,因而廣泛利用於汽車喊配件等的成形。 於遞鑄成形用材料,長年以來均使用軟f的聚氯乙烯粉 末’但若在可_的凝固點以下便會損及質感,且隨時間的 Μ過所發㈣可_脫除’而亦有因表皮收縮造成尺寸變化 變大等不ΜΙΊ因而’針對取代軟質的聚氣乙雜末,改 為使用聚胺基甲㈣樹脂粉末的情形進行各種檢討。 ® 例如’提案有將乙烯基單體的水分散液混合於熱可塑性聚 胺基曱酸醋樹脂的水分散液中並進行聚合,而獲得含有由熱 可塑性聚胺基甲酸g旨樹脂所形成之核層、與由乙烯基單體的 聚合體所形成之殼層的核殼結構粒子的瀝鑄成形用粉末組 成物(例如參照下述專利文獻1)。 專利文獻1.日本專利特開2005_96432號公報 【發明内容】 (發明所欲解決之問題) 097138844 200925210 然而,對>飞車内裝配件等除要求質感之外,尚亦要求機械 強度、長期耐熱性。 本發明之目的在於提供可形成粉體流動性、成形性、色不 均、及質感均優異,且機械物性、耐藥性及長期耐熱性亦均 •優異之成形品的粒子狀聚胺基甲酸酯樹脂組成物、其製造方 法、及由該粒子狀聚胺基甲酸酯樹脂組成物成形的成形品。 (解決問題之手段) © 為達成上述目的,本發明的粒子狀聚胺基曱酸酯樹脂組成 物,係含有:在水分散媒中合成的熱可塑性聚胺基甲酸酯樹 脂、乙烯基單體聚合體、熱交聯性單體、及相對於熱交聯性 单體100質篁份為0.1〜6質量份的聚合防止劑。 本發明的粒子狀聚胺基曱酸酯樹脂組成物中,乙烯基單體 聚合體較佳係由芳香族乙烯基單體35〜70質量%、及α,万-乙烯性不飽和羧酸烷基醋30〜65質量%的聚合反應所獲得。 ❹ 本發明的粒子狀聚胺基曱酸酯樹脂組成物中,乙烯基單體 聚合體係相對於熱可塑性聚胺基甲酸酯樹脂1〇〇質量份,較 佳為含有5〜40質量份。 本發明的粒子狀聚胺基甲酸酯樹脂組成物中,熱交聯性單 體係相對於熱可塑性聚胺基甲酸酯樹脂1〇〇質量份,較佳含 有2〜10質量份。 本發明的粒子狀聚胺基甲酸酯樹脂組成物,較佳係將熱可 塑性聚胺基曱酸酯樹脂及乙烯基單體聚合體的水分散液、與 097138844 4 200925210 熱交聯性單體及聚合防止劑的水分散液進行混合後,再利用 喷霧乾燥而獲得。 本發明的成形品係將上述粒子狀聚胺基甲酸醋樹脂組成 ‘ 物’利用瀝鑄成形而獲得。 •本發明的成形品係適用為汽車内裝配件。 本發明的粒子狀聚胺基曱酸酯樹脂組成物之製造方法,係 將熱可塑性聚胺基曱酸酯樹脂及乙烯基單體聚合體的水分 ❹ 散液、與熱交聯性單體及聚合防止劑的水分散液進行混合 後,施行噴霧乾燥。 (發明效果) 根據本發明的粒子狀聚胺基曱酸酯樹脂組成物,藉由相對 於熱父聯性單體1〇〇質量份,含有〇1〜6質量份聚合防止 劑,則可對在成形過程中的熱交聯性單體之硬化反應進行控 制’可在不損及粒子狀聚胺基甲酸酯樹脂組成物的成形性的200925210 VI. Description of the invention: [Technical field to which the invention pertains] The tree side is in the form of a particulate polyamine-based resin, a method for producing the same, and a molded article, in other words, about a well-suited town (si coffee) The formed particulate form of the polyurethane is a resin composition, a method for producing the same, and a molded article in which the particulate polyurethane resin composition is formed. [Prior Art] The egg material is easily formed into a complex Shaped products, which have a uniform wall thickness and good material yield, are widely used in the forming of automobile shouting parts, etc. For the material for casting and casting, PVC powder of soft f has been used for a long time. Below the freezing point, it will damage the texture, and it will be removed according to the time (4), and the size change will be increased due to the shrinkage of the epidermis, so it is changed to replace the soft gas. Various reviews have been made for the use of polyaminomethyl (tetra) resin powders. ® For example, it is proposed to mix and polymerize an aqueous dispersion of a vinyl monomer in an aqueous dispersion of a thermoplastic polyamine phthalic acid resin. Obtained A powder composition for leaching and casting containing a core layer formed of a thermoplastic resin and a core-shell structure particle formed of a polymer layer of a polymer of a vinyl monomer (for example, refer to the following patent) [1] Patent Document 1. Japanese Patent Laid-Open Publication No. 2005-96432 [Draft of the Invention] (Problems to be Solved by the Invention) 097138844 200925210 However, in addition to the required texture, the mechanical strength is required for the interior parts of the vehicle. In the present invention, it is an object of the present invention to provide a molded article which is excellent in fluidity, moldability, color unevenness, and texture, and which is excellent in mechanical properties, chemical resistance, and long-term heat resistance. A urethane resin composition, a method for producing the same, and a molded article formed of the particulate urethane resin composition. (Means for Solving the Problem) © The particle of the present invention for achieving the above object The polyamino phthalate resin composition comprises: a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymer, a thermally crosslinkable monomer, And a polymerization preventive agent in an amount of 0.1 to 6 parts by mass based on 100 parts by mass of the thermally crosslinkable monomer. In the particulate polyaminophthalate resin composition of the present invention, the vinyl monomer polymer is preferably The polymerization reaction is carried out in an amount of 35 to 70% by mass of the aromatic vinyl monomer and 30 to 65% by mass of the α, 10,000-ethylenically unsaturated carboxylic acid alkyl vinegar. 粒子 The particulate polyamino phthalate resin of the present invention In the composition, the vinyl monomer polymerization system preferably contains 5 to 40 parts by mass based on 1 part by mass of the thermoplastic urethane resin. The composition of the particulate polyurethane resin of the present invention The thermally crosslinkable single system preferably contains 2 to 10 parts by mass based on 1 part by mass of the thermoplastic urethane resin. The particulate polyurethane resin composition of the present invention Preferably, the aqueous dispersion of the thermoplastic polyamine phthalate resin and the vinyl monomer polymer is mixed with an aqueous dispersion of 097138844 4 200925210 heat crosslinkable monomer and a polymerization preventive agent, and then reused. Obtained by spray drying. The molded article of the present invention is obtained by leaching and casting the above-mentioned particulate polyurethane carboxylic acid resin composition. • The molded article of the present invention is suitable for use in automotive interior fittings. The method for producing a particulate polyamino phthalate resin composition of the present invention is a water absorbing liquid of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and a thermally crosslinkable monomer and After the aqueous dispersion of the polymerization preventive agent was mixed, spray drying was carried out. (Effect of the Invention) The particulate polyamino phthalate resin composition of the present invention contains 1 to 6 parts by mass of a polymerization inhibitor per 1 part by mass of the heat-parent monomer. Control of the hardening reaction of the thermally crosslinkable monomer during the molding process can be performed without impairing the formability of the particulate polyurethane resin composition

情況下,導入交聯構造。藉此,可在保持著聚胺基曱酸酯樹 脂原本的外觀、觸感、成形性之情況下,提升長期耐熱性。 此外藉由3有在水分散媒中合成的熱可塑性聚胺基甲酸酯 樹脂、乙烯基單體聚合體、熱交聯性單體、及聚合防止劑, 則可提升成的外觀、觸感、成形性及長期耐熱性。 所以本發明的粒子狀聚胺基卩_樹脂組成物係粉體流 動眭成形r生均優異,由該粒子狀聚胺基甲酸醋樹脂組成物 成形的成形品,倍0 ^ ,, '巴不均、貝感、機械物性、耐藥性及長期 097138844 200925210 耐熱性均優異。 再者,本發明的粒子狀聚胺基甲酸酯樹脂組成物之製造方 法’係在將熱可塑性聚胺基曱酸酯樹脂及乙烯基單體聚合體 的水分散液、與熱交聯性單體及聚合防止劑的水分散液進行 混合後,藉由施行喷霧乾燥,便可輕易地製造各成分均句分 散的粒子狀聚胺基甲酸酯樹脂組成物。 【實施方式】 ❹ 本發明的粒子狀聚胺基甲酸酯樹脂組成物係含有:熱可塑 性聚胺基曱酸酯樹脂、乙烯基單體聚合體、熱交聯性單體及 聚合防止劑。 本發明中’熱可塑性聚胺基甲酸酯樹脂係藉由將異氛酸醋 基末端預聚物、與鏈伸長劑’在水系分散媒中進行反應便可 獲得。 異氰酸酯基末端預聚物係由異氰酸酯、多元醇、視需要的 Ο —元醇及/或單胺所合成。 異氰酸醋係只要屬於聚胺基曱酸酯樹脂製造時所使用的 有機異氰酸酯便可’其餘並無特別的限制,較佳有如脂環族 聚異氰酸酯及/或脂肪族聚異氰酸酯。 脂環族聚異氰酸酯可舉例如:1,3-二異氰酸環戊醋、14_ 二異氰酸環己醋、1,3-二異氰酸環己酯、異氰酸醋_3異氮 酸酯基甲基-3, 5, 5-三曱基環己酯、4, 4’-亞甲基雙(環己基 異氰酸酯)、曱基-2,4-二異氰酸環己酯、甲基__26_二異氛 097138844 6 200925210 酸環己酯、1,3-雙(異氰酸酯基曱基)環己烷或丨,4_雙(異氰 酸酯基甲基)環己烷及該等的異構物混合物、丨,3_雙(異氰酸 酯基乙基)環己烷、或1,4~雙(異氰酸酯基乙基)環己烷、及 該等的異構物混合物等。 • 脂環族聚異氰酸酯中,較佳為例如:由反式-反式、反式- 順式、順式-順式等3種異構物混合的4, 4, _亞曱基雙(環己 基異氰酸酯)、反式-反式異構物比較高的44,—亞曱基雙 ❹(環己基異氰酸醋)、!,3_雙(異級醋基甲基)環己烧、或 U-雙(異氰酸酯基甲基)環己烧、及該等的異構物混合物。 再者,脂肪族聚異氰酸酯可舉例如:三亞甲基二異氛酸 酯、四亞f基二異氰酸醋、六亞曱基二異氛酸酿、五亞甲基 二異氰酸醋、六亞甲基二異氰_、1>2_二異氰酸丙醋、^― 二異氰酸丁3旨、2,3-二異氰酸丁自旨、13_二異氰酸丁醋、 2’4’4-或2, 2, 4_三甲基六亞甲基二異氰酸醋、2, 6_二異氰 ❹酸酯甲基己酸酯等。 再者 吳亂酸酿係在不損及成形品的長期耐熱性之範圍 内,亦可併用單異氰酸醋。單異氰酸@旨可舉例如:異氣酸甲 醋、異氰㈣乙自旨、異氰酸正己酯、異氰酸環己自旨、異氛酸 2-乙基己酯、異氰酸苯酯、異氰酸苄酯等。 該等異氰酸酯係可單獨使用、或亦可 係單獨制脂«飾旨^外,當併用料^較佳 況’相對於所併用之異氰酸酯的總莫耳,脂環族聚異 097138844 200925210 較佳係含有70莫耳%以上,更佳80莫耳%以上。 本發明中,多元醇可舉例如:聚醚多元醇、聚酯多元醇、 聚碳酸酯多元醇,以及在該等多元醇中,使苯乙烯、丙烯腈、 (甲基)丙烯酸酯等乙烯基單體進行聚合的聚合物多元醇 等,且數量平均分子量400〜5000,或者羥基價 10〜125mgKOH/g的高分子量多元醇。高分子量多元醇的數量 平均分子量較佳為1400〜3000,更佳1500〜2500。另一方面, ❹ 使用聚合物多元醇時,經基價較佳為20〜80mgKOH/g左右。 聚醚多元醇可舉例如:聚丙二醇、聚丁醚二醇等。 聚丙二醇可舉例如:以低分子量多元醇或低分子量聚胺作 為起始劑的環氧乙烷、環氧丙烷等環氧烷之加成聚合物(包 括2種以上環氧烷的無規及/或嵌段共聚合體)。 另外,低分子量多元醇係具有2以上羥基且數量平均分子 量60〜400的化合物,可舉例如:乙二醇、丙二醇、1,4-丁 φ 二醇、1,3-丁二醇、1,2-丁 二醇、1,6-己二醇、新戊二醇、 烷(7〜22)二醇、二乙二醇、三乙二醇、二丙二醇、1,3-或 1,4-環己烷二曱醇、及該等的混合物;1,4-環己二醇、烷 -1,2-二醇(C17〜20)、氩化雙酚 A、l,4-二羥基-2-丁烯、2, 6-二甲基-1-辛烯-3, 8-二醇、雙酚A等二元醇;例如:丙三醇、 三羥曱基丙烷等三元醇;例如:四羥曱基曱烷、季戊四醇、 二季戊四醇、D-山梨糖醇、木糖醇、D-甘露糖醇、D-甘露醇 等具有4以上羥基的多元醇等。 097138844 8 200925210 聚丁醚二醇可舉例如:利用四氫呋喃的陽離子聚合所獲得 的開環聚合物,或使四氫呋喃的重複單位、與新戊二醇等之 上述二元醇進行共聚合的非晶性聚丁醚二醇等。 聚酯多元醇係有如將上述二元醇與多元酸,在公知條件下 •進行反應而獲得的縮聚物。 多元酸可舉例如:草酸、丙二酸、琥珀酸、曱基琥珀酸、 戊二酸、己二酸、1,1-二甲基-1,3-二羧基丙烷、3-曱基-3-φ 乙基戊二酸、壬二酸、癸二酸、其他的脂肪族二羧酸(碳數 11〜13)、氳化二聚酸、順丁烯二酸、反丁烯二酸、衣康酸、 鄰苯二甲酸、間苯二甲酸、對苯二曱酸、曱苯二羧酸、二聚 酸、海特酸等羧酸、及由該等羧酸所衍生的酸酐、酸i化物 等。 再者,聚醋多元醇係有如:以上述二元醇作為起始劑,將 例如ε -己内酯、γ -戊内醋等内酯類施行開環聚合而獲得的 G 聚己内酯多元醇、聚戊内酯多元醇,以及使該等與上述二元 醇進行共聚合的内酯系多元醇等。 聚碳酸酯多元醇係例如:以上述二元醇為起始劑的碳酸乙 烯酯開環聚合物,可舉例如:諸如1,4-丁二醇、1,5-戊二 醇、1,6-己二醇等二元醇,與開環聚合物進行共聚合的非晶 性聚碳酸醋多元醇等。 再者,多元醇係可併用上述低分子量多元醇。 一元醇可舉例如:甲醇、乙醇、丙醇、丁醇、2-乙基己醇、 097138844 9 200925210 其他的烷醇(C5~38)、以及脂肪族不飽和醇(9~24)、烯醇、 2-丙烯-1-醇、烷二烯醇(〇6〜8)、3,7-二曱基-1,6-辛二烯_3- 醇等。 單胺可舉例如:二曱胺、二乙胺、二正丙胺、二異丙胺、 二正丁胺、二異丁胺、二第三丁胺、二己胺、2-乙基己胺、 3-曱氧基丙胺、3-乙氧基丙胺、3-(2-乙基己氧基丙胺)、 3-(十二烷氧基)丙胺、N,N-二曱基-1,3-丙二胺、咮淋等。 ❹ 另外,一元醇及/或單胺係用於進行熱可塑性聚胺基曱酸 酯樹脂的分子量調整,而視需要調配。 ❹ 在異氰酸酯基末端預聚物的合成時,係依相對於多元醇、 及視需要的一元醇及/或單胺之活性氫基(經基及胺基),異 氰酸酯的異氰酸酯基當量比(異氰酸酯基/活性氫基)成為例 1〜4、較佳1.4〜2. 5的比例調配,並進行反應。若上述 當量比未滿1.1,熱可塑性聚胺基甲酸㈣脂過度成為言八 子量’而有降低成形性的情況。反之,若當量比超= 况 =生聚胺基甲酸醋樹脂的成形品變硬,有損及觸感的情、、、 該反應係例如在氣環境下,依反應 7〇〜90。(:,持續進杵只由 又叫的C、較佳 反應系統卜當時間2~7小時、較㈣小時,在 _時點便結束^所需異氣贼基含有量(例如μ重量 係現需要’可添加胺類或有機金屬化合物等 再者,該反應 097138844 200925210 觸媒。觸媒較佳可舉例如有機金屬化合物,此種有機金屬化 合物可舉例如:醋酸錫、辛酸錫、油酸錫、月桂酸錫、二醋 酸二丁錫、二月桂酸二曱錫、二月桂酸二丁錫、二月桂酸二 辛錫、二氯二丁鍚、辛酸鉛、環烷酸鉛、環烷酸鎳、環烷酸 鈷、辛烯酸銅、鉍系觸媒等。觸媒可單獨使用、或可併用2 種以上,例如相對於多元醇100質量份,添加例如0. 001〜5 質量份,較佳0. 01~3質量份。 ❹ 然後,使所獲得之異氰酸酯基末端預聚物、與鏈伸長劑, 在水系分散媒中進行鏈伸長反應,獲得熱可塑性聚胺基曱酸 醋樹脂。 本發明中,鏈伸長劑可舉例如:脂環族二胺、脂肪族二胺 等二胺,或諸如上述二元醇、上述三元醇等低分子量多元醇 等。 脂環族二胺可舉例如:1-胺基-3-胺基曱基-3, 5, 5-三曱基 G 環己烷、雙(4-胺基環己基)曱烷、二胺基環己烷、3, 9-雙(3- 胺基丙基)-2, 4, 8, 10-四呤螺[5, 5]十一烷、1,3-及1,4-雙 (胺基曱基)環己烷、及該等的混合物等。 脂肪族二胺可舉例如:乙二胺、丙二胺、己二胺、聯氨、 1,2-二胺基乙烧、1,2-二胺基丙烧、1,3-二胺基戊烧等。該 等鏈伸長劑中,二胺較佳可舉例如:1-胺基-3-胺基曱基 -3, 5, 5-三曱基環己烷、雙(4-胺基環己基)甲烷、1,3-及 1,4-雙(胺基曱基)環己烷、及該等的混合物、己二胺。此外, 097138844 11 200925210 低分子量多元醇較佳可舉例如:乙二醇、14_丁二醇、i 六亞曱基二醇、l 4—環己二醇、1,3-、1,4-環己烷二曱醇、 及该專的混合物等。 當聚異氣酸醋係使用4,4’_亞曱基雙(環己基異氮酸醋) 的情況’較佳為1,雙(胺基甲基)環己燒、己二胺等二胺、 及乙二醇。 鏈伸長劑係可單獨使用、或併用2種以上。 ❹ 鏈伸㈣係依㈣於異級雜末端預料㈣異氰_旨 基’鏈伸長劑的活性氫基(胺基及經基)之當量比(活性氫基/ 異亂酸醋基)成為例如O.H.卜較佳〇4〜1〇5的比例進行 調配。 水系分散㈣實質未使異氰_基末端預雜及熱可塑 f生基f酸gaΜ脂溶解的水或水性溶劑,水性溶劑可舉例 如:水及_(例如甲醇、乙醇等)的混合溶液等。 © 鏈伸長反應巾’何先在異氰義基末端預聚物中調 配入水系分散媒,藉由使異氰酸醋基末端預聚物分散於水系 分散媒中,調製得預聚物水分散液。 水系刀散媒係相對於異氰酸醋基末端預聚⑯100質量 份。調配入例如60〜400質量份,較佳80〜120質量份。 再者,較佳係與水系分散媒-起調配乳化劑。乳化劑可舉 例如.聚氧乙稀燒基㈣等非離子型界面活性劑;聚氧乙稀烧 基驗硫㈣等陰離子型界面活性劑等。乳化劑可單獨使用、 097138844 12 200925210 或亦可併用2種以上。此外,乳化劑係相對於異氰酸酯美末 端預聚物100質量份,例如調配入〇 ^ . 貝重份,較佳 0. 5〜5質量份。 然後’在預聚物水分散液中調配入鏈伸長劑。鏈伸長劑係 可對異氰酸酯基末端預聚物以統括或分批方式添 。 小、口,或者亦 可採取滴下方式。 再者,鏈伸長劑係可調製成水溶液,溫度係調整為例如 〇 10〜80°C ’較佳15〜50Ϊ ’更佳15〜4〇ΐ。 另一方面,預聚物水分散液的溫度係調整為例如ι〇〜ι〇〇 °C ’較佳15〜80°C,更佳20〜60°C。 然後,鏈伸長反應中,例如在2(Mm:,較佳係經鍵伸 長劑的水溶液添加後,再於2Q〜6(rc中,雖依比例而有所差 異,但將進行0. 5〜48小時反應。另外,視需要亦可適當添 加上述觸媒。 © 藉此’可依熱可雛聚絲樹脂的水分散液(聚胺 基甲酸酯分散體)形式獲得。 本發明中,乙稀基單體聚合體係例如芳香族乙稀基單體、 與α’ 乙烯性不飽和竣酸燒基醋的共聚合體,藉由使芳香 族乙嫦基單體與《,点-乙稀性不飽和幾酸烧基醋,進行自由 基共聚合反應便可獲得。 芳香族乙烯基單體係可舉例如:苯乙稀、α 一甲基苯乙稀 等苯乙稀系單體;或例如乙烯基?苯、乙基乙烯苯等焼基乙 097138844 13 200925210 烯苯;或例如乙烯基萘等多環芳香族單乙烯基單體。 該等芳香族乙烯基單體係可單獨使用、或併用2種以上。 此外’該等之中,較佳為苯乙烯。 • α,乙烯性不飽和羧酸烷基酯係可舉例如:丙烯酸乙 -酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸環己酯、丙烯酸異壬 醋、丙烯酸I乙基己醋、f基丙_甲酉旨、甲基丙稀酸丁 酉旨、曱基丙婦酸環己醋、甲基丙烯酸I乙基己酉旨等狀(甲 ❹基)丙稀㈣。此外乙烯性不飽和魏燒基醋係可 舉例如:丙烯腈、甲基丙烯腈等氰乙婦或二氰乙烯等。 該等L /3、乙烯性不飽和紐烧基醋可單獨使用、或併用 2種以上。此外,該等之中,較佳為甲基丙婦酸甲醋、 丙烯酸丁 S旨。 然後,為使芳香族乙埽基單體與α,石一乙烤性不飽和叛酸 烧基醋進行自由基共聚合反應,相對於該等單體總量,依芳 ®香族乙稀基單體35〜7〇質量%、較佳45〜65質量%,α,点-乙烯性不飽和緩酸燒基醋30〜65質量%、較佳35~55質量。/。 的比例進行„周配,並添力口自由基聚合起始劑。 自由基聚合起始劑可舉例如:過硫酸鹽、有機^氧化物、 偶氮系化合物等。 過硫酸鹽可舉例如:過硫酸納、過硫酸鉀、過硫酸錄等。 有機過氧化物可舉例如:1,卜二(過氧化第三己 基)-3,3’5~三甲基環己燒、1,卜二(過氧化第三己基)-2-曱 097138844 200925210 基環己烧、1,卜二(過氧化第三丁基)環己燒等過氧化嶋醇 類;或例如··二第三丁基過氧化物等二烷基過氧化物類·或 例如:過氧化二月桂醯、二(3_甲基苯甲酸基)過氧化物、苯 甲醯基(3-甲基笨甲醯基)過氧化物、過氧化二苯甲酿基等二 •醒基過氧化物類;或例如:己酸一1,1,3,3-四甲基過&化; 基-2-乙醋、2, 5-二甲基_2, 5_二(2 一乙基過氧化己醯基)己 烧、己酸過氧化第三己基_2_乙酯、己酸過氧化第三丁基_2一 ❹乙酯、單碳酸過氧化第三己基異丙酯、月桂酸過氧化第三丁 S曰、單碳酸過氧化第三丁基異丙酯、單碳酸過氧化第三丁基 -2-乙基己酯、2, 5-二甲基-2, 5-二(過氧化苯曱醯基)己烷等 過氧化酯類等。 偶氮系化合物可舉例如:偶氮雙異丁腈、2, 2, _偶氮雙 (2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丁腈)、二甲基 -2, 2’ -偶氮雙(2-曱基丙酸酯)、2, 2,-偶氮雙((2-(2-咪唑啉 © _2_基)丙烷、甲基丙烷異丁酸二甲酯、2, 2, 7-偶氮雙[N-(2一 羧基)-2-甲基丙脒]四水合物、2, 2,-偶氮雙[2-甲基 -N-[l,l-雙(羥曱基)-2-羥乙基]丙醯胺]、2,2,_偶氮雙 [N-(2-經乙基)-2-曱基丙醯胺]、2, 2’-偶氮雙(2, 4-二曱基 -4-曱氧基戊腈)、1,Γ -偶氮雙[環己一ι_腈]等。 該等自由基聚合起始劑係可單獨使用、或併用2種以上。 此外,5亥專之中,較佳為二曱基-2, 2,-偶氮雙(2-曱基丙酸 酯)、2, 2’ -偶氮雙(2-曱基丁腈)。 097138844 15 200925210 自由基聚合起始劑係相對於單體總量1〇〇 質量份,添加例 如ο.1〜2.0質量份,較佳質量份。 再者,自由基共聚合反應中,為了進行乙稀基單體聚合體 的为子里§周整,亦可添加鏈轉移劑。 鏈轉移劑可舉例如:第三(十二妓)硫醇、硫甘醇酸-2- 乙基己醋等硫醇類;或例如基苯乙烯二聚體等苯乙稀 二聚體類等。 ❹ 該等鏈轉移劑係可單獨使用、或併用2種以上。此外,該 等之中,較佳為a _甲基苯乙烯二聚體。 鏈轉移劑係相對於單體總量1〇〇質量份,添加例如〇〜1〇 質量份,較佳〇· 〜5質量份,更佳〇· 〇1〜2質量份。 再者,自由基共聚合反應中,視需要可添加聚合用乳化 劑、缓衝劑等公知添加劑。 然後,自由基共聚合反應中,係將上述單體在例如反應溫 ©度20〜9(TC、較佳60〜90。〇下,進行反應時間〇. 5〜2〇小時、 較佳1〜1 〇小時的反應。 乙烯基單體聚合體係可在水分散媒中合成的熱可塑性聚 胺基曱酸酯樹脂之外,另行依照上述條件進行合成,並將其 調配入熱可塑性聚胺基曱酸酯樹脂的水分散液中。此外,乙 稀基單體聚合體亦可藉由在熱可塑性聚胺基甲酸醋樹脂或 異氰酸酯基末端預聚物的水分散液中’添加預先將上述單 體、自由基聚合起始劑及視需要的鏈轉移劑、聚合用乳化 097138844 16 200925210 射'缓衝_合而形成的單趙乳化液,便可 者的方法’可更均勻地調配人熱可塑性聚胺μ酸== 乙稀基單體聚合體,且可提升製造步驟中的操作性。 乙烯基單體聚合體係相對於熱<塑性聚胺基甲酸酯樹脂 1 1〇〇質量份,例如調配5〜40質量份,最好15〜30質量份。 本發明中,熱交聯性單體係具有複數之乙烯性不飽和鍵的 化合物’可舉例如:乙二醇二(曱基)丙烯酸酯、丙二醇二(甲 ❹ 基)丙烯酸酯、丁二醇二(曱基)丙烯酸酯、戊二醇二(甲基) 丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基) 丙烯酸酯、壬二醇二(曱基)丙烯酸酯、寡聚乙二醇二(曱基) 丙烯酸酯等烷二醇二(曱基)丙烯酸酯;或例如:三羥甲基丙 烷三(曱基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、季戊四錄 四(甲基)丙稀酸醋、二季戊四醇玉(甲基)丙烯酸醋、一季戍 四醇六(曱基)丙烯酸酯等烷多元酵聚(曱基)丙烯酸酯;或例 ❹如:順丁烯二酸二烯丙酯、反丁烯>酸二烯丙酯、衣康酿〆 烯丙酯等不飽和羧酸二烯丙酯;或例如:胺基甲酸乙酯二(甲 基)丙烯酸酯;或例如:聚丁二烯>(曱基)丙烯酸酯荨β該 等之中,較佳為二季戊四醇五(甲基)丙烯酸酯、二季戊四酵 六(曱基)丙烯酸酯。 該等熱交聯性單體可單獨使用、或併用2種以上。此外口 該等之中,較佳為烷多元醇聚(甲基)丙烯酸酯。熱交聯性單 體係相對於熱可塑性聚胺基曱酸酯樹脂100質量份’調配入 097138844 17 200925210 例如2〜10質量份,較佳4〜8質量份。 :對苯醌、對甲氣蜓、萘In this case, the cross-linking structure is imported. Thereby, the long-term heat resistance can be improved while maintaining the original appearance, feel, and formability of the polyaminophthalate resin. Further, by having a thermoplastic polyurethane resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent which are synthesized in an aqueous dispersion medium, the appearance and touch can be improved. , formability and long-term heat resistance. Therefore, the particulate polyamine hydrazine-resin composition of the present invention is excellent in powder flow enthalpy, and the molded article formed from the particulate urethane resin composition is 0 ^ , , '巴Uniformity, shelling, mechanical properties, drug resistance and long-term 097138844 200925210 Excellent heat resistance. Further, the method for producing a particulate polyurethane resin composition of the present invention is based on an aqueous dispersion of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and thermal crosslinking property. After mixing the monomer and the aqueous dispersion of the polymerization preventive agent, the particulate polyurethane resin composition in which the components are uniformly dispersed can be easily produced by spray drying. [Embodiment] The particulate polyurethane resin composition of the present invention contains a thermoplastic polyamine phthalate resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent. In the present invention, the 'thermoplastic urethane resin is obtained by reacting an oleic acid terminal prepolymer and a chain extender' in an aqueous dispersion medium. The isocyanate-based terminal prepolymer is synthesized from an isocyanate, a polyhydric alcohol, an optional quinone alcohol and/or a monoamine. The isocyanate vinegar is not particularly limited as long as it belongs to the organic isocyanate used in the production of the polyamino phthalate resin, and is preferably an alicyclic polyisocyanate and/or an aliphatic polyisocyanate. The alicyclic polyisocyanate may, for example, be 1,3-diisocyanate cyclopentaacetic acid, 14-diisocyanate cyclohexanoic acid, 1,3-diisocyanate cyclohexyl ester, isocyanic acid vinegar_3 aza Acid ester methyl-3,5,5-trimethylcyclohexyl ester, 4,4'-methylenebis(cyclohexyl isocyanate), fluorenyl-2,4-diisocyanate cyclohexyl ester, A __26_二异式097138844 6 200925210 Cyclohexyl acrylate, 1,3-bis(isocyanatodecyl)cyclohexane or hydrazine, 4_bis(isocyanatemethyl)cyclohexane and these isomers Mixture, hydrazine, 3_bis(isocyanatoethyl)cyclohexane, or 1,4-bis(isocyanateethyl)cyclohexane, and mixtures of such isomers, and the like. • Among the alicyclic polyisocyanates, for example, 4, 4, _indenyl bis (cyclo) mixed by three isomers such as trans-trans, trans-cis, cis-cis, and the like Hexyl isocyanate), trans-trans isomer relatively high 44,-fluorenylene dioxime (cyclohexyl isocyanate),! , 3_bis(iso-hydroxymethyl)cyclohexane, or U-bis(isocyanatemethyl)cyclohexane, and mixtures of such isomers. Further, examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetra-f-butyl diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate; Hexamethylene diisocyanide _, 1 > 2 - diisocyanate propyl vinegar, ^ - diisocyanate butyl 3, 2,3-diisocyanate butyl, 13 - diisocyanate 2'4'4- or 2, 2, 4_trimethylhexamethylene diisocyanate, 2,6-diisocyanurate methylhexanoate, and the like. Further, the sulphuric acid can be used in combination with the monoisocyanate in a range which does not impair the long-term heat resistance of the molded article. Monoisocyanuric acid is intended to be, for example, isoammonic acid methyl vinegar, isocyanide (tetra) ethane, tetrahexyl isocyanate, isocyanate, ethyl 2-ethylhexyl isocyanate, isocyanic acid Phenyl ester, benzyl isocyanate, and the like. The isocyanates may be used singly or in the form of a separate grease. When the materials are used in combination with the total moles of the isocyanate used, the alicyclic polyiso 097138844 200925210 is preferred. It contains 70 mol% or more, more preferably 80 mol% or more. In the present invention, the polyhydric alcohol may, for example, be a polyether polyol, a polyester polyol or a polycarbonate polyol, and a vinyl group such as styrene, acrylonitrile or (meth)acrylate in the polyol. A polymer polyol or the like obtained by polymerization of a monomer, and a high molecular weight polyol having a number average molecular weight of 400 to 5,000 or a hydroxyl group of 10 to 125 mgKOH/g. The number average molecular weight of the high molecular weight polyol is preferably from 1400 to 3,000, more preferably from 1,500 to 2,500. On the other hand, when the polymer polyol is used, the base price is preferably about 20 to 80 mgKOH/g. The polyether polyol may, for example, be polypropylene glycol or polybutylene glycol. The polypropylene glycol may, for example, be an addition polymer of an alkylene oxide such as ethylene oxide or propylene oxide using a low molecular weight polyol or a low molecular weight polyamine as a starting agent (including randomization of two or more kinds of alkylene oxides). / or block copolymer). Further, the low molecular weight polyol is a compound having 2 or more hydroxyl groups and having a number average molecular weight of 60 to 400, and examples thereof include ethylene glycol, propylene glycol, 1,4-butane diol, and 1,3-butylene glycol. 2-butanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3- or 1,4- Cyclohexanediethanol, and mixtures thereof; 1,4-cyclohexanediol, alkane-1,2-diol (C17-20), argon bisphenol A, 1,4-dihydroxy-2 a glycol such as butene, 2,6-dimethyl-1-octene-3, 8-diol or bisphenol A; for example, a trihydric alcohol such as glycerol or trihydroxydecylpropane; for example: A polyhydric alcohol having 4 or more hydroxyl groups, such as tetrahydrononyl decane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, and D-mannitol. 097138844 8 200925210 The polybutylene glycol may, for example, be a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran or a repeating unit of tetrahydrofuran or a non-copolymerization of the above-mentioned diol such as neopentyl glycol. Polybutylene glycol and the like. The polyester polyol is a polycondensate obtained by reacting the above-mentioned diol with a polybasic acid under known conditions. Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, mercapto succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-mercapto-3. -φ ethyl glutaric acid, sebacic acid, sebacic acid, other aliphatic dicarboxylic acids (carbon number 11 to 13), deuterated dimer acid, maleic acid, fumaric acid, clothing Carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, terpene dicarboxylic acid, dimer acid, halo acid, and the like, and anhydrides and acid compounds derived from the carboxylic acids Wait. Further, the polyglycol polyol is, for example, a G-polycaprolactone obtained by subjecting a lactone such as ε-caprolactone or γ-pental vinegar to ring-opening polymerization using the above-mentioned diol as a starting agent. An alcohol or a polyvalerolactone polyol, and a lactone-based polyol which copolymerizes the above-mentioned diol. The polycarbonate polyol is, for example, a vinyl carbonate ring-opening polymer using the above diol as a starting agent, and examples thereof include, for example, 1,4-butanediol, 1,5-pentanediol, 1,6. a diol such as hexanediol, an amorphous polycarbonate polyol copolymerized with a ring-opening polymer, or the like. Further, as the polyol, the above low molecular weight polyol may be used in combination. The monohydric alcohol may, for example, be methanol, ethanol, propanol, butanol, 2-ethylhexanol, 097138844 9 200925210 other alkanols (C5~38), and aliphatically unsaturated alcohols (9-24), enols. 2-propen-1-ol, alkadienol (〇6-8), 3,7-dimercapto-1,6-octadiene-3-ol, and the like. The monoamine may, for example, be diamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-third-butylamine, dihexylamine, 2-ethylhexylamine, 3 - alkoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxypropylamine), 3-(dodecyloxy)propylamine, N,N-dimercapto-1,3-propane Diamine, sputum and so on. Further, monohydric alcohol and/or monoamine are used for the molecular weight adjustment of the thermoplastic polyamine phthalate resin, and may be blended as needed. ❹ In the synthesis of the isocyanate-based terminal prepolymer, the isocyanate equivalent ratio (isocyanate) of the isocyanate relative to the active hydrogen group (trans group and amine group) of the polyol and, if desired, the monohydric alcohol and/or the monoamine The base/active hydrogen group is blended in the proportion of Examples 1 to 4, preferably 1.4 to 2.5, and the reaction is carried out. If the above equivalent ratio is less than 1.1, the thermoplastic poly (carbamic acid) tetracarboxylic acid is excessively large and has a reduced formability. On the other hand, if the equivalent ratio is super = condition = the molded article of the raw polyurethane carboxylic acid resin is hard, which is detrimental to the feeling of touch, and the reaction is, for example, in an atmosphere, depending on the reaction. (:, continuous advancement only by the called C, better reaction system Bu time 2 to 7 hours, compared to (four) hours, at the end of _ point ^ the required amount of thief base (such as μ weight is now required 'Addition of an amine or an organometallic compound, etc., the reaction 097138844 200925210 Catalyst. The catalyst is preferably an organometallic compound, for example, tin acetate, tin octylate, tin oleate, Tin laurate, dibutyltin diacetate, diterpene tin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dichlorodimidine, lead octoate, lead naphthenate, nickel naphthenate, 001〜5质量份。 0. 01 to 3 parts by mass. ❹ Then, the obtained isocyanate group-terminated prepolymer and the chain extender are subjected to a chain elongation reaction in an aqueous dispersion medium to obtain a thermoplastic polyamine phthalic acid vinegar resin. The chain extender may, for example, be an alicyclic diamine or a fat. a diamine such as an aliphatic diamine or a low molecular weight polyol such as the above diol or the above triol. The alicyclic diamine may, for example, be 1-amino-3-aminoindolyl-3, 5 , 5-trimethyl G, cyclohexane, bis(4-aminocyclohexyl)decane, diaminocyclohexane, 3,9-bis(3-aminopropyl)-2, 4, 8, 10-tetraspiro[5,5]undecane, 1,3- and 1,4-bis(aminomercapto)cyclohexane, and mixtures thereof, etc. Examples of aliphatic diamines are: Diamine, propylenediamine, hexamethylenediamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane, etc. These chain extenders The diamine is preferably, for example, 1-amino-3-aminoindolyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, 1,3- And 1,4-bis(aminomercapto)cyclohexane, and the like, hexamethylenediamine. Further, 097138844 11 200925210 The low molecular weight polyol preferably has, for example, ethylene glycol or 14-butanediol. , i hexamethylene glycol, l 4 - cyclohexanediol, 1,3-, 1,4-cyclohexanedimethanol, and the special mixture, etc. When the polyisophthalic acid vinegar is used 4, 4 The case of _-indenyl bis(cyclohexyl isocyanate) is preferably 1, a diamine such as bis(aminomethyl)cyclohexane or hexamethylenediamine, and ethylene glycol. The chain extender can be used alone. Use or use two or more kinds in combination ❹ Chain extension (4) is based on (4) Equivalent ratio of active hydrogen group (amine group and warp group) of isocyanate-chain base elongation agent (active hydrogen group / The dissimilar acid vinegar group is formulated such that the ratio of OH is preferably 〇 4 to 1 〇 5. The water dispersion (4) does not substantially dissolve the isocyanate-based end and the thermoplastic water, or the hydrolyzable The aqueous solvent and the aqueous solvent may, for example, be a mixed solution of water and _ (for example, methanol or ethanol). © Chain Stretch Reaction Tray 'Which is first formulated into an aqueous dispersion medium in an isocyanide terminal prepolymer, and the prepolymer aqueous dispersion is prepared by dispersing the isocyanate end prepolymer in an aqueous dispersion medium. . The aqueous knife media was prepolymerized to 16100 parts by mass relative to the isocyanate end. The compounding amount is, for example, 60 to 400 parts by mass, preferably 80 to 120 parts by mass. Further, it is preferred to formulate an emulsifier with an aqueous dispersion medium. The emulsifier may, for example, be a nonionic surfactant such as polyoxyethylene sulphide (IV) or an anionic surfactant such as polyoxyethylene sulphur (IV). The emulsifier may be used alone, 097138844 12 200925210 or two or more types may be used in combination. 5〜5质量份。 The emulsifier is preferably used in an amount of 0.5 parts by mass, preferably 0.5 parts by weight, based on 100 parts by weight of the isocyanate terminal prepolymer. Then, the chain extender is formulated in the aqueous prepolymer dispersion. The chain extender can be added to the isocyanate-based terminal prepolymer in an integrated or batchwise manner. Small, mouth, or drop method. Further, the chain extender is adjusted to be an aqueous solution, and the temperature is adjusted to, for example, 〇 10 to 80 ° C ', preferably 15 to 50 Å', more preferably 15 to 4 Å. On the other hand, the temperature of the prepolymer aqueous dispersion is adjusted to, for example, ι 〇〇 to ι ° ° C. preferably from 15 to 80 ° C, more preferably from 20 to 60 ° C. 5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5 The reaction may be carried out for 48 hours. Further, the above-mentioned catalyst may be appropriately added as needed. © This can be obtained in the form of an aqueous dispersion (polyurethane dispersion) of the heat-cleavable filament resin. In the present invention, A dilute-based monomer polymerization system such as an aromatic vinyl monomer, and a copolymer of α'ethylenically unsaturated decanoic acid vinegar, by making an aromatic ethylenic monomer and ", point-ethylene is not The saturated acid-based vinegar is obtained by radical copolymerization. The aromatic vinyl single system may, for example, be a styrene monomer such as styrene or α-methylstyrene; or, for example, ethylene. Base benzene, ethyl vinyl benzene, etc. thiol 097138844 13 200925210 olefin benzene; or polycyclic aromatic monovinyl monomer such as vinyl naphthalene. The aromatic vinyl single system can be used alone or in combination 2 In addition, among these, styrene is preferred. • α, ethylene is not Examples of the alkyl carboxylic acid esters include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, isophthalic acid acrylate, ethyl hexyl acrylate, and f-propyl propyl group. Alkyl acetonate, thioglycolic acid hexanoic acid vinegar, methacrylic acid I ethyl hexyl methacrylate (meth) propylene (4). Further, the ethylenically unsaturated Wei ketone vinegar can be exemplified by: Cyanide or dicyandiamide such as acrylonitrile or methacrylonitrile, etc. These L/3, ethylenically unsaturated butyl ketones may be used singly or in combination of two or more. It is a methyl acetoacetate methyl vinegar or a butyl acrylate. Then, in order to carry out a radical copolymerization reaction of the aromatic ethyl thiol monomer with the α, succinyl-stained unsaturated sulphuric acid vinegar, The total amount of monomers, such as yifang® fragrant vinyl monomer 35~7〇% by mass, preferably 45~65% by mass, α, point-ethylene unsaturated sulphuric acid vinegar 30~65% by mass, Preferably, the ratio of 35 to 55 mass% is carried out, and the radical polymerization initiator is added. The radical polymerization initiator may, for example, be: Sulfate, organic oxide, azo compound, etc. Persulfate may, for example, be sodium persulfate, potassium persulfate or persulfate. The organic peroxide may, for example, be 1, and the second is peroxide. Trihexyl)-3,3'5~trimethylcyclohexene, 1,di(diacetylhexyl peroxide)-2-oxime 097138844 200925210 base ring hexane, 1, bis (peroxide tert-butyl) a peroxy sterol such as cyclohexane; or a dialkyl peroxide such as di-tert-butyl peroxide or, for example, dilauroyl peroxide or bis(3-methylbenzoic acid) a peroxide, a benzamidine (3-methyl benzoyl) peroxide, a dibenzoic peroxide such as a diphenyl benzoate; or, for example, caproic acid-1,1, 3,3-Tetramethyl over & keto-2-ethyl vinegar, 2, 5-dimethyl-2, 5_bis(2-ethylhexyloxyhexyl) hexane, hexanoic acid peroxidation Third hexyl-2-ethyl ester, butyl hexanoate hexanoate, monohexyl isopropyl monoperoxide, dimethyl sulphate peroxidate, succinic acid peroxidized Tributyl isopropyl ester, monocarbonic acid peroxidation A peroxy ester such as a third butyl-2-ethylhexyl ester or a 2, 5-dimethyl-2, 5-di(benzoyl phenyl) hexane. Examples of the azo compound include azobisisobutyronitrile, 2,2, azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-methylbutyronitrile). ), dimethyl-2, 2'-azobis(2-mercaptopropionate), 2, 2,-azobis((2-(2-imidazoline)-2-yl)propane, methyl Dimethyl propane isobutyrate, 2, 2, 7-azobis[N-(2-carboxy)-2-methylpropionamidine] tetrahydrate, 2, 2,-azobis[2-methyl -N-[l,l-bis(hydroxyindenyl)-2-hydroxyethyl]propanamide], 2,2,-azobis[N-(2-ethyl)-2-indenyl Indoleamine], 2, 2'-azobis(2,4-dimercapto-4-indolyl valeronitrile), 1, Γ-azobis[cyclohexamethylene-1-carbonitrile], etc. The base polymerization initiator may be used singly or in combination of two or more. In addition, among the 5th, it is preferably dimercapto-2, 2,-azobis(2-mercaptopropionate), 2 2'-azobis(2-mercaptobutyronitrile) 097138844 15 200925210 The radical polymerization initiator is added in an amount of, for example, ο.1 to 2.0 parts by mass, preferably 1 part by mass, based on the total amount of the monomers. In addition, in the free radical copolymerization, in order to carry out the ethylene monomer The chain transfer agent may be added in the middle of the polymer, and a chain transfer agent may be added. The chain transfer agent may, for example, be a mercaptan such as a third (twelve oxime) thiol or a thioglycolic acid-2-ethylhexyl vinegar; Or, for example, a styrene dimer such as a styrene dimer, etc. ❹ These chain transfer agents may be used singly or in combination of two or more. Further, among these, a-methylbenzene is preferred. The ethylene glycol dimer is added in an amount of, for example, 〇1 to 1 part by mass, preferably 〇·5 parts by mass, more preferably 1 to 2 parts by mass, based on 1 part by mass of the total amount of the monomers. Further, in the radical copolymerization reaction, a known additive such as an emulsifier for polymerization or a buffer may be added as needed. Then, in the radical copolymerization reaction, the monomer is, for example, at a reaction temperature of 20 to 9 ( TC, preferably 60 to 90. Under the reaction, the reaction time is 5 〇 2 〇 hours, preferably 1 〜 1 〇 hr. The vinyl monomer polymerization system can be synthesized in a water dispersion medium of thermoplastic polyamine In addition to the phthalic acid ester resin, it is synthesized according to the above conditions and formulated into a thermoplastic polyamine phthalate. In addition, the ethylene monomer polymer can also be added by adding the above monomer in advance in the aqueous dispersion of the thermoplastic polyurethane resin or the isocyanate-based terminal prepolymer. Base polymerization initiator and optional chain transfer agent, emulsification for polymerization 097138844 16 200925210 shot of 'buffer_combined single Zhao emulsion, the method can be more evenly blended with human thermoplastic polyamine μ Acid == ethylene monomer polymer, and can improve the operability in the manufacturing step. The vinyl monomer polymerization system is 1 part by mass relative to the heat & plastic polyurethane resin, for example, 5 ~ 40 parts by mass, preferably 15 to 30 parts by mass. In the present invention, the compound having a plurality of ethylenically unsaturated bonds in the heat-crosslinkable single system can be exemplified by ethylene glycol bis(indenyl) acrylate, propylene glycol bis(methyl decyl) acrylate, butylene glycol. Di(indenyl)acrylate, pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, decanediol di(decyl) An alkanediol bis(indenyl) acrylate such as acrylate or oligoethylene glycol bis(indenyl) acrylate; or, for example, trimethylolpropane tris(mercapto) acrylate or glycerol tris(methyl) Alkenyl poly(poly(decyl) acrylates such as acrylate, pentaerythritol tetrakis (meth) acrylate vinegar, dipentaerythritol jade (meth) acrylate vinegar, and one quarter decyl alcohol hexa(meth) acrylate Or an example of a diallyl ester of an unsaturated carboxylic acid such as diallyl maleate, butylene, diallyl, or propyl allylate; or, for example, amide Ethyl di(meth) acrylate; or for example: polybutadiene > (fluorenyl) acrylate 荨β Among the, preferred is dipentaerythritol penta (meth) acrylate, dipentaerythritol yeast hexa (Yue-yl) acrylate. These thermally crosslinkable monomers may be used alone or in combination of two or more. Further, among these, an alkyl polyol poly(meth)acrylate is preferred. The heat crosslinkable single system is blended with 100 parts by mass of the thermoplastic polyurethane phthalate resin to 097138844 17 200925210, for example, 2 to 10 parts by mass, preferably 4 to 8 parts by mass. : p-benzoquinone, p-methane, naphthalene

• 2, 5-二第三戊基氫酿等氫g_ ;或例如:對甲氧基吩、* 本發明中,聚合防止劑可舉例如: 醌、菲醌、曱醌、2, 5-二苯基斟芏赌, 二丁基•對甲盼氮酿早甲趟等盼類等。 該等聚合防止劑係可單獨使用、或併用2種以上。此外 ©該等之中,難為氫醌、對甲氧細。聚合防止劑係相對於 熱交聯性單體100質量份,調配例如〇1〜6質量份,較佳 〇· 1〜5質量份’更佳〇·卜4質量份。若聚合防止劑的調3 數未滿0. 1質量份,則色不均、質感、甚至長期耐熱性等降 低。反之,若聚合防止劑的調配份數超過6質量份,色不均、 長期耐熱性等降低。若聚合防止劑的調配份數在上述範圍 内’則可獲得色不均、質感均優異,且機械物性、耐藥性及 〇 長期耐熱性均優異的成形品。 熱父聯性單體及聚合防止劑較佳係與乳化劑及後述添加 劑一起調製成水分散液之後’再將該水分散液調配於含有熱 可塑性聚胺基甲酸酯樹脂及乙烯基單體聚合體的水分散媒 中並進行混合。 然後’將由上述各成分所調配成的水分散媒,利用施行例 如喷霧乾燥,便可獲得本發明的粒子狀聚胺基曱酸酯樹脂組 成物。 097138844 18 200925210 根據此種製造方法,可輕易地製得各成分均勻分散的粒子 狀聚胺基甲酸醋樹脂組成物。 所獲得之粒子狀聚胺基曱酸酯樹脂組成物的體積平均粒 徑,係例如50〜300 /zm,較佳80〜200 μιη。若體積平均粒徑 未滿50,則因粉體流動性降低,導致成形時發生不均。 反之,若體積平均粒徑超過300 y in,則有成形品表面上發 生針孔的情況。 ❹ 在粒子狀聚胺基曱酸酯樹脂組成物中,視需要尚可添加其 他的公知添加劑,例如:可塑劑、抗黏連(anti_M〇cking) 劑、耐熱安定劑、耐光安定劑、離型劑、以及抗氧化劑、紫 外線吸收劑、顏料、染料、滑劑、填充材、抗水解劑等。該 等添加劑可在各成分進行合成時添加,或者在各成分進行混 合•分散時添加,甚至可在粒子狀聚胺基曱酸酯樹脂組成物 進行分離·乾燥後添加。 ❹ 然後’本發明的粒子狀聚胺基曱酸酯樹脂組成物中,藉由 相對於熱交聯性單體丨〇〇質量份含有〇·卜6質量份的聚合防 止劑’可對成形過程中的熱交聯性單體之硬化反應進行控 制’可在不損及粒子狀聚胺基甲酸酯樹脂組成物之成形性的 情況下,導入交聯構造。藉此,可在保持著聚胺基甲酸酯樹 脂原本的外觀、觸感、成形性之情況下,提升長期耐熱性。 此外’藉由含有在水分散媒中所合成的熱可塑性聚胺基甲酸 酯樹脂、乙烯基單體聚合體、熱交聯性單體、及聚合防止劑, 097138844 19 200925210 可提升成形品的外觀、觸感、成形性及長期耐熱性。 所以,本發明的粒子狀聚胺基曱酸酯樹脂組成物係粉體流 動性、成形性均優異,由該粒子狀聚胺基甲酸酯樹脂組成物 所成形的成形品係色不均、質感、機械物性、耐藥性及長期 耐熱性均優異。 因此’本發明的粒子狀聚胺基曱酸g旨樹脂組成物除可使用 作為碳粉黏結劑之外’尚可適用於瀝鑄成形,可使用於施行 © 瀝鑄成形的傢俱類坐塾與沙發、或玩具等各種領域。特別係 本發明的粒子狀聚胺基曱酸醋樹脂組成物,最適用於利用遞 鑄成形(瀝鑄成型)所成形的汽車内裝配件。 而且,將本發明的粒子狀聚胺基甲酸酯樹脂組成物施行瀝 鍀形成而獲得的成形品、特別是汽車内裝配件,係色不均、 質感、機械物性、对藥性及長期对熱性等均優異。 [實施例] © 其次,針對本發明根據製造例、實施例及比較例進行說 明,惟本發明並不僅侷限於下述實施例。 [實施例1] <熱可塑性聚胺基曱酸酯樹脂之合成> 在安裝有氮導入管及攪拌棒的聚合容器中,投入: Takelac® U-2720C商品名、三井化學 P0LYURETHANES 公司 製、聚酯二醇)56. 4質量份、Take lac® ϋ-2710(商品名、三 井化學POLYURETHANES公司製、聚酯二醇)18. 8質量份、及 097138844 20 200925210• Hydrogen g_ such as 2,5-di-p-diylhydrogen; or, for example, p-methoxyphene, * In the present invention, the polymerization inhibitor may, for example, be fluorene, phenanthrenequinone, anthracene, 2, 5-di Phenyl 斟芏 gambling, dibutyl • a pair of hope for nitrogen, early hyperthyroidism and other expectations. These polymerization inhibitors may be used alone or in combination of two or more. In addition, among these, it is difficult to be hydroquinone or p-methoxy. The polymerization inhibitor is formulated in an amount of, for example, 1 to 6 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of the thermally crosslinkable monomer, more preferably 4 parts by mass. If the number of the polymerization inhibitor is less than 0.1 part by mass, color unevenness, texture, and even long-term heat resistance are lowered. On the other hand, when the number of the polymerization inhibitors exceeds 6 parts by mass, color unevenness, long-term heat resistance, and the like are lowered. When the number of the polymerization inhibitors is within the above range, a molded article excellent in color unevenness and texture, and excellent in mechanical properties, chemical resistance, and long-term heat resistance can be obtained. The hot-parent monomer and the polymerization preventive agent are preferably prepared into an aqueous dispersion together with an emulsifier and an additive described later, and then the aqueous dispersion is formulated to contain a thermoplastic polyurethane resin and a vinyl monomer. The polymer is mixed in an aqueous dispersion medium. Then, the particulate polyaminophthalate resin composition of the present invention can be obtained by subjecting, for example, spray drying to the aqueous dispersion prepared by the above respective components. 097138844 18 200925210 According to this production method, a particulate polyurethane resin composition in which the components are uniformly dispersed can be easily obtained. The volume average particle diameter of the particulate polyaminophthalate resin composition obtained is, for example, 50 to 300 /zm, preferably 80 to 200 μm. If the volume average particle diameter is less than 50, the fluidity of the powder is lowered, resulting in unevenness during molding. On the other hand, when the volume average particle diameter exceeds 300 y in, pinholes may occur on the surface of the molded article. ❹ In the particulate polyamino phthalate resin composition, other known additives may be added as needed, such as: plasticizer, anti-adhesion (anti_M〇cking) agent, heat stabilizer, light stabilizer, release type Agents, as well as antioxidants, ultraviolet absorbers, pigments, dyes, slip agents, fillers, anti-hydrolysis agents, and the like. These additives may be added during the synthesis of the respective components, or may be added during the mixing or dispersion of the components, or may be added after the separation and drying of the particulate polyamino phthalate resin composition. ❹ Then, in the particulate polyamino phthalate resin composition of the present invention, the molding process can be carried out by using a polymerization inhibitor which contains 6 parts by mass of 〇·b relative to the heat-crosslinkable monomer. The curing reaction of the heat crosslinkable monomer is controlled to introduce a crosslinked structure without impairing the formability of the particulate polyurethane resin composition. Thereby, the long-term heat resistance can be improved while maintaining the original appearance, touch, and formability of the polyurethane resin. Further, by containing a thermoplastic polyurethane resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent synthesized in an aqueous dispersion, 097138844 19 200925210 can be used to lift a molded article. Appearance, feel, formability and long-term heat resistance. Therefore, the particulate polyamino phthalate resin composition of the present invention is excellent in powder fluidity and moldability, and the molded article formed from the particulate urethane resin composition is uneven in color. Excellent texture, mechanical properties, drug resistance and long-term heat resistance. Therefore, the "particulate composition of the particulate polyamino phthalic acid g of the present invention can be used as a toner binder in addition to being used as a toner binder", and can be used for the manufacture of furniture such as leaching and casting. Various fields such as sofas and toys. In particular, the particulate polyamine phthalic acid vinegar resin composition of the present invention is most suitable for automotive interior parts formed by transfer molding (leaf casting). Further, the molded article obtained by subjecting the particulate polyurethane resin composition of the present invention to leaching formation, particularly automobile interior parts, has color unevenness, texture, mechanical properties, drug resistance, and long-term heat resistance. Excellent. [Examples] Next, the present invention will be described based on the production examples, examples, and comparative examples, but the present invention is not limited to the following examples. [Example 1] <Synthesis of Thermoplastic Polyuryl Ester Resin Resin> In a polymerization container to which a nitrogen introduction tube and a stirring rod were attached, a product of Takelac® U-2720C, manufactured by Mitsui Chemicals P0LYURETHANES Co., Ltd., 5质量份,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

2-乙基己醇0. 5質量份,在80°C下施行1小時攪拌混合。 在該混合液中,添加4, 4’ -亞甲基雙(環己基異氰酸 酯)(Sumika Bayer Urethane股份有限公司製、商品名: Desmodur W)21. 6質量份,再在80°C下施行2小時攪拌混 合。然後,在該混合液中,再添加Stanoct®(商品名、API2-mmolhexanol 0.5 parts by mass, stirred and mixed at 80 ° C for 1 hour. To the mixed liquid, 4,4'-methylene bis(cyclohexyl isocyanate) (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur W) was added in an amount of 21.6 parts by mass, and then carried out at 80 ° C. 2 Mix and mix for an hour. Then, add Stanoct® (trade name, API) to the mixture.

Corporation公司製、錫系觸媒)〇. 〇〇3質量份,並依90t: 以下的溫度持續進行2小時攪拌混合。然後,確認NC0質量 ❹ %降低至2. 83質量%後,經冷卻而獲得異氰酸酯基末端預聚 物。 將異氰酸酯基末端預聚物97.28質量份,投入於不銹鋼製 燒杯中,調溫至60°C,添加SUNN0L® TD3130(商品名、LION 公司製、乳化劑31質量%水溶液)13. 56質量份,使用T.K. HOMO DISPER(商品名、特殊機化工業公司製、高速攪拌機) 施行10分鐘攪拌。在該混合物中添加去離子水6. 〇質量份 ❹後,施行30分鐘授拌混合。再添加去離子水質量份, 獲得異氰酸醋基末端預聚物的水分散液。然後,添加2. 7 質篁份1,6-己二胺的20質量%水溶液(依水溶液計13. 56質 罝份)後,升溫至50 C,進行一晚熟成,獲得熱可塑性聚胺 基甲酸酯樹脂的水分散液(固形份5〇質量%)。 &lt;乙烯基單體聚合體之合成&gt; 使苯乙稀及甲基丙烯酸甲醋分別依成為6〇質量%、4〇質 量%的方式進行混合後,相對於料的單魏量丨⑽質量 097138844 21 200925210 份,添加0·5質量份的α-曱基苯乙烯二聚體,再添加25 質量%Aqual〇nHS-1025水溶液(商品名、第一工業製藥公司 製)0. 48質量份、2質量%碳酸氫納水溶液1. 〇質量份、去離 子水9. 50質量份,施行均勻混合,便調製得單體乳化液。 在具備有回流冷卻機、氮導入管及撥拌棒的聚合容器中, 投入依上述所獲得熱可塑性聚胺基曱酸酯樹脂的水分散液 200質量份(依固形份計係1〇〇質量份),加熱升溫至8〇χ:。 ❹經升溫至80。(:後,添加2質量%過硫酸鈉水溶液&amp; 〇質量 份’施行10分鐘攪拌。 然後,相對於熱可塑性聚胺基曱酸酯樹脂1〇〇重量份,依 單體總量成為20重量份的方式,將單體乳化液歷時3小時 連續進料於熱可塑性聚胺基曱酸酯樹脂的水分散液中。 待進料結束後,利用去離子水1. 62質量份將進料管線洗 淨’再在80°C下施行2小時熟成,獲得含有熱可塑性聚胺 ❺基曱酸醋樹脂及乙烯基單體聚合體的水系介質(固形份50 質量%)。 &lt;熱交聯性單體及聚合防止劑之調配&gt; 相對於含有熱可塑性聚胺基曱酸酯樹脂及乙烯基單體聚 合體的水系介質固形份(即,熱可塑性聚胺基曱酸酯樹脂及 乙烯基單體聚合體)100質量份,調配入:KAYARAD DPHA(商 品名、日本化藥公司製、二季戊四醇六丙烯酸酯與二季戊四 醇五丙烯酸酯的混合物)6質量份、對甲氧基酚0. 06質量份 097138844 22 200925210 (即,相對於熱交聯性單體100質量份為1質量份)、SUNN0L® TD-3130 〇. 19質量份、Irganox 245(商品名、汽巴超級化 學公司製、耐熱安定劑)〇. 1質量份、TINUVIN® 765(商品名、 汽巴超級化學公司製、耐光安定劑)〇. 5質量份、TINUVIN® 213(商品名、汽巴超級化學公司製、紫外線吸收劑)〇.5質 量份、Silicon TSF-451-3000(Momentive Performance Materials ·日本公司製、離型劑)〇. 5質量份、及去離子水 © 5. 15質量份,調製得水分散液(添加劑水分散液)。 然後,將該水分散液調配入含有熱可塑性聚胺基甲酸酯樹 脂及乙烯基單體聚合體的水系介質中,施行10分鐘攪拌。 經攪拌後’使用喷霧乾燥機(大川原化工機公司製,L-12), 依霧化器旋轉數5000min_1、熱風溫度1〇〇。(:施行喷霧乾燥, 便獲得粒子狀聚胺基曱酸酯樹脂組成物。 &lt;顏料之調配&gt; Ο 將所獲得之粒子狀聚胺基曱酸酯樹脂組成物1 〇〇質量 份、顏料的0.6質量份碳黑/碳酸鈣分散體(SUMIKA COLOR 公司製、商品名:PV-817)、及0.4質量份碳黑/碳酸鈣分散 體(SUMIKA COLOR公司製、商品名:pv-801),投入韓蘇攪 拌機中,並依旋轉速度γΟΟπάιΤ1施行1分鐘攪拌,將粒子狀 聚胺基甲酸酯樹脂組成物施行著色。 [實施例2~20、比較例1〜5] 除設定為表1〜表3所示組成及調配比例以外’其餘均依 097138844 23 200925210 照與實施例1相同的方法,製造粒子狀聚胺基甲酸酯樹脂組 成物,並著色。 (物性評估) 針對依各實施例及各比較例所獲得之粒子狀聚胺基曱酸 - 酯樹脂組成物(以下簡稱「各粉末」)的粉體性,即黏連、粉 體流動性(靜止角),依以下的方法施行測定。再將尺寸 150mmxl50mmx3mm之具壓鑄紋(cast embossing)的模具加熱 ❹至240 C後,將各粉末300g灑於模具上並靜置8秒鐘後, 將未熔融的多餘粉末甩落。接著,在250X:下靜置6〇秒於 後,經水冷,成形為片材。然後’依照以下的方法施行成形 品物性的測定。結果如表1〜表3所示。 另外,各粉末的平均粒徑係100~13〇/zm左右。各粉末的 平均粒徑係使用粒度分析儀(日機裝(股)製、型號·' MICROTRAC HRA)。 ' ❹ &lt; 黏連〉 將各粉末100g在40°c下靜置?4 J祛始, 贤罝Z4小時後’利用4〇網目的 _網施行處理後’計鼻篩網殘餘比例(%)。 &lt;粉體流動性(靜止角)&gt; 利用依據JIS R-9301-2的注入沐a &amp;t &quot;土入去轭灯粉末靜止角(。)的測 定。 &lt;熔融性(背面光澤)&gt; 使用光澤度計(日本電色工業公司製、型號々os&quot;咖 097138844 24 200925210 VG2000),施行片材背面(無壓鑄紋之一面)光澤的測定。光 澤越间,判斷為粉末的熔融性越高,光澤越低,判斷為發生 了粉末未熔解的情況。 &lt;色不均(目視)&gt; 針對片材表面的色不均依照以下的基準施行評估。 (評估基準) 「〇」:無色不均、呈均勻。 ❿ 「△」:僅發現些微色不均。 「χ」:發現明顯色不均。 〈質感(折皺紋性)&gt; 將片材在180彎折狀態下保持2〇秒鐘後,再復原為原本 樣子並靜置一晝夜。依目視進行觀察經彎折的地方,並依照 以下的基準施行評估。 (評估基準) © 「〇」:未發現折敵紋。 「△」:僅發現些微折皺紋。 ^ χ」:發現明顯折敵紋。 &lt;交聯性(凝膠分率)&gt; 將片材粉碎’秤取約4g ’將其在23°C下,於500ml四氫 吱喃(以下簡稱「THF」)中浸潰24小時。然後,使用抽氣器 施行減壓過滤。將濾紙上所堆積之未溶解於THF中的未溶解 物利用丙酮洗淨,吹附將氮氣而使丙酮充分地蒸發後,在氮 097138844 25 200925210 環境下’於40 C烤箱中靜置20小時。然後,秤量未溶解於 THF中的未溶解物。將未溶解物的質量除以浸潰於THF前的 片材質量,並乘上100,求得凝膠分率(〇/〇)。 &lt;拉伸強度(彈性模數)及斷裂拉伸&gt; 實施片材的拉伸試驗,測定分別發生斷裂時的彈性模數 (MPa)、及發生斷裂時的標線間之拉伸(%)。具體而言,係根 據JIS K-6251所記載的方法,利用jIS_4號啞鈴對試驗片 ❹施行衝壓,並使用拉伸試驗機(ORIENTEC公司製、商品名: 萬能拉伸試驗裝置RTA-500型)’依拉伸速度300mm/分的條 件施行測定。另外,關於斷裂拉伸係將拉伸的「%」依數值 表示。 &lt;耐藥性(耐醇性)&gt; 在片材表面上將乙醇利用0.lml容量的吸管滴下數滴,在 25C下保持1小時後,接著在80°C下保持1小時後,將該 Φ片材的表面利驗水濕卿布施行擦拭,並依目視觀察表面 的狀I將無變化的狀態評為「5級」,將表面完全溶解的 狀態評為「1級」,並將二者間的狀態依每〇. 5級施行評估。 &lt;财熱性(強度保持率及外觀變化)&gt; 將所絲的表皮在12(rc熱風循環式烤箱中靜置5Q0小時 後,針對熱處理前後的表皮之拉伸強度,依照上述拉伸強度 及斷裂拉伸的測定方法施行測定。將熱處理後的表皮之拉伸 強度除以熱處理前的拉伸強度,並乘上1GG,求得強度保持 097138844 26 200925210 率(%)。 再者,使用光澤度計(曰本電色工業(股)製、型號:Gloss Meter VG2000),施行熱處理後的表皮之具壓鑄紋面之光澤 測定。光澤越高,判斷為發生了外觀變化。另外,熱處理前 的表皮之光澤全部為1.1。Manufactured by Corporation, tin-based catalyst 〇. 〇〇 3 parts by mass, and stirred at a temperature of 90t: for 2 hours. Then, it was confirmed that the NC0 mass ❹ % was lowered to 2.83 mass%, and after cooling, an isocyanate group terminal prepolymer was obtained. The amount of the isocyanate group-terminated prepolymer was 97.28 parts by mass, and the mixture was placed in a stainless steel beaker, and the temperature was adjusted to 60° C., and a total of 13.56 parts by mass of SUNN0L® TD3130 (product name, manufactured by LION Corporation, emulsifier 31% by mass aqueous solution) was added. Stirring was carried out for 10 minutes using TK HOMO DISPER (trade name, manufactured by Kosei Kogyo Co., Ltd., high speed mixer). Add deionized water to the mixture. 6. After the mass fraction, carry out mixing for 30 minutes. Further, a part by mass of deionized water was added to obtain an aqueous dispersion of an isocyanate-terminated prepolymer. Then, after adding a 2.7 mass% aqueous solution of hexamethylenediamine (1,6-hexanediamine in terms of an aqueous solution), the temperature was raised to 50 C, and the mixture was aged overnight to obtain a thermoplastic polyamine group. An aqueous dispersion of a formate resin (solid content: 5% by mass). &lt;Synthesis of Vinyl Monomer Polymer&gt; After mixing styrene and methacrylic acid methyl ketone to 6 〇 mass% and 4 〇 mass%, respectively, the 魏(10) mass relative to the material 097 138 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 2 mass% sodium hydrogencarbonate aqueous solution 1. 〇 mass part, deionized water 9.50 parts by mass, and uniformly mixed to prepare a monomer emulsion. 200 parts by mass of an aqueous dispersion of the thermoplastic polyamine phthalate resin obtained as described above in a polymerization vessel equipped with a reflux condenser, a nitrogen introduction tube, and a mixing rod (based on the solid content) Parts), heating up to 8 〇χ:. The temperature is raised to 80. (: After that, a 2% by mass aqueous sodium persulfate solution &amp; 〇 mass part was added and stirred for 10 minutes. Then, with respect to 1 part by weight of the thermoplastic polyaulate phthalate resin, 20 parts by weight based on the total amount of the monomers. In a portion, the monomer emulsion is continuously fed to the aqueous dispersion of the thermoplastic polyamine phthalate resin for 3 hours. After the end of the feed, the feed line is 1.62 parts by mass of deionized water. The "cleaning" was further carried out at 80 ° C for 2 hours to obtain an aqueous medium (solid content: 50% by mass) containing a thermoplastic polyamine-based phthalic acid vinegar resin and a vinyl monomer polymer. &lt;Heat crosslinkability Preparation of monomer and polymerization inhibitor&gt; Relative to aqueous medium solids containing thermoplastic polyamine phthalate resin and vinyl monomer polymer (ie, thermoplastic polyurethane resin and vinyl monomer) The mass of the methoxy phenol is 0. 06 mass. 097138844 22 20 0925210 (that is, 1 part by mass based on 100 parts by mass of the thermally crosslinkable monomer), SUNN0L® TD-3130 〇. 19 parts by mass, Irganox 245 (trade name, Ciba Super Chemical Co., Ltd., heat stabilizer)〇 1 part by mass, TINUVIN® 765 (trade name, Ciba Super Chemical Co., Ltd., light stabilizer) 质量. 5 parts by mass, TINUVIN® 213 (trade name, Ciba Super Chemical Co., Ltd., UV absorber) 〇.5 Parts by mass, Silicon TSF-451-3000 (Momentive Performance Materials, manufactured by Nippon Co., Ltd., release agent) 5. 5 parts by mass, and deionized water © 5.15 parts by mass, prepared aqueous dispersion (additive aqueous dispersion) Then, the aqueous dispersion was formulated into an aqueous medium containing a thermoplastic urethane resin and a vinyl monomer polymer, and stirred for 10 minutes. After stirring, 'using a spray dryer (Okawakawa Chemical Co., Ltd.) Company system, L-12), according to the atomizer rotation number 5000min_1, hot air temperature 1〇〇. (: spray drying, to obtain a particulate polyamino phthalate resin composition. &lt;Pigment blending &gt; Ο The obtained particle shape Base phthalate resin composition: 1 part by mass, 0.6 parts by mass of pigment, carbon black/calcium carbonate dispersion (manufactured by SUMIKA COLOR, trade name: PV-817), and 0.4 parts by mass of carbon black/calcium carbonate dispersion (manufactured by SUMIKA COLOR Co., Ltd., trade name: pv-801), it was put into a Hansu blender, and stirred at a rotation speed of γΟΟπάιΤ1 for 1 minute to color the particulate polyurethane resin composition. [Examples 2 to 20, Comparative Examples 1 to 5] In the same manner as in Example 1, except that the composition and the mixing ratio shown in Tables 1 to 3 were set, the same procedure as in Example 1 was carried out to produce a particulate polyamine group. The formate resin composition is colored. (Evaluation of physical properties) The powdery properties of the particulate polyamine phthalic acid-ester resin composition (hereinafter referred to as "each powder") obtained in each of the examples and the comparative examples, that is, adhesion and powder fluidity ( The angle of repose was measured by the following method. Further, a cast embossing mold having a size of 150 mm x 150 mm x 3 mm was heated to 240 C, and 300 g of each powder was sprinkled on the mold and allowed to stand for 8 seconds, and then the unmelted excess powder was dropped. Subsequently, it was allowed to stand at 250X: for 6 seconds, and then formed into a sheet by water cooling. Then, the physical properties of the molded article were measured in accordance with the following method. The results are shown in Tables 1 to 3. Further, the average particle diameter of each powder is about 100 to 13 Å/zm. The average particle diameter of each powder was a particle size analyzer (manufactured by Nikkiso Co., Ltd., model: 'MicroTRAC HRA). ' ❹ &lt; Adhesion> 100 g of each powder was allowed to stand at 40 ° C? 4 J 祛 , 罝 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 &lt;Powder fluidity (resting angle)&gt; The measurement of the angle of reciprocation of the yoke lamp powder using the injection of a & t &quot; according to JIS R-9301-2. &lt;Fusibility (backside gloss)&gt; The gloss of the back surface of the sheet (one side of the non-compressed cast) was measured using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., model os os &quot; coffee 097138844 24 200925210 VG2000). When the gloss is higher, it is judged that the higher the meltability of the powder, the lower the gloss, and it is judged that the powder is not melted. &lt;Color unevenness (visual)&gt; The color unevenness on the surface of the sheet was evaluated in accordance with the following criteria. (Evaluation criteria) "〇": colorless unevenness and uniformity. 「 “△”: Only some uneven color is found. "χ": I noticed uneven color. <Texture (wrinkle)&gt; After the sheet was held in a 180-fold state for 2 seconds, it was returned to its original state and left to stand overnight. Observe the bent place according to the visual observation and perform the evaluation according to the following criteria. (Evaluation Criteria) © "〇": No folds were found. "△": Only a few wrinkles were found. ^ χ": I found a significant fold of the enemy. &lt;Crosslinkability (gel fraction)&gt; The sheet was pulverized and weighed to about 4 g. This was immersed in 500 ml of tetrahydrofuran (hereinafter referred to as "THF") at 23 ° C for 24 hours. Then, decompression filtration was performed using an aspirator. The undissolved material which was not dissolved in THF, which was deposited on the filter paper, was washed with acetone, and nitrogen was blown off to sufficiently evaporate the acetone, and then allowed to stand in a 40 C oven for 20 hours under the environment of nitrogen 097138844 25 200925210. Then, the undissolved matter which was not dissolved in THF was weighed. The mass of the undissolved matter was divided by the mass of the sheet before immersion in THF, and multiplied by 100 to obtain a gel fraction (〇/〇). &lt;Tensile Strength (Elastic Modulus) and Tensile Stretching&gt; The tensile test of the sheet was carried out, and the modulus of elasticity (MPa) at the time of occurrence of the fracture and the stretching between the marks at the time of the fracture were measured (%) ). Specifically, the test piece was pressed by a jIS_4 dumbbell according to the method described in JIS K-6251, and a tensile tester (manufactured by ORIENTEC Co., Ltd., trade name: universal tensile test device RTA-500 type) was used. 'Measurement was carried out under the conditions of a tensile speed of 300 mm/min. In addition, the "%" of the stretched tensile system is expressed by a numerical value. &lt;Drug resistance (alcohol resistance)&gt; A few drops of ethanol were dropped on a surface of a sheet by a pipette of 0.1 ml capacity, and after holding at 25 C for 1 hour, followed by holding at 80 ° C for 1 hour, The surface of the Φ sheet was subjected to wiping, and the state of the surface was evaluated as "5 grade" according to the visual observation of the surface I, and the state in which the surface was completely dissolved was rated as "grade 1", and The status between the two is evaluated according to each level. &lt;Fluidity (strength retention and appearance change)&gt; After the skin of the silk was allowed to stand in a 12 (rc hot air circulation oven) for 5Q0 hours, the tensile strength of the skin before and after the heat treatment was determined according to the above tensile strength and The measurement method of the tensile elongation was measured, and the tensile strength of the heat-treated skin was divided by the tensile strength before heat treatment, and multiplied by 1 GG to obtain a strength of 097138844 26 200925210 (%). The measurement of the gloss of the die-cast surface of the skin after heat treatment was carried out (the product of Sakamoto Electric Co., Ltd., model: Gloss Meter VG2000). The higher the gloss, the change in appearance was judged. In addition, the skin before heat treatment The gloss is all 1.1.

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IT: V 0 s 笃 CC 1 ΙΛ 勹 q· t、 1 C CO ύ CO to oo 〇c 1 I 1 1 1 1 L〇 o o* 03 s § in c&gt; oo 0.48 1—^ 11.12 CO 1 ΙΛ &lt;=3 1 Τ Ο m o m c&gt; m c&gt; Ξ o ^- ιή V 另 0 0 t—1 1 〇 OO 1*H 和 τ—Η § CO d cd LC oo C3C ) ] 1 1 1 1 L〇 o c— (ΝΪ § LO o oo 〇 — 11.12 1 1 r—t (=&gt; LO C&gt; LO C3 Lrt 〇 2 O* 0¾ cc r·^ V C 0 2¾ CN1 CO »—H 1 〇〇 03 Η £ 率 遛 tO 兹 ¢- 1 m i b 1 &lt;7) 7 /—s N c3 1 N m 05 罕 $ pH ! 1 p «ΊΝ ! •w 1« g P | W g &lt;z&gt; i M SK s 屮 OJ 1 _ CO i «Η 1 φι Φκ $ Φ ^QK &gt;H g i 1 要 I ! 1 I ί i g 1 i s » 幾 ♦ s [IMP-3A L〇 兮 C&lt;1 I m eg Ϊ i CO %. i 1—H g 2 f o CO Ψ '&lt; p 1 叫 6 ‘oil 1 辟 ς~\ /^\ tffl: 1 bUL 电 S 寒 απ Κ- «3 1 8 i I ¥ 赛 9 1 想 i 8 1 辦 i $ 株 1 鮏 ¥ m 8 1 灌 换: 1 雔 % ζ^&gt; «r l 茶 Ιΐφλ 缠 sst- 愛 tO 难 凇 am 囊 « 蚕 I t 1 溜 ο t l sS| ,琢 %I 蚌3啉 φ| m Si 眷 疾 •W g U 〇鼻 # I &lt;〇S 鉍5 g 狴 奮 1〇 翹 ®- i 寶1 Ιι 5 I % 露 1 — i i 〇 Γ^Λ--------- _ If# --- 里 —--- 6Z 200925210 組成 比較例1 比較例2 比較例2 比較例4 比較例5 熱可1 g性胺基甲酸乙酯樹脂(質量份) 100 100 100 100 100 異氰酸酯 Desmodur W(質量份) 21.6 21.6 21.6 21.6 21.6 多元醇 U-2720C質量份) 56.4 56.4 56.4 56.4 56.4 U-2710C質量份) 18.8 18.8 18.8 18.8 18.8 C-2090C質量份) — — — — — 1,4-BD(質量份) — — — — — ΙΌ_249(質量份) — 一 — — — 1,4-Η)(質量份) — — — — — PTG2000(質量份) — 一 — — — PTG1000(質量份) — — — — — 一元醇 2-EtHA(質量份) 0.5 0.5 0.5 0.5 0.5 鏈伸長劑 1, 6-HDA(質量份) 2.7 2.7 2.7 2.7 2.7 乙烯;1 k單體聚合體(質量份) 20 0 20 20 20 芳香族乙烯基單體 St(質量%) 60 — 60 60 60 丙烯酸酯 MMA(質量90 40 — 40 40 40 鏈轉移劑 MSD(相對於單體100質量份的質量份) 0.5 — 0.5 0.5 0.5 單體乳化液(相對於熱可塑性 胺基甲酸乙酯樹脂100質量份 的質量份) 2%過硫義水溶液 8 — 8 8 8 25%Aqualon HS-1025水溶液 0.48 — 0.48 0.48 0.48 2%*炭酸氫納水溶液 1 — 1 1 1 去離子水 11.12 — 11.12 11.12 11.12 熱交聯性單體(質量份) DPHA 6 6 — 6 6 ΤΜΡ-3Α — — — — — 聚合防止劑(相對於熱交 聯性單體100質量份的質量份) m 0. 0025 1 — 0.05 7 HQ — — — — — 水分散液(相對於熱可塑性胺 基甲酸乙酯樹脂100質量份的 質量份) Irganox 245 0.1 0.1 0.1 0.1 0.1 UNWIN® 765 0.5 0.5 0.5 0.5 0.5 TINUVIP 213 0.5 0.5 0.5 0.5 0.5 rSF-451-3000 0.5 0.5 0.5 0.5 0.5 TD3130 0.19 0.19 0.00 0.19 0.19 去離子水 5.11 5.15 1.07 5.11 5.39 評估 舰性 黏連(%) &lt;1 45 &lt;1 &lt;1 &lt;1 粉體流動性(靜止角X〇) 30 51 30 32 32 成形性 熔融性(背面光澤) 4 65 62 11 65 色不均(目視) X X 〇 X Δ 質感(折皺级性) X 〇 〇 〇 〇 交聯性(凝膠分率)(%) 25 38 15 39 45 機械物性 拉伸強度(彈性模數)(MPa) 8.9 7.9 8.5 9.1 9.3 斷裂拉伸(%) 320 700 620 400 520 耐藥性(耐醇性X等級) 4 3 3 4 3.5 耐熱性 強度保持率(%) 52 60 42 55 58 外觀變化(光澤) 3.2 4.2 25 3.1 3.5 097138844 30 200925210 另外,表1〜表3中,組成的代號係如下述: U-2720 :己二酸酯系聚酯多元醇(數量平均分子量2000、三 井化學POLYURETHANES公司製) U-2710 :己二酸酯系聚酯多元醇(數量平均分子量1〇〇〇、三 井化學POLYURETHANES公司製) C-2090 :聚碳酸酯二醇(數量平均分子量2000、KURARAY公 司製) ❿ TONE0249 :聚己内酯二醇(數量平均分子量2000、Dow Chemical公司製) PTG2000 :聚丁醚二醇(數量平均分子量2000、Hodogaya Chemical公司製) PTG1000 :聚丁醚二醇(數量平均分子量1000、Hodogaya Chemical公司製) 1,4-BD : 1,4-丁二醇 ❹ 2-EtHA : 2-乙基己醇 1,6-HDA : 1,6_ 己二胺 St :苯乙烯 MMA :曱基丙烯酸甲酯 MSD: α-曱基苯乙烯二聚體 DPHA : KAYARAD DPHA(二季戊四醇六丙烯酸酯及二季戊四醇 五丙稀酸醋的混合物、日本化藥公司製) ΤΜΡ-3Α :三羥曱基丙烷三丙烯酸酯 097138844 31 200925210 MQ :對甲氧基酚 HQ :氫醌 另外,上述說明係提供作為本發明例示的實施形態,其僅 止於例示而已,不可作為限定解釋。舉凡熟習此技術領域的 技術者所輕易思及的本發明變形例,均涵蓋於後述申請專利 範圍中。 (產業上之可利用性) 3 本發明的粒子狀聚胺基曱酸酯樹脂組成物係適合用於瀝 鑄成形。 ❹ 097138844 32t 霊g CO » ^ 03 inch CO L〇0〇oo 1 丨i 1 1 i uO os 5 Λ =〇〇r—t !N1 — f 1 &lt; C^J 1 a-γ F—♦ 1 1 r —H o L〇o LO 〇=&gt; Si =&gt; ?3 V &lt;] Λ JO 3〇&lt; o! 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IT: V 0 s 笃CC 1 ΙΛ 勹q· t, 1 C CO ύ CO to oo 〇c 1 I 1 1 1 1 L〇oo* 03 s § in c&gt; oo 0.48 1—^ 11.12 CO 1 ΙΛ &lt;=3 1 Τ Ο mom c&gt; m c&gt; Ξ o ^- ιή V Another 0 0 t—1 1 〇OO 1*H and τ—Η § CO d cd LC oo C3C ) ] 1 1 1 1 L〇oc— (ΝΪ § LO o oo 〇— 11.12 1 1 r —t (=&gt; LO C&gt; LO C3 Lrt 〇2 O* 03⁄4 cc r·^ VC 0 23⁄4 CN1 CO »—H 1 〇〇03 Η £ rate 遛tO ¢ - 1 mib 1 &lt;7) 7 / —s N c3 1 N m 05 Rarely $ pH ! 1 p «ΊΝ ! •w 1« g P | W g &lt;z&gt; i M SK s 屮OJ 1 _ CO i «Η 1 φι Φκ $ Φ ^QK &gt ;H gi 1 want I ! 1 I ί ig 1 i s » ♦ s [IMP-3A L〇兮C&lt;1 I m eg Ϊ i CO %. i 1—H g 2 fo CO Ψ '&lt; p 1 Call 6 'oil 1 ς ς~\ /^\ tffl : 1 bUL 电 S 寒απ Κ- «3 1 8 i I ¥赛赛 9 1 想i 8 1 办 i $ 株1 鮏¥ m 8 1 Exchange: 1 雔% ζ^&gt; «rl Tea Ιΐφλ sst- Love tO difficult to sam sac « silkworm I t 1 溜 ο s sS| , 琢 % I 蚌 3 φ φ | m Si dysentery • W g U 〇 nose # I &lt; 〇 S 铋 5 g 狴 〇 〇 〇 ® - i 宝1 Ιι 5 I % 露1 - ii 〇Γ^Λ--------- _ If# --- 里—--- 6Z 200925210 Composition Comparative Example 1 Comparative Example 2 Comparative Example 2 Comparative Example 4 Comparative Example 5 Heat 1 g of urethane resin (parts by mass) 100 100 100 100 100 Isocyanate Desmodur W (parts by mass) 21.6 21.6 21.6 21.6 21.6 Polyol U-2720C parts by mass) 56.4 56.4 56.4 56.4 56.4 U -2710C parts by mass) 18.8 18.8 18.8 18.8 18.8 C-2090C parts by mass) — — — — — 1,4-BD (parts by mass) — — — — —ΙΌ—249 (parts by mass) — 一 — — — 1,4-Η ) (mass parts) — — — — — PTG2000 (mass parts) — 一— — — PTG1000 (parts by mass) — — — — — Monol 2-EtHA (parts by mass) 0.5 0.5 0.5 0.5 0.5 Chain extender 1, 6-HDA (parts by mass) 2.7 2.7 2.7 2.7 2.7 Ethylene; 1 k Monomer polymer (parts by mass) 20 0 20 20 20 Aromatic vinyl monomer St (% by mass) 60 — 60 60 60 Acrylate MMA (mass 90 40 — 40 40 40 chain transfer agent MSD (relative to monomer 100) Parts by mass of the mass part) 0.5 - 0.5 0.5 0.5 Monomer emulsion (parts by mass relative to 100 parts by mass of the thermoplastic urethane resin) 2% persulfate aqueous solution 8 - 8 8 8 25% Aqualon HS-1025 Aqueous solution 0.48 — 0.48 0.48 0.48 2%* aqueous solution of sodium hydrogencarbonate 1 — 1 1 1 Deionized water 11.12 — 11.12 11.12 11.12 Thermally crosslinkable monomer (parts by mass) DPHA 6 6 — 6 6 ΤΜΡ-3Α — — — — — The polymerization preventive agent (parts by mass relative to 100 parts by mass of the thermally crosslinkable monomer) m 0. 0025 1 - 0.05 7 HQ — — — — — aqueous dispersion (100 parts by mass relative to the thermoplastic urethane resin) Parts by mass) Irganox 245 0.1 0.1 0.1 0.1 0.1 UNWIN® 765 0.5 0 .5 0.5 0.5 0.5 TINUVIP 213 0.5 0.5 0.5 0.5 0.5 rSF-451-3000 0.5 0.5 0.5 0.5 0.5 TD3130 0.19 0.19 0.00 0.19 0.19 Deionized water 5.11 5.15 1.07 5.11 5.39 Evaluation of ship-based adhesion (%) &lt;1 45 &lt; 1 &lt;1 &lt;1 Powder fluidity (resting angle X〇) 30 51 30 32 32 Formability meltability (back gloss) 4 65 62 11 65 Color unevenness (visual) XX 〇X Δ Texture (wrinkle grade) X 〇〇〇〇 crosslinkability (gel fraction) (%) 25 38 15 39 45 Mechanical properties Tensile strength (modulus of elasticity) (MPa) 8.9 7.9 8.5 9.1 9.3 Tensile at break (%) 320 700 620 400 520 Resistance (Alcohol resistance X grade) 4 3 3 4 3.5 Heat resistance strength retention (%) 52 60 42 55 58 Appearance change (gloss) 3.2 4.2 25 3.1 3.5 097138844 30 200925210 In addition, Table 1 to Table 3 The composition code is as follows: U-2720: Adipate polyester polyol (quantitative average molecular weight 2000, manufactured by Mitsui Chemicals POLYURETHANES Co., Ltd.) U-2710: Adipate polyester polyol (quantitative average Molecular weight 1〇〇〇, manufactured by Mitsui Chemicals POLYURETHANES Co., Ltd.) C-2090: Polycarbonate diol (quantity Molecular Weight 2000, manufactured by Kuraray Co., Ltd.) ❿ TONE0249: Polycaprolactone diol (quantitative molecular weight: 2000, manufactured by Dow Chemical Co., Ltd.) PTG2000: polybutylene glycol (quantitative molecular weight: 2000, manufactured by Hodogaya Chemical Co., Ltd.) PTG1000: polybutylene ether Glycol (quantitative average molecular weight: 1000, manufactured by Hodogaya Chemical Co., Ltd.) 1,4-BD: 1,4-butanediol ❹ 2-EtHA: 2-ethylhexanol 1,6-HDA: 1,6-hexanediamine St :styrene MMA: methyl methacrylate MSD: α-mercaptostyrene dimer DPHA : KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacetic acid vinegar, manufactured by Nippon Kayaku Co., Ltd.) ΤΜΡ- 3Α: Trihydroxydecylpropane triacrylate 097138844 31 200925210 MQ: p-methoxyphenol HQ: hydroquinone In addition, the above description is provided as an exemplified embodiment of the present invention, which is merely illustrative and not to be construed as limiting. Modifications of the present invention which are readily apparent to those skilled in the art are covered by the scope of the appended claims. (Industrial Applicability) 3 The particulate polyamino phthalate resin composition of the present invention is suitable for use in leaching and casting. 097 097138844 32

Claims (1)

200925210 七、申請專利範圍: 1· 一種粒子狀聚胺基甲酸酯樹脂組成物,係含有··在水分 散媒中合成的熱可塑性聚胺基曱酸酯樹脂、乙烯基單體聚合 體、熱交聯性單體、及相對於熱交聯性單體100質量份為 0. 1〜6質量份的聚合防止劑。 2. 如申請專利範圍第1項之粒子狀聚胺基曱酸酯樹腊組 成物,其中,乙烯基單體聚合體係由芳香族乙烯基單體 ❹ 35〜70質量%、及α,召-乙烯性不飽和羧酸烷基酯3〇〜65質 量%的聚合反應所獲得。 3. 如申請專利範圍第1項之粒子狀聚胺基甲酸酯樹脂組 成物,其中,乙烯基單體聚合體係相對於熱可塑性聚胺基曱 酸醋樹脂100質量份,含有5〜40質量份。 4. 如申請專利範圍第1項之粒子狀聚胺基曱酸酯樹脂組 成物,其中,熱交聯性單體係相對於熱可塑性聚胺基曱酸酯 ❹ 樹脂1〇〇質量份,含有2〜10質量份。 5. 如申請專利範圍第1項之粒子狀聚胺基曱酸酯樹脂組 成物’係將熱可塑性聚胺基甲酸酯樹脂及乙烯基單體聚合體 的水分散液、與熱交聯性單體及聚合防止劑的水分散液進行 混合後’藉由喷霧乾燥而獲得。 6. —種成形品,係將含有在水分散媒中合成的熱可塑性聚 胺基甲酸酯樹脂、乙烯基單體聚合體、熱交聯性單體及相對 於熱交聯性單體100質量份為〇.卜6質量份之聚合防止劑的 097138844 33 200925210 粒子狀聚胺基甲酸酯樹脂組成物,藉由瀝鑄成形而獲得。 7. 如申請專利範圍第6項之成形品,係汽車内裝配件。 8. —種粒子狀聚胺基曱酸酯樹脂組成物之製造方法,係將 熱可塑性聚胺基曱酸酯樹脂及乙烯基單體聚合體的水分散 液、與熱交聯性單體及聚合防止劑的水分散液進行混合後, 施行喷霧乾燥。 097138844 34 200925210 四、指定代表圖: (一) 本案指定代表圖為:無 (二) 本代表圖之元件符號簡單說明: 無 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: 益200925210 VII. Patent Application Range: 1. A particulate polyurethane resin composition containing a thermoplastic polyamine phthalate resin or a vinyl monomer polymer synthesized in a water dispersion medium. 1〜6质量份的聚合剂剂。 The heat-crosslinkable monomer, and the amount of the heat-crosslinkable monomer is 0. 1~6 parts by mass of the polymerization inhibitor. 2. The particulate polyaminophthalate wax composition according to claim 1, wherein the vinyl monomer polymerization system is composed of an aromatic vinyl monomer ❹ 35 to 70% by mass, and α, It is obtained by a polymerization reaction of an alkyl group of an ethylenically unsaturated carboxylic acid of from 3 65 to 65% by mass. 3. The particulate polyurethane resin composition according to claim 1, wherein the vinyl monomer polymerization system contains 5 to 40 masses per 100 parts by mass of the thermoplastic polyamine phthalic acid resin. Share. 4. The particulate polyamino phthalate resin composition of claim 1, wherein the thermally crosslinkable single system contains 1 part by mass of the thermoplastic polyurethane phthalate resin. 2 to 10 parts by mass. 5. The particulate polyamino phthalate resin composition as claimed in claim 1 is an aqueous dispersion of a thermoplastic polyurethane resin and a vinyl monomer polymer, and thermal crosslinkability. The aqueous dispersion of the monomer and the polymerization preventive agent is mixed and obtained by spray drying. 6. A molded article comprising a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymer, a heat crosslinkable monomer, and a heat crosslinkable monomer 100 The mass fraction is 097138844 33 200925210 of a polymerization preventive agent of 0.02 parts by mass. The particulate polyurethane resin composition is obtained by leaching and casting. 7. For the molded article of the sixth application patent, it is an automotive interior fitting. 8. A method for producing a particulate polyamino phthalate resin composition, comprising: an aqueous dispersion of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and a thermally crosslinkable monomer; After the aqueous dispersion of the polymerization preventive agent was mixed, spray drying was carried out. 097138844 34 200925210 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: beneficial 097138844 2097138844 2
TW97138844A 2007-10-11 2008-10-09 Granular polyurethane resin composition, method for producing the same, and molded article of the same TW200925210A (en)

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