TWI472564B - A thermoplastic resin foam, a thermoplastic resin foam manufacturing method, and a light reflection material - Google Patents
A thermoplastic resin foam, a thermoplastic resin foam manufacturing method, and a light reflection material Download PDFInfo
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Description
本發明，係關於一種具有均一且微細之氣泡的熱可塑性樹脂發泡體及其製造方法。又，本發明關於一種使用具有均一且微細之氣泡之熱可塑性樹脂發泡體的光反射材。The present invention relates to a thermoplastic resin foam having uniform and fine bubbles and a method for producing the same. Further, the present invention relates to a light reflecting material using a thermoplastic resin foam having uniform and fine bubbles.
以往，作為照明或液晶背光之反射板，使用將光反射性優異之塗料塗布於金屬板而成者、或是將光反射性優異之樹脂膜等積層於金屬板而成者。近年來，於照明器具或液晶顯示器等領域，要求更進一步之省電化、高效率化。特別是於電子看板或顯示器之領域，省空間化的需求亦不斷提高，而上述之反射板難以因應省空間化。Conventionally, as a reflector for illumination or liquid crystal backlight, a coating material having excellent light reflectivity is applied to a metal plate, or a resin film having excellent light reflectivity is laminated on a metal plate. In recent years, in the fields of lighting fixtures, liquid crystal displays, and the like, further power saving and high efficiency have been demanded. Especially in the field of electronic billboards or displays, the need for space saving is also increasing, and the above-mentioned reflectors are difficult to cope with space saving.
因此，將光反射性優異之具有微細氣泡(例如，1μm左右)之樹脂片利用作為照明或液晶背光之反射板等(例如，參照專利文獻1)。然而，專利文獻1所記載之樹脂片，係使結晶性樹脂之聚對酞酸乙二酯發泡而成，故會於成形性上產生障礙。Therefore, a resin sheet having fine bubbles (for example, about 1 μm) having excellent light reflectivity is used as a reflector for illumination or liquid crystal backlight (for example, see Patent Document 1). However, the resin sheet described in Patent Document 1 is obtained by foaming a polyethylene terephthalate of a crystalline resin, which causes an obstacle in moldability.
另一方面，不使用結晶性之樹脂而使用非晶性之樹脂的發泡體，雖然成形性優異，但是於發泡時，不僅微細之氣泡，亦容易產生1mm以上之巨大氣泡，而有難以作為光反射材等之各種成形品使用的問題。On the other hand, a foam in which an amorphous resin is used without using a crystalline resin is excellent in moldability, but at the time of foaming, not only fine bubbles but also large bubbles of 1 mm or more are likely to be generated, which is difficult. It is used as a molded article of various materials such as a light-reflecting material.
因此，提出一種藉由以未達非晶性熱可塑性樹脂之玻璃轉移溫度(Tg)發泡，而具有均一氣泡徑的非晶性熱可塑性樹脂片(例如，參照專利文獻2)。然而，若以低於Tg之溫度發泡，則無法提昇發泡倍率，故不僅無法得到所要之性能，且於成本上亦不利。Therefore, an amorphous thermoplastic resin sheet having a uniform cell diameter by foaming at a glass transition temperature (Tg) which is less than the amorphous thermoplastic resin has been proposed (for example, see Patent Document 2). However, if foaming is carried out at a temperature lower than Tg, the expansion ratio cannot be increased, so that not only the desired properties are not obtained, but also the cost is disadvantageous.
專利文獻1：日本特許第2713556號公報Patent Document 1: Japanese Patent No. 2713556
專利文獻2：日本特許第3459447號公報Patent Document 2: Japanese Patent No. 3459447
本發明之課題在於，解決上述之問題點，提供一種具有微細且均一之氣泡徑、成形性優異的熱可塑性樹脂發泡體及使用其之光反射率高的光反射材。又，本發明之課題在於，提供一種具有微細且均一之氣泡徑的熱可塑性樹脂發泡體之製造方法。An object of the present invention is to provide a thermoplastic resin foam having a fine and uniform cell diameter and excellent moldability, and a light-reflecting member having high light reflectance using the same. Further, an object of the present invention is to provide a method for producing a thermoplastic resin foam having a fine and uniform cell diameter.
本發明人等，為了解決上述課題，經潛心研究的結果發現，藉由對非晶性熱可塑性樹脂添加特定量的熔融型結晶成核劑，可製造具有微細且均一之氣泡徑的非晶性熱可塑性樹脂發泡體。本發明係根據此見解而完成者。In order to solve the above problems, the inventors of the present invention have found that by adding a specific amount of a molten crystal nucleating agent to an amorphous thermoplastic resin, it is possible to produce a amorphous having a fine and uniform bubble diameter. Thermoplastic resin foam. The present invention has been completed on the basis of this finding.
亦即，本發明提供：That is, the present invention provides:
<1> 一種熱可塑性樹脂發泡體，其特徵在於，係使相對於非晶性熱可塑性樹脂(A)100質量份含有熔融型結晶成核劑(B)0.25～2.5質量份的熱可塑性樹脂組成物發泡而得，且於內部具有平均氣泡徑為10μm以下之氣泡。<1> A thermoplastic resin foam containing 0.25 to 2.5 parts by mass of a molten crystal nucleating agent (B) per 100 parts by mass of the amorphous thermoplastic resin (A). The composition was obtained by foaming, and had bubbles having an average cell diameter of 10 μm or less inside.
<2> 如<1>所記載之熱可塑性樹脂發泡體，其中，該熔融型結晶成核劑(B)，係下述通式(1)所表示之化合物，<2> The thermoplastic resin foam according to the above-mentioned item (1), wherein the molten crystal nucleating agent (B) is a compound represented by the following formula (1).
通式(1) R1 -(CONHR2 )a General formula (1) R 1 -(CONHR 2 ) a
[式中，R1 表示碳數2～30之飽和或不飽和之脂肪族多羧酸殘基、碳數4～28之飽和或不飽和之脂環式多羧酸殘基、或碳數6～28之芳香族多羧酸殘基。R2 表示碳數1～18之烷基、碳數2～18之烯基、碳數3～12之環烷基或環烯基、苯基、萘基、蒽基。a表示2～6之整數。][Wherein, R 1 represents a saturated or unsaturated, having 2 to 30 carbon atoms of the aliphatic polycarboxylic acid residue, a saturated or unsaturated 4 to 28 carbon atoms of the alicyclic polycarboxylic acid residue, or a C 6 ～28 aromatic polycarboxylic acid residue. R 2 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, a phenyl group, a naphthyl group or an anthracenyl group. a represents an integer from 2 to 6. ]
<3> 如<1>或<2>所記載之熱可塑性樹脂發泡體，其中，該熔融型結晶成核劑(B)，係選自1,3,5-苯三甲酸三(三級丁基醯胺)、1,3,5-苯三甲酸三環己基醯胺、1,3,5-苯三甲酸三(2-甲基環己基醯胺)、1,3,5-苯三甲酸三(4-甲基環己基醯胺)、1,4-環己烷二羧酸二醯替苯胺(1,4-cyclohexanedicarboxylic acid dianilide)、1,4-環己烷二羧酸二環己基醯胺、1,4-環己烷二羧酸二苄基醯胺、2,6-萘二羧酸二環己基醯胺、1,2,3,4-丁烷四羧酸四環己基醯胺及1,2,3,4-丁烷四羧酸四醯替苯胺中之至少1種醯胺化合物。<3> The thermoplastic resin foam according to <1> or <2>, wherein the molten crystal nucleating agent (B) is selected from the group consisting of 1,3,5-benzenetricarboxylic acid three (three-stage) Butyl decylamine), 1,3,5-benzenetricarboxylic acid tricyclohexyl decylamine, 1,3,5-benzenetricarboxylic acid tris(2-methylcyclohexyl decylamine), 1,3,5-benzene Tris(4-methylcyclohexyldecylamine) formic acid, 1,4-cyclohexanedicarboxylic acid dianilide, 1,4-cyclohexanedicarboxylic acid dicyclohexyl Indoleamine, 1,4-cyclohexanedicarboxylic acid dibenzyl decylamine, 2,6-naphthalene dicarboxylic acid dicyclohexyl decylamine, 1,2,3,4-butane tetracarboxylic acid tetracyclohexyl fluorene At least one guanamine compound of an amine and tetrakis-aniline of 1,2,3,4-butanetetracarboxylic acid.
<4> 如<1>至<3>中任一項所記載之熱可塑性樹脂發泡體，其中，該熱可塑性樹脂發泡體，於UL-94之垂直燃燒試驗法為V-0、V-1或V-2。The thermoplastic resin foam according to any one of <1> to <3> wherein the thermoplastic resin foam is V-0, V in the vertical burning test method of UL-94. -1 or V-2.
<5> 如<1>至<4>中任一項所記載之熱可塑性樹脂發泡體，其中，該非晶性熱可塑性樹脂(A)為聚碳酸酯。The thermoplastic resin foam according to any one of <1> to <4> wherein the amorphous thermoplastic resin (A) is a polycarbonate.
<6> 一種光反射材，其特徵在於，係使用<1>至<5>中任一項所記載之熱可塑性樹脂發泡體所成形。以及<6> A light-reflecting material which is formed by using the thermoplastic resin foam according to any one of <1> to <5>. as well as
<7> 一種熱可塑性樹脂發泡體之製造方法，其係由以下步驟所構成：對非晶性熱可塑性樹脂100質量份，熔融分散0.25～2.5質量份之熔融型結晶成核劑以得到熱可塑性樹脂組成物之步驟；使該組成物固化，對該組成物於加壓下含浸惰性氣體，藉此使該熔融型結晶成核劑析出之步驟；以及對含浸有該惰性氣體之該組成物，於開放壓下以非晶性熱可塑性樹脂之玻璃轉移溫度以上的溫度進行加熱，藉此使其發泡之步驟。<7> A method for producing a thermoplastic resin foam, comprising: melt-dispersing 0.25 to 2.5 parts by mass of a molten crystal nucleating agent to obtain heat by 100 parts by mass of the amorphous thermoplastic resin; a step of plasticizing the composition of the resin; curing the composition, impregnating the composition with an inert gas under pressure, thereby precipitating the molten crystal nucleating agent; and treating the composition impregnated with the inert gas The step of heating at a temperature equal to or higher than the glass transition temperature of the amorphous thermoplastic resin under open pressing.
此處，上述多羧酸殘基，係指由各多羧酸除去所有羧基之殘基。Here, the above polycarboxylic acid residue means a residue in which all carboxyl groups are removed from each polycarboxylic acid.
本發明，可提供具有微細且均一之氣泡徑、成形性優異的熱可塑性樹脂發泡體及其製造方法、以及使用其之光反射率高的光反射材。According to the present invention, it is possible to provide a thermoplastic resin foam having a fine and uniform cell diameter and excellent moldability, a method for producing the same, and a light-reflecting member having a high light reflectance using the same.
本發明之上述及其他特徵及優點，由下述之記載可明白。The above and other features and advantages of the present invention will be apparent from the description.
本發明之熱可塑性樹脂發泡體，可使含有非晶性熱可塑性樹脂(A)與熔融型結晶成核劑(B)的熱可塑性樹脂組成物發泡而得。首先，說明本發明之熱可塑性樹脂發泡體所使用之非晶性熱可塑性樹脂。The thermoplastic resin foam of the present invention can be obtained by foaming a thermoplastic resin composition containing the amorphous thermoplastic resin (A) and the molten crystal nucleating agent (B). First, an amorphous thermoplastic resin used in the thermoplastic resin foam of the present invention will be described.
(A) 非晶性熱可塑性樹脂(A) Amorphous thermoplastic resin
本發明中，非晶性熱可塑性樹脂，係指未含結晶成分之熱可塑性樹脂之意。本發明中之非晶性熱可塑性樹脂，可舉例如聚苯醚、聚苯醚與聚苯乙烯之聚合物合金、聚甲基丙烯酸甲酯、聚碳酸酯、聚醚醯亞胺、聚醚碸、聚烯丙碸(polyallyl sulfone)、聚芳酯(polyarylate)、聚醯胺醯亞胺、環狀烯烴共聚物、降莰烯系樹脂、熱可塑性彈性體等。此等可單獨使用，亦可混合2種以上使用。其中，由難燃化之容易度及發泡片之機械特性的觀點考量，特別以聚碳酸酯為佳。In the present invention, the amorphous thermoplastic resin means a thermoplastic resin which does not contain a crystalline component. The amorphous thermoplastic resin in the present invention may, for example, be a polyphenylene ether, a polymer alloy of polyphenylene ether and polystyrene, a polymethyl methacrylate, a polycarbonate, a polyether quinone, or a polyether oxime. Polyallyl sulfone, polyarylate, polyamidoximine, cyclic olefin copolymer, norbornene resin, thermoplastic elastomer, and the like. These may be used singly or in combination of two or more. Among them, polycarbonate is preferred from the viewpoint of easiness of flame retardation and mechanical properties of the foamed sheet.
本發明中，由再循環的觀點考量，熱可塑性樹脂以非交聯為佳。本發明中之熱可塑性樹脂，熱可塑性樹脂中之交聯部分之質量分率(以下，於本說明書中，亦稱為交聯度)以未達10%為佳。亦可以使熱可塑性樹脂之交聯度較佳為未達10%的方式添加交聯劑或交聯助劑。In the present invention, from the viewpoint of recycling, the thermoplastic resin is preferably non-crosslinked. In the thermoplastic resin of the present invention, the mass fraction of the crosslinked portion in the thermoplastic resin (hereinafter, also referred to as the degree of crosslinking in the present specification) is preferably less than 10%. It is also possible to add a crosslinking agent or a crosslinking assistant so that the degree of crosslinking of the thermoplastic resin is preferably less than 10%.
(B) 熔融型結晶成核劑(B) Melt-type crystal nucleating agent
所謂熔融型結晶成核劑，係表示具有如下特徵之成核劑：若添加於熱可塑性樹脂，則於熔融捏合時會熔融分散於樹脂中，於降溫凝固過程中會凝集固化(結晶化)析出。本發明中，於加熱成形時，熔融型結晶成核劑(B)係熔融分散於非晶性熱可塑性樹脂(A)。成形後之降溫固化時或於氣體含浸時，熔融型結晶成核劑(B)係於非晶性熱可塑性樹脂(A)中析出。其結果，熔融型結晶成核劑(B)結晶化。於發泡過程中，析出之熔融型結晶成核劑(B)會成為氣泡核生成的起點。其結果，可得內部均勻具有平均氣泡徑為10μm以下之微細氣泡，且直徑1mm以上之巨大氣泡之發生已減低的發泡體。藉由成形上述之發泡體，可得到具有高反射率之反射板。The crystallization nucleating agent is a nucleating agent which is characterized in that it is melt-dispersed in a resin during melt-kneading when it is added to a thermoplastic resin, and is solidified (crystallized) during precipitation and solidification. . In the present invention, the molten crystal nucleating agent (B) is melt-dispersed in the amorphous thermoplastic resin (A) during heat molding. The molten crystal nucleating agent (B) is precipitated in the amorphous thermoplastic resin (A) during the temperature-lowering curing after molding or during gas impregnation. As a result, the molten crystal nucleating agent (B) is crystallized. During the foaming process, the precipitated molten crystal nucleating agent (B) becomes the starting point of bubble nucleation. As a result, it is possible to obtain a foam having a uniform internal bubble diameter of 10 μm or less and a large number of bubbles having a diameter of 1 mm or more. By forming the above-mentioned foam, a reflector having high reflectance can be obtained.
本發明所使用之熔融型結晶成核劑，以具有醯胺鍵之醯胺化合物為佳。可舉例如耐綸6、耐綸66、耐綸6.66、耐綸6.6T、耐綸610、耐綸612、耐綸MDX6、耐綸11、耐綸12、耐綸46(皆為商品名)等耐綸系之聚合物、及胺基酸、多肽、內醯胺類等。所使用之醯胺化合物，特佳為下述通式(1)所表示之醯胺化合物。The molten crystal nucleating agent used in the present invention is preferably a guanamine compound having a guanamine bond. For example, nylon 6, nylon 66, nylon 6.66, nylon 6.6T, nylon 610, nylon 612, nylon MDX6, nylon 11, nylon 12, nylon 46 (all are trade names), etc. A nylon-based polymer, an amino acid, a polypeptide, an indoleamine, and the like. The guanamine compound to be used is particularly preferably a guanamine compound represented by the following formula (1).
通式(1) R1 -(CONHR2 )a General formula (1) R 1 -(CONHR 2 ) a
式中，R1 表示碳數2～30之飽和或不飽和之脂肪族多羧酸殘基、碳數4～28之飽和或不飽和之脂環式多羧酸殘基、或碳數6～28之芳香族多羧酸殘基。R2 表示碳數1～18之烷基、碳數2～18之烯基、碳數3～12之環烷基或環烯基、苯基、萘基、蒽基。a表示2～6之整數。In the formula, R 1 represents a saturated or unsaturated, having 2 to 30 carbon atoms of the aliphatic polycarboxylic acid residue, a saturated or unsaturated 4 to 28 carbon atoms of the alicyclic polycarboxylic acid residue, or a C 6 ~ 28 aromatic polycarboxylic acid residues. R 2 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, a phenyl group, a naphthyl group or an anthracenyl group. a represents an integer from 2 to 6.
本發明中之醯胺化合物，可舉例如1,3,5-苯三甲酸三(三級丁基醯胺)、1,3,5-苯三甲酸三環己基醯胺、1,3,5-苯三甲酸三(2-甲基環己基醯胺)、1,3,5-苯三甲酸三(4-甲基環己基醯胺)、1,4-環己烷二羧酸二醯替苯胺、1,4-環己酸二羧酸二環己基醯胺、1,4-環己酸二羧酸二(2-甲基二環己基醯胺)、1,4-環己酸二羧酸二苄基醯胺、2,6-萘二羧酸二環己基醯胺、1,2,3,4-丁烷四羧酸四環己基醯胺及1,2,3,4-丁烷四羧酸四醯替苯胺，可單獨使用1種、或組合2種以上。其中，以1,3,5-苯三甲酸三環己基醯胺、或N,N’-二環己基-2,6-萘二羧酸二環己基醯胺為特佳。The guanamine compound in the present invention may, for example, be tris(tert-butyl decylamine) 1,3,5-benzenetricarboxylic acid, tricyclohexyl decylamine 1,3,5-benzenetricarboxylic acid, 1,3,5 -tris(3-methylcyclohexyldecylamine), 1,3,5-benzenetricarboxylic acid tris(4-methylcyclohexyldecylamine), 1,4-cyclohexanedicarboxylic acid diterpene Aniline, 1,4-cyclohexanoic acid dicarboxylic acid dicyclohexyl decylamine, 1,4-cyclohexanoic acid dicarboxylic acid bis(2-methyldicyclohexyl decylamine), 1,4-cyclohexanoic acid dicarboxyl Acid dibenzyl decylamine, 2,6-naphthalene dicarboxylic acid dicyclohexyl decylamine, 1,2,3,4-butane tetracarboxylic acid tetracyclohexyl decylamine and 1,2,3,4-butane Tetrabenzoic acid tetracarboxylic acid may be used alone or in combination of two or more. Among them, tricyclohexyl decylamine 1,3,5-benzenetricarboxylic acid or N,N'-dicyclohexyl-2,6-naphthalene dicarboxylic acid dicyclohexyl decylamine is particularly preferred.
本發明中之醯胺化合物的添加量，相對於該非晶性熱可塑性樹脂100質量份，為0.25～2.5質量份，較佳為0.5～1.5質量份，再更佳為0.5～1.0質量份。其量若過少，則無法期待巨大氣泡之抑制效果。另一方面，配合量若過多，則由於醯胺化合物無法熔融，故會於製品表面以異物的形態析出。The amount of the guanamine compound to be added in the present invention is 0.25 to 2.5 parts by mass, preferably 0.5 to 1.5 parts by mass, more preferably 0.5 to 1.0 part by mass, per 100 parts by mass of the amorphous thermoplastic resin. If the amount is too small, the suppression effect of the large bubbles cannot be expected. On the other hand, if the compounding amount is too large, the guanamine compound cannot be melted, and thus the surface of the product is precipitated as a foreign matter.
本發明中，熱可塑性樹脂發泡體，較佳為滿足UL-94之垂直燃燒試驗法之V-0、V-1或V-2。為了滿足上述之判定基準，發泡前之樹脂組成物以含有難燃劑為佳。本發明中可使用之難燃劑的種類，並無特別限制，只要為一般之橡膠、樹脂等聚合物所使用之難燃劑即可。可舉例如溴系難燃劑、磷系難燃劑、氮系難燃劑、無機系難燃劑、有機金屬鹽化合物、聚矽氧樹脂系難燃劑、氟樹脂系難燃劑、萜烯樹脂系難燃劑、具難燃性之非晶性熱可塑性樹脂等。本發明中，上述之難燃劑可為單獨1種、或組合2種以上。In the present invention, the thermoplastic resin foam is preferably V-0, V-1 or V-2 which satisfies the vertical burning test method of UL-94. In order to satisfy the above criteria, the resin composition before foaming preferably contains a flame retardant. The type of the flame retardant which can be used in the present invention is not particularly limited, and may be any flame retardant used for a polymer such as rubber or resin. For example, a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an inorganic flame retardant, an organic metal salt compound, a polyoxygen resin-based flame retardant, a fluororesin-based flame retardant, and a terpene A resin-based flame retardant, a non-flammable amorphous thermoplastic resin, and the like. In the present invention, the above-mentioned flame retardant may be used alone or in combination of two or more.
溴系化合物之難燃劑，可舉例如溴化雙酚A型環氧聚合物、五溴苄基丙烯酸酯、溴化聚碳酸酯寡聚物、三系難燃劑、四溴雙酚A、雙(三溴苯氧基)乙烷、四溴雙酚A-雙(2-羥基***)、四溴雙酚A-雙(2,3-二溴丙醚)、四溴雙酚A-雙(二烯丙基醚)、六溴環十二烷、聚二溴苯醚、十溴二苯醚、溴化鄰苯二甲酸酯等，但並不限於此等。其中，較佳為十溴二苯醚。Examples of the flame retardant of the bromine-based compound include brominated bisphenol A type epoxy polymer, pentabromobenzyl acrylate, brominated polycarbonate oligomer, and three Flame retardant, tetrabromobisphenol A, bis(tribromophenoxy)ethane, tetrabromobisphenol A-bis(2-hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromo) Propyl ether), tetrabromobisphenol A-bis(diallyl ether), hexabromocyclododecane, polydibromophenyl ether, decabromodiphenyl ether, brominated phthalate, etc. Not limited to this. Among them, decabromodiphenyl ether is preferred.
當使用溴系化合物作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為0.1～20質量份，較佳為0.5～15質量份，再更佳為1～10質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響機械特性。When a bromine-based compound is used as the flame retardant, the content of the flame retardant is 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 100 parts by mass of the amorphous thermoplastic resin. ~10 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
磷系化合物之難燃劑，以磷酸酯化合物較佳。本發明中之磷酸酯化合物，可舉例如磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三辛酯、磷酸三丁氧乙酯、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯、磷酸辛基二苯酯、磷酸三(2-乙基己基)酯、磷酸二異丙基苯酯、磷酸三二甲苯酯、磷酸參(異丙基苯)酯、磷酸三萘酯、雙酚A雙磷酸酯、氫醌雙磷酸酯、間苯二酚雙磷酸酯、間苯二酚-磷酸二苯酯、三磷酸三氧苯酯、磷酸甲苯二苯酯、聚磷酸銨(ammonium polyphosphate)等，但並不限於此等。再者，亦可舉將各種取代基導入於此等而成之化合物、或此等之寡聚物、聚合物等。其中，較佳為聚磷酸銨。A flame retardant of a phosphorus compound is preferably a phosphate compound. The phosphate compound in the present invention may, for example, be trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributyloxyethyl phosphate, triphenyl phosphate, tricresyl phosphate or toluene phosphate. Diphenyl ester, octyl diphenyl phosphate, tris(2-ethylhexyl) phosphate, diisopropylphenyl phosphate, trixyl phosphate, cisplatin phosphate, trinaphthyl phosphate , bisphenol A diphosphate, hydroquinone diphosphate, resorcinol diphosphate, resorcinol-diphenyl phosphate, trioxyphenyl triphosphate, toluene diphenyl phosphate, ammonium polyphosphate (ammonium Polyphosphate), etc., but is not limited to this. Further, a compound obtained by introducing various substituents thereto or the like, or an oligomer or a polymer thereof may be mentioned. Among them, ammonium polyphosphate is preferred.
當使用磷系化合物作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為1～30質量份，較佳為3～25質量份，再更佳為5～15質量份。若其量過少，則無法維持所欲之難燃性，而其若過多，則會影響到機械特性。When a phosphorus-based compound is used as the flame retardant, the content of the flame retardant is 1 to 30 parts by mass, preferably 3 to 25 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the amorphous thermoplastic resin. ~ 15 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
氮系難燃劑，可舉例如三聚氰胺、三聚氰酸、三聚氰胺三聚氰酸酯、三聚氰胺磷酸酯等三化合物、聚磷酸三聚氰胺(melamine polyphosphate)、硫酸三聚氰胺(melamine sulfate)、尿素、異三聚氰酸酯(isocyanurate)等，但並不限於此等。其中，較佳為聚磷酸三聚氰胺。Examples of the nitrogen-based flame retardant include melamine, cyanuric acid, melamine cyanurate, and melamine phosphate. The compound, melamine polyphosphate, melamine sulfate, urea, isocyanurate, etc., but is not limited thereto. Among them, melamine polyphosphate is preferred.
當使用氮系化合物作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為1～100質量份，較佳為5～75質量份，再更佳為10～50質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When a nitrogen-based compound is used as the flame retardant, the content of the flame retardant is 1 to 100 parts by mass, preferably 5 to 75 parts by mass, more preferably 10 parts by mass based on 100 parts by mass of the amorphous thermoplastic resin. ~50 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
無機系難燃劑，可舉例如氫氧化鋁、氫氧化鈣、氫氧化鎂、碳酸鎂、三氧化銻、四氧化銻、五氧化銻、銻酸鈉(sodium antimonite)、氨基磺酸胍(guanidine sulfamate)、磷酸胍(guanidine phosphate)、磷酸甲脒基脲(guanylurea phosphate)、磷酸三聚氰胺(melamine phosphate)等胍鹽、硼酸鋅、硼酸銨、硼酸、碳酸氫氧銨鋁、鉬酸銨、鉬氧化物、氧化鉬、苯甲醯鐵莘(benzoylferrocene)、鐵莘、氧化錫、水合錫化合物、錫酸鋅等錫化合物、芳香族次磺醯胺、乙醯丙酮、柳醛、8-羥喹啉、二甲基乙二肟之金屬鹽等之無機錯合物、磷-氮化合物、鈣-鋁酸鹽水合物、鈣-鋁-矽酸鹽、鋯化合物、碳鈉鋁石、脂肪族磺酸鹽、芳香族磺酸鹽、芳香族磺醯胺鹽、磺醯亞胺鹽(sulfimide salt)、醯亞胺二磷酸四酯鹽、氟化脂肪族磺酸鹽等鹼、鹼土類金屬鹽等，但並不限於此等。其中，較佳為氫氧化鎂。Examples of the inorganic flame retardant include aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonite, and guanidine sulfamate. Sulfamate), guanidine phosphate, guanylurea phosphate, melamine phosphate, cesium salt, zinc borate, ammonium borate, boric acid, aluminum ammonium hydrogencarbonate, ammonium molybdate, molybdenum oxidation , molybdenum oxide, benzoylferrocene, iron strontium, tin oxide, hydrated tin compound, tin stannate and other tin compounds, aromatic sulfoximine, acetamidine, aldehyde, 8-hydroxyquinoline Inorganic complexes such as metal salts of dimethylglyoxime, phosphorus-nitrogen compounds, calcium-aluminate hydrates, calcium-aluminum-tellurates, zirconium compounds, dawsonite, aliphatic sulfonic acids a salt, an aromatic sulfonate, an aromatic sulfonamide salt, a sulfimide salt, a quinone imine diphosphate salt, a fluorinated aliphatic sulfonate, an alkali or an alkaline earth metal salt, But it is not limited to this. Among them, magnesium hydroxide is preferred.
當使用無機系化合物作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為10～200質量份，較佳為30～150質量份，再更佳為50～100質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When an inorganic compound is used as the flame retardant, the content of the flame retardant is 10 to 200 parts by mass, preferably 30 to 150 parts by mass, more preferably 50% by mass based on 100 parts by mass of the amorphous thermoplastic resin. ~100 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
有機金屬鹽化合物，可舉例如芳香族磺酸之金屬鹽、全氟烷烴磺酸鹽之金屬鹽。該金屬鹽之金屬之種類，可舉例如鹼金屬、鹼土類金屬等。本發明中之有機金屬鹽化合物，可舉例如4-甲基-N-(4-甲基苯基)磺醯基-苯磺醯胺之鉀鹽、二苯碸-3-磺酸鉀、二苯碸-3-3-二磺酸鉀、對甲苯磺酸鈉、全氟丁烷磺酸鉀鹽等，但並不限於此等。其中，較佳為全氟丁烷磺酸鉀鹽。The organometallic salt compound may, for example, be a metal salt of an aromatic sulfonic acid or a metal salt of a perfluoroalkanesulfonate. The type of the metal of the metal salt may, for example, be an alkali metal or an alkaline earth metal. The organometallic salt compound in the present invention may, for example, be a potassium salt of 4-methyl-N-(4-methylphenyl)sulfonyl-benzenesulfonamide, potassium dibenzoin-3-sulfonate or the like. Potassium phenylhydrazine-3-3-disulfonate, sodium p-toluenesulfonate, potassium perfluorobutanesulfonate, etc., but is not limited thereto. Among them, potassium perfluorobutanesulfonate is preferred.
當使用有機金屬鹽化合物作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為0.1～10質量份，較佳為0.1～5質量份，再更佳為0.1～2質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When the organometallic salt compound is used as the flame retardant, the content of the flame retardant is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the amorphous thermoplastic resin. 0.1 to 2 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
聚矽氧樹脂系難燃劑，可舉例如聚(二甲基矽氧烷)、聚(二苯基矽氧烷)、聚(甲基苯基矽氧烷)等聚有機矽氧烷、環氧變性聚有機矽氧烷、甲基丙烯基變性聚有機矽氧烷、胺基變性聚有機矽氧烷等矽油、矽樹脂、矽橡膠、矽粉等，但並不限於此等。其中，較佳為聚(二甲基矽氧烷)。Examples of the polyoxygenated resin-based flame retardant include polyorganosiloxanes such as poly(dimethyloxane), poly(diphenylphosphoxane), and poly(methylphenyloxane), and rings. Oxygen-denatured polyorganosiloxane, methacryl-based polyorganosiloxane, amine-modified polyorganosiloxane such as eucalyptus oil, oxime resin, ruthenium rubber, ruthenium powder, etc., but are not limited thereto. Among them, poly(dimethyloxane) is preferred.
當使用聚矽氧樹脂系難燃劑作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為0.05～8質量份，較佳為0.1～5質量份，再更佳為0.1～2質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When a polyoxygenated resin-based flame retardant is used as the flame retardant, the content of the flame retardant is 0.05 to 8 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the amorphous thermoplastic resin. More preferably, it is 0.1 to 2 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
氟樹脂系難燃劑，可舉例如氟系金屬鹽、聚四氟乙烯、四氟乙烯與六氟丙烯之共聚物、氟系酞醯亞胺等，但並不限於此等。其中，較佳為聚四氟乙烯。The fluororesin-based flame retardant may, for example, be a fluorine-based metal salt, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene, or a fluorine-based sulfimine, but is not limited thereto. Among them, polytetrafluoroethylene is preferred.
當使用氟樹脂系難燃劑作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為0.05～8質量份，較佳為0.1～5質量份，再更佳為0.1～2質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When a fluororesin-based flame retardant is used as the flame retardant, the content of the flame retardant is 0.05 to 8 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the amorphous thermoplastic resin. Preferably, it is 0.1 to 2 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
萜烯樹脂系難燃劑，可舉α-蒎烯樹脂、β-蒎烯樹脂、薴樹脂、雙戊烯樹脂、β-蒎烯/薴樹脂、氫化薴樹脂、芳香族變性萜烯樹脂、酚變性萜烯樹脂等，但並不限於此等。其中，較佳為α-蒎烯樹脂。The terpene resin-based flame retardant may, for example, be an α-pinene resin, a β-pinene resin, an anthracene resin, a dipentene resin, a β-pinene/indene resin, a hydrogenated hydrazine resin, an aromatically modified terpene resin, or a phenol. Denatured terpene resin or the like, but is not limited thereto. Among them, α-pinene resin is preferred.
當使用萜烯樹脂系難燃劑作為難燃劑時，難燃劑之含量，相對於非晶性熱可塑性樹脂100質量份，為1～30質量份，較佳為2～20質量份，再更佳為5～15質量份。若其量過少，則無法維持所欲之難燃性，而其若過多則會影響到機械特性。When a terpene resin-based flame retardant is used as the flame retardant, the content of the flame retardant is 1 to 30 parts by mass, preferably 2 to 20 parts by mass, based on 100 parts by mass of the amorphous thermoplastic resin. More preferably, it is 5 to 15 parts by mass. If the amount is too small, the desired flame retardancy cannot be maintained, and if it is too large, the mechanical properties are affected.
具有難燃性之非晶性熱可塑性樹脂，可舉聚氯乙烯、聚醚醯亞胺、聚醚碸、聚碸、聚醯胺醯亞胺，但並不限於此等。其中，較佳為聚氯乙烯。The non-flammable amorphous thermoplastic resin may, for example, be polyvinyl chloride, polyether quinone, polyether oxime, polyfluorene or polyamidoximine, but is not limited thereto. Among them, polyvinyl chloride is preferred.
其他之難燃劑，亦可使用硼酸銨、硼酸鋅。又，本發明中，上述難燃劑，可為單獨1種，亦可組合2種以上。For other flame retardants, ammonium borate or zinc borate can also be used. Further, in the present invention, the flame retardant may be used alone or in combination of two or more.
本發明中，對於發泡前之熱可塑性樹脂，除熔融型結晶成核劑之外，於不損及本發明目的之範圍，亦可適當配合結晶成核劑、結晶化促進劑、氣泡成核劑、抗氧化劑、抗靜電劑、抗紫外線劑、光安定劑、螢光增白劑、顏料、染料、相溶化劑、潤滑劑、強化劑、可塑劑、增黏劑、減黏劑等各種添加劑。又，亦可在由所得之非晶性熱可塑性樹脂發泡片所構成之反射材，積層含有上述添加劑之樹脂層，或亦可塗敷含有上述添加劑之塗料。其中，由防止紫外線所致之非晶性熱可塑性樹脂之劣化的觀點考量，較佳為，將含有抗紫外線劑等之層賦予在由非晶性熱可塑性樹脂發泡片所構成之反射材的至少一表面上。In the present invention, the thermoplastic resin before foaming may be appropriately blended with a crystallization nucleating agent, a crystallization accelerator, or a bubble nucleation in addition to the molten crystal nucleating agent without impairing the object of the present invention. Agents, antioxidants, antistatic agents, anti-UV agents, light stabilizers, fluorescent brighteners, pigments, dyes, compatibilizers, lubricants, enhancers, plasticizers, tackifiers, viscosity reducers, etc. . Further, a resin layer containing the above additive may be laminated on the reflective material composed of the obtained amorphous thermoplastic resin foamed sheet, or a coating material containing the above additive may be applied. In view of the deterioration of the amorphous thermoplastic resin by the ultraviolet ray, it is preferable to apply a layer containing an ultraviolet ray-resistant agent or the like to the reflective material composed of the amorphous thermoplastic resin foamed sheet. At least on one surface.
以下，說明本發明之非晶性熱可塑性樹脂發泡片的製造方法。Hereinafter, a method for producing the amorphous thermoplastic resin foamed sheet of the present invention will be described.
將於非晶性熱可塑性樹脂(A)加入熔融型結晶成核劑(B)與視需要之其他樹脂或添加物所得之混合物，使用例如捏合機或擠製機等進行熔融捏合，藉此製作樹脂組成物。捏合溫度或捏合時間等捏合條件，可以非晶性熱可塑性樹脂(A)及熔融型結晶成核劑(B)之熔融溫度適當地設定。例如，若為聚碳酸酯時，較佳在270℃以上。又，亦可適當地設定壓力。使用擠製機等將樹脂組成物成形為片狀，藉由將該樹脂片與隔離件重疊捲繞，以製成滾筒狀。將該滾筒保持於加壓惰性氣體環境氣氛中，藉此使該樹脂薄片含有惰性氣體。再者，將含有惰性氣體之該樹脂片於常壓下加熱至非晶性熱可塑性樹脂(A)之玻璃轉移溫度(Tg)以上，使其發泡。藉由加熱至Tg以上，可抑制不均一之氣泡的生成。如此可製得熱可塑性樹脂發泡片。該熱可塑性樹脂發泡片之中，交聯部分之質量分率未達10%。交聯度，可藉由將發泡薄片浸漬於可溶解非交聯部分的溶劑，計算相對於原發泡體總重量之不溶部分的重量分率來求得。例如，當為聚碳酸酯發泡體時，可藉由一邊將發泡體浸漬於二氯甲烷溶液中，一邊攪拌12小時左右，來除去可溶部分。The amorphous thermoplastic resin (A) is added to a mixture of the molten crystal nucleating agent (B) and, if necessary, other resins or additives, and is melt-kneaded by, for example, a kneader or an extruder, thereby producing Resin composition. The kneading conditions such as the kneading temperature or the kneading time can be appropriately set in the melting temperature of the amorphous thermoplastic resin (A) and the molten crystal nucleating agent (B). For example, in the case of polycarbonate, it is preferably at least 270 °C. Further, the pressure can be appropriately set. The resin composition is formed into a sheet shape by using an extruder or the like, and the resin sheet and the separator are superposed and wound to form a roll. The roller is held in a pressurized inert gas atmosphere, whereby the resin sheet contains an inert gas. In addition, the resin sheet containing an inert gas is heated under normal pressure to a glass transition temperature (Tg) of the amorphous thermoplastic resin (A) to be foamed. By heating to a temperature higher than Tg, generation of uneven bubbles can be suppressed. Thus, a thermoplastic resin foamed sheet can be obtained. In the foamed sheet of the thermoplastic resin, the mass fraction of the crosslinked portion is less than 10%. The degree of crosslinking can be determined by immersing the foamed sheet in a solvent capable of dissolving the non-crosslinked portion, and calculating the weight fraction of the insoluble portion relative to the total weight of the original foam. For example, in the case of a polycarbonate foam, the soluble portion can be removed by stirring the foam in a dichloromethane solution while stirring for about 12 hours.
本發明中，上述惰性氣體，可舉例如氦、氮、二氧化碳、氬等。其中，由對樹脂之氣體滲透度(速度、溶解度)的觀點考量，以二氧化碳較佳。In the present invention, the inert gas may, for example, be hydrazine, nitrogen, carbon dioxide or argon. Among them, carbon dioxide is preferred from the viewpoint of gas permeability (speed, solubility) of the resin.
樹脂片至飽合狀態為止之惰性氣體滲透時間及惰性氣體含浸量，係隨使其發泡之樹脂的種類、惰性氣體的種類、滲透壓力及片的厚度而不同。The inert gas permeation time and the inert gas impregnation amount of the resin sheet to the saturated state differ depending on the type of the resin to be foamed, the type of the inert gas, the permeation pressure, and the thickness of the sheet.
又，於該方法，亦可於以加壓惰性氣體環境氣氛使由樹脂片與隔離件所構成之滾筒含有惰性氣體之前，使樹脂片含有有機溶劑。Further, in this method, the resin sheet may contain an organic solvent before the drum composed of the resin sheet and the separator contains an inert gas in a pressurized inert gas atmosphere.
有機溶劑，可舉例如苯、甲苯、甲乙酮、甲酸乙酯、丙酮、乙酸、二烷、間甲酚、苯胺、丙烯腈、酞酸二甲酯、硝乙烷、硝甲烷、苄醇等。其中，由操作性及經濟性的觀點考量，以丙酮為佳。The organic solvent may, for example, be benzene, toluene, methyl ethyl ketone, ethyl formate, acetone, acetic acid, or the like. Alkane, m-cresol, aniline, acrylonitrile, dimethyl phthalate, nitrate, methane, benzyl alcohol, and the like. Among them, acetone is preferred from the viewpoint of operability and economy.
本發明中，存在於本發明之熱可塑性樹脂發泡體的氣泡的平均直徑在10μm以下。其中，較佳在5μm以下，特佳在2μm以下。若平均氣泡徑過大，則無法得到所欲之高反射率。In the present invention, the bubbles of the thermoplastic resin foam of the present invention have an average diameter of 10 μm or less. Among them, it is preferably 5 μm or less, and particularly preferably 2 μm or less. If the average bubble diameter is too large, the desired high reflectance cannot be obtained.
本發明之發泡體的發泡倍率，較佳為1.1～10，更佳為2～5。The foaming ratio of the foam of the present invention is preferably from 1.1 to 10, more preferably from 2 to 5.
本發明中，熱可塑性樹脂發泡體之光的總反射率，以97%以上為佳。其中，更佳為98.5%以上，特佳為99%以上。又，此處所敘述之總反射率，係使用分光光度計(U-4100：日立先端科技股份有限公司製)，使氧化鋁白色板(210-0740：Hitachi High-Tech Fielding Corporation製)之550nm波長之反射率為100%，而以相對值所表示者。In the present invention, the total reflectance of the light of the thermoplastic resin foam is preferably 97% or more. Among them, it is more preferably 98.5% or more, and particularly preferably 99% or more. In addition, the total reflectance described here is a 550 nm wavelength of an alumina white plate (210-0740: manufactured by Hitachi High-Tech Fielding Corporation) using a spectrophotometer (U-4100: manufactured by Hitachi Advanced Technology Co., Ltd.). The reflectance is 100%, and is expressed as a relative value.
接著，說明本發明之光反射材。Next, the light reflecting material of the present invention will be described.
於本發明之熱可塑性樹脂發泡體，形成有微細且均一之氣泡徑的氣泡。藉由此微細且均一之氣泡，本發明之熱可塑性樹脂發泡體具備高反射率。本發明之熱可塑性樹脂發泡體，活用高反射率及良好之成形性，可使用於例如照明用反射板、電子看板用反射板、液晶電視或行動電話背光之反射板等。In the thermoplastic resin foam of the present invention, bubbles having a fine and uniform bubble diameter are formed. The thermoplastic resin foam of the present invention has high reflectance by the fine and uniform bubbles. The thermoplastic resin foam of the present invention can be used for, for example, a reflector for illumination, a reflector for an electronic signboard, a reflector for a liquid crystal television or a backlight for a mobile phone, etc., in order to utilize high reflectance and good formability.
以下，根據實施例以更詳細地說明本發明，但本發明並不限於此等。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
[實施例1～9及比較例1～7][Examples 1 to 9 and Comparative Examples 1 to 7]
表1顯示實施例1～9及比較例1～7之樹脂組成物之各成分的含量(表中的數字，除特別說明以外，係指質量份)。將表中所示之各成分以同向雙軸擠製機進行熔融捏合而製得發泡前之薄片。擠製時之溫度，係以擠製溫度示於實施例、比較例之表。Table 1 shows the contents of the respective components of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 (the numbers in the table refer to parts by mass unless otherwise specified). Each of the components shown in the table was melt-kneaded by a co-rotating extruder to obtain a sheet before foaming. The temperature at the time of extrusion is shown in the table of the examples and the comparative examples at the extrusion temperature.
表中所示之各成分材料如以下。The ingredients of the ingredients shown in the table are as follows.
非晶性熱可塑性樹脂(A)Amorphous thermoplastic resin (A)
A1：「SI8000L」(商品名，住友Dow工業公司製)，難燃聚碳酸酯，非晶性A1: "SI8000L" (trade name, Sumitomo Dow Industrial Co., Ltd.), flame retardant polycarbonate, amorphous
A2：「NOVAREX S2000」(商品名，三菱工程塑料公司製)，聚碳酸酯，非晶性A2: "NOVAREX S2000" (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), polycarbonate, amorphous
A3：FS1300(商品名，SUMITOMO BAKELITE Corporation製)，聚醚碸，非晶性A3: FS1300 (trade name, manufactured by SUMITOMO BAKELITE Corporation), polyether oxime, amorphous
A4：SA1206(商品名，Unitika公司製)，聚對酞酸乙二酯，結晶性A4: SA1206 (trade name, manufactured by Unitika), polyethylene terephthalate, crystallinity
熔融型結晶成核劑(B)Melt crystal nucleating agent (B)
B1：「NJSTAR TF-1」(商品名，新日本理化公司製)，1,3,5-苯三甲酸三環己基醯胺B1: "NJSTAR TF-1" (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), tris-hexyl decylamine 1,3,5-benzenetricarboxylate
B1：「NJSTAR NU100」(商品名：新日本理化公司製)，N,N’-二環己基-2,6-萘二羧酸二環己基醯胺B1: "NJSTAR NU100" (trade name: manufactured by Nippon Chemical and Chemical Co., Ltd.), N,N'-dicyclohexyl-2,6-naphthalene dicarboxylic acid dicyclohexyl decylamine
難燃劑Flame retardant
C1：「X-40-9805」(商品名：信越化學工業公司製)，聚矽氧化合物C1: "X-40-9805" (trade name: Shin-Etsu Chemical Co., Ltd.), polyoxygenated compound
C2：「Hostaflon TF1620」(商品名，住友3M公司製)，聚四氟乙烯C2: "Hostaflon TF1620" (trade name, manufactured by Sumitomo 3M), Teflon
接著，將發泡前之片置入壓力容器，於17℃中，以6MPa之壓力含浸碳酸氣體使其滲透。滲透時間為48小時以上。Next, the sheet before foaming was placed in a pressure vessel, and impregnated with carbon dioxide gas at a pressure of 6 MPa at 17 ° C to permeate it. The penetration time is more than 48 hours.
將滲透有碳酸氣體之片由壓力容器取出，立即置入設定在既定溫度之恆溫槽內使其發泡。發泡時間為60秒以內。將發泡時之溫度作為發泡溫度示於表1。The sheet in which the carbonic acid gas was permeated was taken out from the pressure vessel, and immediately placed in a thermostatic chamber set at a predetermined temperature to be foamed. The foaming time is within 60 seconds. The temperature at the time of foaming is shown in Table 1 as the foaming temperature.
對發泡後之片，進行下述之評價。將所得之實施例1～9及比較例1～7的評價結果示於表1。The film after foaming was subjected to the following evaluation. The evaluation results of the obtained Examples 1 to 9 and Comparative Examples 1 to 7 are shown in Table 1.
(1) 熔融分散性(1) Melt dispersibility
以目視觀察擠製所得之發泡前之片的表面。將熔融型結晶成核劑於捏合時熔融分散，而無法以目視觀察到成核劑之凝集物者，判定為熔融分散性良好，而若有凝集物則判定為不良。另，未使用熔融型結晶成核劑者，不評價熔融分散性。The surface of the pre-expanded sheet obtained by extrusion was visually observed. When the molten crystal nucleating agent was melt-dispersed at the time of kneading, the aggregate of the nucleating agent could not be visually observed, and it was judged that the melt dispersibility was good, and if it was aggregated, it was judged to be defective. Further, in the case where a molten crystal nucleating agent is not used, the melt dispersibility is not evaluated.
(2) 巨大氣泡之有無(2) Whether there are huge bubbles
以目視觀察擠製所得之發泡前之片的表面，若存在有直徑超過1mm之氣泡，則判定具有巨大氣泡，若無則判定為無巨大氣泡。The surface of the sheet before foaming obtained by extrusion was visually observed, and if there were bubbles having a diameter of more than 1 mm, it was judged that there was a large bubble, and if not, it was judged that there was no large bubble.
(3) 發泡倍率(3) Foaming ratio
以水中取代法所測得之發泡片之比重(ρf)、與發泡前之樹脂之比重(ρs)之比ρs/ρf來計算。The ratio ρs/ρf of the specific gravity (ρf) of the foamed sheet measured by the water substitution method to the specific gravity (ρs) of the resin before foaming was calculated.
(4) 氣泡徑(4) Bubble diameter
根據ASTM D3576-77來求得。拍攝片之截面的掃描電子顯微鏡(SEM)照片，於所拍攝之SEN照片上在水平方向與垂直方向畫直線，求出直線橫跨氣泡之弦長度t的平均值。令照片之倍率為M，代入下述式求出平均氣泡徑d。It is obtained according to ASTM D3576-77. A scanning electron microscope (SEM) photograph of the cross section of the photographing sheet was drawn in a horizontal direction and a vertical direction on the photographed SEN photograph, and the average value of the straight line spanning the chord length t of the bubble was obtained. Let the magnification of the photograph be M, and substitute the following formula to obtain the average bubble diameter d.
d=t/(0.616×M)d=t/(0.616×M)
其中，巨大氣泡部，由於相對於微細部氣泡徑大幅不同，故除去其來進行測量。Among them, the large bubble portion has a large difference in the diameter of the bubble with respect to the fine portion, and is removed for measurement.
(5) 反射率(5) Reflectivity
使用分光光度計(U-4100：日立先端科技股份有限公司製)，以分光狹縫4nm之條件測量550nm波長之總反射率。於表1，以相對值顯示以固定有氧化鋁之微粉末的白板(210-0740：Hitachi High-Tech Fielding Corporation製)之總反射率為100%時各發泡片的總反射率。The total reflectance at a wavelength of 550 nm was measured using a spectrophotometer (U-4100: manufactured by Hitachi Advanced Technology Co., Ltd.) under the condition of a slit slit of 4 nm. In Table 1, the total reflectance of each of the foamed sheets when the total reflectance of the white plate (210-0740: manufactured by Hitachi High-Tech Fielding Corporation) to which the fine powder of alumina was fixed was displayed as a relative value.
(6) 成形性(6) Formability
以目視判斷成形後之發泡片之型再現性(邊緣之銳利度、底面之凹陷等)。當型再現性高時判定為良好，不佳時則判定為不良。The type reproducibility (sharpness of the edge, depression of the bottom surface, etc.) of the foamed sheet after molding was visually judged. When the type reproducibility is high, it is judged to be good, and when it is not good, it is judged to be bad.
(7) 難燃性(7) Flame retardancy
將發泡後、成形前之片裁切成既定的尺寸，依據Underwriter Laboratories UL-94、第5版(1996)之50W(20mm)垂直燃燒試驗方法進行評價。The sheet after foaming and before forming was cut into a predetermined size, and evaluated according to the 50W (20 mm) vertical burning test method of Underwriter Laboratories UL-94, 5th Edition (1996).
(8) 交聯度(8) Crosslinking degree
將發泡片浸漬於二氯甲烷溶液中攪拌12小時。測量浸漬前後之發泡片的重量，藉由浸漬後之重量除以浸漬前之重量，求出交聯度。The foamed sheet was immersed in a dichloromethane solution and stirred for 12 hours. The weight of the foamed sheet before and after the immersion was measured, and the degree of crosslinking was determined by dividing the weight after immersion by the weight before immersion.
由表1的結果可知，藉由在非晶性熱可塑性樹脂添加熔融型結晶成核劑，減低了巨大氣泡的產生。同時，此發泡體具有高反射率。As is apparent from the results of Table 1, the addition of the molten crystal nucleating agent to the amorphous thermoplastic resin reduces the generation of large bubbles. At the same time, this foam has a high reflectance.
本發明可提供一種具有微細且均一之氣泡徑、成形性優異之熱可塑性樹脂發泡體及使用其之光反射率高之光反射材。The present invention can provide a thermoplastic resin foam having a fine and uniform cell diameter and excellent moldability, and a light-reflecting member having high light reflectance using the same.
雖與其實施態樣一起說明本發明，但只要本發明未特別指定，於說明之任一細部皆非欲用以限定本發明，在不違反所附之申請專利範圍所示之發明之精神與範圍下，應作廣義地解釋。The present invention is described with respect to the embodiments thereof, and the invention is not intended to limit the scope of the invention, and the spirit and scope of the invention as set forth in the appended claims. Next, it should be interpreted broadly.
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