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Publication number
TWI542681B
TWI542681B TW102123223A TW102123223A TWI542681B TW I542681 B TWI542681 B TW I542681B TW 102123223 A TW102123223 A TW 102123223A TW 102123223 A TW102123223 A TW 102123223A TW I542681 B TWI542681 B TW I542681B
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TW
Taiwan
Prior art keywords
magnesium hydroxide
resin
heat shielding
shielding material
heat
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TW102123223A
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English (en)
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TW201408763A (zh
Inventor
Tsukasa Nakamura
Hitoshi Manabe
Daisuke Kudo
Shigeo Miyata
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Kyowa Chem Ind Co Ltd
Sea Water Chemical Inst Inc
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Publication of TW201408763A publication Critical patent/TW201408763A/zh
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B2001/7691—Heat reflecting layers or coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/24—Structural elements or technologies for improving thermal insulation
    • Y02A30/254—Roof garden systems; Roof coverings with high solar reflectance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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Description

遮熱材
本發明係關於紅外線的反射能力優異，且對可見光的穿透性優異之遮熱材。
能源價格有日漸高漲的傾向，省能源在廣範圍領域中已成為共通的課題。利用在屋頂塗佈遮熱塗料、或在窗玻璃上黏貼加入有遮熱材的樹脂薄膜，俾抑制因夏季的太陽光而造成的室內溫度上升的方法正急遽拓展。又，農業領域中，為了使可見光穿透，但防止溫室內必要以上的溫度上升，俾良好地保持農作物的育成，係使用遮熱薄膜或薄片。
此種遮熱製品所使用的遮熱材係鋁或銀的金屬薄片、氧化鈦、氧化鋅、珍珠顏料等。該等遮熱材會將溫度上升原因的紅外線予以反射，在夏季時防止室內溫度上升，在冬季時防止室內溫度下降。但是，該等遮熱材具有透明性差、成形品表面粗糙、容易著色等缺點。因此，若黏貼於窗戶便會導致視界變差。又，農業用溫室內的植物生育係由於植物所需要的可見光之穿透減少，因而有所阻礙。又，有不易製作透明、無色的塗料等問題。
本發明之目的係在於提供：對溫度上升原因的紅外線之反射能力優異，且對可見光穿透性優異的遮熱材。又，本發明之目的 係在於提供：含有該遮熱材的樹脂組成物及成形品。
本發明者發現高寬深比板狀結晶氫氧化鎂的紅外線反射能力優異，且對可見光的穿透性優異，遂完成本發明。
即，本發明的遮熱材係以結晶的橫寬為1μm以上，且結晶的厚度為0.2μm以下之板狀結晶氫氧化鎂作為有效成分。又，本發明的樹脂組成物係含有100重量份的樹脂、及1~50重量份的上述遮熱材。又，本發明的成形品係將上述樹脂組成物予以成形而得。又，本發明的將板狀結晶氫氧化鎂使用為紅外線遮熱材之方法，該板狀結晶氫氧化鎂係結晶的橫寬為1μm以上，且結晶的厚度為0.2μm以下。
<遮熱材> (高寬深比板狀結晶氫氧化鎂)
本發明的遮熱材係以結晶的橫寬較大且結晶的厚度較薄之高寬深比板狀結晶氫氧化鎂作為有效成分。高寬深比板狀結晶氫氧化鎂的結晶橫寬為1μm以上、較佳為2μm以上、更佳為3μm以上。又，結晶的厚度為0.2μm以下、較佳為0.1μm以下、更佳為0.05μm以下。
上述板狀結晶氫氧化鎂在樹脂中的配向性優異、光反射率高。結果，能將溫度上升原因的紅外線良好地反射，俾使其穿透率降低。寬深比係定義為結晶的橫寬/厚度之比。
高寬深比板狀結晶氫氧化鎂的結晶橫寬越大，則配向性(成形面與結晶的橫向呈平行)越佳，越接近鏡面反射，遮熱效果提升。 另一方面，結晶的厚度越薄，則越提升可見光的穿透率，透明性良好。習知的氫氧化鎂結晶係橫寬約為1μm以下，且厚度約為0.5μm以上。因此，結晶的配向性不良且厚度較厚，故透明性差、遮熱效果小。
為提升與樹脂間之相溶性、分散性，高寬深比板狀結晶氫氧化鎂可經表面處理後使用。作為表面處理劑，係使用：高級脂肪酸或其鹼金屬鹽、磷酸酯、陰離子系界面活性劑；矽烷、鋁、鈦酸酯等偶合劑等等。表面處理係可藉由相對於高寬深比板狀結晶氫氧化鎂的重量，使0.1~10重量%的表面處理劑溶解於水或醇等有機溶劑中，在水等液狀介質中施行攪拌下添加高寬深比板狀結晶氫氧化鎂的濕式法實施。或者，亦可藉由將板狀結晶氫氧化鎂粉末利用諸如漢歇爾攪拌機等攪拌機施行攪拌下，添加上述表面處理劑之所謂乾式法實施。
為提升其容積比重俾使與樹脂進行混練時的加工性良好，板狀結晶氫氧化鎂亦可經成形為例如直徑0.5~5mm之粒狀後使用。成形係可使用擠出造粒、滾動造粒等以往公知手段實施。
(高寬深比板狀結晶氫氧化鎂之製造)
高寬深比板狀結晶氫氧化鎂係在微結晶氫氧化鎂與單羧酸/或其金屬鹽之共存下，於100℃以上、較佳係150~250℃施行攪拌下，施行較佳2~10小時的水熱處理便可製造。
單羧酸亦可在利用於水溶性鎂鹽水溶液中添加當量以上的NaOH等鹼，較佳於0~40℃進行反應的共沉法製造氫氧化鎂的階段，於共沉反應前添加至鎂的鹵化物、硝酸鹽、單羧酸鹽等水溶性鎂鹽，利用氫氧化鈉等鹼進行共沉後，施行水熱處理。單羧酸係相對於氫氧化鎂，依莫耳比添加較佳0.01以上、更佳係0.1~1.0。
作為水溶性鎂鹽，較佳係可列舉如：氯化鎂、硝酸鎂、醋酸鎂。單羧酸較佳係可列舉如：醋酸、丙酸、丁酸、甘醇酸、乳酸。
<樹脂組成物>
再者，本發明的樹脂組成物係含有100重量份的樹脂、及1~50重量份的上述遮熱材。
作為樹脂，較佳係從熱可塑性樹脂、熱硬化性樹脂及橡膠所構成群組中選擇之至少一種樹脂。作為樹脂，係可例示：聚乙烯、乙烯與α-烯烴的共聚合體；乙烯與醋酸乙烯酯、丙烯酸乙酯或丙烯酸甲酯的共聚合體、聚丙烯、丙烯與其他α-烯烴的共聚合體、聚丁烯-1、聚4-甲基戊烯-1、聚苯乙烯、苯乙烯與丙烯腈、乙烯與丙二烯橡膠或丁二烯的共聚合體、聚醋酸乙烯酯、聚乙烯醇、聚丙烯酸酯、聚甲基丙烯酸酯、聚胺甲酸酯、聚酯、聚醚、聚醯胺、ABS、聚碳酸酯、聚苯硫醚等熱可塑性樹脂；酚樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂、醇酸樹脂等熱硬化性樹脂；EPDM、SBR、NBR、乙烯與其他α-烯烴(例如丙烯、辛烯等)的共聚合橡膠、丁基橡膠、氯化戊二烯橡膠、異戊二烯橡膠、氯磺化橡膠、矽橡膠、氟橡膠、氯化丁基橡膠、溴化丁基橡膠、表氯醇橡膠、氯化聚乙烯橡膠等。
作為樹脂組成物，係可列舉遮熱塗料。此情況，作為樹脂，係可含有例如：酚樹脂塗料、醇酸樹脂塗料、胺基醇酸樹脂塗料、氯乙烯樹脂塗料、丙烯酸系樹脂塗料、環氧樹脂塗料、矽樹脂塗料、聚胺甲酸酯樹脂塗料、氟樹脂塗料、油性塗料等。
相對於100重量份的樹脂，遮熱材在樹脂組成物中的含量係0.1~100重量份、較佳係1~50重量份。
樹脂組成物係在將樹脂與上述遮熱材進行混合後，利用以往公知的混練手段便可製造。例如，將樹脂與遮熱材利用雙螺桿擠出機施行加熱熔融混合後，予以顆粒化便可製造。
<成形品>
將樹脂組成物利用擠出成形、射出成形、真空成形、充氣成形、狹縫成形等慣用成形機、手段，予以成形為薄膜、薄片、厚壁成形品等便可獲得成形品。作為成形品，係可列舉：黏貼於窗戶玻璃上的遮熱薄膜、屋頂等處所使用的遮熱塗料、用以調節溫室內溫度的農業用遮熱薄膜或薄片、戶外使用的樹脂成形品等。
<使用為遮熱材之方法>
本發明係包含將結晶的橫寬為1μm以上，且結晶的厚度為0.2μm以下的高寬深比板狀結晶氫氧化鎂使用為紅外線遮熱材之方法。
[實施例]
以下，利用實施例說明本發明，惟本發明並不僅侷限於該等實施例。
[實施例1] (氫氧化鎂之調製)
在一級試劑氯化鎂與醋酸鈉之混合水溶液(Mg=2莫耳/L、醋酸鈉=1.2莫耳/L、30℃)20L中，於攪拌下，添加8莫耳/L的一級試劑氫氧化鈉水溶液(30℃)8L，使其進行共沉反應。將該反應物裝入容量50L熱壓鍋中，於170℃施行8小時水熱處理。取出水熱處理物，經減壓過濾、水洗後，利用攪拌機使濾餅分散於水中。加熱至約 80℃後，於攪拌下添加將40g硬脂酸(純度90%)利用氫氧化鈉中和並加熱溶解而成的水溶液1L，施行表面處理。然後，將施行強制過濾、水洗所獲得之濾餅利用造粒用雙螺桿擠出機造粒成直徑約2mm，利用烤箱於約120℃乾燥。
採取表面處理前的一部分試料，施行利用X射線繞射、SEM、及液態氮吸附法之BET比表面積測定。
X射線繞射的結果係鑑定為氫氧化鎂。SEM測定的結果，各個結晶係接近六角形的板狀結晶外形，厚度為0.07μm、橫寬為3.2μm。所因此，寬深比為50。BET比表面積為12m2/g。
(薄片之成形)
相對於LLDPE(直鏈低密度聚乙烯)100重量份，將造粒物10重量份、抗氧化劑(IRGANOX 1010)0.1重量份進行混合後，使用布拉班德粉質儀(Brabender)施行熔融混練。將混練物使用壓製成形機成形為厚度1mm、長134mm、寬99mm的薄片。針對該薄片使用分光光度計，測定可見光(380~780nm)穿透率與近紅外線(780~2500nm)反射率。結果示於表1。
將該薄片裝設於僅1方向設有40mm見方之窗口且經利用絕熱劑覆蓋的紙製箱體之窗部分，距離10.5cm照射紅外線燈(185W)，測定箱體內的溫度及薄片溫度。結果示於表1。結果可知，調配有本發明遮熱材的樹脂薄片係透明性良好(因為可見光線穿透率高)，且可抑制室內溫度上升。
[實施例2] (氫氧化鎂之調製)
在實施例1中，依高寬深比板狀結晶氫氧化鎂的製造條件，除取代醋酸鈉，改為使用丙酸鈉1.6莫耳之外，其餘均與實施例1同樣地實施而製造氫氧化鎂。表面處理前的該物質經X射線繞射的結果係鑑定為氫氧化鎂。SEM測定的結果，各個結晶係接近六角形的板狀結晶外形，厚度為0.05μm、橫寬為4.5μm。因此，寬深比為90。BET比表面積為8.2m2/g。
(薄片之成形)
將所獲得之造粒物依照與實施例1同樣的方式成形為薄片並施行遮熱試驗。結果示於表1。可知實施例2亦呈現與實施例1同樣的傾向。
[比較例1]
將市售氫氧化鎂(厚度0.3μm、橫寬0.9μm、BET比表面積6m2/g、寬深比3)依照與實施例1同樣的方式利用硬脂酸鈉施行表面處理後，與實施例1同樣地施行遮熱試驗，結果示於表1。由表1可知，市售氫氧化鎂的透明性差，近紅外線反射率、遮熱性均劣於本發明的遮熱材。
[比較例2]
使用在橫寬約15μm雲母的表面上形成有氧化鈦的珍珠顏料系市售遮熱材，依照與實施例1同樣的方式製成LLDPE薄片。其評估結果示於表1。由表1可知，市售遮熱材的透明性差。
(對照先前技術之功效)
本發明的遮熱材係紅外線反射能力優異，且可見光穿透性優異。又，本發明的樹脂組成物及成形品係具有呈現透明性優異、表面光澤優異的高級感之外觀。
(產業上之可利用性)
本發明的遮熱材係可應用於以遮熱為目的之任何用途。可列舉如：黏貼於住家、汽車等的窗玻璃上之遮熱薄膜、屋頂等處所使用的遮熱塗料、用以調節溫室內溫度的農業用遮熱薄膜或薄片、戶外使用的傢俱等樹脂成形品等等。

Claims (8)

  1. 一種遮熱材，係以結晶的橫寬為1μm以上，且結晶的厚度為0.2μm以下之高寬深比板狀結晶氫氧化鎂作為有效成分，該遮熱材係直徑為0.5~5mm之粒狀者。
  2. 如申請專利範圍第1項之遮熱材，其中，高寬深比板狀結晶氫氧化鎂的橫寬為2μm以上，且厚度為0.1μm以下。
  3. 如申請專利範圍第1項之遮熱材，其中，高寬深比板狀結晶氫氧化鎂的橫寬為3μm以上，且厚度為0.1μm以下。
  4. 如申請專利範圍第1項之遮熱材，其中，高寬深比板狀結晶氫氧化鎂的橫寬為3μm以上，且厚度為0.05μm以下。
  5. 一種樹脂組成物，係含有100重量份的樹脂、及1~50重量份的申請專利範圍第1項之遮熱材。
  6. 一種成形品，係將申請專利範圍第5項之樹脂組成物予以成形而得。
  7. 如申請專利範圍第6項之成形品，其係薄膜。
  8. 一種將申請專利範圍第1項之遮熱材使用為紅外線遮熱材之方法。
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