TWI449713B - A resin composition, a hard coat agent, a film, and a molded article - Google Patents
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- TWI449713B TWI449713B TW098109467A TW98109467A TWI449713B TW I449713 B TWI449713 B TW I449713B TW 098109467 A TW098109467 A TW 098109467A TW 98109467 A TW98109467 A TW 98109467A TW I449713 B TWI449713 B TW I449713B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08J5/18—Manufacture of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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Description
本發明係關於樹脂組成物、硬塗劑、薄膜及成形體之製造方法。The present invention relates to a resin composition, a hard coating agent, a film, and a method for producing a molded body.
自以往，於家電製品之膜片開關(membrane switch)或自動販賣機之仿真罐等，係使用塗佈有熱硬化型樹脂之薄膜。Conventionally, a film coated with a thermosetting resin has been used for a membrane switch of a home electric appliance or a simulation can of a vending machine.
又，將相較於熱硬化型樹脂，耐擦傷性較優異之紫外線硬化型樹脂予以塗佈、硬化而成之成形用薄膜逐漸普及。尤其，行動電話、隨身式音樂播放器、觸控面板等電子設備框體或汽車內裝材，要求硬度、耐擦傷性、耐污染性、光澤感等，因此，於彼等用途，開始應用將紫外線硬化型樹脂予以塗佈、硬化成的成形用薄膜(參照專利文獻1~3)。In addition, a film for forming which is coated and hardened with an ultraviolet curable resin having excellent scratch resistance is gradually popularized compared with a thermosetting resin. In particular, mobile phone frames, portable music players, touch panels and other electronic equipment frames or automotive interior materials require hardness, scratch resistance, stain resistance, gloss, etc. Therefore, for their use, application will begin. A film for molding which is applied and cured by an ultraviolet curable resin (see Patent Documents 1 to 3).
專利文獻1：國際公開第00/34396號小冊、專利文獻2：日本特開2005-8717號公報專利文獻3：日本特開2004-305863號公報Patent Document 1: International Publication No. 00/34396, and Patent Document 2: JP-A-2005-8717 Patent Document 3: Japanese Patent Laid-Open Publication No. 2004-305863
塗佈有熱硬化型樹脂之薄膜，硬度或耐擦傷性低，容易受傷，造成外觀顯著劣化。另一方面，將紫外線硬化型樹脂予以塗佈、硬化成的成形用薄膜，由於剛直且容易有裂痕，欠缺成形性，僅能使用在比較平坦的構造體成形。A film coated with a thermosetting resin has low hardness or scratch resistance and is easily damaged, resulting in significant deterioration in appearance. On the other hand, the film for forming which is applied and cured by the ultraviolet curable resin is straight and easily cracked, and lacks formability, and can be molded only in a relatively flat structure.
本發明有鑑於以上之點，目的在於提供硬度或耐擦傷性高且成形性亦良好的樹脂組成物、硬塗劑、薄膜、及成形體的製造方法。In view of the above, it is an object of the present invention to provide a resin composition, a hard coating agent, a film, and a method for producing a molded article which have high hardness and scratch resistance and good moldability.
以下詳細說明本發明。The invention is described in detail below.
本發明之樹脂組成物，其特徵在於包含：具有2個以上丙烯醯基之多官能聚合性化合物，及可對於丙烯醯基進行加成反應之化合物。The resin composition of the present invention is characterized by comprising a polyfunctional polymerizable compound having two or more acrylonitrile groups and a compound capable of undergoing an addition reaction to an acrylonitrile group.
本發明之樹脂組成物，於一次硬化狀態，具有即使成形亦不易產生裂痕的柔軟性，同時，也不易發黏。又，本發明之樹脂組成物，於二次硬化狀態，硬度或耐擦傷性優異。The resin composition of the present invention has a softness which is less likely to cause cracks even when formed in a single-hardening state, and is also less likely to be sticky. Further, the resin composition of the present invention is excellent in hardness or scratch resistance in the secondary hardening state.
又，一次硬化意指：對於丙烯醯基之加成反應。又，二次硬化，係指藉由照射紫外線或電子束等活性能量射線進行的自由基聚合。Further, primary hardening means: an addition reaction to an acrylonitrile group. Further, secondary hardening refers to radical polymerization by irradiation with an active energy ray such as ultraviolet rays or electron beams.
本發明之具2個以上丙烯醯基之多官能聚合性化合物，自由基反應性非常高，由速硬性及高硬度之觀點而言，具有優勢性。具2個以上丙烯醯基之多官能聚合性化合物，例如二丙烯酸1,4-丁二酯、二丙烯酸1,6-己二酯、二丙烯酸新戊二酯、二丙烯酸聚乙二酯、二丙烯酸羥基三甲基乙酸新戊二酯、二丙烯酸二環戊酯、己內酯變性二丙烯酸二環戊烯酯、氧乙烯變性二丙烯酸磷酸酯、烯丙基化二丙烯酸環己酯、二丙烯酸三聚異氰酸酯、三羥甲基丙烷三丙烯酸酯、三丙烯酸二季戊四酯、丙酸變性三丙烯酸二季戊四酯、三丙烯酸季戊四酯、氧丙烯變性三羥甲基丙烷三丙烯酸酯、參(丙烯醯氧乙基)異三聚氰酸酯、五丙烯酸二季戊四酯、丙酸變性五丙烯酸二季戊四酯、六丙烯酸二季戊四酯、己內酯變性六丙烯酸二季戊四酯等。The polyfunctional polymerizable compound having two or more acrylonitrile groups of the present invention has a very high radical reactivity and is advantageous from the viewpoint of rapid hardness and high hardness. a polyfunctional polymerizable compound having two or more acrylonitrile groups, such as 1,4-butane diacrylate, 1,6-hexanedicarboxylate, neopentyl diacrylate, polyethylene diacrylate, and Hydroxytrimethylacetate neopentyl acrylate, dicyclopentanyl diacrylate, caprolactone denatured dicyclopentenyl diacrylate, oxyethylene modified diacrylate phosphate, allylated cyclohexyl diacrylate, diacrylic acid Trimeric isocyanate, trimethylolpropane triacrylate, dipentaerythritol triacrylate, propionic acid modified dipentaerythritol triacrylate, pentaerythritol triacrylate, oxypropylene denatured trimethylolpropane triacrylate, ginseng (Propylene oxiranyl) isomeric cyanurate, dipentaerythritol pentaacrylate, propionic acid denatured dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone denatured dipentaerythritol hexaacrylate, and the like.
官能基數愈多的丙烯酸酯，表面硬度愈高，為較佳。該等可以單獨使用，或組合2種以上使用。具有2個以上丙烯醯基之多官能聚合性化合物，可為單體或預聚物，又，也可為氨酯丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯等。The acrylate having a higher number of functional groups has a higher surface hardness, which is preferable. These may be used alone or in combination of two or more. The polyfunctional polymerizable compound having two or more acrylonitrile groups may be a monomer or a prepolymer, or may be a urethane acrylate, an epoxy acrylate, a polyester acrylate or the like.
本發明使用之可對於丙烯醯基進行加成反應之化合物，係指可與具2個以上丙烯醯基之多官能聚合性化合物進行加成反應之化合物。藉該加成反應，樹脂組成物進行一次硬化(B階段化)，因此，樹脂組成物之黏性消失或減少。利用此，將樹脂組成物塗佈於薄膜後，藉由賦予促進加成反應之條件，能防止薄膜彼此阻礙(blocking)，或成形時薄膜與模具阻礙。可對於丙烯醯基進行加成反應之化合物，只要是具有親核性之化合物即可，具體而言以胺化合物為佳。The compound which can be used for the addition reaction of the propylene fluorenyl group used in the present invention means a compound which can undergo an addition reaction with a polyfunctional polymerizable compound having two or more acrylonitrile groups. By this addition reaction, the resin composition is once hardened (B-staged), and therefore, the viscosity of the resin composition disappears or decreases. According to this, after the resin composition is applied to the film, the conditions for promoting the addition reaction can be prevented, and the film can be prevented from blocking each other, or the film and the mold can be inhibited during molding. The compound which can be subjected to an addition reaction with an acrylonitrile group may be a compound having a nucleophilic property, and specifically, an amine compound is preferred.
胺化合物，例如具1級或2級胺者，例如：甲胺、乙二胺、二乙三胺、三乙四胺、四乙五胺、五乙六胺、六亞甲二胺、苯胺、苯乙胺、金剛烷胺(amantadine)、哌，或含胺基之矽烷偶聯劑等低分子量胺。本發明中，低分子量胺係指，例如DETA(二乙三胺)、TETA(三乙四胺)、PEHA(五乙六胺)等乙二胺衍生物，其分子量例如以50~400之範圍為適當。又，胺化合物，亦可使用以胺作為重複構造之多元胺。藉由併用低分子量胺與多元胺，能輕易地調整樹脂組成物之硬化性。又，若併用低分子量胺與多元胺，當樹脂組成物處於一次硬化之狀態時，更不易產生黏性。多元胺之分子量例如以1萬~20萬之範圍為適當。An amine compound, for example, a compound having a grade 1 or a grade 2, such as methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, aniline, Phenylethylamine, amantadine, piperazine Or a low molecular weight amine such as an amine-containing decane coupling agent. In the present invention, the low molecular weight amine means, for example, an ethylenediamine derivative such as DETA (diethylenetriamine), TETA (triethylenetetramine), or PEHA (pentaethylenehexamine), and the molecular weight thereof is, for example, in the range of 50 to 400. To be appropriate. Further, as the amine compound, a polyamine having an amine as a repeating structure can also be used. The hardenability of the resin composition can be easily adjusted by using a combination of a low molecular weight amine and a polyamine. Further, when a low molecular weight amine and a polyamine are used in combination, when the resin composition is once hardened, viscosity is less likely to occur. The molecular weight of the polyamine is, for example, suitably in the range of 10,000 to 200,000.
胺化合物之使用量，取決於使用之胺化合物之胺價，相對於具有2個以上丙烯醯基之多官能聚合性化合物100重量份，以0.1~50重量份之範圍為佳，0.5~30重量份之範圍更佳，5~25重量份之範圍尤佳。樹脂組成物之一次硬化不充分時，可藉由增加胺化合物之配合量，或提高多元胺在胺化合物中所佔比例，使硬化性提高。另一方面，當樹脂組成物之使用期限短時，可藉由減少胺化合物的配合量，或使多元胺在胺化合物中所佔比例減低，而延長使用期限。又，胺價愈大之化合物，胺化合物之反應性愈大，能減少胺化合物之添加量，表面物性亦為良好，為較佳。The amount of the amine compound used depends on the amine valence of the amine compound to be used, and is preferably in the range of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight based on 100 parts by weight of the polyfunctional polymerizable compound having two or more acrylonitrile groups. The range is better, especially in the range of 5 to 25 parts by weight. When the primary hardening of the resin composition is insufficient, the hardenability can be improved by increasing the compounding amount of the amine compound or increasing the proportion of the polyamine in the amine compound. On the other hand, when the use period of the resin composition is short, the lifespan can be extended by reducing the compounding amount of the amine compound or reducing the proportion of the polyamine in the amine compound. Further, the compound having a higher amine value has a higher reactivity with the amine compound, and the amount of the amine compound added can be reduced, and the surface physical properties are also good, which is preferable.
藉由與前述可對於丙烯醯基進行加成反應之化合物同時配合感溫性觸媒，能容易兼顧一次硬化性及樹脂組成物之使用期限。亦即，感溫性觸媒於常溫沒有觸媒活性(或低活性)，因此能增長樹脂組成物之使用期限，於高溫由於急速發揮活性，故能使一次硬化性提升。又，若配合感溫性觸媒，則當樹脂組成物處於一次硬化狀態時，更不易產生黏性。By simultaneously mixing the temperature-sensitive catalyst with the compound which can be subjected to the addition reaction to the acrylonitrile group, the primary hardenability and the life of the resin composition can be easily achieved. In other words, since the temperature sensitive catalyst has no catalytic activity (or low activity) at normal temperature, the life of the resin composition can be increased, and the primary curing property can be improved by rapidly exerting activity at a high temperature. Further, when a temperature sensitive catalyst is blended, when the resin composition is in a primary hardening state, viscosity is less likely to occur.
感溫性觸媒之具體例，以係強鹼之DBU(二氮雜雙環十一烯)或DBN(二氮雜雙環壬烯)之鹽尤佳。DBU或DBN之鹽，與各種溶劑之互溶性亦優異，相較於使用習知3級胺或無機系鹼性觸媒，能以更溫和條件達到反應產率之提升。As a specific example of the temperature sensitive catalyst, a salt of DBU (diazabicycloundecene) or DBN (diazabicyclononene) which is a strong base is particularly preferable. The salt of DBU or DBN is also excellent in miscibility with various solvents, and the reaction yield can be improved under milder conditions than the conventional tertiary amine or inorganic alkaline catalyst.
DBU或DBN之鹽，例如：DBU-苯酚鹽、DBU-辛酸鹽、DBU-油酸鹽、DBU-對甲苯磺酸鹽、DBU-甲酸鹽、DBN-苯酚鹽、DBN-辛酸鹽、DBN-油酸鹽、DBN-對甲苯磺酸鹽、DBN-甲酸鹽甲胺等。此外，例如：脒鹼或胍鹼之鹽等。又，若為對於有機溶劑可溶且具脫質子作用之強鹼鹽，則也可使用。該等感溫性觸媒可單獨使用或混合2種以上使用。又，若為能促進對於丙烯醯基之加成反應的觸媒，則不限於前述感溫性觸媒，能與可發揮觸媒活性之方法同時使用。Salts of DBU or DBN, for example: DBU-phenate, DBU-octanoate, DBU-oleate, DBU-p-toluenesulfonate, DBU-formate, DBN-phenolate, DBN-octanoate, DBN- Oleate, DBN-p-toluenesulfonate, DBN-formate methylamine, and the like. Further, for example, a salt of a purine base or a purine base or the like. Further, it can also be used as a strong base salt which is soluble in an organic solvent and has a protonation action. These temperature sensitive catalysts may be used singly or in combination of two or more. Further, the catalyst which can promote the addition reaction to the acrylonitrile group is not limited to the above-mentioned temperature sensitive catalyst, and can be used simultaneously with a method capable of exhibiting catalyst activity.
感溫性觸媒之配合量，相對於具2個以上丙烯醯基之多官能聚合性化合物100重量份，以5~20重量份之範圍較佳。藉由在該範圍內，當樹脂組成物處於-次硬化狀態時，更不容易產生黏性。The amount of the thermosensitive catalyst is preferably in the range of 5 to 20 parts by weight based on 100 parts by weight of the polyfunctional polymerizable compound having two or more acrylonitrile groups. By being within this range, when the resin composition is in the -hardened state, viscosity is less likely to occur.
本發明之樹脂組成物，藉由照射紫外線或電子束等活性能量射線，而進行二次硬化。進行紫外線硬化時，可使用超高壓水銀燈、高壓水銀燈、低壓水銀燈、碳弧、金屬鹵化物燈等，於100~400nm，較佳為200~400nm之波長區域，照射具有50~300mJ/cm2 之能量的紫外線。為防止妨礙硬化，也可在氮氣等鈍性氣體下進行照射。The resin composition of the present invention is subjected to secondary hardening by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. When performing ultraviolet curing, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like may be used, and the irradiation is in a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, and the irradiation has a temperature of 50 to 300 mJ/cm 2 . The ultraviolet rays of energy. In order to prevent the hardening from being hardened, it is also possible to irradiate under a passive gas such as nitrogen.
利用紫外線使硬化時，相對於具2個以上丙烯醯基之多官能聚合性化合物100重量份，宜添加紫外線硬化型起始劑3~10重量份，藉使添加量為3重量以上，熱硬化後不易殘留黏性，藉由使添加量在10重量份以下，能抑制過度硬化反應，確保成形性。When curing by ultraviolet light, it is preferable to add 3 to 10 parts by weight of the ultraviolet curable initiator to 100 parts by weight of the polyfunctional polymerizable compound having two or more acrylonitrile groups, and the amount of addition is 3 parts by weight or more, and it is thermally hardened. After the adhesiveness is not easily retained, the amount of addition is 10 parts by weight or less, and the excessive hardening reaction can be suppressed to ensure moldability.
紫外線硬化型起始劑，例如：1-羥基環己基苯酮、2,2-二甲氧基-2-苯基苯乙酮、氧葱酮(xanthone)、茀酮、苯甲醛、茀、蒽醌、三苯胺、咔唑、3-甲基苯乙酮、4-氯二苯基酮、4,4’-二甲氧基二苯基酮、4,4’-二胺基二苯基酮、米蚩酮、安息香丙醚、安息香乙醚、苄基二甲基縮酮、l-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙-1-酮、2-羥基-1-[4-[4-(2-羥基-2-甲基-丙醯基)-苄基]-苯基]-2-甲基-丙-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、硫氧蔥酮(thioxanthone)、二乙基硫氧葱酮、2-異丙基硫氧蔥酮、2-氯硫氧葱酮、2-甲基-1-[4-(甲硫)苯基]-2-啉-丙-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙-(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦等，市售品例如ITgacure 127、184、369、651、500、819、907、2959(以上(Ciba Japan公司製，商品名)等。該等紫外線硬化型起始劑可併用2種以上。UV curable initiators, for example: 1-hydroxycyclohexyl benzophenone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine Anthracene, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorodiphenyl ketone, 4,4'-dimethoxydiphenyl ketone, 4,4'-diaminodiphenyl ketone , Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-[4 -(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2- Methyl-propenyl)-benzyl]-phenyl]-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone (thioxanthone), diethyl thioxanthone, 2-isopropylthioxanthene, 2-chlorothioxanthene, 2-methyl-1-[4-(methylthio)phenyl]-2- Porphyrin-propan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4- Commercially available products such as ITgacure 127, 184, 369, 651, 500, 819, 907, and 2959 (manufactured by Ciba Japan Co., Ltd., etc.), etc. Two or more types can be used in combination.
又，利用電子束使樹脂組成物硬化時，可使用公知的電子束照射裝置。電子束之照射量以10~200kGy為佳，30~100kGy更佳。藉由為10kGy以上，能使樹脂組成物確實硬化，藉由為200kGy以下，能減低對於電子束照射裝置之負荷，為經濟的。Further, when the resin composition is cured by an electron beam, a known electron beam irradiation apparatus can be used. The irradiation amount of the electron beam is preferably 10 to 200 kGy, and more preferably 30 to 100 kGy. When the composition is 10 kGy or more, the resin composition can be surely cured, and if it is 200 kGy or less, the load on the electron beam irradiation device can be reduced, which is economical.
本發明之硬塗劑，其特徵在於：包含前述(1)之樹脂組成物。使用本發明之硬塗劑形成之硬塗層，於一次硬化狀態，具即使成形也不易發生裂痕的柔軟性，同時不易產生黏性。又，使用本發明之硬塗劑形成之硬塗層，於二次硬化之狀態，硬度或耐擦傷性優異。The hard coating agent of the present invention is characterized by comprising the resin composition of the above (1). The hard coat layer formed by using the hard coating agent of the present invention has a softness which is less likely to be cracked even if it is formed in a once-hardened state, and is less likely to cause stickiness. Further, the hard coat layer formed by using the hard coat agent of the present invention is excellent in hardness or scratch resistance in the state of secondary hardening.
本發明之硬塗劑，可維持前述(1)之樹脂組成物的狀態，亦可適當添加其他成分。The hard coating agent of the present invention can maintain the state of the resin composition of the above (1), and other components can be appropriately added.
本發明之薄膜特徵在於：於薄膜基材上形成由前述(1)之樹脂組成物所構成之硬塗層。The film of the present invention is characterized in that a hard coat layer composed of the resin composition of the above (1) is formed on a film substrate.
本發明之薄膜例如可為硬塗層處於一次硬化狀態者。構成本發明之薄膜的硬塗層，由於具有不易產生裂痕之柔軟性。因此本發明之薄膜不易於硬塗層產生裂痕，能成形為設計性優異的深縫隙或複雜構造。The film of the present invention may be, for example, a hard coat layer in a once hardened state. The hard coat layer constituting the film of the present invention has flexibility which is less likely to cause cracks. Therefore, the film of the present invention does not easily cause cracks in the hard coat layer, and can be formed into a deep gap or a complicated structure excellent in design.
又，構成本發明之薄膜的硬塗層，即使為未成二次硬化之狀態仍不易產生黏性，因此，能防止薄膜彼此阻礙或成形時薄膜與模具阻礙。又，二次硬化後之硬塗層，硬度或耐擦傷性優異。Further, since the hard coat layer constituting the film of the present invention is less likely to be viscous even in a state in which it is not hardened twice, it is possible to prevent the film from being blocked from the mold when the films are prevented from each other or formed. Further, the hard coat layer after secondary hardening is excellent in hardness or scratch resistance.
本發明之薄膜，宜在較硬塗層更為上層具有保護層。即使處於一次硬化狀態之硬塗層未具有充分硬度，仍能藉由包含保護層，在例如將薄膜成形時，不易於硬塗層產生傷痕等。保護層例如可藉由將溶解或分散於溶劑之樹脂塗佈到硬塗層後，使溶劑揮發而形成。藉由此舉，不會如使用由附黏着劑之薄膜等構成之保護層時，黏着劑殘留在硬塗層表面之發生外觀上問題之虞。The film of the present invention preferably has a protective layer on top of the harder coating. Even if the hard coat layer in the once hardened state does not have sufficient hardness, it is possible to prevent the hard coat layer from being scratched or the like by, for example, forming the film by including the protective layer. The protective layer can be formed, for example, by applying a resin dissolved or dispersed in a solvent to a hard coat layer and volatilizing the solvent. As a result, when the protective layer composed of a film with an adhesive or the like is used, the appearance of the adhesive remains on the surface of the hard coat layer.
用於形成保護層使用之樹脂，宜具有能儘可能保護一次硬化狀態之硬塗層之硬度，且與硬塗層之密接性良好，又，從硬塗層剝離時不會殘留於表面的樹脂。如此種樹脂，例如：聚乙烯醇(PVA)、聚氧乙烯(PEO)、聚乙烯醇變性之聚乙烯基乙縮醛樹脂、聚丙烯酸鈉等，分散於溶劑之樹脂，例如：乙酸乙烯酯乳劑、乙烯乙酸乙烯酯(EVA)乳劑、丙烯酸系乳劑、丙烯酸基苯乙烯乳劑、偏氯乙烯乳劑、氨酯乳劑、分散型氟樹脂等。其中，以聚乙烯醇較佳。The resin used for forming the protective layer preferably has a hardness of a hard coat layer which can protect the primary hardened state as much as possible, and has good adhesion to the hard coat layer, and a resin which does not remain on the surface when peeled off from the hard coat layer. . Such a resin, for example, polyvinyl alcohol (PVA), polyoxyethylene (PEO), polyvinyl alcohol denatured polyvinyl acetal resin, sodium polyacrylate, etc., a resin dispersed in a solvent, for example, a vinyl acetate emulsion , ethylene vinyl acetate (EVA) emulsion, acrylic emulsion, acrylic styrene emulsion, vinylidene chloride emulsion, urethane emulsion, dispersion fluororesin, and the like. Among them, polyvinyl alcohol is preferred.
又，在形成保護層之樹脂中，亦可添加染料、顏料、消光劑、抗靜電劑、消泡劑、塗平劑、増黏劑、pH調整劑、耐水化劑、交聯劑等。形成於硬塗層上之保護層，可在二次硬化前適當除去。Further, a dye, a pigment, a matting agent, an antistatic agent, an antifoaming agent, a leveling agent, a bismuth adhesive, a pH adjuster, a water resistance agent, a crosslinking agent, and the like may be added to the resin forming the protective layer. The protective layer formed on the hard coat layer can be appropriately removed before secondary hardening.
本發明之薄膜，例如可對於薄膜基材施以離型處理，使成為能轉印於硬塗層之轉印薄膜。於此情形，可將硬塗層轉印到其他構件(可為其他薄膜)之表面。離型處理，例如矽酮處理等。The film of the present invention can be subjected to a release treatment to the film substrate, for example, so that the film can be transferred onto the hard coat layer. In this case, the hard coat layer may be transferred to the surface of other members (which may be other films). Release treatment, such as anthrone treatment.
本發明之薄膜，例如可為推壓於模型材，並成形者。構成本發明之薄膜的硬塗層，即使成形也不易發生裂痕。The film of the present invention can be, for example, pressed against a mold material and formed. The hard coat layer constituting the film of the present invention is less likely to be cracked even if it is formed.
本發明之薄膜，例如硬塗層可藉由活性能量射線而成二次硬化狀態。於此狀態時，硬塗層的硬度或耐擦傷性優異。The film of the present invention, for example, a hard coat layer, can be in a secondary hardened state by active energy rays. In this state, the hardness and scratch resistance of the hard coat layer are excellent.
本發明之薄膜中，薄膜基材例如：聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚萘二甲酸乙二酯薄膜、聚乙烯薄膜、聚丙烯薄膜、賽珞凡、二乙醯基纖維素薄膜、三乙醯基纖維素薄膜、乙醯基纖維素丁酸酯薄膜、聚氯乙烯薄膜、聚偏氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚碸薄膜、聚醚醚酮薄膜、聚醚碸薄膜、聚醚醯亞胺薄膜、聚醯亞胺薄膜、氟樹脂薄膜、耐綸薄膜、丙烯酸系樹脂薄膜等。In the film of the present invention, the film substrate is, for example, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyethylene film, a polypropylene film, cellophane. Ethylene, ethylene glycol cellulose film, triethylene glycol cellulose film, ethylene glycol cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymerization Film, polystyrene film, polycarbonate film, polymethylpentene film, polyfluorene film, polyetheretherketone film, polyether enamel film, polyether phthalimide film, polyimine film, fluororesin Film, nylon film, acrylic resin film, and the like.
又，為了提升薄膜基材與樹脂組成物之密接性，可以對於薄膜基材利用砂磨法或溶劑處理法等施加表面之凹凸化處理，或電暈放電處理、鉻酸處理、火燄處理、熱風處理、臭氧、紫外線照射處理等表面之氧化處理等表面處理。Further, in order to improve the adhesion between the film substrate and the resin composition, the surface of the film substrate may be subjected to surface roughening treatment by a sanding method or a solvent treatment method, or a corona discharge treatment, a chromic acid treatment, a flame treatment, or a hot air. Surface treatment such as oxidation treatment of surfaces such as treatment, ozone, and ultraviolet irradiation treatment.
將樹脂組成物對於薄膜基材塗布之方法不特別限制，能使用公知方法例如凹版塗佈法、桿塗法、刀塗法、輥塗法、刮刀塗佈法、模塗法。例如進行塗佈並進行乾燥、硬化處理，使乾燥、硬化處理後之膜厚成為1~200μm。The method of applying the resin composition to the film substrate is not particularly limited, and a known method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a knife coating method, or a die coating method can be used. For example, coating, drying, and hardening treatment are performed, and the film thickness after drying and hardening treatment is 1 to 200 μm.
本發明之成形體之製造方法，其特徵在於：將前述(3)之薄膜推壓到模型材，脫型後，利用活性能量射線，使前述硬塗層二次硬化。In the method for producing a molded article of the present invention, the film of the above (3) is pressed against a mold material, and after the release, the hard coat layer is secondarily cured by an active energy ray.
依照本發明，成形時硬塗層不易發生裂痕。又，硬塗層即使於未進行二次硬化之狀態也不易產生黏性，因此，能防止薄膜彼此阻礙，或成形時薄膜與模具之阻礙。又，二次硬化後之硬塗層，硬度或耐擦傷性優異。According to the present invention, the hard coat layer is less likely to crack when formed. Further, the hard coat layer is less likely to be viscous even in a state where it is not subjected to secondary hardening, and therefore, it is possible to prevent the films from being hindered from each other or the film and the mold from being formed during molding. Further, the hard coat layer after secondary hardening is excellent in hardness or scratch resistance.
對於本發明之薄膜成形體(成形體)6之製造方法之具體例，依照圖1(a)~(d)說明。首先，將樹脂組成物1塗布在薄膜基材9(圖1(a))。此時，樹脂組成物1為液狀。其次，將樹脂組成物1藉由加熱、乾燥使熱硬化，形成硬塗層2，得到成形用薄膜5(圖1(b))。此時，硬塗層2為固體，處於一次硬化之狀態。其次，推壓成形用薄膜5到模型材(未圖示)，脫型後(圖1(C))，照射紫外線，使硬塗層2二次硬化，得薄膜成形體6(圖1(d))。Specific examples of the method for producing the film formed body (molded body) 6 of the present invention will be described with reference to Figs. 1(a) to 1(d). First, the resin composition 1 is applied to the film substrate 9 (Fig. 1 (a)). At this time, the resin composition 1 is in a liquid state. Next, the resin composition 1 is thermally cured by heating and drying to form the hard coat layer 2, thereby obtaining a film 5 for molding (Fig. 1 (b)). At this time, the hard coat layer 2 is a solid and is in a state of being once hardened. Next, the film 5 for forming is pressed to a mold material (not shown), and after being released (Fig. 1 (C)), ultraviolet rays are irradiated to harden the hard coat layer 2 to obtain a film formed body 6 (Fig. 1 (d) )).
說明本發明之實施形態。An embodiment of the present invention will be described.
將表1~表3所示各成分配合，製造實施例1-1~1-18及比較例1~2之樹脂組成物。又，表1~表3表示以固體成分換算之配合量。樹脂組成物，為A劑、B劑之兩劑式，各別製造A劑、B劑。A劑包含表1~表3中A劑之欄記載的成分，為以MEK(甲乙酮)為溶劑之固體成分40重量%之溶液。B劑包含表1~表3中B劑之欄記載之成分，為以甲苯作為溶劑的溶液。The resin compositions of Examples 1-1 to 1-18 and Comparative Examples 1 and 2 were produced by blending the components shown in Tables 1 to 3. Further, Tables 1 to 3 show the blending amounts in terms of solid content. The resin composition is a two-part formula of the A agent and the B agent, and the A agent and the B agent are separately produced. The agent A includes the components described in the column of the agent A in Tables 1 to 3, and is a solution of 40% by weight of a solid component of MEK (methyl ethyl ketone) as a solvent. The agent B contains the components described in the column of the agent B in Tables 1 to 3, and is a solution containing toluene as a solvent.
使用樹脂組成物時，將A劑及B劑以重量比1：1混合。又，B劑之固體成分比，設定為當A劑與B劑以重量比1：1混合時，樹脂組成物之配合比以固體成分換算時成為表1~表3所示配合比。When a resin composition is used, the A agent and the B agent are mixed at a weight ratio of 1:1. In addition, when the solid content ratio of the B agent is set to be 1:1 in a weight ratio of the A agent and the B agent, the mixing ratio of the resin composition is a compounding ratio shown in Tables 1 to 3 when converted into a solid content.
又，表1~表3中，U-15HA，為新中村化學工業(股)公司製之氨酯丙烯酸酯之商品名。BEAMSET371為荒川化學工業(股)公司製丙烯酸丙烯酸酯之商品名。ARONIXM7300K為東亞合成(股)公司製之聚酯丙烯酸酯之商品名。Further, in Tables 1 to 3, U-15HA is a trade name of urethane acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BEAMSET371 is the trade name of acrylic acrylate manufactured by Arakawa Chemical Industries Co., Ltd. ARONIXM7300K is the trade name of polyester acrylate made by East Asia Synthetic Co., Ltd.
DPHA(六丙烯酸二季戊四酯)、U-15HA、BEAMSET371，及ARONIX M7300K，各相當於具2個以上丙烯醯基之多官能聚合性化合物。DPHA (dipentaerythritol hexaacrylate), U-15HA, BEAMSET 371, and ARONIX M7300K each correspond to a polyfunctional polymerizable compound having two or more acrylonitrile groups.
又，irg2959為Ciba Japan製之UV起始劑之商品名。BYK310，為BYK-Chemie Japan(股)公司製之塗平劑之商品名。Further, irg2959 is a trade name of a UV starter manufactured by Ciba Japan. BYK310 is the trade name of the coating agent manufactured by BYK-Chemie Japan Co., Ltd.
又，DETA(二乙三胺)、TETA(三乙四胺)，及PEHA(五乙六胺)，各相當於低分子量胺。Further, DETA (diethylenetriamine), TETA (triethylenetetramine), and PEHA (pentaethylenehexamine) each correspond to a low molecular weight amine.
又，POLYMENT NK-350及POLYMENT NK-380，各為日本觸媒(股)公司製之多元胺之商品名。In addition, POLYMENT NK-350 and POLYMENT NK-380 are each trade names of polyamines manufactured by Nippon Shokubai Co., Ltd.
又，U-CAT SA 1，為SAN-APRO(股)公司製之DBU-苯酚鹽之商品名。U-CAT SA 102為SAN-APRO(股)公司製之CBU-辛酸鹽之商品名。U-CAT1102，為SAN-APRO(股)公司製之DBN-辛酸鹽之商品名。Further, U-CAT SA 1 is a trade name of DBU-phenolate manufactured by SAN-APRO Co., Ltd. U-CAT SA 102 is the trade name of CBU-octanoate manufactured by SAN-APRO Co., Ltd. U-CAT1102 is a trade name of DBN-octanoate manufactured by SAN-APRO Co., Ltd.
U-CAT SA1、U-CAT SA 102，及U-CAT 1102，各相當於感溫性觸媒。U-CAT SA1, U-CAT SA 102, and U-CAT 1102, each corresponding to a temperature sensitive catalyst.
將前述(a)製造之樹脂組成物，塗佈於厚度100μm之PET薄膜(東洋紡績(股)公司製，商品名：COSMOSAIN A4300-188)，使硬化後之膜厚成為5μm。The resin composition produced in the above (a) was applied to a PET film (manufactured by Toyobo Co., Ltd., trade name: COSMOSAIN A4300-188) having a thickness of 100 μm, and the film thickness after curing was 5 μm.
其次，將塗布的樹脂組成物於110℃乾燥3分鐘(使一次硬化)，形成固體的硬塗層，得到成形用薄膜。其次，將該成形用薄膜推壓到模型材，並脫型。之後，使用紫外線照射機，以200mJ/cm2 之強度照射紫外線，進行硬塗層之紫外線硬化(二次硬化)，完成薄膜成形體。Next, the applied resin composition was dried at 110 ° C for 3 minutes (to be hardened once) to form a solid hard coat layer to obtain a film for molding. Next, the film for forming is pressed against the mold material and released. Thereafter, ultraviolet rays were irradiated with an intensity of 200 mJ/cm 2 using an ultraviolet ray irradiator, and ultraviolet curing (secondary hardening) of the hard coat layer was performed to complete the film formed body.
對於前述(a)~(b)製造之樹脂組成物及成形用薄膜，測試外觀、使用期限、黏性、成形性，及鉛筆硬度。試驗方法及評價基準如下。The resin composition and the film for molding produced in the above (a) to (b) were tested for appearance, service life, viscosity, moldability, and pencil hardness. The test methods and evaluation criteria are as follows.
(外觀)以目視觀察塗膜外觀。塗膜透明則評價為○，若為白化則評價為×。(Appearance) The appearance of the coating film was visually observed. When the coating film was transparent, it was evaluated as ○, and when it was whitened, it was evaluated as ×.
(使用期間)測定樹脂組成物於常溫下直到凝膠化為止之時間。(黏性)將樹脂組成物塗佈在PET薄膜，於110℃乾燥3分鐘後，以食指觸摸樹脂組成物進行判斷。判斷基準如下。又，僅對於比較例2，在樹脂組成物經二次硬化後，也同樣地進行試驗。5：完全無黏性4：幾乎無黏性3：大概無黏性2：有若干黏性1：有黏性殘存(成形性)將成形用薄膜(硬塗層為一次硬化之狀態)抵壓到成形用模具，若不產生斷裂，則評價為○，若產生斷裂，則評價為×。又，僅對於比較例2，對於二次硬化後之成形用薄膜，也同樣地進行試驗。(鉛筆硬度)對於成形用薄膜(硬塗層為二次硬化之狀態)，依據JIS K5400，進行鉛筆硬度試驗。試驗於鉛筆硬度為2H及H之情形進行。又，於各鉛筆硬度，進行5次試驗。5次當中，將硬塗層未有傷痕之次數記載於上表1~表3。(Usage period) The time until the gelation of the resin composition at normal temperature was measured. (Adhesiveness) The resin composition was applied to a PET film, and dried at 110 ° C for 3 minutes, and then judged by touching the resin composition with the index finger. The judgment criteria are as follows. Further, in Comparative Example 2, the test was carried out in the same manner after the resin composition was secondarily hardened. 5: Completely non-adhesive 4: Almost non-adhesive 3: Probably non-sticky 2: There are some stickiness 1: Viscous residual (formability) The film for forming (hard coat is once hardened) is pressed When the mold for molding was not broken, it was evaluated as ○, and when it was broken, it was evaluated as ×. Further, in Comparative Example 2, the film for molding after secondary curing was also tested in the same manner. (Pencil Hardness) For the film for forming (the state in which the hard coat layer is secondary hardened), a pencil hardness test was performed in accordance with JIS K5400. The test was carried out in the case where the pencil hardness was 2H and H. Further, five tests were performed on each pencil hardness. Among the five times, the number of times the hard coat layer was not scratched was described in Tables 1 to 3 above.
評價結果如上表1~表3所示。如表1~表3所示，實施例1-1~1-18，硬塗層之外觀良好，樹脂組成物之使用期間長，一次硬化狀態之硬塗層不產生黏性，成形用薄膜之成形性亦為良好。又，二次硬化狀態之硬塗層，硬度高。The evaluation results are shown in Tables 1 to 3 above. As shown in Tables 1 to 3, in Examples 1-1 to 1-18, the appearance of the hard coat layer was good, the use period of the resin composition was long, and the hard coat layer in the primary hardened state did not cause stickiness, and the film for forming was used. Formability is also good. Further, the hard coat layer in the secondary hardened state has high hardness.
尤其，併用低分子量胺及多元胺之實施例1-1，相較於僅配合低分子量胺與多元胺其中之一的實施例1-8~1-9，更不易產生黏性。又，配合感溫性觸媒之實施例1-1，相較於未配合感溫性觸媒之實施例1-10，更不易產生黏性。In particular, Example 1-1 in which a low molecular weight amine and a polyamine were used in combination was less likely to cause stickiness than Example 1-8 to 1-9 in which only one of a low molecular weight amine and a polyamine was blended. Further, in Example 1-1 in which the temperature sensitive catalyst was blended, the viscosity was less likely to occur than in Examples 1-10 in which the temperature sensitive catalyst was not blended.
基本上，與前述實施例1(a)~(b)以同樣方式，製造成形用薄膜。惟，本實施例2中，形成硬塗層，使其一次硬化後，將PVA塗佈在硬塗層，形成保護層。之後，與前述實施例1以同樣方式，形成薄膜成形體。最後，將保護層剝離。本實施例2中，由於係以在硬塗層上形成有保護層之狀態成形，因此，不易使硬塗層受傷。又，將保護層剝離後，硬塗層表面完全未有殘留痕跡。Basically, a film for forming was produced in the same manner as in the above-described Examples 1 (a) to (b). However, in the second embodiment, a hard coat layer was formed and once hardened, PVA was applied to the hard coat layer to form a protective layer. Thereafter, a film formed body was formed in the same manner as in the foregoing Example 1. Finally, the protective layer is peeled off. In the second embodiment, since the protective layer is formed on the hard coat layer, the hard coat layer is less likely to be injured. Further, after the protective layer was peeled off, there was no residue at all on the surface of the hard coat layer.
基本上與前述實施例1之(a)~(b)以同樣方式，製造成形用薄膜。惟，本實施例3，係形成硬塗層，並使其一次硬化後，在硬塗層上貼附附有黏著劑之薄膜，並形成保護層。之後，與前述實施例1以同樣方式，得到薄膜成形體。最後，將保護層剝離。本實施例3中，由於係於硬塗層上形成有保護層之狀態進行成形，故不易使硬塗層受傷。惟，將保護層剝離後，硬塗層之表面，有某程度的黏著劑殘留。A film for forming was produced in substantially the same manner as in (a) to (b) of the above-mentioned Example 1. However, in the third embodiment, a hard coat layer was formed and hardened once, and a film with an adhesive was attached to the hard coat layer to form a protective layer. Thereafter, a film formed body was obtained in the same manner as in the above Example 1. Finally, the protective layer is peeled off. In the third embodiment, since the molding is performed in a state in which the protective layer is formed on the hard coat layer, it is difficult to injure the hard coat layer. However, after the protective layer is peeled off, a certain amount of adhesive remains on the surface of the hard coat layer.
基本上與前述實施例1之(a)~(b)同樣進行，製造成形用薄膜。惟，本實施例中，塗佈樹脂組成物之薄膜基材，使用離型PET薄膜(東洋紡績(股)製，商品名：TN110)。該離型PET薄膜施以離型處理，之後，能輕易地從樹脂組成物所構成之層(硬塗層)離型。Basically, in the same manner as in (a) to (b) of the above-described first embodiment, a film for molding was produced. However, in the present embodiment, a film substrate to which a resin composition is applied is a release PET film (manufactured by Toyobo Co., Ltd., trade name: TN110). The release PET film is subjected to a release treatment, and thereafter, it can be easily released from a layer (hard coat layer) composed of a resin composition.
本實施例之成形用薄膜可作為轉印薄膜使用。轉印薄膜例如可如以下使用。首先，使成形用薄膜當中形成有硬塗層之側抵接於成形材料側，進行成形。此時，硬塗層為一次硬化狀態。其次，除去離型PET薄膜。此時，成形材料表面貼附有硬塗層。其次，照射紫外線，使硬塗層二次硬化。又，本實施例之成形用薄膜，也可用於模內射出成形。The film for forming of this embodiment can be used as a transfer film. The transfer film can be used, for example, as follows. First, the side on which the hard coat layer is formed in the film for forming is brought into contact with the side of the molding material to be molded. At this time, the hard coat layer is once hardened. Next, the release PET film was removed. At this time, a hard coat layer is attached to the surface of the molding material. Next, the ultraviolet ray is irradiated to harden the hard coat layer twice. Further, the film for forming of the present embodiment can also be used for in-mold injection molding.
又，本發明不限於前述實施例，當然可於不脫離本發明的範圍內，以各種態樣實施。Further, the present invention is not limited to the foregoing embodiments, and various modifications can be made without departing from the scope of the invention.
1．．．樹脂組成物1. . . Resin composition
2．．．硬塗層2. . . Hard coating
5．．．成形用薄膜5. . . Forming film
6．．．薄膜成形體6. . . Film formed body
9．．．薄膜基材9. . . Film substrate
圖1(a)~(d)說明薄膜成形體之製造方法。1(a) to (d) illustrate a method of producing a film formed body.
1．．．樹脂組成物1. . . Resin composition
2．．．硬塗層2. . . Hard coating
5．．．成形用薄膜5. . . Forming film
6．．．薄膜成形體6. . . Film formed body
9．．．薄膜基材9. . . Film substrate
Claims (31)
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| JP5422787B2 (en) * | 2009-11-13 | 2014-02-19 | 名阪真空工業株式会社 | LAMINATED FILM AND METHOD FOR PRODUCING MOLDED BODY |
| KR101291937B1 (en) * | 2011-04-15 | 2013-07-31 | (주)엘지하우시스 | Hard-coating composition and sheet for forming hard-coating with excellent low temperature formability and slip property |
| CN103631459B (en) * | 2012-08-26 | 2016-12-21 | 宝宸（厦门）光学科技有限公司 | Touch-control sensing layer and manufacture method thereof |
| WO2014175312A1 (en) * | 2013-04-26 | 2014-10-30 | 富士フイルム株式会社 | Transfer material, substrate with transfer layer, touch panel, manufacturing methods therefor, and information display device |
| CN105765713A (en) * | 2013-11-12 | 2016-07-13 | 捷恩智株式会社 | Heat sink |
| FR3022544B1 (en) * | 2014-06-23 | 2018-01-05 | Arkema France | MULTIFUNCTIONAL ACRYLIC OLIGOMERS OF BRANCHED STRUCTURE, BY POLYADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES. |
| JPWO2021140875A1 (en) * | 2020-01-08 | 2021-07-15 | ||
| WO2024080249A1 (en) * | 2022-10-11 | 2024-04-18 | 株式会社レゾナック | Resin film-forming material and resin film |
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| KR20100139060A (en) | 2010-12-31 |
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