201235188 六、發明說明： 【發明所屬之技術領域】 本發明係關於一射出成形用硬塗層薄膜層合體、其製 造方法、及利用其硬塗層薄膜層合體之射出成形體之製造 方法，爲有關在以例如汽車、航空機、大樓、學校、各種 商店等之窗戶玻璃或汽車、航空機等之燈具外罩，及除了 照明外罩以外，在以電腦、攜帯型電子機器等之殼體或各 種零件爲首被廣泛地利用的聚碳酸酯樹脂、PMMA (聚甲 基丙烯酸甲酯）樹脂、或PET (聚對苯二甲酸乙二酯）樹 脂之成形品之製造爲必需的射出成形用硬塗層薄膜層合體 、其製造方法、及利用其之射出成形體之製造方法。 【先前技術】 已往，聚碳酸酯等之熱塑性樹脂之射出成形品，由於 相較於玻璃、金屬爲輕量等之理由，故作爲此等之替代材 料而被廣泛地使用著。然而，由於聚碳酸酯樹脂等之表面 硬度較玻璃爲低，容易受傷，故爲了防範於此，於表面塗 佈塗料或貼合硬化性薄膜等，來進行保護表面。 例如，特開2008-260202號公報（專利文獻1 )中揭 示著一種有關射出成形用硬塗層薄膜之發明，其係具備有 :由含有聚碳酸酯樹脂與聚酯樹脂之混合樹脂組成物所成 的基材層、及由含有丙烯酸系聚合物之紫外線硬化型樹脂 組成物之硬化物所成的硬塗層。又，特開2002- 1 759號公 報（專利文獻2)中揭示著一種有關已表面硬化之聚碳酸 201235188 酯樹脂成形品之製造方法，其係將硬化性塗層劑塗佈於樹 脂薄膜上，將該塗層劑半硬化後，將此安裝於模具內將聚 碳酸酯樹脂射出成形，將樹脂薄膜剝離後再進而使塗層劑 硬化。其中，於此專利文獻 2中並舉例，在具有 RnSi(OH)4.n構造之有機砂院中爲已添加膠質氧化砂之聚砂 氧（silicone )系塗層劑或丙烯酸系塗層劑來作爲較佳使 用者。 然而至今爲止，在作爲保護射出成形樹脂表面之硬塗 層而主要被使用的丙烯酸系或聚矽氧系之塗層劑，於耐受 傷性此點，仍無法稱得上爲足夠。又，爲了使樹脂成形品 能成爲使用於更寬廣之用途，一方面能展現出足夠的表面 硬度’一方面對於射出成形品之密著性亦爲優異，且能同 時滿足對於模具的追循性（tracking )之硬塗層薄膜層合 體，變得更爲需要。 [先前技術文獻] [專利文獻] [專利文獻1]特開2008-260202號公報 [專利文獻2]特開2002-1759號公報 【發明內容】 [發明所欲解決的課題] 本發明係爲了解決上述課題者，以提供作爲聚碳酸酯 樹脂、PMMA樹脂或pet樹脂之成形品之硬塗層之表面硬 201235188 度爲非常高，且對於樹脂成形品之密著性或對於模具之追 循性爲優異之射出成形用硬塗層薄膜層合體爲目的。又， 本發明以提供製造如此般之射出成形用硬塗層薄膜層合體 之方法爲目的。更，本發明以提供利用此硬塗層薄膜層合 體之射出成形體之製造方法爲目的。 [解決課題之手段] 爲了達成前述目的，本發明人等經深入硏究之結果， 適宜爲，使含有具有光硬化性之籠型半矽氧烷樹脂之光硬 化性樹脂組成物硬化作爲硬塗層，將此硬塗層與含有聚碳 酸酯、聚甲基丙烯酸甲酯或聚對苯二甲酸乙二酯之一種以 上之基材層進行層合一體化，並藉由安裝於模具內，而可 介隔著基材層將高表面硬度之硬塗層密著性良好地形成於 聚碳酸酯樹脂、PMMA樹脂或PET樹脂之成形品表面，且 ，發現亦能滿足對於模具之追循性，遂而完成本發明。 即，本發明之要旨如同以下》 [1] 一種射出成形用硬塗層薄膜層合體，其係具備有由 聚碳酸酯、聚甲基丙烯酸甲酯及聚對苯二甲酸乙二酯所成 之群所選出之一種樹脂之單層或由二種以上之複數層所成 之基材層，與在該基材層之單面層合一體化之硬塗層之射 出成形用硬塗層薄膜層合體，其特徵爲前述硬塗層爲使含 有具有光硬化性之籠型半矽氧烷樹脂之光硬化性樹脂組成 物硬化，厚度爲由20μιη以上所成，於波長5 50nm之透過 率爲90%以上’且’玻璃轉移溫度爲2301以上。 201235188 [2] 如[1]之射出成形用硬塗層薄膜層合體，其中，前 述籠型半矽氧烷樹脂，係使下述一般式（1): RS iX3 ...(1) 〔式（1)中，R示爲具有（甲基）丙烯醯基之有機官能 基或乙烯基，X示爲由烷氧基或乙醯氧基所選出之水解基 〕所示矽化合物在有機極性溶劑及鹼性觸媒存在下產生水 解反應之同時使一部份縮合，並使所得到的水解生成物進 而在非極性溶劑及鹼性觸媒存在下產生再縮合而得到者。 [3] 如[1]或[2]之射出成形用硬塗層薄膜層合體，其中 ，前述籠型半矽氧烷樹脂係下述一般式（2)： [R S ΐ Ο 3 /2 ] n ...(2) 〔式（2)中，R示爲具有（甲基）丙烯醯基之有機官能 基或乙烯基，η示爲8、10、12或14〕所示籠型半矽氧烷 樹脂。 [4] 如[2]或[3]之射出成形用硬塗層薄膜層合體，其中 ，前述R係下述一般式（3)： 【化1】[Technical Field] The present invention relates to a hard coat film laminate for injection molding, a method for producing the same, and a method for producing an injection molded body using the hard coat film laminate. In the case of window glazings such as automobiles, aircrafts, buildings, schools, various shops, etc., or the exterior of luminaires for automobiles and aircraft, and in addition to illuminating enclosures, housings or various parts such as computers and portable electronic equipment are used. The hard-coat film for injection molding is required for the production of a polycarbonate resin, a PMMA (polymethyl methacrylate) resin, or a molded article of PET (polyethylene terephthalate) resin which is widely used. A laminate, a method for producing the same, and a method for producing an injection molded article using the same. [Prior Art] Conventionally, an injection-molded article of a thermoplastic resin such as polycarbonate has been widely used as a substitute for these materials because of the light weight of glass or metal. However, since the surface hardness of a polycarbonate resin or the like is lower than that of glass, it is likely to be injured. Therefore, in order to prevent this, a surface coating coating or a curable film is applied to protect the surface. For example, JP-A-2008-260202 (Patent Document 1) discloses an invention of a hard coat film for injection molding, which is composed of a mixed resin composition containing a polycarbonate resin and a polyester resin. A base layer formed and a hard coat layer formed of a cured product of an ultraviolet curable resin composition containing an acrylic polymer. Further, JP-A-2002-175 (Patent Document 2) discloses a method for producing a surface-hardened polycarbonate 201235188 ester resin molded article by applying a curable coating agent onto a resin film. After the coating agent is semi-hardened, the polycarbonate resin is injection molded in the mold, and the resin film is peeled off, and then the coating agent is cured. Among them, in Patent Document 2, for example, in an organic sand chamber having a RnSi(OH)4.n structure, a silicone coating agent or an acrylic coating agent to which a colloidal oxide sand has been added is used. As a better user. However, an acrylic or polyoxylized coating agent which is mainly used as a hard coat layer for protecting the surface of the injection molding resin has not been sufficiently satisfactory in terms of resistance to damage. In addition, in order to make the resin molded article usable for a wider use, it is possible to exhibit sufficient surface hardness. On the one hand, it is excellent in adhesion to the injection molded article, and can simultaneously satisfy the followability to the mold. A hard coat film laminate of (tracking) has become more desirable. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-260202 [Patent Document 2] JP-A-2002-1759 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention is to solve The surface of the hard coat layer which is a molded article of a polycarbonate resin, a PMMA resin or a pet resin has a very high surface hardness of 201235188, and the adhesion to the resin molded article or the followability to the mold is It is an object of excellent hard coat film laminate for injection molding. Further, the present invention has an object of providing a method of producing such a hard coat film laminate for injection molding. Furthermore, the present invention has an object of providing a method for producing an injection molded body using the hard coat film laminate. [Means for Solving the Problem] In order to achieve the above-described object, the inventors of the present invention have made it possible to harden a photocurable resin composition containing a photocurable cage-type hemidecane resin as a hard coat. a layer, the hard coat layer is laminated and integrated with one or more base material layers containing polycarbonate, polymethyl methacrylate or polyethylene terephthalate, and is mounted in a mold by The hard coat layer having a high surface hardness can be formed on the surface of a molded article of a polycarbonate resin, a PMMA resin or a PET resin with good adhesion to the base material layer, and it is found that the followability to the mold can also be satisfied. The present invention has been completed. That is, the gist of the present invention is as follows [1] A hard coat film laminate for injection molding, which is composed of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. a single layer of a resin selected from the group or a base layer formed of a plurality of layers of two or more layers, and a hard coat film layer for injection molding of a hard coat layer laminated and integrated on one side of the base material layer In combination, the hard coat layer is formed by curing a photocurable resin composition containing a photocurable cage-type hemidecane resin, and has a thickness of 20 μm or more and a transmittance of 90 at a wavelength of 50 nm. % or more 'and' glass transition temperature is 2301 or more. [2] The hard coat film laminate for injection molding according to [1], wherein the cage-type hemidecane resin is the following general formula (1): RS iX3 (1) In (1), R is an organic functional group having a (meth)acryl fluorenyl group or a vinyl group, and X is a hydrolyzable group selected from an alkoxy group or an ethoxy group. In the presence of a basic catalyst, a partial hydrolysis is carried out while a hydrolysis reaction is generated, and the obtained hydrolyzate is further recondensed in the presence of a non-polar solvent and a basic catalyst. [3] The hard coat film laminate for injection molding of [1] or [2], wherein the cage type hemidecane resin is the following general formula (2): [RS ΐ Ο 3 /2 ] n (2) [In the formula (2), R is represented by an organofunctional group having a (meth)acryloyl group or a vinyl group, and n is represented by a cage type hemi-oxygen represented by 8, 10, 12 or 14] Alkane resin. [4] The hard coat film laminate for injection molding of [2] or [3], wherein the R is a general formula (3): [Chemical Formula 1]
.· ♦(3) 〔式（3)中，R1示爲氫原子或甲基，m示爲1〜3之整數 〕所示有機官能基。 [5]如[1]〜[4]中任一項之射出成形用硬塗層薄膜層合 體，其中，於前述硬塗層側之表面進而具備有塑膠薄膜之 -8 - 201235188 覆蓋層。 [6] 如[1]〜[5]中任一項之射出成形用硬塗層 體，其中，前述基材層之厚度爲30〜300 μιη之範 [7] —種射出成形用硬塗層薄膜層合體之製造 係使由聚碳酸酯、聚甲基丙烯酸甲酯及聚對苯二 酯所成之群所選出之一種樹脂之單層或由二種以 層所成之基材層，與硬塗層層合一體化之射出成 層薄膜層合體之製造方法；其特徵爲藉由將含有 化性之籠型半矽氧烷樹脂之光硬化性樹脂組成物 材層之單面，並使硬化，而形成厚度爲20μιη以 長 5 5 0nm之透過率爲 90%以上，且，玻璃轉 230 °C以上之硬塗層。 [8] —種射出成形體之製造方法，其特徵係將 聚碳酸酯、聚甲基丙烯酸甲酯及聚對苯二甲酸乙 之群所選出之一種樹脂之單層或由二種以上之複 之基材層，與在該基材層之單面層合一體化之硬 出成形用硬塗層薄膜層合體配置於射出成形模內 以該狀態於模內將聚碳酸酯、聚甲基丙烯酸甲酯 二甲酸乙二酯之任何一種進行射出，而在進行樹 之同時，使前述硬塗層薄膜層合體一體化於樹脂 表面。 [9] 如[8]之射出成形體之製造方法，其中， 層係使含有具有光硬化性之籠型半矽氧烷樹脂之 樹脂組成物硬化，厚度爲由20μιη以上所成 薄膜層合 圍。 方法，其 甲酸乙二 上之複數 形用硬塗 具有光硬 塗佈於基 上，於波 移溫度爲 具備有由 二酯所成 數層所成 塗層之射 ，並藉由 或聚對苯 脂之成形 成形體之 前述硬塗 光硬化性 ，於波長 201235188♦ (3) In the formula (3), R1 is a hydrogen atom or a methyl group, and m is an integer of 1 to 3, which is an organic functional group. [5] The hard coat film laminate for injection molding according to any one of [1] to [4], wherein the surface of the hard coat layer further comprises a cover layer of a plastic film -8 - 201235188. [6] The hard-coating body for injection molding according to any one of [1] to [5] wherein the thickness of the base material layer is 30 to 300 μm [7] - a hard coat for injection molding The film laminate is produced by a single layer of a resin selected from the group consisting of polycarbonate, polymethyl methacrylate and polyparaphenylene ester or a substrate layer formed by two layers, and A method for producing an injection-layered film laminate in which a hard coat layer is integrated; characterized in that a photocurable resin containing a curable cage-type hemidecane resin is formed on one side of a material layer and hardened Further, a hard coat layer having a thickness of 20 μm, a transmittance of 550 nm or more, and a glass transition of 230 ° C or more was formed. [8] A method for producing an injection molded body, characterized by a single layer of a resin selected from the group consisting of polycarbonate, polymethyl methacrylate and polyethylene terephthalate or a complex of two or more The base material layer is disposed in the injection molding die in a hard-coating hard coat film laminate which is laminated and integrated on one side of the base material layer, and polycarbonate or polymethacrylic acid is molded in the mold in this state. Either one of methyl ester dicarboxylate is ejected, and the hard coat film laminate is integrated on the surface of the resin while the tree is being carried out. [9] The method for producing an injection molded article according to [8], wherein the resin composition comprising a photo-curable cage-type semi-oxyalkylene resin is cured to have a thickness of 20 μm or more. The method is characterized in that the complex form of the formic acid ethylene is hard-coated on the substrate by a hard coating, and the wave-transfer temperature is a coating having a coating layer formed by a plurality of diesters, and by poly-p-phenylene ester. The hard coating hardenability of the formed molded body at the wavelength 201235188
5 5 0nm之透過率爲90%以上，且，玻璃轉移溫度爲23 0°C 以上。 [10] 如[9]之射出成形體之製造方法，其中，前述籠型 半矽氧烷樹脂，係使下述一般式（1): R S i X 3 · · · (1) 〔式（1)中，R示爲具有（甲基）丙烯醯基之有機官能 基或乙烯基，X示爲由烷氧基或乙醯氧基所選出之水解基 〕所示矽化合物在有機極性溶劑及鹼性觸媒存在下產生水 解反應之同時使一部份縮合，並使所得到的水解生成物進 而在非極性溶劑及鹼性觸媒存在下產生再縮合而得到者。 [11] 如[9]或[10]之射出成形體之製造方法，其中，前 述籠型半矽氧烷樹脂係下述一般式（2): [RSi03/2]„ ---(2) 〔式（2)中，R示爲具有（甲基）丙烯醯基之有機官能 基或乙烯基，η示爲8、10、12或14〕所示籠型半矽氧烷 樹脂。 [12] 如[10]或[11]之射出成形體之製造方法，其中， 前述R係下述一般式（3): 【化2】The transmittance of 5 50 nm is 90% or more, and the glass transition temperature is 23 0 ° C or more. [10] The method for producing an injection molded body according to [9], wherein the cage-type hemidecane resin is the following general formula (1): RS i X 3 · · · (1) [Formula (1) In the formula, R is an organic functional group having a (meth)acryl fluorenyl group or a vinyl group, and X is a hydrolyzable group selected from an alkoxy group or an ethoxy group. The oxime compound is in an organic polar solvent and a base. In the presence of a catalytic catalyst, a partial hydrolysis is carried out while a hydrolysis reaction is generated, and the obtained hydrolyzed product is further recondensed in the presence of a nonpolar solvent and an alkaline catalyst. [11] The method for producing an injection molded body according to [9] or [10] wherein the cage-type hemidecane resin is the following general formula (2): [RSi03/2] „ ---(2) [In the formula (2), R is shown as an organofunctional group having a (meth)acryl fluorenyl group or a vinyl group, and n is a cage type hemidecoxy hydride resin represented by 8, 10, 12 or 14]. [12] The method for producing an injection molded body according to [10] or [11], wherein the R is a general formula (3): [Chemical 2]
〔式（3)中，R1示爲氫原子或甲基’ m示爲1〜3之整數 〕所示有機官能基。 -10- 201235188 [13] 如[8]〜[12]中任一項之射出成形體之製造方法， 其中，於前述硬塗層側之表面進而具備有塑膠薄膜之覆蓋 層。 [14] 如[8]〜[13]中任一項之射出成形體之製造方法， 其中，前述基材層之厚度爲30〜300μηι之範圍。 [15] 如[8]〜[14]中任一項之射出成形體之製造方法， 其中，前述射出成形用硬塗層薄膜層合體，係由已捲取成 捲狀之狀態連續地供給於射出成形模內。 [16] 如[8]〜[14]中任一項之射出成形體之製造方法， 其中，前述射出成形用硬塗層薄膜層合體，係由已裁切成 薄片狀之狀態一張一張地供給於射出成形模內。 [發明之效果] 本發明係將含有聚碳酸酯、聚甲基丙烯酸甲酯或聚對 苯二甲酸乙二酯之一種以上之基材層，與使指定的光硬化 性樹脂組成物硬化的硬塗層藉由進行層合構造體，以維持 足夠的表面硬度之狀態，而產生可使用於薄膜嵌入成形之 效果。即，由於本發明之射出成形用硬塗層薄膜層合體， 係由含有具有光硬化性之籠型半矽氧烷樹脂之光硬化性樹 脂組成物來形成硬塗層，故對於模具之追循性優異，且對 於射出成形品之表面可賦予高表面硬度。又，由於是介隔 著含有聚碳酸酯、聚甲基丙烯酸甲酯或聚對苯二甲酸乙二 酯之一種以上之基材層來將硬塗層形成於射出成形品之表 面，故密著性優異，並可防止如硬塗層之剝離。 -11 - 201235188 又，本發明係將具備有含有聚碳酸酯、聚甲基丙烯酸 甲酯或聚對苯二甲酸乙二酯之一種以上之基材層，與硬塗 層之射出成形用硬塗層薄膜層合體配置於射出成形模內， 藉由以該狀態於模內將聚碳酸酯樹脂、PMMA樹脂或PET 樹脂進行射出，而在進行樹脂之成形之同時，使前述硬塗 層薄膜層合體一體化於樹脂成形體之表面，藉此可得到能 利用作爲玻璃或金屬之替代材料之射出成形體。特別是藉 由以含有具有光硬化性之籠型半矽氧烷樹脂之光硬化性樹 脂組成物來形成指定的硬塗層，以維持足夠的表面硬度之 狀態，對於模具之追循性優異，且對於射出成形品之表面 賦予高表面硬度。又，由於是介隔著含有聚碳酸酯、聚甲 基丙烯酸甲酯或聚對苯二甲酸乙二酯之一種以上之基材層 來將硬塗層形成於射出成形品之表面，故密著性優異，可 防止如硬塗層之剝離之同時，於射出成形之際，與成形爲 同時性之一體化爲可能的，生產性優異。 [實施發明的最佳型態] 以下，詳細地說明本發明。 圖1中爲表示本發明之射出成形用硬塗層薄膜層合體 1之一實施型態。此硬塗層薄膜層合體1，係由使硬塗層2 與塑膠薄膜之覆蓋層3層合一體化於由聚碳酸酯、PMM A 及PET所成之群所選出之一種樹脂之單層或由二種以上之 複數層所成之基材層4之單面所成者。形成基材層之樹脂 可使用薄膜狀者，適宜爲，可將由聚碳酸酯、PMMA及 -12- 201235188 PET所成之群所選出之一種之樹脂薄膜單獨地作爲基材層 來使用，亦可將層合有二種以上之樹脂薄膜之複數層者作 爲基材層來使用。之中尤以，由聚碳酸酯薄膜、PMMA薄 膜或PET薄膜之單層所成之基材層、或聚碳酸酯薄膜與 PMMA薄膜之2張貼合之基材層，更爲適宜。 又，關於基材層之厚度，包含由單層所成之情形與由 複數層所成之情形，均較佳爲30〜300μηι之範圍。若較 3 Ομπι小時，作爲基材層之強度會不足，並有破斷之虞。 相反地，若較3 00μηι大時，射出成形時對於模具形狀之追 循性會降低。又，在本發明所使用的聚碳酸酯、ΡΜΜΑ及 PET之各樹脂中，分別將紫外線吸收劑、可塑劑、顏料等 作爲添加劑來使用亦無妨》尙，在本發明中，雖射出成形 用硬塗層薄膜層合體之整體厚度未特別限制，但較佳爲使 成爲具有在各層所分別進行說明之適宜之厚度範圍者。 本發明中，前述硬塗層2，適宜爲使含有具有光硬化 性之籠型半矽氧烷樹脂之光硬化性樹脂組成物硬化，厚度 爲由20μηι以上所成，玻璃轉移溫度爲230°C以上，且， 由在波長5 50nm之透過率爲90%以上之透明樹脂層所成。 如此般地，適宜之硬塗層（透明樹脂層）之厚度，宜 爲20μηι以上，較佳爲20〜400μηι之範圍，更佳之厚度爲 50〜80μιη之範圍。若厚度爲未滿20μιη時，無法得到足夠 的表面硬度，相反地，若厚度超過400^»«時，會損及柔軟 性，有難以得到例如具有曲面般之成型物之情形。 若將本發明之硬塗層薄膜層合體假設作爲汽車或航空 -13- 201235188 機之窗戶玻璃用來使用時，因直射日光表面會成爲高溫》 又，作爲電腦或攜帯型電子機器等之殼體用來使用時，於 機器內部會產生熱。因此，爲了防止熱所導致的變形，硬 塗層之耐熱性變得必須，形成硬塗層之樹脂之玻璃轉移溫 度宜爲23 0°C以上，較佳爲25 0°C以上。又，在汽車或航空 機之窗戶玻璃、電腦或攜帯型電子機器之液晶顯示部分， 爲了確保視認性，於波長5 5 0 n m之透過率宜爲9 0 %以上。 又，爲了形成如此般適宜之硬塗層，光硬化性樹脂組 成物中前述籠型半矽氧烷樹脂之含有量，相對於光硬化性 樹脂組成物之質量，較佳爲成爲3質量％以上，更佳爲在 5〜70質量％之範圍內。前述含有量若未滿3%質量時，於 射出成型用硬塗層薄膜層合體中透明樹脂層之玻璃轉移溫 度有變低之傾向，對於射出成型時之模具溫度，有變得耐 熱性不足之虞。另一方面，前述含有量若超過70質量％時 ，會損及硬塗層之韌性，因操作在表面會生成龜裂等，而 有產生外觀不良之虞。藉由如此般地調整籠型半矽氧烷樹 脂之含有量，可調整硬塗層之玻璃轉移溫度，例如，即使 前述籠型半矽氧烷樹脂之含有量爲相同之情形，由於藉由 與前述籠型半矽氧烷樹脂所倂用之其他樹脂等而玻璃轉移 溫度會有所變動，故藉由適宜調整前述籠型半矽氧烷樹脂 之含有量，可調整透明樹脂層之玻璃轉移溫度。尙，硬塗 層之玻璃轉移溫度之上限値，考量含有有機物時，爲 4 5 0 °C左右。 本發明中，形成適宜的硬塗層之籠型半矽氧烷樹脂， -14- 201235188 係具有光硬化性之籠型半矽氧烷樹脂。作爲如此般的籠型 半矽氧烷樹脂，例如使下述一般式（1): RSiX3 ...(1) 所示矽化合物在有機極性溶劑及鹼性觸媒存在下產生水解 反應之同時使一部份縮合，並使所得到的水解生成物進而 在非極性溶劑及鹼性觸媒存在下產生再縮合而得到者。尙 ，前述一般式（1)中，R示爲具有（甲基）丙烯醯基之 有機官能基或乙烯基，X示爲烷氧基、乙醯氧基等之水解 基。 又’本發明中，如此般之籠型半矽氧烷樹脂，較佳爲 下述一般式（2): [RS ϊ Ο 3 /2 ] n ...(2) 所示籠型半矽氧烷樹脂。尙，前述一般式（2)中，R示 爲具有（甲基）丙烯醯基之有機官能基或乙烯基，η示爲 8、 10、 12 或 14。 更，本發明中，前述R較佳爲一般式（3 )： 【化3】In the formula (3), R1 is represented by a hydrogen atom or a methyl group 'm is an integer of 1 to 3'. The method for producing an injection molded article according to any one of the above aspects, wherein the surface of the hard coat layer further comprises a coating layer of a plastic film. [14] The method for producing an injection molded article according to any one of [8] to [13] wherein the thickness of the base material layer is in the range of 30 to 300 μm. [15] The method for producing an injection molded article according to any one of [8], wherein the hard coat film laminate for injection molding is continuously supplied in a state of being wound up in a roll shape. Injection into the forming mold. [16] The method for producing an injection molded article according to any one of [8] to [14] wherein the hard coat film laminate for injection molding is cut into a sheet shape. The ground is supplied into the injection molding die. [Effects of the Invention] The present invention relates to a base layer containing one or more of polycarbonate, polymethyl methacrylate or polyethylene terephthalate, and a hardened layer which hardens a specified photocurable resin composition. The coating is subjected to a laminated structure to maintain a sufficient surface hardness to produce an effect that can be used for film insertion molding. In other words, the hard coat film laminate for injection molding of the present invention forms a hard coat layer from a photocurable resin composition containing a photocurable cage-type hemidecane resin, so that the mold is followed. It is excellent in properties and can impart high surface hardness to the surface of the injection molded article. Further, since the hard coat layer is formed on the surface of the injection molded article by interposing one or more base material layers containing polycarbonate, polymethyl methacrylate or polyethylene terephthalate, it is adhered to Excellent in properties and can prevent peeling such as hard coating. -11 - 201235188 Further, the present invention is provided with one or more base material layers containing polycarbonate, polymethyl methacrylate or polyethylene terephthalate, and a hard coat for injection molding. The layered film laminate is placed in an injection molding die, and the polycarbonate resin, the PMMA resin, or the PET resin is injected into the mold in this state, and the hard coat film laminate is formed while the resin is being molded. The surface of the resin molded body is integrated, whereby an injection molded body which can be used as a substitute for glass or metal can be obtained. In particular, a predetermined hard coat layer is formed by using a photocurable resin composition containing a photocurable cage-type hemidecane resin to maintain a sufficient surface hardness, and the mold is excellent in followability. Further, a high surface hardness is imparted to the surface of the injection molded article. Further, since the hard coat layer is formed on the surface of the injection molded article by interposing one or more base material layers containing polycarbonate, polymethyl methacrylate or polyethylene terephthalate, it is adhered to It is excellent in the ability to prevent the peeling of the hard coat layer, and it is possible to integrate with the molding at the time of injection molding, and it is excellent in productivity. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Fig. 1 shows an embodiment of the hard coat film laminate 1 for injection molding of the present invention. The hard coat film laminate 1 is formed by laminating a hard coat layer 2 and a cover layer 3 of a plastic film into a single layer of a resin selected from the group consisting of polycarbonate, PMM A and PET or It is formed by one side of the base material layer 4 formed by two or more plural layers. The resin forming the substrate layer may be a film. It is preferable to use a resin film selected from the group consisting of polycarbonate, PMMA, and -12-201235188 PET as a substrate layer. A plurality of layers in which two or more kinds of resin films are laminated are used as a substrate layer. In particular, a base material layer formed of a single layer of a polycarbonate film, a PMMA film or a PET film, or a base material layer in which two sheets of a polycarbonate film and a PMMA film are bonded together is more preferable. Further, the thickness of the base material layer is preferably in the range of 30 to 300 μm, including the case of forming a single layer and the case of forming a plurality of layers. If it is less than 3 Ομπι, the strength of the substrate layer will be insufficient and there will be a break. On the contrary, when it is larger than 3 00 μη, the followability to the shape of the mold at the time of injection molding is lowered. Further, in the respective resins of polycarbonate, ruthenium and PET used in the present invention, it is also possible to use an ultraviolet absorber, a plasticizer, a pigment or the like as an additive, and in the present invention, the injection molding hard is used. The overall thickness of the coating film laminate is not particularly limited, but it is preferred to have a suitable thickness range for each layer. In the present invention, the hard coat layer 2 is preferably cured by a photocurable resin composition containing a photocurable cage-type hemidecane resin, and has a thickness of 20 μm or more, and a glass transition temperature of 230 ° C. The above is also made of a transparent resin layer having a transmittance of 90% or more at a wavelength of 50 to 50 nm. In this manner, the thickness of the suitable hard coat layer (transparent resin layer) is preferably 20 μm or more, preferably 20 to 400 μm, and more preferably 50 to 80 μm. If the thickness is less than 20 μm, sufficient surface hardness cannot be obtained. Conversely, when the thickness exceeds 400^»«, the flexibility is impaired, and it is difficult to obtain a molded article having a curved surface, for example. If the hard coat film laminate of the present invention is assumed to be used as a window glass for a car or an aircraft-13-201235188 machine, the surface of the sun will become a high temperature due to the direct sunlight, and as a casing of a computer or a portable electronic device. When the body is used, heat is generated inside the machine. Therefore, in order to prevent deformation due to heat, the heat resistance of the hard coat layer becomes necessary, and the glass transition temperature of the resin forming the hard coat layer is preferably 23 ° C or higher, preferably 25 ° C or higher. Further, in the liquid crystal display portion of a window glass, a computer or a portable electronic device of an automobile or an aircraft, in order to ensure visibility, the transmittance at a wavelength of 5 5 0 n m is preferably 90% or more. In addition, the content of the cage-type hemidecane resin in the photocurable resin composition is preferably 3% by mass or more based on the mass of the photocurable resin composition. More preferably, it is in the range of 5 to 70% by mass. When the content is less than 3% by mass, the glass transition temperature of the transparent resin layer in the injection-coated hard coat film laminate tends to be low, and the mold temperature at the time of injection molding is insufficient. Hey. On the other hand, when the content is more than 70% by mass, the toughness of the hard coat layer is impaired, and cracks or the like are formed on the surface, which may cause defects in appearance. By adjusting the content of the cage hemidecane resin in such a manner, the glass transition temperature of the hard coat layer can be adjusted, for example, even if the content of the above-mentioned cage type hemidecane resin is the same, The glass transition temperature may vary depending on other resins used in the cage-type hemidecane resin, and the glass transition temperature of the transparent resin layer can be adjusted by appropriately adjusting the content of the above-mentioned cage-type hemidecane resin. .尙, the upper limit of the glass transition temperature of the hard coat layer is about 450 °C when considering organic matter. In the present invention, a cage-type hemidecane resin which is a suitable hard coat layer is formed, and -14-201235188 is a photocurable cage-type hemidecane resin. As such a cage-type hemidecane resin, for example, the ruthenium compound represented by the following general formula (1): RSiX3 (1) is hydrolyzed in the presence of an organic polar solvent and a basic catalyst. A part of the condensation is obtained, and the obtained hydrolyzate is further obtained by recondensing in the presence of a nonpolar solvent and a basic catalyst.尙 In the above general formula (1), R is an organic functional group or a vinyl group having a (meth)acryl fluorenyl group, and X is a hydrolyzable group such as an alkoxy group or an ethoxylated group. Further, in the present invention, the cage-type hemidecane resin as described above is preferably the following general formula (2): [RS ϊ Ο 3 /2 ] n (2) Alkane resin. That is, in the above general formula (2), R is an organic functional group or a vinyl group having a (meth)acryl fluorenyl group, and n is 8, 10, 12 or 14. Furthermore, in the present invention, the R is preferably a general formula (3):
• · · ( 3 ) 所示有機官能基。尙’前述一般式（3)中，R1示爲氫原 子或甲基。又’前述一般式（3)中，m示爲1〜3之整數 如此般之籠型半砍氧院樹脂，較佳爲樹脂中的砂原子 -15- 201235188 全數爲含有由具有（甲基）丙烯醯基之有機官能基所成的 反應性官能基’且’爲分子量分布及分子構造爲已控制的 籠型半矽氧烷樹脂。又，如此般之籠型半矽氧烷樹脂之分 子構造，可不必爲完全封閉的多面體’例如，一部份可爲 開裂般之構造。又，如此般之籠型半矽氧烷樹脂之平均分 子量亦未特別限定，如此般之籠型半矽氧烷樹脂可爲寡聚 物。 在本發明所謂的光硬化性樹脂組成物，只要是照射活 性能源線而可硬化之樹脂組成物即可，未特別限制。如此 般之光硬化性樹脂組成物中，可含有前述籠型半矽氧烷以 外的其他樹脂。如此地可與籠型半矽氧烷樹脂混合使用的 其他樹脂方面，只要是與籠型半矽氧烷樹脂爲具有相溶性 及反應性之樹脂即可，未特別限定，例如，作爲具有（甲 基）丙烯醯基之樹脂，舉例如（甲基）丙烯酸、（甲基） 丙烯酸甲酯等：雖與前述籠型半矽氧烷爲不具直接反應性 ，但作爲可倂用之樹脂，舉例如環氧樹脂、胺甲酸乙酯樹 脂、聚矽氧樹脂。又，如此般之光硬化性樹脂組成物，只 要是在不妨礙光硬化性之範圍，可進而含有塡充料（filler )系添加物。作爲塡充料系添加物之具體例，舉例如氧化 矽、氧化鋁、氧化鈦等之微粒子塡充料、或玻璃纖維短纖 維或長纖維、苯乙.烯或聚酯等之塑膠纖維。 又，如此般之光硬化性樹脂組成物，通常爲進而含有 光聚合開始劑。作爲如此般之光聚合開始劑，例如，舉例 如院基苯酮（alkyl phenone)系、醯基膦氧化物系、二茂 -16- 201235188 鈦系等之光聚合開始劑。作爲如此般之光聚合開始劑之具. 體例，舉例如（X-羥基烷基苯酮、雙乙醯苯乙酮、二苯酮、 苄基、苄醯基異丁醚 '苄基二甲基縮酮、（1-羥基環己基 )苯酮、（1-經基-1-甲基乙基）苯酮、（α-經基異丙基） Cp -異丙基苯基）酮、二乙基噻吨酮、乙基菌肽 '雙（二 乙基胺基）二苯酮等。 尙’作爲如此般之光硬化性樹脂組成物，爲了調整黏 度等’可使用含有習知的溶劑來作爲稀釋劑，就考量溶劑 之揮發除去步驟與需要時間而使生產效率降低等之觀點而 言’以及就於硬化薄膜內部存在有殘留溶劑等而導致所謂 的成形薄膜之特性降低之觀點而言，溶劑之含有量較佳爲 使用5 %以下者，更佳爲使用未含有溶劑者> 接著，對於製造如以上說明之本發明之射出成形用硬 塗層薄膜層合體之方法進行說明。本發明之射出成形用硬 塗層薄膜層合體，例如，對於作爲基材層爲單獨使用聚碳 酸酯薄膜之情形，可事先準備聚碳酸酯薄膜，並將前述光 硬化性樹脂組成物塗佈於前述聚碳酸酯薄膜層之表面後， 使硬化，藉由使形成前述透明樹脂層而予以製造。 作爲如此般塗佈光硬化性樹脂組成物之方法，未特別 限定，可適宜地採用習知的方法。作爲塗佈裝置，可採用 習知的塗佈裝置，但若使用塗佈頭來產生硬化反應時，由 於凝膠狀之附著物會成爲條紋或異物之原因，故宜爲不使 紫外線接觸到塗佈頭般來進行設定者爲佳。又，作爲塗佈 方式，可採用凹板塗佈、輥塗佈、逆輥塗佈、刀塗佈、口 -17- 201235188 模式塗佈、唇嘴塗佈、刮刀塗佈、擠壓塗佈、滑動塗佈（ slide coat)、線桿塗佈、簾塗佈、押出塗佈、旋轉塗佈等 之習知塗佈方法。 又，作爲將光硬化性樹脂組成物塗佈後使硬化之方法 ，例如，可採取使紫外線產生於塗佈後的光硬化性樹脂組 成物上，進行照射而使光硬化之所謂的紫外線照射法。作 爲使用於如此般之方法之紫外線燈，例如，舉例如金屬鹵 素燈、高壓水銀燈、低壓水銀燈、脈衝型氙燈、氙/水銀 混合燈、低壓殺菌燈、無電極燈。此等紫外線燈之中，又 以使用金屬鹵素燈或高壓水銀燈爲佳。又，照射條件會依 分別的燈之條件而有所差異，只要是照射曝光量爲20〜 10000mJ/cm2之範圍即可，較佳爲在1〇〇〜i〇〇〇〇mJ/cm2之 範圍。又，就光能源之有效利用之觀點而言，對於紫外線 燈，較佳爲裝配有橢圓型、拋物線型、擴散型等之反射板 ’更，作爲冷卻對策，亦可裝配斷熱濾器（thermal cut off filter )等。 又’對於紫外線燈之照射部位，較佳爲裝配有冷卻裝 置。藉由如此般之冷卻裝置，可抑制由紫外線燈所產生的 熱所誘發的射出成形用硬塗層薄膜層合體之熱變形。作爲 如此般之冷卻裝置之冷卻方式，可採取空冷方式、水冷方 式等之習知方法。 尙’藉由如此般之紫外線照射法來使光硬化性樹脂組 成物硬化時，由於紫外線硬化反應爲自由基反應，故會因 爲氧而受到反應抑制（reaction inhibition)。因此，就抑 -18- 201235188 制在光硬化性樹脂組成物之硬化反應中因氧之反應抑制之 觀點而言，於塗佈光硬化性樹脂組成物後，較佳爲將該表 面使用由透明的塑膠薄膜所成的覆蓋層進行覆蓋。又，藉 由如此般將光硬化性樹脂組成物之表面以覆蓋層進行覆蓋 ，宜爲使光硬化性樹脂組成物之表面之氧濃度成爲1 %以 下，較佳爲使成爲〇. 1 %以下。爲了使成爲如此般小的氧 濃度，較佳爲採用表面無空孔，且氧透過率爲小之透明塑 膠薄膜。作爲如此般之薄膜材質，例如，舉例如PET (聚 對苯二甲酸乙二酯）、PEN (聚2,6萘二甲酸乙二酯）、 PBT (聚對苯二甲酸丁二酯）、PC (聚碳酸酯）、聚丙烯 、聚乙烯、醋酸酯樹脂、丙烯酸系樹脂、氟化乙烯基系樹 脂、聚醯胺、聚芳酯、塞洛凡、聚醚颯、降莰烯系樹脂等 之塑膠。此等塑膠，可單獨一種或組合二種以上予以使用 。如此般之塑膠薄膜，由於必須與硬化後之光硬化性樹脂 組成物（硬塗層）爲可剝離的，故較佳使用在塑膠薄膜之 表面爲施予有矽塗佈、氟塗佈等易剝離處理者。 接著，對於本發明相關之射出成形體8之製造方法進 行說明。首先，使硬塗層2與塑膠薄膜之覆蓋層3爲已層 合一體化之硬塗層薄膜層合體，與由聚碳酸酯、聚甲基丙 烯酸甲酯及聚對苯二甲酸乙二酯所成之群所選出之一種樹 脂之單層或由二種以上之複數層所成之基材層4之單面配 置於射出成形模內。例如，如圖2 ( a )所示般，將硬塗層 薄膜層合體1以平面狀之狀態配置於第1射出成形模5之 凹部內。此時，使硬塗層薄膜層合體1之塑膠薄膜之覆蓋 -19- 201235188 層3配置成爲鄰接於第1射出成形模5之凹部壁面。 之後，如圖2 ( b )_所示般，將第2射出成形模6疊合 於第1射出成形模5後鎖緊，並以此狀態介隔著射出澆口 將熱塑性樹脂射出於模5、6內之凹部》此時，進行著熱 塑性樹脂之射出成形，在樹脂成形體被形成之同時，前述 硬塗層薄膜層合體被一邊賦形並一邊一體化於該樹脂成形 體之表面。之後，藉由將圖3之位於表面之塑膠薄膜之覆 蓋層3予以剝離，得到表面爲具備有硬塗層部之射出成形 體8。 又，圖4爲表示具備有連續供給硬塗層薄膜層合體1 之機構之射出成形機之整體模擬圖。在此，將圖2之第2 射出成型6配置於固定側定模板（platen ) 1 1，將前述第 1射出成形模5配置於可動側定模板9，使硬塗層薄膜層 合體1成爲沿著可動側定模板9般地由薄膜裝塡機1 3供 給於第1射出成形模5，藉由使可動側定模板9移動來將 第1射出成形模5與第2射出成形模6疊合，鎖緊後，藉 由自噴嘴1 2射出熱塑性樹脂，而得到射出成形體8。之後 ’藉由操作薄膜裝塡機，可將用來得以下一個射出成形體 之硬塗層薄膜層合體1進行供給。尙，薄膜裝塡機，只要 是由供給側爲具有連續捲出之機構即可，並非必須具有用 來捲取之機構。 作爲前述射出成形用樹脂，即作爲構成前述樹脂成形 體7之熱塑性樹脂’只要是能與前述基材層（含有聚碳酸 酯、聚甲基丙烯酸甲酯或聚對苯二甲酸乙二酯之—種以上 -20- 201235188 之基材層）4熔融一體化，且具有透明性之熱塑性樹脂即 可，未特別限定，適宜地可爲聚碳酸酯樹脂、PMMA樹脂 或PET樹脂。 又，前述射出成形用樹脂中，可摻合防氧化劑、光安 定劑、紫外線吸收劑、潤滑劑、反增塑劑等之各種添加劑 等。 前述射出成形模之形狀，可使用平面形狀模具及具有 曲率之模具。具有曲率之模具，宜使設定成伸長率成爲 0.1 %〜1 0%般之R與到達端部之長度及凹陷量者。 【實施方式】 [實施例] 以下，基於實施例及比較例將本發明更具體地予以說 明，惟，本發明並不僅限定於以下之實施例。尙’若無特 別告知，「份」表示爲「質量份」。 (實施例1 ) 將下述構造式（4 ) -21 - 201235188 【化4】• · · (3) The organic functional group shown.尙' In the above general formula (3), R1 is represented by a hydrogen atom or a methyl group. Further, in the above general formula (3), m is shown as an integer of 1 to 3, such as a cage-type semi-coffsite resin, preferably a sand atom in the resin -15 - 201235188. The total number is contained by having (meth) The reactive functional group 'and' formed by the organofunctional group of the acrylonitrile group is a molecular weight distribution and a molecular structure of a controlled cage hemidecane resin. Further, the molecular structure of the cage-type semi-oxyalkylene resin may not necessarily be a completely closed polyhedron. For example, a part may be a crack-like structure. Further, the average molecular weight of the cage-type hemidecane resin is not particularly limited, and thus the cage-type hemidecane resin may be an oligomer. The photocurable resin composition of the present invention is not particularly limited as long as it is a resin composition which can be cured by irradiation with an active source. The photocurable resin composition as described above may contain other resins than the above-mentioned cage-type hemidecane. The other resin which can be used in combination with the cage-type hemidecane resin is not particularly limited as long as it is compatible with the cage-type hemidecane resin, and is, for example, The resin of the acryl-based group, for example, (meth)acrylic acid, methyl (meth)acrylate or the like: although it is not directly reactive with the above-mentioned cage-type hemidecane, it is, for example, a resin which can be used as a resin. Epoxy resin, urethane resin, polyoxyn resin. Further, the photocurable resin composition as described above may further contain a filler-based additive as long as it does not impair the photocurability. Specific examples of the ruthenium-based additive include fine particles of cerium oxide, alumina, and titanium oxide, or plastic fibers such as glass fiber short fibers or long fibers, styrene or polyester. Further, such a photocurable resin composition usually contains a photopolymerization initiator. As such a photopolymerization initiator, for example, a photopolymerization initiator such as an alkyl phenone system, a mercapto phosphine oxide system or a ferrocene-16-201235188 titanium system can be exemplified. As such a photopolymerization initiator, for example, (X-hydroxyalkylphenone, acetophenone, benzophenone, benzyl, benzamidine isobutyl ether 'benzyl dimethyl Ketal, (1-hydroxycyclohexyl)benzophenone, (1-cyano-1-methylethyl)benzophenone, (α-pyridylisopropyl) Cp-isopropylphenyl)one, diethyl A thioxanthone, an ethyl peptide "bis(diethylamino) benzophenone, and the like.作为 ' As a photocurable resin composition as described above, in order to adjust the viscosity, etc., a solvent containing a conventional solvent can be used as a diluent, and the solvent removal step and the time required to reduce the production efficiency are considered. 'and the content of the solvent is preferably 5% or less, more preferably, the solvent is not contained, from the viewpoint of the presence of a residual solvent or the like in the cured film, and the characteristics of the so-called formed film are lowered. A method of producing the hard coat film laminate for injection molding of the present invention as described above will be described. In the case of using a polycarbonate film as a base material layer, for example, a polycarbonate film can be prepared in advance, and the photocurable resin composition can be applied to the surface of the hard coat film laminate for injection molding of the present invention. After the surface of the polycarbonate film layer is cured, it is cured by forming the transparent resin layer. The method of applying the photocurable resin composition in this manner is not particularly limited, and a conventional method can be suitably employed. As the coating device, a conventional coating device can be used. However, when a coating head is used to cause a hardening reaction, since the gel-like deposit may become a streak or a foreign matter, it is preferable not to contact the ultraviolet ray. It is better to make the setting as the cloth head. Further, as the coating method, concave plate coating, roll coating, reverse roll coating, knife coating, port -17-201235188 mode coating, lip coating, blade coating, extrusion coating, and the like may be employed. A conventional coating method such as slide coating, wire bar coating, curtain coating, extrusion coating, spin coating, or the like. In addition, as a method of applying a photocurable resin composition and curing it, for example, a so-called ultraviolet irradiation method in which ultraviolet rays are generated on the photocurable resin composition after application and is cured by irradiation can be employed. . As the ultraviolet lamp used in such a method, for example, a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a pulse type xenon lamp, a helium/mercury hybrid lamp, a low pressure germicidal lamp, and an electrodeless lamp are used. Among these ultraviolet lamps, it is preferable to use a metal halide lamp or a high pressure mercury lamp. Further, the irradiation conditions may differ depending on the conditions of the respective lamps, as long as the irradiation exposure amount is in the range of 20 to 10000 mJ/cm 2 , preferably in the range of 1 〇〇 to i 〇〇〇〇 mJ/cm 2 . . Further, from the viewpoint of effective use of light energy, it is preferable to use an elliptical, parabolic, or diffuse type reflector for the ultraviolet lamp. Further, as a cooling countermeasure, a thermal cut can be attached. Off filter ) and so on. Further, it is preferable to equip the irradiated portion of the ultraviolet lamp with a cooling device. According to such a cooling device, thermal deformation of the hard coat film laminate for injection molding which is induced by heat generated by the ultraviolet lamp can be suppressed. As a cooling method of such a cooling device, a conventional method such as an air cooling method or a water cooling method can be employed. When the photocurable resin composition is cured by such an ultraviolet irradiation method, the ultraviolet curing reaction is a radical reaction, and therefore reaction inhibition is caused by oxygen. Therefore, from the viewpoint of suppressing the reaction of oxygen in the hardening reaction of the photocurable resin composition by the method of -18-201235188, after applying the photocurable resin composition, it is preferred to use the surface transparently. The cover layer made of the plastic film is covered. In addition, it is preferable that the surface of the photocurable resin composition is coated with a coating layer, and the oxygen concentration of the surface of the photocurable resin composition is preferably 1% or less, preferably 〇. 1% or less. . In order to achieve such a small oxygen concentration, it is preferred to use a transparent plastic film having no voids on the surface and a small oxygen permeability. As such a film material, for example, PET (polyethylene terephthalate), PEN (polyethylene 2,6 naphthalate), PBT (polybutylene terephthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, fluorinated vinyl resin, polyamine, polyarylate, celoliban, polyether oxime, norbornene resin, etc. plastic. These plastics may be used alone or in combination of two or more. Such a plastic film is preferably peelable after being cured with a photocurable resin composition (hard coat layer), so that it is preferably used for applying a bismuth coating or a fluorine coating on the surface of the plastic film. Strip the processor. Next, a method of manufacturing the injection molded body 8 according to the present invention will be described. First, the hard coat layer 2 and the cover layer 3 of the plastic film are laminated and integrated hard coat film laminates, and are made of polycarbonate, polymethyl methacrylate and polyethylene terephthalate. A single layer of a resin selected from the group or a single layer of the substrate layer 4 made of a plurality of layers or more is disposed in the injection molding die. For example, as shown in Fig. 2 (a), the hard coat film laminate 1 is placed in a planar shape in the concave portion of the first injection molding die 5. At this time, the cover layer -19-201235188 of the plastic film of the hard coat film laminate 1 is placed adjacent to the wall surface of the recess of the first injection mold 5. Then, as shown in FIG. 2(b)_, the second injection molding die 6 is superposed on the first injection molding die 5, and then locked, and the thermoplastic resin is projected out of the die 5 in this state through the injection gate. In the case of the concave portion of the first embodiment, the thermoplastic resin is formed by injection molding, and the resin coating body is formed, and the hard coat film laminate is formed on the surface of the resin molded body while being formed. Thereafter, the covering layer 3 of the plastic film on the surface of Fig. 3 is peeled off to obtain an injection molded body 8 having a surface having a hard coat portion. Moreover, FIG. 4 is an overall simulation view showing an injection molding machine including a mechanism for continuously supplying the hard coat film laminate 1. Here, the second injection molding 6 of FIG. 2 is placed on the fixed side platen 1 , and the first injection molding die 5 is placed on the movable side fixing die 9 to form the hard coat film laminate 1 along the edge. The movable side fixing die plate 9 is supplied to the first injection molding die 5 by the film mounting machine 13 , and the first injection molding die 5 and the second injection molding die 6 are superposed by moving the movable side stationary die plate 9 . After the locking, the injection molded body 8 is obtained by ejecting the thermoplastic resin from the nozzle 12. Thereafter, the hard coat film laminate 1 for obtaining the following one of the injection molded bodies can be supplied by operating the film mounter.尙, the film loading machine is not required to have a mechanism for winding up as long as it is a mechanism having a continuous winding out from the supply side. The injection molding resin, that is, the thermoplastic resin constituting the resin molded body 7 can be combined with the base material layer (containing polycarbonate, polymethyl methacrylate or polyethylene terephthalate). The above-mentioned -20-201235188 base material layer 4 is not particularly limited as long as it is melt-integrated and has a transparent thermoplastic resin, and may suitably be a polycarbonate resin, a PMMA resin or a PET resin. Further, the injection molding resin may be blended with various additives such as an antioxidant, a photostabilizer, an ultraviolet absorber, a lubricant, and a reverse plasticizer. The shape of the injection molding die can be a flat mold and a mold having a curvature. The mold having a curvature is preferably set such that the elongation is 0.1% to 10%, and the length of the end portion and the amount of the depression are reached. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.尙’ If there is no special notice, “parts” is expressed as “parts by mass”. (Example 1) The following structural formula (4) -21 - 201235188 [Chemical 4]
(4) 所示半矽氧烷25份、二新戊四醇（日本化藥公司製、商 品名「KAYARAD DPHA」）65份、二羥甲基三環癸烷二 丙烯酸酯（共榮公司化學公司製、商品名「LIGHT ACRYLATE DCP-A」）10份及羥基環己基苯酮（ CIB ASPECIALTY CHEMICALS 公司製、商品名「 IRGACURE184」）2 · 5份均勻地混合攪拌後，進行脫泡得 到液狀光硬化性樹脂組成物。 接著，將所得到的液狀光硬化性樹脂組成物以成爲硬 化後之厚度爲〇.〇5mm般地塗佈於已事先以矽烷偶合劑（ 信越化學工業製、商品名「KBE-903」）進行表面處理的 聚碳酸酯薄膜（住友化學製、商品名「TECNOLO Y COOO 」）上。之後，將透明覆蓋薄膜（材質：聚對苯二甲酸乙 二酯，於波長5 50nm之光透過率90%以上）壓著於已塗佈 的光硬化性樹脂使成爲覆蓋層後，藉由使用金屬鹵素燈以 6400mJ/cm2之照射曝光量將紫外線照射於硬塗層使硬化， 得到如圖1所示般，由聚碳酸酯樹脂所成之基材層4-硬塗 層2-覆蓋層3之三層構造所成的射出成形用硬塗層薄膜層 -22- .201235188 合體1。 接著，如圖2(a)所示般’使覆蓋層3之一部份以鄰 接於第1射出成形模具之凹部壁面之樣態’將硬塗層薄膜 層合體1以平面狀之狀態配置於第1射出成形模5內後， 將第2射出成形模具疊合於第1射出成形模具之上，以此 狀態，藉由從射出澆口將已事先以1 20 °C使乾燥24小時之 聚碳酸酯樹脂（出光股份有限公司製、商品名「TARFLON 1 900」）以樹脂溫度280°C、模具溫度80°C、設定射出壓 力1 700kg/cm2、射出時間3秒之條件，進行射出於模具內 之凹部，得到如圖3所示般，在由聚碳酸酯樹脂所成的樹 脂成形體7之表面爲具備有由硬塗層薄膜層合體1所成的 硬塗層部之厚度爲3mm之射出成形體8。 對於具備有如上述般所得到硬塗層部之射出成形體8 ，如以下般地進行表面硬度及強度評價。結果如表1所示 <表面硬度評價法> 對於具體有硬塗層部之成形體，依據JIS K5 600-5 -4 刮痕硬度（鉛筆法）來進行。又，進行鋼絲絨試驗。鋼絲 絨試驗爲使用橡皮擦試驗機（股份有限公司本光製作所製 )，使用鋼絲絨#〇〇〇〇來予以進行，以荷重5 00g使鋼絲絨 往反。 <強度評價法> -23- 201235188 對於具備有硬塗層部之成形體進行彎曲試驗。試，驗方 法方面，係將120mmx30mm之試驗片放置於中央爲開口的 基座上（開口部：80mmx50mm )，由上方將押芯尖端R: SR5、速度：5mm/cm、押入深度爲到40mm爲止所進行押 入時之彎曲應力、及硬塗層之表面狀態進行觀察。 (實施例2) 將上述液狀光硬化性樹脂組成物以硬化後之厚度成爲 0.025mm般地進行塗佈，並使用與實施例1相同之方法得 到具備有硬塗層部之射出成形體8後，與實施例1進行相 同之評價。結果如表1所示。 (實施例3) 將聚碳酸酯薄膜與PMMA薄膜爲已貼合的聚碳酸酯. PMMA薄膜（住友化學製、商品名「TECNOLOY C001」 )之聚碳酸酯薄膜側，事先以矽烷偶合劑（信越化學工業 製、商品名「KBE-903」）進行表面處理。將上述液狀光 硬化性樹脂組成物以硬化後之厚度成爲0.0 7 m m般地塗佈 於已表面處理之聚碳酸酯薄膜側，並使用與實施例1相同 之方法得到具備有硬塗層部之射出成形體8後，與實施例 1進行相同之評價。結果如表1所示。 (比較例1 ) 將上述液狀光硬化性樹脂組成物以硬化後之厚度成爲 -24- 201235188 0.015mm般地進行塗佈，並使用與實施例1相同之方法得 到具備有硬塗層部之射出成形體8後，與實施例1進行相 同之評價。結果如表1所示。 (比較例2) 作爲比較例，將已施予丙烯酸系硬塗層之三菱瓦斯化 學製商品名Iupilon Sheet MR58 (厚度0.65mm)貼著至聚 碳酸酯薄片之表面，並與實施例1進行相同之評價。結果 如表1所示。 (實施例4) 將上述液狀光硬化性樹脂組成物以硬化後之厚度成爲 0.1 mm般地塗佈於已事先以矽烷偶合劑（信越化學工業製 、商品名「KBE-903」）進行表面處理之PMMA薄膜（住 友化學製、商品名「TECNOLOY S001G」），並使用與實 施例1相同之方法得到射出成形用硬塗層薄膜層合體1。 之後，使用與實施例1相同之方法，藉由使射出樹脂成爲 PMMA樹脂（住友化學製、商品名「SUMIPEX HT55X」） ，並以樹脂溫度2 5 0°C、模具溫度80°C、設定射出壓力 1 29MPa、射出時間6秒之條件進行射出，得到如圖3所示 般，在由PMMA樹脂所成的樹脂成形體7之表面爲具備有 由硬塗層薄膜層合體1所成的硬塗層部之厚度爲1.6mm之 射出成形體8。與實施例1進行相同之評價。結果如表1 所示。 -25- 201235188 (實施例5 ) 將上述構造式（4)所示半矽氧烷15份、二新戊四醇 (日本化藥公司製' 商品名「KAYARAD DPHA」）55份 、二羥甲基三環癸烷二丙烯酸酯（共榮公司化學公司製、 商品名「LIGHT ACRYLATE DCP-A」）30份及羥基環己 基苯酮（CIBASPECIALTY CHEMICALS公司製、商品名 「IRGACURE1 84」）2.5份均勻混合攪拌後，進行脫泡得 到液狀光硬化性樹脂組成物。 將上述液狀光硬化性樹脂組成物以硬化後之厚度成爲 0.050mm般地進行塗佈，並使用與實施例1相同之方法得 到具備有硬塗層部之射出成形體8後，與實施例1進行相 同之評價。結果如表1所示。 (實施例6) 將上述構造式（4)所示半矽氧烷70份、二新戊四醇 (日本化藥公司製、商品名「KAYARAD DPHA」）20份 、二羥甲基三環癸烷二丙烯酸酯（共榮公司化學公司製、 商品名「LIGHT ACRYLATE DCP-A」）10份及羥基環己 基苯酮（CIBASPECIALTY CHEMICALS公司製、商品名 「IRGACURE184」）2 _ 5份均勻混合攪拌後，進行脫泡得 到液狀光硬化性樹脂組成物。 將上述液'狀光硬化性樹脂組成物以硬化後之厚度成爲 0.05 0mm般地進行塗佈，並使用與實施例1相同之方法得 -26- 201235188 到具備有硬塗層部之射出成形體8後，與實施例1進行相 同之評價。結果如表1所示。 -27- 201235188 【1® 比較例2 X α g ^ _ 10这擗 2.1 N 無龜裂 比較例1 X 寸 500g 以1000次 無傷痕 200 N 無龜裂 實施例6 X 500g 以6次 有傷痕 200 N 無龜裂 實施例5 as 500g 以300次 無傷痕 200 N 無龜裂 實施例4 a\ 500g 以1000次 無傷痕 40 N 無龜裂 實施例3 Os 500g 以1000次 無傷痕 200 N 無龜裂 實施例2 ffi 卜 500g 以1000次 無傷痕 200 N 無龜裂 實施例1 K as 500g 以1000次 無傷痕 200 N 無龜裂 刮痕硬度(鉛筆法） 鋼絲絨試驗 最大彎曲應力 表面狀態 租鏺 If -28- 201235188 (參考例） 將上述實施例1所使用的液狀光硬化性樹脂組成物以 硬化後之厚度成爲0.050mm般地塗佈於基材層用PET上 ’由其上方，將另外的覆蓋層用PET壓著於已塗佈的光硬 化性樹脂後，使用超高壓水銀燈以6400mJ/Cm2之照射曝 光量照射紫外線，使硬塗層硬化。硬化後，藉由將基材層 用及覆蓋層用PET分別進行剝離，得到僅爲硬塗層之薄膜 <光線透過率測定> 僅爲硬塗層之光線透過率，係使用分光光度計（股份 有限公司曰立製作所製、Spectrophotometer U-4000)進行 測定’結果於5 50nm之透過率爲9 1 .7%。結果如圖5所示 <動態黏彈性測定> 僅爲硬塗層之玻璃轉移溫度，係藉由動態黏彈性測定 裝置（股份有限公司UBM製、DVE-V4 Rheospectoler)進 行測定。結果如同圖6所示，以tan5所表示的玻璃轉移 溫度’爲無法觀測到至2 3 0。(：爲止之測定。尙，在此，E， 示爲儲藏彈性率，E，，示爲損失彈性率，tanS = E，，/E，。 又’對於使用實施例5及實施例6之光硬化性樹脂組 成物’亦同樣地進行光線透過率、動態年彈性測定，透過 率雖均爲90%以上，但在至23(TC爲止之測定無法觀測到 -29- 201235188 玻璃轉移溫度。 1J 明 說 單 簡 式 圖 [圖1]圖1爲表示本發明之硬塗層薄膜層合體之斷面 模擬圖。 [圖2]圖2爲表示使用本發明之硬塗層薄膜層合體來 進行嵌入成型之樣態之斷面模擬圖。 [圖3]圖3爲表示藉由嵌入成型所得到的射出成形體 之斷面模擬圖。 [圖4]圖4爲表示在本發明之射出成形體之製造方法 中所使用射出成形機之一例之模擬圖。 [圖5]圖5爲表示在本發明之硬塗層薄膜層合體中f堇 硬塗層之光線透過率。 [圖6]圖6爲表示在本發明之硬塗層薄膜層合體中僅 硬塗層之玻璃轉移溫度之測定結果。 【主要元件符號說明】 1:射出成形用硬塗層薄膜層合體 2 :硬塗層 3 :覆蓋層 4 :基材層 5 :第1射出成形模 6 :第2射出成形模 7 :樹脂成形體 -30- 201235188 8 :射出成形體 9 :可動側定模板 I 0 :牽桿 II :固定側定模板 12 :噴嘴 13 :薄膜裝塡機(4) 25 parts of hemi-oxyalkylene, dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA"), 65 parts, and dimethylol tricyclodecane diacrylate (Kongrong Chemical Co., Ltd.) 10 parts of the company's product name, "LIGHT ACRYLATE DCP-A", and hydroxycyclohexyl benzophenone (manufactured by CIB ASPECIALTY CHEMICALS, trade name "IRGACURE 184") 2 · 5 parts are uniformly mixed and stirred, and then defoamed to obtain a liquid Photocurable resin composition. Then, the obtained liquid photocurable resin composition was applied to a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBE-903") in a thickness of 〇. A surface-treated polycarbonate film (manufactured by Sumitomo Chemical Co., Ltd., trade name "TECNOLO Y COOO"). Thereafter, a transparent cover film (material: polyethylene terephthalate having a light transmittance of 90% or more at a wavelength of 50 nm) is pressed against the applied photocurable resin to form a cover layer, and then used. The metal halide lamp irradiates the hard coat layer with ultraviolet light at a radiation exposure of 6400 mJ/cm 2 to obtain a substrate layer 4-hard coat layer 2 - cover layer 3 made of a polycarbonate resin as shown in FIG. The hard coat film layer for injection molding formed by the three-layer structure is a -22-.201235188. Then, as shown in Fig. 2 (a), the hard coat film laminate 1 is placed in a planar state in a state in which one portion of the cover layer 3 is adjacent to the wall surface of the concave portion of the first injection molding die. After the first injection molding die 5 is placed, the second injection molding die is superposed on the first injection molding die, and in this state, it is dried by the injection gate at a temperature of 1 20 ° C for 24 hours. Carbonate resin (trade name "TARFLON 1 900", manufactured by Idemitsu Co., Ltd.) was injected at a resin temperature of 280 ° C, a mold temperature of 80 ° C, an injection pressure of 1 700 kg / cm 2 , and an injection time of 3 seconds. As shown in Fig. 3, the inner surface of the resin molded body 7 made of a polycarbonate resin has a thickness of 3 mm which is provided with a hard coat layer made of the hard coat film laminate 1. The molded body 8 is injected. The injection molded body 8 having the hard coat layer obtained as described above was evaluated for surface hardness and strength as follows. The results are shown in Table 1. <Surface hardness evaluation method> The molded body having the hard coat portion was carried out in accordance with JIS K5 600-5 -4 scratch hardness (pencil method). Also, a steel wool test was performed. The steel wool test was carried out using an eraser tester (manufactured by Benguang Manufacturing Co., Ltd.) using steel wool #〇〇〇〇, and the steel wool was reversed at a load of 500 g. <Strength Evaluation Method> -23- 201235188 A bending test was performed on a molded body having a hard coat portion. For the test and test method, the test piece of 120mmx30mm is placed on the base with the opening at the center (opening: 80mmx50mm), and the tip of the core is R: SR5, the speed is 5mm/cm, and the depth is up to 40mm. The bending stress at the time of pushing and the surface state of the hard coat layer were observed. (Example 2) The liquid photocurable resin composition was applied in a thickness of 0.025 mm after curing, and an injection molded body 8 having a hard coat layer was obtained by the same method as in Example 1. Thereafter, the same evaluation as in Example 1 was carried out. The results are shown in Table 1. (Example 3) A polycarbonate film and a PMMA film were bonded to a polycarbonate film. A PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name "TECNOLOY C001") was used as a polycarbonate film side, and a decane coupling agent was previously used. Surface treatment is carried out in the chemical industry, trade name "KBE-903". The liquid photocurable resin composition was applied to the surface of the surface-treated polycarbonate film with a thickness of 0.07 mm after curing, and a hard coat portion was obtained in the same manner as in Example 1. After the molded body 8 was injected, the same evaluation as in Example 1 was carried out. The results are shown in Table 1. (Comparative Example 1) The liquid photocurable resin composition was applied in a thickness of -24 to 201235188 0.015 mm after curing, and a hard coat portion was obtained by the same method as in Example 1. After the molded body 8 was injected, the same evaluation as in Example 1 was carried out. The results are shown in Table 1. (Comparative Example 2) As a comparative example, a brand name Iupilon Sheet MR58 (thickness: 0.65 mm) manufactured by Mitsubishi Gas Chemical Co., Ltd. to which an acrylic hard coat layer was applied was attached to the surface of a polycarbonate sheet, and was carried out in the same manner as in Example 1. Evaluation. The results are shown in Table 1. (Example 4) The surface of the above-mentioned liquid photocurable resin composition was applied to a surface having a thickness of 0.1 mm after curing, which was previously subjected to a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBE-903"). The PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name "TECNOLOY S001G") was treated, and the hard coat film laminate 1 for injection molding was obtained in the same manner as in Example 1. Then, in the same manner as in the first embodiment, the injection resin was made into a PMMA resin (manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMIPEX HT55X"), and the resin was set at a resin temperature of 250 ° C and a mold temperature of 80 ° C. The pressure was 1 29 MPa and the injection time was 6 seconds, and as shown in Fig. 3, the surface of the resin molded body 7 made of PMMA resin was provided with a hard coat layer formed of the hard coat film laminate 1. The injection molded body 8 having a thickness of the layer portion of 1.6 mm. The same evaluation as in Example 1 was carried out. The results are shown in Table 1. -25-201235188 (Example 5) 15 parts of the semi-oxoperane shown in the above structural formula (4), and 55 parts of dipentaerythritol ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.), 30 parts of a tricyclodecane diacrylate (manufactured by Kyoei Chemical Co., Ltd., trade name "LIGHT ACRYLATE DCP-A") and hydroxycyclohexyl benzophenone (manufactured by CIBASPECIALTY CHEMICALS, trade name "IRGACURE 1 84") 2.5 parts uniform After mixing and stirring, defoaming was performed to obtain a liquid photocurable resin composition. The liquid photocurable resin composition was applied in a thickness of 0.050 mm after curing, and an injection molded body 8 having a hard coat layer was obtained in the same manner as in Example 1, and an example was given. 1 Perform the same evaluation. The results are shown in Table 1. (Example 6) 70 parts of hemi-oxyalkylene represented by the above structural formula (4), dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA"), 20 parts, and dimethylol tricyclic oxime 10 parts of alkane diacrylate (trade name "LIGHT ACRYLATE DCP-A", manufactured by Kyoei Chemical Co., Ltd.) and hydroxycyclohexyl benzophenone (manufactured by CIBASPECIALTY CHEMICALS, trade name "IRGACURE 184") 2 _ 5 parts were uniformly mixed and stirred. The foaming was carried out to obtain a liquid photocurable resin composition. The liquid-like photocurable resin composition was applied in a thickness of 0.05 mm after curing, and -26-201235188 was obtained in the same manner as in Example 1 to an injection molded body having a hard coat portion. After 8 , the same evaluation as in Example 1 was carried out. The results are shown in Table 1. -27- 201235188 [1® Comparative Example 2 X α g ^ _ 10 This 擗 2.1 N No cracking Comparative Example 1 X inch 500g 1000 times without scratches 200 N No cracking Example 6 X 500g 6 times with scars 200 N No cracking Example 5 as 500g 300 times without scratches 200 N No cracking Example 4 a\500g 1000 times without scratch 40 N No cracking Example 3 Os 500g 1000 times without scratches 200 N No cracking Example 2 ffi Bu 500g 1000 times without scratches 200 N No cracking Example 1 K as 500g 1000 times without scratches 200 N No crack scratch hardness (pencil method) Steel wool test Maximum bending stress Surface state rent If -28-201235188 (Reference Example) The liquid photocurable resin composition used in the above-mentioned Example 1 was applied to the PET for the base material layer as a thickness of 0.050 mm after curing. After the coating layer was pressed against the applied photocurable resin with PET, ultraviolet rays were irradiated with an exposure amount of 6400 mJ/cm 2 using an ultrahigh pressure mercury lamp to harden the hard coat layer. After hardening, the base material layer and the cover layer are peeled off by PET to obtain a film which is only a hard coat layer. <Light transmittance measurement> Only the light transmittance of the hard coat layer is used, and a spectrophotometer is used. (Measurement by Spectrophotometer U-4000, manufactured by Hitachi, Ltd.) The result was a transmittance of 91.7% at 550 nm. The results are shown in Fig. 5. <Dynamic viscoelasticity measurement> The glass transition temperature of only the hard coat layer was measured by a dynamic viscoelasticity measuring apparatus (manufactured by UBM Co., Ltd., DVE-V4 Rheospectoler). As a result, as shown in Fig. 6, the glass transition temperature ' represented by tan5 was not observed to be 203. (Measurement up to: 尙, here, E is shown as storage elastic modulus, E, and is shown as loss elastic modulus, tanS = E,, /E, and again. For the use of the light of Example 5 and Example 6. Similarly, the curable resin composition was measured for light transmittance and dynamic annual elasticity, and the transmittance was 90% or more. However, the glass transition temperature of -29-201235188 could not be observed up to 23 (TC measurement). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional simulation view showing a hard coat film laminate of the present invention. [Fig. 2] Fig. 2 is a view showing the use of the hard coat film laminate of the present invention for insert molding. [Fig. 3] Fig. 3 is a cross-sectional simulation view showing an injection molded body obtained by insert molding. Fig. 4 is a view showing a method of manufacturing the injection molded body of the present invention. A simulation diagram of an example of an injection molding machine used in the present invention. [Fig. 5] Fig. 5 is a view showing the light transmittance of the hard coat layer of the hard coat film laminate of the present invention. [Fig. 6] Fig. 6 is a view showing The measurement result of the glass transition temperature of only the hard coat layer in the hard coat film laminate of the present invention [Description of main component symbols] 1: Hard coat film laminate 2 for injection molding: Hard coat layer 3: Cover layer 4: Base material layer 5: First injection molding die 6: Second injection molding die 7: Resin molded body -30- 201235188 8 : Injection molded body 9 : movable side fixed plate I 0 : tie rod II : fixed side fixed plate 12 : nozzle 13 : film mounted machine