JP6357910B2 - OPTICAL POLYURETHANE COMPOSITION, THIN FILM MOLDED BODY, OPTICAL FILM, AND METHOD FOR PRODUCING THIN FILM MOLDED BODY - Google Patents

Description

  The present invention relates to an optical polyurethane composition, a thin film molded article, an optical film, and a method for producing a thin film molded article.

  More specifically, the optical polyurethane composition of the present invention is a urethane having an isocyanate group at the molecular end obtained by reacting an aliphatic and / or alicyclic polyisocyanate with an aliphatic and / or alicyclic polyol. A basic agent containing a prepolymer, a curing agent containing a compound having reactivity with an isocyanate group, and a specific hindered phenolic antioxidant and a specific thioether antioxidant are essentially blended. It is possible to exhibit performances such as excellent heat-resistant yellowing, bleed resistance, flexibility, and transparency that have not been achieved in the past.

  The thin film molded body of the present invention is obtained by using the optical polyurethane composition, and can exhibit unprecedented excellent performances such as heat yellowing resistance, bleed resistance, flexibility, and transparency. It is useful for a wide range of optical applications such as members (for example, optical films and optical sheets), light guide members, optical coating materials, fibers, electronic / electrical materials, food packages, cosmetic packages, decorative films, and the like.

  In recent years, many electronic devices and parts such as liquid crystal televisions, mobile phones, game machines and other electrical / electrical equipment, communication equipment, office equipment, entertainment equipment, medical equipment, daily life equipment, etc., where the market is rapidly expanding, Thin film molding such as a light guide film (optical film) and a light guide sheet (optical sheet) for transmitting light emitting diode light (LED light) incident from the side surface in a planar shape, provided with a liquid crystal display part and a switching part. The body is used.

  Conventionally, polycarbonate (PC) resin, polymethyl methacrylate (PMMA) resin, and the like have been used for these thin film molded bodies. However, all of these resins are too hard to have a low flexibility when processed into a thin film, and there is a problem that the use as a thin film molded product is limited.

  In addition, the silicon resin is rich in flexibility and excellent in heat-resistant yellowing, but there are problems such as high price, inferior productivity and workability, and the use is limited.

  On the other hand, polyurethane resins have been used by being processed into thin film molded bodies such as films and sheets, taking advantage of flexibility.

  However, the thin film molded body obtained by using the polyurethane resin has relatively good performance such as flexibility, stretchability, and toughness, but (1) the antioxidant used as an additive is present on the surface of the molded body. Bleed (a phenomenon in which powder squirts or the surface becomes sticky) and causes blocking (a phenomenon in which the surfaces of the work pieces are in close contact with each other and are difficult to separate), (2) Inferior to heat-resistant yellowing, especially LED The portion close to the heat source such as yellowing over time is difficult to apply to optical applications such as optical members (for example, optical films, optical sheets) that require high transparency. There was a problem.

  Various proposals have been made to improve such problems. For example, a two-component urethane resin composition comprising a liquid A containing a polyol component and a liquid B containing a polyisocyanate component, wherein the polyol component has a trifunctional or higher functionality having a hydroxyl value of 550 to 675 mgKOH / g The polyisocyanate component contains an alicyclic polyisocyanate and an isocyanate group residual prepolymer of the alicyclic polyisocyanate, and the isocyanate group content is 26.0 to 30.0% by mass. A two-component urethane resin composition is known (for example, see Patent Document 1).

  According to the said patent document 1, it is excellent in the compatibility of a polyol component and an isocyanate component, and can say that the urethane resin composition which can obtain the hardening body which is uniform and has a high glass transition temperature can be provided.

  However, since the urethane resin composition of Patent Document 1 is inferior in heat-resistant yellowing, it is easily yellowed by heat generation during use when used in an LED or the like, and is used for an optical member that requires particularly high transparency. It was difficult to apply to thin film molded bodies (for example, optical films, optical sheets, etc.).

  In addition, the antioxidant as an additive bleeds out of the molded body on the surface of the thin film molded body, causing blocking when the thin film molded body is laminated, or contaminating an article in contact with the thin film molded body. It was. In particular, bleeding of antioxidants from products has become a serious problem in fields such as food packaging and cosmetic packaging that place importance on safety, quality and aesthetics (transparency, gloss, touch, etc.).

  A polyurethane composition comprising a polyol composition and an isocyanate group-containing compound, wherein the polyol composition comprises a hydroxyl group-containing conjugated diene polymer hydride, an antioxidant, a light stabilizer, an ultraviolet absorber, and a curing catalyst. A composition is known (for example, refer to Patent Document 2).

  According to Patent Document 2, it is possible to provide a polyurethane having improved yellowing resistance, transparency, heat resistance, and weather resistance.

  However, Patent Document 2 is also inferior in heat yellowing resistance, bleed resistance, transparency and the like as in Patent Document 1, and has not been solved yet and has been a practical problem.

  As described above, a thin film molded body (for example, a film or a sheet) using a conventional polyurethane resin has relatively good performances such as flexibility, stretchability, and toughness. The antioxidant of this product bleeds to the surface of the molded body, causing troubles such as blocking during storage of the thin film molded body. (2) Inferior to heat-resistant yellowing, especially in the vicinity of heat sources such as LEDs. However, there are still problems to be solved, such as difficulty in application to optical applications such as optical members (for example, optical films and optical sheets) that require high transparency.

JP 2012-131852 A JP 2011-231317 A

  An object of the present invention is to provide an optical polyurethane composition having excellent heat-resistant yellowing resistance, bleed resistance, flexibility, and transparency, a thin film molded body, an optical film, and a thin film molded body using the same Is to provide.

  As a result of diligent investigations to solve the above problems, the present inventors have made molecular ends obtained by reacting aliphatic and / or alicyclic polyisocyanates with aliphatic and / or alicyclic polyols. Essential agent containing urethane prepolymer having isocyanate group, curing agent containing compound reactive to isocyanate group, and specific hindered phenolic antioxidant and specific thioether antioxidant By blending, it has been found that an optical polyurethane composition capable of expressing performances such as excellent heat-resistant yellowing resistance, bleed resistance, flexibility, transparency, etc., which has never been obtained, can be obtained, and the present invention has been completed. It was.

  That is, the present invention contains an isocyanate group-terminated urethane prepolymer (C) obtained by reacting an aliphatic and / or alicyclic polyisocyanate (A) with an aliphatic and / or alicyclic polyol (B). A two-component curable polyurethane composition comprising a main agent for reacting, a curing agent containing an isocyanate group-reactive compound (D), and a hindered phenolic antioxidant (E1) and a thioether antioxidant (E2). In the polyurethane composition, [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (o Siethylene)], 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, at least one hindered phenol antioxidant (E1) 0.5-3 The present invention relates to an optical polyurethane composition characterized by containing 0.1% by mass of dilauryl-3,3-thiodipropionate as a thioether-based antioxidant (E2).

  The present invention is a cured coating film obtained by applying and curing the optical polyurethane composition on a substrate, and the thickness of the cured coating film is in the range of 10 to 2000 μm. The present invention relates to a molded body.

  The present invention is a cured coating film obtained by applying and curing the optical polyurethane composition on a substrate, the film thickness of the cured coating film is in the range of 10 to 200 μm, and JIS K7361- The total light transmittance measured in accordance with No. 1 is 92.0% or more.

  The present invention is a cured coating film obtained by applying the optical polyurethane composition on a substrate and curing it at room temperature or curing at a temperature of 60 to 180 ° C. It is related with the manufacturing method of the thin film molded object characterized by being a film with a film thickness of 10-200 micrometers, or a sheet | seat which exceeds 200 micrometers and is 800 micrometers or less.

  Since the optical polyurethane composition of the present invention can exhibit performances such as excellent heat-resistant yellowing resistance, bleed resistance, flexibility, transparency, etc., which are not conventional, for example, optical members (for example, optical films, optical sheets, etc.) It is useful for thin film molded products suitable for a wide range of optical applications such as light guide members, optical coating materials, fibers, electronic / electrical materials, food packages, cosmetic packages, decorative films, and the like.

<Optical polyurethane composition>
First, the essential structure of the optical polyurethane composition of the present invention will be described below.

(A) Aliphatic polyisocyanate, alicyclic polyisocyanate The optical polyurethane composition of the present invention comprises an aliphatic and / or alicyclic polyisocyanate (A) and an aliphatic and / or alicyclic polyol (B). And a main component containing a urethane prepolymer (C) having an isocyanate group at the molecular end obtained by reacting (hereinafter referred to as “isocyanate group-terminated urethane prepolymer (C)”) and the reactivity with respect to the isocyanate group. And a specific hindered phenolic antioxidant (E1) and a specific thioether-based antioxidant (E2) containing the compound (D) (hereinafter referred to as “isocyanate group-reactive compound (D)”). ) Both essential.

  The isocyanate group-terminated urethane prepolymer (C) can be obtained by reacting the polyisocyanate (A) and the polyol (B) according to a known method, and the reaction method and reaction conditions are not particularly limited.

  The polyisocyanate (A) refers to a compound having two or more isocyanate groups (hereinafter also referred to as NCO groups) in the molecule.

  As the polyisocyanate (A), any of known aliphatic polyisocyanates and alicyclic polyisocyanates can be used.

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, and tetramethylxylylene diisocyanate.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate. Can be mentioned.

  Among these polyisocyanates (A), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) and hexamethylene diisocyanate are preferable from the viewpoint of appropriate reactivity with the polyol (B) and workability. These may be used alone or in combination of two or more.

  In the present invention, it is essential to use an aliphatic and / or alicyclic polyisocyanate as the polyisocyanate (A), but when only an aromatic polyisocyanate is used without using the polyisocyanate. The initial transparency and yellowness are lowered, and heat yellowing is significantly deteriorated, so that it is difficult to achieve the object of the present invention.

  An aromatic polyisocyanate may be used in combination with the polyisocyanate (A) as long as the object of the present invention is not impaired.

  The aromatic polyisocyanate is a known one such as diphenylmethane diisocyanate (MDI; 4,4′-form, 2,4′-form or 2,2′-form, or a mixture thereof, crude MDI), carbodiimide-modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, xylene diisocyanate, tolylene diisocyanate (TDI; 2,4 or 2,6 thereof, or they And xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene diisocyanate and the like.

(B) Aliphatic polyol, alicyclic polyol Examples of the aliphatic polyol and alicyclic polyol used in the present invention include polyester polyol, polyether polyol, polycarbonate polyol, and low molecular weight glycol.

  The polyester polyol is usually produced using a polycarboxylic acid and a polyol as raw materials.

  The polycarboxylic acid that can be used for the production of the polyester polyol may be any polycarboxylic acid having no aromatic skeleton, such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride. And aliphatic polycarboxylic acids such as fumaric acid; or alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.

  In the present invention, in addition to the polycarboxylic acid, derivatives thereof can also be used, and examples thereof include reactive derivatives such as lower esters such as methyl ester, acid anhydrides, and acid halides. .

  In addition, as long as the object of the present invention is not impaired, a polycarboxylic acid having an aromatic skeleton (that is, an aromatic polycarboxylic acid) may be used together with the polycarboxylic acid not having the aromatic skeleton.

  Examples of the aromatic polycarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, and p-hydroxybenzoic acid. Examples include acid, p- (2-hydroxyethoxy) benzoic acid, trimellitic acid, pyromellitic acid and the like.

  The polyol that can be used for the production of the polyester polyol may be any polyol that does not have an aromatic skeleton, such as ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3. -Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol Aliphatic polyols such as 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol; 1,4-cyclohexa Dimethanol, include alicyclic polyols such as hydrogenated bisphenol A. These may be used alone or in combination of two or more.

  In the present invention, in addition to the polyester polyol, a polyester polyol obtained by ring-opening addition polymerization of a lactone (for example, ε-caprolactone, γ-butyrolactone, etc.) can also be used.

  In addition, as long as the objective of this invention is not impaired, you may use together the polyol which has an aromatic skeleton with the polyol which does not have the said aromatic skeleton.

Examples of the polyol having an aromatic skeleton include aromatic polyols such as dihydroxynaphthalene, bisphenol A, bisphenol S, bisphenol AF, bisphenol Si ₂ , and alkylene oxide adducts thereof.

  In addition, as a raw material for producing the polyester polyol, for example, alcohols such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, and aconite sugar; or amines can be used. These may be used alone or in combination of two or more.

  The polyester polyol includes polyester diols, polyamide polyester diols, and the like obtained by using polycarboxylic acids, polyols, polyamines and the like other than the above.

  The number average molecular weight (hereinafter also referred to as “Mn”) of the polyester polyol is desirably set in consideration of the target melt viscosity at the time of use of the isocyanate group-terminated urethane prepolymer (C), preferably 300 to 5000. The range is more preferably 500-3500. If the Mn of the polyester polyol is within such a range, the reaction can be controlled normally and a urethane prepolymer having an appropriate melt viscosity can be obtained.

  Examples of the polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene propylene glycol (PEPG), polytetramethylene glycol (PTMG), modified polytetramethylene glycol (PTXG), or glycerin, Poly (oxyalkylene) glycols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide using compounds having at least three hydroxyl groups such as trimethylolpropane, pentaerythritol and sorbitol as starting materials Can be mentioned. Among these, polytetramethylene glycol (PTMG, Mn = 650 to 2000) and modified polytetramethylene glycol (PTXG, Mn = 800 to 5000) are preferable. The polyether polyol may have any structure of linear, branched and cyclic.

  Mn of the polyether polyol is preferably in the range of 500 to 3500, more preferably in the range of 600 to 3000, and still more preferably in the range of 650 to 2000. If the Mn of the polyether polyol is within such a range, an abnormal viscosity increase of the isocyanate group-terminated urethane prepolymer (C) does not occur, and a urethane prepolymer having an appropriate melt viscosity can be obtained.

  A polyol obtained by ring-opening addition polymerization of a lactone (for example, ε-caprolactone or the like) to the polyether polyol such as polytetramethylene glycol can also be used.

  Moreover, as said polycarbonate polyol, the polyol etc. which are obtained by esterifying carbonic acid and an aliphatic polyol can also be used, for example. Specifically, diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol (PTMG), and dimethyl carbonate And reaction products with phosgene and the like. These may be used alone or in combination of two or more.

  Examples of the low molecular weight glycol include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- Aliphatic polyols such as 1,3-propanediol and 2-methyl-1,3-propanediol, or alicyclic polyols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A Or glycerin, Trimethylolpropane, etc. trifunctional or more hydroxyl group-containing compound pentaerythritol and the like, and also 1,4-butanediol Among these, trimethylolpropane, diethylene glycol is preferred. The low molecular weight glycol may have a linear, branched, or cyclic structure.

  The molecular weight of the low molecular weight glycol is preferably in the range of 50 to 300, more preferably in the range of 50 to 200. If the molecular weight of the low molecular weight glycol is within such a range, when used as the polyol (B), the reactivity can be controlled more easily, and the moldability (yield, molding unevenness) becomes better. preferable.

  Moreover, as said polyol (B), the polycaprolactone polyol obtained by the ring-opening polymerization of a caprolactone monomer, an acrylic polyol, polyolefin polyol, a castor oil-type polyol etc. can be used, for example.

  Furthermore, you may use another polyol with the said polyol (B) in the range which does not inhibit the objective of this invention.

  Examples of the other polyols are obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide on a starting material having at least three hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Polyether polyols such as poly (oxyalkylene) glycol and poly (oxytetramethylene) glycol; or polyvalent carboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, maleic acid, phthalic acid and ethylene glycol, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, ne Polycondensation of polyhydric alcohols such as pentyl glycol, 2, -methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol Polyester polyol obtained by polymerization; or polymer polyol for polymerizing ethylenically unsaturated monomers such as acrylonitrile and styrene in the presence of polylactone polyol, polyether ester polyol, polycarbonate polyol, polybutadiene polyol, polyether ester polyol, etc. Is mentioned.

  Polyamines can also be used in combination. Examples of the polyamine include ethylenediamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, diaminocyclohexane, methyldiaminocyclohexane, piperazine, and norbornenediamine.

(C) Isocyanate group-terminated urethane prepolymer Next, the isocyanate group-terminated urethane prepolymer (C) used in the present invention will be described.

  In the optical polyurethane composition of the present invention, molecular terminals obtained by reacting the aliphatic and / or alicyclic polyisocyanate (A) with the aliphatic and / or alicyclic polyol (B) according to a conventional method. The main component is urethane prepolymer (C) having an isocyanate group (hereinafter referred to as “isocyanate group-terminated urethane prepolymer (C)”).

  The “main agent” in the present invention refers to a composition exceeding 50% by mass with respect to the total amount of the composition.

  In the isocyanate group-terminated urethane prepolymer (C), the isocyanate group (hereinafter referred to as “NCO group”) of the polyisocyanate (A) is also referred to as a hydroxyl group (hereinafter referred to as “OH group”) of the polyol (B). Can be reacted by a known method under the condition that the equivalent ratio is excessive.

  In the synthesis of the isocyanate group-terminated urethane prepolymer (C), the isocyanate equivalent of the polyisocyanate (A) (hereinafter referred to as “NCO equivalent”) and the hydroxyl equivalent of the polyol (B) (hereinafter referred to as “OH equivalent”). )) (Ie, [NCO / OH equivalent ratio]) may be set in consideration of target physical properties, product quality, reaction behavior, and the like, and is not particularly limited. It is preferable to carry out in the range of ˜20.0 / 1.0, and more preferably in the range of 2.0 / 1.0 to 13.0 / 1.0.

  As a method for synthesizing the isocyanate group-terminated urethane prepolymer (C), for example, [Method 1] Polyisocyanate (A) charged in a reaction vessel is dropped, divided, batched, etc. with a polyol (B) from which moisture has been removed. A method of charging by an appropriate means and reacting until the hydroxyl group of the polyol (B) substantially disappears, or [Method 2] Polyisocyanate (A) is added to the polyol (B) from which water is charged in the reaction vessel. ) In an appropriate manner such as dropping, dividing, or batch, and reacting until the hydroxyl group of the polyol (B) is substantially eliminated.

  In order to allow the reaction to proceed safely and normally while gently controlling the exotherm during the reaction, a charging method by dropping or dividing is more preferable.

  The isocyanate group-terminated urethane prepolymer (C) is usually produced without a solvent, but may be produced by reacting in a solvent. When making it react in a solvent, what is necessary is just to use the solvent which does not inhibit reaction, and the kind is not specifically limited. It is desirable to remove the solvent used in the reaction by an appropriate method such as heating under reduced pressure or distilling off the thin film during or after the reaction.

  The reaction conditions (temperature, time, pressure, etc.) of the isocyanate group-terminated urethane prepolymer (C) may be set within a range that can be normally controlled in consideration of reaction behavior (safety, stability), product quality, etc. There is no particular limitation. Usually, it is preferable to carry out the reaction at a reaction temperature of 50 to 90 ° C. under a reaction time of 2 to 24 hours. The pressure may be normal pressure, pressurization, or reduced pressure.

  As the reaction method, for example, a known reaction method such as batch, semi-continuous or continuous can be selected, and is not particularly limited.

  Moreover, when manufacturing the said isocyanate group terminal urethane prepolymer (C), a urethanization catalyst can be used as needed. The said catalyst can be suitably added in the arbitrary steps of a raw material preparation process and a reaction process. Moreover, the addition method of a catalyst is not specifically limited, such as lump, division | segmentation, and continuous.

  As the urethanization catalyst, known catalysts can be used, for example, nitrogen-containing compounds such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methylmorpholine; or titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, Organometallic compounds such as tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octylate, dibutyltin dilaurate; or iron chloride, Examples include inorganic compounds such as zinc chloride.

  Usually, the reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon, but may be performed in a dry air atmosphere or in a condition where moisture is not mixed, such as a sealed condition.

  The isocyanate equivalent of the isocyanate group-terminated urethane prepolymer (C) (hereinafter also referred to as “NCO equivalent”) is preferably in the range of 100 to 10,000, and more preferably in the range of 200 to 1,000. If the NCO equivalent of (C) is within such a range, an abnormal increase in viscosity does not occur and the workability is excellent.

  The “isocyanate equivalent” (unit: g / eq) in the present invention is a value measured according to JIS K 7301 described later.

  In the present invention, commercially available products may be used as the urethane prepolymer. For example, Duranate TSA-100 (trade name; manufactured by Asahi Kasei Chemicals Corporation, hexamethylene diisocyanate trimer and 2-ethylhexyl alcohol isocyanate prepolymer). Polymer), TSS-100 (made by the company), TSE-100 (made by the company), TSR-100 (made by the company), THA-100 (made by the company), D101 (made by the company), A201H (made by the company), Examples include TKA-100 (manufactured by the same company).

(D) Isocyanate group-reactive compound Next, the curing agent to be blended with the main agent will be described below.

  The curing agent is referred to as a compound (D) having reactivity with an isocyanate group (hereinafter referred to as “isocyanate group-reactive compound (D)”). ).

  In the present invention, as the isocyanate group-reactive compound (D), a compound having an active hydrogen atom such as the polyol or the polyamine (hereinafter referred to as “active hydrogen atom-containing compound”) can be used.

  Examples of the isocyanate group-reactive compound (D) include active hydrogen-containing compounds having a functional group having no aromatic skeleton, such as aliphatic polyols, alicyclic polyols, aliphatic polyamines, and alicyclic polyamines. .

  Among the isocyanate group-reactive compounds (D), aliphatic polyols are preferable. For example, it is possible to select a low molecular weight glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol, and the hindered phenol antioxidant. The solubility between (E1) and the thioether-based antioxidant (E2) is better, and it is more preferable because a solution having a high concentration can be prepared.

(E1) hindered phenolic antioxidant, (E2) thioether antioxidant The optical polyurethane composition of the present invention comprises a specific hindered phenolic antioxidant (E1) and a specific thioether antioxidant ( For the first time, by combining the two types of E2) in an essential combination, excellent performances such as heat-resistant yellowing resistance, bleed resistance, flexibility, and transparency, which are unprecedented, can be exhibited.

  Examples of the hindered phenol antioxidant (E1) include [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2. , 4,8,10-tetraoxaspiro [5,5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], 3 -(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate and the like. Among these, [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxa is preferable. Spiro [5,5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], more preferably [2- { 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane. These may be used alone or in combination of two or more.

  As a commercial item of the said hindered phenolic antioxidant (E1), for example, Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd., [2- {3- (3-tert-butyl-4-hydroxy- 5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane), Irganox 245 (trade name, manufactured by Ciba Specialty Chemicals, Inc., bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)]), Irganox 1076 (trade name, manufactured by Ciba Specialty Chemicals, 3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate.

  The compounding quantity of the said antioxidant (E1) is the range of 0.5-3 mass% in an optical polyurethane composition, Preferably it is the range of 1-2 mass%. If the blending amount of (E1) is within such a range, the dispersion stability is further improved, and the thioether-based antioxidant (E2) acts synergistically with each other, and has excellent heat yellowing resistance and bleed resistance. Can exhibit transparency.

  However, when the blending amount of the antioxidant (E1) is less than 0.5% by mass, it becomes difficult to obtain good heat-resistant yellowing, and the object of the present invention cannot be achieved. Moreover, also when the compounding quantity of the said antioxidant (E1) exceeds 3 mass%, it becomes difficult to obtain favorable heat-resistant yellowing, and the objective of this invention cannot be achieved.

  The thioether-based antioxidant (E2) used essentially in the present invention is dilauryl-3,3-thiodipropionate.

  In the present invention, dilauryl-3,3-thiodipropionate, among other thioether antioxidants (E2), is selectively combined with the specific hindered phenol antioxidant (E1). , Excellent effects can be expressed.

  As a commercial item of the said thioether type | system | group antioxidant (E2), for example, Sumilizer TPL-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Irganox PS-800 ((trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)), etc. Is mentioned.

  The compounding quantity of the said thioether type | system | group antioxidant (E2) is the range of 0.1-2 mass% in an optical polyurethane composition, Preferably it is the range of 0.2-1 mass%. If the blending amount of the (E2) is within such a range, the dispersion stability is further improved, and the synergistic action with the hindered phenol antioxidant (E1) is achieved. Effects such as bleed and transparency can be exhibited.

  However, when the blending amount of the antioxidant (E2) is less than 0.1% by mass, it becomes difficult to obtain good heat-resistant yellowing, and the object of the present invention cannot be achieved. Moreover, also when the compounding quantity of the said antioxidant (E2) exceeds 2 mass%, it becomes difficult to obtain favorable heat-resistant yellowing, and the objective of this invention cannot be achieved.

  Thus, the optical polyurethane composition of the present invention is formulated by using a specific hindered phenolic antioxidant (E1) and a specific thioether-based antioxidant (E2) in an amount within a specific range. In this case, it is possible to obtain effects such as excellent heat-resistant yellowing, bleed resistance, flexibility, and transparency that have not been obtained in the past.

  The optical polyurethane composition of the present invention can be obtained by blending and mixing the main agent and the curing agent prepared as described above according to the formulation.

  The mixing ratio of the main agent and the curing agent, that is, [the total number of NCO groups (α) of the isocyanate group-terminated urethane prepolymer (C) as the main agent] / [isocyanate group reactive compound (D) as the curing agent is The total number of moles (β) of the NCO-reactive group (ie, OH group + NH group) is preferably in the range of β / α = 1 / 0.5 to 1 / 1.2, more preferably 1 The range is /0.6 to 1 / 1.1.

  When the mixing ratio [(β) / (α)] of the main agent and the curing agent is within such a range, a cured product having good release properties can be obtained.

  When using the (E1) and (E2) together as in the present invention, rather than using the hindered phenolic antioxidant (E1) alone or the thioether antioxidant (E2) alone. However, it is possible to obtain a remarkable effect in terms of heat yellowing resistance, bleed resistance, flexibility, transparency and the like.

  Usually, the curing agent in which the hindered phenol antioxidant (E1) and the thioether antioxidant (E2) are dissolved and the main agent are stored separately, and the curing agent or the main agent is used at the time of use. It is preferable to perform molding by blending and mixing the necessary amount.

  In order to uniformly contain the hindered phenol-based antioxidant (E1) and the thioether-based antioxidant (E2) in the thin film molded body, the polyol (B), which is a raw material for the optical polyurethane composition, In addition, it is preferable to use the urethane prepolymer (C) and an additive such as a plasticizer used as necessary in the production of a thin film molded article in a state of being previously dissolved, mixed, or dispersed.

  In addition to the raw materials described above, various additives can be used in the optical polyurethane composition of the present invention at any stage of the production process within a range not departing from the object of the present invention.

  Examples of such additives include foam stabilizers, antioxidants, defoamers, abrasive grains, fillers, pigments, dyes, colorants, thickeners, surfactants, flame retardants, plasticizers, lubricants, charging agents. Known agents such as an inhibitor, a heat stabilizer, a tackifier, a curing catalyst, a stabilizer, a silane coupling agent, and a wax can be used. Further, as necessary, conventionally known thermoplastic resins, thermosetting resins, and the like can be appropriately selected and used as the blending resin within a range not impairing the object of the present invention. In addition, the said additive is only an example, As long as the objective of this invention is not inhibited, the kind and usage-amount are not specifically limited.

As the tackifier, for example, rosin resins, rosin ester resins, hydrogenated rosin ester resins, terpene resins, terpene phenol resins, and hydrogenated terpene resin, a C ₅ based as petroleum resins aliphatic resins, C ₉ based it can be an aromatic resin, and C ₅ system and the C ₉ based copolymer resin.

  Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trioctyl phosphate, epoxy plasticizer, toluene-sulfoamide, chloroparaffin, adipine Acid esters, castor oil and the like can be used. Examples include methyl acid phosphate (AP-1) and acrylic surface conditioner (BYK-361N).

  As said stabilizer, a hindered phenol compound, a sulfur compound, a benzotriazole compound, a hindered amine compound etc. can be used, for example.

  As the filler, for example, silicic acid derivatives, talc, metal powder, calcium carbonate, clay, carbon black and the like can be used.

<Thin film molding, optical film>
The thin film molded article of the present invention is obtained using the optical polyurethane composition, and has unprecedented performances such as heat-resistant yellowing resistance, bleed resistance, flexibility, and transparency.

  Examples of the thin film molded body include optical members (for example, optical films and optical sheets), light guide members, optical coating materials, fibers, electronic / electrical materials, food packages, cosmetic packages, decorative films, and coating films. Various forms are mentioned.

  The thin film molded body of the present invention is a cured coating film obtained by applying and curing the optical polyurethane composition on a substrate, and the thickness of the cured coating film is 2000 μm or less, preferably 10 It is the range of -2000 micrometers, More preferably, it is the range of 10-1000 micrometers, More preferably, it is the range of 10-800 micrometers.

  In the present invention, a member having a thickness of 200 μm or less is defined as “film” and a member having a thickness exceeding 200 μm is defined as “sheet” in accordance with a standard generally called in Japan.

  The optical film of the present invention is a cured coating film obtained by applying and curing the optical polyurethane composition on a substrate, and the thickness of the cured coating film is preferably in the range of 10 to 200 μm.

  Furthermore, since the optical film of the present invention has a total light transmittance of 92.0% or more as measured in accordance with JIS K7361-1, it is excellent in light transmittance, particularly for optical applications such as a light guide film. It can be used suitably.

<Manufacturing method of thin film molded body>
As a manufacturing method of the thin film molded body of the present invention, for example, the optical polyurethane composition of the present invention is applied on a release substrate and cured or heated under normal temperature conditions (preferably 60 to 180 ° C.). Of the cured coating film, the film thickness of the cured coating film is 20000 μm or less, preferably 10 to 2000 μm, more preferably 10 to 1000 μm, and still more preferably 10 to 10 μm. Examples thereof include a method of obtaining a thin film molded body having a thickness of 800 μm (for example, a cured product such as a film, a sheet, and a coating film).

  Examples of the substrate include metals (plates, foils, etc.), plastics (plates, sheets, films, etc.), papers (release papers, etc.), glass, ceramics, wood plates (decorative plates, etc.), ceramics, cloths, and the like. There is no particular limitation.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited only to these examples.

  Further, in the present invention, unless otherwise specified, “part” is “part by mass” and “%” is “mass%”.

  The measurement method and evaluation method used in the present invention are as follows.

[Method for measuring isocyanate equivalent of isocyanate group-terminated urethane prepolymer (C)]
The isocyanate equivalent (unit: g / eq) of the isocyanate group-terminated urethane prepolymer (C) used in the present invention is a value measured according to JIS K 7301. Specifically, the obtained urethane prepolymer sample was precisely weighed in an Erlenmeyer flask, dissolved in dry toluene, added with 10 ml of a di-n-butylamine solution, made uniform, and then allowed to stand. A standard solution of 5N hydrochloric acid was quantified by neutralization titration using bromcresol green as an indicator.

[Method for producing thin film molded body]
The polyurethane compositions obtained in Examples and Comparative Examples were immediately poured into a mold having a predetermined shape that had been preheated to 80 ° C. After the injection, it was left as it was for 2 hours, and the molded product was taken out to obtain a thin film molded body having a thickness of 2 mm.

[Evaluation Method and Criteria for Initial Yellowness (YI ₀ ) of Thin Film Molded Body]
The yellow index (YI ₀ ) in the thickness direction of the thin film molded bodies obtained in Examples and Comparative Examples was measured with a multi-light source spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS Z8722, and the following criteria It evaluated according to.
Judgment criteria for initial yellowness ○: When YI _{0 in the} thickness direction is 0.7 or less, the initial yellowness is excellent.
X: When YI _{0 in the} thickness direction exceeds 0.7, the initial yellowness is inferior.

[Evaluation method and criteria for heat-resistant yellowing of thin film moldings]
The thin film molded body prepared above is exposed to 120 ° C. for 96 hours in a dryer, and the yellowness after exposure (yellow index: YI ₁ ) is measured according to JIS Z8722. Measured by the company) and evaluated according to the following criteria.
Criteria for determining heat-resistant yellowing ○: When YI _{1 in the} thickness direction is 1.0 or less, heat-resistant yellowing is excellent.
X: When YI _{1 in the} thickness direction exceeds 1.0, the heat resistant yellowing is inferior.

[Evaluation method and criteria for bleed resistance of thin film molded product]
The thin film molded body prepared above was left in a constant temperature and humidity chamber adjusted to 23 ° C. × 50% relative humidity for 14 days, and then the surface of the thin film molded body was visually and touched and evaluated according to the following criteria.
Judgment criteria for bleed resistance ○: When there is no bleed, excellent bleed resistance.
X: When there is a bleed, the bleed resistance is poor.

[Transparency evaluation method and criteria for thin-film moldings]
The total light transmittance (%) of the thin film molded body prepared above was measured according to JIS K7361-1 by NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and evaluated according to the following criteria.
Criteria for transparency ○: When the total light transmittance is 91.0% or more, the transparency is excellent.
X: When the total light transmittance is less than 91.0%, the transparency is poor.

[Evaluation method and criteria for flexibility of thin film moldings]
The flexibility of the film prepared above was judged by JIS A hardness. In addition, when the film was rich in flexibility and could not be measured with JIS A hardness, it was measured with ASKER C hardness and indicated.
Judgment criteria for flexibility ◯: When the JIS A hardness is 98 or less, the flexibility is excellent.
X: When JIS A hardness exceeds 98, it is inferior to a softness | flexibility.

[Synthesis Example 1]
≪Synthesis of isocyanate group-terminated urethane prepolymer (C1) ≫
In a reaction vessel, polyoxytetramethylene glycol (trade name, PTMG-1000, manufactured by Mitsubishi Chemical Corporation, number average molecular weight (Mn), which was previously heated and melted at 50 ° C. as an aliphatic polyol (B). 1000 parts.) 114 parts were added and stirring was started.
Next, 100 parts of 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as “hydrogenated MDI”) was added as the alicyclic polyisocyanate (A), and the internal temperature was raised to 85 ° C. while paying attention to heat generation. Thereafter, the mixture was stirred for 3 hours while maintaining the temperature to obtain an isocyanate group-terminated urethane prepolymer (C1) (hydrogenated MDI prepolymer having an isocyanate equivalent of 400).

[Example 1]
To 100 parts of the urethane prepolymer (C1) obtained in Synthesis Example 1, 1.0 part of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as a hindered phenol antioxidant (E1), and a thioether type 0.4 part of Sumilizer TPL-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant (E2), 0.5 part of Sanol LS-765 (trade name, manufactured by Sankyo Corporation) as a weathering stabilizer, urethane 0.01 parts of a conversion catalyst Neostan U-100 (trade name, manufactured by Nitto Kasei Co., Ltd.) was blended and dissolved and mixed at an internal temperature of 80 ° C. while stirring.
Next, 10.4 parts of an isocyanate group-reactive compound (D1) (1,4 butanediol / trimethylolpropane = 4/6 mass ratio mixture) as a curing agent was added and mixed and stirred, and the optical polyurethane of the present invention. After preparing the composition (X1), it was immediately poured into a mold having a predetermined shape that had been preheated to 80 ° C. After the injection, it was left as it was for 2 hours, and the molded product was taken out to obtain a thin film molded body (P1) having a thickness of 2 mm.
The thin film molded article (P1) of the present invention obtained by using the optical polyurethane composition (X1) has excellent heat yellowing resistance, bleed resistance, transparency, and moderate flexibility (surface hardness). It was. The evaluation results of Example 1 are summarized in Table 1.

[Examples 2 and 3]
Examples 2 and 3 are the same as Example 1 except that the types and amounts used of the urethane prepolymer (C), isocyanate group-reactive compound (D), antioxidant, etc. used are changed as shown in Table 1. In the same manner, the optical polyurethane compositions (X2) and (X3) of the present invention were prepared, and the thin film molded products (P2) and (P3) of the present invention were obtained using the same.

  The thin film molded bodies (P2) and (P3) all had excellent heat-resistant yellowing resistance, bleed resistance, transparency, and appropriate flexibility (surface hardness). The evaluation results of Examples 2 and 3 are summarized in Table 1.

[Examples 4 to 6]
Examples 4-6 are Duranate TSA-100 (trade name, manufactured by Asahi Kasei Chemicals Corporation, isocyanate prepolymer which is a reaction product of hexamethylene diisocyanate trimer and 2-ethylhexyl alcohol) as urethane prepolymer (C2). Except that PTXG-1800 (trade name, manufactured by Asahi Kasei Fibers Co., Ltd., a copolymer of tetrahydrofuran and neopentyl glycol, number average molecular weight 800 to 5000) is used as the isocyanate group-reactive compound (D2). Prepared the optical polyurethane compositions (X4) to (X6) of the present invention in the same manner as in Example 1 except that the types and amounts used of the antioxidants were changed as shown in Table 1. Using this, the thin film molded bodies (P4) to (P6) of the present invention were obtained.
The thin film molded bodies (P4) to (P6) all had excellent heat yellowing resistance, bleed resistance, transparency, and appropriate flexibility (surface hardness). The evaluation results of Examples 4 to 6 are summarized in Table 1.

  In Examples 2, 4, and 5, two different types of antioxidants were used as the hindered phenol-based antioxidant (E1).

[Comparative Examples 1-6]
Comparative Examples 1 to 6 are the same as in Example 1 except that the types and amounts used of the urethane prepolymer (C), isocyanate group-reactive compound (D), antioxidant, and the like used are changed as shown in Table 2. The same operation was performed to prepare polyurethane compositions (X7) to (X12), respectively, and thin film molded products (P7) to (P12) were obtained using the polyurethane compositions.
The thin film molded body (P7) obtained in Comparative Example 1 was inferior in bleed resistance and poor in practicality.
The thin film molded bodies (P8) to (P12) obtained in Comparative Examples 2 to 6 were all inferior in heat yellowing and poor in practicality.
The evaluation results of Comparative Examples 1 to 6 are summarized in Table 2.

  In addition, the symbol in Table 1 and Table 2 means the following name.

Hydrogenated MDI: 4,4′-dicyclohexylmethane diisocyanate MDI: diphenylmethane diisocyanate PTMG-1000: trade name, manufactured by Mitsubishi Chemical Corporation, polyoxytetramethylene glycol, number average molecular weight 1000
Duranate TSA-100: trade name, manufactured by Asahi Kasei Chemicals Corporation, isocyanate prepolymer that is a reaction product of hexamethylene diisocyanate trimer and 2-ethylhexyl alcohol BG: 1,4-butanediol TMP: trimethylolpropane PTXG- 1800: trade name, manufactured by Asahi Kasei Fibers Co., Ltd., a copolymer of tetrahydrofuran and neopentyl glycol, number average molecular weight 800-5000
Sumilizer GA-80: trade name, manufactured by Sumitomo Chemical Co., Ltd., hindered phenol antioxidant, [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1 -Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane)
Irg245: trade name, Irganox 245, manufactured by Ciba Specialty Chemicals, hindered phenol antioxidant, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (Oxyethylene)
Irg1076: trade name, Irganox 1076, manufactured by Ciba Specialty Chemicals Co., Ltd., 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate Sumilizer TPL-R: product name, manufactured by Sumitomo Chemical Co., Ltd. , Thioether antioxidant, dilauryl-3,3-thiodipropionate ADK STAB AO-503: trade name, manufactured by ADEKA Corporation, thioether antioxidant, di (tridecyl) -3,3′-thiodipropionate PS802FF: trade name, manufactured by Yangzhou Sunchem Co., Ltd., thioether-based antioxidant, distearyl-3,3′-thiodipropionate, Sumitizer TP-D: trade name, manufactured by Sumitomo Chemical Co., Ltd., thioether-based antioxidant, penta Erythrityl tetrakis (3-laurylthiop Pioneto)
Sumilizer GP: trade name, manufactured by Sumitomo Chemical Co., Ltd., phosphorus antioxidant SANOL LS-765: trade name, manufactured by Sankyo Co., Ltd., hindered amine light stabilizer, bis (2,2,6,6) decanedioate -Pentamethyl-4-piperidinyl)
Neostan U-100: trade name, manufactured by Nitto Kasei Co., Ltd., tin-based catalyst)

  Since the optical polyurethane composition of the present invention can exhibit performances such as excellent heat-resistant yellowing resistance, bleed resistance, flexibility, transparency, etc., which are not conventional, for example, optical members (for example, optical films, optical sheets, etc.) It is useful for thin film molded products suitable for a wide range of optical applications such as light guide members, optical coating materials, fibers, electronic / electrical materials, food packages, cosmetic packages, decorative films, and the like.

Claims (6)

A main agent containing an isocyanate group-terminated urethane prepolymer (C) obtained by reacting an aliphatic and / or alicyclic polyisocyanate (A) with an aliphatic and / or alicyclic polyol (B); and an isocyanate group and a curing agent containing a reactive compound (D), wherein in the base resin or curing agent, an optical two-component curing comprising a hindered phenol antioxidant (E1) and thioether-based antioxidant (E2) Type polyurethane composition comprising:
The aliphatic and / or alicyclic polyol (B) contains a polyester polyol having a number average molecular weight of 300 to 5000 or a polyether polyol having a number average molecular weight of 500 to 3500,
The hindered phenol antioxidant (E1) is [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4, 8,10-tetraoxaspiro [5,5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], 3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate and containing at least one selected from the group consisting of
The thioether-based antioxidant (E2) contains dilauryl-3,3-thiodipropionate,
Oite the two-part curable polyurethane composition for optical, and from 0.5 to 3% by weight the content of the hindered phenol antioxidant (E1), the content of the thioether-based antioxidant (E2) is 2 part curable polyurethane composition for optical, wherein 0.1 to 2% by mass Rukoto. The hindered phenol antioxidant (E1) is [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8. The optical two-component curable type according to claim 1, wherein the thioether-based antioxidant (E2) is dilauryl-3,3-thiodipropionate, 10-tetraoxaspiro [5,5] undecane. Polyurethane composition. The two-component curable polyurethane composition for optical use according to claim 1 or 2, wherein an isocyanate equivalent of the isocyanate group-terminated urethane prepolymer (C) is in a range of 100 to 10,000 g / eq. It is a thin film molded object containing the cured coating film of the optical two-component curable polyurethane composition as described in any one of Claims 1-3, Comprising: The film thickness of the said cured coating film is the range of 10-2000 micrometers. A thin film molded article characterized by the above. An optical film comprising a cured coating film of the two-component curable polyurethane composition for optics according to any one of claims 1 to 3, wherein the thickness of the cured coating film is in the range of 10 to 200 µm, And the total light transmittance measured based on JISK7361-1 is 92.0% or more, The optical film characterized by the above-mentioned. Curing by coating the optical two-component curable polyurethane composition according to any one of claims 1 to 3 on a substrate and curing it at room temperature or curing at 60 to 180 ° C. a method of manufacturing a thin film shaped body comprising a coating film, thin film, wherein the cured coating film, wherein the thickness 1 0～200Myuemu film, or less of the sheet thickness 800μm beyond the thickness 200μm Manufacturing method of a molded object.