TW201000499A - Resin composition, hard-coating agent, film, and method for production of molded article - Google Patents

Abstract

Disclosed is a resin composition which is characterized by comprising a polyfunctional polymerizable compound having two or more acryloyl groups and a compound capable of being added to an acryloyl group.

Description

201000499 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a resin composition, a hard coating agent, a film, and a molded body. [Prior Art] A film coated with a thermosetting resin has been used from a conventional meinbrane switch or a simulation can of a vending machine. Further, a film for forming which is obtained by coating and hardening an ultraviolet curable resin having excellent scratch resistance as compared with a thermosetting resin is gradually obtained. In particular, mobile phone frames, portable music players, touch panels and other electronic equipment frames or automotive interior materials require hardness, scratch resistance, stain resistance, gloss, etc. Therefore, for their use, application will begin. A thin film for forming which is applied and cured by an ultraviolet curable resin (see Patent Documents 1 to 3). CITATION LIST Patent Document 1: International Publication No. 00/34396, and Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. (Problem to be solved by the invention) A film coated with a thermosetting resin, which has low hardness or scratch resistance

2013-10379-PF 201000499 Easy to damage, resulting in significant deterioration in appearance. On the other hand, the film for forming which is coated and hardened by the ultraviolet curing type of the ray-cured type of X-ray is straight and easily cracked, and the formability is lacking, and it can be molded only in a relatively flat structure. In view of the above, it is an object of the present invention to provide a resin composition, a hard coating agent, and a method for producing a film-shaped body which have high hardness and scratch resistance and good moldability. (Means for Solving the Problem) The present invention will be described in detail below. (1) Resin composition of the present invention The resin composition of the present invention comprises a polyfunctional polymerizable compound having two or more acrylonitrile groups, and a compound which can undergo an addition reaction to an acrylonitrile group. The resin composition of the present invention has a softness which is less likely to cause cracks even when it is formed in a single-hardening state, and is also less likely to be sticky. Further, the composition of the tree of the month of April is in the state of secondary hardening, and the hardness or scratch resistance is excellent. Further, primary hardening means: an addition reaction to an acrylonitrile group. Further, secondary hardening refers to radical polymerization by irradiation of active energy rays such as ultraviolet rays or electron beams. Neopentyl diacrylate The polyfunctional polymerizable compound having two or more acrylonitrile groups of the present invention reacts free radicals! ·Life and non-hanging two, from the point of view of fast hardness and high hardness, have an advantage! A polyfunctional polymerizable compound having two or more acrylonitrile groups, such as i, 4-butadiene diacrylate, U-hexane diacetate, polyethylene glycol propionate, and hydroxyl group diacrylate

20i3-iC379-PF 201000499 Neopentyl glycol acetate, dicyclopentanyl diacrylate, caprolactone modified dicyclopentyl acrylate, oxyethylene diacrylate phosphate, allylated diacrylate Cyclohexyl ester, trimeric isocyanate, tris(hydroxymethyl)

Acrylic acid vinegar, dipentaquat tetraacetic acid, propionic acid denatured dipentaerythritol triacrylate, pentaerythritol triacrylate, oxypropylene denatured trishydroxypropyl propane triacrylate, ginseng (propylene oxyethyl) Isocyanurate, dipentaerythritol pentaacrylate, dipentaerythritol diacetate, dipentaerythritol hexaacrylate, caprolactone denatured dipentaerythritol hexaacrylate, etc. The more the acrylate having a larger number of bases, the higher the surface hardness. These may be used singly or in combination of two or more. The polyfunctional polymerizable compound having two or more acrylonitrile groups may be a monomer or a prepolymer, or may be a urethane acrylate, an epoxy acrylate, a polyester acrylate or the like. The compound which can be subjected to an addition reaction to an acrylonitrile group used in the present invention means a compound which can be subjected to a ruthenium addition reaction with a polyfunctional polymerizable compound having two or more acrylonitrile groups. By this addition reaction, the resin composition is subjected to I-hardening (B-stage), and therefore, the viscosity of the resin composition disappears or decreases. By applying the resin composition to the film, it is possible to prevent the films from blocking each other by imparting conditions for promoting the addition reaction, or to block the film and the mold when the film is formed. The addition reaction of the propylene fluorenyl group may be carried out as long as it is a compound having nucleophilicity, and specifically, an amine compound is preferred. Amine, diamine amination: such as with a grade 1 or a grade 2 amine, such as: methylamine, ethylenediamine ditriethyltetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethyleneamine , amantadine, piperazine, or

2〇13-1〇3?9-PF 201000499 Low molecular weight amine such as amine group; In the present invention, the low molecular weight amine means, for example, an ethylenediamine derivative such as DETA (diethylenetriamine) 'TETA (triethylenetetramine) or pEHA (pentaethylenehexamine), and its molecular weight is, for example, 〜4〇〇 The scope is appropriate. Further, as the amine compound, a polyamine which has an amine as a repeating structure can also be used. The hardenability of the resin composition can be easily adjusted by using a combination of a low molecular weight amine and a polyamine. Further, if a low molecular weight amine and a polyamine are used in combination, when the resin composition is once hardened, viscosity is less likely to occur. The molecular weight of the polyamine is suitably in the range of, for example, 10,000 to 200,000. The amount of the amine compound to be used depends on the amine valence of the amine compound to be used, and is preferably in the range of from 1 to 50 parts by weight based on 1 part by weight of the polyfunctional polymerizable compound having two or more acrylonitrile groups. 〇· 5~3〇 The range of parts by weight is better. The range of 5~25 parts by weight is especially good. When the secondary hardening of the resin composition is insufficient, the hardenability can be improved by increasing the compounding amount of the amine compound or increasing the proportion of the polyamine in the amine compound. On the other hand, when the use period of the resin composition is short, the use period can be extended by reducing the compounding of the amine compound or reducing the proportion of the polyamine in the amine compound. Further, the compound having a higher amine value has a higher reactivity with the amine compound, and the food b decreases the amount of the amine compound added, and the surface physical properties are also good, which is preferable. By combining the temperature-sensitive catalyst with the compound which can be subjected to the addition reaction to the acrylonitrile group, the primary hardenability and the life of the resin composition can be easily achieved. That is, the temperature sensitive catalyst has no catalytic activity (or low activity) at normal temperature, so that the life of the resin composition can be increased, and the primary curing property can be improved by rapidly exhibiting activity at a high temperature. Further, when a temperature sensitive catalyst is blended, when the resin composition is once hardened, it is less likely to cause stickiness in 2013-1O379-P? 6 201000499. As a specific example of the thermosensitive catalyst, a salt of DBU (diazabicyclohexadecene) or DBN (diazabicyclononene) which is a strong base is particularly preferable. The salt of DBU or DBN is also excellent in miscibility with various solvents, and the reaction yield can be improved in a milder condition than using a conventional amine or an inorganic catalyst. Salts of DBU or DBN, for example: DBU - benzene salt, DBU - octoate, DBU - oleate, DBU - p-toluenesulfonate, DBU - formate, dBN - streptophenolate, DM-octanoate, Dm - oleate, DBN - p-toluene sulfonate, DBN-formate methylamine, and the like. In addition, for example, the salt of the test or test. Further, it can also be used as a strong base salt which is soluble in an organic solvent and has a protonation action. These temperature sensitive catalysts may be used singly or in combination of two or more. Further, the catalyst which promotes the addition reaction to the acrylonitrile group is not limited to the above-mentioned temperature sensitive catalyst, and can be used simultaneously with a method capable of exhibiting catalyst activity. The amount of the thermosensitive catalyst is compared with two or more

Polyfunctional polymerizable compound 10. The parts by weight are preferably in the range of 5 to 2 parts by weight. By being within this range, when the resin composition is in the -hardened state, it is less likely to cause stickiness. The composition of the moon and the moon is made by irradiating ultraviolet rays or electron beams, and so on. For UV curing, ultra-high pressure mercury lamps, high-pressure water gates, mercury lamps, low-pressure mercury lamps, carbon arcs, metal halide lamps, etc. can be used in 1〇〇~4〇

Unm is preferably in the wavelength region of 2 〇〇 to 40 〇 nm, and irradiates ultraviolet rays having Sb I of 50 to 3 〇〇inJ/cro2 曰 ^ , , , . In order to prevent the hardening from being impeded, it is also possible to irradiate under a blunt gas such as nitrogen. When it is hardened by ultraviolet rays, the pairing and the projection are for 2013-1037 9~pp 7 201000499 having two or more acrylonitrile groups. The polyfunctional polymerizable compound 1 〇〇 里 2: Injury should be added UV curing initiator 3 to 10 parts by weight, the amount of addition is 3 or more, and it is not easy to remain sticky after heat hardening. By adding «: 1 part by weight or less, the excessive hardening reaction can be suppressed 5 to ensure formability.

Ultraviolet-curing initiator, 屯, L, such as ··· 1 monohydroxycyclohexyl ketone, 2, 2 -dimethoxy-phenyl phenyl 7 ^ _, oxygen, ketone (xanthone), ketone , stupid formaldehyde, hydrazine, hydrazine, r茇 face ^ - this amine, azole, '3 - methyl acetophenone, 4 - wind i, a base, 4, 4' ~ -»#; «. — hurricane ·Diphenyl ketone, 4,4,monodiaminodiphenyl hydrazine, qigui 嗣, 客*弃工丁2〗 Female fragrant propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, Bu (4 1-isopropylphenyl)-2-yl-2-methylpropenylethoxyphenyl]-2-yl-yl-2-methyl-1-propan-1-one, 2-hydroxy- [4 - (2 - hydroxy - 2 - fluorenyl-propenyl) ~ benzyl] - phenyl] 2 - methyl propyl ketone, 2-hydroxy -2- 2 - 甲 - 丨 - 坌 i name, one丫1一基基丙~i-ketone, thioxanthone (th1〇xanthone), diethyl thioxanthone, 2-isopropylthioxanthone, 2 chlorothioxanthone, 2 A [4-(methylthio)phenyl]-2-yl-propan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, (2,6-decyloxybenzidine Base)_2, 4, 4-trimethylpentyl oxidized glandular sputum, inch ' ψ sold items such as irgacure 127, 184, 369, 651, 5 〇〇, 9 907, 2959 (above (manufactured by Ciba Japan) These ultraviolet curing type initiators may be used in combination of two or more kinds. Further, when the resin composition is cured by an electron beam, a ten-beam irradiation apparatus of a known mine can be used. The irradiation amount of the electron beam is 1 〇. 2〇〇kGy is preferable, and 3〇1 〇OkGy is more preferable. It is economical to reduce the load on the electronic east irradiation device by making the resin composition 201000499 hardened by being 1 or more and being 20OkGy or less. (2) Hard coating agent of the present invention

The hard coating agent of the present invention, which comprises the resin composition of the above (1). The hard coat layer formed by using the hard coat agent of the present invention has a softness which is less likely to be cracked even if it is formed in a once hardened state, and is less likely to cause stickiness. Further, the hard coat layer formed by using the hard coat agent of the present invention is excellent in hardness or scratch resistance in the state of secondary hardening. a hard coating agent of the present invention can maintain the above-mentioned (state of the resin composition of the crucible), and other components can be appropriately added. (3) Film of the present invention (film for molding) The film of the present invention is characterized by: a film substrate A hard coat layer composed of the resin composition of the above (1) is formed thereon. The film of the present invention may be, for example, a hard coat layer in a primary hardened state. The hard coat layer constituting the film of the present invention is soft. The film of the invention is not easy to cause cracks in the hard coat layer, and can be: a deep gap or a complicated structure excellent in leaf setting property. Further, the hard coat layer constituting the film of the present invention, that is, the crucible is not hardened twice, and the heart is still not easily produced. Viscosity, therefore, prevents film and mold from being hindered when the films are blocked or formed. Further, the hard coat layer after secondary hardening is excellent in hardness or scratch resistance. The film of the present invention should be higher on the hard coat layer. It has a protective layer. Even if it is in a hard servant + into &, the hard upper layer does not have sufficient hardness, it can still be hard-coated by including a protective layer, for example, when the pen is formed as a enamel film. Produce

2013-1Q379-PF 9 201000499 A protective layer such as a scratch can be formed, for example, by applying a resin dissolved or dispersed in a solvent to a hard coat layer and then volatilizing the solvent. By this, it is not possible to use the protective layer composed of the film of the adhesive or the like, and the adhesive remains on the surface of the hard coat layer. The resin used for forming the protective layer preferably has a hardness capable of protecting the hard coat layer of one person as much as possible, and has good adhesion to the hard coat layer, and does not remain on the surface when peeled off from the hard coat layer. Resin. Such a resin, such as polyvinyl alcohol (m), polyoxyethylene (10), polyvinyl alcohol denatured polyvinyl acetal resin, sodium polyacrylate, etc., a resin dispersed in a solvent, for example, vinyl acetate g The emulsion, the ethyl acetate (m) emulsion, the acrylic emulsion, the acrylic-based ethylene emulsion, the vinylidene chloride emulsion, the urethane emulsion, and the dispersion type fluororesin. Among them, polyethylene glycol is preferred. Further, in the resin forming the protective layer, a dye, a pigment, a matting agent, an antistatic agent, an antifoaming agent, a leveling agent, a tackifier, a pH adjuster, a financiating agent, a crosslinking agent, and the like may be added. The protective layer formed on the hard coat layer can be appropriately removed before the secondary hardening. Further, for example, the film of the present invention can be subjected to a release treatment on a film substrate to form a transfer film which can be transferred to a hard crucible or a hard soil layer. In this case, the hard coat layer can be transferred to the surface of other members (which can be 1 film). Release treatment, such as dream ketone treatment. The film of the present invention, for example, can be formed into a mold material and formed. The hard coat layer constituting the film of the present invention is formed even if it is formed. The film of the present invention, for example, the hard coat _ _ ^ soil layer may be deformed by active energy rays to form a two-person hardened state. In this state, 吏The hardness or scratch resistance of the soil layer is excellent. 20^3^1〇379-Pf 10 201000499. In the film, the film base is, for example, thin, poly(p-butylene dicarboxylate) & Poly-Qindicarboxylic acid B-polyethylene film, polypropylene thin bismuth, bismuth-binding film, poor sulphate, diethyl hydrazine ketone - ethyl ketone cellulose film, acetyl cellulose butyrate (tetra) membrane, film , ene film, polyvinylidene chloride film, polyethyl propylene glycol film, ethylene 虱 埽 埽: 埽 film, film, poly film, poly bis-diamine thick film, polyimide film 1 wax film An oleic acid-based resin film, etc. genus film, propylene and 'in order to improve the film substrate and resin composition, the film substrate may be smeared by sanding, and may be applied by a treatment such as a preparation process or a corona discharge. Treatment of bumps ^ ^ ^ Roller treatment, flame treatment, treatment, ozone, ultraviolet radiation The resin composition is treated on the film base surface at the hot air of the oxidation surface of the surface. The method of etching the field A + 1 cloth is not particularly limited, and: j is, for example, a gravure coating method, a smear coating method, a knife coating method, or a roll coating method. For example, the coating method is dried, and hardened, and the thickness after drying and hardening treatment is changed to 2. 2. (4) Manufacturing method of the molded body of the present invention The soil method is characterized in that: the film of the above (3) is pressed to the model y y] after the material is removed, the active hard ray is used to harden the hard coat layer twice. The hard coat layer is less prone to cracking. Moreover, the hard coat layer is less likely to be sticky even if it is not subjected to -+ 仃-_ human hardening, therefore,

2013-10379-PF 201000499 'Or a barrier to film and mold during forming. Moreover, it is excellent in hardness or scratch resistance. The hard coat layer after the secondary hardening can be prevented from being blocked by each other; and the specific example of the method for producing the film formed crucible (molded body) 6 of the present invention will be described with reference to Figs. 1 (4) to (4). First, the resin composition i is applied to the film substrate 9 (Fig. 1 (a)). At this time, the resin composition 1 is in a liquid state. Then, the resin composition i is thermally cured by heating and drying to form the hard coat layer 2, thereby obtaining a film 5 for molding (Fig. i(8)). At this time, the hard coat layer 2 is in a state in which the solid body 'is in a hardened state. Next, the film 5 for forming is pressed to a mold material (not shown), and after being released (Fig. (c)), ultraviolet rays are irradiated to harden the hard coat layer 2 to obtain a film formed body 6 (Fig. 1 (Fig. 1 d)). [Embodiment] (Best Mode for Carrying Out the Invention) An embodiment of the present invention will be described. Example 1 (a) Production of Resin Composition (Hard Coating Agent) The components shown in Tables 1 to 3 were blended to prepare the resin compositions of Examples I to W-18 and Comparative Examples 1 to 2. Further, Tables 1 to 3 show the amounts blended in terms of solid content. The resin composition is a two-part formula of the A agent and the b agent, and the A agent and the B agent are separately produced. The agent A includes the component described in the column of the agent A in Tables 1 to 3, and is a solution of 4% by weight of the solid component of MEK (anthraquinone) as a solvent. The agent B contains the components described in the column of the β agent in Tables 1 to 3, and is a solution containing a solvent as a solvent. When a resin composition is used, the tanning agent and the tanning agent are mixed at a weight ratio of 1:1. 20^3-10379-PF ι ' 201000499 In addition, when the solid content ratio of the B agent is set to be 1:1 by weight ratio of the A agent and the B agent, the compounding ratio of the resin composition is converted into solid content. ~ Table 3 shows the mix ratio. [Table 1] Example 1-1 1-2 1-3 1-4 1-5 1 - 6 1-7 A Agent polyfunctional polymerizable compound DPHA (polyfunctional monomer) 100 100 100 100 100 100 100 U- 15HA (urethane acrylate) BEAMSET371 (acrylic acrylate) ARONIX M7300K (polyester acrylate) UV initiator Irg2959 5 5 5 5 5 5 5 Coating agent BYK310 0.5 0.5 0.5 0.5 0.5 0.5 0.5 B Low molecular weight Amine DETA (diethylenetriamine) TETA (triethylenetetramine) PEHA (pentaethylenehexamine) 5 2.5 10 5 5 5 5 Polyamine POLYMENT NK-350 POLYMENT NK-380 10 10 10 5 20 10 10 Temperature sensitive touch Medium U-CAT SA 1 (DBU-phenolate) U-CAT 102 (CBU-octanoate) U-CAT 1102 (DBN-octanoate) 10 10 10 10 10 5 20 Evaluation of visual 〇〇〇〇〇〇Δ Term time (time from room temperature until gelation) >24 >24 12 >24 >24 >24 >24 Viscous finger touch (at 11 (TC drying after 3 minutes at room temperature) Determination) 4 3 5 4 5 3 5 Formability fracture resistance 〇〇〇〇〇〇〇 pencil hardness (750g negative荷) 2H (on PET) 1/5 1/5 0/5 2/5 0/5 2/5 0/5 Η (ΡΠ上) 5/5 5/5 4/5 5/5 4/5 5/ 5 3/5 2013-10379-PF 13 201000499 [Table 2] Example 1 - 8 1-9 1-10 1-11 1-12 1-13 1 - 14 1-15 A agent polyfunctional polymerizable compound DPHA ( Polyfunctional monomer) 100 100 100 100 100 100 100 100 U-15HA (Acetoacetate) BEAMSET371 (Acrylic acrylate) ARONIX M7300K (Polyester acrylate) UV starter Irg2959 5 5 5 5 5 5 5 5 Coating agent BYK310 0.5 0,5 0'5 0.5 0.5 0.5 0,5 0.5 B Agent Low molecular weight amine DETA (diethylenetriamine) δ TETA (triethylenetetramine) 5 PEHA (pentaethylene hexamine) — 5 5 5 5 δ polyamine POLYMENT NK-350 10 POLYMENT NK-380 10 — 10 10 10 10 10 Temperature sensitive catalyst U-CAT SA 1 (DBU-stupole) 10 U—CAT 102 (CBU—octanoate) 10 U-CAT 1102 (DBN-octanoate) 10 10 - 10 10 10 Evaluation Appearance Visual 〇〇〇〇〇〇〇 π Use time (time from room temperature until gelation) >24 >24 > 24 >2 4 >24 >24 >24 >24 Viscous finger touch (measured at room temperature after i) o°c drying for 3 minutes) 3 2 2 5 5 4 2 2 Formability fracture resistance〇〇〇〇 Wrong pen hardness (750g load) 2H (on PET) 2/5 3/5 2/5 0/5 0/5 1/5 1/5 1/5 H (on PET) 5/5 5/ 5 5/5 5/5 4/5 5/5 5/5 5/5

2013-10379-PF 201000499 [Table 3] / \ Example Comparative Example 1-16 1-17 1 - 18 1 2 A Agent Polyfunctional Polymerizable Compound DPHA (Polyfunctional Monomer) 100 100 U-15HA (Gas Ester C晞酸酷) 100 BEAMSET371 (acrylic acrylate) 100 ARONIX M7300K (polyester vinegar vinegar) 100 UV initiator Irg2959 5 5 5 5 5 coating agent BYK310 0.5 0. 5 0.5 0.5 0.5 B agent low molecular weight amine DETA (Diethylenetriamine) TETA (triethylenetetramine) PEHA (pentaethylenehexamine) 5 5 5 — Polyamine POLYMENT NK-350 POLYMENT NK-380 10 10 10 — Temperature sensitive catalyst U-CAT SA 1 (DBU - Streptophenolate) U-CAT 102 (CBU-octanoic acid) U-CAT 1102 (DBN-octanoate) 10 10 10 10 — Evaluate visual appearance 〇Δ 〇〇〇〇 expiration time (at room temperature until gelation) Time until) 12 2min >24 >24 >24 Viscous finger touch (measured at room temperature after litre drying for 3 minutes) 5 5 4 1 1 5 Formability fracture resistance X pencil hardness (750g load) 2Η (ΡΕΤ上) 0/5 0/5 0/5 4/5 5/5 Η ( ΡΕΤ上) 4/5 5/5 2/5 5/5 5/5 After hard hardening and hardening again, Table 1~3, U-15HA, is made by Xinzhongcun Chemical Industry Co., Ltd. Ammonia S is the trade name of the acrylic acid S. BEAMSET3 71 is the trade name of acrylic acrylate manufactured by Arakawa Chemical Industry Co., Ltd. ARONIXM7300K is the trade name of polyester acrylate made by East Asia Synthetic Co., Ltd. 2013-10379-PF 15 201000499 DPHA (diquaternium tetrahexaacrylate), hydrazine-15HA, BEAMSET371, and ARON IX Μ7300Κ each correspond to a multi-functional polymerizable compound having two or more acrylonitrile groups. Further, irg2959 is a trade name of a UV starter manufactured by Ciba Japan. BYK31 0 is the trade name of the leveling agent manufactured by BYK-Chem i e Japan Co., Ltd. Further, DETA (diethylenetriamine), TETA (triethylenetetramine), and PETA (pentaethyleneamine) each correspond to a low molecular weight amine. Further, POLYMENT M-350 and POLYMENT NK-380 are each trade names of polyamines manufactured by Japan Catalyst Co., Ltd. Also U-CAT SA is the trade name of DBU-Phenol salt produced by APR0 (shares) company. U-CAT SA 102 is the trade name of CBU-octanoate manufactured by SAN-APR0 (share). U - CAT1102, the trade name of DBN-octanoate made by SAN - APR0 (share) company. U-CAT SA1, U-CAT SA 102, and U-CAT 1102, each corresponding to a temperature sensitive catalyst. (b) Production of a film and a molded article A film of a resin composition of the above-mentioned (a) is applied to a PET film (manufactured by Toyobo Co., Ltd., trade name: COSMOSAIN A4300-188) Thick becomes 5" m. Next, the applied resin composition was dried at 11 ° C for 3 minutes (to be hardened once) to form a solid hard coat layer to obtain a film for molding. Next, the film for forming is pressed against the mold material and released. Thereafter, the ultraviolet ray irradiator was used to irradiate the ultraviolet ray at an intensity of 200 mJ/cm 2 for hard coating.

2013-10379-PF 201000499 Ultraviolet curing (secondary hardening) 'Complete the thin tantalum formed body. (C) Evaluation of resin composition and film for molding Test appearance, use period, viscosity, enthalpy, formability, and pencil hardness. The test methods and evaluation criteria are as follows. Shout (appearance) to visually observe the appearance of the film. When the coating film was transparent, it was evaluated as 〇, and if the rabbit was whitened, it was evaluated as X. Horse /. (during use) The resin composition was measured and cut while it was under the dish until it gelled. (Adhesiveness) The resin composition was applied to a PET film, and after the hour, the resin composition was touched with the index finger. Further, in Comparative Example 2, the surface grease was subjected to the test. Dry 3 at iio °c. The judgment criteria are as follows - after hardening, they are also the same

5 : Completely non-adhesive 4 : Almost non-adhesive 3 : Probably no stickiness 2 : There are some stickiness 1 : Residual stickiness (formability) The film for forming (hard coat is the state of hardening) Pressing to 'Open' with a mold, MM, 'breaking' is evaluated as 〇, and if rupture occurs, it is evaluated as X. Further, the version of the rainbow / $ was only for the comparative example 2, and for the film for forming after the secondary hardening, ψ ρη 挺, Χ was also tested. (Wrong pen hardness) For, ^ shape with enamel film (hard coat is secondary hardening state), according to JIS Κ 5400, cold >, 仃 pencil hardness test. The test was carried out in the case where the pencil hardness was 2013-10375-Pp 201000499? Further, five tests were performed on each pencil hardness. D human field, the number of times the hard coating has no scars is recorded in Table 3 above. The evaluation results are shown in Tables 1 to 3 above. As shown in Table 3, the actual appearance of the hard coat layer is: -1~b 18', and the hard coat layer in the 'hardened state' is not pure, and the film properties for forming are also For the good. Further, the hard coat layer in the secondary hardened state has high hardness. In particular, the use of low molecular weight amines and polyamines is less susceptible to stickiness than the implementation of only low molecular weight amines and polyamines. Further, the embodiment of the thermosensitive catalyst is less susceptible to stickiness than the embodiment in which the temperature sensitive catalyst is not combined. [Example 2] The same procedure as in the above-mentioned Example 1 (a) to (b) was carried out. However, in the present Example 2, a hard coat layer was formed to substantially form a thin sheet at a time. After hardening, PVA was applied to the hard coat layer to form a protective layer. Thereafter, a film formed body was formed in the same manner as in the above-described Example 1. Finally, the layer is peeled off. In the second embodiment, since the protective layer is formed on the hard coat layer, it is difficult to injure the hard coat layer due to & Further, after the protective layer was peeled off, there was no residue at all on the surface of the hard coat layer. (Example 3) A film for forming was produced in the same manner as in the above-mentioned Example 1 (a) to (b). However, in the third embodiment, a hard coat layer was formed and hardened once, and a film with an adhesive attached thereto was attached to the hard coat layer to form a protective layer. Thereafter, the foregoing Example i was obtained in the same manner to obtain a film-formed 20:3-103^&-Pf 201000499 body. Finally, the protective layer is peeled off. In the third embodiment, since the protective layer is formed on the hard coat layer, the hard coat layer is less likely to be damaged. However, after the protective layer is peeled off, a certain amount of adhesive remains on the surface of the hard coat layer. (Example 4) A film for forming was produced in substantially the same manner as in (a) to (b) of the above-mentioned Example 1. However, in the present embodiment, (4) the film substrate of the resin composition, ί uses a release PET film (manufactured by Toyobo Co., Ltd., trade name: TN110). After the release PET film is subjected to the release treatment, the layer (hard coat layer) composed of the resin composition can be easily released. The film for forming of this embodiment can be used as a transfer film. The transfer film can be used, for example, as follows. In the tongue soil, the side on which the hard main layer is formed among the film for forming is brought into contact with the side of the molding material, and the molding is performed. At this time, the hard coat layer is once hardened. Next, remove the I ^ PET film from I. At this time, the surface of the molded material is attached with a hard coat layer. The ray is irradiated with ultraviolet rays to make the hard coat layer secondary and the shape of the lotus seed of the present embodiment is p-shaped. The four-layer film can also be used for in-mold injection. It is of course possible not to deviate from the present invention. The present invention is not limited to the scope of the foregoing embodiments, and can be implemented in various aspects. [Simple description of the figure] Manufacturing method of the shape body [Explanation of main component symbols]

2013-10375-PF 201000499 1 Resin composition 2 Hard coat 5 Forming film 6 Film forming body 9 Film substrate 2013-1G3'79-PF 2 0

Claims (1)

201000499 VII, the scope of application for patents: eight. The compound of the above-mentioned polyfunctional polymerizable compound, and the compound which can be cultivated for a long time to undergo an addition reaction with an acrylonitrile group. 2. The resin composition of claim 1, wherein the compound which can be subjected to an addition reaction to a propylene sulfonate group contains an aminated character 3. The resin composition of claim 2, wherein the amine compound comprises a low molecular weight amine and a polyamine. The resin composition of any one of the items is as defined in claims 1 to 3, wherein a temperature sensitive catalyst is further included. A hard coating agent comprising the resin composition of any one of claims 1 to 4. A film comprising a hard coat layer comprising the tree test article of any one of claims 1 to 4 on the film substrate. 7. The film of claim 6, wherein the hard coat layer is in a hardened state.薄膜 8. The film of claim 6 or 7, wherein the film is further layered than the hard coat layer and has a protective layer. 9. The film of claim 8, wherein the protective layer is formed by applying a resin dissolved or dispersed in a solvent to the hard coat layer: the solvent is volatilized. The film of item 9 of the second aspect of the invention wherein the protective layer is formed of a polyvinyl alcohol. 2013-10379-PF 21 201000499 中 中 1 As in the scope of patent application No. 6 to 1 离 The film substrate is subjected to release treatment i2. If the scope of application 苐6 to II is pressed against the mold material, and formed. A thin crucible of any one of the items, and the hard coat layer can be transferred. A film according to any one of the preceding claims, wherein the film is in a secondary hardening state by the film of any one of the active energy ray according to the sixth aspect of the invention. 14. A method for manufacturing a shaped body, which is characterized in that: the enamel film of any of the items in items 6 to 11 of the application scope is pressed against the model material, and the hunting is performed by the active energy ray line. The hard coat layer is hardened twice. 2〇-3-i〇379-PF 22