JP2016221922A - Film for processing, processed film, and method for producing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for processing which enables good processing even when a hard coat film having high hardness and excellent scratch resistance is obtained, and to provide a method for producing the same.SOLUTION: There are provided a film for processing having a semi-cured film formed by semi-curing an active energy ray curable resin composition containing a photopolymerization initiator having the absorption maximum in a wavelength region of equal to or longer than 250 nm and shorter than 365 nm and a photopolymerization initiator having the absorption maximum in a wavelength region of equal to or longer than 365 nm and shorter than 410 nm on a film substrate with UV-LED having an emission peak in a wavelength region of equal to or longer than 365 nm and shorter than 410 nm; and a processed film formed by punching and/or cutting the film for processing, and then curing the semi-cured film with irradiation with light having an emission wavelength in a wavelength region of equal to or longer than 250 nm and shorter than 365 nm.SELECTED DRAWING: None

Description

  The present invention relates to a processing film used for an application requiring processing such as a scattering prevention film used for a liquid crystal panel or an organic EL display, and a processed film obtained by processing the processing film.

  In portable electronic terminals such as smartphones and mobile personal computers, hard coat films are used for the purpose of protecting the image display unit and preventing glass panels from scattering. The hard coat film used for such a portable electronic terminal is likely to be scratched, and since scratches are easily visible in the image display portion, high surface hardness and excellent scratch resistance are required.

  As a hard coat film excellent in surface hardness and scratch resistance, for example, a hard hard coat film in which a base material having a specific elastic modulus and a hard hard coat layer are combined at a specific thickness is disclosed ( Patent Document 1).

JP 2008-095064 A

  The hard coat film has a high surface hardness and scratch resistance. However, in response to a request for thinning of a member accompanying reduction in thickness of a portable electronic terminal, a request for glassless image display device, etc. The coating film is required to have higher hardness and improved scratch resistance.

  However, when the hardness of the hard coat film is further increased, cracks at the time of processing tend to occur, and cracks at the time of processing tend to be prominently generated particularly in cutting and punching of fine dimensions.

  In particular, a hard coat film used for a portable electronic terminal may be subjected to various cutting processes and punching processes such as processing into a shape corresponding to the terminal shape and formation of micro holes for transmitting and receiving audio signals. Since there are many, suppression of the crack at the time of a process is especially high request | requirement in a portable electronic terminal use.

  The present invention provides a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm on a film substrate. The above-mentioned problems are solved by a processing film having a semi-cured film obtained by semi-curing an active energy ray-curable resin composition containing a semi-cured UV-LED having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm. .

  Since the processing film of the present invention can be processed well even when a hard coat film having high hardness and excellent scratch resistance is obtained, it can be suitably applied to applications in which various types of processing are provided. . In particular, it can be suitably applied to portable electronic terminal applications and the like that are often subjected to various cutting processes and punching processes.

  General light irradiators such as halogen lamps have strong light diffusibility, and even in the normal manufacturing process where continuous production is required, even when a cut filter is used, the diffused light cannot be cut sufficiently. Therefore, when obtaining a hard coat film having high hardness and excellent scratch resistance, it may be difficult to ensure suitable workability. In contrast, the processing film of the present invention having the above-described configuration can achieve suitable processability. Further, according to the processing film and the manufacturing method of the present invention, it is preferable because it is easy to suitably control high hardness, excellent scratch resistance, and good workability, and the degree of freedom of light irradiation conditions is high. A processed film having hardness and scratch resistance can be obtained with good yield.

  The processing film of the present invention has a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm and a photopolymerization start having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm on a film substrate. It is a processing film having a semi-cured film obtained by semi-curing an active energy ray-curable resin composition containing an agent (X2) with a UV-LED having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm.

  The UV-LED having the emission peak wavelength in the long wavelength region can be cured suitable for processing the entire film by being semi-cured by curing with a photopolymerization initiator having a long wavelength absorption maximum. Polymerization by a photopolymerization initiator on the short wavelength side can be suppressed by irradiation with light having a narrow wavelength range by the UV-LED, and light having a long wavelength exceeding 410 nm can be suppressed.

  As the active energy ray-curable resin composition used in the present invention, a resin composition containing an active energy ray-curable compound that is cured by active energy rays can be used. As the active energy ray-curable compound, a compound used for a hard coating agent can be used as appropriate, and a polyfunctional (meth) acryloyl compound (A) having a (meth) acryloyl group can be preferably used.

  The polyfunctional (meth) acryloyl compound (A) is not particularly limited, but can be semi-cured (B-staged) by photopolymerization even if the concentration of the functional group curable by light is increased. As a result, it is possible to achieve both workability and scratch resistance. From such a viewpoint, the polyfunctional type (meth) acryloyl compound (A) has a double bond equivalent of 500 g / eq. The following are preferable.

  Specifically, such a polyfunctional type (meth) acryloyl compound (A) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate , Benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate , Phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxy Diethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol ( Acrylate), 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxy Propyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) ) Acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) a Mono (meth) acrylates such as acrylate, adamantyl mono (meth) acrylate;

  Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Di (meth) acrylates such as polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate Tri (meth) acrylates such as;

  Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) A tetrafunctional or more functional (meth) acrylate such as acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc. It is done.

  Among these, a trifunctional or higher functional (meth) acrylate monomer is preferable because a coating film with higher hardness can be obtained. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. Dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  As a polymerization component in the composition used in the present invention, the double bond equivalent is 500 g / eq. In addition to the following polyfunctional (meth) acryloyl compounds, epoxy (meth) acrylate and urethane (meth) acrylate are used in combination to further follow the shape of the object to be worn and punching workability. Can be improved.

  Specific examples of the epoxy (meth) acrylate used here include epoxy (meth) acrylate obtained by reacting an epoxy resin with (meth) acrylic acid or an anhydride thereof.

  The epoxy resin to be reacted with such (meth) acrylic acid or its anhydride is specifically a diglycidyl ether of a dihydric phenol such as hydroquinone or catechol; 3,3′-biphenyldiol, 4,4′-biphenyl Diglycidyl ethers of biphenol compounds such as diols; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5 -Polyglycidyl ethers of naphthol compounds such as naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, binaphthol, bis (2,7-dihydroxynaphthyl) methane; ', 4 "- Chile Gin triglycidyl ether of tris phenol; phenol novolak type epoxy resin, novolak type epoxy resins such as cresol novolak resin

  Various types such as the biphenol compound, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compound, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc. A polyglycidyl ether of a polyether-modified aromatic polyol obtained by ring-opening polymerization with a cyclic ether compound;

  Examples thereof include polyglycidyl ethers of lactone-modified aromatic polyols obtained by polycondensation of the biphenol compounds, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compounds and lactone compounds such as ε-caprolactone.

  On the other hand, examples of the urethane (meth) acrylate include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, and, if necessary, a polyol compound.

  Here, the polyisocyanate compound is, for example, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m -Aliphatic diisocyanates such as tetramethylxylylene diisocyanate;

  Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate , Aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate, and other nurate type polyisocyanate compounds having an isocyanurate ring structure in the molecule.

  Here, examples of the nurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule include those obtained by reacting various diisocyanate monomers with a monoalcohol and / or a diol. Examples of the diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and each may be used alone or in combination of two or more. Monoalcohols used in the reaction are hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n- Octadecanol, n-nonadecanol and the like can be mentioned, and the diol includes ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, Examples include 3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. These monoalcohols and diols may be used alone or in combination of two or more.

  Next, the hydroxyl group-containing (meth) acrylate compound is, specifically, the hydroxyl group-containing (meth) acrylate compound (c) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy. Butyl (meth) acrylate, neopentyl glycol mono (meth) acrylate 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate Aliphatic (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate;

(Meth) acrylic acid 4-hydroxyphenyl, (meth) acrylic acid β-hydroxyphenethyl, (meth) acrylic acid 4-hydroxyphenethyl, (meth) acrylic acid 1-phenyl-2-hydroxyethyl, (meth) acrylic acid 3 (Meth) acrylate compounds having an aromatic ring in the molecular structure such as -hydroxy-4-acetylphenyl and 2-hydroxy-3-phenoxypropyl acrylate, and other compounds obtained by adding a cyclic ester compound to the hydroxyl group-containing acryloyl group-containing compound Etc.

  Here, examples of the cyclic ester compound include γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, and 3-pentene-4-. Orido, 12-dodecanolide, γ-dodecanolactone and the like.

  Next, the polyol compound specifically includes hydroquinone, catechol, 1,4-benzenedimethanol, 3,3′-biphenyldiol, 4,4′-biphenyldiol, biphenyl-3,3′-dimethanol, Biphenyl-4,4′-dimethanol, bisphenol A, bisphenol B, bisphenol F, bisphenol S, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-naphthalenediol, binaphthol, bis (2,7 -Aromatic polyols such as dihydroxynaphthyl) methane, 4,4 ', 4 "-methylidynetrisphenol;

  Polyether modification obtained by ring-opening polymerization of the aromatic polyol and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Aromatic polyols;

  Lactone-modified aromatic polyol obtained by polycondensation of the aromatic polyol and a cyclic ester compound described later:

  An aromatic ring-containing polyester polyol obtained by reacting an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid with the aromatic polyol;

  Examples thereof include aromatic ring-containing polyester polyols obtained by reacting aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid and the like with the aliphatic polyols.

  In the active energy ray-curable resin composition used in the present invention, the active energy ray-curable compound as described above may be appropriately selected and used. In particular, the scratch resistance of the cured film when used as a processed film. When the compound (a1) having a double bond equivalent of less than 105 g / mol is 50% by mass or more and the compound (a2) having a double bond equivalent of 105 g / mol or more and 200 g / mol or less It is preferable to contain.

  As the compound (a1), for example, a compound having a double bond equivalent of less than 105 g / mol is used. The double bond equivalent is the value obtained by dividing the molecular weight of the compound by the number of moles of the double bond group (CH2 = CH-) of one molecule of the compound [molecular weight of compound / double molecule of one compound. The number of moles of the linking group] (g / mol).

  As the compound (a1), a compound having a double bond equivalent of 70 g / mol or more and less than 105 g / mol is used in order to further improve the durability such as scratch resistance of the obtained hard coat film. It is more preferable to use a material of 80 g / mol or more and less than 105 g / mol, and it is more preferable to use a material of 85 g / mol or more and 103 g / mol or less.

  Further, the compound (a1) is used in an amount of 50% by mass or more based on the total amount of the solid content of the active energy ray-curable resin composition in order to obtain a hard coat film having very excellent scratch resistance. Is preferred.

  Specifically, the compound (a1) is preferably used in the range of 50% by mass to 95% by mass with respect to the total solid content contained in the active energy ray-curable resin composition, It is more preferable to use in the range of 95% by mass, and it is particularly preferable to use in the range of 70% by mass to 95% by mass in order to obtain a hard coat film having even more excellent scratch resistance.

  As said compound (a1), the polyfunctional (meth) acrylate which is a compound which has a 3 or more (meth) acryloyl group in a molecule | numerator can be used, for example.

  Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tri (meth). ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa, etc. (meth) acrylate, it can be combined used alone or two or more.

  As the polyfunctional (meth) acrylate, in order to further improve the durability such as scratch resistance of the obtained hard coat film, as described above, one having a double bond equivalent of less than 105 g / mol should be used. It is more preferable to use a material in the range of 70 g / mol to less than 105 g / mol, more preferably 80 g / mol to less than 105 g / mol, and more preferably 85 g / mol to 103 g / mol. It is particularly preferred to use one.

  Examples of the polyfunctional (meth) acrylate having a double bond equivalent within the above range include pentaerythritol tetraacrylate (double bond equivalent: 88.0 g / mol), pentaerythritol triacrylate (double bond equivalent: 99.3 g / mol). ) Dipentaerythritol hexaacrylate (double bond equivalent: 96.3 g / mol), dipentaerythritol pentaacrylate (double bond equivalent: 102.0 g / mol), and the like. Dipentaerythritol hexaacrylate, dipentaerythritol It is preferable to use pentaacrylate.

  The compound (a1) includes a compound (a1-1) having a double bond equivalent of 100 g / mol or less, and a hydroxyl group-containing compound (a1) having a double bond equivalent of more than 100 g / mol and less than 105 g / mol. -2) is preferably used in combination in order to obtain a hard coat film having further excellent scratch resistance.

  Examples of the compound (a1-1) include pentaerythritol tetraacrylate (double bond equivalent: 88.0 g / mol), pentaerythritol triacrylate (double bond equivalent: 99.3 g / mol) dipentaerythritol hexaacrylate ( (Double bond equivalent: 96.3 g / mol) can be used, and among them, dipentaerythritol hexaacrylate (double bond equivalent: 96.3 g / mol) is preferable.

  The compound (a1-1) is preferably used in the range of 40% by mass to 80% by mass and used in the range of 40% by mass to 70% by mass with respect to the solid content of the active energy ray-curable resin composition. More preferably, it is more preferable to use in the range of 45 mass% to 70 mass%.

  Moreover, as said compound (a1-2), dipentaerythritol pentaacrylate (double bond equivalent: 102.0 g / mol) etc. can be used, for example.

  The compound (a1-2) is preferably used in a range of 10% by mass to 40% by mass and used in a range of 15% by mass to 40% by mass with respect to the solid content of the active energy ray-curable resin composition. More preferably, it is more preferably used in the range of 20% by mass to 40% by mass, and particularly preferably in the range of 20% by mass to 35% by mass in order to obtain even more excellent scratch resistance. preferable.

  Moreover, the mass ratio [(a1-1) / (a1-2)] of the compound (a1-1) and the compound (a1-2) forms a hard coat film having suitable plastic hardness. In order to further improve the durability such as scratch resistance of the hard coat layer (a1), it is preferably in the range of 50/50 to 90/10, and in the range of 55/45 to 90/10. Is more preferable, and the range of 60/40 to 90/10 is even more preferable.

  In addition, the active energy ray-curable resin composition is obtained using a hard coat agent containing a combination of the compound (a2) having a double bond equivalent of 105 g / mol to 200 g / mol together with the compound (a1). It is preferable to use the obtained hard coat layer in order to obtain a hard coat film having further excellent scratch resistance.

  As said compound (a2), it is preferable to use the compound (a2-1) which has a (meth) acryloyl group and a urethane bond, for example, It is more preferable to use various urethane (meth) acrylates, 2 in a molecule | numerator It is preferable to use urethane (meth) acrylate having at least one (meth) acryloyl group, and more preferable to use urethane (meth) acrylate having at least four (meth) acryloyl groups in the molecule. Use of urethane (meth) acrylate having 5 or more (meth) acryloyl groups inside suppresses curing shrinkage of the active energy ray-curable resin composition and is excellent in high surface hardness and durability. It is particularly preferable when forming a hard coat layer.

  In addition, as the urethane (meth) acrylate, it is easy to suppress aggregation and crystallization of the resin before coating film formation. For example, in order to easily suppress point defects related to appearance quality after coating film formation, It is preferable to use an aliphatic urethane (meth) acrylate, and it is more preferable to use a so-called chain aliphatic urethane (meth) acrylate that does not have an aromatic structure or an aliphatic cyclic structure.

  As the compound (a2-1) such as urethane (meth) acrylate, it is preferable to use a compound obtained by reacting, for example, polyisocyanate and (meth) acrylate having a hydroxyl group.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, Alicyclic polyisocyanates such as 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane can be used.

  As said polyisocyanate, the trimer of the said aliphatic polyisocyanate or alicyclic polyisocyanate can also be used.

  As the polyisocyanate, hexamethylene diisocyanate, which is an aliphatic diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, or isophorone diisocyanate can be used to obtain a hard coat film with further excellent durability such as scratch resistance. Is preferable.

  Examples of the (meth) acrylate having a hydroxyl group that can be used in the production of the compound (a2-1) include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, and propylene oxide-modified tri Methylolpropane di (meth) acrylate, glycerin di (meth) acrylate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate and the like can be used alone or in combination of two or more.

  Among them, as the (meth) acrylate having a hydroxyl group, it is possible to use pentaerythritol tri (meth) acrylate or dipentaerythritol penta (meth) acrylate, which makes the hard coat layer more excellent in durability such as scratch resistance. It is preferable when obtaining the hard coat film provided with.

  The compound (a2-1) can be produced by subjecting the polyisocyanate and the (meth) acrylate having a hydroxyl group to a urethanization reaction in the presence of a urethanization catalyst.

  Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, and dibutyltin. Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

  As the compound (a2-1) obtained by the above method, one type can be used alone, or two or more types can be used in combination.

  The compound (a2) is preferably contained in an amount of 5% by mass to 50% by mass with respect to the solid content of the active energy ray-curable resin composition, and preferably 5% by mass to 40% by mass. It is more preferable to include 5% by mass to 30% by mass in order to obtain a hard coat film having higher surface hardness and excellent durability such as scratch resistance.

  The mass ratio [(a1) / (a2)] of the compound (a1) and the compound (a2) is 95/5 to 50 / in order to further improve the durability such as scratch resistance of the cured film. It is preferably in the range of 50, more preferably in the range of 95/5 to 60/40, further preferably in the range of 95/5 to 70/30, and in the range of 90/10 to 75/25. It is particularly preferred that

  The total amount of the compound (a1) and the compound (a2) used is based on 100 parts by mass of the solid content of the active energy ray-curable resin composition in order to obtain a hard coat film having even higher scratch resistance. 70.0 parts by mass to 99.95 parts by mass, more preferably 75.0 parts by mass to 99.5 parts by mass, and 80.0 parts by mass to 99.5 parts by mass. Is more preferable.

  In addition to those described above, a mono (meth) acrylate having one (meth) acryloyl group in the molecule and two (meth) acryloyl groups in the molecule, as long as the effects of the present invention are not impaired. Those containing other (meth) acrylates such as di (meth) acrylate can be used. The amount used thereof is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less, with respect to 100 parts by mass in total of the compound (a1) and the compound (a2).

  Two active energy ray-curable compositions containing the compound (a1) and the compound (a2) contained in the active energy ray-curable resin composition and the active energy ray-curable compound that can be used as necessary. The heavy bond equivalent is preferably in the range of 95 g / mol to 500 g / mol, more preferably in the range of 95 g / mol to 300 g / mol, and in the range of 95 g / mol to 150 g / mol. It is further preferable for obtaining a hard coat film having even more excellent scratch resistance.

  Next, in the present invention, as a photopolymerization initiator, a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm. ).

  Here, as the photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2 -Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{[4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} 2-methyl-propan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-pheny -Acetoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl- [1- (methylvinyl) phenyl] propanone] can be mentioned. Among these, 1-hydroxy-cyclohexyl-phenyl ketone (IRGACURE 184, manufactured by BASF Japan Ltd.), oligo [2-hydroxy-2-methyl- [1- (methylvinyl) phenyl] propanone] is particularly preferable from the viewpoint of surface curability. (ESACURE ONE manufactured by Lamberti) is preferable.

  Examples of the photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, ethoxy (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -One, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzo Ruokishimu)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1- (O-acetyl oxime), and the like. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) is particularly preferable from the viewpoint of coating film transparency and curability.

  Here, the blending ratio of these photopolymerization initiators is 1 to 20 masses of the photopolymerization initiator (X1) with respect to 100 mass parts of the active energy beam curable compound contained in the active energy beam curable resin composition. Part, more preferably 5 to 20 parts by mass, and the photopolymerization initiator (X2) is blended in the range of 0.01 to 20 parts by mass, more preferably 0.01 to 15 parts by mass from the viewpoint of curability. preferable.

  The active energy ray-curable resin composition used in the present invention may contain various photosensitizers in addition to the photopolymerization initiator (X1) and the photopolymerization initiator (X2). Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles or other nitrogen-containing compounds, and these can be used alone or in two types. You may use the above together. The addition amount in the case of adding these photosensitizers is in the range of 0.01 to 25 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound contained in the active energy ray-curable resin composition. Is preferred.

  The active energy ray-curable resin composition used in the present invention may contain various other additives as necessary. Examples of various additives include organic solvents, colorants, slip agents, and the like.

  The organic solvent usually has a boiling point of 50 to 180 ° C., because it has good workability at the time of coating and is quick to dry before curing. For example, methanol, isopropyl alcohol, n-butanol, isobutanol, etc. Alcohol solvents; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone An aromatic solvent such as toluene and xylene. The organic solvent may be used alone or in combination of two or more. Although the usage-amount of an organic solvent is not specifically limited, Usually, it is the range from which the solid content concentration of a coating agent will be 5-70 weight%.

  The colorant is not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments described in the Paint Raw Materials Handbook 1970 edition (edited by the Japan Paint Industry Association) Organic pigments and inorganic pigments such as green pigments, blue pigments, purple pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. A single colorant may be used, or two or more colorants may be used in combination.

  Further, when a slip agent is contained, for example, the surface of the processing film is roughened, so that the processing film can be easily wound and blocking is difficult to occur. In addition, resistance to rubbing and scratching can be increased. Examples of the slip agent include waxes such as polyethylene wax, paraffin wax, synthetic wax and montan wax, and synthetic resins such as silicone and fluorine. The slip agent is sufficient for preventing blocking and frictional scratch resistance, and for ensuring the transparency of the processing film. The slip agent is 0 with respect to 100 parts by mass of the solid content in the coating agent used in the present invention. It is preferable that it is 0.01-15 mass parts, and it is especially preferable that it is 0.03-6 mass parts.

  Moreover, in order to improve the surface hardness of the cured film obtained, you may contain an inorganic particle. As the inorganic particles, inorganic particles such as silica, zirconia, titania, barium titanate, ITO, and ATO can be used. Among these, silica particles are preferable for obtaining excellent transparency and dispersibility.

  The average particle diameter of the silica particles that are the primary particles constituting the silica particles is preferably in the range of 1 to 50 nm. However, since higher packing can be realized without impairing transparency, the range of 1 to 40 nm is more preferable. The range of 1 to 20 nm is more preferable. In addition, the average particle diameter of the silica particle which is a primary particle is calculated | required from the result observed with the transmission electron microscope.

  As the silica particles, for example, those produced by a wet method can be used. Moreover, although the precipitation method and the gel method are known as a wet method, the silica particle manufactured by any method can be used. Furthermore, in order to obtain silica particles having a primary average particle size of the size used in the present invention, reaction conditions (pH) of sodium silicate, which is a raw material of silica particles, and mineral acid such as sulfuric acid are used for both precipitation and gel methods. , Adjusting raw material concentration, reaction temperature, etc.).

  In order to suitably disperse the silica particles in the active energy curable resin composition, the surface of the silica particles is preferably modified with an organic group. As a surface treatment agent when modifying with an organic group, a silane compound or a silazane compound, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, Hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisiloxane, trimethylmethoxysilane, ethyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane, Acryloxypropyl methoxysilane, metalloxypropyl methoxysilane, and methoxysilane-terminated perfluoropolyether “Dow Corning 2” 634 Coating ”(manufactured by Dow Corning Toray),“ Fluorolink S10 ”(manufactured by Solvay Solexis), which is a perfluoropolyether having an ethoxysilane terminal, and the like.

  The apparatus used for dispersing the silica particles includes a ball mill, a bead mill, a rod mill, a SAG mill, a high-pressure pulverizing roll, a vertical axis impactor (VSI) mill, a colloid mill, a conical mill, a disk mill, an edge mill, a hammer mill, a mortar, and a jet mill. Etc.

  As the active energy ray-curable resin composition, various antifouling agents can be used for the purpose of imparting slipperiness and contamination resistance on the surface of the obtained hard coat film.

  As the antifouling agent, conventionally known ones can be used, but in order to further improve the slipperiness and contamination resistance of the surface of the obtained hard coat film, an active energy ray-curable compound having a fluorine atom and a silicon atom. An antifouling agent containing can be used.

  As the active energy ray-curable compound having a fluorine atom and a silicon atom, for example, a compound having a fluorine atom and a silicon atom among compounds having a fluorocarbon chain, a siloxane chain, or a hydrocarbon chain may be used. it can.

  Specifically, it is preferable to use those having a poly (perfluoroalkylene ether) chain as the fluorocarbon chain and having a cyclopolysiloxane structure, and divalent at both ends of the poly (perfluoroalkylene ether) chain. It is preferable to use a compound having a structure in which a cyclopolysiloxane structure is bonded via a linking group, and a (meth) acryloyl group is bonded to the cyclopolysiloxane structure via a divalent linking group.

  The active energy ray-curable compound having a fluorine atom and a silicon atom is preferably contained in a range of 0.05 to 5% by mass in the active energy ray-curable compound contained in the active energy ray-curable resin composition. It is more preferable that it is contained in the range of 0.1 to 2% by mass in order to achieve both more excellent surface hardness and antifouling property.

  The active energy ray-curable compound used in the present invention is preferably in the range of 0.5 to 500 mPa · s in terms of coating suitability.

The processing film of the present invention is
(1) On a film substrate, a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm, and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm. A step of applying an active energy ray-curable resin composition to be contained on a film substrate;
(2) The active energy ray-curable resin composition applied on the film substrate is irradiated with UV-LED light having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm to be semi-cured on the film substrate. Forming a film;
It can obtain with the manufacturing method of the film for processing which has this.

  Methods for applying the active energy ray-curable resin composition to the film substrate include gravure coating, roll coating, spray coating, lip coating, comma coating and other coating methods, gravure printing, screen printing, etc. The printing method etc. are mentioned.

  After applying an active energy ray-curable resin composition to a film substrate, a semi-cured film is formed by irradiating LED-UV light having a specific light emission wavelength region to obtain a desired processing film. it can. In this invention, the semi-hardened film | membrane which the said photoinitiator (X2) selectively reacted by irradiation of LED-UV light which has this specific light emission wavelength range can be obtained. Therefore, it is possible to form a processing film in which the unreacted photopolymerization initiator (X1) is present in the semi-cured film.

  Here, as the irradiation condition of LED-UV light, the absorbance of the photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm is extremely close to zero, and the absorbance at both 365 nm is in a wavelength region where the absorbance is significantly different. Examples include conditions having a light source having an emission peak.

In the case of semi-curing, the integrated exposure amount of UV-LED light having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm is preferably 100 to 700 mJ / cm ² , and more preferably 200 to 500 mJ / cm ^3. preferable.

  In the case of forming a semi-cured film by irradiating the ultraviolet ray, the irradiation with the ultraviolet ray is preferably performed in an inert gas atmosphere such as nitrogen gas in order to suppress oxygen inhibition of radical polymerization.

  Moreover, it is preferable that the water contact angle of the semi-hardened film | membrane surface of a film for processing is less than 70 degrees, It is more preferable that it is 50-68 degrees, It is further more preferable that it is 55-65 degrees. By irradiating the UV-LED light so that the contact angle falls within the range, it is possible to realize a suitable workability that is tack-free and is not easily cracked or cracked.

  The water contact angle is the water contact angle on the surface of the semi-cured film of the active energy ray curable composition to be used. In the active energy ray curable composition, additives such as slip agents and antifouling agents are used. Is a water contact angle of a semi-cured film formed using a composition excluding these additives. The composition excluding the additive is a composition containing an active energy ray-curable compound and a polymerization initiator when forming a semi-cured film, and has a (meth) acryloyl group as the active energy ray-curable compound. When a polyfunctional type (meth) acryloyl compound is used, it is a composition comprising the polyfunctional type (meth) acryloyl compound having the (meth) acryloyl group and a polymerization initiator. The polyfunctional type (meth) acryloyl compound does not include so-called additives such as a reactive antifouling agent having a fluorine atom or a silicon atom.

In the present invention, by setting the cured state of the semi-cured film to the cured state having the water contact angle, it is possible to realize a processed film with suitable processability that is tack-free and is not easily cracked or cracked. The cured state can be evaluated using IR (infrared spectroscopy). The cured state is 1640-1620 cm ⁻¹ vinyl group C═C stretching vibration band, 1430-1400 cm ⁻¹ vinyl group CH in-plane variable bending vibration band of IR spectrum before and after reaction, 820-800 cm ⁻¹ vinyl group CH. The intensity ratio of the out-of-plane variable vibration band can be evaluated.

  As an application of the processing film described above, the film itself can be used for processing that requires processing such as molding or punching, such as protection of liquid crystal panels and glass screen panels of organic EL displays, etc. Examples thereof include a hard coat film used for preventing scattering, or a transfer material for a decorative sheet of a molded product such as plastic or metal.

  Although it can select suitably as a film base material by the use of the film for a process, a resin film, metal foil, etc. are mentioned, for example. When used as a hard coat film, a resin film can be suitably used. For example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane film, diacetyl cellulose film, triacetyl cellulose film Acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, Polyethersulfone film, polyetherimide film, poly Imide film, fluororesin film, nylon film, it is possible to use an acrylic resin film or the like.

  As the base material, it is preferable to use a material having an elastic modulus in the range of 3 GPa to 15 GPa from the viewpoint of easily suppressing warpage of the processing film and effectively suppressing a decrease in surface hardness. It is more preferable to use those having an elastic modulus in the range of ˜12 GPa, and it is more preferable to use those having an elastic modulus in the range of 3 GPa to 10 GPa. In addition, since the hard coat film obtained using the base material having the elastic modulus in the above range is relatively flexible, the hard coat film is applied to the adherend having a gentle curved surface portion or the like, for example. Since it can stick along a part, it is preferable.

  As the base material, it is preferable to use a highly transparent material even when the hard coat film is installed on the surface of a display of an information display device, because good visibility can be secured. The total light transmittance of the substrate is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more.

  As said base material, what was provided with the primer layer can be used for the purpose of improving the adhesiveness with the semi-hardened film and cured film of an active energy ray curable resin composition further.

  In addition, as the base material, a sand blast is used for the purpose of further improving the adhesion with a semi-cured film or a cured film of the active energy ray-curable resin composition, or another arbitrary layer such as an adhesive layer. Surface treatments such as surface unevenness treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment, etc. may be used. it can.

  As said base material, the resin film containing an antistatic agent etc. can be used among the said resin films.

  Examples of the antistatic agent include nonoxypolyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, Examples include fatty acid glycerin ester and alkyl polyethyleneimine. Examples of the cationic system include alkylamine salts, alkyl quaternary ammonium salts, and alkyl imidazoline derivatives. An acrylate compound having ethylene oxide as a skeleton can also be used. Polyaniline, polypyrrole, polythiophene, poly3,4-ethylenedioxythiophene, and derivatives thereof can be used as the conductive polymer. As the metal oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, antimony suboxide, or the like can be used. In addition, an ion conduction type antistatic agent in which metal ions such as lithium ions are mixed can also be used.

  The base film used in the film of the present invention may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 μm. Moreover, what is necessary is just to use the thing of suitable thickness suitably according to the purpose to use. For example, in order to obtain suitable processability while suppressing warpage, it is preferable to use a substrate in the range of 20 to 300 um.

  The material of the base film is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate; a polyolefin resin such as polypropylene, polyethylene, or polymethylpentene-1. Cellulose acetates such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc .; acrylics such as polymethyl methacrylate Resin; Vinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Polystyrene Polyamide; Polycarbonate; Polysulfone; Polyethersulfone; Polyetheretherketone; Polyimide resin such as polyimide and polyetherimide; Norbornene resin (for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin (for example, (“Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Appel” manufactured by Mitsui Chemicals, Inc.), etc. Further, a laminate of two or more substrates made of these resins is used. You may use.

  The phase composed of the active energy ray-curable composition formed on one side or both sides of the substrate is preferably in the range of 3 μm to 100 μm in thickness, and more preferably in the range of 8 μm to 80 μm in thickness. In the range of 8 μm to 60 μm, it is possible to suppress deterioration of characteristics such as surface hardness of the processed film without causing excessive warpage of the processing film and the processed film.

The processed film of the present invention is further subjected to the above steps,
(3) A step of stamping and / or cutting a film substrate on which a semi-cured film is formed, and then irradiating light having an emission wavelength in a wavelength region of 250 nm or more and less than 365 nm to cure the semi-cured film,
By passing through, it can be set as the hard coat film (processed film) by which the process was given.

  According to the production method of the present invention, it is possible to obtain a processed film that is suitably processed without cracking, chipping, or cracking even by punching and / or cutting.

  When curing a semi-cured film, a device that irradiates various active energy rays can be used. For example, in the case of ultraviolet rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless source Examples include lamps (fusion lamps), chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, and LEDs.

  When the semi-cured film is further cured by irradiating with the ultraviolet rays, the irradiation with the ultraviolet rays is preferably performed in an inert gas atmosphere such as nitrogen gas in order to suppress oxygen inhibition of radical polymerization.

  In addition to the irradiation of the active energy ray, if heating or the like can be performed, the active energy ray may be irradiated after the irradiation if necessary, and the active energy ray may be irradiated after the heating. May be.

  The processed film preferably has a total thickness of 135 μm to 400 μm, more preferably a thickness of 150 μm to 350 μm, and a thickness of 150 μm to 300 μm. However, it is preferable because it is possible to achieve both a level of scratch resistance that can prevent the polarizing plate and the like from being damaged, and a reduction in thickness and weight of a final product such as a portable electronic terminal.

  As the processed film, it is preferable to use a film having a surface hardness of 2H or more, preferably a hard coat layer constituting the film, and to use a film having a hardness of 3H or more to the processed film. Even if it is a case where it laminates | stacks and it is a case where it is a processed film with an adhesive layer, since the fall of the surface hardness can be suppressed, it is preferable.

  Moreover, as a processed film of this invention, what provided the adhesive layer on the single side | surface can be used. As the pressure-sensitive adhesive layer, it is preferable to use a layer having a suitable adhesive force and excellent in transparency.

  The pressure-sensitive adhesive layer preferably has a thickness in the range of 5 μm to 150 μm, more preferably has a thickness in the range of 10 μm to 100 μm, more preferably in the range of 15 μm to 50 μm. It is preferable to use a material having a thickness because it can contribute to a reduction in thickness while having a suitable adhesive force.

  By making the total thickness of the processed film with an adhesive layer 600 μm or less, preferably 180 to 300 μm, it is possible to suitably perform punching even in the fine processing.

  Since the processing film detailed above is excellent in fine workability, the resulting processed film with an adhesive layer is a fine hole for a speaker or a microphone terminal, in particular, a minimum width of 3 mm or less, preferably several millimeters of about 1 to 3 mm. The punching process of the order becomes possible, and it can be suitably applied to the screen panel use of a portable electronic terminal that requires fine processing.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these.

(Synthesis Example 1: Synthesis of urethane acrylate (A1))
In a flask equipped with a stirrer, a gas introduction tube, a condenser and a thermometer, Aronix M-403 [manufactured by Toa Gosei Co., Ltd., dipentaerythritol hexaacrylate (hereinafter abbreviated as DP6A) and dipentaerythritol pentaacrylate (hereinafter, Abbreviated as DP5A), DP6A / DP5A (mass ratio) = 45/55, hydroxyl value 99 mg KOH / g] 1309 parts by mass, dibutyltin diacetate 0.3 part by mass, Sumilizer BHT [manufactured by Sumitomo Chemical Co., Ltd., Antioxidant] 4.48 parts by mass and methoquinone [manufactured by Seiko Chemical Co., Ltd., polymerization inhibitor] 0.45 parts by mass were added, and the temperature was gradually raised while uniformly mixing.

When the temperature in the flask reached 60 ° C., 184.8 parts by mass of Desmodur H (manufactured by Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate) was added, followed by reaction at 80 ° C. for 5 hours. 1493.8 parts by weight of a mixture of urethane acrylate and DP6A (urethane acrylate / DP6A (mass ratio) = 61/39, solid content: 100% by mass) by reacting until the infrared absorption spectrum of 2250 cm ⁻¹ shown disappears Obtained.

[Adjustment of coating agent (1)]
100 parts by mass of dipentaerythritol hexaacrylate (“DPHA” manufactured by Toa Gosei Co., Ltd., containing 35% by mass of dipentaerythritol pentaacrylate; hereinafter abbreviated as “DPHA”), photopolymerization initiator (“BASF Japan Co., Ltd.” "Irgacure 184D", 1-hydroxycyclohexyl phenyl ketone; hereinafter abbreviated as "Irg.184D") 10 parts by mass, photopolymerization initiator ("Darocur TPO" manufactured by BASF Japan Ltd., 2,4,6-trimethylbenzoyl) -Diphenyl-phosphine oxide; hereinafter abbreviated as "TPO") 0.5 parts by mass was uniformly stirred and then diluted with methyl ethyl ketone to prepare a coating agent (1) having a nonvolatile content of 50% by mass.

[Adjustment of coating agent (2)]
80 parts by mass of dipentaerythritol hexaacrylate (“DPHA” manufactured by Toa Gosei Co., Ltd., 35% by mass of dipentaerythritol pentaacrylate; hereinafter abbreviated as “DPHA”), urethane acrylate obtained in Synthesis Example 1 (A1 ) 20 parts by mass, photopolymerization initiator (“Irgacure 184D” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone; hereinafter abbreviated as “Irg.184D”), 10 parts by mass, photopolymerization initiator (BASF Japan) “Darocur TPO” manufactured by Co., Ltd., 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; hereinafter abbreviated as “TPO”) After 0.5 parts by mass is uniformly stirred, it is diluted with methyl ethyl ketone. Preparation of coating agent (2) with 50% non-volatile content It was.

Example 1
An HC film was applied using the prepared coating agent (1). Specifically, a polyester resin film having a thickness of 38 μm was used as the base sheet, and the composition (1) was applied on the film so as to have a thickness of 20 μm. Then, the film which has a semi-hardened (B-staging) film | membrane was obtained by irradiating with an ultraviolet-ray. Ultraviolet rays irradiate the coating film with an LED irradiation device (LED irradiation device manufactured by CCS, HLDL-100X90V0-PSC, emission peak wavelength 405 nm) so that the integrated light intensity is 400 mJ / cm ² at an irradiation intensity of 67 mW / cm ^2. did.

(Example 2)
A film having a semi-cured (B-staged) film was obtained in the same manner as in Example 1 except that the coating agent (2) was used instead of the coating agent (1).

(Comparative Example 1)
Semi-cured (B-staged) in the same manner as in Example 1, except that a metal halide lamp was used instead of the LED, and the irradiation intensity was 67 mW / cm ² and the integrated light quantity was 400 mJ / cm ² . ) A film having a membrane was obtained.

(Comparative Example 2)
Semi-cured (B-stage) in the same manner as in Example 2 except that a metal halide lamp was used instead of the LED, and the irradiation intensity was 67 mW / cm ² and the integrated light quantity was 400 mJ / cm ^2. A film having a membrane was obtained.

  The following evaluation was performed about the film obtained by the said Example and comparative example. The results obtained are as shown in the table below.

[Adhesion evaluation]
The semi-cured film surface of the obtained film was folded outward, and the degree of peeling of the coating film when a crack occurred on the semi-cured film surface was evaluated.
○: No peeling ×: With peeling

[Flexibility evaluation]
The semi-cured film surface of the obtained film was folded outward, the diameter of the folded film when a crack occurred on the semi-cured film surface was read and evaluated by the numerical value.

[Appearance evaluation]
The appearance of the semi-cured film of the obtained film was visually evaluated.
○: Wrinkle hole ×: Wrinkle

[Curl evaluation]
The semi-cured film surface of the obtained film was cut to a size of 3 cm × 3 cm with a cutter, and the average value of the heights of the four corners when placed on a horizontal measuring table was measured.

[Cutability evaluation]
The surface of the semi-cured film was cut onto a cloth with a cutter on the surface of the semi-cured film of the obtained film, and the degree of peeling of the cut surface was evaluated by visual observation.
○: No peeling ×: With peeling

[Measurement of water contact angle]
A sample obtained by cutting the obtained film into a 1 × 5 cm rectangle and fixing it to a glass plate with double-sided tape with the semi-cured film facing up is placed on the stage of an automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd. Then, the contact angle after 1 second was measured after 4 to 4.5 μL of purified water was deposited. The average of the values obtained by repeating this operation five times was taken as the value of the water contact angle.

  As shown in the above table, the processing film of the present invention had suitable processability. Moreover, the film which the hardness of the Martens hardness of a cured film has a hardness of 250 Mpa or more was obtained by irradiating the processing film of Examples 1-2 with ultraviolet rays and making it harden | cure. On the other hand, the film of the comparative example was inferior in workability.

Claims (7)

  An activity containing a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm on a film substrate. A processing film comprising a semi-cured film obtained by semi-curing an energy ray-curable resin composition with a UV-LED having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm.   The processing film according to claim 1, wherein a water contact angle on the surface of the semi-cured film is 70 ° or less. Processing film according to claim 1 or 2 integrated exposure amount of UV-LED is 100~700mJ / cm ^2.   4. A processed film obtained by stamping and / or cutting the processing film according to claim 1 and then curing the semi-cured film by light irradiation having an emission wavelength in a wavelength region of 250 nm or more and less than 365 nm. (1) On a film substrate, a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm, and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm. A step of applying an active energy ray-curable resin composition to be contained on a film substrate;
(2) The active energy ray-curable resin composition applied on the film substrate is irradiated with UV-LED light having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm to be semi-cured on the film substrate. Forming a film;
The manufacturing method of the film for processing characterized by having. The method for producing a processing film according to claim 5, wherein an integrated exposure amount of the UV-LED light is 100 to 700 mJ / cm ² . (1) On a film substrate, a photopolymerization initiator (X1) having an absorption maximum in a wavelength region of 250 nm or more and less than 365 nm, and a photopolymerization initiator (X2) having an absorption maximum in a wavelength region of 365 nm or more and less than 410 nm. A step of applying an active energy ray-curable resin composition to be contained on a film substrate;
(2) The active energy ray-curable resin composition applied on the film substrate is irradiated with UV-LED light having an emission peak wavelength in a wavelength region of 365 nm or more and less than 410 nm,
Forming a semi-cured film on the film substrate;
(3) A step of stamping and / or cutting a film substrate on which a semi-cured film is formed, and then irradiating light having an emission wavelength in a wavelength region of 250 nm or more and less than 365 nm to cure the semi-cured film,
A process for producing a processed film, comprising: