WO2006115085A1 - Composition de resine durcissable par un rayon actinique et articles et moulages fabriques a partir de celle-ci - Google Patents

Composition de resine durcissable par un rayon actinique et articles et moulages fabriques a partir de celle-ci Download PDF

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Publication number
WO2006115085A1
WO2006115085A1 PCT/JP2006/307913 JP2006307913W WO2006115085A1 WO 2006115085 A1 WO2006115085 A1 WO 2006115085A1 JP 2006307913 W JP2006307913 W JP 2006307913W WO 2006115085 A1 WO2006115085 A1 WO 2006115085A1
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Prior art keywords
meth
mass
resin composition
parts
active energy
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PCT/JP2006/307913
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English (en)
Japanese (ja)
Inventor
Naoto Kidokoro
Nobuyuki Koike
Shigetoshi Nishizawa
Toshiyuki Kiyonari
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Dainippon Ink And Chemicals, Inc.
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Publication of WO2006115085A1 publication Critical patent/WO2006115085A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to an active energy ray-curable resin composition that can be used as a protective layer of an article and forms a high-hardness cured film.
  • Sarakuko relates to an article having a cured film of the composition and a molded article comprising a cured product of the resin composition.
  • An article is affected by the contact between the articles, contact with other articles, or the environment in which the article is placed, and external changes such as damage or deformation and the materials constituting the article deteriorate. Undergo internal changes.
  • a protective layer is provided on the surface of the article or the article itself is strengthened.
  • Plastics are used in various fields for reasons such as good workability, light weight, and low cost. However, while the processability is good, there is a problem that the soft surface is easily scratched. In order to solve this problem, a method of providing a protective layer by coating a hard coat material on the surface is generally used.
  • Thermosetting resin compositions such as silicon-based resin compositions, acrylic resin compositions, and melamine-based resin compositions have been used as this hard coat material. Due to its long length, there was a problem that it could not be applied to articles such as plastic films that are vulnerable to heat.
  • active energy ray-curable resin compositions have advantages such as (1) fast curing, (2) low energy cost, and (3) curing at low temperatures. It is rapidly adopted as a hard coat material.
  • a hard coating material for film it is hardened immediately upon irradiation with an active energy ray such as an ultraviolet ray to form a hard coating, so it has excellent hardness, scratch resistance, stain resistance, etc. Because it can be processed continuously, it has become mainstream.
  • a transfer method in which a protective layer is used as a protective layer, and the protective layer becomes the outermost layer of the article after transfer.
  • This transfer method is used for articles in the field of home appliances, automobiles, etc., and is used in the outer panel of refrigerators and mobile phone casings.
  • the active energy ray-curable resin composition can also be used for the protective layer provided on this transfer material, but since it is used by an unspecified number of consumers, it requires higher hardness and higher scratch resistance, and In order to improve the workability at the time of transfer, the curl of the transfer material is required to be small.
  • the active energy ray resin composition is immediately cured by irradiation with an active energy ray such as ultraviolet rays to form a hard film
  • the active energy ray resin composition is in contact with the mold.
  • an optical sheet such as a Fresnel lens sheet is manufactured by this method.
  • higher hardness and higher scratch resistance are required, and in order to improve workability, there is a need for an active energy ray-curable resin composition that has a low curing shrinkage and curling of the cured coating. Yes.
  • an active energy ray-curable resin composition having high, hardness, high, and scratch resistance, radiation curable polyfunctional (meta) having at least two (meth) attaloyl groups and hydroxyl groups in one molecule.
  • Radiation curable resin composition containing a polyfunctional urethane atreate obtained by reacting acrylate and polyisocyanate see, for example, Patent Document 1
  • a polyol having a condensed polycyclic structure and a polyisothene see, for example, Patent Document 1
  • an active energy ray-curable coating composition which contains urethane acrylate resin consisting of cyanate and a compound having a hydroxyl group and a (meth) atalyloyl group as an essential component.
  • these active energy ray-curable resin compositions have small cure shrinkage but low hardness or increase hardness. Therefore, when polyfunctional acrylate dipentaerythritol is added to oxalate, etc., cure shrinkage is reduced. There was a problem of getting bigger.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-113648
  • Patent Document 2 JP 2002-212500 A
  • Patent Document 3 Japanese Patent Laid-Open No. 9-290491
  • the problem to be solved by the present invention is that an active film capable of obtaining a cured film having a small curing shrinkage force S, a high hardness, and a high scratch resistance when cured by irradiation with active energy rays such as ultraviolet rays. It is to provide an energy ray curable resin composition, an article having a protective layer made of the cured film, and a molded article made of a cured product of the resin composition.
  • the present invention relates to a urethane alkoxide which is an addition reaction product of polyisocyanate (al) and acrylate (a2) having one hydroxyl group and two or more (meth) taroloyl groups in one molecule.
  • Relate (A) and a (meth) atalylate polymer (bl) having a reactive functional group in the side chain have a functional group capable of reacting with the reactive functional group (X, ⁇ unsaturated compound ( an active energy one-line curable resin composition comprising a polymer (B) reacted with (2) and reacted with (2), and an article having a protective layer made of the cured film.
  • the present invention provides a molded article made of a cured product of the resin composition.
  • the active energy ray-curable resin composition of the present invention has an active energy such as ultraviolet rays.
  • an active energy such as ultraviolet rays.
  • a cured film having a curing shrinkage, a high hardness, and a high scratch resistance can be obtained, which is useful as a protective layer for a film.
  • the curing shrinkage is small, curling can be suppressed even in a large film, and it is suitable as a material for a protective layer for an optical film of a large screen display such as a liquid crystal display.
  • the protective layer can also be used as a protective layer for plastic articles such as home appliances and mobile phone casings.
  • the protective layer can also be applied to a method of forming by a transfer method in which the protective layer is prepared as a transfer material and then transferred to become the outermost layer of the plastic article.
  • a molded article comprising the cured product of the active energy ray-curable resin composition of the present invention by curing the active energy beam-curable resin composition of the present invention while being in contact with the mold.
  • This molded body can be used as an optical sheet such as a Fresnel lens.
  • polyisocyanate (al) used in the present invention examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4, 4 , 1-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4, 4-diphenylmethane diisocyanate, etc .; dicyclohexylmethane diisocyanate, isophorone diisocyanate Isocyanate groups bonded to alicyclic hydrocarbons such as cyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenol diisocyanate, 1,4-cyclohexane diisocyanate, etc.
  • alicyclic diisocyanate Compound having two (hereinafter abbreviated as alicyclic diisocyanate); trimethylene diisocyanate, hexamethylene diisocyanate Aliphatic compound having two Isoshianeto groups combined binding hydrocarbon (hereinafter, referred to as aliphatic Jiisoshianeto.) And the like. These polyisocyanates can be used alone or in combination of two or more.
  • polyisocyanates al
  • isophorone diisocyanate norbornane diisocyanate
  • hydrogenated xylylene diisocyanate among which aliphatic diisocyanate or alicyclic diisocyanate are preferred.
  • Hydrogenated methylene bisphenol diisocyanate and hexamethylene diisocyanate are preferred.
  • norbornane diisocyanate Nate is most preferred.
  • Examples of the attalylate (a2) having one hydroxyl group and two or more (meth) atalyloyl groups in one molecule used in the present invention include, for example, trimethylolpropane di (meth) acrylate and pentaerythritol tris.
  • polyatalylates of polyhydric hydroxyl group-containing compounds such as (meth) acrylate and dipentaerythritol penta (meth) acrylate, and adducts of these poly acrylates with ⁇ -force prolatatone, Examples include adducts of these polyacrylates and alkylene oxides, and epoxy acrylates.
  • talates (a2) can be used alone or in combination of two or more.
  • “(meth) acrylate” refers to one or both of metatalylate and acrylate, and the same applies to “(meth) atalyloyl group” and “(meth) acrylic acid”. is there.
  • acrylates (a2) acrylates having one hydroxyl group and three to five (meth) taroloyl groups in one molecule are preferred.
  • examples of such acrylates include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and these are particularly preferred because a hard coating film can be obtained.
  • the urethane acrylate (A) used in the present invention can be obtained by subjecting two components of the polyisocyanate (al) and the acrylate (a2) to an addition reaction.
  • the ratio of the acrylate (a2) to 1 equivalent of isocyanate in the polyisocyanate (al) is usually preferably 0.1 to 50 force, more preferably 0.1 to 10 as the hydroxyl equivalent. 2 is more preferred.
  • the reaction temperature between the polyisocyanate (al) and the attalylate (a2) is preferably 30 to 150 ° C, more preferably 50 to 100 ° C.
  • the end point of the reaction for example, can be confirmed by determining loss and the infrared absorption spectrum of 2250 cm _1 showing a Isoshiane one bets group, a Isoshianeto group content by the method described in JIS K 7301- 1995.
  • a catalyst can be used for the purpose of shortening the reaction time.
  • the catalyst include basic catalysts (amines such as pyridine, pyrrole, triethylamine, jetyramine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine) and acidic catalysts (copper naphthenate, cobalt naphthenate).
  • Naphthenic acid dumbbell tributoxyaluminum, tetrabutoxytrititanium, tetrabutoxyzirconium and other metal alkoxides, aluminum chloride and other Lewis acids, dibutyl Tin compounds such as tin dilaurate and dibutyltin diacetate).
  • an acidic catalyst is preferred, and a tin compound is most preferred.
  • Catalyst is polyisocyanate
  • the molecular weight of the urethane acrylate (A) is preferably in the range of 500 to 1,500. When the molecular weight is within this range, a cured film having a sufficiently high hardness can be obtained and the curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced.
  • the blending amount of the urethane acrylate (A) in 100 parts by weight of the total amount of the resin components in the resin composition is preferably 5 to 90 parts by weight, and more preferably 10 to 70 parts by weight. 10 to 60 parts by mass Force S is more preferable. If the blending amount of urethane acrylate (A) is within this range, a cured film having a sufficiently high hardness can be obtained, and curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced. .
  • the reactive functional group of the (meth) acrylate polymer (bl) having a reactive functional group in the side chain used in the present invention is preferably a hydroxyl group, a carboxyl group, an epoxy group or the like.
  • the functional groups that can react with these reactive functional groups (X, ⁇ unsaturated compounds (b2) include isocyanate groups, carboxyl groups, acid halide groups, hydroxyl groups, epoxy groups, etc.
  • a ( ⁇ ) unsaturated compound (b2) having a functional group capable of reacting with the reactive functional group is added to the (meth) acrylate polymer (bl) having a reactive functional group in the side chain.
  • the method for producing the polymer (B) having a reacted (meth) atallyloyl group can be produced by any conventional known method without any particular limitation. For example, the following production methods (1) to (3 ).
  • (meth) acrylate polymer (bl) As the (meth) acrylate polymer (bl), a (meth) acrylate polymer or copolymer having a hydroxyl group as a reactive functional group in the side chain is used, and a part of the hydroxyl group is used. In all, a, j8-unsaturated compound (b2) is reacted with (meth) acryloylethyl isocyanate, (meth) acrylic acid, (meth) acrylic acid chloride, etc. How to introduce.
  • (meth) acrylate polymer (bl) a (meth) acrylate polymer or copolymer having a carboxyl group as a reactive functional group in the side chain is used. All, a, j8-unsaturated compound (b2) is reacted with an acrylate containing a hydroxyl group and a (meth) acryloyl group, or an atelate containing an epoxy group and a (meth) acryloyl group, ) A method for introducing an attailoyl group.
  • the (meth) acrylate polymer (bl) As the (meth) acrylate polymer (bl), a (meth) acrylate polymer or copolymer having an epoxy group as a reactive functional group in the side chain is used, and a part or all of the epoxy group is used. And a, j8-unsaturated compound (b2) by reacting (meth) acrylic acid or an acrylate having a carboxyl group and an allyloyl group to introduce a (meth) attaroyl group.
  • a polymer ( ⁇ ) can be easily obtained by reacting an (meth) acrylate polymer or copolymer having an epoxy group with an ⁇ , ⁇ unsaturated carboxylic acid. it can.
  • the (meth) atalylate polymer having an epoxy group is, for example, a glycidyl (meth) acrylate or a (meth) acrylate having an alicyclic epoxy group (for example, Daicel Chemical Industries).
  • the (meth) acrylate copolymer having an epoxy group is changed to the (meth) acrylate having the epoxy group, and (meth) acrylate, styrene, butyl acetate, atta It can be obtained by copolymerizing two or more types of monomers using ⁇ , ⁇ unsaturated monomers having no carboxyl group such as mouth-tolyl as raw materials.
  • ⁇ , j8-unsaturated monomer having a carboxyl group instead of ⁇ , j8-unsaturated monomer
  • a cross-linking reaction is caused in the copolymerization reaction with glycidyl (meth) acrylate, which causes viscosity increase and gelling.
  • Examples of ex and ⁇ -unsaturated carboxylic acids that react with the (meth) acrylate polymer or copolymer having an epoxy group include (meth) acrylic acid, carboxyl group, and attalyl group. (For example, “Biscoat 2100” manufactured by Osaka Organic Chemical Co., Ltd.) and the like.
  • the polymer ( ⁇ ) obtained by the above production method has a weight average molecular weight of 5,000 to 80,000 force S preferred ⁇ , 5,000 to 50,000 force preferred ⁇ , 8,000 ⁇ 35,000 power ⁇ more preferred! / ⁇ .
  • the weight average molecular weight is 5,000 or more, the effect of reducing cure shrinkage is large.
  • the weight average molecular weight is 80,000 or less, the hardness is sufficiently high.
  • the equivalent of the (meth) atalyloyl group in the polymer ( ⁇ ) is 100 to 300 gZeq, and more preferably 200 to 300 gZeq.
  • the (meth) atallyloyl group equivalent of the polymer (B) is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.
  • the weight average molecular weight of the polymer (B) and the (meth) taroloyl group equivalent are satisfied.
  • the type of monomer and polymer to be used, the amount of these used, etc. may be appropriately selected.
  • the blending amount of the polymer (B) in 100 parts by mass of the total amount of the resin components in the composition is preferably 5 to 90 parts by mass, more preferably 10 to 70 parts by mass. 15 to 50 parts by mass Force S More preferable. If the blending amount of the polymer (B) is within this range, a cured film having a sufficiently high hardness can be obtained and curing shrinkage can be reduced. Can do.
  • the active energy ray-curable resin composition of the present invention includes the urethane acrylate (A).
  • radically polymerizable monomers (C) may be added.
  • examples of the radically polymerizable monomers (C) include the following.
  • Trimethylol propane tri (meth) acrylate triethylene oxide modified trimethylol propane tri (meth) acrylate, tripropylene oxide modified glycerol tri (meth) acrylate, triethylene oxide modified glycerol tri ( (Meth) attalylate, triechlorochlorohydrin-modified glycerol tri (meth) atalylate, 1, 3, 5-trichlorohexahydros-triazine
  • Tris (atallyroyloxychetyl) isocyanurate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethyleneoxide modified bentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, diethylene oxide modified ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol pent acrylate (for example, “Charad” manufactured by Nippon Kayaku Co., Ltd.
  • the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule has an effect of increasing hardness. Because there is, it is preferable.
  • examples of such polyfunctional (meth) acrylates include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexatarate. These may be used alone or in combination of two or more.
  • radical polymerizable monomers (C) monomers having an acid group such as a carboxyl group, a phosphoric acid group and a sulfonic acid group, a monomer having an amino group, an alkoxysilyl group It is preferable to use a monomer having an alkoxy titanyl group because the adhesion to the substrate can be improved.
  • a monomer having a fluorocarbon chain, a dimethylsiloxane chain, or a hydride-opened carbon chain having 12 or more carbon atoms can improve the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance. It is preferable because it is possible.
  • the total amount of the urethane acrylate (A) and the polymer (B) is 100 parts by mass.
  • 10 to 300 parts by mass are preferable.
  • 20 to 200 parts by mass is more preferable.
  • 20 to: LOO parts by mass is more preferable.
  • the active energy ray-curable resin composition of the present invention includes the urethane acrylate (A) and the polymer (B) as well as a urethane acrylate (other than the urethane acrylate (A)).
  • D) may be accepted.
  • urethane acrylate (D) after addition reaction of a polyol and the polyisocyanate (al), acrylate having one hydroxyl group and two or more (meth) attalyloyl groups in one molecule. Examples thereof include those obtained by addition reaction of (a2).
  • the blending amount of this urethane acrylate (D) in the resin composition is 5 to 5 parts by weight based on 100 parts by weight of the total amount of the urethane acrylate (A) and the polymer (B). LOO parts by mass are preferred. 10 to 50 parts by mass are more preferred.
  • the active energy ray-curable resin composition of the present invention refers to a resin composition that cures when irradiated with active energy rays.
  • Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, j8 rays, and ⁇ rays. Active energy when using ultraviolet light
  • a photopolymerization initiator is added to the linear curable resin composition. If necessary, further add a photosensitizer.
  • ionizing radiation such as electron beam, ⁇ -ray, j8-ray, and ⁇ -ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.
  • intramolecular cleavage type photopolymerization initiators can be broadly classified into intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators.
  • the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy 2-methyl-1 ferrule 1-one, benzyl dimethyl ketal, 1- (4-isopropyl phenol).
  • the hydrogen abstraction type photopolymerization initiator for example, benzophenone, ⁇ -benzoyl methyl benzoate-4 phenol-penzophenone, 4, 4, dichroic benzophenone, hydroxybenzophenone, 4- Benzyl 4'-methyl-diphenyl sulfide, acrylylated benzophenone, 3, 3 ', 4, 4'-tetra (t-butylperoxycarbol) benzophenone, 3, 3, 1-dimethyl-4-methoxybenzophenone Benzophenone compounds such as 2 isopropylthioxanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, 2,4 dicyclothioxanthone and the like thixanthone compounds such as Michlerketone, 4,4, Aminobenzophenone compounds; 1 0 Butyl 2 Chlorotalidone, 2 Ethylanthraki Emissions, 9, 10 Fuenansuren
  • the photosensitization suitably used for the active energy ray-curable resin composition of the present invention include, but are not limited to, amines such as aliphatic amines and aromatic amines, ureas such as O-tolylthiourea, sodium jetyl dithiophosphate, S-benzylisothiu-mu-P -Sulfur compounds such as toluene sulfonate.
  • amines such as aliphatic amines and aromatic amines
  • ureas such as O-tolylthiourea
  • sodium jetyl dithiophosphate sodium jetyl dithiophosphate
  • S-benzylisothiu-mu-P -Sulfur compounds such as toluene sulfonate.
  • the amount of the photopolymerization initiator and photosensitizer used is preferably 0.1 to 20% by mass with respect to 100 parts by mass of the resin component in the active energy ray-curable resin composition. 0.5 to 1
  • the active energy ray-curable resin composition of the present invention may be blended with various additives as necessary, and may be diluted with a solvent as desired.
  • the additive include a polymerization inhibitor, an antioxidant, a leveling agent, an antifoaming agent, a coating surface improver (wetting property, slip property improving agent, etc.), a plasticizer, and a colorant. .
  • Solvents used for dilution include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and ethyl solvate; methyl ethyl ketone, methyl isobutyl ketone, And ketones such as cyclohexanone. These solvents may be used alone or in combination of two or more.
  • the cured coating of the active energy ray-curable resin composition of the present invention has a curing shrinkage force, a high hardness, and high scratch resistance
  • the article is affected by cure shrinkage. Can be protected without any problems.
  • the cured film of the active energy ray-curable resin composition of the present invention is useful as a hard coat material for forming a protective layer of various articles. Examples of this article include plastic, paper, and cellulose such as wood, ceramics such as glass, and articles having metal strength such as iron and aluminum, and are particularly useful for protecting articles made of plastic.
  • the surface of the article may be provided with a handle or an easy adhesion layer.
  • the thickness of the cured coating is usually 0.5 to 500 / ⁇ ⁇ , preferably 3 to 50 ⁇ m, particularly preferably 4 to 30 ⁇ m. When the thickness of the cured film is within this range, high hardness and high scratch resistance can be obtained.
  • a plastic film having a cured coating of the active energy ray-curable resin composition of the present invention has the above active energy ray-curable resin composition on a film substrate, and the weight of the resin composition after drying is preferably 0.5 to 500 gZm 2 , preferably 3 to 50 gZm 2 . Alternatively, it is applied so as to be 4 to 30 g / m 2 (in terms of film thickness, usually 0.5 to 500 / ⁇ ⁇ , preferably 3 to 50 / ⁇ ⁇ , particularly preferably 4 to 30 m). After drying, it can be obtained by irradiating active energy rays to form a cured film.
  • the amount of the cured film formed on the film substrate is less than 0.5 gZm 2 , the film substrate itself may be affected by the hardness, and a sufficiently high hardness may not be obtained. In addition, if it is 500 gZm 2 or more, there is a problem that the base material is deformed by the polymerization heat at the time of curing, so it is necessary to devise cooling or the like at the time of curing.
  • Examples of the film substrate include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene, polyethylene, and polymethylpentene-11; and cellulose-based materials such as triacetyl cellulose.
  • the thickness of the film substrate is preferably 20 to 500 m force S.
  • the film to be used may be one provided with a handle or an easy adhesion layer.
  • Examples of the method for applying the active energy ray-curable resin composition of the present invention to a film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and transfer coating. Dip coat, spinner coat, wheeler coat, brush coating, solid coating with silk screen, wire bar coating, flow coating, and the like. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire-bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained. In addition, also when apply
  • the active energy ray-curable resin composition of the present invention can also be suitably used as a hard coating material for plastic molded articles. Since the cured film of the resin composition has small curing shrinkage, the cured film peels off from the substrate even when an impact is applied from the outside to the protective layer having good adhesion to the surface of the plastic molded body as the substrate. In addition, the protective layer has a high hardness and a high scratch resistance.
  • the plastic molded article having a cured coating of the active energy ray-curable resin composition of the present invention is coated with the resin composition on the surface of the plastic molded article by, for example, spray coating or date coating, and then dried. Thereafter, it can be obtained by irradiating an active energy ray to form a cured film.
  • the material of the plastic molded body include, but are not limited to, for example, polyacrylic resin, polyphenylene oxide 'polystyrene resin, polycarbonate resin, styrene copolymer resin, polystyrene resin, polyamide resin, ABS resin. Examples include fats. These plastic moldings may be provided with a handle, a thin metal layer, or an easy adhesion layer.
  • the active energy ray-curable resin composition of the present invention is applied to a molded article other than a plastic material, the same application method as that for a plastic molded body can be used.
  • the film on which the cured coating is formed is cured before the plastic is molded.
  • the film is attached to the surface of the plastic so that it becomes the outermost surface, and then the plastic is molded with the film.
  • the film may be attached to the plastic surface by melting and bonding the film and the plastic at a high temperature or by using an adhesive.
  • a molded product formed with plastic may be pasted with a film formed with a cured film and secondarily molded in accordance with the outer shape of the molded product.
  • a transfer material provided with a protective layer made of a cured coating of the active energy ray-curable resin composition of the present invention in advance.
  • the transfer material is attached to the surface of the article using a transfer method such as a hydraulic transfer method so that the protective layer of the transfer material becomes the outermost layer of the article after the transfer.
  • a transfer method such as a hydraulic transfer method
  • Examples of a method for producing a molded body made of a cured product of the active energy ray-curable resin composition of the present invention include the following methods.
  • An active energy ray-curable resin composition of the present invention is applied onto a substrate having a shape, and a cured product is formed by irradiating active energy rays.
  • the active energy ray-curable resin composition of the present invention is applied onto a base material that transmits active energy rays and has a shape.
  • a method of forming a cured product by irradiating an active energy ray to form a cured product, and then removing the cured product from a mold and a substrate.
  • the active energy ray-curable resin composition of the present invention is applied to the surface of a mold such as a mold, and further, an active energy ray is irradiated to form a cured product.
  • the molded body made of the cured product of the active energy ray-curable resin composition of the present invention obtained by the above method has small curing shrinkage, high hardness, and high scratch resistance, There is no scratch on contact with the article. Therefore, it is very useful.
  • a low pressure mercury lamp When ultraviolet rays are used as a device for irradiating active energy rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, mercury Examples include xenon lamps, short arc lamps, helium-powered dominium lasers, argon lasers, sunlight, and LEDs.
  • a flashing xenon flash lamp is used to form the cured substrate. It is preferable because it can reduce the effect of heat.
  • the article forming the protective layer is a film substrate such as a cellulose film, a polyester film, a polystyrene film, a polyamide film, or a polycarbonate film.
  • a film substrate such as a cellulose film, a polyester film, a polystyrene film, a polyamide film, or a polycarbonate film.
  • yellowing or deterioration occurs due to electron beam irradiation. Therefore, yellowing or deterioration of the film substrate can be prevented by setting the acceleration voltage to 30 to 150 kV.
  • PE3A pentaerythritol tritalylate
  • PE4A pentaerythritol tetratalate
  • urethane Atari rate (A1) Z pentaerythritol tetra ⁇ click Relate mixture (weight ratio A mixture of 80Z20 and a butyl acetate solution having a nonvolatile content of 80% by mass was obtained.
  • the molecular weight (calculated value) of urethane acrylate (A1) is 802.
  • urethane Atari rate (A2) ZDPHA mixture (a mixture of weight ratio 54Z56, nonvolatile butyl acetate min 80 mass 0/0 solution) was obtained.
  • the molecular weight (calculated value) of urethane acrylate (A2) is 1,216.
  • IPDI isophorone diisocyanate
  • Urethane acrylate (A3) ZPE4A mixture (mass ratio 80Z20 mixture, non-volatile 80% by weight butyl acetate solution) was obtained.
  • the molecular weight (calculated value) of urethane acrylate (A3) is 818.
  • GMA glycidyl methacrylate
  • MIBK methyl isobutyl ketone
  • AIBN 2, 2, azobisisobuty-tolyl
  • nBMA n-butyl methacrylate
  • MIBK MIBN 7.5 parts by weight
  • AIBN AIBN 7.5 parts by weight
  • the temperature was raised to 110 ° C and reacted for 8 hours. Thereafter, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the non-volatile content was 50% by mass, and the polymer (B 2) (non-volatile content 50 mass ° / ( ⁇
  • the polymer (B2) thus obtained had a weight average molecular weight of 8,800 (in terms of polystyrene by GPC) and a (meth) taroloyl group equivalent of 240 gZeq.
  • Synthesis Example 4 the same procedure was performed as in Synthesis Example 4 except that the first charged lauryl mercabtan was changed to 1.3 parts by mass, and the dripped lauryl mercabtan was then changed to 3.7 parts by mass. ) (Non-volatile content 50 mass ° / ( ⁇ MIBK solution) was obtained. The weight average molecular weight of the obtained polymer (B3) was 31 000 (in terms of polystyrene by GPC). The equivalent weight was 300 gZeq.
  • the active energy ray-curable resin composition of the present invention was prepared as follows. did.
  • a MIBK solution of the polymer (B2) obtained in Synthesis Example 5 (non-volatile content 50% by mass) 76 parts by mass, DPHA 39 parts by mass, SiAO. 2 parts by mass and HCPK 3 parts by mass were uniformly mixed to obtain a resin composition. (3) was obtained.
  • the resin composition (1) to (7) and the resin composition (C1) to (C5) obtained above are made of polyethylene terephthalate (hereinafter referred to as “PET”) film base (Toyobo Co., Ltd.) “Cosmo Shine A4100 # 100” (thickness: 100 m), coated with a wire bar (# 4), heated at 60 ° C for 1 minute, and then irradiated with UV light in an air atmosphere (Japan Battery) "GS30 type UV irradiation device” manufactured by Co., Ltd., lamp: 120WZcm 2 metal halide lamps, lamp height: 20cm, irradiation light quantity: 0.5jZcm 2 ), irradiated with ultraviolet rays, with a film thickness of 5-6 / ⁇ ⁇ A film having a cured coating was obtained.
  • PET polyethylene terephthalate
  • the surface of the cured film of the film for evaluation obtained above was measured in accordance with JIS ⁇ 5600-5-4: 1999, pencil hardness was measured at a load of 500 g, and the surface hardness was evaluated according to the following criteria: 7 pieces.
  • Pencil hardness is 3H or more.
  • Pencil hardness is 2H or less.
  • Curl value (mm) 10— (minimum length between two adjacent points + length between two other adjacent points) Z2
  • the curl value is less than 8 mm.
  • the haze value of the evaluation film obtained above was measured with a haze meter NDH2000 (Nippon Denshoku Co., Ltd.). From the obtained haze value, transparency was evaluated according to the following criteria.
  • ⁇ Haze value is 0.1% or less.
  • the base material obtained above is a PET evaluation film, and in the preparation of the evaluation film, the PET film base material is a triacetyl cellulose (hereinafter referred to as “TAC”) film base material (Fuji A film for evaluation was prepared in the same manner except that the film was replaced with “TAC” manufactured by Photographic Film Co., Ltd. (thickness: 80 m).
  • TAC triacetyl cellulose
  • These evaluation films were made in accordance with JIS K5400, and 100 grids were made by making 11 vertical and horizontal cuts at lmm intervals on the film surface.
  • the number of cells remaining without peeling was counted, and the adhesion was evaluated according to the following criteria.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Urethane 1 route (A1) 27.2 44.8 34.4 16 32
  • PET Number of cells remaining in peel test
  • PET 100 100 100 100 100 100 100 100 100 Adhesion evaluation (PET) 0 oo OO Number of cells remaining in peel test (TAG) 100 100 100 100 100 100 100 100 100 100 Adhesion evaluation (TAC) o ⁇ ⁇ ⁇ o
  • the film having a cured coating of the active energy ray-curable resin composition of the present invention of Example 17 has a sufficiently high L, surface hardness, and transparency. It turned out that the curl of the film was small.
  • the film having a cured coating of the active energy ray-curable resin composition of Comparative Example 15 containing no urethane acrylate (A) or polymer (B) is: The surface hardness was insufficient or the curl was large.
  • the active energy ray-curable resin composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays, a cured film having small curl, high hardness, and high scratch resistance is obtained. Therefore, it is useful as a protective layer for a film.
  • active energy rays such as ultraviolet rays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L’invention concerne une composition de résine durcissable par un rayon actinique caractérisée en ce qu’elle comprend un acrylate d'uréthane (A) qui est un produit de la réaction d'addition d'un polyisocyanate (a1) avec un acrylate (a2) ayant un groupe hydroxyle et deux groupes (méth)acryloyle ou plus par molécule et un polymère (B) ayant un groupe (méth)acryloyle qui est obtenu par la réaction d’un polymère de (méth)acrylate (b1) ayant un groupe fonctionnel réactif dans la chaîne latérale avec un composé α,β-insaturé (b2) ayant un groupe fonctionnel qui réagit avec le groupe fonctionnel réactif. La composition peut être durcie par irradiation avec un rayon actinique tel que la lumière UV de façon à donner un film durci ayant une dureté élevée et une forte résistance à la rayure avec peu de rétrécissement lors du durcissement.
PCT/JP2006/307913 2005-04-25 2006-04-14 Composition de resine durcissable par un rayon actinique et articles et moulages fabriques a partir de celle-ci WO2006115085A1 (fr)

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EP3117989A1 (fr) * 2014-03-12 2017-01-18 FUJIFILM Corporation Stratifié barrière, film barrière au gaz, film stratifié, poche de solution de perfusion, et procédé de production d'un stratifié barrière
JP2020074001A (ja) * 2015-04-10 2020-05-14 富士フイルム株式会社 透明フィルム、偏光板、及び画像表示装置

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2011034035A1 (ja) * 2009-09-18 2013-02-14 Dic株式会社 活性エネルギー線硬化型樹脂組成物、その硬化物及びフィルム
KR101802215B1 (ko) * 2010-03-31 2017-11-28 디아이씨 가부시끼가이샤 활성 에너지선 경화형 수지 조성물, 그 경화물 및 필름
JP5035652B2 (ja) * 2010-12-22 2012-09-26 Ｄｉｃ株式会社 分散体の製造方法、分散体、塗料、塗膜、及びフィルム
KR101447775B1 (ko) * 2012-05-08 2014-10-06 (주)엘지하우시스 감촉 특성이 우수한 코팅 조성물, 그 제조방법 및 이를 이용한 전사시트
JP6057121B2 (ja) * 2012-11-02 2017-01-11 Dic株式会社 活性エネルギー線硬化性組成物、その硬化物及びその硬化塗膜を有する物品
JP6071108B2 (ja) * 2013-03-13 2017-02-01 荒川化学工業株式会社 光硬化型樹脂組成物およびこれを用いて得られる光学用フィルム
CN104129189B (zh) * 2013-05-02 2017-09-29 荒川化学工业株式会社 转印用装饰膜
WO2015068682A1 (fr) * 2013-11-11 2015-05-14 Dic株式会社 Composition durcissable par rayonnement d'énergie active, produit durci associé, et article comprenant un film de revêtement durci associé
TWI681997B (zh) * 2014-06-13 2020-01-11 日商東亞合成股份有限公司 硬化型組成物
US10562996B2 (en) 2015-02-06 2020-02-18 Mitsubishi Gas Chemical Company, Inc. Curable resin composition, cured product, and laminate
WO2016208785A1 (fr) * 2015-06-24 2016-12-29 삼성전자 주식회사 Film de revêtement dur pour dispositif d'affichage et dispositif d'affichage le comprenant
JP2021116374A (ja) * 2020-01-28 2021-08-10 荒川化学工業株式会社 アンダーコート剤、硬化物及び積層物
CN113801291B (zh) * 2021-04-27 2023-05-12 杭州福斯特电子材料有限公司 感光树脂组合物、感光干膜抗蚀剂和pcb板的制作方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11263893A (ja) * 1998-01-14 1999-09-28 Nippon Shokubai Co Ltd （メタ）アクリル系樹脂組成物およびその製造方法
JP2000241970A (ja) * 1998-12-25 2000-09-08 Mitsubishi Chemicals Corp 感光性組成物及び感光性印刷版
JP2001290267A (ja) * 2000-02-01 2001-10-19 Mitsubishi Chemicals Corp 光重合性組成物、感光性平版印刷版及び印刷版の製版方法
JP2002114830A (ja) * 2000-10-05 2002-04-16 Toagosei Co Ltd 硬化性組成物
JP2003122002A (ja) * 2001-10-18 2003-04-25 Mitsubishi Chemicals Corp 光重合性組成物、感光性平版印刷版及び印刷版の製版方法
JP2003207890A (ja) * 2002-01-10 2003-07-25 Goo Chemical Co Ltd 感光性樹脂組成物、フォトソルダーレジストインク、プリント配線板及びドライフィルム
JP2003315990A (ja) * 2002-04-25 2003-11-06 Mitsubishi Chemicals Corp 画像形成材料及び画像形成方法
JP2006070112A (ja) * 2004-08-31 2006-03-16 Hitachi Chem Co Ltd 光硬化性樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11263893A (ja) * 1998-01-14 1999-09-28 Nippon Shokubai Co Ltd （メタ）アクリル系樹脂組成物およびその製造方法
JP2000241970A (ja) * 1998-12-25 2000-09-08 Mitsubishi Chemicals Corp 感光性組成物及び感光性印刷版
JP2001290267A (ja) * 2000-02-01 2001-10-19 Mitsubishi Chemicals Corp 光重合性組成物、感光性平版印刷版及び印刷版の製版方法
JP2002114830A (ja) * 2000-10-05 2002-04-16 Toagosei Co Ltd 硬化性組成物
JP2003122002A (ja) * 2001-10-18 2003-04-25 Mitsubishi Chemicals Corp 光重合性組成物、感光性平版印刷版及び印刷版の製版方法
JP2003207890A (ja) * 2002-01-10 2003-07-25 Goo Chemical Co Ltd 感光性樹脂組成物、フォトソルダーレジストインク、プリント配線板及びドライフィルム
JP2003315990A (ja) * 2002-04-25 2003-11-06 Mitsubishi Chemicals Corp 画像形成材料及び画像形成方法
JP2006070112A (ja) * 2004-08-31 2006-03-16 Hitachi Chem Co Ltd 光硬化性樹脂組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3117989A1 (fr) * 2014-03-12 2017-01-18 FUJIFILM Corporation Stratifié barrière, film barrière au gaz, film stratifié, poche de solution de perfusion, et procédé de production d'un stratifié barrière
EP3117989A4 (fr) * 2014-03-12 2017-03-29 FUJIFILM Corporation Stratifié barrière, film barrière au gaz, film stratifié, poche de solution de perfusion, et procédé de production d'un stratifié barrière
JP2020074001A (ja) * 2015-04-10 2020-05-14 富士フイルム株式会社 透明フィルム、偏光板、及び画像表示装置

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KR20070120177A (ko) 2007-12-21

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