CN103168051A - Active energy ray-curable resin composition and coating agent - Google Patents

Active energy ray-curable resin composition and coating agent Download PDF

Info

Publication number
CN103168051A
CN103168051A CN2012800033926A CN201280003392A CN103168051A CN 103168051 A CN103168051 A CN 103168051A CN 2012800033926 A CN2012800033926 A CN 2012800033926A CN 201280003392 A CN201280003392 A CN 201280003392A CN 103168051 A CN103168051 A CN 103168051A
Authority
CN
China
Prior art keywords
methyl
acrylate
energy ray
based compound
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012800033926A
Other languages
Chinese (zh)
Inventor
辻本笃志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Synthetic Chemical Industry Co Ltd
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Synthetic Chemical Industry Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Publication of CN103168051A publication Critical patent/CN103168051A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/10—Esters of organic acids
    • C09D101/14—Mixed esters, e.g. cellulose acetate-butyrate
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints

Abstract

The purpose of the present invention is to provide an active energy ray-curable resin composition, which has a configuration that contains (A) a urethane (meth)acrylate compound and (B) a polysaccharide derivative and forms a coating film that is capable of covering up projections and recesses formed because of fine particles or foreign substances present inside a coating material even if the coating film is formed by thin-film coating, and which exhibits excellent effects on appearance, smoothness and transparency of the coating film. The purpose of the present invention is to provide especially an active energy ray-curable resin composition for forming a coating film that has excellent transparency and followability to a design, said active energy ray-curable resin composition being capable of forming a thin coating film on a base that has a fine design without filling up the designed portion, while covering up projections and recesses formed because of fine particles or foreign substances contained in the cured coating film.

Description

Actinic energy ray curable resion composition and coating agent
Technical field
The present invention relates to actinic energy ray curable resion composition and coating agent, more specifically, relate to the outward appearance that is used to form film coated surface, the smoothness of film coated surface, the actinic energy ray curable resion composition of filming of transparency excellence and the coating agent that has used it to form.
Background technology
All the time, actinic energy ray curable resion composition, because the irradiation with radiation by the utmost point short period of time finishes to solidify, therefore is widely used as coating agent, caking agent or the anchor coating agent etc. of various base materials.
Make actinic energy ray curable resion composition in the situation that the surface cure of plastic basis material and form cured coating film, the adaptation of contraction, raising and plastic basis material in order to suppress to solidify, or in order to improve the surface hardness of cured coating film, the particulate such as compounding mineral filler in actinic energy ray curable resion composition sometimes.
For example, put down in writing a kind of curable resin composition in patent documentation 1, it contains: radiation curable multifunctional (methyl) acrylate that has (methyl) acryl more than at least 2 and active hydrogen in molecule reacts the colloidal silica that the polyfunctional carbamate, acrylate that forms and primary particle size are 1～200 nanometer with polyisocyanates; Put down in writing a kind of antistatic hard coating resin combination in patent documentation 2; it is for using dispersion agent to be dispersed with the antistatic hard coating resin combination that primary particle size is the znic antimonite sol below 0.5 micron in ultra-violet solidified (methyl) acrylate that has at least more than one (methyl) acryl in molecule, thereby the mist degree of making while filming is transparent below 1.5.
On the other hand; as mentioned above; actinic energy ray curable resion composition is also useful as anchor coating agent; for example in patent documentation 3, put down in writing a kind of bottom-coating UV curable paint of metal evaporation, it contains: using and be selected from least a kind of monomer in (methyl) vinylformic acid two ring pentyl ester, (methyl) vinylformic acid two cyclopentenes esters and (methyl) isobornyl acrylate as having compound and the Photoepolymerizationinitiater initiater of at least 2 (methyl) acryls in vinylformic acid (being) resin of constituent, molecule.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-113649 communique
Patent documentation 2: Japanese kokai publication hei 10-231444 communique
Patent documentation 3: TOHKEMY 2002-347175 communique
Summary of the invention
the problem that invention will solve
Therefore easily, yet in above-mentioned patent documentation 1 and 2, disclosed technology, because compounding in actinic energy ray curable resion composition has particulate, forms concavo-convexly on the surface of cured coating film, the smoothness of cured coating film and the transparency are insufficient.And then, except above-mentioned particulate, utilize to filter wait during the painting order and the fine foreign matter of sneaking in the microgel do not removed fully etc., painting process etc. also easily forms concavo-convex on the cured coating film surface, easily smoothness and the transparency are caused to detrimentally affect.
In addition, in the situation that coating has the base material of fine appearance design, in order to prevent the obstruction of appearance design part, require the filming of cured coating film such below 10 μ m, but disclosed technology in above-mentioned patent documentation 3 in the situation that the thickness that primary coat is filmed reach below 10 μ m, the problem that existence can't hidden substrate (with reference to [0054] section of the Publication of patent documentation 3).
Like this, in recent years, especially at anchor, be coated with in purposes, require the filming of cured coating film, but the thickness of cured coating film becomes thinner,, because the impact of the particulate contained in cured coating film, foreign matter etc. makes hiddenly concavo-convexly to become more difficult, be difficult to take into account filming and concavo-convex disguise.
Thereby, under this background, the object of the present invention is to provide the actinic energy ray curable resion composition with following characteristics and the coating agent that has used it, even described actinic energy ray curable resion composition in the situation that the thin thickness of cured coating film also can be hidden particulate by existing in coating, foreign matter etc. cause concavo-convex, be used to form smoothness and the excellent cured coating film of the transparency.
for the scheme of dealing with problems
Thereby, the inventor has repeated in depth research in view of described situation, found that a kind of actinic energy ray curable resion composition, it is by containing polysaccharide derivates in the actinic energy ray curable resion composition that makes to contain carbamate (methyl) acrylate based compound, the viscosity that can increase while making the solvent composition evaporation changes, suppressing film coated surface floats, therefore can hidden cured coating film surface concavo-convex, for obtaining the smoothness with respect to level and smooth base material, the cured coating film that the transparency is excellent, obtain the outward appearance of filming with respect to the base material with fine appearance design, the cured coating film that the transparency is excellent, thereby completed the present invention.
That is, purport of the present invention relates to the actinic energy ray curable resion composition that contains carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B).
In addition, in the present invention, also provide the coating agent that contains aforementioned actinic energy ray curable resion composition, the coating agent that especially is used as the silane coupling agent of metal evaporation.
the effect of invention
Even actinic energy ray curable resion composition of the present invention utilizes the film application to form and films, also can the hidden particulate by existing in coating, it is concavo-convex that foreign matters etc. cause, there is the outward appearance of filming, smoothness, the effect that the transparency is excellent, especially with respect to the base material with fine appearance design, can not stop up its appearance design part, can carry out the film application, and the particulate that can hiddenly contain in cured coating film, the impact of foreign matter and cause concavo-convex, there is the servo-actuated property of appearance design, the effect that the transparency is excellent, therefore as coating agent, especially the silane coupling agent of metal evaporation is particularly useful.
Embodiment
Below the present invention is described in detail.
Actinic energy ray curable resion composition of the present invention contains carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B).
It should be noted that; in the present invention; (methyl) acrylic refers to acrylic or methacrylic acid group, and (methyl) acryl refers to acryl or methacryloyl, and (methyl) acrylate refers to acrylate or methacrylic ester.
(carbamate (methyl) acrylate based compound (A))
As the carbamate used in the present invention (methyl) acrylate based compound (A), can enumerate (methyl) acrylate based compound (a1) of the hydroxyl of sening as an envoy to, the reaction of polyisocyanates based compound (a2) and polyvalent alcohol based compound (a3) and carbamate (methyl) the acrylate based compound (A1) that obtains, carbamate (methyl) the acrylate based compound (A2) that perhaps makes (methyl) acrylate based compound (a1) of hydroxyl and polyisocyanates based compound (a2) reaction and obtain, among these, can only use separately a kind, also can be used in combination two or more.
Among these, from the viewpoint of giving the cementability between plastic basis material and undercoat, undercoat and metal steam plated film, consider, preferred carbamate (methyl) acrylate based compound (A1), thereby in the situation that to add particulate and make coating agent in order to give functional to filming, preferred carbamate (methyl) acrylate based compound (A2), can consider target is filmed and given each physical property and suitably select.
The weight-average molecular weight of the carbamate used in the present invention (methyl) acrylate based compound (A) is preferably 500～50000, and more preferably 1000～30000.When described weight-average molecular weight is too small, the tendency that exists cured coating film to become fragile, and when excessive, exist viscosity to uprise and reluctant tendency.
It should be noted that, above-mentioned weight-average molecular weight is the weight-average molecular weight converted based on the polystyrene standard molecular weight, use 3 posts by series connection in high performance liquid chromatograph (Showa Denko K. K's system, " Shodex GPC system-11 type "): Shodex GPC KF-806L (exclusion limit molecular weight: 2 * 10 7, separating ranges: 100～2 * 10 7, theoretical plate number: 10,000 column plates/root, filler material: styrene diethylene benzene copoly mer, packing material size: 10 μ m) measure.
The viscosity of above-mentioned carbamate (methyl) acrylate based compound (A) under 60 ℃ is preferably 500～150,000 mPas, is particularly preferably 500～120,000 mPas, more preferably 1000～100,000 mPas.Described viscosity is outside above-mentioned scope the time, the tendency that exists coating to reduce.
It should be noted that, the measuring method of viscosity utilizes E type viscometer to carry out.
<carbamate (methyl) acrylate based compound (A1)>
As (methyl) acrylate based compound (a1) of hydroxyl, such as listing (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) vinylformic acid-(methyl) acrylic acid hydroxy alkyl esters such as the own ester of 6-hydroxyl, 2-hydroxyethyl acryl phosphonic acid ester, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester, caprolactone modification-2-hydroxyethyl (methyl) acrylate, (methyl) vinylformic acid dipropylene glycol ester, fatty acid modified-glycidyl (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate, glycerine two (methyl) acrylate, 2-hydroxyl-3-acryloxy propyl methyl acid esters, tetramethylolmethane three (methyl) acrylate, caprolactone modification tetramethylolmethane three (methyl) acrylate, oxyethane modification tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, caprolactone modification Dipentaerythritol five (methyl) acrylate, oxyethane modification Dipentaerythritol five (methyl) acrylate etc.
Among these, (methyl) crylic acid hydroxy ester based compound with 1 ethylenically unsaturated group can relax the cure shrinkage formed while filming, thereby preferably, more preferably (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) vinylformic acid-(methyl) acrylic acid hydroxy alkyl esters such as the own ester of 6-hydroxyl, reactivity and versatility excellence while especially using (methyl) vinylformic acid-2-hydroxyl ethyl ester, thereby preferably.
In addition, they can use a kind or be used in combination two or more.
As polyisocyanates based compound (a2), such as listing the fragrant family polyisocyanates such as tolylene diisocyanate, diphenylmethanediisocyanate, many phenylmethanes polyisocyanates, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene vulcabond, naphthalene diisocyanate; The fatty family polyisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate, Lysine triisocyanate; Hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene dimethylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, 1, the ester ring types such as two (isocyanato-methyl) hexanaphthenes of 3-are polyisocyanates; Perhaps 3 polymers compounds of these polyisocyanates or polymer compound, allophanate type polyisocyanates, biuret type polyisocyanates, water dispersive polyisocyanate (for example, " AQUANATE100 " of Nippon Polyurethane Industry Co., Ltd.'s system, " AQUANATE110 ", " AQUANATE200 ", " AQUANATE210 " etc.) etc.
Among these, the few viewpoint from yellowing, preferably used the fatty family vulcabond such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate; Hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene dimethylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, 1, the ester ring types such as two (isocyanato-methyl) hexanaphthenes of 3-are vulcabond, particularly preferably be, the viewpoint little from cure shrinkage considered, can use isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene dimethylene diisocyanate, more preferably, consider from the viewpoint of reactive and versatility excellence, can use isophorone diisocyanate.
As polyvalent alcohol based compound (a3), such as listing polyethers, be that polyvalent alcohol, polyester are that polyvalent alcohol, polycarbonate-based polyvalent alcohol, polyolefin polyvalent alcohol, polyhutadiene are that polyvalent alcohol, (methyl) vinylformic acid (ester) are polyvalent alcohol, polysiloxane series polyvalent alcohol etc.
As above-mentioned polyethers, being polyvalent alcohol, is random copolymers or the segmented copolymer of polyvalent alcohol, these polyalkylene glycols such as listing polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, polyhexamethylene glycol etc. containing the polyethers of alkylidene group structure.
Be polyvalent alcohol as above-mentioned polyester, for example can list the polycondensate of polyvalent alcohol and polycarboxylic acid; The ring-opening polymerization polymer of cyclic ester (lactone); The reactant of these 3 kinds of compositions of polyvalent alcohol, polycarboxylic acid and cyclic ester etc.
As aforementioned polyvalent alcohol, for example can list ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, trimethylene, 1, the 4-tetramethylene glycol, 1, the 3-tetramethylene glycol, the 2-methyl isophthalic acid, the 3-trimethylene, 1, 5-pentamethylene glycol, neopentyl glycol, 1, the 6-hexamethylene glycol, the 3-methyl isophthalic acid, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, glycerine, TriMethylolPropane(TMP), trimethylolethane, cyclohexanediol class (1, 4-cyclohexanediol etc.), bisphenols (dihydroxyphenyl propane etc.), glycitols (Xylitol, Sorbitol Powder etc.) etc.
As aforementioned polycarboxylic acid, such as listing the aliphatic dicarboxylic acids such as propanedioic acid, toxilic acid, fumaric acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid; The ester ring type dicarboxylic acid such as Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid; Terephthalic acid, m-phthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, to aromatic dicarboxylic acids such as phenylene dicarboxylic acids, trimellitic acid etc.
As aforementioned cyclic ester, such as listing propiolactone, Beta-methyl-δ-valerolactone, 6-caprolactone etc.
As above-mentioned polycarbonate-based polyvalent alcohol, for example can list the reactant of polyvalent alcohol and phosgene; The ring-opening polymerization polymer of cyclic carbonate (alkylene carbonates etc.) etc.
As aforementioned polyvalent alcohol, can list illustrated polyvalent alcohol etc. in the explanation that aforementioned polyester is polyvalent alcohol, as above-mentioned alkylene carbonates, such as listing ethylene carbonate, carbonic acid trimethylene ester, carbonic acid tetramethylene ester, carbonic acid hexa-methylene ester etc.
It should be noted that, polycarbonate polyol so long as have the compound that carbonic acid ester bond, end are hydroxyl in molecule and get final product, also can have carbonic acid ester bond and ester bond in the lump.
Be polyvalent alcohol as said polyolefins, can list homopolymer or multipolymer with ethene, propylene, butylene etc. and there is the polyolefin polyvalent alcohol of hydroxyl as stable hydrocarbon skeleton and its molecular end.
As above-mentioned polyhutadiene, be polyvalent alcohol, can list the polyhutadiene that multipolymer with divinyl has hydroxyl as hydrocarbon skeleton and its molecular end is polyvalent alcohol.
Polyhutadiene is that polyvalent alcohol can be also all or part of hydrogenated butadiene polymer polyvalent alcohol formed that is hydrogenated of the ethylenically unsaturated group that comprises in its structure.
As above-mentioned (methyl) vinylformic acid (ester), it is polyvalent alcohol, can list (methyl) vinylformic acid (ester) that has at least 2 hydroxyls in the molecule of the polymkeric substance of (methyl) acrylate or multipolymer is polyvalent alcohol, as described (methyl) acrylate, for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) alkyl acrylates such as (methyl) vinylformic acid stearyl etc.
As above-mentioned polysiloxane series polyvalent alcohol, such as listing dimethyl polysiloxane polyvalent alcohol, methyl phenyl silicone polyvalent alcohol etc.
Among these, preferred polyester is that polyvalent alcohol, polyethers are polyvalent alcohol, and the viewpoint of the mechanical properties excellences such as flexibility when solidifying considers, particularly preferably polyester is polyvalent alcohol.
Weight-average molecular weight as above-mentioned polyvalent alcohol based compound (a3), be preferably 500～8000, is particularly preferably 550～5000, and more preferably 600～3000.When the molecular weight of polyvalent alcohol based compound (a3) is excessive, the tendency that while exist solidifying, the mechanical properties such as hardness of film reduces, and when too small, have the tendency that cure shrinkage is large, stability reduces.
Manufacture method about carbamate (methyl) acrylate based compound (A1), usually, (methyl) acrylate based compound (a1) of above-mentioned hydroxyl, polyisocyanates based compound (a2), polyvalent alcohol based compound (a3) are dropped in reactor and react and get final product in the lump or respectively, from the stability of reaction, the viewpoint that reduces by product etc., consider, polyvalent alcohol based compound (a3) is reacted in advance with polyisocyanates based compound (a2), and the gained reaction product is reacted with (methyl) acrylate based compound (a1) of hydroxyl is useful.
Polyvalent alcohol based compound (a3) can be used known reaction method with reacting of polyisocyanates based compound (a2).Now, for example the mol ratio by the hydroxyl in the isocyanate group by polyisocyanates based compound (a2) and polyvalent alcohol based compound (a3) is made as common 2n:(2n-2) (n is the integer more than 2) left and right, obtain residual have isocyanate group containing after carbamate (methyl) the acrylate based compound of terminal isocyanate group, can carry out addition reaction with (methyl) acrylate based compound (a1) of hydroxyl.
The addition reaction of the reaction product that above-mentioned polyvalent alcohol based compound (a3) is reacted in advance with polyisocyanates based compound (a2) and obtain and (methyl) acrylate based compound (a1) of hydroxyl also can be used known reaction method.
The mol ratio of reacting about (methyl) acrylate based compound (a1) of reaction product and hydroxyl, in for example isocyanate group of polyisocyanates based compound (a2), it is 2, in the situation that the hydroxyl of (methyl) acrylate based compound (a1) of hydroxyl is 1, reaction product: (methyl) acrylate based compound (a1) of hydroxyl is the 1:2 left and right, isocyanate group at polyisocyanates based compound (a2) is 3, in the situation that the hydroxyl of (methyl) acrylate based compound (a1) of hydroxyl is 1, reaction product: (methyl) acrylate based compound (a1) of hydroxyl is the 1:3 left and right.
In the addition reaction of (methyl) acrylate based compound (a1) of this reaction product and hydroxyl, the time point reached below 0.5 % by weight by the residual isocyanate base containing ratio in reaction system finishes reaction, can obtain carbamate (methyl) acrylate based compound (A1).
Described polyvalent alcohol based compound (a3) and polyisocyanates based compound (a2) react so that in the reacting of (methyl) acrylate based compound (a1) of its reaction product and hydroxyl, in order to promote reaction, also preferably use catalyzer, as described catalyzer, such as listing the organometallic compounds such as dibutyl tin laurate, trimethylammonium stannic hydroxide, tetra-n-butyl tin; The metal-salts such as zinc octoate, stannous octoate, cobalt naphthenate, tin protochloride, tin chloride; Triethylamine, benzyl diethylamine, Isosorbide-5-Nitrae-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecylene, N, N, N ', N '-tetramethyl--1, the amine series catalysts such as 3-butanediamine, N-ethylmorpholine; Bismuth trinitrate, bismuth bromide, bismuth iodide, bismuth sulfide etc.; And the bismuth organic compound such as di lauric dibutyl bismuth, two lauric acid dioctyl bismuths; The bismuth series catalysts such as organic acid bismuth salt such as 2 ethyl hexanoic acid bismuth salt, bismuth naphthenate salt, isodecyl acid bismuth salt, neodecanoic acid bismuth salt, lauric acid bismuth salt, toxilic acid bismuth salt, bismuth stearate salt, bismuth trioleate salt, linolic acid bismuth salt, bismuth acetate salt, two neodecanoic acid bismuth salt, two bismuth salicylate salt, two bismuth gallate salt etc., wherein, what be applicable to is dibutyl tin laurate, 1,8-diazabicyclo [5,4,0] undecylene.
In addition, polyvalent alcohol based compound (a3) and polyisocyanates based compound (a2) react so that in the reacting of (methyl) acrylate based compound (a1) of its reaction product and hydroxyl, can use the organic solvent do not had with the functional group of isocyanic ester radical reaction, for example, the ester such as ethyl acetate, butylacetate class; The ketone such as methylethylketone, methyl iso-butyl ketone (MIBK); The organic solvents such as the fragrant same clan such as toluene, dimethylbenzene.
In addition, temperature of reaction is generally 30～90 ℃, is preferably 40～80 ℃, and the reaction times is generally 2～10 hours, is preferably 3～8 hours.
About carbamate (methyl) the acrylate based compound (A1) used in the present invention, from applying flexibly structural performance, be that the viewpoint of the cementability of itself and metal steam coating is considered, preferably there is the ethylenically unsaturated group below 20, particularly preferably there is the ethylenically unsaturated group below 10, more preferably there is the ethylenically unsaturated group below 5.
The weight-average molecular weight of gained carbamate (methyl) acrylate based compound (A1) is preferably 500～50000, and more preferably 1000～30000.When described weight-average molecular weight is too small, the tendency that exists cured coating film to become fragile, and when excessive, exist viscosity to uprise and reluctant tendency.
It should be noted that above-mentioned weight-average molecular weight and above-mentioned similarly mensuration.
The viscosity of carbamate (methyl) acrylate based compound (A1) under 60 ℃ is preferably 500～150,000 mPas, is particularly preferably 500～120,000 mPas, more preferably 1000～100,000 mPas.Described viscosity is outside above-mentioned scope the time, the tendency that exists coating to reduce.
In addition, the measuring method of viscosity and the above-mentioned E type viscometer that similarly utilizes carry out.
<carbamate (methyl) acrylate based compound (A2)>
Carbamate in the present invention (methyl) acrylate based compound (A2) makes (methyl) acrylate based compound (a1) of hydroxyl react and obtain with polyisocyanates based compound (a2).
About carbamate (methyl) the acrylate based compound (A2) used in the present invention, from the viewpoint of the hardness of cured coating film, consider, preferably there is the ethylenically unsaturated group more than 3, particularly preferably there is the ethylenically unsaturated group more than 4, more preferably there is the ethylenically unsaturated group more than 6, among these, carbamate (methyl) acrylate that extremely preferably makes tetramethylolmethane three (methyl) acrylate react with isophorone diisocyanate to form, there are 6 ethylenically unsaturated groups.
In addition, the upper limit of the ethylenically unsaturated group that carbamate (methyl) acrylate based compound (A2) is contained is generally 30, is preferably below 25.
It should be noted that, in order to adjust the number of ethylenically unsaturated group, can suitably select (methyl) acrylate based compound (a1) and the polyisocyanates based compound (a2) of hydroxyl and use, for example, in the situation that the compound that use has 3 ethylenically unsaturated groups is as (methyl) acrylate based compound (a1) of hydroxyl and use diisocyanate cpd as polyisocyanates based compound (a2), the ethylenically unsaturated group number in carbamate (methyl) acrylate based compound (A2) is 6.
About the manufacture method of carbamate (methyl) acrylate based compound (A2), according to the manufacture method manufacture of above-mentioned carbamate (methyl) acrylate based compound (A1), get final product.
It should be noted that, the mol ratio of reacting about (methyl) acrylate based compound (a1) of polyisocyanates based compound (a2) and hydroxyl, in for example isocyanate group of polyisocyanates based compound (a2), it is 2, in the situation that the hydroxyl of (methyl) acrylate based compound (a1) of hydroxyl is 1, polyisocyanates based compound (a2): (methyl) acrylate based compound (a1) of hydroxyl is the 1:2 left and right, isocyanate group at polyisocyanates based compound (a2) is 3, in the situation that the hydroxyl of (methyl) acrylate based compound (a1) of hydroxyl is 1, polyisocyanates based compound (a2): (methyl) acrylate based compound (a1) of hydroxyl is the 1:3 left and right.
In the addition reaction of (methyl) acrylate based compound (a1) of this polyisocyanates based compound (a2) and hydroxyl, the time point reached below 0.5 % by weight by the residual isocyanate base containing ratio in reaction system finishes reaction, can obtain carbamate (methyl) acrylate based compound (A2).
The weight-average molecular weight of gained carbamate (methyl) acrylate based compound (A2) is preferably 500～50000, and more preferably 1000～30000.When described weight-average molecular weight is too small, the tendency that exists cured coating film to become fragile, and when excessive, exist viscosity to uprise and reluctant tendency.
In addition, above-mentioned weight-average molecular weight and above-mentioned similarly mensuration.
The viscosity of carbamate (methyl) acrylate based compound (A2) under 60 ℃ is preferably 500～150,000 mPas, is particularly preferably 500～120,000 mPas, 1000～100,000 mPas more preferably.Described viscosity is outside above-mentioned scope the time, the tendency that exists coating to reduce.
In addition, the measuring method of viscosity and the above-mentioned E type viscometer that similarly utilizes carry out.
(polysaccharide derivates (B))
Polysaccharide in the present invention refers to the sugar that a plurality of monose molecules are situated between and are formed by the glycosidic link bonding, is 10 compounds that above monose bonding forms.They can obtain with the form of biological biosynthetic products, be with biosynthetic products itself or manually carry out the form of the compound that chemically changed forms, be widely used in the material group of the daily necessities such as food and fiber, papermaking, makeup, toothpaste preparation, caking agent (paste), medical treatment etc. in industry.
Polysaccharide derivates in the present invention (B) refers to and is derived from biosynthetic products itself and biosynthetic products is carried out to the whole of compound of polysaccharide that the manual change forms.
As the polysaccharide derivates used in the present invention (B), comprise homopolysaccharide class, heteropolysaccharide, for example can list α-1,4-dextran (amylose starch, amylopectin), α-1,6-dextran (dextran), β-1,4-dextran (Mierocrystalline cellulose), β-1,6-dextran (pustulan), β-1, the 3-dextran (for example, curdlan, Sizofiran etc.), α-1,3-dextran, β-1, alpha-glucan derivative or the beta-glucan derivatives such as 2-dextran (Crown Gall polysaccharide); β-1; 4-Polygalactan, β-1; 4-mannocarolose, α-1,6-mannocarolose, β-1,2-Polylevulosan (fructan) (synanthrin), β-2; 6-Polylevulosan (levan (levan)), β-1; 4-xylan, β-1,3-xylan, β-Isosorbide-5-Nitrae-chitosan, β-1; 4-N-ethanoyl chitosan (chitin), amylopectin, agarose, Lalgine etc., can also comprise starch that contains amylose starch etc.
Among these, from the viewpoint of the consistency with carbamate (methyl) acrylate based compound, solvent, consider, be preferably alpha-glucan derivative or beta-glucan derivative, be particularly preferably the beta-glucan derivative, more preferably derivatived cellulose.
As polysaccharide derivates (B), be preferably the hydroxyl of polysaccharide all or part of quilt-C (O) R ,-C (O) NH (R) ,-C (O) N (R) (R) and-other substituting group of R and so on replaces the polysaccharide derivates (B) formed.Herein, aromatic series or heteroaromatic that the ester ring type group that R is the carbonatoms aliphatic group that is 1～3, carbonatoms is 3～10 or carbonatoms are 4～20, this R itself also can be substituted base and at random replace.Other substituent one kind or two or morely also can be substituted.
As preferred polysaccharide derivates (B), can list the acidylate polysaccharide.As the preferred acyl group of acidylate polysaccharide, can list ethanoyl, butyryl radicals, benzoyl, methyl benzoyl, dimethylbenzoyl, chlorobenzene formacyl, dichloro-benzoyl base.
In addition, as polysaccharide derivates (B), from can be hidden the concavo-convex viewpoint that causes such as particulate by existing in coating, foreign matter consider, preferred number average molecular weight (Mn) is 5,000～200,000, be particularly preferably 7,500～150,000, more preferably 10,000～100,000.When described number-average molecular weight is too small, can't by the foreign matter that suppresses particulate, sneak into float hidden concavo-convex, therefore exist to be difficult to obtain and there is the tendency that surface smoothness and transparent film hardening are filmed, and when excessive, the tendency that has solvability to solvent, reduces with the consistency of other composition.
Above-mentioned number-average molecular weight is the number-average molecular weight converted based on the polystyrene standard molecular weight, by 3 posts of use of connect in high performance liquid chromatograph (Japanese Waters company system, " Waters2695 (main body) " and " Waters2414 (detector) "): Shodex GPC KF-806L (exclusion limit molecular weight: 2 * 10 7, separating ranges: 100～2 * 10 7, theoretical plate number: 10,000 column plates/root, filler material: styrene diethylene benzene copoly mer, packing material size: 10 μ m) measure.
In the present invention, among above-mentioned, as applicable polysaccharide derivates (B), such as listing the acetic acid alkylated cellulose resins such as cellulose acetate butyrate resin, cellulose acetate propionate resin; Rhodia resin etc.
In addition, above-mentioned polysaccharide derivates (B) can only be used singly, or in combination of two or more kinds separately.
In the present invention, content as polysaccharide derivates (B), preferably, with respect to 100 weight part carbamate (methyl) acrylate based compounds (A), more than being preferably 3 weight parts, be particularly preferably 3～1000 weight parts, more preferably 5～500 weight parts, extremely be preferably 8～100 weight parts.When the content of polysaccharide derivates (B) is too much, make the levelling property of cured coating film reduce or when the primary coat purposes for metal evaporation, make the cementability of cured coating film and metal steam coating reduce or the reduction of active energy ray-curable component proportions, thereby have the tendency that is difficult to obtain sufficient film coated surface hardness.
On the other hand, when the content of polysaccharide derivates (B) is very few, the tendency that exists concavo-convex effect that hidden particulate by existing in coating, foreign matter etc. cause to reduce.
(ethylenically unsaturated monomer (C))
As above-mentioned ethylenically unsaturated monomer (C), get final product so long as there is the ethylenically unsaturated monomer (not comprising carbamate (methyl) acrylate based compound (A)) of 1 above ethylenically unsaturated group in 1 molecule, for example can list monofunctional monomer, difunctional monomer, the above monomer of trifunctional.
As monofunctional monomer, so long as the monomer that contains 1 ethylenically unsaturated group gets final product, for example can list vinylbenzene, Vinyl toluene, chloro-styrene, alpha-methyl styrene, (methyl) methyl acrylate, (methyl) ethyl propenoate, vinyl cyanide, vinyl-acetic ester, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid phenoxy ethyl, 2-phenoxy group-2-hydroxypropyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, the chloro-2-hydroxypropyl of 3-(methyl) acrylate, single (methyl) vinylformic acid glyceryl ester, (methyl) glycidyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid three ring decyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) n-butyl acrylate, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, the positive stearyl ester of (methyl) vinylformic acid, (methyl) benzyl acrylate, phenol ring oxidative ethane modification (methyl) acrylate, nonylphenol epoxy pronane modification (methyl) acrylate, half ester (methyl) acrylate of 2-(methyl) acryloxy-phthalic acid derivatives such as 2-hydroxypropyl phthalic ester, (methyl) vinylformic acid chaff ester, (methyl) vinylformic acid card must ester, (methyl) benzyl acrylate, (methyl) vinylformic acid butoxyethyl, (methyl) allyl acrylate, acryloyl morpholine, 2-hydroxyethyl acrylamide, N-methylol (methyl) acrylamide, NVP, the 2-vinyl pyridine, 2-(methyl) acryloxy ethyl phosphate ester acid monoesters etc.
In addition, except aforesaid monofunctional monomer, also can list acrylic acid Michael addition adducts or 2-acryloxy ethyl dicarboxylic acid monoesters, as acrylic acid Michael addition adducts, can list acrylic acid dimer, methacrylic acid dipolymer, vinylformic acid trimer, methacrylic acid trimer, vinylformic acid tetramer, methacrylic acid tetramer etc.In addition, as the carboxylic acid with specified substituent, be 2-acryloxy ethyl dicarboxylic acid monoesters, such as listing 2-acryloxy ethyl monomester succinate, 2-methacryloxyethyl monomester succinate, 2-acryloxy ethyl phthalic monoester, 2-methacryloxyethyl phthalic monoester, 2-acryloxy ethyl hexahydrophthalic acid monoesters, 2-methacryloxyethyl hexahydrophthalic acid monoesters etc.In addition, also can list the oligomer ester acrylate.
As difunctional monomer, so long as the monomer that contains 2 ethylenically unsaturated groups gets final product, for example can list two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid polypropylene glycol ester, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid DOPCP, oxyethane modified bisphenol A type two (methyl) acrylate, epoxy pronane modification bisphenol A-type two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,6-hexylene glycol oxyethane modification two (methyl) acrylate, two (methyl) vinylformic acid glyceryl ester, tetramethylolmethane two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, Diethylene Glycol diglycidylether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxypivalic acid modification neopentyl glycol two (methyl) acrylate, isocyanuric acid oxyethane modification diacrylate, 2-(methyl) acryloxy ethyl phosphate ester acid diester etc.
As the monomer more than trifunctional, so long as the monomer that contains 3 ethylenically unsaturated groups gets final product, for example can list trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl TriMethylolPropane(TMP), glycerine polyglycidyl ether many (methyl) acrylate, isocyanuric acid oxyethane modification triacrylate, oxyethane modification Dipentaerythritol five (methyl) acrylate, oxyethane modification Dipentaerythritol six (methyl) acrylate, oxyethane modification tetramethylolmethane three (methyl) acrylate, oxyethane modification tetramethylolmethane four (methyl) acrylate, caprolactone modification Dipentaerythritol five (methyl) acrylate, caprolactone modification Dipentaerythritol six (methyl) acrylate, caprolactone modification tetramethylolmethane three (methyl) acrylate, caprolactone modification tetramethylolmethane four (methyl) acrylate, succsinic acid modification tetramethylolmethane three (methyl) acrylate etc.
These ethylenically unsaturated monomers (C) may be used singly or in combination of two or more.
In the present invention, among above-mentioned ethylenically unsaturated monomer (C), thereby make its crosslinked formation network structure by irradiating active energy beam, the viewpoint of the weather resistance such as the water tolerance from raising is filmed, thermotolerance is considered, be preferably the polyfunctional monomer that contains the ethylenically unsaturated group more than 2, and then consider from the viewpoint of the network structure that forms high-order, be preferably the multi-functional monomer of the ethylenically unsaturated group contained more than 3.
Particularly, for example from the viewpoint of filming of the network structure that can obtain being formed with high-order, consider, be preferably tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.
In the present invention, as the content of ethylenically unsaturated monomer (C), with respect to 100 weight part carbamate (methyl) acrylate based compounds (A), be preferably 10～500 weight parts, be particularly preferably 20～300 weight parts, more preferably 30～100 weight parts.When the content of ethylenically unsaturated monomer (C) is too much, the tendency that while having evaporation metal, the cementability of undercoat and metal steam coating reduces, and when very few, existence can't be by the tendency of the crosslinked network structure that forms high-order, the weather resistance reduction of filming.
(Photoepolymerizationinitiater initiater (D))
In the present invention, preferably, except carbamate (methyl) acrylate based compound (A), polysaccharide derivates (B), also containing being useful on the curing Photoepolymerizationinitiater initiater (D) that is utilized active energy beam to carry out.
As Photoepolymerizationinitiater initiater (D), such as listing diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholinyl (4-sulphomethyl phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetophenones such as acetone oligopolymer; The bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, bitter almond oil camphor ethyl isobutyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyl-diphenylsulfide, 3,3 ', 4,4 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone, 4-benzoyl-N, N-dimethyl-N-[2-(1-oxo-2-propenyloxy group) ethyl] benzophenone such as xylylene benzyl brometo de amonio, (4-benzoyl benzyl) trimethyl ammonium chloride; ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxy-of 1-thioxanthone, 2-(3-dimethylamino-2-hydroxyl)-3,4-dimethyl-9H-thioxanthone-thioxanthene ketones such as 9-ketone methochloride; 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4, the acylphosphine oxide classes such as 4-trimethylammonium-amyl group phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxides etc.It should be noted that, these Photoepolymerizationinitiater initiaters (D) can only be used singly, or in combination of two or more kinds separately.
In addition, as their auxiliary agent, can also be used in combination trolamine, tri-isopropanolamine, 4,4 '-bis-(dimethylamino) benzophenone (michaelis ketone), 4,4 '-bis-(diethylin) benzophenone, 2-dimethylaminoethyl phenylformic acid, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.
Among these, preferably use benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, benzoyl isopropyl ether, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.
Content as Photoepolymerizationinitiater initiater (D), with respect to 100 weight part carbamate (methyl) acrylate based compounds (A) (being its summation while containing ethylenically unsaturated monomer (C)), be preferably 0.1～40 weight part, be particularly preferably 1～20 weight part, extremely be preferably 2～20 weight parts.
When the content of Photoepolymerizationinitiater initiater (D) is very few, exists and to cause solidifying bad tendency, and too much the time, have the tendency of the tendency that stability of solution reduces such as separating out or easily cause embrittlement, painted problem from coating.
Therefore, can obtain the actinic energy ray curable resion composition that contains carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B), preferably also contains ethylenically unsaturated monomer (C), Photoepolymerizationinitiater initiater (D) of the present invention, as required, can also further add surface conditioner, flow agent, stopper etc.
As surface conditioner, be not particularly limited, such as listing Synolac etc.
Described Synolac has the effect of the cementability of the effect of making film, raising and metal steam surfacing while giving coating.
As flow agent, so long as there is the flow agent of giving the effect of masking liquid to the wettability of base material, reducing capillary effect, can use known common flow agent, such as using organic-silicon-modified resin, fluorine modified resin, alkyl-modified resin etc.
As stopper, for example can list para benzoquinone, naphthoquinones, toluquinone, 2,5-phenylbenzene para benzoquinone, quinhydrones, 2,5 di tert butylhydroquinone, toluhydroquinone, hydroquinone monomethyl ether, single tertiary butylated hydroquinone, p-ten.-butylcatechol etc.
In addition, can also compounding oil in actinic energy ray curable resion composition of the present invention, antioxidant, fire retardant, static inhibitor, weighting agent, stablizer, toughener, matting agent, abrasive, organic fine particles, inorganic particles, macromolecular compound (vinylformic acid (being) resin, vibrin, epoxy resin etc.) etc.
In addition, actinic energy ray curable resion composition of the present invention as required the compounding organic solvent adjust viscosity and use.As described organic solvent, such as listing the alcohols such as methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol; The ketones such as acetone, mibk, methylethylketone, pimelinketone; The cellosolve classes such as ethyl cellosolve; The fragrant same clan such as toluene, dimethylbenzene; The glycol ethers such as propylene glycol monomethyl ether; The acetate esters such as methyl acetate, ethyl acetate, butylacetate; Diacetone alcohol etc.Above-mentioned these organic solvents may be used singly or in combination of two or more.
While being used in combination two or more, from the viewpoint of appearance of film, consider, preferably, the combination of the alcohols such as ketone, methyl alcohol such as the glycol ethers such as propylene glycol monomethyl ether and methylethylketone; The combination of the alcohols such as the ketones such as methylethylketone and methyl alcohol; From the alcohols such as methyl alcohol, select two or more to be used in combination etc.
Actinic energy ray curable resion composition of the present invention can be used above-mentioned organic solvent usually to be diluted to 3～60 % by weight, preferably to be diluted to 5～40 % by weight and to coat base material.
It should be noted that, when manufacturing actinic energy ray curable resion composition of the present invention, blending means to carbamate (methyl) acrylate based compound (A), polysaccharide derivates (B), ethylenically unsaturated monomer (C), Photoepolymerizationinitiater initiater (D) is not particularly limited, and can be mixed according to the whole bag of tricks.
Actinic energy ray curable resion composition of the present invention is effectively with the curable resin composition of filming that is used to form of the top paint, anchor coating agent etc. of the various base materials of opposing, (in the situation that the coating composition of organic solvent diluting after actinic energy ray curable resion composition is coated to base material, after further making it dry), irradiate active energy beam and be cured.Be not particularly limited the wet type coating method such as can listing spraying, showering, dip-coating, roller coat, spin coating, silk screen printing etc. as coating process.
As described active energy beam, except light such as far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays, outside the hertzian wave such as X ray, gamma-rays, can also utilize electron beam, proton ray, neutron ray etc., from aspects such as the acquisition easiness of curing speed, irradiating unit, prices, it is favourable utilizing uviolizing to be cured.In addition, while carrying out electron beam irradiation, do not use Photoepolymerizationinitiater initiater (D) can solidify yet.
As the method be cured by irradiation ultraviolet radiation, need only use and send the high pressure mercury vapour lamp of the light of 150～450nm wavelength region may, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED etc., carry out 30～3000mJ/cm 2the irradiation of left and right gets final product.
After irradiation ultraviolet radiation, also can be heated as required and seek to solidify fully.
As coating film thickness (solidify after thickness), usually be preferably 1～50 μ m, be particularly preferably 2～30 μ m, 3～25 μ m more preferably.Wherein especially in the situation of scumbling, be preferably 1～15 μ m, in the situation that thick painting is preferably 15～30 μ m, be particularly preferably 15～25 μ m.
In the present invention, even utilize the film application to form, film, also can be hidden concavo-convex, base material self exists concavo-convex etc. the impact that cause such as particulate by existing in coating, foreign matter, therefore very effective when scumbling.
As the base material of the coating object of actinic energy ray curable resion composition of the present invention, can list polyolefin-based resins, polyester based resin, polycarbonate-based resin, acrylonitrile butadient styrene (ABS), polystyrene resin etc., their products formed (film, sheet, cup etc.), metal (aluminium, copper, iron, SUS, zinc, magnesium, their alloy etc.), glass etc.
In addition, actinic energy ray curable resion composition of the present invention also is preferably used as the anchor coating agent of metal evaporation, particularly, be preferred for following multilayer structure making: actinic energy ray curable resion composition of the present invention is coated to the substrate surfaces such as plastics, after by the irradiation active energy beam, it being solidified, evaporation metal on coated surface, and further form as required top coat thereon, thus the multilayer structure making of making.
As described plastic basis material, such as usually using ABS, polycarbonate, vinylformic acid (being) resin, polyamide resin, their composite base material or composite base material of previous materials that glass fibre, inorganics are mixed etc.
As the thickness of the cured coating film of above-mentioned actinic energy ray curable resion composition, dry film thickness is preferably 1～30 μ m, is particularly preferably 2～15 μ m.
In addition, as the metal of wanting evaporation, such as listing aluminium (Al), tin (Sn), indium (In), indium-Xi (InSn) etc.
Of the present invention contain carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B) even actinic energy ray curable resion composition utilize the film application to form to film, also can be hidden particulate by existing in coating, foreign matter etc. cause concavo-convex, there is the smoothness of filming, the effect that the transparency is excellent.And actinic energy ray curable resion composition of the present invention is as coating, tackiness agent, caking agent, bonding caking agent, China ink, protection coating agent, anchor coating agent, magnetic powder coating adhesive, for sandblast, the various coating film forming material such as overlay film, plate is useful.Wherein, the anchor coating agent as metal evaporation is very useful.
Embodiment
Below, list embodiment the present invention is carried out to more specific description, but the present invention is not limited to following embodiment in being no more than the scope of its purport.It should be noted that, in example, " part ", " % " refer to weight basis.
As carbamate (methyl) acrylate based compound (A), prepared following compound.
(A-1): possessing thermometer, agitator, water-cooled condenser, drop into 16.1g (0.07 mole) isophorone diisocyanate in the four neck flasks that nitrogen is blown into mouthful, the difunctionality polyester polyol (hydroxyl value 54mgKOH/g) of (75.2g 0.04 mole), hydroquinone monomethyl ether 0.02g as stopper, dibutyl tin laurate 0.02g as catalysts, under 60 ℃, reaction is 3 hours, drop into 8.6g (0.07 mole) vinylformic acid 2-hydroxyl ethyl ester, under 60 ℃, reaction is 3 hours, reach 0.3% time point end reaction at the residual isocyanate base, obtain difunctionality urethane acrylate (A-1) (weight-average molecular weight 10, 000, viscosity under 60 ℃ is 15, 000mPas).
As polysaccharide derivates (B), prepared following material.
(B-1): cellulose acetate butyrate is resin (Eastman Chemical Company system, trade(brand)name " CAB551-0.01 ": number-average molecular weight 16,000)
(B-2): cellulose acetate butyrate is resin (Eastman Chemical Company system, trade(brand)name " CAB551-0.2 ": number-average molecular weight 30,000)
(B-3): cellulose acetate butyrate is resin (Eastman Chemical Company system, trade(brand)name " CAB500-5 ": number-average molecular weight 57,000)
(B-4): cellulose acetate butyrate is resin (Eastman Chemical Company system, trade(brand)name " CAB381-20 ": number-average molecular weight 70,000)
(B-5): cellulose acetate propionate is resin (Eastman Chemical Company system, trade(brand)name " CAB504-0.2 ": number-average molecular weight 15,000)
As ethylenically unsaturated monomer (C), prepared following material.
(C-1): pentaerythritol triacrylate
As Photoepolymerizationinitiater initiater (D), prepared following material.
(D-1): 1-hydroxycyclohexylphenylketone (BASF japan ltd. system, " Irgacure184 ")
As acrylic resin (B ') solution, prepared following solution.
(B '-1): possess that reflux exchanger, agitator, nitrogen are blown into mouthful and four neck round-bottomed flasks of thermometer in drop into 55 parts of ethyl acetate, 45 parts of toluene, warming while stirring to 90 ℃, with within 2 hours, dripping to the solution that has added 0.05 part of azobis isobutyronitrile as polymerization starter (AIBN) to form in 100 parts of butyl acrylates.Thereafter, be dissolved with appending after 2 hours the polymerization starter solution that 0.05 part of AIBN forms in 10 parts of ethyl acetate after 1 hour, under refluxing, reaction is 7 hours, then by ethyl acetate, dilute, thereby obtain vinylformic acid (being) resin (B '-1) solution (weight-average molecular weight 180,000, number-average molecular weight 65,000, solids component 30%).
(embodiment 1～11)
According to the ratio shown in table 1 with the above-mentioned carbamate of solids component conversion compounding (methyl) acrylate based compound (A), polysaccharide derivates (B), ethylenically unsaturated monomer (C), Photoepolymerizationinitiater initiater (D) after, the solids component be diluted to except Photoepolymerizationinitiater initiater by ethyl acetate reaches 30%, obtains actinic energy ray curable resion composition.
(comparative example 1)
After 100 parts of carbamates of solids component conversion compounding (methyl) acrylate based compounds (A), 42.9 parts of ethylenically unsaturated monomers (C), 5.7 parts of Photoepolymerizationinitiater initiaters (D), the solids component be diluted to except Photoepolymerizationinitiater initiater (D) by ethyl acetate reaches 30%, obtains actinic energy ray curable resion composition.
(comparative example 2)
In embodiment 1, except using acrylic resin (B '-1), replace polysaccharide derivates (B-1), operation, obtain actinic energy ray curable resion composition similarly to Example 1.
For the gained actinic energy ray curable resion composition, carry out following evaluation.
Evaluation result is shown in table 1.
The formation of<evaluation use cured coating film>
For above-mentioned resulting actinic energy ray curable resion composition, 0.1 part of particulate of 100 parts of compoundings of composition (vinylformic acid (ester) microballon: median size 5 μ m that will obtain removed solvent from actinic energy ray curable resion composition, Shin Nihon Oil Co., Ltd's system, " NMB-0520 ") material that the forms mode that reaches 4～5 μ m with cured coating film with excellent painting machine coats with the easy polyethylene terephthalate thin film base material (thickness 125 μ m) of adhesive linkage, under 60 ℃, drying is after 5 minutes, use the high pressure mercury vapour lamp of 1 80W, carry out uviolizing (cumulative exposure 800mJ/cm from the height of 18cm 2 times with the line speed of 3.4m/ minute 2), obtain cured coating film.
It should be noted that, actinic energy ray curable resion composition of the present invention contains carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B), and the compounding of above-mentioned particulate is disguise in order to estimate concaveconvex shape and specially compounding.
<smoothness (surfaceness)>
For the cured coating film obtained for carrying out above-mentioned evaluation utilizing film coated surface to form, use surfaceness meter (company of Tokyo Seimitsu Co., Ltd system, " SURFCOM480A "), at strainer kind: Gaussian, λ s strainer: cutoff 300, calculate under the condition of specification: JIS ' 01, evaluation length 10mm, finding speed 0.3mm/s, cutoff 0.8mm and measured, measure the surface roughness Ra value.
[evaluation]
◎ Ra value is lower than 0.050
Zero Ra value is more than 0.050 and lower than 0.100
△ Ra value is more than 0.100 and lower than 0.120
* Ra value is more than 0.120
<the transparency>
For the cured coating film obtained for carrying out above-mentioned evaluation utilizing film coated surface to form, use haze meter (Japanese electric look Industrial Co., Ltd system, " NDH2000 "), measure haze value.
[evaluation]
Zero haze value is lower than 0.9
* haze value is more than 0.9
<adaptation>
For the cured coating film obtained for carrying out above-mentioned evaluation utilizing film coated surface to form, according to JISK5400 (nineteen ninety version), to draw lattice adhesive tape method, estimate the base material adaptation.
[evaluation]
0 100/100 (all closely sealed)
* 99/100～0/100 (part is peeled off～is all peeled off)
[table 1]
Figure BDA00003072817200251
Known according to above-mentioned evaluation result, by containing carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B) though the cured coating film of the embodiment 1～11 that obtains of actinic energy ray curable resion composition contain particulate, also can obtain smoothness excellence, cured coating film that the transparency is excellent.
Surface smoothness, the transparency of the cured coating film of the comparative example 1 obtained by the actinic energy ray curable resion composition that does not contain polysaccharide derivates (B) on the other hand, are poor.
In addition, the transparency excellence of the cured coating film of the comparative example 2 obtained by the actinic energy ray curable resion composition that contains acrylic resin (B ') and replace polysaccharide derivates (B), but smoothness is poor, does not have hidden concavo-convex effect.
It should be noted that, in above-described embodiment, show the specific embodiment of the present invention, but above-described embodiment is only simple illustration, does not do limited explanation.The clear and definite various distortion of those skilled in the art are also included within scope of the present invention.
utilizability on industry
Of the present invention contain carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B) even actinic energy ray curable resion composition utilize the film application to form to film, also can be hidden particulate by existing in coating, foreign matter etc. cause concavo-convex, there is the smoothness of filming, the effect that the transparency is excellent.And actinic energy ray curable resion composition of the present invention is as coating, tackiness agent, caking agent, bonding caking agent, China ink, protection coating agent, anchor coating agent, magnetic powder coating adhesive, for sandblast, the various coating film forming material such as overlay film, plate is useful.Wherein, the anchor coating agent as metal evaporation is very useful.

Claims (8)

1. an actinic energy ray curable resion composition, is characterized in that, it contains carbamate (methyl) acrylate based compound (A) and polysaccharide derivates (B).
2. actinic energy ray curable resion composition according to claim 1, is characterized in that, polysaccharide derivates (B) is derivatived cellulose.
3. actinic energy ray curable resion composition according to claim 1 and 2, is characterized in that, the number-average molecular weight of polysaccharide derivates (B) is 10,000～100,000.
4. according to the described actinic energy ray curable resion composition of any one in claim 1～3, it is characterized in that, the content of polysaccharide derivates (B) is more than 3 weight parts with respect to 100 weight part carbamate (methyl) acrylate based compounds (A).
5. according to the described actinic energy ray curable resion composition of any one in claim 1～4, it is characterized in that, it contains ethylenically unsaturated monomer (C).
6. according to the described actinic energy ray curable resion composition of any one in claim 1～5, it is characterized in that, it also contains Photoepolymerizationinitiater initiater (D).
7. a coating agent, is characterized in that, it contains the described actinic energy ray curable resion composition of any one in claim 1～6.
8. coating agent according to claim 7, is characterized in that, it is as the silane coupling agent of metal evaporation.
CN2012800033926A 2011-01-21 2012-01-20 Active energy ray-curable resin composition and coating agent Pending CN103168051A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011-010837 2011-01-21
JP2011010837 2011-01-21
PCT/JP2012/051147 WO2012099231A1 (en) 2011-01-21 2012-01-20 Active energy ray-curable resin composition and coating agent

Publications (1)

Publication Number Publication Date
CN103168051A true CN103168051A (en) 2013-06-19

Family

ID=46515848

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012800033926A Pending CN103168051A (en) 2011-01-21 2012-01-20 Active energy ray-curable resin composition and coating agent

Country Status (5)

Country Link
JP (1) JP5921893B2 (en)
KR (1) KR101839639B1 (en)
CN (1) CN103168051A (en)
TW (1) TWI550035B (en)
WO (1) WO2012099231A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108137762A (en) * 2015-12-22 2018-06-08 日本合成化学工业株式会社 Actinic energy ray curable resion composition and its manufacturing method
CN109196009A (en) * 2016-06-17 2019-01-11 日本合成化学工业株式会社 Actinic energy ray curable resion composition and the smears formed using it

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6399504B2 (en) * 2013-07-02 2018-10-03 東洋工業塗料株式会社 Vehicle lamp parts using phosphorescent paint (with gloss) for coating on metal vapor-deposited films
JP6011895B2 (en) * 2014-09-30 2016-10-25 荒川化学工業株式会社 Undercoat agent for substrate with copper thin film, substrate with copper thin film, method for producing substrate with copper thin film, and conductive film
JP6943117B2 (en) * 2016-10-07 2021-09-29 三菱ケミカル株式会社 Undercoating agent composition for metal thin film, undercoating agent for metal thin film, base film with undercoat layer and laminated film with metal thin film layer
KR101949091B1 (en) * 2018-06-12 2019-05-21 허권 Inorganic paint composition with herb medicine
WO2023195442A1 (en) * 2022-04-04 2023-10-12 幸士 生田 Photocurable composition, cured product and method for producing cured product

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001261916A (en) * 2000-03-17 2001-09-26 Kawamura Inst Of Chem Res Resin composite material having common continuous structure and method for producing the same
CN1693991A (en) * 2004-05-07 2005-11-09 东进世美肯株式会社 Photoresist resin composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3641116B2 (en) * 1997-10-14 2005-04-20 東京応化工業株式会社 Photosensitive composition for sandblasting and photosensitive film using the same
JP2001190274A (en) * 2000-01-11 2001-07-17 Kansai Paint Co Ltd Method for producing granular formed product for immoibilizing enzyme or microorganism cell
JP2001261758A (en) * 2000-03-17 2001-09-26 Kawamura Inst Of Chem Res Resin composite having coconinuous structure and method for producing the same
JP2001278926A (en) * 2000-03-31 2001-10-10 Osaka Gas Co Ltd Photocurable composition and coating film
JP4735003B2 (en) * 2005-03-31 2011-07-27 住友ベークライト株式会社 Transparent resin molding and coating film
JP5026012B2 (en) * 2006-07-25 2012-09-12 大日本塗料株式会社 In-mold coating composition and in-mold coating product using the same
US8263677B2 (en) * 2009-09-08 2012-09-11 Creative Nail Design, Inc. Removable color gel basecoat for artificial nail coatings and methods therefore

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001261916A (en) * 2000-03-17 2001-09-26 Kawamura Inst Of Chem Res Resin composite material having common continuous structure and method for producing the same
CN1693991A (en) * 2004-05-07 2005-11-09 东进世美肯株式会社 Photoresist resin composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108137762A (en) * 2015-12-22 2018-06-08 日本合成化学工业株式会社 Actinic energy ray curable resion composition and its manufacturing method
CN109196009A (en) * 2016-06-17 2019-01-11 日本合成化学工业株式会社 Actinic energy ray curable resion composition and the smears formed using it
CN109196009B (en) * 2016-06-17 2021-03-19 三菱化学株式会社 Active energy ray-curable resin composition and coating agent formed using same

Also Published As

Publication number Publication date
TW201235424A (en) 2012-09-01
KR20130140725A (en) 2013-12-24
JP2012162715A (en) 2012-08-30
JP5921893B2 (en) 2016-05-24
KR101839639B1 (en) 2018-03-16
WO2012099231A1 (en) 2012-07-26
TWI550035B (en) 2016-09-21

Similar Documents

Publication Publication Date Title
CN103380157B (en) Active-energy-curable resin composition and coating agent
CN103168051A (en) Active energy ray-curable resin composition and coating agent
CN105916923B (en) Plastic film
CN104736611B (en) Hard coat film
CN105143322B (en) Plastic foil
TWI625359B (en) Active energy ray-curable resin composition, coating agent composition, and laminate
CN102408823B (en) The plastic sheeting of active energy line curing thin film non-water-based primer and the plastic sheeting of active energy line curing thin film
CN1984936A (en) Active energy ray curable resin composition, method for producing the same, and coating agent composition using the same
TW201542602A (en) Urethane (meth)acrylate compound, active-energy-ray-curable resin composition, and coating agent
CN104812853A (en) Composition for hardcoat and molded article with hardcoat layer
TW201610014A (en) Active-energy-curing resin composition, coating material, coating film, and laminate film
JP2014122338A (en) Active energy ray curable resin composition, coating agent composition, and laminated body
WO2015019898A1 (en) Active energy ray-curable resin composition, undercoating agent containing same, and molded article
JP2017210607A (en) Active energy ray-curable adhesive composition and adhesive composition for acrylic resin member using the same
JP2016121346A (en) Method of producing urethane (meth)acrylate
JP4863464B2 (en) Method for manufacturing laminate exhibiting iris color
CN105189568A (en) Radiation-curable resin composition, undercoating agent containing same, and molding
JP6358789B2 (en) Active energy ray-curable resin composition and coating agent
CN101857659A (en) Resin combination
JP6617912B2 (en) Active energy ray-curable resin composition, coating agent for undercoat containing the same, and molded article
JP2015143350A (en) Active energy ray curable composition and coating agent, and novel urethane bond-containing compound
JP6561912B2 (en) Active energy ray-curable adhesive composition for plastic film or sheet
JP6733259B2 (en) Active energy ray curable resin composition
WO2017110845A1 (en) Active energy ray-curable resin composition and method for producing same
JP6452320B2 (en) Urethane (meth) acrylate-based compound, active energy ray-curable resin composition, and coating agent composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20130619