CN101857659A - Resin combination - Google Patents
Resin combination Download PDFInfo
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- CN101857659A CN101857659A CN201010155451A CN201010155451A CN101857659A CN 101857659 A CN101857659 A CN 101857659A CN 201010155451 A CN201010155451 A CN 201010155451A CN 201010155451 A CN201010155451 A CN 201010155451A CN 101857659 A CN101857659 A CN 101857659A
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- acrylate
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides shrinking percentage when solidifying low, can access and have high rigidity, do not produce and curl or the resin combination of the cured film of crackle and use the protective cover of this resin combination.A kind of resin combination, wherein, contain by making carbamate (methyl) acrylate that the reaction of glycerine (methyl) acrylate (a) and ester ring type polyisocyanate compound obtains or by making glycerine (methyl) acrylate (a) and (a) carbamate (methyl) acrylate, (methyl) acrylate and the Photoepolymerizationinitiater initiater that obtain of in addition (methyl) acrylate (a-1) and polyisocyanate compound (b) reaction.
Description
Technical field
The present invention relates to comprise with glycerine (methyl) acrylate is the resin combination of carbamate (methyl) acrylate of raw material.In addition, the cured film of resin combination of the present invention have good hardness, with the adaptation of base material and scuff resistance etc., it is few to curl, the generation of crackle is also few, therefore can be as the protective cover of plastics film or compact shell.
Background technology
At present, use processibility in the industrial community, the transparency is good and at all good plastics of each side such as light weight, cheapness, optical characteristics.But,, therefore, generally be coated with protective cover from the teeth outwards because plastics, have shortcomings such as the easy scratch in surface than softnesses such as glass.In the protective cover, as the protective cover that is used to improve surface hardness, multiple thermosetting coatings such as known polysiloxane-based coating, acrylic coating, melamine class coating.Wherein, polysiloxane-based hard coating is because performance, best in quality thereby mainly used but then, also has shortcomings such as length set time, price height.
Therefore, developed and used the photosensitivity acrylic acid or the like hard coating (referring to Patent Document 1) that remedies polysiloxane-based hard coating shortcoming.The acrylic acid or the like hard coating solidifies immediately by the irradiation ultraviolet radiation isoradial, and processing treatment speed is fast.In addition, hardness, scuff resistance etc. are good, and cheap, have therefore become the main flow in hard coat field.Be particularly suitable for the continuous processing of the film of polyester etc.
As plastics film, polyester film, acrylic acid or the like film, polycarbonate film, vinyl chloride film, triacetylcellulose film, polyethersulfone film etc. are arranged, and polyester film is most widely used because have various excellent characteristic.This polyester film is extensive use of as the main body or the casting of electronic device such as switch, mobile phone or computer, MP3 player of the functional film of CRT flat panel TV, touch panel, liquid-crystal display (LCD), plasma display (PDP), OLED display etc., tame electrical article with surface film, whole kitchen surface soiling film, electronic material aspect as disperse film or automobile shading film, blank of anti-glass.These article all are coated with hard coat in order to prevent its galled spots.In addition, except that plastics film, the related member of liquid crystal around the material that obtains behind the coating hard coat on the sheet material of polycarbonate or acrylic acid or the like etc. or the substrate also is used for CD or backlight.
In recent years, require functional beyond this hard coat performance of scuff resistance.For example, be provided with the display body such as CRT, LCD, PDP of film, owing to reflection is difficult to observe display picture, eyes are tired easily, and therefore, according to purposes, the hard coat that need have anti-surface reflection function is handled (referring to Patent Document 2).
Requiring to have functional hard coat on the other hand, also carrying out raising Study on Hardness as the original purpose of hard coat.For example, in patent documentation 3, improve hardness by in resin combination, adding the polyfunctional carbamate acrylate.But the cure shrinkage of the polyfunctional carbamate acrylate of use is big, has problems such as observing the crackle generation.In addition, its addition or form overall formation and have restriction.
In patent documentation 4 and patent documentation 5, put down in writing the resin combination that comprises carbamate (methyl) acrylate that glycerine (methyl) acrylate (a) and polyisocyanate compound (b) is reacted and obtain.In patent documentation 4, put down in writing with weight-average molecular weight more than 10000 polymkeric substance and isocyanuric acid three acryloyl-oxy ethyl esters serve as must composition, be used for as the resin combination of printed wiring with the overlay film of protection masks such as soldering-resistance layer; but; failed call hardness and scuff resistance are not considered shrinking percentage yet.In patent documentation 5, put down in writing the three-dimensional contouring composition that contains the improved silica particulate, but do not had record about hard coat.
Patent documentation 1: Japanese kokai publication hei 9-48934 communique
Patent documentation 2: Japanese kokai publication hei 9-145903 communique
Patent documentation 3: TOHKEMY 2001-113648 communique
Patent documentation 4: Japanese kokai publication sho 62-290705 communique
Patent documentation 5: Japanese kokai publication hei 9-87513 communique
Summary of the invention
In the tendency of the film thining of base material; in order to develop harder protective cover; the method that attempted the high material of the hardness of materials used itself, improves degree of crosslinking and set film thickness thicker still, exists to crack and because thick film makes problems such as the degree of crosslinking raising causes curling.
The object of the present invention is to provide and improve above-mentioned shortcoming, can access and can carry out the thick film coating and hardness is good and do not produce and curl or the cured film of crackle, and the low resin combination of shrinking percentage when solidifying.
The inventor has carried out research extensively and profoundly in order to address the above problem, and found that the resin combination with specific compound and composition can address the above problem, and has finished the present invention.
That is, the present invention relates to:
(1) a kind of resin combination, wherein, contain by making glycerine (methyl) acrylate (a) and ester ring type polyisocyanate compound react carbamate (methyl) acrylate (A), (methyl) acrylate (B) and the Photoepolymerizationinitiater initiater (C) that obtains;
(2) a kind of resin combination, wherein, contain by making glycerine (methyl) acrylate (a) and (a) carbamate (methyl) acrylate (A-1), (methyl) acrylate (B) and the Photoepolymerizationinitiater initiater (C) that obtain of in addition (methyl) acrylate (a-1) and polyisocyanate compound (b) reaction;
(3) above-mentioned (1) or (2) described resin combination, it is used for supercoat.
According to the present invention, provide shrinking percentage when solidifying low, can access to have high rigidity and do not produce and curl or the resin combination of the cured film of crackle and use the protective cover of this resin combination.
Embodiment
Below, the present invention is described in detail.
The carbamate that uses in the resin combination of the present invention (methyl) acrylate (A) obtains by making glycerine (methyl) acrylate (a) and polyisocyanate compound (b) reaction.(methyl) acryloyl radix that glycerine (methyl) acrylate (a) has is not particularly limited.
The carbamate that uses in the resin combination of the present invention (methyl) acrylate (A-1) by make glycerine (methyl) acrylate (a) and (a) in addition (methyl) acrylate (a-1) and polyisocyanate compound (b) reaction obtain.(methyl) acryloyl radix that glycerine (methyl) acrylate (a) has is not particularly limited.
As operable glycerine (methyl) acrylate (a) in the resin combination of the present invention, can enumerate: glycerine diacrylate, glycerine dimethacrylate, glycerine one acrylate monomethyl acrylate, Glycerol dimer triacrylate, Glycerol dimer trimethacrylate etc.Wherein, preferably glycerine diacrylate, glycerine dimethacrylate, glycerine one acrylate monomethyl acrylate.
As operable in the resin combination of the present invention (a) (methyl) acrylate (a-1) in addition, then be not particularly limited as long as have the active hydrogen base, can enumerate: simple function or multifunctional (methyl) acrylate such as hydroxyl (methyl) acrylate, Pentaerythritols, methylol class, epoxy acrylate class.
As (a) (methyl) acrylate (a-1) in addition, for example can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, cyclohexanedimethanol one (methyl) acrylate, polyoxyethylene glycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate, (methyl) vinylformic acid-2-hydroxyl-hydroxyl (methyl) acrylate such as 3-phenoxy group propyl ester; Pentaerythritols such as tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol two (methyl) acrylate; Methylol classes such as TriMethylolPropane(TMP) two (methyl) acrylate; Epoxy acrylate classes such as dihydroxyphenyl propane diepoxy acrylate.
In addition, these (a) (methyl) acrylate (a-1) in addition can use separately or two or more mixing is used.
As operable in the resin combination of the present invention (a) (methyl) acrylate (a-1) in addition, preferably multifunctional (methyl) acrylate, above (methyl) acrylate of further preferred trifunctional, wherein, preferred pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate or their mixture.
As operable polyisocyanate compound (b) in the resin combination of the present invention, then be not particularly limited so long as contain the compound of two above isocyanate group in a part, for example can enumerate: aliphatic polyisocyanate compound, aromatic polyisocyanate compound, ester ring type polyisocyanate compound, their trimer or polymer compound, biuret type polyisocyanates, allophanate type polyisocyanates etc.Trimer or polymer compound are meant that three isocyanate group form the compound of one or more isocyanuric acid ester ring structure.In addition, polyisocyanate compound (b) can use separately or two or more mixing is used.
As aliphatic polyisocyanate compound, for example can enumerate: 1, hexamethylene-diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, the hydrogenation of benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, 1, the 3-cyclohexyl diisocyanate, 1, the 4-cyclohexyl diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, between tetramethylxylene diisocyanate, to tetramethylxylene diisocyanate, 1,4-fourth vulcabond, 1,12-dodecane vulcabond, 2,2,4-trimethyl-cyclohexane vulcabond, 2,4,4-trimethyl-cyclohexane vulcabond, 2,2,4-trimethylammonium-1, hexamethylene-diisocyanate, 2,4,4-trimethylammonium-hexamethylene diisocyanate, lysinediisocyanate, norbornene alkyl diisocyanate etc.
As the aromatic polyisocyanate compound, for example can enumerate: tolylene diisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, triazine vulcabond, 1,4-phenylene diisocyanate, 1,6-phenylene diisocyanate etc.
As the ester ring type polyisocyanate compound, for example can enumerate: cyclohexyl diisocyanate, hydrogenated tolylene diisocyanate, dimethyl cyclohexane vulcabond, 4,4-methylene radical two (cyclohexyl isocyanate), isophorone diisocyanate, norbornane triisocyanate, norbornene alkyl diisocyanate etc.
As the polyisocyanate compound among the present invention (b), preferred aliphat polyisocyanate compound, more preferably ester ring type polyisocyanates, further preferred isophorone diisocyanate and Trimerization of Isophorone Diisocyanate thing or polymer compound etc.
The carbamate that uses among the present invention (methyl) acrylate (A) obtains by making glycerine (methyl) acrylate (a) and polyisocyanate compound (b), preferred ester ring type polyisocyanate compound reaction.(A-1) by make glycerine (methyl) acrylate (a) and (a) in addition (methyl) acrylate (a-1) and polyisocyanate compound (b) reaction obtain.(A) with (A-1) can in resin combination of the present invention, use separately separately, perhaps also can be used in combination.With respect to glycerine (methyl) acrylate (a) and (a) active hydrogen base 1 equivalent in addition (methyl) acrylate (a-1), polyisocyanate compound (b) is generally 0.1～50 normal scope in the isocyanate group equivalent, preferred 0.1～10 normal scope.Temperature of reaction is generally 30～150 ℃, preferred 50～100 ℃ scope.The terminal point of reaction is by with excessive n-Butyl Amine 99 and remaining isocyanate quantitative response, and calculates with the method for 1N hydrochloric acid back titration, is that moment below the 0.5 quality % is as terminal point with isocyanic ester.
In order to shorten these reaction times, can add catalyzer.As this catalyzer, can use in basic catalyst and the acidic cpd any one.As basic catalyst, for example can enumerate: amines such as pyridine, pyrroles, triethylamine, diethylamine, dibutylamine, ammonia; Phosphine such as tributylphosphine, triphenylphosphine class.In addition, as an acidic catalyst, for example can enumerate: metal alkoxide classes such as copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, four titanium butoxide, tetrabutyl zirconate; Louis's acids such as aluminum chloride; Tin compounds such as 2-ethyl hexane tin, three lauric acid tin octylates, dibutyl tin laurate, oxalic acid tin octylate.The addition of these catalyzer is generally more than 0.1 mass parts, below 1 mass parts with respect to polyisocyanate compound (b) 100 mass parts.
In addition, during reaction for the polymerization in preventing to react, preferred use stopper (for example, 4-methoxyphenol, 2,4-dimethyl-6-tert.-butyl phenol, 3-hydroxythiophenol, para benzoquinone, 2,5-dihydroxyl para benzoquinone, thiodiphenylamine etc.), the usage quantity of this stopper is more than the 0.01 quality %, below the 1 quality % with respect to reaction mixture, more than the preferred 0.05 quality %, below the 0.5 quality %.Temperature of reaction is 60～150 ℃, preferred 80～120 ℃.
In the resin combination of the present invention, when the solid shape of establishing resin combination of the present invention was divided into 100 quality %, above-mentioned (A) and/or usage quantity (A-1) were generally more than the 5 quality %, below the 97 quality %, more than the preferred 21 quality %, below the 80 quality %.
Be not particularly limited as (methyl) acrylate (B) that uses among the present invention, can enumerate: (methyl) acrylate more than simple function (methyl) acrylate, difunctionality (methyl) acrylate, the trifunctional, polyester (methyl) acrylate, carbamate (methyl) origoester acrylate, polyester (methyl) origoester acrylate, epoxy (methyl) origoester acrylate etc.
As simple function (methyl) acrylate, for example can enumerate: acryloyl morpholine; (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-hydroxyl (methyl) acrylate such as 4-hydroxyl butyl ester; Hexanaphthene-1,4-dimethanol one (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclo pentyl ester (dicyclopentanyl (meth) acrylate), (methyl) vinylformic acid double cyclopentenyl ester (dicyclopentenyl (meth) acrylate)), (methyl) vinylformic acid double cyclopentenyl oxygen ethyl ester (dicyclopentenyl oxyethyl (meth) acrylate)) etc. aliphatics (methyl) acrylate; (methyl) phenoxyethyl acrylate, phenyl (many) oxyethyl group (methyl) acrylate, (methyl) vinylformic acid are to aromatic series (methyl) acrylate such as cumyl ethyl phenoxy, (methyl) vinylformic acid tribromo-benzene 2-ethoxyethyl acetate, (methyl) vinylformic acid benzene sulphur ethyl ester, (methyl) vinylformic acid-2-hydroxyl-3-benzene oxygen propyl ester, phenylphenol (many) oxyethyl group (methyl) acrylate, phenylphenol epoxy (methyl) acrylate.
As difunctionality (methyl) acrylate, can enumerate: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, dihydroxyphenyl propane (many) oxyethyl group two (methyl) acrylate, dihydroxyphenyl propane (many) propoxy-two (methyl) acrylate, Bisphenol F (many) oxyethyl group two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid DOPCP (for example, Nippon Kayaku K. K's system KAYARADHX-220, HX-620 etc.) etc.
As multifunctional (methyl) acrylate more than the trifunctional, can enumerate: methylol classes such as two (TriMethylolPropane(TMP)s) four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trishydroxymethyl octane three (methyl) acrylate, TriMethylolPropane(TMP) (many) oxyethyl group three (methyl) acrylate, TriMethylolPropane(TMP) (many) propoxy-three (methyl) acrylate, TriMethylolPropane(TMP) (many) oxyethyl group (many) propoxy-three (methyl) acrylate; Pentaerythritols such as tetramethylolmethane three (methyl) acrylate, tetramethylolmethane (many) oxyethyl group four (methyl) acrylate, tetramethylolmethane (many) propoxy-four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate; Isocyanuric acid three [(methyl) acrylyl oxy-ethyl] ester of isocyanuric acid three [(methyl) acrylyl oxy-ethyl] ester, caprolactone modification etc.; Epoxy acrylate classes such as dihydroxyphenyl propane diepoxy acrylate.
As (gathering) ester (methyl) acrylate, for example can enumerate: ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyoxyethylene glycol, glycolss such as polypropylene glycol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,4-diethyl-1, the 5-pentanediol, 2-butyl-2-ethyl-1, straight or branched alkyl diol classes such as ammediol, hexanaphthene-1, ester ring type alkyl diol classes such as 4-dimethanol, reaction product (gathering) esterdiol of diol compound such as dihydroxyphenyl propane (many) oxyethyl group glycol or dihydroxyphenyl propane (many) propoxy-glycol and aforesaid diprotic acid or its acid anhydrides and (methyl) acrylic acid reaction product etc.
As carbamate (methyl) origoester acrylate, for example can enumerate: make diol compound (for example, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,4-diethyl-1, the 5-pentanediol, 2-butyl-2-ethyl-1, ammediol, hexanaphthene-1, the 4-dimethanol, polyoxyethylene glycol, polypropylene glycol, many oxyethyl groups of dihydroxyphenyl propane glycol or many propoxy-of dihydroxyphenyl propane glycol etc.) or these diol compounds and diprotic acid or its acid anhydrides are (for example, Succinic Acid, hexanodioic acid, nonane diacid, dimeracid, m-phthalic acid, terephthalic acid, phthalic acid or their acid anhydrides) the reaction product polyester glycol, with organic multiple isocyanate (for example, 1,4-fourth vulcabond, 1, hexamethylene-diisocyanate, 2,2,4-trimethylammonium-1, hexamethylene-diisocyanate, 2,4,4-trimethylammonium-1, chain stable hydrocarbon isocyanic ester such as hexamethylene-diisocyanate, isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methane diisocyanate, methylene bis(4-, hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, cyclic saturated hydrocarbon isocyanic ester such as hydrogenated tolylene diisocyanate, 2, the 4-tolylene diisocyanate, 1, the 3-xylylene diisocyanate, PPDI, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond, 6-sec.-propyl-1, the 3-phenylene diisocyanate, 1, aromatic polyisocyanates such as 5-naphthalene diisocyanate) reaction, the reaction product that obtains with hydroxyl (methyl) acrylate addition etc. then.
As (gathering) ester (methyl) origoester acrylate, for example can enumerate: reaction product (gathering) esterdiol of above-mentioned diol compound and above-mentioned di-carboxylic acid or its acid anhydrides and (methyl) acrylic acid reaction product etc.
In the resin combination of the present invention, when the solid shape of establishing resin combination of the present invention was divided into 100 quality %, the usage quantity of above-mentioned (B) composition was generally more than the 0 quality %, below the 94 quality %, more than the preferred 20 quality %, below the 79 quality %.
As the Photoepolymerizationinitiater initiater (C) that uses as required in the resin combination of the present invention, for example can enumerate: bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, bitter almond oil camphor ethyl isobutyl ether; Methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-acetophenones such as 1-ketone; Anthraquinone classes such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2, thioxanthene ketones such as 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone; Ketal classes such as methyl phenyl ketone dimethyl ketal, dibenzoyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 4, benzophenones such as 4 '-dimethylamino benzophenone; 2,4, phosphine oxide classes such as 6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,4,6-Three methyl Benzene formyl) phenylphosphine oxide; Deng.In addition, particularly, can easily obtain Ciba Specialty Chemicals corporate system Irgacure 184 (1-hydroxycyclohexylphenylketones), Irgacure 907 (2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholinyl propane-1-ketone), the system Le シ リ of BASF AG Application TPO (2 from the market, 4,6-Three methyl Benzene formyl diphenyl phosphine oxide) etc.In addition, these Photoepolymerizationinitiater initiaters can use separately or two or more mixing is used.
In the resin combination of the present invention, when the solid shape of establishing resin combination of the present invention was divided into 100 quality %, the usage quantity of above-mentioned (C) composition was more than the 0 quality %, below the 10 quality %, more than the preferred 1 quality %, below the 7 quality %.
In addition, also can use curing catalyst (D) among the present invention.As operable curing catalyst, for example can enumerate: hydrogen donors such as amine, 2-mercaptobenzothiazole such as trolamine, diethanolamine, N methyldiethanol amine, phenylformic acid-2-methylamino-ethyl ester, dimethylamino methyl phenyl ketone, p-(dimethylamino)-benzoic acid isopentyl ester, EPA.When the solid shape of establishing resin combination of the present invention was divided into 100 quality %, the usage quantity of these curing catalysts was more than the 0 quality %, below the 5 quality %.
As the thinner (E) that uses as required in the resin combination of the present invention, for example can enumerate: lactone such as gamma-butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Geng Neizhi, α-ethanoyl-gamma-butyrolactone, 6-caprolactone; Dioxane, 1, ethers such as 2-Methylal(dimethoxymethane), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dibutylester, propylene glycol monomethyl ether, dihydroxypropane single-ether, triethylene glycol dme, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, TEG diethyl ether; Carbonates such as ethylene carbonate, Texacar PC; Ketones such as methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl phenyl ketone; Phenols such as phenol, cresols, xylenol; Ester classes such as ethyl acetate, butylacetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, Trivalin SF acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate; Hydro carbons such as toluene, dimethylbenzene, diethylbenzene, hexanaphthene; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, mono chloro benzene; Organic solvent classes such as oil such as sherwood oil, petroleum naphtha series solvent; 2H, fluorine-containing alcohols such as 3H-C3-Fluoroalcohol; Hydrogen fluorine ethers such as perfluorobutyl methyl ethers, perfluoro butyl ethyl ether; Alcohols such as methyl alcohol, ethanol, Virahol, n-propyl alcohol; Have the Pyranton of ketone and both performances of alcohol etc. concurrently.These materials can use separately or two or more mixing is used.
In the resin combination of the present invention, the usage quantity of above-mentioned (E) composition is a scope more than the 0 quality %, below the 90 quality % with respect to resin combination total amount of the present invention, and preferred 0 quality % is above, below the 80 quality %.
In addition, can add flow agent, defoamer, UV light absorber, photostabilizer, antioxidant, stopper, linking agent in the resin combination of the present invention as required waits and gives objective function respectively.As flow agent, can enumerate: fluorochemicals, polysiloxane compounds, acrylic compounds etc.; As UV light absorber, can enumerate: benzotriazole compound, benzophenone compound, compound in triazine class etc.; As photostabilizer, can enumerate: hindered amine compound, benzoate compounds etc.; As antioxidant, can enumerate: phenolic compound etc.; As stopper, can enumerate: hydroquinone monomethyl ether, methyl hydroquinone, Resorcinol etc.; As linking agent, can enumerate: aforesaid polyisocyanates, melamine compound etc.
Resin combination of the present invention can obtain by above-mentioned (A) composition, (A-1) composition, (B) composition, (C) composition and (D) composition, (E) composition and other composition that use are as required mixed with random order.
Resin combination of the present invention can followingly obtain: above-mentioned resin combination is applied on the base material, make the dried thickness of this resin combination be generally that 0.1 μ m is above, 50 μ m are following, preferred 1 μ m is above, below the 20 μ m, dry back irradiation ultraviolet radiation forms cured film.
As base material film, for example can enumerate: polyester, polypropylene, polyethylene, polyacrylic ester, polycarbonate, triacetyl cellulose, polyethersulfone, cycloolefin polymer etc.The film that uses can be provided with pattern or easy adhesive layer, can carry out surface treatments such as corona treatment, also can carry out the demoulding and handle.
As the coating process of above-mentioned resin combination, for example can enumerate: metering bar coater coating, the coating of line rod (メ イ ヤ バ Yi Tu worker), airblade coating, intaglio plate coating, the coating of counter-rotating intaglio plate, the coating of nick version, the coating of little counter-rotating intaglio plate coating machine, the coating of slit die coating machine, dip coated, spin coating, spraying etc.
The irradiation ultraviolet radiation for curing, but also can use electron rays etc.When utilizing ultraviolet ray to be cured, can use to have the UV irradiation equipment as light source such as xenon lamp, high pressure mercury vapour lamp, metal halide lamp, regulate light quantity, configured light sources etc. as required.When using high pressure mercury vapour lamp, has 80～120W/cm for every
2The lamp of energy preferably is cured with 5～60m/ minute transfer rate.On the other hand, when utilizing electron rays to be cured, the preferred electron rays booster machinery that uses with 100～500eV energy, can not use Photoepolymerizationinitiater initiater (C) this moment.
Resin combination of the present invention can be used as the various coated materials of pottery, timber, paper, printing paper, fibers etc. such as plastics such as metals such as printing ink, aluminium, iron, copper, vinylchlorid, acrylic resin, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, glass, is used for purposes such as surface treatment agent, tackiness agent, plastic material, shaped material, plywood, tackiness agent, tackiness agent.As purposes more specifically, can be used for ink areas such as plano-convex printing ink, flexographic printing ink, base gravure ink, silk-screen ink, gloss paint field, field, paper coating agent, carpenter with paint field, beverages can with coating agent or printing-ink field, flexible packaging film coating agent, printing-ink or tackiness agent, temperature-sensitive paper, thermosensitive film with coating agent, printing-ink, tackiness agent, tackiness agent or coating optical fibers agent, forming process with purposes such as film coated agent.
In the such use since resin combination of the present invention shrinking percentage when solidifying low, have high rigidity, do not produce and curl or crackle, therefore, particularly can be used for the purposes such as hard coating of plastics film or compact shell.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, still, the invention is not restricted to these embodiment.In addition, among the embodiment, if not otherwise specified, " part " expression " mass parts ".
Synthesis example 1
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add glycerine one acrylate monomethyl acrylate 344.35g (1.54 moles), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip isophorone diisocyanate 155.65g (0.70 mole) and also make internal temperature be no more than 80 ℃, add the back, NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Synthesis example 2
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add glycerine one acrylate monomethyl acrylate 262.60g (1.17 moles), methylethylketone 125.00g, as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip T-1890 (isophorone diisocyanate trimer) 237.40g (0.36 mole) and make internal temperature be no more than 80 ℃, add the back 80 ℃ of reactions, NCO content is reached moment below 0.1% as reaction end, obtain containing the resin solution of 80% urethane acrylate.
Synthesis example 3
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 65/35 of glycerine one acrylate monomethyl acrylate 187.14g (0.84 mole), pentaerythritol triacrylate and tetramethylol methane tetraacrylate, hydroxyl equivalent: 458.9g/Eq) 187.08g (0.41 mole), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip isophorone diisocyanate 125.78g (0.57 mole) and also make internal temperature be no more than 80 ℃, add the back, NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Synthesis example 4
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 65/35 of glycerine one acrylate monomethyl acrylate 80.42g (0.36 mole), pentaerythritol triacrylate and tetramethylol methane tetraacrylate, hydroxyl equivalent: 458.9g/Eq) 240.83g (0.52 mole), methylethylketone 125.00g, as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip T-1890 (isophorone diisocyanate trimer) 178.75g (0.27 mole) and make internal temperature be no more than 80 ℃, add the back 80 ℃ of reactions, NCO content is reached moment below 0.1% as reaction end, obtain containing the resin solution of 80% urethane acrylate.
Synthesis example 5
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 65/35 of glycerine one acrylate monomethyl acrylate 149.51g (0.67 mole), pentaerythritol triacrylate and tetramethylol methane tetraacrylate, hydroxyl equivalent: 458.9g/Eq) 149.50g (0.33 mole), methylethylketone 125.00g, as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip T-1890 (isophorone diisocyanate trimer) 200.99g (0.30 mole) and make internal temperature be no more than 80 ℃, add the back 80 ℃ of reactions, NCO content is reached moment below 0.1% as reaction end, obtain containing the resin solution of 80% urethane acrylate.
Synthesis example 6
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 65/35 of glycerine one acrylate monomethyl acrylate 209.60g (0.94 mole), pentaerythritol triacrylate and tetramethylol methane tetraacrylate, hydroxyl equivalent: 458.9g/Eq) 70.07g (0.15 mole), methylethylketone 125.00g, as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip T-1890 (isophorone diisocyanate trimer) 220.34g (0.33 mole) and make internal temperature be no more than 80 ℃, add the back 80 ℃ of reactions, NCO content is reached moment below 0.1% as reaction end, obtain containing the resin solution of 80% urethane acrylate.
Synthesis example 7
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 40/60 of glycerine one acrylate monomethyl acrylate 197.71g (0.88 mole), Dipentaerythritol five acrylate and dipentaerythritol acrylate, hydroxyl equivalent: 1311.2g/Eq) 197.69g (0.15 mole), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip isophorone diisocyanate 104.60g (0.47 mole) and also make internal temperature be no more than 80 ℃, add the back, NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Synthesis example 8
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 40/60 of glycerine one acrylate monomethyl acrylate 163.51g (0.73 mole), Dipentaerythritol five acrylate and dipentaerythritol acrylate, hydroxyl equivalent: 1311.2g/Eq) 163.49g (0.36 mole), methylethylketone 125.00g, as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip T-1890 (isophorone diisocyanate trimer) 173.01g (0.26 mole) and make internal temperature be no more than 80 ℃, add the back 80 ℃ of reactions, NCO content is reached moment below 0.1% as reaction end, obtain containing the resin solution of 80% urethane acrylate.
Compare synthesis example 1
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add glycerine one acrylate monomethyl acrylate 372.58g (1.67 moles), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip hexamethylene diisocyanate 127.42g (0.76 mole) and also make internal temperature be no more than 80 ℃, add the back, aforementioned NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Compare synthesis example 2
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 65/35 of pentaerythritol triacrylate and tetramethylol methane tetraacrylate, hydroxyl equivalent: 458.9g/Eq) 409.77g (0.89 mole), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip isophorone diisocyanate 90.23g (0.41 mole) and also make internal temperature be no more than 80 ℃, add the back, aforementioned NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Compare synthesis example 3
In possessing reflux exchanger, stirrer, thermometer and thermostatic reactor, add mixture (the mass parts ratio of mixture: 40/60 of Dipentaerythritol five acrylate and dipentaerythritol acrylate, hydroxyl equivalent: 1311.2g/Eq) 464.23g (0.35 mole), as the 4-methoxyphenol 0.25g of stopper, as the dibutyl tin laurate 0.25g of urethane catalysts and stir, making internal temperature is 50 ℃.Then, drip isophorone diisocyanate 35.77g (0.16 mole) and also make internal temperature be no more than 80 ℃, add the back, aforementioned NCO content is reached moment below 0.1% as reaction end, obtain urethane acrylate 80 ℃ of reactions.
Embodiment 1～10 and comparative example 1～5
The resin combination that material-mix shown in table 1 and the table 2 is formed utilizes metering bar coater to be applied to through on the PET film (film thickness 125 μ m) of easy gluing processing, after about 80 ℃～about 100 ℃ of dryings, (JAPAN STORAGE BATTERY CO is LTD.:CS30L-1-1) at high pressure mercury vapour lamp: 120W/cm with ultraviolet radiation device
2, lamp height: 10cm, line speed: 10m/ minute (energy: about 300mW/cm
2, about 200mJ/cm
2) condition under be cured, obtain the hard coat film of the about 5 μ m of thickness.In addition, unit is " part " in table 1 and the table 2.
Hard coat film to embodiment 1～10, comparative example 1～5 obtain carries out the evaluation of following project, and the result is as shown in table 3.
(pencil hardness)
According to JIS K 5600-5-4, use pencil scraping experiment machine, measure the pencil hardness of filming of above-mentioned composition.Particularly, have on the polyester film of cured film to be measured, applying the scraping of the about 5mm of load of 750g from above with the angles of 45 degree with pencil, with in five times more than four times the pencil hardness of no marking represent.
(adaptation)
Cut out the crosswise cut channel with cutter on the film surface behind the light fastness test, the sticking glass adhesive tape is peeled off with the angle of 90 degree from it.
Zero: do not have and peel off
*: produce and peel off
(scuff resistance)
On steel wool #0000, apply 200g/cm
2Load and come and go the situation of Visual Confirmation cut 10 times.
Zero: no marking
*: produce cut
(curling)
The polyester film that will have cured film to be measured is cut into 5cm * 5cm, places after 1 hour in 80 ℃ drying oven, returns back to room temperature.Be determined at the four limits height separately of perk on the horizontal stand, with four limit sums as measured value (unit: mm).At this moment, curling of base material self is 0mm.
(viscosity)
The resin combination that material-mix shown in table 1 and the table 2 is formed is applied to through on the PET film (film thickness 125 μ m) of easy gluing processing with metering bar coater, after about 80 ℃～about 100 ℃ of dryings, with absorbent cotton wiping on dried coating, the viscosity of evaluated for film.
Estimate zero: absorbent cotton does not adhere to
*: on the raw-silk waste of absorbent cotton adheres to and films
(outward appearance)
States such as the crackle on visual judgement surface, albefaction, muddiness.
Estimate zero: good
*: produce significant crackle
(cure shrinkage)
Add the Irg.184 of 3 quality % in the compound that in synthesis example 1～8, comparison synthesis example 1～3, obtains as light trigger, use metering bar coater to be applied on the glass substrate, and use the ultraviolet radiation device irradiation ultraviolet radiation, obtain the cured article of the about 200 μ m of thickness.Wherein, the compound for synthesis example 2, synthesis example 4～6, synthesis example 8 uses behind the evaporating solvent MEK from the resin solution that contains urethane acrylate.The heavy film proportion with cured article of liquor ratio before cure shrinkage solidifies down according to 25 ℃ calculates by following mathematical expression (1), and its result is as shown in table 4.
Mathematical expression (1)
Cure shrinkage=(film proportion-liquor ratio is heavy)/film proportion * 100
Table 3
| Pencil hardness | Adaptation | Scuff resistance | Curl | Viscosity | Outward appearance | |
| Embodiment 1 | ??2H | ??○ | ??○ | ??10 | ??× | ??○ |
| Embodiment 2 | ??2H | ??○ | ??○ | ??10 | ??○ | ??○ |
| Embodiment 3 | ??3H | ??○ | ??○ | ??14 | ??× | ??○ |
| Embodiment 4 | ??3H | ??○ | ??○ | ??17 | ??× | ??○ |
| Embodiment 5 | ??3H | ??○ | ??○ | ??13 | ??○ | ??○ |
| Embodiment 6 | ??3H | ??○ | ??○ | ??11 | ??○ | ??○ |
| Embodiment 7 | ??3H | ??○ | ??○ | ??17 | ??× | ??○ |
| Embodiment 8 | ??3H | ??○ | ??○ | ??17 | ??× | ??○ |
| Embodiment 9 | ??2H | ??○ | ??○ | ??11 | ??○ | ??○ |
| Embodiment 10 | ??3H | ??○ | ??○ | ??12 | ??○ | ??○ |
| Comparative example 1 | ??2H | ??○ | ??○ | ??20 | ??× | ??○ |
| Comparative example 2 | ??3H | ??○ | ??○ | ??22 | ??× | ??○ |
| Comparative example 3 | ??3H | ??○ | ??○ | ??28 | ??× | ??○ |
| Comparative example 4 | ??3H | ??○ | ??○ | ??35 | ??× | ??○ |
| Comparative example 5 | ??3H | ??○ | ??○ | ??28 | ??× | ??○ |
Table 4
| Cure shrinkage | |
| The compound of synthesis example 1 | ??8 |
| The compound of synthesis example 2 | ??8 |
| The compound of synthesis example 3 | ??9 |
| The compound of synthesis example 4 | ??9 |
| The compound of synthesis example 5 | ??8 |
| Cure shrinkage | |
| The compound of synthesis example 6 | ??8 |
| The compound of synthesis example 7 | ??9 |
| The compound of synthesis example 8 | ??9 |
| The compound that compares synthesis example 1 | ??12 |
| The compound that compares synthesis example 2 | ??11 |
| The compound that compares synthesis example 3 | ??10 |
From the result of table 3 as can be seen, in the film of the cured film with resin combination of the present invention, hardness, adaptation, scuff resistance are good, and it is little to curl, and does not crack.In addition, in containing the embodiment 2,5,6,9,10 that comprises the trimeric carbamate of ester ring type polyisocyanates (methyl) acrylate, viscosity is good.In addition, from the result of table 4 as can be seen, the carbamate that contains in the resin combination of the present invention (methyl) acrylate, the contraction during curing is little, therefore has to suppress to curl or effect that crackle produces.
Industrial applicability
By the hard coat film that resin combination of the present invention obtains, hardness, adaptation, marresistance are good, and the contraction during curing is little, does not produce curling or crackle. Therefore, resin combination of the present invention can be as the protective coating of plastic sheeting or compact shell.
Claims (3)
1. resin combination, wherein, contain by making glycerine (methyl) acrylate (a) and ester ring type polyisocyanate compound react carbamate (methyl) acrylate (A), (methyl) acrylate (B) and the Photoepolymerizationinitiater initiater (C) that obtains.
2. resin combination, wherein, contain by making glycerine (methyl) acrylate (a) and (a) carbamate (methyl) acrylate (A-1), (methyl) acrylate (B) and the Photoepolymerizationinitiater initiater (C) that obtain of in addition (methyl) acrylate (a-1) and polyisocyanate compound (b) reaction.
3. resin combination as claimed in claim 1 or 2, it is used for supercoat.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009090580A JP2010241917A (en) | 2009-04-03 | 2009-04-03 | Resin composition |
| JP2009-090580 | 2009-04-03 |
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|---|---|
| CN101857659A true CN101857659A (en) | 2010-10-13 |
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|---|---|---|---|
| CN201010155451A Pending CN101857659A (en) | 2009-04-03 | 2010-04-02 | Resin combination |
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| JP (1) | JP2010241917A (en) |
| KR (1) | KR20100110724A (en) |
| CN (1) | CN101857659A (en) |
| TW (1) | TW201036997A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159940A (en) * | 2012-03-07 | 2014-11-19 | Dic株式会社 | Urethane (meth)acrylate resin composition and coating material |
| CN109562596A (en) * | 2016-08-10 | 2019-04-02 | 阿科玛法国公司 | The compound of functional group containing cyclic structure primitive, urethane/urea base connection unit and free redical polymerization |
| CN115895403A (en) * | 2022-12-28 | 2023-04-04 | 江阴通利光电科技有限公司 | Hardening liquid for PETG (polyethylene terephthalate glycol) membrane, PETG composite membrane and preparation method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102246121B1 (en) * | 2019-05-13 | 2021-04-29 | 주식회사 오플렉스 | UV-curable urethane-based pressure-sensitive adhesive and surface protective film using the same |
| JP7054753B1 (en) | 2021-06-28 | 2022-04-14 | アイカ工業株式会社 | Hardcourt resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5179186A (en) * | 1990-06-07 | 1993-01-12 | Bayer Aktiengesellschaft | Photosetting impression materials |
| WO2007046741A1 (en) * | 2005-10-18 | 2007-04-26 | Perstorp Specialty Chemicals Ab | Dual cure composition |
| CN101283065A (en) * | 2005-10-10 | 2008-10-08 | Sscp株式会社 | Low viscosity multi-functional urethane acrylate oligomer-containing high solid uv curable coating compostion |
| EP2003173A1 (en) * | 2006-03-31 | 2008-12-17 | Mitsui Chemicals, Inc. | Photocurable coating material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2725136B2 (en) * | 1992-11-13 | 1998-03-09 | 竹本油脂株式会社 | Optical three-dimensional molding method and three-dimensional molded object |
| JP4315507B2 (en) * | 1999-01-08 | 2009-08-19 | ナブテスコ株式会社 | Photo-curable resin composition with excellent heat resistance |
-
2009
- 2009-04-03 JP JP2009090580A patent/JP2010241917A/en active Pending
-
2010
- 2010-02-04 TW TW099103285A patent/TW201036997A/en unknown
- 2010-02-26 KR KR1020100017447A patent/KR20100110724A/en not_active Application Discontinuation
- 2010-04-02 CN CN201010155451A patent/CN101857659A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5179186A (en) * | 1990-06-07 | 1993-01-12 | Bayer Aktiengesellschaft | Photosetting impression materials |
| CN101283065A (en) * | 2005-10-10 | 2008-10-08 | Sscp株式会社 | Low viscosity multi-functional urethane acrylate oligomer-containing high solid uv curable coating compostion |
| WO2007046741A1 (en) * | 2005-10-18 | 2007-04-26 | Perstorp Specialty Chemicals Ab | Dual cure composition |
| EP2003173A1 (en) * | 2006-03-31 | 2008-12-17 | Mitsui Chemicals, Inc. | Photocurable coating material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159940A (en) * | 2012-03-07 | 2014-11-19 | Dic株式会社 | Urethane (meth)acrylate resin composition and coating material |
| CN104159940B (en) * | 2012-03-07 | 2016-11-23 | Dic株式会社 | Carbamate (methyl) acrylate resin composition and lining material |
| CN109562596A (en) * | 2016-08-10 | 2019-04-02 | 阿科玛法国公司 | The compound of functional group containing cyclic structure primitive, urethane/urea base connection unit and free redical polymerization |
| CN109562596B (en) * | 2016-08-10 | 2022-02-01 | 阿科玛法国公司 | Compounds containing cyclic structural units, urethane/ureido linking units and free-radically polymerizable functional groups |
| CN115895403A (en) * | 2022-12-28 | 2023-04-04 | 江阴通利光电科技有限公司 | Hardening liquid for PETG (polyethylene terephthalate glycol) membrane, PETG composite membrane and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010241917A (en) | 2010-10-28 |
| TW201036997A (en) | 2010-10-16 |
| KR20100110724A (en) | 2010-10-13 |
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