CN101250252A - Polyurefhane resin for primer of decorative sheet and primer of decorative using the same - Google Patents
Polyurefhane resin for primer of decorative sheet and primer of decorative using the same Download PDFInfo
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- CN101250252A CN101250252A CNA2008100083032A CN200810008303A CN101250252A CN 101250252 A CN101250252 A CN 101250252A CN A2008100083032 A CNA2008100083032 A CN A2008100083032A CN 200810008303 A CN200810008303 A CN 200810008303A CN 101250252 A CN101250252 A CN 101250252A
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Abstract
The invention provides a polyurethane prime coat which is particularly suitable for the part exposing to the water (cold or hot water) and moisture (vapor), and comprises excellent durability such as water resistance and moisture resistance, and is used for decorative sheet. The invention also discloses polyurethane resin for prime coat of the decorative sheet and the prime coat of the decorative sheet using the same, characterized in that the polyurethane resin for prime coat of the decorative sheet is obtained by the following reactions from (A) to (G), crosslinking point content from (D) in the polyurethane resin is 0.01 to 0.1 mmol/g. (A) acrylic acid polyatomic alcohol with 1000 to 30000 of number-average molecular weight; (B) polycarbonate polyatomic alcohol with 500 to 3000 of number-average molecular weight; (C) low molecule diol with the molecule weight less than 500; (D) low molecule triol with the molecule weight less than 500; (E) organic diisocyanate; (F) low molecule diamine with the molecule weight less than 500; (G), amino alcohols with the molecule weight less than 500.
Description
Technical field
The present invention relates to be used as the polyurethane series priming paint that the cosmetic sheet of the interior material of buildingss such as dwelling house and external decorative material of door and window, the daily apparatus class of furniture, residential equipment and household appliances etc. is used, say in further detail, relate to and for example be specially adapted to that bathroom and kitchen etc. are exposed to the polyurethane series priming paint that the cosmetic sheet position, that comprise the excellent in te pins of durability of water tolerance, wet fastness in water (cold water or hot water) or the moisture (water vapor) is used like that.
Background technology
At present, the cosmetic sheet of using as the decorative steel plate that is used in the extraneous adornment of for example refrigerator and the interior finish in bathroom, unit etc., be extensive use of the cosmetic sheet of following formation: on the backing material plate that constitutes by opaque colored polyolefin resin film etc., folder is established by printing and is waited the patterned layer form, the stacked transparent thermoplastic resin's layer that is made of biaxially stretched polyester based resin molding etc. and the cosmetic sheet (patent documentation 1～3 etc.) that forms.
Patent documentation 1: Japanese kokai publication sho 63-280627 communique
Patent documentation 2: Japanese kokai publication hei 10-166499 communique
Patent documentation 3: Japanese kokai publication hei 10-258488 communique
But, this uses in the cosmetic sheet of existing adhesive system and has following situation, promptly, in the bathroom interior finish that becomes humid tropical condition owing to the hot water of bath and the warm water of shower etc., be exposed to the splashing of warm water of tap water and water-heater, from the kitchen in the hot gas of cooker and the hot water that overflows etc., near position etc. around the window of surface sweating and exterior wall when cold, peel off with the expansion of decorative cover at stacked interface etc.
Under this situation,, use priming paint usually in order to improve cementability.The two-solution curing type urethane resin of the pure and mild polyisocyanates of acrylic acid multielement has for example been proposed as priming paint in the patent documentation 4.The following vinylformic acid that obtains-polyester-polyurethane multipolymer has been proposed: make acrylic polyol, polyester polyol, di-isocyanate reaction obtain prepolymer, make this prepolymer chain growth and make vinylformic acid-polyester-polyurethane multipolymer in the patent documentation 5 with diamines.
Patent documentation 4: TOHKEMY 2005-313411 communique
Patent documentation 5: TOHKEMY 2001-260109 communique
But these priming paint are not fully to satisfy wet fastness under exacting terms more (for example boiling experiment).
Summary of the invention
The invention effect
Can provide according to the present invention around the water particularly require wet fastness with wallpaper etc. the priming paint of cosmetic sheet with urethane resin, and use the priming paint of its cosmetic sheet.
The problem that invention will solve
The object of the present invention is to provide the priming paint that is specially adapted to such cosmetic sheet that is exposed to the excellent in te pins of durability position, that comprise water tolerance, wet fastness in water (cold water or hot water) and the moisture (water vapor) such as for example bathroom and kitchen etc. with urethane resin and use the priming paint of its cosmetic sheet.
The means of dealing with problems
In order to solve this problem, the contriver has carried out research repeatedly, found that the priming paint of following cosmetic sheet is with urethane resin and use the priming paint of its cosmetic sheet can solve foregoing problems, thereby has finished the present invention.
That is, the present invention is the invention shown in following (1)～(4).
(1) the priming paint urethane resin of cosmetic sheet is characterized in that, it reacts the priming paint urethane resin of the cosmetic sheet that obtains for making following (A)～(G), and the cross-linking set content from (D) in this urethane resin is 0.01～0.1mmol/g.
(A) number-average molecular weight is 1000～30000 acrylic polyol
(B) number-average molecular weight is 500～3000 polycarbonate polyol
(C) low-molecular-weight diol of molecular weight less than 500
(D) the low molecule triol of molecular weight less than 500
(E) organic diisocyanate
(F) the low molecule diamines of molecular weight less than 500
(G) amino alcohol of molecular weight less than 500
(2) the priming paint urethane resin of the cosmetic sheet of aforementioned (1) is characterized in that, (C) low-molecular-weight diol, (E) organic diisocyanate, and (F) low molecule diamines be compound with ring texture.
(3) the priming paint urethane resin of the cosmetic sheet of aforementioned (1) or (2) is characterized in that, low molecule triol (D) is a TriMethylolPropane(TMP).
(4) priming paint of cosmetic sheet is characterized in that, with respect to each urethane resin of 100 mass parts aforementioned (1)～(3), also uses 1～20 mass parts (being scaled solids component respectively) polyisocyanate curing agent.
Embodiment
The present invention is the priming paint urethane resin of cosmetic sheet, it is characterized in that, its (A)～(G) described later by making reaction obtains, and is 0.01～0.1mmol/g from the cross-linking set content of (D).Under the very few situation of cross-linking set content, wet fastness, humidity resistance etc. becomes insufficient.Under the too much situation of cross-linking set content, resin self is easily gelation during fabrication.
(A) used in the present invention acrylic polyol obtains by the polyreaction that contains unsaturated double-bond compound (Acrylic Acid Monomer).Polyreaction is generally Raolical polymerizable.As this Acrylic Acid Monomer, can enumerate alkyl acrylate, the vinylformic acid cycloalkyl ester, phenyl acrylate, the vinylformic acid benzene methyl, esters of acrylic acids such as glycidyl acrylate, alkyl methacrylate, the methacrylic acid cycloalkyl ester, phenyl methacrylate, the methacrylic acid benzene methyl, methyl acrylic esters such as glycidyl methacrylate, vinyl acetate, vinyl acetate based compounds such as propionate, vinyl alkyl ethers such as methoxy ethylene, vinyl hexamethylene ether, vinyl phenyl ether, the vinyl benzene methyl ether, vinyl ether based compound classes such as vinyl glycidyl ether, vinyl cyanide, acrylonitrile compounds classes such as methacrylonitrile, vinylbenzene, Vinyl toluene, alpha-methyl styrenes etc. contain the aromatics class of ethylenical unsaturated double bonds, maleic acid diester classes such as dialkyl maleate, dialkyl fumarate classes such as dialkyl fumarate, methylene-succinic acid diester classes such as dimethyl itaconate, N, dialkyl group acrylic amides such as N-DMAA, the N-vinyl pyrrolidone, heterocycle vinyl compounds such as 2-vinyl pyridine etc., vinylformic acid 2-hydroxyl ethyl ester, Propylene glycol monoacrylate, the polyoxyethylene glycol mono acrylic ester, the polypropylene glycol mono acrylic ester, the 6-caprolactone affixture of vinylformic acid 2-hydroxyl ethyl ester, the Beta-methyl valerolactone affixture of vinylformic acid 2-hydroxyl ethyl ester, single vinylformic acid glyceryl ester, esters of acrylic acids such as glycerol diacrylate, methacrylic acid 2-hydroxyl ethyl ester, Rocryl 410, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, the 6-caprolactone affixture of methacrylic acid 2-hydroxyl ethyl ester, the Beta-methyl valerolactone affixture of methacrylic acid 2-hydroxyl ethyl ester, monomethyl vinylformic acid glyceryl ester, methyl acrylic esters such as two (methacrylic acid) glyceryl ester, vinyl carbinol, glycerin monoallyl ether, allylic cpd classes such as glycerine diallyl ether etc.Among the present invention employed acrylic polyol preferably with the hydroxy acryl acid monomer that is selected from vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester and be selected from alkyl acrylate and the Acrylic Acid Monomer of alkyl methacrylate (preferred especially methyl acrylate, methyl methacrylate) as necessary composition.
Employed among the present invention (A) acrylic polyol is counted 20～80 quality % with solids component, more preferably 20～50 quality % with respect to the content of the priming paint usefulness urethane resin of cosmetic sheet.Under the situation that contains the quantity not sufficient lower limit of acrylic polyol, the variation such as weathering resistance of the priming paint of gained.
As (B) used in the present invention polycarbonate polyol, be to pass through ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-4-butyl-1, ammediol, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1, the 4-cyclohexanediol, 1,4 cyclohexane dimethanol, the dimeracid glycol, the oxyethane of dihydroxyphenyl propane or propylene oxide adduct, two (beta-hydroxyethyl) benzene, xylylene-glycol, glycerine, TriMethylolPropane(TMP), in the low molecular polylol classes such as tetramethylolmethane more than one and ethylene carbonate, diethyl carbonate, the dealcoholization of low molecular carbon acid esters such as diphenyl carbonate, dephenolize reaction and the material that obtains.In the present invention, preferred polycarbonate polyol is the polycarbonate polyol that the low-molecular-weight diol by carbonatoms 2～10 obtains, and by 1,6-hexylene glycol deutero-polycarbonate polyol is because the easiest acquisition is therefore preferred especially.
In addition, can use above-mentioned (A) acrylic acid multielement pure and mild (B) polycarbonate polyol macromolecule polyol in addition as required.Can enumerate number-average molecular weight in this macromolecule polyol and be 500～3000 for example polyester polyol, polyesteramide polyvalent alcohol, polyether glycol, polyester ether polylol, polyolefin polyhydric alcohol, animals and plants and be polyvalent alcohol, dimer acids polyvalent alcohol, hydrogenated dimer acids is polyvalent alcohol etc.In addition, so long as number-average molecular weight is the material that on average contains 1 above active hydrogen group in 500～3000 and 1 molecule, then can also use Resins, epoxy, polyamide resin, vibrin, acrylic resin, Gum Rosin, urea resin, melmac, resol, coumarone resin, polyvinyl alcohol etc. to contain resin of active hydrogen group etc.
Preferred (C) low-molecular-weight diol is molecular weight less than 500, is preferably below 300 among the present invention, and has the compound of 2 alcoholic extract hydroxyl groups in 1 molecule.Particularly, can enumerate ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-4-butyl-1, ammediol, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1, the oxyethane of 4-cyclohexanediol, 1,4 cyclohexane dimethanol, dimeracid glycol, dihydroxyphenyl propane or propylene oxide adduct, two (beta-hydroxyethyl) benzene, xylylene-glycol etc.In the present invention, preferred dissolution is good and can give the alicyclic diol of weather resistance, and is preferred especially 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol.
(D) used in the present invention low molecule triol is molecular weight less than 500, is preferably below 300, and has the compound of 3 alcoholic extract hydroxyl groups in 1 molecule.Specifically be enumerated as glycerine, TriMethylolPropane(TMP), hexanetriol etc.Do not use under the situation of (D) low molecule triol, water tolerance, the humidity resistance of the priming paint of gained significantly reduce.In the present invention, in order effectively crosslinking structure to be imported resin matrix, preferred all hydroxyls are the TriMethylolPropane(TMP) of the high primary hydroxyl of reactivity.
Employed among the present invention (E) organic diisocyanate can be enumerated tetramethylene diisocyanate, hexamethylene diisocyanate, the 2-methyl isophthalic acid, 5-pentane vulcabond, the decamethylene vulcabond, the 3-methyl isophthalic acid, 5-pentane vulcabond, aliphatic diisocyanates such as lysinediisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenyl methane diisocyanate, the hydrogenation of benzene dimethylene diisocyanate, the hydrogenation tetramethylxylylene diisocyanate, alicyclic diisocyanates such as cyclohexyl diisocyanate, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 2,4 '-'-diphenylmethane diisocyanate, 2,2 '-'-diphenylmethane diisocyanate, 1, the 5-naphthalene diisocyanate, 1, the 4-naphthalene diisocyanate, PPDI, m-benzene diisocyanate, the phthalal vulcabond, the mphenylenedimethylim-vulcabond, the terephthalylidene vulcabond, tetramethylxylylene diisocyanate, 4,4 '-the phenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenyl methane-4,4 '-vulcabond, 4,4 '-the diphenyl propane vulcabond, 3,3 '-dimethoxy phenylbenzene-4,4 '-aromatic diisocyanates such as vulcabond, these two or more mixture, the urethane modifier of these organic diisocyanate, allophanate-modified thing, the urea modifier, biuret modified thing, urea diketone (uretdione) modifier, urea imines (uretoimine) modifier, isocyanurate-modified thing, carbodiimide modified thing etc.Preferred (E) organic diisocyanate is the alicyclic diisocyanate of the physical strength excellence of little, the weathering resistance of the possibility of gelation and resin when making among the present invention, preferred especially isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate.
(F) used in the present invention hangs down molecule diamines molecular weight less than 500, specifically can enumerate aliphatie diamines such as tetramethylene-diamine, hexamethylene-diamine, dodecyl diamines, alicyclic diamines such as isophorone diamine, hydrogenation diphenylmethane diamine, hydrogenation of benzene dimethylene diamines, aromatic diamines such as tolylene diamine, diphenylmethane diamine etc.In the present invention, when the dissolving resin of considering gained, physical strength, preferred isophorone diamine.
(G) used in the present invention amino alcohol is the material that uses for (number average) molecular weight of adjusting resin during with urethane resin at the priming paint of making cosmetic sheet, is directed to the end of polyurethane series resin skeleton.Should (G) amino alcohol be the compound that has hydroxyl and primary amino and/or secondary amino group in molecular weight less than 500 and 1 molecule.Specifically can enumerate monoethanolamine, diethanolamine, single Propanolamine, dipropanolamine etc.
The priming paint of cosmetic sheet of the present invention is following method (prepolymer method) with the synthetic method of urethane resin: make the low molecule triol of aforesaid (A) acrylic polyol, (B) polycarbonate polyol, (C) low-molecular-weight diol, (D) and (E) organic diisocyanate under the condition of isocyanate group surplus, react, obtain containing the prepolymer of isocyanate group, then make this prepolymer carry out chainpropagation, until reaching the regulation molecular weight with (F) low molecule diamines and (G) amino alcohol.
Catalysts during as the pre-polymerization physical reaction can use known so-called urethane catalyzer.Specifically can list organometallic compounds such as dibutyl tin laurate, two lauric acid dioctyl tins, organic amine such as triethylenediamine, triethylamine and salt thereof etc.
As the reaction unit of urethane resin used in the present invention, as long as can realize above-mentioned reaction, any device all can, can enumerate the mixed milling devices such as reactor, kneading machine, single shaft or multiaxis extrusion reaction device that for example have whipping appts.The preferred synthetic method of the urethane resin among the present invention is the prepolymer method in solution.
Prepolymer method in solution is narrated in more detail.When making urethane resin, at first, will (A) acrylic polyol, (B) polycarbonate polyol, (C) low-molecular-weight diol, (D) hang down molecule triol and be dissolved in the organic solvents such as ketone with active hydrogen group, ester, hydrocarbon system.
As this organic solvent, so long as toluene, aromatic hydrocarbons series solvents such as dimethylbenzene, pentane, hexane, aliphatic hydrocarbon series solvents such as octane, pentamethylene, hexanaphthene, clicyclic hydrocarbon series solvents such as methylcyclohexane, acetone, methylethylketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, pimelinketone, ketone series solvents such as methylcyclohexanone, diethyl ether, 1, the 4-diox, ether series solvents such as tetrahydrofuran (THF), glycol dimethyl ether, the ethylene glycol monomethyl ether acetic ester, Propylene Glycol Dimethyl Ether, cellosolve series solvents such as propylene glycol monomethyl ether acetate, vinyl acetic monomer, monobasic acid ester series solvents such as N-BUTYL ACETATE, dimethyl adipate, Succinic acid dimethylester, diester classes such as dioctyl phthalate, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc. just are not particularly limited the inactive material of isocyanate group.In addition, with the diluting solvent that reacts after finishing, can also use the so pure series solvent of Virahol when reacting with amino as isocyanate group.In addition, toluene easily residues in the ethylene series base material in the present invention, does not therefore preferably use toluene.
In above-mentioned polyhydric alcohol solutions, add (E) organic diisocyanate, add the urethane catalyzer as required after, to make temperature of reaction be 30～100 ℃, be preferably 50～80 ℃, carries out a few hours reaction, the synthetic polyurethane prepolymer solution that contains isocyanate group.The mol ratio (R value) of isocyanate group/hydroxyl of this moment is preferably 1.1～2.5, is preferably 1.1～2.0 especially.
Under the situation of R value less than 1.1, the weather resistance of the final polyurethane series priming paint that obtains, resistance to blocking reduce.In addition, the R value surpasses under 2.5 the situation, and urethane resin reduces the solvability and the adaptation of solvent.
In the polyurethane prepolymer solution that contains isocyanate group that obtains like this, add (F) low molecule diamines and (G) amino alcohol, carry out transfer reaction.By being 30～80 ℃ in temperature of reaction, being preferably and reacting under 30～50 ℃, can obtain solution as the urethane resin of target to the isocyanate group disappearance.
Gel permeation chromatography (GPC) method by utilizing polystyrene calibration curve is measured the number-average molecular weight of urethane resin, is preferably 5000～100000, is preferably 8000～50000 especially.Under the situation of number-average molecular weight less than 5000, weather resistance reduces.Number-average molecular weight surpasses under 100000 the situation, mobile variation, operability variation.
The priming paint of cosmetic sheet of the present invention is with in the urethane resin, can cooperate auxiliary binder such as such additive such as pigment, dyestuff, thixotropic agent, fire retardant, antioxidant, UV light absorber, defoamer, thickening material, dispersion agent, tensio-active agent, rust-preventive agent, antiseptic-germicide, sanitas, catalyzer, weighting agent and soluble cotton and use in above-mentioned urethane resin.
The priming paint of cosmetic sheet of the present invention is the priming paint material that cooperates polyisocyanate curing agent in the urethane resin in aforesaid cosmetic sheet.
With respect to 100 mass parts urethane resins, the addition of polyisocyanate curing agent is 1～20 mass parts (being scaled solids component respectively).Under the very few situation of polyisocyanate curing agent use level, do not see the raising of the rerum natura that gained is filmed.In addition, under the too much situation of solidifying agent use level, become the solidifying agent molecule not crosslinked as host polyurethane molecular and therefore bonded state just is difficult to still cause that rerum natura improves.As polyisocyanate curing agent, can enumerate CORONATE (registered trademark) HX, the CORONATE HL of the hexamethylene diisocyanate modified version in the commodity of Nippon Polyurethane Industry Co., Ltd. for example, CORONATE L, the CORONATE2030 of tolylene diisocyanate modified version, CORONATE2031 etc., these can separately or mix and use.
Embodiment
Below, embodiments of the invention are described, but the present invention is not subjected to these restriction.In addition, among below the embodiment and comparative example, " part " and " % " means " mass parts " and " quality % " respectively.
Embodiment 1
[manufacturing of urethane resin]
In the reaction vessel that has agitator, thermometer, water cooler and nitrogen ingress pipe, add 429.1 parts of AC-1,306.5 parts of PC-1,4.4 parts of CHDM, 2.1 parts of TMP, be mixed to evenly.Then, add 50.1 parts of IPDI, 39.4 parts of H
12Behind the MDI, add 0.03 part of DOTDL as the urethane catalyzer, under stream of nitrogen gas, reacted while stirring under 80 ℃ 4 hours, obtaining isocyanate group content is the terminal polyurethane prepolymer solution of isocyanate group of 0.387mmol/g.Then, add 910 parts of MEK, 23 parts of MIBK, make it even, add, under 40 ℃, carry out 1 hour transfer reaction, obtain polyurethane resin solution PU-3 in advance by 210 parts of IPA, 21.9 parts of IPDA, 3.9 portions of amine mixed solutions that MEA constitutes.The PU-3 solids component is 30.0%, and viscosity is 680mPas.
Embodiment 2～3, comparative example 1～3
With reaction vessel, step similarly to Example 1, use each raw material to obtain urethane resin PU-1～2,4～5 according to the charging shown in the table 1.In addition, gelation takes place in comparative example 3 (PU-6) when transfer reaction, the evaluation after therefore can not carrying out.
Table 1
| Comparative example | Embodiment | Comparative example | ||||
| 1 | 2 | 1 | 2 | 3 | 3 | |
| Acrylic acid multielement alcoholic solution (part) AC-1 | 427.1 | 427.7 | 429.1 | 430.3 | 432.4 | 434.3 |
| Polycarbonate diol (part) PC-1 | 305.1 | 305.5 | 306.5 | 307.3 | 308.9 | 310.2 |
| Low-molecular-weight diol (part) CHDM | 4.4 | 4.4 | 4.4 | 4.4 | 4.4 | 4.5 |
| Low molecule triol (part) TMP | 0.0 | 0.6 | 2.1 | 4.1 | 7.2 | 10.4 |
| Organic diisocyanate (part) IPDI H 12MDI | 49.9 39.3 | 50.0 39.3 | 50.1 39.4 | 50.3 39.6 | 50.5 39.7 | 50.7 39.9 |
| Urethane catalyzer (part) DOTDL | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Pre-polymer solution NCO content (mmol/g) | 0.443 | 0.426 | 0.387 | 0.331 | 0.247 | 0.164 |
| Organic solvent (part) MEK MIBK | 910 24 | 910 23 | 910 23 | 910 22 | 910 21 | 910 19 |
| Amine aqueous solution (part) IPA IPDA MEA | 210 28.9 1.6 | 210 27.0 2.2 | 210 21.9 3.9 | 210 18.8 3.4 | 210 12.4 3.8 | 210 7.1 3.4 |
| The viscosity (mPas) that polyurethane resin solution title cross-linking set content (mmol/g) number-average molecular weight (ten thousand) solids component (%) is 25 ℃ | PU-1 0.000 1.49 30.2 500 | PU-2 0.008 1.50 29.9 520 | PU-3 0.026 1.51 30.0 680 | PU-4 0.051 1.52 30.1 700 | PU-5 0.090 1.51 29.9 850 | PU-6 0.129 gelation |
In embodiment 2～3, comparative example 1～3, table 1,
The MIBK solution of the co-polypropylene acid polyvalent alcohol of AC-1:MMA and HEMA
Hydroxyl value=5.6mgKOH/g (solids component)
Solids component=40%
Number-average molecular weight=20000
*MMA: methyl methacrylate
HEMA: methacrylic acid 2-hydroxyl ethyl ester
MIBK: methyl iso-butyl ketone (MIBK)
PC-1: by 1, the polycarbonate diol that 6-HD and DEC obtain
Number-average molecular weight=2000
*1,6-HD:1,6-hexylene glycol
DEC: diethyl carbonate
TMP: TriMethylolPropane(TMP)
IPDI: isophorone diisocyanate
H
12MDI: hydrogenated diphenyl methane diisocyanate
DOTDL: two lauric acid dioctyl tins
MEK: methylethylketone
MIBK: methyl iso-butyl ketone (MIBK)
IPA: Virahol
IPDA: isophorone diamine
MEA: monoethanolamine
[priming paint evaluation]
Embodiment 4
PU-3 is used for host carries out the priming paint evaluation.Solidifying agent uses CORONATE (registered trademark) HX.The proportioning of host/solidifying agent is host/solidifying agent=100/3.8 (being scaled solids component respectively).Estimate adaptation, resistance to blocking, the weathering resistance (boiling/do not boil) of priming paint.
CORONATE HX: the product of Nippon Polyurethane Industry Co., Ltd.
The isocyanurate-modified polyisocyanates of hexamethylene diisocyanate.
*Boil condition: coated sample (with reference to following) is put into boiling water boiled 20 minutes.
(1) adaptation
With the priming paint that cooperates host/solidifying agent and obtain, coat on the discharge process face of Corona discharge Treatment stretching polyethylene terephthalate (being designated hereinafter simply as PET) film that thickness is 15 μ m with line rod spreader, 70 ℃ the heating 30 seconds after, slaking at room temperature 1 day, at coated face sticking glass paper sealing tape, again it is peeled off rapidly then.In addition, after being boiled subject to the foregoing, the coated sample that obtains equally estimates.
In addition, with priming paint being coated PET with above-mentioned same step, 70 ℃ the heating 30 seconds after, slaking at room temperature 1 day, be coated with acrylic acid series electron(beam)curing type resin then on the priming paint coated face, the electron rays of irradiation 5Mrad boiled/do not boil after 1 second, on resin-coated of acrylic acid series electron(beam)curing type, be cut into checkerboard with cutter, peel off rapidly behind the sticking glass paper sealing tape.
Priming paint glue spread: count 3g/m with resinous principle
2
The resin-coated amount of electron(beam)curing type: count 5g/m with resinous principle
2
Estimate◎: film and be not stripped from fully
Zero: film residual 80%～100%.
△: film residual 50%～80%.
*: it is only residual below 50% to film.
(2) resistance to blocking
With priming paint being coated on the discharge process face of PET film with above-mentioned same method, surface, the inside is superimposed 40 ℃ of slakings after 7 days, under 50 ℃, 80RH%,, estimate resistance to blocking with pressing sticking experimental installation to apply the loading 24 hours of 0.5MPa.In addition, after being boiled subject to the foregoing, the coated sample that obtains equally estimates.
Priming paint glue spread: count 3g/m with resinous principle
2
EstimateZero: when peeling off, can not peel off with having resistance fully, do not have coming off of filming.
△: the resistance when peeling off is big slightly, and that a little as seen films comes off.
*: the resistance when peeling off is big, and that as seen films comes off.
(3) weathering resistance
With priming paint being coated on the discharge process face of PET film with above-mentioned same method, 40 ℃ of slakings after 7 days, at room temperature left standstill one day, then it is installed in the QUV trier of Q-PANEL company production, after repeating the circulation below 10 times, rapidly it is being peeled off behind the sticking glass paper sealing tape on the coated face.In addition, after being boiled subject to the foregoing, the coated sample that obtains equally estimates.
1 round-robin condition of QUV trier:
70 ℃ * 8 hours (Dry)+50 ℃ * 4 hours (Wet)
Irradiation energy: 0.59 (W/m
2/ nm)
Priming paint glue spread: count 3g/m with resinous principle
2
EstimateZero: film residual 80～100%.
△: film residual 50%～80%.
*: it is only residual below 50% to film.
Embodiment 5～6, comparative example 4～5
Carry out the priming paint evaluation similarly to Example 4.The proportioning of host/solidifying agent is identical with embodiment 4.
Table 2
| Boil | Comparative example | Embodiment | ||||
| 4 | 5 | 4 | 5 | 6 | ||
| Urethane resin | PU-1 | PU-2 | PU-3 | PU-4 | PU-5 | |
| Adaptation (PET/ priming paint) | Have or not | × ◎ | △ ◎ | ◎ ◎ | ◎ ◎ | ◎ ◎ |
| (electron(beam)curing is resin-coated) | Have or not | △ ◎ | △ ◎ | ◎ ◎ | ◎ ◎ | ◎ ◎ |
| Resistance to blocking | Have or not | × ○ | △ ○ | ○ ○ | ○ ○ | ○ ○ |
| Weathering resistance | Have or not | × ○ | △ ○ | ○ ○ | ○ ○ | ○ ○ |
Good especially by the adaptation after priming paint of the present invention boils table 2 illustrate, in addition, resistance to blocking and weathering resistance also are greatly improved.On the other hand, the result in comparative example is, resistance to blocking and weathering resistance show and the equal performance of priming paint of the present invention, but the adaptation after boiling is poor especially.
Claims (4)
1. the priming paint urethane resin of cosmetic sheet is characterized in that, it reacts the priming paint urethane resin of the cosmetic sheet that obtains for making following (A)～(G), and the cross-linking set content from (D) in this urethane resin is 0.01～0.1mmol/g.
(A) number-average molecular weight is 1000～30000 acrylic polyol
(B) number-average molecular weight is 500～3000 polycarbonate polyol
(C) low-molecular-weight diol of molecular weight less than 500
(D) the low molecule triol of molecular weight less than 500
(E) organic diisocyanate
(F) the low molecule diamines of molecular weight less than 500
(G) amino alcohol of molecular weight less than 500
2. the priming paint urethane resin of cosmetic sheet according to claim 1 is characterized in that, (C) low-molecular-weight diol, (E) organic diisocyanate, and (F) low molecule diamines be compound with ring texture.
3. the priming paint urethane resin of cosmetic sheet according to claim 1 and 2 is characterized in that, low molecule triol (D) is a TriMethylolPropane(TMP).
4. the priming paint of cosmetic sheet is characterized in that, with respect to each described urethane resin of 100 mass parts claims 1～3, also uses 1～20 mass parts (being scaled solids component respectively) polyisocyanate curing agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007041542 | 2007-02-22 | ||
| JP2007-041542 | 2007-02-22 | ||
| JP2007041542A JP4993408B2 (en) | 2007-02-22 | 2007-02-22 | Polyurethane resin for decorative sheet primer and primer for decorative sheet using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101250252A true CN101250252A (en) | 2008-08-27 |
| CN101250252B CN101250252B (en) | 2011-01-19 |
Family
ID=39779793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100083032A Expired - Fee Related CN101250252B (en) | 2007-02-22 | 2008-02-22 | Polyurefhane resin for primer of decorative sheet and primer of decorative using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4993408B2 (en) |
| CN (1) | CN101250252B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102317389A (en) * | 2009-02-25 | 2012-01-11 | 日本聚氨酯工业株式会社 | Paint base composition |
| CN102574979A (en) * | 2009-09-18 | 2012-07-11 | Dic株式会社 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN105968289A (en) * | 2015-03-12 | 2016-09-28 | 东曹株式会社 | Ultraviolet light absorber resistance polyurethane composition and coating material using the same |
| CN106010207A (en) * | 2016-05-28 | 2016-10-12 | 河北宝源工程橡塑有限公司 | Two-component environment-friendly polyurethane waterproof coating and preparation method thereof |
| CN108250383A (en) * | 2018-01-19 | 2018-07-06 | 盐城工学院 | More degree of cross linking polyurethane elastomers and preparation method thereof |
| CN111315570A (en) * | 2017-11-07 | 2020-06-19 | 东洋制罐集团控股株式会社 | Moisture barrier laminated film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200946551A (en) * | 2008-03-31 | 2009-11-16 | Toyo Kohan Co Ltd | Polyurethane resins containing cycloaliphatic and/or aromatic component and phase difference films using them |
| JP2010047679A (en) * | 2008-08-21 | 2010-03-04 | Nippon Polyurethane Ind Co Ltd | Polyurethane resin for ink binder, ink binder and ink using the same |
| CN101798475B (en) * | 2010-02-25 | 2011-05-25 | 浙江圣奥家具制造有限公司 | UV coating |
| CN106010201A (en) * | 2016-08-05 | 2016-10-12 | 吴静 | Preparation method of aqueous two-component polyacrylic polyol white primer specially used for reaction kettles, and product thereof |
| JP7075813B2 (en) * | 2018-03-29 | 2022-05-26 | Ｕｂｅ株式会社 | Coating resin composition for civil engineering and construction, hardened material, civil engineering and building structure, and coating method for civil engineering and building structure. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1002762A7 (en) * | 1989-01-20 | 1991-05-28 | Recticel | METHOD FOR PRODUCING AND APPLYING sprayable, light stable polyurethane. |
| KR100363920B1 (en) * | 1994-10-04 | 2003-02-26 | 미네소타 마이닝 앤드 매뉴팩춰링 캄파니 | Two parts of a reactive polyurethane composition and a self-healing and scratch-resistant coating made of this composition |
| JP3772341B2 (en) * | 1999-11-30 | 2006-05-10 | 日本ポリウレタン工業株式会社 | Printing ink binder and printing ink |
-
2007
- 2007-02-22 JP JP2007041542A patent/JP4993408B2/en active Active
-
2008
- 2008-02-22 CN CN2008100083032A patent/CN101250252B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317389A (en) * | 2009-02-25 | 2012-01-11 | 日本聚氨酯工业株式会社 | Paint base composition |
| CN102317389B (en) * | 2009-02-25 | 2013-11-06 | 日本聚氨酯工业株式会社 | Primer composition |
| CN102574979A (en) * | 2009-09-18 | 2012-07-11 | Dic株式会社 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN102574979B (en) * | 2009-09-18 | 2013-11-06 | Dic株式会社 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN105968289A (en) * | 2015-03-12 | 2016-09-28 | 东曹株式会社 | Ultraviolet light absorber resistance polyurethane composition and coating material using the same |
| CN105968289B (en) * | 2015-03-12 | 2020-12-25 | 东曹株式会社 | Ultraviolet absorber-resistant polyurethane composition and coating material using the same |
| CN106010207A (en) * | 2016-05-28 | 2016-10-12 | 河北宝源工程橡塑有限公司 | Two-component environment-friendly polyurethane waterproof coating and preparation method thereof |
| CN111315570A (en) * | 2017-11-07 | 2020-06-19 | 东洋制罐集团控股株式会社 | Moisture barrier laminated film |
| US11981785B2 (en) | 2017-11-07 | 2024-05-14 | Toyo Seikan Group Holdings, Ltd. | Water-barrier laminated film |
| CN108250383A (en) * | 2018-01-19 | 2018-07-06 | 盐城工学院 | More degree of cross linking polyurethane elastomers and preparation method thereof |
| CN108250383B (en) * | 2018-01-19 | 2020-09-08 | 盐城工学院 | Polyurethane elastomer with multiple crosslinking degrees and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101250252B (en) | 2011-01-19 |
| JP4993408B2 (en) | 2012-08-08 |
| JP2008201967A (en) | 2008-09-04 |
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