CN102317390B - Material set of forming polyurethane resin coating film formed on substrate - Google Patents
Material set of forming polyurethane resin coating film formed on substrate Download PDFInfo
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- CN102317390B CN102317390B CN2010800080646A CN201080008064A CN102317390B CN 102317390 B CN102317390 B CN 102317390B CN 2010800080646 A CN2010800080646 A CN 2010800080646A CN 201080008064 A CN201080008064 A CN 201080008064A CN 102317390 B CN102317390 B CN 102317390B
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- urethane resin
- polyvalent alcohol
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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
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Abstract
Provided is a material set of a polyurethane resin coating film with excellent film strength formed on a substrate. The material set comprises both a polyol component prepared by reacting a polycarbonate polyol with polycaprolactone polyol and an isocyanato-terminated prepolymer prepared by reacting polytetramethylene glycol with a polyisocyanate, wherein the mass ratio of the polycarbonate polyol to the polycaprolactone polyol is 65/35 or higher. Further, the polyol component may additionally contain both an organometallic curing catalyst which takes the form of fine powder at ordinary temperatures, and a cure retarder.
Description
Technical field
The present invention relates to the solvent free urethane resin mould material of being covered with paint, lacquer, colour wash, etc. on base material for example being formed at.
Background technology
The field that utilizes of urethane resin relates to the multiple fields such as electric material, automobile rail truck material and civil construction material.
These urethane resins utilize field, coating for example arranged.Polyurethane resin coating is multiplex in the field of building, civil construction thing and vehicle, covers with paint, lacquer, colour wash, etc. good appearance, and film performance is good, and weather resistance is good.
Although polyurethane resin coating is many and organic solvent is together used, this situation makes the improvement of environmental problem and job safety problem etc. become large problem.
In order to solve this problem, the water system of the resin of use and solvent free are carried out respectively multiple research (for example referring to Patent Document 1).
But, about the former water system, there is on operating surface the homogeneity of shortcoming coated face or energy and time that must be large when dry, the not enough problem such as water tolerance and hydrolytic resistance on the physical property face.
On the other hand, although the latter's solvent free is fewer in the problems referred to above of following water system to produce, but follow solvent free, the resin solution high viscosity, can not be coated with, on the contrary, to reduce the viscosity of resin solution in order being coated with, to there is the problem of on physical property face intensity or durability degree deficiency.
Patent documentation 1: TOHKEMY 2008-303250 communique
Summary of the invention
The present invention is for forming in view of above-mentioned problem, and purpose is to be provided under condition of no solvent, and film toughness is good is formed at the urethane resin mould material group on base material.
The urethane resin mould material group be formed on base material of the present invention, it is characterized in that, the prepolymer (prepolymer) that the end that is reacted the polyvalent alcohol of gained by polycarbonate polyol (polycarbonate polyol) with polycaprolactone polyol (polycaprolactone polyol) and reacted gained by polytetramethylene glycol (polytetramethylene glycol) with polymeric polyisocyanate (polyisocyanate) has isocyanate group is formed, and polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio.
The urethane resin mould material group be formed on base material of the present invention, is characterized in that, is preferably, and the prepolymer that described polyvalent alcohol and described end have isocyanate group is all liquid at normal temperatures.
The urethane resin mould material group be formed on base material of the present invention, is characterized in that, is preferably, and described polyvalent alcohol further contains organo-metallic catalyst and the sclerous reaction inhibitor that under normal temperature, the sclerous reaction of micronized is used.
The urethane resin mould material group be formed on base material of the present invention, is characterized in that, is preferably, and described polyvalent alcohol is obtained by the reaction of polycarbonate polyol, polycaprolactone polyol and aliphatic diol (aliphatic glycol).
The urethane resin mould material group be formed on base material of the present invention, it is characterized in that, be preferably, described polycarbonate polyol is by 1, the 6-hexylene glycol (1,6-hexanediol) and the reaction of dialkyl carbonate (dialkyl carbonate) and obtaining.
The urethane resin mould material group be formed on base material of the present invention is characterized in that be preferably, aforementioned polymeric polyisocyanate is aliphatic diisocyanate.
The urethane resin mould material group be formed on base material of the present invention, is characterized in that, is preferably, and aforementioned aliphatic diisocyanate is hexamethylene diisocyanate (hexamethylene diisocyanate).
The urethane resin mould material group be formed on base material of the present invention, reacted the polyvalent alcohol of gained with polycaprolactone polyol (polycaprolactone polyol) by polycarbonate polyol (polycarbonate polyol), and the prepolymer (prepolymer) that the end that is reacted gained by polytetramethylene glycol (polytetramethylene glycol) with polymeric polyisocyanate (polyisocyanate) has an isocyanate group is formed, polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio, therefore the polyurethane film good strength formed on base material.
Embodiment
Embodiments of the present invention as described below.
Present embodiment be formed at the urethane resin mould material group (following sometimes referred to as urethane resin mould material group) on base material, for example, as coating, for covering with paint, lacquer, colour wash, etc. film being covered with paint, lacquer, colour wash, etc. on base material to form.But be not limited to this use, as long as can produce effect of the present invention, also can be on other base material, forming urethane resin film.
The following urethane resin mould material group of present embodiment the 1st example of explanation, the prepolymer that polyvalent alcohol and end is had to isocyanate group is managed respectively, when forming film, with sclerosis, together with catalyzer, is used in conjunction with.Therefore, the storage stability when using polyvalent alcohol and end to carry out taking care of for a long time before having the prepolymer of isocyanate group is good.The urethane resin mould material group of present embodiment the 2nd example further coordinates, contains the sclerous reaction of micronized at normal temperatures and uses with organo-metallic catalyst and sclerous reaction inhibitor in polyvalent alcohol.Therefore, urethane resin mould material group operability in use is good.
The urethane resin mould material group of present embodiment the 1st example and the 2nd example be all the solvent free mould material that does not contain the organic solvent that likely produces any environmental problem etc.
At first the urethane resin mould material group on base material that is formed at of present embodiment the 1st example is described.
The urethane resin mould material group of the 1st example is, by polycarbonate polyol, with polycaprolactone polyol, reacted gained polyvalent alcohol, and the prepolymer of the end that is reacted gained by polytetramethylene glycol with polymeric polyisocyanate with isocyanate group formed, polycarbonate polyol is more than 65/35 to the ratio (polycarbonate polyol/polycaprolactone polyol) of polycaprolactone polyol by quality ratio.
Prepolymer any one or both that polyvalent alcohol and end have isocyanate group can be solid state under normal temperature.But the operability (getting polarity) during from storage and carrying etc. and coordinate both and do not want the viewpoint that heating and melting is processed while carrying out sclerous reaction when forming film, the prepolymer that polyvalent alcohol and end have isocyanate group is all preferably liquid at normal temperatures.
The polycarbonate polyol of one of polyvalent alcohol raw material, kind is not particularly limited, can be suitably via the polyvalent alcohol of for example short chain and the dehydrochlorination reaction of phosgene (phosgene), or the transesterify condensation reaction of the polyvalent alcohol of short chain and the low molecular carbon acid esters such as dialkyl carbonate (dialkyl carbonate), carbonic acid alkene ester (alkylene carbonate) or diaryl carbonate (diaryl carbonate) etc. and obtaining.
This short chain polyvalent alcohol can be enumerated for example 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, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 3-methyl isophthalic acid, the 5-pentanediol, the dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, hexanaphthene-1, the 4-glycol, hexanaphthene-1, the 4-dimethanol, dimeracid glycol (dimmer acid diol), glycerine, TriMethylolPropane(TMP), the oxyethane of dihydroxyphenyl propane (bisphenol A) and propylene oxide adduct equimolecular quantity are less than 500 short chain polyvalent alcohol.
Dialkyl carbonate such as methylcarbonate, diethyl carbonate etc., carbonic acid alkene ester such as NSC 11801 (ethylene carbonate), propylene carbonate (propylene carbonate) etc., diaryl carbonate such as diphenyl carbonate (diphenyl carbonate) etc.
These can be used alone or mix two or more use.
But, from more improving the viewpoint of the physical strength of the urethane resin film obtained, be preferably to use by the crystallinity performance and give the polycarbonate polyol of the straight chain aliphatic diols of physical strength, be especially preferably that 1,6-hexylene glycol reacts with dialkyl carbonate and the polycarbonate polyol that obtains.
The polycaprolactone polyol of one of polyvalent alcohol raw material for example aforementioned polycarbonate short chain polyvalent alcohol used as initiator, a side of the 6-caprolactone that 6-caprolactone and alkyl are replaced or both open loops in conjunction with and obtain.
Easily adjust or obtain the viewpoint of high stability in storage from the molecular weight of polyvalent alcohol, polyvalent alcohol is preferably when coordinating polycarbonate polyol and polycaprolactone polyol, coordinate aliphatic diol again and carry out the polyvalent alcohol of transesterification reaction gained.
Aliphatic diol can be enumerated ethylene glycol, 1,2-propylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, neopentyl glycol etc.From more improving the viewpoint of the physical strength of the urethane resin film obtained, aliphatic diol is preferably molecular weight below 200, and best especially is 1,6-hexylene glycol.
For the mixing ratio of polyvalent alcohol raw material, polycarbonate polyol is more than 65/35 to the ratio (polycarbonate polyol/polycaprolactone polyol) of polycaprolactone polyol by quality ratio.The upper limit of ratio does not have specific, and polycarbonate polyol also can approach approximately 100%, still, from normal temperature, as fluid operated viewpoint, is preferably below 75% (ratio is 75/25).In addition, as the polyvalent alcohol raw material, further use in the situation of aliphatic diol, mixing ratio is to take the interior number that aliphatic diol is polycarbonate polyol to calculate [(polycarbonate polyol+aliphatic diol)/polycaprolactone polyol].
End has the polytetramethylene glycol of one of raw material of the prepolymer of isocyanate group, and molecular weight is not particularly limited, but, from the outward appearance viewpoint of the urethane resin film that obtains, being preferably number-average molecular weight is more than 500.
Have the polymeric polyisocyanate of another raw material of the prepolymer of isocyanate group as end, kind is not particularly limited, and for example 2,4 toluene diisocyanate is (hereinafter to be referred as 2,4-TDI), 2,6-TDI, 4,4 '-diphenylmethanediisocyanate (hereinafter to be referred as 4,4 '-MDI), 2,4 '-MDI, 2,2 '-MDI, l,5 naphthylene diisocyanate (1,5-naphthylene diisocyanate), Isosorbide-5-Nitrae-naphthalene diisocyanate, to benzene thiazolinyl vulcabond (p-phenylene diisocyanate), isophthalic thiazolinyl vulcabond, o-Xylol thiazolinyl vulcabond (o-xylylene diisocyanate), m-xylene thiazolinyl vulcabond, p-Xylol thiazolinyl vulcabond, tetramethyl xylene thiazolinyl vulcabond, 4,4 '-diphenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, 3,3 '-dimethoxy phenylbenzene-4, the aromatic diisocyanate of 4 '-vulcabond etc., tetramethylene diisocyanate (tetramethylene diisocyanate), hexamethylene diisocyanate (hereinafter to be referred as HDI), the 2-methyl isophthalic acid, 5-pentane vulcabond, the 3-methyl isophthalic acid, 5-pentane vulcabond, the aliphatic diisocyanate of lysinediisocyanate (lysine diisocyanate) etc., isophorone diisocyanate (hereinafter to be referred as IPDI), hydrogenated tolylene diisocyanate, hydrogenated diphenyl methane diisocyanate (hereinafter to be referred as H12MDI), hydrogenated xylene diisocyanate (hereinafter to be referred as H6XDI), the hydrogenation tetramethylxylene diisocyanate, the alicyclic diisocyanate of cyclohexyl diisocyanate etc., and their mixture of more than two kinds, the affixture of these organic diisocyanates (adduct) modification body, biuret (biuret) modification body, isocyanic acid biradical (uretodion) modification body, uretonimine base (uretonimine) modification body, isocyanuric acid ester (isocyanurate) modification body, carbodiimide (carbodiimide) modification body etc.In the present embodiment example, the outward appearance of the urethane resin film coordinate with polyvalent alcohol easily while manufacturing from polyurethane film, obtained, the viewpoint of physical strength, be preferably aliphatic diisocyanate, alicyclic diisocyanate, especially with hexamethylene diisocyanate (HDI) the best.
End has the prepolymer of isocyanate group, and the content that is preferably isocyanic ester is 4～12 quality %, and the content of unreacted polymeric polyisocyanate is below 1 quality %.
The mixing ratio of the prepolymer that polyvalent alcohol when film forms and end have isocyanate group does not especially strictly limit, but, better example is, to 1 mole of the hydroxyl in polyvalent alcohol, it is 0.90～1.10 to coordinate that the end of take has isocyanate group in the prepolymer of isocyanate group.
Secondly, the urethane resin mould material group on base material that is formed at of present embodiment the 2nd example is described.
The urethane resin mould material group be formed on base material of the 2nd example is, the polyvalent alcohol that is formed at the urethane resin mould material group on base material of above-mentioned present embodiment further contains organo-metallic catalyst that under normal temperature, the sclerous reaction of micronized is used and the urethane resin mould material group of sclerous reaction inhibitor.
Thus, be scattered in the state of polyvalent alcohol by maintaining organo-metallic catalyst that sclerous reaction uses, adding general sclerous reaction when forming urethane resin film on base material compares by the situation of organo-metallic catalyst, can seek so-called serviceable time prolongation, more can prevent the delay of setting time.Below illustrate.
As long as organo-metallic catalyst is for producing the organometallic compound of the catalyst action of sclerous reaction in specific stiffening temperature condition, be not particularly limited, such as adopting normal temperature solid chemical compound in the malate compound, oxide compound, ester cpds, mercaptan (mercaptide) compound and the inner complex that contain the metals such as Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La or their mixture.Wherein, the organo-tin compound of micronized under better use normal temperature.
Organo-tin compound can be enumerated distearyl acid two fourth tin, two fourth tin maleic acid salt polymkeric substance, two (maleic acid alkyl ester) salt of two fourth tin, two (two fourth tin maleic acid alkyl esters) maleic acid salt, two fourth tin s, o-sulfhedryl carbonate polymkeric substance, distearyl acid two hot tin, two hot tin maleic acid salt polymkeric substance, two (maleic acid alkyl ester) salt of two hot tin, two (two hot tin maleic acid alkyl esters) maleic acid salt, two hot tin s, o-sulfhedryl carbonate polymkeric substance, two sad two hot tin (dioctyl tin dioctoate), oxidation two hot tin etc., wherein can adopt the organo-tin compound of normal temperature solid.
The particle diameter of organo-metallic catalyst is preferably below 70 μ m, is more preferred from below 50 μ m.
The addition of organo-metallic catalyst to polyvalent alcohol, the total amount of the prepolymer that the polyvalent alcohol used for urethane resin mould material group and end have isocyanate group, be preferably the scope of 50～2,000ppm, is more preferred from the scope of 80～1,500ppm.In order to prepare desirable reactivity, except adding above-mentioned organo-metallic series catalysts, might as well add the tertiary amine series catalysts.
The sclerous reaction inhibitor can contain at least a kind or their mixture of phosphoric acid, phosphorous acid, acid phosphoric acid ester, acid phosphorous acid ester, from taking into account the viewpoint that the serviceable time is long and setting time is short, the better acid phosphoric acid ester of carbonatoms 1～18 and their mixture of adopting.Above-mentioned acid phosphoric acid ester can be enumerated etherophosphoric acid, diethyl phosphoric acid, acidic isopropyl phosphate (isopropyl acid phosphate), acid butyl phosphate (butyl acid phosphate), acid phosphoric acid-2-ethylhexyl (2-ethyl hexyl acid phosphate), two (2-ethylhexyl) esters (bis (2-ethylhexyl) acid phosphate) of acid phosphoric acid, acid phosphoric acid isodecyl ester (isodecyl acid phosphate), acid lauryl phosphate (lauryl acid phosphate), acid phosphoric acid 13 esters (trideyl acid phosphate), acid phosphoric acid stearate (stearyl acid phosphate), acid phosphoric acid isostearate (isostearyl acid phosphate), acid phosphoric acid oleic acid ester (oleyl acid phosphate), acid phosphoric acid stearate (stearyl acid phosphate) etc.
The addition of sclerous reaction inhibitor to polyvalent alcohol, the polyvalent alcohol used for urethane resin mould material group and have the total amount of the prepolymer of isocyanate group, be preferably the scope of 25～1,000ppm, be more preferred from the scope of 40～750ppm, further be more preferred from the scope of 50～600ppm.
Secondly, form the method for urethane resin film on the base material that is formed at the urethane resin mould material group on base material for the 1st example of using present embodiment or the 2nd example, it is example that the urethane resin of take forms the method for filming as coating is used on base material, diagrammatic illustration.
At first, under normal temperature, urethane resin mould material group of present embodiment etc. is mixed with separate-type paper etc., prepare mould material (raw material) solution.Now, for example, with to 1 mole of hydroxyl in polyvalent alcohol, end has the mode that in the prepolymer of isocyanate group, isocyanate group is 0.90～1.10, adjust each content of prepolymer that polyvalent alcohol and end have isocyanate group, and, in the situation that present embodiment the 1st example has mixed solution 100 mass parts of the prepolymer of isocyanate group for polyvalent alcohol and end, add the sclerosis catalyzer of 0.001～0.5 mass parts ratio.And, during situation that mould material (raw material) is solid under normal temperature, till being heated to liquefied with proper temperature.
Then, the mould material of liquefied is coated on the base materials such as metal sheet, made afterwards its drying, sclerosis.
For the sclerosis catalyzer added, in the situation of the urethane resin mould material group of present embodiment the 2nd example, also use the sclerous reaction inhibitor when using above-mentioned organo-metallic catalyst, but in the situation of the urethane resin mould material group of present embodiment the 1st example, sclerosis is not particularly limited with catalyzer, can suitably use for example triethylamine, Triethylene Diamine, N-Methylimidazole, N-ethylmorpholine, 1,8-diaza-bicyclo-5, the amine of 4,0-hendecene-7 (DUB) etc.; The organo-metallic classes such as the malate compound that contains the metals such as Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La, oxide compound, carboxylate, mercaptan (mercaptide) compound and inner complex etc., concrete is the organo-metallic classes such as lime acetate, stannous octoate, dilauryl two fourth tin, the hot tin of dilauryl two (DOTDL).
Present embodiment described above be formed at urethane resin mould material group on base material etc., the good strength of the urethane resin film formed on base material.The intensity of urethane resin film, estimate with TB (tensile strength), EB (extensibility) and TR (rupture strength) as described later.
Present embodiment be formed at urethane resin mould material group on base material etc., can be used as coating etc. and be formed at the resin molding on base material, suitably use.Perhaps, in addition, also applicable to caking agent, synthetic leather and plastic film etc.
[embodiment]
Enumerate embodiment and comparative example, further illustrate the present invention.The present invention is not limited to the embodiment of following explanation.
(preparation example of polyvalent alcohol)
Each condition with table 1 coordinates raw material, in 2 liters of separable flasks, makes nitrogen bubble, and stirs 24 hours (60rpm) at 190 ℃, makes it carry out transesterification reaction and obtains the polyvalent alcohol of one of the material of urethane resin mould material group.
[table 1]
In table 1 and following each table, the unit of the amount of each composition of cooperation is all mass parts.The unit of hydroxyl value is mg KOH/g.
Each polyvalent alcohol raw material meaned with mark in table 1 is as follows.
ο 1,6-HD:1,6-hexylene glycol.
ο PCD-HG-1000: by the polycarbonate diol of the number-average molecular weight 1000 of the de-ethanol synthesis gained of 1,6-hexylene glycol and diethyl carbonate.
ο PCD-HG-2000: by the polycarbonate diol of the number-average molecular weight 2000 of the de-ethanol synthesis gained of 1,6-hexylene glycol and diethyl carbonate.
ο PCD-HG-5000: by the polycarbonate diol of the number-average molecular weight 5000 of the de-ethanol synthesis gained of 1,6-hexylene glycol and diethyl carbonate.
ο PCL-210: make the 6-caprolactone open loop be incorporated into two functional group's polycaprolactone glycols of the number-average molecular weight 1000 of BDO gained, initiator is ethylene glycol.
ο PCL-220: make the 6-caprolactone open loop be incorporated into two functional group's polycaprolactone glycols of the number-average molecular weight 2000 of BDO gained, initiator is ethylene glycol.
ο PCL-320: make the trifunctional polycaprolactone glycol of 6-caprolactone open loop in conjunction with the number-average molecular weight 2000 of gained at BDO, initiator is TriMethylolPropane(TMP).
(preparation example of polymeric polyisocyanate)
As each condition cooperation raw material of table 2, in separable flask, make nitrogen bubble, and the ammonia ester (urethane) carried out under 80 ℃ 4 hours is changed reaction.Afterwards, at 140 ℃, 0.3Torr, carry out thin film distillation, remove unreacted HDI and obtain the polymeric polyisocyanate of one of the material of urethane resin mould material group.
[table 2]
In table 2, each polymeric polyisocyanate raw material meaned with mark is as follows.
ο HDI: hexamethylene diisocyanate
ο PTG-250: the polytetramethylene glycol of number-average molecular weight 250 (polypropylene glycol)
ο PTG-650: the polytetramethylene glycol of number-average molecular weight 650
ο PTG-1000: the polytetramethylene glycol of number-average molecular weight 1000
ο PTG-2000: the polytetramethylene glycol of number-average molecular weight 2000
ο PPG-600: the polypropylene glycol of number-average molecular weight 600
ο PPG-1000: the polypropylene glycol of number-average molecular weight 1000
In table 2, the C-HX of isocyanates is as follows.
ο C-HX:CORONATE HX (
for Nippon Polyurethane Industry Co., Ltd. registered trademark), for the polymeric polyisocyanate of isocyanuric acid ester (isocyanurate) modification of hexamethylene diisocyanate, isocyanate content=21.0%, viscosity (25 ℃) is 2500mPas.
(embodiment 1～12 and comparative example 1～6)
Polyvalent alcohol and polymeric polyisocyanate coordinate with each condition of table 3～table 5,100 mass parts of mixed solution that there is the prepolymer of isocyanate group with respect to polyvalent alcohol and end, add the dilauryl two hot tin (DOTDL) of the conduct sclerosis of 0.01 mass parts with catalyzer, prepare polyurethane film (film) and estimated.For polyvalent alcohol, be normal temperature solid and through the cooperation person of solidifying, catalyzer is used in the rear interpolation sclerosis of processing at heating and melting, prepares polyurethane film (film), is estimated.
[table 3]
[table 4]
[table 5]
(evaluating characteristics)
By the polyvalent alcohol of each condition of embodiment 1～12 and comparative example 1～6 and the firm mixed liquid of isocyanic ester, flow on separate-type paper, cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine (bar coater), 120 ℃ harden 10 minutes, obtain polyurethane film (film).Using this polyurethane film as sample, carry out following each evaluation item.
ο TB (intensity while breaking)
TB is benchmark evaluation according to JIS K6251.The unit of TB value is MPa.
Based on wishing that according to purposes the TB value is the consideration more than 20, take that this is worth as boundary line difference embodiment and comparative example.
ο EB (range of extension while breaking)
EB is benchmark evaluation according to JIS K6251.The unit of EB value is %.
Based on wishing that according to purposes the EB value is the consideration more than 300, take that this is worth as boundary line difference embodiment and comparative example.
ο TR (tear strength)
TR is benchmark evaluation according to JIS K6252.The unit of TR value is kN/m.
Based on wishing that according to purposes the TR value is the consideration more than 30, take that this is worth as boundary line difference embodiment and comparative example.
(embodiment 13)
The sclerous reaction inhibitor (JP-508) that adds respectively the OH-5 of 1000g, the organo-metallic catalyst of 2g (NW-96), 1g in the separable flask of 2 liters, stir 30 minutes at 25 ℃.Thus, JP-508 evenly mixes with polyvalent alcohol, obtains the polyvalent alcohol premixture that NW-96 is scattered in state in polyvalent alcohol (below be designated as OH-10).And, the KS-1010A-1 that NW-96 is the organo-tin compound series catalysts (oxysuccinic acid dioctyltin polymkeric substance; Common medicine Co., Ltd's system) and adipic acid ester be plasticizer PN-250 (Asahi Denka Co., Ltd.'s system) with etc. mass ratio coordinate, till the particle diameter of the mixing one-tenth KS-1010-A of 3 shaft rollers (three roll) is 30 μ m to the maximum and the dispersion treatment product, the acid phosphoric acid ester that JP-508 is Johoku Chemical Co., Ltd.'s system: the mixture of single (acid phosphoric acid-2-ethylhexyl) and two (acid phosphoric acid-2-ethylhexyl).
Temperature regulation is 25 ℃ separately NCO-1 and OH-10 are mixed 30 seconds under 25 ℃ of atmosphere.Firm mixed state is the state that the organo-metallic composition disperses.This mixed solution 400g is packed in the glass specimen bottle processed of capacity 500cc, when standing under 25 ℃ of atmosphere, from mixing, also keeping mobility after 5 hours.Flow on separate-type paper from the liquid be mixed into 5 hours, cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine, 150 ℃ of sclerosis 3 minutes, obtain polyurethane film.The TB of the polyurethane film of gained is that 50MPa, EB are 600%, TR is 80kN/m.
On the other hand, the liquid just mixed is flowed on separate-type paper, cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine, 150 ℃ of sclerosis 3 minutes, obtain polyurethane film.The TB of the polyurethane film of gained is that 50MPa, EB are 600%, TR is 80kN/m.
(embodiment 14)
Add respectively the OH-5 of 1000g, the DOTDL of 0.2g (the hot tin of dilauryl two in the separable flask of 2 liters; The normal temperature solid), the JP-508 of 0.1g, at 25 ℃, stir 30 minutes, obtain the evenly polyvalent alcohol premixture of formation (below be designated as OH-11) of DOTDL and JP-508 and polyvalent alcohol.
Temperature regulation is 25 ℃ separately NCO-1 and OH-11 are mixed 30 seconds under 25 ℃ of atmosphere.Firm mixed state is even.This mixed solution 400g is packed in the glass specimen bottle processed of capacity 500cc, when standing under 25 ℃ of atmosphere, become without mobility through 30 minutes from mixing, even vial is inverted, liquid can not flow out yet.
On the other hand, firm mixed liquid is flowed on separate-type paper, cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine, 150 ℃ of sclerosis 3 minutes, obtain polyurethane film.The TB of the polyurethane film of gained is that 50MPa, EB are 600%, TR is 80kN/m.
Claims (7)
1. the urethane resin mould material group be formed on base material, it is characterized in that, the prepolymer that the end that is reacted the polyvalent alcohol of gained by polycarbonate polyol with polycaprolactone polyol and reacted gained by polytetramethylene glycol with polymeric polyisocyanate has isocyanate group is formed, and polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio.
2. the urethane resin mould material group be formed on base material as claimed in claim 1, is characterized in that, the prepolymer that described polyvalent alcohol and described end have isocyanate group is all liquid at normal temperatures.
3. the urethane resin mould material group be formed on base material as claimed in claim 2, is characterized in that, described polyvalent alcohol further contains organo-metallic catalyst and the sclerous reaction inhibitor for sclerous reaction of micronized under normal temperature.
4. the urethane resin mould material group be formed on base material as described as any one in claim 1～3, it is characterized in that, described polyvalent alcohol is obtained by polycarbonate polyol, polycaprolactone polyol and aliphatic diol reaction, the mixing ratio of these three kinds of polyvalent alcohols is to take the interior number that aliphatic diol is polycarbonate polyol to calculate, that is, with [(polycarbonate polyol+aliphatic diol)/polycaprolactone polyol], calculate.
5. the urethane resin mould material group be formed on base material as claimed in claim 4, is characterized in that, described polycarbonate polyol is reacted and obtained by 1,6-hexylene glycol and dialkyl carbonate.
6. the urethane resin mould material group be formed on base material as described as any one in claim 1～3, is characterized in that, described polymeric polyisocyanate is aliphatic diisocyanate.
7. the urethane resin mould material group be formed on base material as claimed in claim 6, is characterized in that, described aliphatic diisocyanate is hexamethylene diisocyanate.
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| JP2009-060405 | 2009-03-13 | ||
| JP2009060405A JP5429608B2 (en) | 2009-03-13 | 2009-03-13 | Polyurethane resin film material set formed on substrate |
| PCT/JP2010/000591 WO2010103719A1 (en) | 2009-03-13 | 2010-02-02 | Material set of forming polyurethane resin coating film formed on substrate |
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| TWI635204B (en) * | 2014-04-03 | 2018-09-11 | 展麒綠能股份有限公司 | Synthetic leather and manufacturing method thereof |
| CN106519950B (en) * | 2016-11-23 | 2019-11-22 | 北京涑酷特威科技有限公司 | Windshield rubber paint and preparation method thereof |
| DE102017003034A1 (en) * | 2017-03-29 | 2018-10-04 | Mankiewicz Gebr. & Co. Gmbh & Co. Kg | Coating composition, coatings prepared therefrom and their use as erosion protection |
| JP7189883B2 (en) * | 2017-11-13 | 2022-12-14 | 三井化学株式会社 | Polyurethane resin composition, cured product, molded article, fiber-reinforced plastic, and method for producing fiber-reinforced plastic |
| JP6888161B1 (en) * | 2020-10-02 | 2021-06-16 | 大日精化工業株式会社 | Urethane prepolymers, moisture-curable urethane hot-melt resin compositions, and laminates. |
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| WO2004101640A1 (en) * | 2003-05-16 | 2004-11-25 | Daicel Chemical Industries, Ltd. | Polyurethane and surface coating film of synthetic leather using the same |
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| JPS6484413A (en) * | 1987-09-28 | 1989-03-29 | Nippon Polyurethane Kogyo Kk | Magnetic recording medium |
| JPH021718A (en) * | 1988-02-01 | 1990-01-08 | Asahi Chem Ind Co Ltd | Urethane prepolymer and polyurethane coating composition |
| IT1290857B1 (en) * | 1996-12-19 | 1998-12-14 | Enichem Spa | PROCESS FOR THE PREPARATION OF DIOL COPOLYESTER POLYCARBONATES |
| JP2005146089A (en) * | 2003-11-13 | 2005-06-09 | Sanyo Chem Ind Ltd | Polyurethane emulsion |
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