CN102317390A - Be formed at the urethane resin mould material group on the base material - Google Patents
Be formed at the urethane resin mould material group on the base material Download PDFInfo
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- CN102317390A CN102317390A CN2010800080646A CN201080008064A CN102317390A CN 102317390 A CN102317390 A CN 102317390A CN 2010800080646 A CN2010800080646 A CN 2010800080646A CN 201080008064 A CN201080008064 A CN 201080008064A CN 102317390 A CN102317390 A CN 102317390A
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- urethane resin
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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
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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
- 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
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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
- C08G18/4266—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides film toughness good be formed at the urethane resin mould material group on the base material.Urethane resin mould material group; By the polyvalent alcohol of polycarbonate polyol and polycaprolactone polyol reaction gained, and form by the prepolymer that the end that polytetramethylene glycol and polymeric polyisocyanate react gained has a NCO, polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio.And, urethane resin mould material group, polyvalent alcohol further comprises organo-metallic catalyst and the sclerous reaction suppressor factor that the sclerous reaction of micronized is used under the normal temperature.
Description
Technical field
The present invention relates to for example be formed at by the solvent free urethane resin mould material on the covering with paint base material.
Background technology
The field that utilizes of urethane resin relates to multiple fields such as electric material, automobile rail truck material and civil construction material.
Utilizing in the field of these urethane resins, coating is for example arranged.Polyurethane resin coating is used for building more, the field of civil construction thing and vehicle, covers with paint, lacquer, colour wash, etc. good appearance, and film performance is good, and weather resistance is good.
Though polyurethane resin coating is many and organic solvent together uses, this situation makes the improvement of environmental problem and job safety problem etc. become big problem.
In order to solve this problem, the water systemization of the resin of use and solvent free are carried out multiple research (for example the referenced patent document 1) respectively.
But,, have on operating surface the homogeneity of shortcoming coated face or energy and time that must be big when dry, insufficient problems such as water tolerance and hydrolytic resistance on the rerum natura face about the former water systemization.
Relative therewith; Though the latter's solvent free is fewer in the problems referred to above of following water systemization to produce, follows solvent free, the resin solution high viscosityization; Then can not be coated with; On the contrary, to reduce the viscosity of resin solution in order being coated with, then to have intensity or the insufficient problem of durability degree on the rerum natura face.
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 the condition of no solvent, and film toughness is good is formed at the urethane resin mould material group on the base material.
The urethane resin mould material group that is formed on the base material of the present invention; It is characterized in that; Form by the polyvalent alcohol of polycarbonate polyol (polycarbonate polyol) and polycaprolactone polyol (polycaprolactone polyol) reaction gained and by the prepolymer (prepolymer) that the end of polytetramethylene glycol (polytetramethylene glycol) and polymeric polyisocyanate (polyisocyanate) reaction gained has a NCO, polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio.
The urethane resin mould material group that is formed on the base material of the present invention is characterized in that, is preferably, and the prepolymer that said polyvalent alcohol and said end have NCO all is liquid at normal temperatures.
The urethane resin mould material group that is formed on the base material of the present invention is characterized in that, is preferably, and said polyvalent alcohol further contains organo-metallic catalyst and the sclerous reaction suppressor factor that the sclerous reaction of micronized is used under the normal temperature.
The urethane resin mould material group that is formed on the base material of the present invention is characterized in that, is preferably, and said polyvalent alcohol is obtained by the reaction of polycarbonate polyol, polycaprolactone polyol and aliphatic diol (aliphatic glycol).
The urethane resin mould material group that is formed on the base material of the present invention is characterized in that, is preferably, and said polycarbonate polyol is by 1, and the 6-pinakon (1,6-hexanediol) and the reaction of dialkyl carbonate (dialkyl carbonate) and obtaining.
The urethane resin mould material group that is formed on the base material of the present invention is characterized in that be preferably, aforementioned polymeric polyisocyanate is an aliphatic diisocyanate.
The urethane resin mould material group that is formed on the 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 that is formed on the base material of the present invention; By the polyvalent alcohol of polycarbonate polyol (polycarbonate polyol) and polycaprolactone polyol (polycaprolactone polyol) reaction gained, and form by the prepolymer (prepolymer) that the end of polytetramethylene glycol (polytetramethylene glycol) and polymeric polyisocyanate (polyisocyanate) reaction gained has a NCO; Polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio, the polyurethane film good strength that therefore on base material, forms.
Embodiment
Embodiment of the present invention such as following explanation.
This embodiment be formed at the urethane resin mould material group (the following urethane resin mould material group that abbreviates as sometimes) on the base material, for example as coating, be used for covering with paint, lacquer, colour wash, etc. film being covered with paint, lacquer, colour wash, etc. to form on the base material.But be not limited thereto use,, also can be used on other base material, forming urethane resin film as long as can produce effect of the present invention.
Below the urethane resin mould material group of this embodiment the 1st example of explanation is managed polyvalent alcohol and terminal prepolymer with NCO respectively, when forming film, is used with catalyzer with sclerosis.Therefore, the storage stability when using polyvalent alcohol and terminal prepolymer with NCO to carry out before taking care of for a long time is good.The urethane resin mould material group of this embodiment the 2nd example further cooperates, contains the sclerous reaction of micronized at normal temperatures and uses with organo-metallic catalyst and sclerous reaction suppressor factor in polyvalent alcohol.Therefore, urethane resin mould material group operability in use is good.
The urethane resin mould material group of this embodiment the 1st example and the 2nd example all is the solvent free mould material that does not contain the organic solvent that might produce any environmental problem etc.
The urethane resin mould material group on the base material that is formed at of this embodiment the 1st example at first is described.
The urethane resin mould material group of the 1st example does; By the polyvalent alcohol of polycarbonate polyol and polycaprolactone polyol reaction gained, and form by the prepolymer that the end that polytetramethylene glycol and polymeric polyisocyanate react gained has a NCO, 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 terminal has NCO can be solid-like under the normal temperature.But from storage and carry isochronous operability (getting polarity) and when forming film, cooperate both and do not want the viewpoint that heating and melting is handled when carrying out sclerous reaction, polyvalent alcohol and terminal prepolymer with NCO preferably all are liquid at normal temperatures.
The polycarbonate polyol of one of polyvalent alcohol raw material; Kind is not special to be 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 dialkyl carbonate (dialkyl carbonate), carbonic acid alkene ester (alkylene carbonate) or diaryl carbonate low molecular carbon acid esters such as (diaryl carbonate) etc. and getting.
This short chain polyvalent alcohol can be enumerated for example terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1; 2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-pinakon, 1; 8-ethohexadiol, 1,9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, NSC 6366, Diethylene Glycol, dipropylene glycol, hexanaphthene-1; 4-glycol, hexanaphthene-1, the oxyethane of 4-dimethanol, dimeracid glycol (dimmer acid diol), glycerine, TriMethylolPropane(TMP), dihydroxyphenyl propane (bisphenol A) and propylene oxide adduct equimolecular quantity are less than 500 short chain polyvalent alcohol.
Dialkyl carbonate is methylcarbonate, diethyl carbonate etc. for example; Carbonic acid alkene ester is NSC 11801 (ethylene carbonate), propylene carbonate (propylene carbonate) etc. for example, and diaryl carbonate is diphenyl carbonate (diphenyl carbonate) etc. for example.
These can use separately or mix more than 2 kinds and use.
But; From improving the viewpoint of the physical strength of the urethane resin film that obtains more; Be preferably use and give the polycarbonate polyol of the straight chain aliphatic diols of physical strength by the crystallinity performance; Preferable especially is 1, the reaction of 6-pinakon and dialkyl carbonate and the polycarbonate polyol that obtains.
Can the for example aforementioned polycarbonate used short chain polyvalent alcohol of the polycaprolactone polyol of one of polyvalent alcohol raw material is as initiator, a side or both open loops of 6-caprolactone and the substituted 6-caprolactone of alkyl are combined and obtains.
From the adjustment or obtain the viewpoint of high stability in storage easily of the molecular weight of polyvalent alcohol, polyvalent alcohol is preferably when cooperating polycarbonate polyol and polycaprolactone polyol, cooperate aliphatic diol again and carry out the polyvalent alcohol of transesterification reaction gained.
Aliphatic diol can be enumerated terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1; 2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-pinakon, 1; 8-ethohexadiol, 1,9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, NSC 6366 etc.From improving the viewpoint of the physical strength of the urethane resin film that obtains more, aliphatic diol is preferably molecular weight below 200, and best especially is 1, the 6-pinakon.
For the cooperation 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 be near about 100%, still, as fluid operated viewpoint, is preferably below 75% (ratio is 75/25) under the normal temperature.In addition, further use as the polyvalent alcohol raw material under the situation of aliphatic diol, the cooperation ratio is to be that the interior number of polycarbonate polyol calculates [(polycarbonate polyol+aliphatic diol)/polycaprolactone polyol] with the aliphatic diol.
End has the polytetramethylene glycol of one of raw material of the prepolymer of NCO, and molecular weight is not special to be limited, but from the outward appearance viewpoint of the urethane resin film that obtains, being preferably number-average molecular weight is more than 500.
The polymeric polyisocyanate of another raw material that has the prepolymer of NCO as end; Kind is not special to be limited; For example 2; The 4-tolylene diisocyanate is (hereinafter to be referred as 2; 4-TDI), 2; 6-TDI, 4, and 4 '-diphenylmethanediisocyanate (hereinafter to be referred as 4,4 '-MDI), 2; 4 '-MDI, 2; 2 '-MDI, l,5 naphthylene diisocyanate (1,5-naphthylene diisocyanate), 1; The 4-naphthalene diisocyanate, to benzene thiazolinyl vulcabond (p-phenylene diisocyanate), a benzene 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), 2-methyl isophthalic acid, 5-pentane vulcabond, 3-methyl isophthalic acid, affixture (adduct) the modification body of the alicyclic diisocyanate of the aliphatic diisocyanate of 5-pentane vulcabond, LDI (lysine diisocyanate) etc., isophorone diisocyanate (hereinafter to be referred as IPDI), HTDI, hydrogenated diphenyl methane diisocyanate (hereinafter to be referred as H12MDI), hydrogenated xylene diisocyanate (hereinafter to be referred as H6XDI), hydrogenation tetramethylxylene diisocyanate, cyclohexyl diisocyanate etc., the mixture more than 2 kinds that reaches them, these organic diisocyanates, 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 this embodiment example; The outward appearance of the urethane resin film that when polyurethane film is made, cooperates easily, obtains, the viewpoint of physical strength with polyvalent alcohol; Be preferably aliphatic diisocyanate, alicyclic diisocyanate, especially with hexamethylene diisocyanate (HDI) the best.
End has the prepolymer of NCO, and the content that is preferably isocyanic ester is 4～12 quality %, and the content of unreacted polymeric polyisocyanate is below the 1 quality %.
Polyvalent alcohol when film forms and terminal not strict especially qualification of cooperation ratio with prepolymer of NCO; But; Preferable example does, to 1 mole of the hydroxyl in the polyvalent alcohol, has NCO in the prepolymer of NCO with end and is 0.90～1.10 and cooperate.
Secondly, the urethane resin mould material group on the base material that is formed at of this embodiment the 2nd example is described.
The urethane resin mould material group that is formed on the base material of the 2nd example is that the polyvalent alcohol that is formed at the urethane resin mould material group on the base material of above-mentioned embodiment further contains the sclerous reaction of micronized is used under the normal temperature the organo-metallic catalyst and the urethane resin mould material group of sclerous reaction suppressor factor.
Thus; Through keeping the state that organo-metallic catalyst that sclerous reaction uses is scattered in polyvalent alcohol; Add the contrast of general sclerous reaction when forming urethane resin film on the base material with organo-metallic catalyst; Can seek so-called serviceable time prolongation, more can prevent the delay of setting time.Below specify.
As long as organo-metallic catalyst is for producing the organometallic compound of the catalyst action of sclerous reaction in the specific stiffening temperature condition; Then not special the qualification for example can be employed in normal temperature solid chemical compound or their mixture in malate compound, oxide compound, ester cpds, mercaptan (mercaptide) compound and the inner complex of metals such as containing Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La.Wherein, the organo-tin compound of micronized under the preferable 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 normal temperature solid organo-tin compound.
The particle diameter of organo-metallic catalyst is preferably below the 70 μ m, is more preferred from below the 50 μ m.
Organo-metallic catalyst is to the addition of polyvalent alcohol, and the polyvalent alcohol and the end that use for urethane resin mould material group have the total amount of the prepolymer of NCO, are preferably 50～2, and the scope of 000ppm is more preferred from 80～1, the scope of 500ppm.In order to prepare desired response property, except adding above-mentioned organo-metallic series catalysts, might as well add the tertiary amine series catalysts.
The sclerous reaction suppressor factor 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 preferable 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 sclerous reaction suppressor factor is to the addition of polyvalent alcohol; The polyvalent alcohol that uses for urethane resin mould material group and have the total amount of the prepolymer of NCO is preferably 25～1, the scope of 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 the base material for the 1st example of using this embodiment or the 2nd example; With the urethane resin is that coating uses the method that formation is filmed on base material to be example, diagrammatic illustration.
At first, under the normal temperature urethane resin mould material group of this embodiment etc. and separate-type paper etc. are mixed preparation mould material (raw material) solution.At this moment; For example with to 1 mole of hydroxyl in the polyvalent alcohol; It is 0.90～1.10 mode that end has NCO in the prepolymer of NCO; Adjustment polyvalent alcohol and terminal each content of prepolymer with NCO, and under the situation of this embodiment the 1st example, have mixed solution 100 mass parts of the prepolymer of NCO for polyvalent alcohol and end, add the sclerosis of 0.001～0.5 mass parts ratio and use catalyzer.And mould material (raw material) is under the normal temperature during solid situation, is heated to liquid state with proper temperature and turns to and end.
Then, the mould material of liquid stateization is coated on the base materials such as metal sheet, made its drying, sclerosis afterwards.
Catalyzer use in sclerosis for adding, in the situation of the urethane resin mould material group of this embodiment the 2nd example, also uses the sclerous reaction suppressor factor when using above-mentioned organo-metallic catalyst; But in the situation of the urethane resin mould material group of this embodiment the 1st example; Sclerosis does not limit with catalyzer is special, can suitably use for example triethylamine, Triethylene Diamine, N-Methylimidazole, N-ethylmorpholine, 1,8-diaza-bicyclo-5; 4, the amine of 0-hendecene-7 (DUB) etc.; Contain the organo-metallic classes such as malate compound, oxide compound, carboxylate, mercaptan (mercaptide) compound and inner complex of metals such as Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La etc., concrete is lime acetate, stannous octoate, dilauryl two fourth tin, dilauryl two hot tin organo-metallic classes such as (DOTDL).
More than this embodiment of explanation is formed at urethane resin mould material group on the base material etc., the good strength of the urethane resin film that on base material, forms.The intensity of urethane resin film, as after state with TB (tensile strength), EB (extensibility) and TR (rupture strength) and estimate.
This embodiment be formed at urethane resin mould material group on the base material etc., can be used as coating etc. and be formed at the resin molding on the 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 specify the present invention.The present invention is not limited to following illustrated example.
(the preparation example of polyvalent alcohol)
Each condition with table 1 cooperates raw material, and nitrogen is bubbled, 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 OH value is mg KOH/g.
Each polyvalent alcohol raw material of representing with mark in the table 1 is following.
ο 1,6-HD:1,6-pinakon.
ο PCD-HG-1000: by 1, the polycarbonate diol of the number-average molecular weight of taking off the ethanol synthesis gained 1000 of 6-pinakon and diethyl carbonate.
ο PCD-HG-2000: by 1, the polycarbonate diol of the number-average molecular weight of taking off the ethanol synthesis gained 2000 of 6-pinakon and diethyl carbonate.
ο PCD-HG-5000: by 1, the polycarbonate diol of the number-average molecular weight of taking off the ethanol synthesis gained 5000 of 6-pinakon and diethyl carbonate.
ο PCL-210: make the 6-caprolactone open loop be incorporated into 1, two functional group's polycaprolactone glycols of the number-average molecular weight 1000 of 4-butyleneglycol gained, initiator is a terepthaloyl moietie.
ο PCL-220: make the 6-caprolactone open loop be incorporated into 1, two functional group's polycaprolactone glycols of the number-average molecular weight 2000 of 4-butyleneglycol gained, initiator is a terepthaloyl moietie.
ο PCL-320: 1, the 4-butyleneglycol makes the 6-caprolactone open loop combine the trifunctional polycaprolactone glycol of the number-average molecular weight 2000 of gained, and initiator is a TriMethylolPropane(TMP).
(the preparation example of polymeric polyisocyanate)
Each condition like table 2 cooperates raw material, and nitrogen is bubbled, and the ammonia ester (urethane) that under 80 ℃, carried out 4 hours is changed reaction.Afterwards, carry out thin film distillation, remove unreacted HDI and obtain the polymeric polyisocyanate of one of the material of urethane resin mould material group at 140 ℃, 0.3Torr.
[table 2]
In the table 2, following with each polymeric polyisocyanate raw material that mark is represented.
ο HDI: hexamethylene diisocyanate
ο PTG-250: the polytetramethylene glycol of number-average molecular weight 250 (W 166)
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 W 166 of number-average molecular weight 600
ο PPG-1000: the W 166 of number-average molecular weight 1000
The C-HX of isocyanates is following in the table 2.
(
is Nippon Polyurethane Industry Co. to ο C-HX:CORONATE HX; Ltd. registered trademark); Polymeric polyisocyanate for 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 cooperate with each condition of table 3～table 5; 100 mass parts of mixed solution that have the prepolymer of NCO with respect to polyvalent alcohol and terminal; Add the dilauryl two hot tin (DOTDL) of the conduct sclerosis of 0.01 mass parts with catalyzer, preparation polyurethane film (film) is also estimated.For polyvalent alcohol is that normal temperature solid and warp cooperate and curing person, uses catalyzer in the back interpolation sclerosis that heating and melting is handled, and preparation polyurethane film (film) is estimated.
[table 3]
[table 4]
[table 5]
(evaluating characteristics)
Polyvalent alcohol and the firm mixed liquid of isocyanic ester with each condition of embodiment 1～12 and comparative example 1～6; Flow on separate-type paper; Cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine (bar coater), 120 ℃ of sclerosis 10 minutes obtain polyurethane film (film).As sample, carry out following each evaluation item with this polyurethane film.
ο TB (intensity when breaking)
TB is a benchmark evaluation according to JIS K6251.The unit of TB value is MPa.
Based on hoping that according to purposes the TB value is the consideration more than 20, being worth with this is boundary line difference embodiment and comparative example.
ο EB (range of extension when breaking)
EB is a benchmark evaluation according to JIS K6251.The unit of EB value is %.
Based on hoping that according to purposes the EB value is the consideration more than 300, being worth with this is boundary line difference embodiment and comparative example.
ο TR (tear strength)
TR is a benchmark evaluation according to JIS K6252.The unit of TR value is kN/m.
Based on hoping that according to purposes the TR value is the consideration more than 30, being worth with this is boundary line difference embodiment and comparative example.
(embodiment 13)
The sclerous reaction suppressor factor (JP-508) that in 2 liters separable flask, adds the OH-5 of 1000g, the organo-metallic catalyst of 2g (NW-96), 1g respectively stirred 30 minutes at 25 ℃.Thus, JP-508 and polyvalent alcohol uniform mixing obtain the polyvalent alcohol premixture that NW-96 is scattered in state in the polyvalent alcohol (below be designated as OH-10).And NW-96 is KS-1010A-1 (the oxysuccinic acid dioctyltin polymkeric substance of organo-tin compound series catalysts; Common medicine Co., Ltd's system) and adipic acid ester be plasticizer PN-250 (Asahi Denka Co., Ltd.'s system) with etc. mass ratio cooperate; Through the particle diameter of 3 shaft rollers (three roll) mixing one-tenth KS-1010-A be to the maximum till the 30 μ m and dispersion treatment article, JP-508 is the acid phosphoric acid ester of Johoku Chemical Co., Ltd.'s system: the mixture of single (acid phosphoric acid-2-ethylhexyl) and pair (acid phosphoric acid-2-ethylhexyl).
With temperature regulation separately is that 25 ℃ NCO-1 and OH-10 mixed 30 seconds under 25 ℃ of atmosphere.Firm mixed state is an organo-metallic composition dispersive state.This mixed solution 400g is packed in the glass specimen bottle of capacity 500cc, when under 25 ℃ of atmosphere, leaving standstill, after 5 hours, also keeping flowability from mixing.From being mixed into liquid flow after 5 hours 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.
On the other hand, firm blended liquid flow on separate-type paper, is cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine,, obtain polyurethane film 150 ℃ of sclerosis 3 minutes.The TB of the polyurethane film of gained is that 50MPa, EB are 600%, TR is 80kN/m.
(embodiment 14)
In 2 liters separable flask, add the OH-5 of 1000g, the DOTDL of 0.2g (dilauryl two hot tin respectively; The normal temperature solid), the JP-508 of 0.1g, stirred 30 minutes at 25 ℃, obtain the evenly polyvalent alcohol premixture of formation (below be designated as OH-11) of DOTDL and JP-508 and polyvalent alcohol.
With temperature regulation separately is that 25 ℃ NCO-1 and OH-11 mixed 30 seconds under 25 ℃ of atmosphere.Firm mixed state is even.This mixed solution 400g is packed in the glass specimen bottle of capacity 500cc, when under 25 ℃ of atmosphere, leaving standstill, do not have mobilely through becoming in 30 minutes from mixing, even vial is inverted, liquid can not flow out yet.
On the other hand, firm mixed liquid flow on separate-type paper, is cast the film of thickness 100 μ m, planar dimension 300mm * 300mm with excellent coating machine,, obtain polyurethane film 150 ℃ of sclerosis 3 minutes.The TB of the polyurethane film of gained is that 50MPa, EB are 600%, TR is 80kN/m.
Claims (7)
1. urethane resin mould material group that is formed on the base material; It is characterized in that; Form by the polyvalent alcohol of polycarbonate polyol and polycaprolactone polyol reaction gained and by the prepolymer that the end that polytetramethylene glycol and polymeric polyisocyanate react gained has a NCO, polycarbonate polyol is more than 65/35 to the ratio of polycaprolactone polyol by quality ratio.
2. the urethane resin mould material group that is formed on the base material as claimed in claim 1 is characterized in that, the prepolymer that said polyvalent alcohol and said end have NCO all is liquid at normal temperatures.
3. the urethane resin mould material group that is formed on the base material as claimed in claim 2 is characterized in that, said polyvalent alcohol further contains the sclerous reaction of micronized under the normal temperature with organo-metallic catalyst and sclerous reaction suppressor factor.
4. like each described urethane resin mould material group that is formed on the base material in the claim 1～3, it is characterized in that said polyvalent alcohol is obtained by polycarbonate polyol, polycaprolactone polyol and aliphatic diol reaction.
5. the urethane resin mould material group that is formed on the base material as claimed in claim 4 is characterized in that, said polycarbonate polyol is by 1, and 6-pinakon and dialkyl carbonate react and obtain.
6. like each described urethane resin mould material group that is formed on the base material in the claim 1～3, it is characterized in that said polymeric polyisocyanate is an aliphatic diisocyanate.
7. the urethane resin mould material group that is formed on the base material as claimed in claim 6 is characterized in that said aliphatic diisocyanate is a 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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| KR (1) | KR101224777B1 (en) |
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|---|---|---|---|---|
| CN106519950A (en) * | 2016-11-23 | 2017-03-22 | 北京涑酷特威科技有限公司 | Rubber paint for windshield and preparation method thereof |
| CN110691801A (en) * | 2017-03-29 | 2020-01-14 | 美凯威奇兄弟有限责任两合公司 | Coating material composition, coating produced therefrom and use thereof as an abrasive protective layer |
Families Citing this family (4)
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| CN103755910B (en) * | 2013-12-27 | 2016-02-03 | 浙江华峰合成树脂有限公司 | Cold-resistant ethanol-tolerant non yellowing leather urethane resin and method for making thereof |
| TWI635204B (en) * | 2014-04-03 | 2018-09-11 | 展麒綠能股份有限公司 | Synthetic leather and manufacturing method thereof |
| 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. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62280214A (en) * | 1986-05-28 | 1987-12-05 | Dainippon Ink & Chem Inc | Polyurethane resin composition |
| JPH111549A (en) * | 1996-12-19 | 1999-01-06 | Enichem Spa | Production of poly(carbonate diol-co-ester) |
| WO2004101640A1 (en) * | 2003-05-16 | 2004-11-25 | Daicel Chemical Industries, Ltd. | Polyurethane and surface coating film of synthetic leather using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2005146089A (en) * | 2003-11-13 | 2005-06-09 | Sanyo Chem Ind Ltd | Polyurethane emulsion |
| JP5106801B2 (en) * | 2006-06-29 | 2012-12-26 | セメダイン株式会社 | One-part room temperature and moisture-curing shoe repair agent and shoe repair method |
-
2009
- 2009-03-13 JP JP2009060405A patent/JP5429608B2/en active Active
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2010
- 2010-02-02 KR KR1020117017059A patent/KR101224777B1/en active IP Right Grant
- 2010-02-02 WO PCT/JP2010/000591 patent/WO2010103719A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62280214A (en) * | 1986-05-28 | 1987-12-05 | Dainippon Ink & Chem Inc | Polyurethane resin composition |
| JPH111549A (en) * | 1996-12-19 | 1999-01-06 | Enichem Spa | Production of poly(carbonate diol-co-ester) |
| WO2004101640A1 (en) * | 2003-05-16 | 2004-11-25 | Daicel Chemical Industries, Ltd. | Polyurethane and surface coating film of synthetic leather using the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519950A (en) * | 2016-11-23 | 2017-03-22 | 北京涑酷特威科技有限公司 | Rubber paint for windshield and preparation 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 |
| CN110691801A (en) * | 2017-03-29 | 2020-01-14 | 美凯威奇兄弟有限责任两合公司 | Coating material composition, coating produced therefrom and use thereof as an abrasive protective layer |
| US11279846B2 (en) | 2017-03-29 | 2022-03-22 | Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) | Coating material composition, coatings produced therefrom and the use thereof as erosion protection |
| CN110691801B (en) * | 2017-03-29 | 2022-04-26 | 美凯威奇兄弟有限责任两合公司 | Coating material composition, coating produced therefrom and use thereof as an abrasive protective layer |
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| KR101224777B1 (en) | 2013-01-21 |
| KR20110097981A (en) | 2011-08-31 |
| JP5429608B2 (en) | 2014-02-26 |
| CN102317390B (en) | 2013-12-11 |
| WO2010103719A1 (en) | 2010-09-16 |
| TW201033239A (en) | 2010-09-16 |
| JP2010215679A (en) | 2010-09-30 |
| TWI388583B (en) | 2013-03-11 |
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