CN100564420C - The manufacture method of polyisocyantates composition and modulator approach thereof and hard polyurethane foams - Google Patents
The manufacture method of polyisocyantates composition and modulator approach thereof and hard polyurethane foams Download PDFInfo
- Publication number
- CN100564420C CN100564420C CNB2005100039360A CN200510003936A CN100564420C CN 100564420 C CN100564420 C CN 100564420C CN B2005100039360 A CNB2005100039360 A CN B2005100039360A CN 200510003936 A CN200510003936 A CN 200510003936A CN 100564420 C CN100564420 C CN 100564420C
- Authority
- CN
- China
- Prior art keywords
- ratio
- mdi
- group
- reaction
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The object of the present invention is to provide polyisocyantates composition, it can be made for various by adherend all has good cementability and shrinking percentage is low, shape stability is excellent hard polyurethane foams.Be used to make the polyisocyantates composition of hard polyurethane foams, it contains (A0) aggretion type MDI; (A1) make the polyester polyol (a1) and the terminal prepolymer of the 1st isocyanate group of aggretion type MDI prepared in reaction that has sulfo group or sulfonate group in the molecular structure; (A2) make polyethers monohydroxy-alcohol (a2) and the terminal prepolymer of the 2nd isocyanate group of aggretion type MDI prepared in reaction; (A3) type siloxane suds-stabilizing agent.
Description
Technical field
The present invention relates to the manufacture method of polyisocyantates composition and modulator approach thereof and hard polyurethane foams.More particularly, relate to can make for by the polyisocyantates composition of the high hard polyurethane foams of the bonding force of adherend, modulate this polyisocyantates composition method, use the manufacture method of the hard polyurethane foams that this polyisocyantates composition carries out.
In the present invention, so-called " hard polyurethane foams ", if no special instructions, its notion comprises " isocyanurate-modified polyurethane foam ".
Background technology
In the past, hard polyurethane foams was as the thermal insulation material of refrigerator, cold storage warehouse, material of construction etc., and used in the broad range of spraying use.
Polyisocyanates during as the manufacturing hard polyurethane foams uses the aggretion type MDI (polyphenylene polymethylene polyisocyanates) that comprises MDI (diphenylmethanediisocyanate).
On the other hand, the whipping agent when making hard polyurethane foams is from preventing viewpoint such as depletion of the ozone layer, replace 1 of many uses in the past, (hydrogen) Chlorofluorocarbons classes such as 1-two chloro-1-fluoroethanes, and use 1 gradually, 1,1,3,3-pentafluoropropane (below be abbreviated as " HFC-245fa "), 1,1,1,3, hydrogen fluorine carbon such as 3-3-pentafluorobutane (below be abbreviated as " HFC-365mfc ").
In addition, only make water as also existing introduce (for example, with reference to the patent documentation 1) of the hard polyurethane foams of (fully) water foaming formulation of whipping agent.
But, the hydrogen fluorine carbon and the water that use as whipping agent, with in the past (hydrogen) Chlorofluorocarbons class relatively, have problem with uniform mixing (intermiscibility, the dispersiveness) difference of urethane raw (isocyanate composition and polyhydric alcohol composition).If the uniform mixing of whipping agent and urethane raw (intermiscibility, dispersiveness) is low, reactive and foaming efficient (densification) reduces, in the foam of making except cause the surface processing bad, intensity reduces, dimensional stability descends, the bubble cave is thick and under the heat insulating ability that produces outside the degradation, also produce foam for the problem that is descended by the bonding force of adherend (body).
In addition, adopt the hard polyurethane foams of water foaming formulation for not had enough bonding forces by adherend.
Here, for becoming problem in the spraying application that particularly under low temperature environment, is carried out by the decline of the bonding force of adherend (spray construction).
For by the method for the cementability raising of adherend etc., introduced following method as realizing hard polyurethane foams.
(1) use EO and PO affixture to mix the method (with reference to patent documentation 2) of the polyol blends of formation as polyhydroxy reactant with the EO of the PO affixture of the PO affixture of the oxyethane (EO) of tolylene diamine and propylene oxide (PO) affixture, trolamine, glycerine, quadrol and PO affixture, glycerine.
(2) in polyhydric alcohol composition, add in the imidazoles, use the method (with reference to patent documentation 3) of the high aggretion type MDI of the ratio of isomer (4, the isomer of the MDI beyond 4 '-MDI) as the polyisocyanates composition.
(3) when the polyvalent alcohol that uses low functional group number, low hydroxyl value is as polyhydroxy reactant, use the method (with reference to patent documentation 4) of the high aggretion type MDI of isomer proportion as the polyisocyanates composition.
But employing comprises the known method in the past of the method for above-mentioned (1)～(3), can't make the hard polyurethane foams that is all had sufficiently high bonding force by adherend for various.
Patent documentation 1: the spy opens flat 3-91522 communique
Patent documentation 2: the spy opens flat 6-316621 communique
Patent documentation 3: the spy opens flat 6-172485 communique
Patent documentation 4: the spy opens flat 10-204149 communique
Summary of the invention
The present invention is based on above situation and propose.
The 1st purpose of the present invention is to provide polyisocyantates composition, and it can be made for various by adherend all has good cementability and shrinking percentage is low, shape stability is excellent hard polyurethane foams.
The 2nd purpose of the present invention is to provide and the excellent polyisocyantates composition of the homogeneous Combination (intermiscibility/dispersiveness) of hydrogen fluorine carbon and/or water.
It is the foaming formulation of whipping agent with hydrogen fluorine carbon and/or water that the 3rd purpose of the present invention is to provide employing, can make the foamy body height, the polyisocyantates composition of the hard polyurethane foams that cementability and dimensional stability etc. are excellent.
The 4th purpose of the present invention is to provide the modulator approach of the polyisocyantates composition with above-mentioned excellent properties.
The 5th purpose of the present invention is to provide for various is all had good cementability and the manufacture method of the hard polyurethane foams that shrinking percentage is low, shape stability is excellent by adherend.
The 6th purpose of the present invention is to provide the foamy body height, the manufacture method of the hard polyurethane foams that cementability, dimensional stability etc. are excellent.
Polyisocyantates composition of the present invention is the polyisocyantates composition that is used to make hard polyurethane foams, it is characterized in that containing:
(A0) aggretion type MDI,
(A1) make the polyester polyol (a1) that has sulfo group or sulfonate group in the molecular structure and the terminal prepolymer of the 1st isocyanate group of aggretion type MDI prepared in reaction,
(A2) make polyethers monohydroxy-alcohol (a2) and aggretion type MDI prepared in reaction the terminal prepolymer of the 2nd isocyanate group and
(A3) type siloxane suds-stabilizing agent.
In polyisocyantates composition of the present invention, preferred following form:
(1) ratio of MDI (the area ratio that GPC measures) is 20.0～80.0% among the aggretion type MDI.
The terminal prepolymers of (2) the 1st isocyanate group (A1) are 0.05～5.0 quality % with respect to the ratio of the total amount of isocyanate compound.
(3) contain (A4) aqueous ester compound.
(4) being used to make employing is the hard polyurethane foams of the foaming formulation of whipping agent with hydrogen fluorine carbon and/or water.
(5) be used to make the hard polyurethane foams that adopts spraying method to form on by adherend.
Modulator approach of the present invention is the method for modulation polyisocyantates composition of the present invention, it is characterized in that comprising following operation: in the presence of the siloxane-based suds-stabilizing agent (A3) or not, make specific polyester polyol (a1) and the terminal prepolymer (A1) of synthetic the 1st isocyanate group of aggretion type MDI reaction, make polyethers monohydroxy-alcohol (a2) and the terminal prepolymer (A2) of synthetic the 2nd isocyanate group of aggretion type MDI reaction simultaneously.
In modulator approach of the present invention, aggretion type MDI in the reaction vessel of preferably packing into and specific polyester polyol (a1) and the mass ratio of polyethers monohydroxy-alcohol (a2) are 90.0～99.98: 0.01～5.0: 0.01～5.0.
Modulator approach of the present invention is the manufacture method that makes the hard polyurethane foams of polyisocyanate mixtures (A) and polyvalent alcohol (B) reaction in the presence of whipping agent (C), catalyzer (D) and suds-stabilizing agent (E), it is characterized in that: above-mentioned polyisocyanate mixtures (A) contains above-mentioned aggretion type MDI (A0), the terminal prepolymer (A1) of above-mentioned the 1st isocyanate group and the terminal prepolymer (A2) of the 2nd isocyanate group, uses hydrogen fluorine carbon and/or water as above-mentioned whipping agent (C).
In addition, be preferably the method that make to adopt the hard polyurethane foams that spraying method forms on by adherend.
Effect of the present invention is:
(1) adopts polyisocyantates composition of the present invention, can make for various by adherend all has good cementability and shrinking percentage is low, shape stability is excellent hard polyurethane foams.
(2) homogeneous Combination (intermiscibility/dispersiveness) excellence of polyisocyantates composition of the present invention and hydrogen fluorine carbon and/or water.Therefore, even use hydrogen fluorine carbon and/or water, can not produce yet and mix bad caused problem with these whipping agents as whipping agent.
(3) adopt polyisocyantates composition of the present invention, adopting with hydrogen fluorine carbon and/or water is the foaming formulation of whipping agent, can make the foamy body height, the hard polyurethane foams of the homogeneous that cementability and dimensional stability etc. are excellent.
(4) adopt modulator approach of the present invention, can positively modulate polyisocyantates composition with the excellent properties shown in above-mentioned (1)～(3).
(5) adopt manufacture method of the present invention, can make for various by adherend all has good cementability and shrinking percentage is low, shape stability is excellent hard polyurethane foams.
(6) adopt manufacture method of the present invention, can positively make the foamy body height, the hard polyurethane foams that cementability and dimensional stability etc. are excellent.
Embodiment
In polyisocyantates composition of the present invention, contain aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group, the terminal prepolymer (A2) of the 2nd isocyanate group and type siloxane suds-stabilizing agent (A3) and be necessary component.
＜aggretion type MDI (A0) 〉
The aggretion type MDI (A0) that constitutes polyisocyantates composition of the present invention is the MDI (diphenylmethanediisocyanate) of two nucleomes and the mixture (polyphenylene polymethylene polyisocyanates) of the polykaryon (MDI is a condenses) more than three nucleomes.
Aggretion type MDI (A0) can be converted into isocyanate group by phosgenation etc. by the amino of condensation mixture (polyamine) that aniline and formalin condensation reaction are obtained and prepare, raw material ratio of components and reaction conditions when changing condensation can be controlled the composition (nucleome distributes and the isomer constituent ratio) of the aggretion type MDI of final preparation.
The aggretion type MDI that uses among the present invention (A0) can be the reaction solution that is converted into after the isocyanate group, from reaction solution solvent is removed, and a part of MDI is distillated different multiple mixtures such as reaction conditions such as isolating jar of fluid and separation condition.In addition, can be in commercially available aggretion type MDI, having mixed the mixture of MDI.
The ratio of MDI (two nucleomes) is preferably 20.0～80.0% among the aggretion type MDI (A0), and more preferably 25.0～75.0%.
Here, the ratio of the ratio of MDI for obtaining from the peak area ratio that adopts the MDI that GPC (gel permeation chromatograph) measures.
Aggretion type MDI (A0) if in the ratio of MDI surpass 80.0%, the final hard polyurethane foams that forms is for being had the tendency that reduces by the bonding force of adherend and intensity.
On the other hand, when this ratio less than 20.0%, the viscosity increased of the polyisocyantates composition of preparation, for example the spraying processing ease becomes difficult in spraying application.
The MDI of two nucleomes is by 4,4 '-MDI, 2, and 2 '-MDI and 2, these 3 kinds of isomer of 4 '-MDI constitute.
The constituent ratio of these isomer is not particularly limited, but from forming for by the viewpoint of the high hard polyurethane foams of the bonding force of adherend and intensity, 4,4 '-MDI contains proportional 50.0～99.5 quality % that are preferably.
The area percentage at each peak that the constituent ratio of isomer can obtain based on GPC or GC (gas chromatograph) is obtained from detection line.
The average functional group number of aggretion type MDI (A0) is preferably more than 2.2, and more preferably 2.2～3.1.
The isocyanate content of aggretion type MDI (A0) is preferably 28～33 quality %, more preferably 28.5～32.5 quality %.
The acidity of aggretion type MDI (A0) is preferably 0.001～0.2 quality %, more preferably 0.003～0.15 quality %.Like this, can guarantee the storage stability of the polyisocyantates composition for preparing and the reactivity that is fit to.
So-called " acidity " is meant at room temperature and reacts with alcohol, and free acid composition is scaled the value shown in the hydrogenchloride, measures according to JIS K-1603.
The terminal prepolymer (A1) of＜the 1 isocyanate group 〉
The terminal prepolymer of the 1st isocyanate group (A1) that constitutes polyisocyantates composition of the present invention for give the final hard polyaminoester that forms for various by the good cementability of adherend, or make the composition of its raising.
The terminal prepolymer of the 1st isocyanate group (A1) prepares by making specific polyester polyol (a1) and aggretion type MDI reaction.
" the aggretion type MDI " of reaction that supply is used to prepare the terminal prepolymer of the 1st isocyanate group (A1) is identical with " aggretion type MDI (A0) " that stated as the constituent of polyisocyantates composition (coenocytic mixtures that two nucleomes and three nucleomes are above), so no longer explanation.
＜specific polyester polyol (a1) 〉
Supply is used to prepare " specific polyester polyol (a1) " of the reaction of the terminal prepolymer of the 1st isocyanate group (A1), is to have sulfo group (SO in the molecular structure
3H) or sulfonate group (SO
3-) polyester polyol.
Polynary acids and the polyvalent alcohol of specific polyester polyol (a1) by adopting well-established law to make to contain the polyprotonic acid (hereinafter referred to as " specific polyprotonic acid ") that has sulfo group or sulfonate group in the molecular structure or polybasic ester (hereinafter referred to as " specific polybasic ester ") carries out esterification (or transesterification reaction) and prepares.
Here, as " specific polyprotonic acid ", can enumerate 2-sulfo-terephthalic acid 2-sodium, sulfo-terephthalic acid 2-potassium, sulfo-m-phthalic acid 5-sodium, sulfo-m-phthalic acid 5-potassium, sulfo-m-phthalic acid 5-lithium etc.
As " specific polybasic ester ", can enumerate these specific polybasic ester thing (C such as methyl esters, ethyl ester, propyl ester, butyl ester
1Above ester).
As the polyprotonic acid beyond the specific polyprotonic acid, as aliphatic dicarboxylic acid, can enumerate oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, sebacic acid, nonane diacid, dodecylic acid, fumaric acid, toxilic acid, oxysuccinic acid, tartrate etc., and, can enumerate phthalic acid, m-phthalic acid, terephthalic acid, naphthalic acid etc. as aromatic dicarboxylic acid.
As polyvalent alcohol, can enumerate ethylene glycol, glycol ether, propylene glycol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 6-hexylene glycol, neopentyl glycol, Hydrogenated Bisphenol A, 1, the 2-propylene glycol, 1, the 2-butyleneglycol, the 2-methyl isophthalic acid, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, the 2-methyl isophthalic acid, the 6-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, 2-ethyl-2-butyl-1, ammediol, 2,2-diethyl-1, ammediol, 3,3-dimethyl-1, the 5-pentanediol, 2-methyl-2-ethyl-1, ammediol, 3-methyl-3-ethyl-1, the 5-pentanediol, 2-methyl-2-propyl group-1, ammediol, 3-methyl-3-propyl group-1, the 5-pentanediol, 2-methyl-2-butyl-1, ammediol, 3-methyl-3-butyl-1, the 5-pentanediol, 3,3-diethyl-1, the 5-pentanediol, 3-ethyl-3-butyl-1, the 5-pentanediol, 2-ethyl-2-propyl group-1, ammediol, 3-ethyl-3-propyl group-1, the 5-pentanediol, 2,2-dibutyl-1, ammediol, 3,3-dibutyl-1,5-pentanediol, 2,2-dipropyl-1, ammediol, 3,3-dipropyl-1,5-pentanediol, 2-butyl-2-propyl group-1, ammediol, 3-butyl-3-propyl group-1, the 5-pentanediol, 2-ethyl-1, ammediol, 2-propyl group-1, ammediol, 2-butyl-1, ammediol, 3-ethyl-1, the 5-pentanediol, 3-propyl group-1, the 5-pentanediol, 3-butyl-1, the 5-pentanediol, 2-ethyl-1, the 6-hexylene glycol, 2-propyl group-1, the 6-hexylene glycol, 2-butyl-1, the 6-hexylene glycol, 5-ethyl-1, the 9-nonanediol, 5-propyl group-1, the 9-nonanediol, 5-butyl-1, the 9-nonanediol, dipropylene glycol, triethylene glycol, the tetramethyl glycol, the pregnancy glycol, ten methylene glycols, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, two sorbitans etc.
As the number-average molecular weight of specific polyester polyol (a1), be preferably 500～3000, more preferably 800～2500.
When number-average molecular weight was too small, the polyurethane foam for preparing self produced fragility.On the other hand, when number-average molecular weight is excessive, with the intermiscibility variation of aggretion type MDI (isocyanate compound).
As the sulfo group that contains in the specific polyester polyol (a1) or the ratio of sulfonate group, be preferably 0.1～2.0mmol/g, more preferably 0.1～1.5mmol/g.
When the ratio of sulfo group or sulfonate group is too small, can not embody adhesive effect required for the present invention.On the other hand, when this ratio is excessive, with the intermiscibility variation of aggretion type MDI (isocyanate compound).Can this ratio be controlled by the ratio of the specific polyprotonic acid (ester) in the polynary acids of adjusting supply response.
If enumerate a example as the preferred compound of specific polyester polyol (a1), can enumerate the polynary acids and 1 that sulfo-m-phthalic acid 5-sodium (or 5-sodium sulfo-dimethyl isophthalate) and hexanodioic acid are formed, the 6-hexylene glycol carries out esterification (transesterification reaction and ester reaction) preparation, the adipic acid ester kind polyester polyvalent alcohol that contains sodium sulfonate group of number-average molecular weight 1000～2000.
The terminal prepolymer (A2) of＜the 2 isocyanate group 〉
The terminal prepolymer of the 2nd isocyanate group (A2) is for giving the blended composition of homogeneous of polyisocyantates composition of the present invention and whipping agent (the particularly whipping agent of hydrogen fluorine carbon and/or water composition).
The terminal prepolymer of the 2nd isocyanate group (A2) prepares by making polyethers monohydroxy-alcohol (a2) and aggretion type MDI reaction.
" the aggretion type MDI " of reaction that supply is used to prepare the terminal prepolymer of the 2nd isocyanate group (A2) is identical with " aggretion type MDI (A0) " that stated as the constituent of polyisocyantates composition (coenocytic mixtures that two nucleomes and three nucleomes are above), so no longer explanation.
＜specific polyethers monohydroxy-alcohol (a2) 〉
Supply is used to prepare " polyethers monohydroxy-alcohol (a2) " of the reaction of the terminal prepolymer of the 2nd isocyanate group (A2), can be with following chemical formulation.
Chemical formula: R
1O-(R
2O)
n-H
In above-mentioned chemical formula, R
1The organic group of representing 1 valency ,-(R
2O)-and the expression alkylene oxide group, n represents the number more than 2.
Organic group (R
1) can have carbon atom and hydrogen atom atom in addition, and can be with or without side chain.In addition, a plurality of alkylene oxide group-(R of existence
2O)-and can be identical, also can be different.
Polyethers monohydroxy-alcohol (a2) can be by to have the compound (R of 1 hydroxyl
1OH) be initiator, make cyclic ethers such as oxirane and its addition and prepare.
As R as initiator
1The compound that OH represents can be enumerated methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, 2-Ethylhexyl Alcohol, phenol, benzylalcohol, N-methyl-N-ethylamino alcohol, N, N-diethylamino alcohol etc.
In addition, as with the oxirane of initiator addition, can enumerate oxyethane, propylene oxide, butylene oxide ring etc.
As the number-average molecular weight of polyethers monohydroxy-alcohol (a2), be preferably 150～10000, more preferably 150～8000.
When the number-average molecular weight of polyethers monohydroxy-alcohol (a2) is too small, can't give full play to the blended raising effect of homogeneous with initiator (the particularly whipping agent of hydrogen fluorine carbon and/or water composition).On the other hand, when number-average molecular weight was excessive, the viscosity increased of the polyisocyantates composition of preparation caused operability to reduce.
If enumerate a example, can enumerate and have C as the preferred compound of polyethers monohydroxy-alcohol (a2)
1～20Alkoxyl group as terminal group (R
1O-), have oxyethylene group and/or oxypropylene group as repeating unit [(R
2O)
n-], number-average molecular weight is poly-(ethylene oxide) monohydroxy-alcohol of 500～1000, poly-(propylene oxide) monohydroxy-alcohol, poly-(ethylene oxide-propylene oxide) copolymer analog monohydroxy-alcohol.
＜type siloxane suds-stabilizing agent (A3) 〉
As the type siloxane suds-stabilizing agent (A3) that constitutes polyisocyantates composition of the present invention, be not particularly limited, can use all as the known in the past material (dimethyl polysiloxane and polysiloxane-polyether copolymer) of hard polyurethane foams with suds-stabilizing agent.
As type siloxane suds-stabilizing agent (A3) part or all, can use the polysiloxane-polyether copolymer (hereinafter referred to as " siloxanes that contains the active hydrogen base ") that contains the active hydrogen base.
Employing contains the polyisocyantates composition of the present invention of the type siloxane suds-stabilizing agent with active hydrogen base, can realize the further raising with the homogeneous Combination of whipping agent (the particularly dispersiveness of whipping agent in the intermiscibility of the whipping agent of forming with hydrogen fluorine carbon and/or water, the composition).
The siloxanes that contains the active hydrogen base is the segmented copolymer that is made of dimethyl polysiloxane structure and polyoxyalkylene structure (polyether structure), for having the compound of active hydrogen base in the molecular structure.
As preferred active hydrogen base, can enumerate hydroxyl, amino, carboxyl, sulfydryl etc., from the viscosity, intermiscibility, dispersed aspect etc. of the polyisocyantates composition of preparation, most preferably hydroxyl.
The average functional group number (mean number of the active hydrogen base that has in 1 molecule) that contains the siloxanes of active hydrogen base is preferably 1～10, and more preferably 1～5, be preferably 1～2 especially.When average functional group number is excessive, the viscosity increased of the polyisocyantates composition of preparation, the operability during foaming reduces easily.
The number-average molecular weight that contains the siloxanes of active hydrogen base is preferably 500～20000, and more preferably 1000～18000.If number-average molecular weight is excessive, viscosity increased, the property handled is poor.
The hydroxyl value that contains the siloxanes of active hydrogen base is preferably 3～300mgKOH/g, more preferably 5～150mgKOH/g.If hydroxyl value is too small, viscosity increased, the property handled is poor, and the foam that forms does not have enough intensity yet.On the other hand, when hydroxyl value is excessive, the polyisocyantates composition of preparation and the homogeneous Combination of whipping agent are fully improved.
The concrete structure that contains the siloxanes of active hydrogen base is shown in following general formula (1)～(9).
(in the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency.M represents the integer more than 2.)
(in the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure.M represents the integer more than 2.)
(in the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency, R
5The organic group of representing 3 valencys.M represents the integer more than 2.)
(in the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency, R
5The organic group of representing 3 valencys.M represents the integer more than 2.)
(following formula is represented segmented copolymer or random copolymers.In the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency.M, n are the integer more than 1.)
(following formula is represented segmented copolymer or random copolymers.In the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency.M, n are the integer more than 1.)
(following formula is represented segmented copolymer or random copolymers.In the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure.M, n are the integer more than 1.)
(following formula is represented segmented copolymer or random copolymers.In the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure.R
4The organic group of representing 1 valency, R
5The organic group of representing 3 valencys.M, n are the integer more than 1.)
(following formula is represented segmented copolymer or random copolymers.In the formula, A represents active hydrogen base, R
3Expression has the organic group of the divalent of polyether structure, R
4The organic group of representing 1 valency, R
5The organic group of representing 3 valencys.M, n are the integer more than 1.)
＜other isocyanate compounds 〉
Polyisocyantates composition of the present invention, contain aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer of the 2nd isocyanate group (A2) as essential isocyanate compound, but in polyisocyantates composition of the present invention, also can contain the isocyanate compound beyond these essential isocyanate compounds.
As such isocyanate compound, can enumerate making aggretion type MDI (or being MDI) and the urethane thing that contains the compound prepared in reaction of active hydrogen base (not comprising and terminal prepolymer of the 1st isocyanate group and the suitable material of the terminal prepolymer of the 2nd isocyanate group), urea thing, allophanic acid esterification thing, biuretized thing, carbodiimide thing, ウ レ ト Application イ ミ Application thing, ウ レ ト ジ オ Application thing, isocyanuric acid esterification thing; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene-1,4-vulcabond, dimethylbenzene-1, aromatic diisocyanates such as 3-vulcabond, tetramethylxylene diisocyanate, m-benzene diisocyanate, PPDI; Tetramethylene diisocyanate, hexamethylene diisocyanate, 3-methyl isophthalic acid, aliphatic diisocyanates such as 5-pentane vulcabond, lysinediisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenyl methane diisocyanate etc.In addition, also can use these polymer or these isocyanic ester and the urethane thing that contains the compound prepared in reaction of active hydrogen base, urea thing, allophanic acid esterification thing, biuretized thing, carbodiimide thing, ウ レ ト Application イ ミ Application thing, ウ レ ト ジ オ Application thing, isocyanuric acid esterification thing etc.These isocyanate compounds can be used singly or two or more kinds in combination.
The ratio of the terminal prepolymer of＜the 1 isocyanate group (A1) 〉
In polyisocyantates composition of the present invention, the terminal prepolymer of the 1st isocyanate group (A1) is preferably 0.05～5.0 quality % with respect to the ratio of isocyanate compound total amount [the essential isocyanate compound that aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer of the 2nd isocyanate group (A2) are formed, and the total amount of the isocyanate compound beyond these essential isocyanate compounds].
Like this, can positively make for various and all had good cementability by adherend and shrinking percentage is low, shape stability is also excellent hard polyurethane foams.
＜aqueous ester compound (A4) 〉
In polyisocyantates composition of the present invention, preferably contain aqueous ester compound (A4).Should " aqueous ester compound (A4) " show aqueous ester compound down for normal temperature.
Here, " ester compound " comprises whole compounds of the molecular structure with hydrogen atom of using organic group (R) replacement organic acid or mineral acid.
Aqueous ester compound (A4) has the effect of the viscosity reduction that makes the polyisocyantates composition that contains it, can further make by its hard polyurethane foams that forms for being improved by the bonding force of adherend simultaneously.
As the concrete example of aqueous ester compound (A4), can enumerate carboxylic acid ester compounds such as vinyl acetic monomer, N-BUTYL ACETATE, phthalic acid dibutyl ester, dimethyl adipate, 6-caprolactone; Carbonats compounds such as methylcarbonate, diethyl carbonate, propylene carbonate; Phosphate compounds such as trimethyl phosphite 99, triethyl phosphate etc., wherein, preferred cyclic carbonats compound.
＜any component 〉
In the scope of not damaging its effect, can contain various any components in the polyisocyantates composition of the present invention.
As this any component, the component that can use all known in the past material (additive etc.) to contain as the polyisocyantates composition that is used for making hard polyurethane foams.
＜polyisocyantates composition 〉
As the isocyanate content of polyisocyantates composition of the present invention, be preferably 25.0～32.0 quality %, more preferably 26.0～32.0 quality %.
Viscosity (25 ℃) as polyisocyantates composition of the present invention is preferably 50～400mPas, more preferably 60～300mPas.
Polyisocyantates composition of the present invention since with homogeneous Combination (dispersiveness of hydrogen fluorine carbon or water in the intermiscibility/composition) excellence of hydrogen fluorine carbon and water, therefore being preferred for adopting with these is that the foaming formulation of whipping agent is made hard polyaminoester.
Adopt polyisocyantates composition of the present invention, in that known polyisocyantates composition was also suitable the spraying application under the out of use low temperature environment aspect cementability in the past, can form for the hard polyurethane foams that is had good cementability by adherend.
Here, as be suitable for polyisocyantates composition of the present invention by adherend, be not particularly limited, can enumerate for example wood type, coagulation great soil group, various metal species, stationery, stone materials, various plastics class, ceramic-like, category of glass, various rubber-like etc.
Use-pattern (constructional method) as polyisocyantates composition of the present invention much less also is not limited to spraying application.
The modulator approach of＜polyisocyantates composition 〉
Modulator approach of the present invention is the method for modulation polyisocyantates composition of the present invention, it comprises following operation: in the presence of the siloxane-based suds-stabilizing agent (A3) or not, make specific polyester polyol (a1) and the terminal prepolymer (A1) of synthetic the 1st isocyanate group of aggretion type MDI reaction, make polyethers monohydroxy-alcohol (a2) and the terminal prepolymer (A2) of synthetic the 2nd isocyanate group of aggretion type MDI reaction simultaneously.
Here, the building-up reactions of the terminal prepolymer of the building-up reactions of the terminal prepolymer of the 1st isocyanate group (A1) and the 2nd isocyanate group (A2), which advanced provisional capital is passable, also can carry out simultaneously.
In addition, also can in the presence of siloxane-based suds-stabilizing agent (A3), carry out one of these building-up reactionss and/or another (promptly, to make its reaction after siloxane-based suds-stabilizing agent (A3) and the reaction raw materials mixing), also can carry out (that is, hybrid silicone is suds-stabilizing agent (A3) in reacted system) in the presence of not at siloxane-based suds-stabilizing agent (A3).
Modulator approach of the present invention is normally packed in the reaction vessel with specific polyester polyol (a1) and/or polyethers monohydroxy-alcohol (a2) and with respect to their excessive aggretion type MDI, makes specific polyester polyol (a1) and/or polyethers monohydroxy-alcohol (a2) and aggretion type MDI (part of Intake Quantity) reaction.
In modulator approach of the present invention, pack into the aggretion type MDI of reaction vessel and the mass ratio [aggretion type MDI: (a1): (a2)] of polyester polyol (a1) and polyethers monohydroxy-alcohol (a2) is preferably 90.0～99.98: 0.01～5.0: 0.01～5.0, more preferably 92.0～99.9: 0.05～4.0: 0.05～4.0, be preferably 94.0～99.8: 0.10～3.0 especially: 0.10～3.0.
When the building-up reactions of the building-up reactions of implementing the terminal prepolymer of the 1st isocyanate group (A1) respectively and the terminal prepolymer of the 2nd isocyanate group (A2), the amount of " reaction vessel of packing into " is the total amount of Intake Quantity separately.
Building-up reactions (urethane reaction) temperature of reaction that is used for preparing terminal prepolymer (A1) of the 1st isocyanate group and the 2nd isocyanate group end prepolymer (A2) is preferably 20～120 ℃, more preferably 40～100 ℃.
In addition, urethane when reaction, can use organometallic compounds such as dibutyl tin dilaurate, two lauric acid, two hot tin as required, known urethane catalyzer such as organic amine such as triethylenediamine or triethylamine or its salt.
The load time of any component (additive), there is no particular restriction.
After reaction finishes, in this system, exist in terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer of the 2nd isocyanate group (A2), also exist and the irrelevant aggretion type MDI of reaction, this aggretion type MDI directly becomes the component [aggretion type MDI (A0)] that constitutes polyisocyantates composition of the present invention.
The manufacture method of＜hard polyurethane foams 〉
Manufacture method of the present invention is the manufacture method that makes the hard polyurethane foams of polyisocyanate mixtures (A) and polyvalent alcohol (B) reaction in the presence of whipping agent (C), catalyzer (D) and suds-stabilizing agent (E), it is characterized in that: above-mentioned polyisocyanate mixtures (A) contains above-mentioned aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer (A2) of the 2nd isocyanate group, uses hydrogen fluorine carbon and/or water as above-mentioned whipping agent (C).
＜polyisocyanate mixtures (A) 〉
" polyisocyanate mixtures (A) " that uses in the manufacture method of the present invention is for containing the mixture of aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer of the 2nd isocyanate group (A2), that is, for constituting the mixture of the contained essential isocyanate compound of polyisocyantates composition of the present invention.
In the scope of not damaging effect of the present invention, also can contain these isocyanate compounds in addition in " polyisocyanate mixtures (A) ".
＜polyvalent alcohol (B) 〉
There is no particular restriction for " polyvalent alcohol (B) " that uses in the manufacture method of the present invention, can enumerate known in the past polyester polyol, polyether glycol, polycarbonate polyol etc.
In addition, the intensity of the hard polyurethane foams that consideration forms etc. can and be used low molecular polylol, low molecular weight polycaprolactone amine, low molecule amino alcohol etc.
As the polyvalent alcohol that uses in the manufacture method of the present invention (B), preferably use the 3 kinds of polyvalent alcohols [polyvalent alcohol (b1)～(b3)] shown in following at least a kind, more preferably use more than 2 kinds.
When only using polyvalent alcohol (b1) and polyvalent alcohol (b3) any a kind, the hard polyurethane foams of formation does not have enough physical strengths sometimes.In addition, only the viscosity of the polyvalent alcohol (B) that is made of polyvalent alcohol (b2) is excessive, has the tendency of operability variation.
＜polyvalent alcohol (b1) 〉
With alkanolamine such as Monoethanolamine MEA BASF, diethanolamine, trolamines, the mixture more than a kind or 2 kinds of aminated compoundss such as polyamines class such as tolylene diamine, quadrol, diethylenetriamine, ammonia, aniline, benzene dimethylamine, diaminodiphenyl-methane is as initiator, make oxiranes such as oxyethane, propylene oxide carry out addition reaction and prepare the polyether glycol of hydroxyl value 50～1000mgKOH/g, preferred 100～900mgKOH/g.In addition, as initiator, can be also with being used to prepare polyvalent alcohol (b2) and the employed polyvalent alcohol of polyvalent alcohol (b3).
＜polyvalent alcohol (b2) 〉
(1) makes spent glycol, propylene glycol, butyleneglycol, glycol ether, dipropylene glycol, three methylene glycols, the tetramethyl glycol, the pregnancy glycol, ten methylene glycols, neopentyl glycol, the 3-methyl isophthalic acid, the 5-pentanediol, glycerine, TriMethylolPropane(TMP), the mixture more than a kind or 2 kinds of the polyvalent alcohol that tetramethylolmethane is such, and hexanodioic acid, propanedioic acid, fumaric acid, succsinic acid, tartrate, oxalic acid, phthalate anhydride, m-phthalic acid, terephthalic acid, 1, the mixture more than a kind or 2 kinds of the compound that 4-cyclohexane dicarboxylic acid etc. are such with the carboxyl (or by carboxyl deutero-group) more than at least 2, adopt the known method manufacturing to prepare hydroxyl value 50～800mgKOH/g, the polyester polyol of preferred 100～700mgKOH/g.
(2) polyester polyol of the preparation of the ring-opening polymerization by lactone (for example 6-caprolactone) class.
(3) the pure and mild polyester moulding of polyester polyols product are decomposed the recovery polyester for preparing.
＜polyvalent alcohol (b3) 〉
With ethylene glycol, propylene glycol, butyleneglycol, glycol ether, three methylene glycols, tetramethyl glycol, pregnancy glycol, pregnancy glycol, ten methylene glycols, neopentyl glycol, 3-methyl isophthalic acid, have 2～6 hydroxyls in such 1 molecule of 5-pentanediol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, the polyvalent alcohol of preferred 2～5 hydroxyls is as initiator, make oxirane addition reactions such as oxyethane, propylene oxide prepare the polyether glycol of hydroxyl value 50～1000mgKOH/g, preferred 100～900mgKOH/g.
In polyvalent alcohol (b1)～(b3), be more than the certain value (lower value) by making hydroxyl value, the physical strength that the hard polyurethane foams that can form is enough.In addition, be below the certain value (higher limit) by making hydroxyl value, the fragilityization of the hard polyurethane foams that can suppress to form.
The average functional group number of polyvalent alcohol (b1) is preferably 2～8, and more preferably 3～6.
The average functional group number of polyvalent alcohol (b2) is preferably 2～4, and more preferably 2～3.
The average functional group number of polyvalent alcohol (b3) is preferably 3～6, and more preferably 3～5.
In polyvalent alcohol (b1)～(b3), be more than the fixed number (lower limit) by making average functional group number, the physical strength that the hard polyurethane foams that can form is enough.In addition, be below the fixed number (upper limit) by making average functional group number, the fragilityization of the hard polyurethane foams that can suppress to form.
When using polyvalent alcohol (b1), the ratio that polyvalent alcohol (b1) accounts for polyvalent alcohol (B) is preferably 40～70 quality %.
When using polyvalent alcohol (b2), the ratio that polyvalent alcohol (b2) accounts for polyvalent alcohol (B) is preferably 10～90 quality %.
When using polyvalent alcohol (b3), the ratio that polyvalent alcohol (b3) accounts for polyvalent alcohol (B) is preferably 10～70 quality %.
The ratio that the total of polyvalent alcohol (b1), polyvalent alcohol (b2) and polyvalent alcohol (b3) accounts for polyvalent alcohol (B) is preferably more than the 80 quality %.
If containing of polyvalent alcohol (b1) is proportional excessive, hyperactivity, it is bad to produce moulding such as hole sometimes.
If containing of polyvalent alcohol (b2) is proportional excessive, the viscosity increased of polyvalent alcohol (B), there are the tendency that worsens in foamy liquid fluidity, fillibility.
If containing of polyvalent alcohol (b3) is proportional excessive, there is the tendency that reduces in the physical strength of the hard polyurethane foams of formation.
As in addition polyvalent alcohol of the polyvalent alcohol (b1)～(b3) of the alcohol that comes from different backgrounds and possess different abilities (B) (below be abbreviated as other polyvalent alcohols), preferably enumerate the polypropylene glycol of ethylene glycol, glycol ether, hydroxyl value 50～150mgKOH/g.
By using at least a kind that from the polypropylene glycol of ethylene glycol, glycol ether, hydroxyl value 50～150mgKOH/g, chooses, the viscosity of polyvalent alcohol (B) is reduced.
Other polyvalent alcohols as the alcohol that comes from different backgrounds and possess different abilities (B) also can use polymer polyatomic alcohol.This polymer polyatomic alcohol is for based on above-mentioned polyether glycol or polyester polyol, graft polymerization or import the vinyl polymer of vinylbenzene or vinyl cyanide or contain the compound of active hydrogen base and the material of the polymkeric substance that polyisocyanates prepares as filler.Polymer content is preferably 1～20 quality % in the polymer polyatomic alcohol.
The viscosity of polyvalent alcohol (B) (25 ℃) is preferably below the 2000mPas, more preferably 100～1800mPas.Prescribe a time limit above last when viscosity, particularly the operability in winter reduces.
＜whipping agent (C) 〉
In manufacture method of the present invention, use hydrogen fluorine carbon and/or water as whipping agent (C).
As the addition of whipping agent (C), when hydrogen fluorine carbon such as use HFC-245fa, HFC-365mfc, HFC-134a, be 1～50 quality % with respect to polyvalent alcohol (B).
In addition, and the addition of water during with hydrogen fluorine carbon and water, be 0.5～5.0 quality % with respect to polyvalent alcohol (B).
In addition, in only making the complete water foaming formulation of water, the addition of water is 2.0～20.0 quality % with respect to polyvalent alcohol (B).
＜catalyzer (D) 〉
" catalyzer (D) " as using in the manufacture method of the present invention can use the known catalyzer that is used for common polyurethane foam.For example, as the urethane catalyzer, can enumerate tin compounds such as N-Methylimidazole, trimethylammonium aminoethylpiperazine, tripropyl amine, tetramethyl-hexamethylene-diamine, triethylenediamine, triethylamine, N-methylmorpholine, dimethylcyclohexylam,ne, dibutyltin diacetate, dibutyl tin dilaurate, metal complexs such as acetyl acetone salt etc.As catalyst for trimerization, can enumerate 2,4,6-three (dimethyl aminoethyl) phenol, 1,3,5-three (dimethylaminopropyl) six hydrogen-triazines such as s-triazine, 2, lead compounds such as the quaternary ammonium compounds such as carboxylate salt of aminated compoundss such as ethylenimine class such as 4-two (dimethylaminomethyl) phenol, 2 ethyl hexanoic acid potassium, 2 ethyl hexanoic acid sodium, Potassium ethanoate, sodium-acetate, 2-ethyl ethylenimine, tertiary amine, diazabicyclo undecylene, lead naphthenate, lead octoate 36, alcoholate such as sodium methylate, phenates compounds such as potassium phenylate etc.These catalyzer can use more than a kind or 2 kinds and use.
The usage quantity of catalyzer (D) is preferably the amount of 0.01～15 quality % with respect to polyvalent alcohol (B).
In addition, the promotor as being used to promote react can use for example carbonate products such as NSC 11801, propylene carbonate.
As the suds-stabilizing agent that uses in the manufacture method of the present invention (E), can enumerate known siloxane type surfactants, can enumerate for example L-5340 of the outstanding Buddhist nun's blocking of Japan, L-5420, L-5421, L-5740, L580, SZ-1142, SZ-1642, SZ-1605, SZ-1649, the SH-190 of Dong Li-DOW CORNING siloxanes system, SH-192, SH-193, SF-2945F, SF-2940F, SF-2936F, SF-2938F, SRX-294A, the F-305 of SHIN-ETSU HANTOTAI's chemical industry system, F-341, F-343, F-374, F-345, F-348, the B-8404 of go one Le De シ ユ ミ Star ト system, B-8407, B-8465, B-8444, B-8467, B-8433, B-8466, B-8870, B-8450, B-8460 etc.(E) usage quantity is preferably the amount of 0.1～5 quality % with respect to polyvalent alcohol (B).
In manufacture method of the present invention, can use additive (in the presence of additive, making the reaction of polyisocyanate mixtures (A) and polyvalent alcohol (B)).As this additive, can enumerate weighting agent, oxidation inhibitor, UV light absorber, pigment-dyestuff, antiseptic-germicide-mould resistant of softening agent, weighting agent, tinting material, fire retardant, organic or inorganic etc.In the present invention, preferably use fire retardant.As fire retardant, can enumerate triethyl phosphate, tricresyl phosphate phosphoric acid esters such as (β-chlorine propyl ester), the phosphate cpd of phosphorous acid esters such as phosphorous acid ethyl ester, diethyl phosphite.
As the concrete operation of manufacture method of the present invention, as described below.
(1) with the polyisocyantates composition that contains the terminal prepolymer (A1) of aggretion type MDI (A0), the 1st isocyanate group, the terminal prepolymer (A2) of the 2nd isocyanate group and type siloxane suds-stabilizing agent (A3) as " A liquid ", with above-mentioned polyvalent alcohol (B) as " B liquid ".
(2) whipping agent (C), catalyzer (D), suds-stabilizing agent (E) and additive (component arbitrarily) are mixed in A liquid and/or the B liquid.Whipping agent (C), catalyzer (D) and suds-stabilizing agent (E) are mixed in the B liquid.In addition, the type siloxane suds-stabilizing agent (A3) that contained in the A liquid originally uses as the material that constitutes suds-stabilizing agent (E) in the operation later on.
(3) A liquid and B liquid are mixed, in the presence of whipping agent (C), catalyzer (D) and suds-stabilizing agent (E), make the polyisocyanate mixtures (A) and polyvalent alcohol (B) reaction that contain aggretion type MDI (A0), the terminal prepolymer (A1) of the 1st isocyanate group and the terminal prepolymer of the 2nd isocyanate group (A2), make the reaction system foaming, solidify.
The mixing device of A liquid and B liquid is not particularly limited, the spray coating foaming machine that the low pressure of the low pressure of the injection of can use for example small-sized mixing machine, using when generally making polyurethane foam foaming usefulness or high pressure foaming machine, slab (slab) foaming usefulness or high pressure foaming machine, continuous lines are used with low pressure or high pressure foaming machine, gunite work etc.The temperature of blended A liquid and B liquid preferably is adjusted to 30～60 ℃ in advance.
Adopt the hard polyurethane foams of manufacture method preparation of the present invention to have amino-formate bond and the such chemical bond (so-called polyurethane foam) of urea key.In addition, because of the difference of creating conditions, can generate the isocyanuric acid ester group when foaming, Zhi Bei isocyanurate-modified polyurethane foam (so-called isocyanuric acid ester foam) also is contained in " hard polyurethane foams " like this.The isocyanuric acid ester group adopts trimer catalyst to make cyanate ester based trimerization and generates, and can make raisings such as physical strength and thermotolerance.
In manufacture method of the present invention, preferred isocyanate index [(in the polyisocyanate mixtures (A) all in the mole number/polyvalent alcohol (B) of isocyanate group all the mole number of active hydrogen bases) * 100], under the situation of so-called polyurethane foam, be preferably 50～140, more preferably 70～130.In addition,, be preferably 140～800, more preferably 150～500 when using trimer catalyst to form under the so-called isocyanuric acid ester foamy situation.Under the situation of polyurethane foam, if isocyanate index less than 50, under isocyanuric acid ester foamy situation, if less than 140, the foam of preparation does not have enough intensity sometimes, shrinks easily.In addition, under the situation of polyurethane foam, if surpass 140, under isocyanuric acid ester foamy situation, if surpass 800, the foamy fragility of preparation increases, and there is the tendency that reduces in cementability.
Embodiment
Followingly the present invention is specifically described, but the present invention is not limited to these embodiment according to embodiment.Following " % " and " part " represents " quality % " and " mass parts " respectively.
＜modulation example 1 〉
According to the prescription shown in the following table 1, use 1.5 parts of (1) 97.0 part of aggretion type MDI, specific 0.5 part of 0.5 part of polyester polyol (a1-1), 0.5 part of polyethers monohydroxy-alcohol (a2-1), type siloxane suds-stabilizing agent (A3-1) and aqueous ester compounds (A4-1), modulation as described below polyisocyantates composition of the present invention (NCO-1).The isocyanate content of this polyisocyantates composition (NCO-1) is 30.0%, and viscosity (25 ℃) is 180mPas.
[modulator approach]
In possessing the reactor that stirrer, cooling tube, nitrogen ingress pipe, thermometer and capacity are 100kg, the aggretion type of packing into MDI (1) is warmed to 60 ℃ while stirring.Then, in reactor, pack into respectively specific polyester polyol (a1-1), polyethers monohydroxy-alcohol (a2-1), type siloxane suds-stabilizing agent (A3-1), aqueous ester compound (A4-1).Pack into finish after, 60 ℃ of reactions 2 hours, modulation obtained polyisocyantates composition of the present invention (NCO-1) while stirring.
＜modulation example 2～8 〉
Except according to the prescription shown in the following table 1, use outside aggretion type MDI (1)～(4), specific polyester polyol (a1-1)～(a1-3), polyethers monohydroxy-alcohol (a2-1)～(a2-2), type siloxane suds-stabilizing agent (A3-1) and the aqueous ester compound (A4-1), and modulate example 1 and similarly modulate polyisocyantates composition of the present invention (NCO-2)～(NCO-8).
The isocyanate content and the viscosity (25 ℃) of the polyisocyantates composition of preparation are shown in table 1 in the lump.
＜relatively modulate example 1 〉
Prepare aggretion type MDI (1) according to the prescription shown in the following table 2.With it as " polyisocyanates (NCO-C1) ".The isocyanate content of this polyisocyanates (NCO-C1) is 31.0%, and viscosity (25 ℃) is 180mPas.
＜relatively modulate example 2 〉
Prepare aggretion type MDI (2) according to the prescription shown in the following table 2.With it as " polyisocyanates (NCO-C2) ".The isocyanate content of this polyisocyanates (NCO-C1) is 31.0%, and viscosity (25 ℃) is 180mPas.
＜relatively modulate example 3 〉
Except according to the prescription shown in the following table 2, replace specific polyester polyol (a1-1) and use outside the polyethers monohydroxy-alcohol (a2-2), with modulation example 1 similarly modulation ratio than the polyisocyantates composition (NCO-C3) of usefulness.The isocyanate content of this polyisocyantates composition (NCO-C3) is 30.0%, and viscosity (25 ℃) is 185mPas.
＜modulation example 9 〉
Except according to the prescription shown in the following table 2, use (1) 88.0 part of aggretion type MDI, specific 0.5 part of 5.0 parts of polyester polyols (a1-1), 5.0 parts of polyethers monohydroxy-alcohols (a2-1), type siloxane suds-stabilizing agent (A3-1) and aqueous ester compound (A4-1) 1.5 especially, similarly modulate the present invention's's (with reference to) polyisocyantates composition (NCO-9) with modulation example 1.The isocyanate content of this polyisocyantates composition (NCO-9) is 26.6%, and viscosity (25 ℃) is 320mPas.
＜modulation example 10 〉
Except according to the prescription shown in the following table 2, use (1) 99.9 part of aggretion type MDI, specific 0.01 part of 0.01 part of polyester polyol (a1-1), 0.01 part of polyethers monohydroxy-alcohol (a2-1), type siloxane suds-stabilizing agent (A3-1) and aqueous ester compound (A4-1) 0.07 especially, similarly modulate the present invention's's (with reference to) polyisocyantates composition (NCO-10) with modulation example 1.The isocyanate content of this polyisocyantates composition (NCO-10) is 31.0%, and viscosity (25 ℃) is 180mPas.
＜with the homogeneous Combination of hydrogen fluorine carbon and water
For the polyisocyantates composition of the present invention (NCO-1)～(NCO-8) of preparation in the above-mentioned modulation example 1～8, relatively modulate in the example 1～2 polyisocyanates (NCO-C1)～(NCO-C2) prepared, relatively modulate the present invention's who relatively uses polyisocyantates composition (NCO-C3) and 9～10 preparations of modulation example (with reference to) of example 3 preparations polyisocyantates composition (NCO-9)～(NCO-10), pair estimate according to following method with the homogeneous Combination of hydrogen fluorine carbon and water.The result is shown in following table 1～2 in the lump.
(with the blended evaluation method of the homogeneous of hydrogen fluorine carbon)
With polyisocyanates (composition) 50g, hydrogen fluorine carbon (HFC-365mfc) 20g pack into the test mixing machine (ラ ボ ミ キ サ one), with 7000rpm carry out 3 second married operation, the outward appearance of visual observation mixture is estimated according to following benchmark after just operating and after through 30 minutes.
(with the blended evaluation method of the homogeneous of water)
With polyisocyanates (composition) 50g and the Purified Water 5g test mixing machine of packing into, with 7000rpm carry out 3 second married operation, the outward appearance of visual observation mixture is estimated according to following benchmark in just operation back and after through 30 minutes.
(metewand)
◎: obtain the emulsified state of homogeneous, this state still keeps after through 30 minutes.
Zero: obtain emulsified state, but after 30 minutes, be separated.
*: just just be separated after the operation.
Table 1
Table 2
In above-mentioned table 1 and table 2, the details of the compound of symbolically (component or reaction raw materials) is as described below.In addition, the unit of these usage quantitys is " part ".
[1] aggretion type MDI (1):
(i) peak area ratio=40% of the MDI that measures with GPC
(ii) among the MDI 4, the ratio of 4 '-MDI=99% (measuring) with GC
(iii) isocyanate content=31.0%
(iv) average functional group number=2.3
(v) acidity=0.01%
[2] aggretion type MDI (2):
(i) peak area ratio=37% of the MDI that measures with GPC
(ii) among the MDI 4, the ratio of 4 '-MDI=83% (measuring) with GC
(iii) isocyanate content=31.0%
(iv) average functional group number=2.3
(v) acidity=0.01%
[3] aggretion type MDI (3):
(i) MDI (two nucleomes)
(ii) 4, the ratio of 4 '-MDI=99% (measuring) with GC
(iii) acidity=0.001%
[4] aggretion type MDI (4):
(i) MDI (two nucleomes)
(ii) 4, the ratio of 4 '-MDI=72% (measuring) with GC
(iii) acidity=0.001%
[5] specific polyester polyol (a1-1)～(a1-3)
(i) make 5-sodium sulfo-dimethyl isophthalate, hexanodioic acid, 1 according to well-established law, the adipic acid ester kind polyester polyvalent alcohol that contains sulfonate group (sodium sulfonate residue) that 6-hexylene glycol reaction (ester reaction and transesterification reaction) obtains.
(ii)(a1-1)：
Number-average molecular weight=1000, containing of sulfonate group be proportional=0.4mmol/g
(iii)(a1-2)：
Number-average molecular weight=2000, containing of sulfonate group be proportional=0.4mmol/g
(iv)(a1-3)：
Number-average molecular weight=1000, containing of sulfonate group be proportional=0.2mmol/g
[6] polyethers monohydroxy-alcohol (a2-1):
(i) initiator=2-Ethylhexyl Alcohol
(ii) number-average molecular weight=800
(iii) PO (propylene oxide)/EO (oxyethane)=100/0 (mass ratio)
[7] polyethers monohydroxy-alcohol (a2-2):
(i) initiator=methyl alcohol
(ii) number-average molecular weight=700
(iii) PO/EO=0/100 (mass ratio)
[8] type siloxane suds-stabilizing agent (A3-1):
Polysiloxane-polyether copolymer " B-8460 " (go one Le De シ ユ ミ Star ト system)
[9] aqueous ester compound (A4-1):
Propylene carbonate
＜modulation example 11～18 〉
Each component is mixed modulation polyhydric alcohol composition (OH-1)～(OH-8) according to the cooperation prescription shown in the following table 3.
Table 3
| Modulation example 11 | Modulation example 12 | Modulation example 13 | Modulation example 14 | Modulation example 15 | Modulation example 16 | Modulation example 17 | Modulation example 18 | |
| Polyhydric alcohol composition | OH-1 | OH-2 | OH-3 | OH-4 | OH-5 | OH-6 | OH-7 | OH-8 |
| Polyvalent alcohol (B-1) | 80 | 80 | 80 | 80 | 80 | |||
| Polyvalent alcohol (B-2) | 80 | 80 | 80 | |||||
| Polyvalent alcohol (B-3) | 20 | 20 | 20 | 20 | 20 | |||
| Polyvalent alcohol (B-4) | 20 | 20 | 20 | |||||
| Whipping agent (C-1) | 24 | 21 | 18 | 30 | 30 | |||
| Whipping agent (C-2) | 6 | 9 | 12 | |||||
| Whipping agent (C-3) | 1 | 1 | 1 | 1 | 3 | 4 | 5 | 1 |
| Catalyzer (D-1) | 7 | 7 | 7 | 7 | 5 | 5 | 5 | 7 |
| Catalyzer (D-2) | 3.5 | 3.5 | 3.5 | |||||
| Catalyzer (D-3) | 4 | 4 | 4 | 4 | 4 | |||
| Suds-stabilizing agent (E-1) | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Fire retardant (F-1) | 25 | 25 | 25 | 25 | 15 | 15 | 15 | 25 |
| Specific polyester polyol (a1-1) | 1 | |||||||
| Add up to | 168.5 | 168.5 | 168.5 | 168.5 | 128.0 | 129.0 | 130.0 | 169.5 |
| Hydroxyl value [mgKOH/g] | 221 | 221 | 221 | 221 | 312 | 358 | 403 | 220 |
In above-mentioned table 3, the details of the compound of symbolically (component) is as described below.In addition, the unit of these usage quantitys is " part ".
[1] polyvalent alcohol (B-1):
With Tetra hydro Phthalic anhydride/glycol ether is the polyester polyol " テ ロ one Le 250 " (U.S. OXID society system) of hydroxyl value=250 of raw material
[2] polyvalent alcohol (B-2):
With Tetra hydro Phthalic anhydride/glycol ether is the polyester polyol " テ ロ one Le 280 " (U.S. OXID society system) of hydroxyl value=110 of raw material
[3] polyvalent alcohol (B-3):
The Mannich class polyether glycol " DK polyvalent alcohol 3773 " of hydroxyl value 450 (the first industrial pharmacy (strain) system)
[4] polyvalent alcohol (B-4):
The Mannich class polyether glycol " DK polyvalent alcohol 3776 " of hydroxyl value 350
[5] whipping agent (C-1): HFC-245fa (セ Application ト ラ Le nitre (strain) system)
[6] whipping agent (C-2): HFC-365mfc (ソ Le ベ イ society system)
[7] whipping agent (C-3): Purified Water
[8] catalyzer (D-1): trimer catalyst " DABCO K15 " (エ ア one プ ロ ダ Network Star system)
[9] catalyzer (D-2): trimer catalyst " DABCO P15 " (エ ア one プ ロ ダ Network Star system)
[10] catalyzer (D-3): lead octoate 36
[11] suds-stabilizing agent (E-1):
Polysiloxane-polyether copolymer " B-8460 " (go one Le De シ ユ ミ Star ト system)
[12] fire retardant (F-1):
Three (β-chloropropyl) phosphoric acid ester " Off ア イ ロ one Le PCF " (ア Network ゾ ノ one ベ Le society system)
[13] specific polyester polyol (a1-1):
Identical with the material of table 1 and table 2 record.
＜embodiment 1～14 〉
According to the combination shown in the following table 4, with the mixed solution of polyisocyantates composition (A liquid) and polyhydric alcohol composition (B liquid) (mixing quality is than=100: 100) spraying application to be pasted with by glued board constitute (glued board of 50mm * 50mm) is (on the 1000mm * 1000mm) by adherend, in the presence of whipping agent (C), catalyzer (D) and suds-stabilizing agent (E), make the reaction of polyisocyanate mixtures (A) and polyvalent alcohol (B), (go up for whole of 1000mm * 1000mm) and form hard polyurethane foams being pasted with by the glued board of adherend.
Here, spray coating foaming condition etc. is following described.
Foaming machine: ガ ス マ one spray coating foaming machine " FF-1600 type "
By the temperature of adherend: 5 ℃
Basic heating (プ ラ イ マ リ ヒ one ) temperature: 45 ℃
Foaming thickness: 30～40mm
＜comparative example 1～5, reference example 1～2 〉
According to the combination shown in the following table 4, with the mixed solution of polyisocyantates composition (A liquid) and polyhydric alcohol composition (B liquid) (mixing quality is than=100: 100) spraying application to be pasted with by glued board constitute (glued board of 50mm * 50mm) (on the 1000mm * 1000mm), (is gone up the formation hard polyurethane foams for whole of 1000mm * 1000mm) being pasted with by the glued board of adherend by adherend.
Here, foaming condition etc. is identical with embodiment 1.
＜for by the cementability of adherend 〉
For being gone up the hard polyurethane foams that forms by adherend (glued board of 50mm * 50mm) in embodiment 1～14, comparative example 1～5 and the reference example 1～2, after leaving standstill 2 hours under 5 ℃ the temperature environment, carry out stripping test, measure for this by the bonding strength of adherend (glued board).The result is shown in table 4 in the lump.
＜foamy normal temperature shrinks (placing the volume change that produces) 〉
From embodiment 1～14, comparative example 1～5 and reference example 1～2 at glued board (the hard polyurethane foams that 1000mm * 1000mm) forms, take the sample of length=100mm, wide=100mm, height (foaming direction)=25mm, with this sample after placing 24 hours under 25 ℃ the temperature condition, measure the size of length once more, measuring the volume of foam velocity of variation, serves as according to estimating with following benchmark.The result is shown in table 4 in the lump.
(metewand)
◎: volume change=less than 2%
Zero: volume change=2% is above, less than 5%
*: volume change=more than 5%
Table 4
| Polyisocyantates composition (kind) | Polyhydric alcohol composition (kind) | Nco index | Become the breast time (cream time) [second] | Heating-up time [second] | Foam core density [kg/m 3] | The normal temperature shrinkability | Bonding strength [N/5cm] | |
| Embodiment 1 | NCO-1 | OH-1 | 181 | ＜1 | 8.0 | 27.5 | ◎ | 19 |
| Embodiment 2 | NCO-1 | OH-2 | 181 | ＜1 | 8.2 | 26.3 | ◎ | 18 |
| Embodiment 3 | NCO-1 | OH-3 | 181 | ＜1 | 8.1 | 27.1 | ◎ | 18 |
| Embodiment 4 | NCO-1 | OH-4 | 181 | ＜1 | 7.9 | 26.9 | ◎ | 19 |
| Embodiment 5 | NCO-1 | OH-5 | 129 | ＜1 | 11.0 | 31.9 | ◎ | 18 |
| Embodiment 6 | NCO-1 | OH-6 | 112 | ＜1 | 10.8 | 30.5 | ◎ | 18 |
| Embodiment 7 | NCO-1 | OH-7 | 100 | ＜1 | 10.5 | 29.7 | ◎ | 17 |
| Embodiment 8 | NCO-2 | OH-1 | 183 | ＜1 | 7.9 | 27.7 | ◎ | 18 |
| Embodiment 9 | NCO-3 | OH-1 | 184 | ＜1 | 8.1 | 27.4 | ◎ | 17 |
| Embodiment 10 | NCO-4 | OH-1 | 181 | ＜1 | 8.4 | 28.0 | ◎ | 20 |
| Embodiment 11 | NCO-5 | OH-1 | 183 | ＜1 | 8.3 | 28.1 | ◎ | 19 |
| Embodiment 12 | NCO-6 | OH-1 | 184 | ＜1 | 8.5 | 27.5 | ◎ | 17 |
| Embodiment 13 | NCO-7 | OH-1 | 181 | ＜1 | 8.0 | 27.6 | ◎ | 17 |
| Embodiment 14 | NCO-8 | OH-1 | 181 | ＜1 | 8.1 | 27.9 | ◎ | 18 |
| Comparative example 1 | NCO-C1 | OH-1 | 188 | ＜1 | 7.7 | 27.2 | ◎ | 4 |
| Comparative example 2 | NCO-C2 | OH-1 | 188 | ＜1 | 8.2 | 27.6 | ◎ | 6 |
| Comparative example 3 | NCO-C3 | OH-1 | 181 | ＜1 | 8.0 | 27.8 | ○ | 5 |
| Comparative example 4 | NCO-C1 | OH-8 | 189 | ＜1 | 7.8 | 26.9 | ◎ | 5 |
| Comparative example 5 | NCO-C2 | OH-8 | 189 | ＜1 | 8.3 | 27.3 | ◎ | 6 |
| Reference example 1 | NCO-9 | OH-1 | 160 | ＜1 | 7.5 | 31.5 | × | 10 |
| Reference example 2 | NCO-10 | OH-1 | 188 | ＜1 | 7.8 | 27.3 | ◎ | 4 |
＜embodiment 15～28, comparative example 6～10, reference example 3～4 〉
According to the combination shown in the following table 5, with the mixed solution of polyisocyantates composition (A liquid) and polyhydric alcohol composition (B liquid) (mixing quality is than=100: 100) spraying application to be pasted with by constitute according to JIS G3312 application hot-dip galvanized steel sheet (glued board of 50mm * 50mm * 0.27mm) (on the 1000mm * 1000mm), (is gone up the formation hard polyurethane foams for whole of 1000mm * 1000mm) by the glued board of adherend (steel plate galvanized) being pasted with this by adherend.Here, spray coating foaming condition etc. is identical with embodiment 1.For being gone up the hard polyurethane foams that forms above-mentioned by adherend (steel plate galvanized), employing and embodiment 1～14, comparative example 1～5 and reference example 1～2 same method are measured for this by the bonding strength of adherend (steel plate galvanized).The result is shown in following table 5 in the lump.
Table 5
| Polyisocyantates composition (kind) | Polyhydric alcohol composition (kind) | Nco index | Bonding strength [N/5cm] for steel plate galvanized | |
| Embodiment 15 | NCO-1 | OH-1 | 181 | 22 |
| Embodiment 16 | NCO-1 | OH-2 | 181 | 20 |
| Embodiment 17 | NCO-1 | OH-3 | 181 | 21 |
| Embodiment 18 | NCO-1 | OH-4 | 181 | 20 |
| Embodiment 19 | NCO-1 | OH-5 | 129 | 20 |
| Embodiment 20 | NCO-1 | OH-6 | 112 | 19 |
| Embodiment 21 | NCO-1 | OH-7 | 100 | 19 |
| Embodiment 22 | NCO-2 | OH-1 | 183 | 21 |
| Embodiment 23 | NCO-3 | OH-1 | 184 | 21 |
| Embodiment 24 | NCO-4 | OH-1 | 181 | 24 |
| Embodiment 25 | NCO-5 | OH-1 | 183 | 21 |
| Embodiment 26 | NCO-6 | OH-1 | 184 | 19 |
| Embodiment 27 | NCO-7 | OH-1 | 181 | 18 |
| Embodiment 28 | NCO-8 | OH-1 | 181 | 20 |
| Comparative example 6 | NCO-C1 | OH-1 | 188 | 6 |
| Comparative example 7 | NCO-C2 | OH-1 | 188 | 6 |
| Comparative example 8 | NCO-C3 | OH-1 | 181 | 4 |
| Comparative example 9 | NCO-C1 | OH-8 | 189 | 5 |
| Comparative example 10 | NCO-C2 | OH-8 | 189 | 6 |
| Reference example 3 | NCO-9 | OH-1 | 160 | 13 |
| Reference example 4 | NCO-10 | OH-1 | 188 | 5 |
＜embodiment 29～42, comparative example 11～15, reference example 5～6 〉
According to the combination shown in the following table 6, with the mixed solution of polyisocyantates composition (A liquid) and polyhydric alcohol composition (B liquid) (mixing quality is than=100: 100) spraying application to be pasted with by aluminum casting paper constitute (glued board of 50mm * 50mm) (on the 1000mm * 1000mm), (is gone up the formation hard polyurethane foams for whole of 1000mm * 1000mm) by the glued board of adherend (aluminum casting paper) being pasted with this by adherend.Here, spray coating foaming condition etc. is identical with embodiment 1.For being gone up the hard polyurethane foams that forms above-mentioned by adherend (aluminum casting paper), employing and embodiment 1～14, comparative example 1～5 and reference example 1～2 same method are measured for this by the bonding strength of adherend (aluminum casting paper).The result is shown in following table 6 in the lump.
Table 6
| Polyisocyantates composition (kind) | Polyhydric alcohol composition (kind) | Nco index | Bonding strength [N/5cm] for aluminum casting paper | |
| Embodiment 29 | NCO-1 | OH-1 | 181 | 20 |
| Embodiment 30 | NCO-1 | OH-2 | 181 | 19 |
| Embodiment 31 | NCO-1 | OH-3 | 181 | 18 |
| Embodiment 32 | NCO-1 | OH-4 | 181 | 19 |
| Embodiment 33 | NCO-1 | OH-5 | 129 | 19 |
| Embodiment 34 | NCO-1 | OH-6 | 112 | 19 |
| Embodiment 35 | NCO-1 | OH-7 | 100 | 18 |
| Embodiment 36 | NCO-2 | OH-1 | 183 | 17 |
| Embodiment 37 | NCO-3 | OH-1 | 184 | 19 |
| Embodiment 38 | NCO-4 | OH-1 | 181 | 19 |
| Embodiment 39 | NCO-5 | OH-1 | 183 | 18 |
| Embodiment 40 | NCO-6 | OH-1 | 184 | 17 |
| Embodiment 41 | NCO-7 | OH-1 | 181 | 18 |
| Embodiment 42 | NCO-8 | OH-1 | 181 | 19 |
| Comparative example 11 | NCO-C1 | OH-1 | 188 | 4 |
| Comparative example 12 | NCO-C2 | OH-1 | 188 | 6 |
| Comparative example 13 | NCO-C3 | OH-1 | 181 | 6 |
| Comparative example 14 | NCO-C1 | OH-8 | 189 | 5 |
| Comparative example 15 | NCO-C2 | OH-8 | 189 | 5 |
| Reference example 5 | NCO-9 | OH-1 | 160 | 11 |
| Reference example 6 | NCO-10 | OH-1 | 188 | 5 |
Polyisocyantates composition of the present invention is applicable to sheet material (board), panel (panel), refrigerator, eaves, door, plank cover window, window frame, coagulation great soil group dwelling house, bathtub, cryostat, machine, cold storage warehouse, slab (slab), antisweat, pipe box various thermal insulation material purposes such as (pipe cover).
Polyisocyantates composition of the present invention is specially adapted to the purposes of being carried out spraying application (spray coating foaming) by adherend for various.
Claims (9)
1. polyisocyantates composition, it is the hard polyurethane foams of the foaming formulation of whipping agent that this polyisocyantates composition is used to make with hydrogen fluorine carbon and/or water, it contains:
(A0) ratio of MDI be 20.0～80.0% polyphenylene polymethylene polyisocyanates,
(A1) to make the number-average molecular weight of the sulfo group of the ratio that has 0.1～2.0mmol/g in the molecular structure or sulfonate group be 500～3000 polyester polyol (a1) with the ratio of MDI be 20.0～80.0% polyphenylene polymethylene polyisocyanates prepared in reaction the terminal prepolymer of the 1st isocyanate group,
(A2) to make number-average molecular weight be 150～10000 polyethers monohydroxy-alcohol (a2) with the ratio of MDI be 20.0～80.0% polyphenylene polymethylene polyisocyanates prepared in reaction the terminal prepolymer of the 2nd isocyanate group and
(A3) type siloxane suds-stabilizing agent, and
The terminal prepolymer of the 1st isocyanate group (A1) is 0.05～5.0 quality % with respect to the ratio of the total amount of isocyanate compound, and the ratio of above-mentioned MDI is the area ratio that GPC measures.
2. the described polyisocyantates composition of claim 1, it contains (A4) aqueous ester compound.
3. claim 1 or 2 described polyisocyantates compositions, it is used to make the hard polyurethane foams that adopts spraying method to form on by adherend.
4. the modulator approach of polyisocyantates composition, it is the method for modulation claim 1 or 2 described polyisocyantates compositions, it comprises following operation:
In the presence of type siloxane suds-stabilizing agent (A3),
The number-average molecular weight that makes the sulfo group of the ratio that has 0.1～2.0mmol/g in the molecular structure or sulfonate group be 500～3000 polyester polyol (a1) with the ratio of MDI be 20.0～80.0% the terminal prepolymer (A1) of synthetic the 1st isocyanate group of polyphenylene polymethylene polyisocyanates reaction and
To make number-average molecular weight be 150～10000 polyethers monohydroxy-alcohol (a2) and the ratio of MDI is 20.0～80.0% the terminal prepolymer (A2) of synthetic the 2nd isocyanate group of polyphenylene polymethylene polyisocyanates reaction,
The terminal prepolymer of the 1st isocyanate group (A1) is 0.05～5.0 quality % with respect to the ratio of the total amount of isocyanate compound, and the ratio of above-mentioned MDI is the area ratio that GPC measures.
5. the modulator approach of the described polyisocyantates composition of claim 4, the ratio of the MDI in the reaction vessel of wherein packing into is that the number-average molecular weight that has the sulfo group of ratio of 0.1～2.0mmol/g or sulfonate group in 20.0～80.0% polyphenylene polymethylene polyisocyanates and the molecular structure is that 500～3000 polyester polyol (a1) and number-average molecular weight are that the mass ratio of 150～10000 polyethers monohydroxy-alcohol (a2) is 90.0～99.98: 0.01～5.0: 0.01～5.0, and the ratio of above-mentioned MDI is the area ratio that GPC measures.
6. the modulator approach of polyisocyantates composition, it is the method for modulation claim 1 or 2 described polyisocyantates compositions, it comprises following operation:
Type siloxane suds-stabilizing agent (A3) not in the presence of,
The number-average molecular weight that makes the sulfo group of the ratio that has 0.1～2.0mmol/g in the molecular structure or sulfonate group be 500～3000 polyester polyol (a1) with the ratio of MDI be 20.0～80.0% the terminal prepolymer (A1) of synthetic the 1st isocyanate group of polyphenylene polymethylene polyisocyanates reaction and
To make number-average molecular weight be 150～10000 polyethers monohydroxy-alcohol (a2) with the ratio of MDI be 20.0～80.0% the terminal prepolymer (A2) of synthetic the 2nd isocyanate group of polyphenylene polymethylene polyisocyanates reaction and
Hybrid silicone class A foam A stablizer (A3) in reacted system,
The terminal prepolymer of the 1st isocyanate group (A1) is 0.05～5.0 quality % with respect to the ratio of the total amount of isocyanate compound, and the ratio of above-mentioned MDI is the area ratio that GPC measures.
7. the modulator approach of the described polyisocyantates composition of claim 6, the ratio of the MDI in the reaction vessel of wherein packing into is that the number-average molecular weight that has the sulfo group of ratio of 0.1～2.0mmol/g or sulfonate group in 20.0～80.0% polyphenylene polymethylene polyisocyanates and the molecular structure is that 500～3000 polyester polyol (a1) and number-average molecular weight are that the mass ratio of 150～10000 polyethers monohydroxy-alcohol (a2) is 90.0～99.98: 0.01～5.0: 0.01～5.0, and the ratio of above-mentioned MDI is the area ratio that GPC measures.
8. the manufacture method of hard polyurethane foams, the manufacture method of this hard polyurethane foams is to make polyisocyanate mixtures (A) and polyvalent alcohol (B) reaction in the presence of whipping agent (C), catalyzer (D) and suds-stabilizing agent (E), and wherein above-mentioned polyisocyanate mixtures (A) contains:
(A0) ratio of MDI be 20.0～80.0% polyphenylene polymethylene polyisocyanates and
(A1) to make the number-average molecular weight of the sulfo group of the ratio that has 0.1～2.0mmol/g in the molecular structure or sulfonate group be 500～3000 polyester polyol (a1) with the ratio of MDI be 20.0～80.0% polyphenylene polymethylene polyisocyanates prepared in reaction the terminal prepolymer of the 1st isocyanate group and
(A2) to make number-average molecular weight be 150～10000 polyethers monohydroxy-alcohol (a2) and the ratio of MDI is the terminal prepolymer of the 2nd isocyanate group of 20.0～80.0% polyphenylene polymethylene polyisocyanates prepared in reaction, and
The terminal prepolymer of the 1st isocyanate group (A1) is 0.05～5.0 quality % with respect to the ratio of the total amount of isocyanate compound,
Use hydrogen fluorine carbon and/or water as above-mentioned whipping agent (C), the ratio of above-mentioned MDI is the area ratio that GPC measures.
9. the manufacture method of the described hard polyurethane foams of claim 8, it is used to make the hard polyurethane foams that adopts spraying method to form on by adherend.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004019103A JP4461417B2 (en) | 2004-01-28 | 2004-01-28 | Polyisocyanate composition and method for producing rigid polyurethane foam |
| JP2004019103 | 2004-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1648147A CN1648147A (en) | 2005-08-03 |
| CN100564420C true CN100564420C (en) | 2009-12-02 |
Family
ID=34879057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100039360A Expired - Fee Related CN100564420C (en) | 2004-01-28 | 2005-01-11 | The manufacture method of polyisocyantates composition and modulator approach thereof and hard polyurethane foams |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4461417B2 (en) |
| CN (1) | CN100564420C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443378B (en) * | 2006-05-15 | 2011-06-15 | 日本聚氨酯工业株式会社 | Aqueous modified polyisocyanate, non-yellowing coating composition, and adhesive composition |
| JP2008138042A (en) * | 2006-11-30 | 2008-06-19 | Toyo Tire & Rubber Co Ltd | Polyol composition for foamed rigid polyurethane foam and method for producing foamed rigid polyurethane foam |
| JP4881139B2 (en) * | 2006-12-05 | 2012-02-22 | 東洋ゴム工業株式会社 | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
| JP6870344B2 (en) * | 2017-01-27 | 2021-05-12 | 東ソー株式会社 | Self-emulsifying polyisocyanate composition |
| WO2018176300A1 (en) * | 2017-03-30 | 2018-10-04 | Dow Global Technologies Llc | A novel mdi-based prepolymer binder for moisture curing binder application |
| KR20210113276A (en) * | 2019-01-07 | 2021-09-15 | 에보니크 오퍼레이션즈 게엠베하 | Preparation of Rigid Polyurethane Foam |
| CN110183609B (en) * | 2019-04-23 | 2021-12-24 | 合肥科天水性科技有限责任公司 | Solvent-free polyurethane resin and application thereof |
| JP6888158B1 (en) * | 2020-06-30 | 2021-06-16 | 株式会社イノアック技術研究所 | Resin composition and foam |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003119449A (en) * | 2001-10-12 | 2003-04-23 | Daiken Trade & Ind Co Ltd | Adhesive for inorganic fiber, mineral fiber board and inorganic board using the same |
| JP2004010806A (en) * | 2002-06-10 | 2004-01-15 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition for rigid polyurethane foam, method of its manufacture and method of manufacturing rigid polyurethane foam therewith |
-
2004
- 2004-01-28 JP JP2004019103A patent/JP4461417B2/en not_active Expired - Fee Related
-
2005
- 2005-01-11 CN CNB2005100039360A patent/CN100564420C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003119449A (en) * | 2001-10-12 | 2003-04-23 | Daiken Trade & Ind Co Ltd | Adhesive for inorganic fiber, mineral fiber board and inorganic board using the same |
| JP2004010806A (en) * | 2002-06-10 | 2004-01-15 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition for rigid polyurethane foam, method of its manufacture and method of manufacturing rigid polyurethane foam therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4461417B2 (en) | 2010-05-12 |
| CN1648147A (en) | 2005-08-03 |
| JP2005213306A (en) | 2005-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100564420C (en) | The manufacture method of polyisocyantates composition and modulator approach thereof and hard polyurethane foams | |
| CN102159613B (en) | Aromatic polyesters, polyol blends comprising same and resultant products therefrom | |
| CN101283014B (en) | Solvent free polyurethane dispersions for hard surface coatings | |
| CN101151290A (en) | Two-component polyurethane compositions that are especially suitable for use as structural adhesives | |
| CN104169318A (en) | Low density full water blown polyurethane rigid foam | |
| CN101351486B (en) | Polyol composition and low-repulsion polyurethane foam | |
| CN101410430B (en) | Process for making a polyurethane foam | |
| WO2008041347A1 (en) | Polyisocyanate composition and method for producing hard polyurethane foam by using the composition | |
| JP4883490B2 (en) | Composition for forming water-foamed rigid polyisocyanurate foam, method for producing water-foamed rigid polyisocyanurate foam using the composition, and water-foamed rigid polyisocyanurate foam obtained by the production method | |
| CN103974990A (en) | Sugar-based polyurethanes, methods for their preparation, and methods of use thereof | |
| JP5891126B2 (en) | Polyurethane resin-forming composition for spray coating and polyurethane resin | |
| CN101392045A (en) | Autocatalytic polyols | |
| CN102762622A (en) | Strength-improving agent for production of polyurethane foam | |
| CN101284901A (en) | Polyisocyanate combination and method for preparing rigid isocyanurate foam using the same | |
| JP3948014B2 (en) | Method for producing rigid polyisocyanurate foam | |
| CN103619904A (en) | Polyol formulations for improved green strength of polyisocyanurate rigid foams | |
| WO2008041348A1 (en) | Polyisocyanate composition and method for producing hard polyurethane foam by using the composition | |
| JP2007217648A (en) | Water-foamable composition for forming rigid polyisocyanurate foam, method for producing water-foamed rigid polyisocyanurate foam using the composition, and water-foamed rigid polyisocyanurate foam obtained by the production method | |
| JP2001316443A (en) | Method for manufacturing hard polyurethane foam | |
| JP2002322231A (en) | Polyisocyanate composition for hard polyurethane foam and method for producing hard polyurethane foam by using the same composition | |
| JP3837735B2 (en) | Polyisocyanate composition for rigid polyurethane foam and method for producing rigid polyurethane foam using the same | |
| JP4207220B2 (en) | Polyisocyanate composition for rigid polyurethane foam, method for producing the composition, and method for producing rigid polyurethane foam using the same | |
| JP4340497B2 (en) | Method for producing rigid polyurethane foam | |
| CN101654505A (en) | Flexible polyurethane foam and method of manufacturing the same | |
| WO2024132805A1 (en) | Polyurethane composite and article comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091202 Termination date: 20120111 |