CN101921383B - Two liquid type polyurethane resin composition - Google Patents
Two liquid type polyurethane resin composition Download PDFInfo
- Publication number
- CN101921383B CN101921383B CN 201010208813 CN201010208813A CN101921383B CN 101921383 B CN101921383 B CN 101921383B CN 201010208813 CN201010208813 CN 201010208813 CN 201010208813 A CN201010208813 A CN 201010208813A CN 101921383 B CN101921383 B CN 101921383B
- Authority
- CN
- China
- Prior art keywords
- hydroxyl value
- solidifying agent
- weight
- minutes
- average hydroxyl
- 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.)
- Active
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 29
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 64
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims abstract description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 13
- 239000000600 sorbitol Substances 0.000 claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 27
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 26
- 235000011187 glycerol Nutrition 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 3
- 125000000466 oxiranyl group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001228 polyisocyanate Polymers 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 239000004359 castor oil Substances 0.000 abstract 1
- 235000019438 castor oil Nutrition 0.000 abstract 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract 1
- 229920001451 polypropylene glycol Polymers 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 150000001718 carbodiimides Chemical class 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 polymethylene Polymers 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Provided is a two liquid type polyurethane resin composition, comprising a main agent (I) containing an isocyanate component and a curing agent (II) containing a polyhydric alcohol component. The invention is characterized in that the main agent (I) comprises an aromatic polyisocyanates (A) or a carbamate prepolymer with an isocyanate group sealing end; the curing agent (II) comprises a castor oil (C), a polypropylene glycol (D) with 100-300 molecular weight, a sorbitol alkylene oxide adduct (E) whose average hydroxyl value is 300-800 mgKOH/g, and a alkylene oxide adduct (F) whose average hydroxyl value is 50-200 mgKOH/g. The two liquid type polyurethane resin composition has advantages of good operation in a primary mixing phase, and solidifying in a quite short time.
Description
Technical field
The compsn of tying up usefulness that the present invention relates to operation property good and within a short period of time of solidified two liquid type polyurethane resin composition and be suitable for tubular fibre.
Background technology
The two liquid type polyurethane resin is widely used in various uses, and wherein, the usefulness of tying up as tubular fibre requires to accelerate set time (hardness demonstration) in order to boost productivity.
For example, in patent documentation 1, disclosing the sealing material that makes the reaction of polymeric polyisocyanate composition and solidifying agent, wherein, is more than the polyether glycol 20 weight % 6 or more and hydroxyl value is 370～680mgKOH/g nominally this solidifying agent contains functional group's number.
But, in the compsn of patent documentation 1, because the high polyvalent alcohol of a large amount of cooperation hydroxyl values, therefore existence as inferior problem: begin to morning time that viscosity rises from mixing, in massive article, accomplish the viscosity increase to being filled into the end, thereby can't make.
In addition; A kind of Embedding Material is disclosed in patent documentation 2, its be the host that constitutes by carbamate prepolymer, with two ends that by hydroxyl value are the hydrocarbon of the pure and mild molecular weight of macromolecular multi-component below 200 of 50～200mgKOH/g be that solidifying agent that the glycol of hydroxyl constitutes reacts and forms.
But, be combined with the solidifying agent of two ends of hydrocarbon for the glycol of hydroxyl, be LV just mixing the back, in than the time faster, accomplish tackify, the operation property in loading levels such as massive article goods how is insufficient.
In addition, in patent documentation 3, disclose and used 1, the 4-butyleneglycol is as solidifying agent.
But above-mentioned 1, two ends of hydrocarbon chains such as 4-butyleneglycol are the glycol of hydroxyl, and crystallinity is high, when particularly waiting under the coldcondition preservation in the winter time, have the problem of in solidifying agent, separating out easily etc. on the storage stability.
Patent documentation 1: TOHKEMY 2002-128858 communique
Patent documentation 2: TOHKEMY 2001-300265 communique
Patent documentation 3: japanese kokai publication hei 7-53665 communique
Summary of the invention
The present invention provides a kind of two liquid type polyurethane resin composition in order to address the above problem, its in the operation property of mixing the initial stage good and provide within a short period of time solidified curable urethane resin thing.
That is, the present invention relates to a kind of two liquid type polyurethane resin composition, be made up of host that contains isocyanate prepolymer composition (I) and the solidifying agent (II) that contains polyhydroxy reactant, wherein, host (I) contains:
(I-1) aromatic poly-isocyanate (A) and/or
The isocyanate-terminated carbamate prepolymer that (I-2) makes aromatic poly-isocyanate (A) obtain with Viscotrol C (B) reaction,
And solidifying agent (II) contains with (C) 10～85 weight %, (D) 1～20 weight %, (E) 0.5～20 weight % and the ratio that (F) surpasses below 10 weight % and the 85 weight %:
(C) Viscotrol C,
(D) molecular weight be 100～300 W 166,
(E) average hydroxyl value be 300～800mgKOH/g Sorbitol Powder the oxirane affixture and
(F) average hydroxyl value is the oxirane affixture of the glycerine of 50～200mgKOH/g.
In the polyurethane resin composition of the present invention, from the reactivity of NCO, the hardness and the good viewpoint of tensile strength of curable urethane resin thing, preferred above-mentioned W 166 (D) is dipropylene glycol and/or tripropylene glycol.
In the polyurethane resin composition of the present invention; Also contain oxirane affixture (G) 0.5～20 weight % that average hydroxyl value is the glycerine of 300～800mgKOH/g through above-mentioned solidifying agent (II); Under the state of hardness that keeps the curable urethane resin thing and tensile strength, host (I) is further reduced with the viscosity of mixing of solidifying agent (II).
In the polyurethane resin composition of the present invention; From the viewpoint that the mixed viscosity of two liquid is further reduced and hardness, elongation and the tensile strength of curable urethane resin thing are excellent more, the average hydroxyl value of preferred above-mentioned solidifying agent (II) is 200～350mgKOH/g.
In the polyurethane resin composition of the present invention, host (I) is counted 0.8～1.3 o'clock with NCO/OH than (mol ratio) with the mixture ratio of solidifying agent (II), can make solidified nature become good, and is therefore preferred.
Polyurethane resin composition of the present invention is particularly useful as the compsn of tying up usefulness of tubular fibre.
Polyurethane resin composition of the present invention, because the firm mixed viscosity rising of host and solidifying agent is very slow, so operation property is good.In addition,, cause that viscosity sharply rises, solidify rapidly, so productivity is also good through behind the certain hour.
Embodiment
Polyurethane resin composition of the present invention is by the host that contains specific isocyanate prepolymer composition (I) and contains the two liquid type polyurethane resin composition that the solidifying agent (II) of specific polyhydroxy reactant constitutes.
The host (I) that contains specific isocyanate prepolymer composition contains:
(I-1) aromatic poly-isocyanate (A) and/or
The isocyanate-terminated carbamate prepolymer that (I-2) makes aromatic poly-isocyanate (A) obtain with Viscotrol C (B) reaction.
When using aromatic poly-isocyanate (A), good aspect active hydrogen group reactive high as host (I).
As aromatic poly-isocyanate (A), can enumerate: tolylene diisocyanate, diphenylmethanediisocyanate, polymethylene polyphenyl Quito isocyanic ester and their part carried out carbodiimide modified, biuret modified, allophanate-modified, the isocyanurate-modified compound that forms etc.Among them; From having the aspect with the hyperergy of hydroxyl, be preferably diphenylmethanediisocyanate, polymethylene polyphenyl Quito isocyanic ester and with their part carry out in carbodiimide modified, biuret modified, allophanate-modified, the isocyanurate-modified compound that forms more than a kind or 2 kinds.Wherein, The good viewpoint of storage stability of, host (I) low, more preferably a polymethylene polyphenyl Quito isocyanic ester and part carried out diphenylmethanediisocyanate that carbodiimide modified forms or their mixture from crystallinity.
As host (I), the viewpoint low from crystallinity, that storage stability is good, the isocyanate-terminated carbamate prepolymer (I-2) that also can use aromatic poly-isocyanate (A) to obtain with Viscotrol C (B) reaction.
Be used to make the aromatic poly-isocyanate (A) of isocyanate-terminated carbamate prepolymer (I-2), together can enumerate and (I-1) the middle identical compound of aromatic poly-isocyanate (A) that uses with preferred illustration.
Viscotrol C (B) can use and be used for general other Viscotrol C of level that isocyanate-terminated carbamate prepolymer is made, and can the average hydroxyl value of illustration be the Viscotrol C of about 160mgKOH/g for example.
The reaction of aromatic poly-isocyanate (A) and Viscotrol C (B) can be carried out according to known method in the past.For example, can have NCO at the end of carbamate prepolymer through the aromatic poly-isocyanate (A) that contains superfluous free isocyanate groups 20～48 weight % is reacted with Viscotrol C (B).
Also can be also with aromatic poly-isocyanate (I-1) and isocyanate-terminated carbamate prepolymer (I-2).
Solidifying agent (II) as the another kind of composition of polyurethane resin composition of the present invention contains following (C)～(F) composition.
Below, each composition is described.
(C) Viscotrol C
Can illustration and the identical Viscotrol C of Viscotrol C (B) that uses in synthetic of host (I-2), can be identical with Viscotrol C (B) also can be different.
Viscotrol C (C) contains 10～85 weight % in solidifying agent (II).In the time of in this scope, can reduce the viscosity of mixing behind host (I) and the solidifying agent (II), realize that simultaneously the tensile strength of curable urethane resin thing becomes good effect.Ratio as the Viscotrol C (C) in the solidifying agent (II) is preferably more than the 20 weight %.Be limited to 75 weight % on preferred.
(D) molecular weight is 100～300 W 166
W 166 (D) have 2 secondary hydroxyls aspect, different with the glycol of the patent documentation with primary hydroxyl 2 and 3.Its result can make and utilize the glycol with primary hydroxyl further lasting for the visbreaking effect of short period, and realizes the also good effect of storage stability of solidifying agent.
Further, the molecular weight range of 100 to 300, it can be sufficiently ensured from the two-liquid mixing time points to the beginning of time increase in viscosity, and the available time (Pot) to an appropriate length, so an excellent effect in productivity.
It as molecular weight the preferred object lesson of 100～300 W 166 (D); For example can enumerate: dipropylene glycol (molecular weight 134, average hydroxyl value is 837mgKOH/g), tripropylene glycol (molecular weight 192, average hydroxyl value is 584mgKOH/g), four Ucar 35 (molecular weight 250; Average hydroxyl value is 449mgKOH/g) in waiting a kind is perhaps more than 2 kinds; Wherein, from usable time shorter aspect proper range, be preferably dipropylene glycol, tripropylene glycol or their combination.
As a reference; The molecular weight of the Ucar 35 outside the scope of the invention be 76 and average hydroxyl value be 1477mgKOH/g, 1, the molecular weight of 4-butyleneglycol be 90 and average hydroxyl value be 1247mgKOH/g; 1, the molecular weight of 6-pinakon be 118 and average hydroxyl value be 951mgKOH/g.
W 166 (D) contains 1～20 weight % in solidifying agent (II).When being less than 1 weight %, big with the firm mixed viscosity of host, operation property variation.On the other hand, when surpassing 20 weight %, put to the time that viscosity rises since two liquid mixing times and to become too short, therefore, can not guarantee sufficient operation property.As the ratio of the W 166 (D) in the solidifying agent (II), the aspect from the visbreaking effect increases is preferably more than the 3 weight %, further is preferably more than the 5 weight %.Be limited to 15 weight % on preferred.
(E) average hydroxyl value is the oxirane affixture of the Sorbitol Powder of 300～800mgKOH/g
The average hydroxyl value of the oxirane affixture (E) of Sorbitol Powder is 300～800mgKOH/g, is preferably 350～600mgKOH/g.
In addition, the oxirane affixture (E) of Sorbitol Powder contains 0.5～20 weight % in solidifying agent (II).In the time of in this scope,, therefore realize the effect that weather resistance is good because the elongation of curable urethane resin thing and tensile strength become good.Ratio as the oxirane affixture (E) of the Sorbitol Powder in the solidifying agent (II) is preferably more than the 1 weight %.Be limited to 10 weight % on preferred.
(F) average hydroxyl value is the oxirane affixture of the glycerine of 50～200mgKOH/g
The average hydroxyl value of the oxirane affixture (F) of glycerine is 50～200mgKOH/g, is preferably 100～200mgKOH/g.Through making average hydroxyl value in above-mentioned scope, the weather resistance of curable urethane resin thing is good.
In addition, average hydroxyl value is that the oxirane affixture (F) of the glycerine of 50～200mgKOH/g contains in solidifying agent (II) and surpasses 10 weight % and below the 85 weight %.Through making use level in above-mentioned scope, can reduce the viscosity of mixing behind host (I) and the solidifying agent (II).Be the ratio of oxirane affixture (F) of the glycerine of 50～200mgKOH/g as the average hydroxyl value in the solidifying agent (II), be preferably more than the 15 weight %, more preferably more than the 20 weight %.Be limited to 70 weight % on preferred.
Be used for above-mentioned (E) and (F) oxirane of composition, can use the known in the past compound that is used to make urethane resin.As such oxirane, can enumerate: oxyethane, propylene oxide and butylene oxide ring etc.
In the two liquid type polyurethane resin composition of the present invention, in addition as curing agent component, can in solidifying agent (II), contain average hydroxyl value is oxirane affixture (G) 0.5～20 weight % of the glycerine of 300～800mgKOH/g.
Average hydroxyl value is the oxirane affixture (G) of glycerine of 300～800mgKOH/g in this scope the time, under the state of hardness that keeps the curable urethane resin thing and tensile strength, host (I) is further reduced with the viscosity of mixing of solidifying agent (II).Average hydroxyl value in the solidifying agent (II) is the ratio of oxirane affixture (G) of the glycerine of 300～800mgKOH/g, is preferably more than the 1 weight %.Be limited to 10 weight % on preferred.
In average hydroxyl value is the oxirane of use in the oxirane affixture (G) of glycerine of 300～800mgKOH/g, can enumerate and (E) and the identical oxirane of oxirane that (F) uses in the composition.
From the viewpoint that the mixed viscosity of two liquid is further reduced and hardness, elongation and the tensile strength of curable urethane resin thing are excellent more, the average hydroxyl value of the above-mentioned solidifying agent (II) that uses in the polyurethane resin composition of the present invention is preferably 200～350mgKOH/g.The average hydroxyl value of solidifying agent (II), can through regulate (C)～(F) composition and as required the cooperation ratio of (G) composition regulate.
Two liquid type polyurethane resin composition of the present invention is made up of host (I) and solidifying agent (II), through mixing them, solidifies beginning, thereby generates the curable urethane resin thing.
According to two liquid type polyurethane resin composition of the present invention; Owing to contain W 166 (D) in the solidifying agent (II), so the storage stability of solidifying agent (II) is good, in addition; Can suppress violent viscosity when mixing with host (I) and rise, guarantee the activity duration (usable time).
From the good viewpoint of solidified nature, host (I) is preferably 0.8～1.3 in NCO/OH than (mol ratio) with the mixture ratio of solidifying agent (II).Preferred NCO/OH is 0.9～1.2 than (mol ratio).
In addition, in case solidify beginning, this curing is just acutely carried out, and gives cured article necessary mechanical characteristics (hardness, elongation, tensile strength).
Polyurethane resin composition of the present invention is particularly useful as tying up with compsn of tubular fibre.
Tubular fibre can be enumerated the tubular fibre that for example is made up of polysulfones, polyacrylonitrile, polymeric amide, rhodia, pvdf etc., ties up agent and ties up the tubular fibre film module that forms etc. and in various uses, use as this hollow fiber bundle is utilized in its end.These hollow fiber bundles tie up in the end that to tie up agent useful as being used to make for compsn of the present invention.
Embodiment
Below, enumerate embodiment etc. the present invention is specified.
1 (manufacturing of host (I)) of preparation example
The preparation of host (I-1)
Will be as polymethylene polyphenyl Quito isocyanic ester (A1) (free NCO amount: 31 weight % of aromatic poly-isocyanate (A); The ミ リ ォ ネ one ト MR-200 that Japanese polyurethane Co., Ltd. makes: trade(brand)name) 50 weight parts with a part is carried out 4 after the carbodiimide modified; 4 '-diphenylmethanediisocyanate (A2) (free NCO amount: 29 weight %; The ミ リ ォ ネ one ト MTL that Japanese polyurethane Co., Ltd. makes: trade(brand)name) 50 weight parts mix, preparation host (I-1).
The free NCO amount of resulting host (I-1) is 30 weight %, is 60mPas 25 ℃ of viscosity of measuring down.
(mensuration of viscosity)
Determinator: rotational viscosimeter (Block Le ッ Network Off ィ one Le De エ Application ジ ニ ァ リ Application グ ラ ボ ラ ト リ one ズ corporate system, trade(brand)name: Brookfield viscometer BM)
Condition determination: measure down at 25 ℃ based on JIS Z8803.
Host (the preparation of I-2A)
To carry out 4 after the carbodiimide modified to a part; (the Viscotrol C カ Network ト Network A that average hydroxyl value: 160mgKOH/g, Itoh Oil Mfg make: trade(brand)name) 15 weight parts mix 4 '-diphenylmethanediisocyanate (A2), 85 weight parts with Viscotrol C (B1); Make its reaction, preparation is as the host of isocyanate-terminated carbamate prepolymer (I-2A).
(the free NCO amount of I-2A) is 23 weight % to resulting host, is 400mPas 25 ℃ of viscosity of measuring down.
Host (the preparation of I-2B)
With polymethylene polyphenyl Quito isocyanic ester (A1) 12.5 weight parts, a part is carried out 4 after the carbodiimide modified; 4 '-diphenylmethanediisocyanate (A2), 76.25 weight parts mix with Viscotrol C (B1) 11.25 weight parts; Make its reaction, preparation is as the host of isocyanate-terminated carbamate prepolymer (I-2B).
(the free NCO amount of I-2B) is 24.7 weight % to resulting host, is 260mPas 25 ℃ of viscosity of measuring down.
2 (preparations of solidifying agent (II)) of preparation example
To mix with the ratio shown in the table, preparation solidifying agent (II-1)～(II-18) investigated average hydroxyl value, viscosity (25 ℃) and storage stability with the composition shown in table 1～4.The result is shown in table 1～4.
Each composition that uses is following.
(C) Viscotrol C
C1: identical (the Viscotrol C カ Network ト Network A that average hydroxyl value: 160mgKOH/g, Itoh Oil Mfg make: trade(brand)name) with the Viscotrol C (B1) that uses in the preparation of host (I)
(D) W 166
D1: dipropylene glycol (molecular weight 134, average hydroxyl value is 837mgKOH/g)
D2: tripropylene glycol (molecular weight 192, average hydroxyl value is 584mgKOH/g)
D3: Ucar 35 (molecular weight 76, average hydroxyl value is 1477mgKOH/g)
D4: W 166 (molecular weight 400, average hydroxyl value is 280mgKOH/g)
D5:1,4-butyleneglycol (molecular weight 90, average hydroxyl value is 1247mgKOH/g)
D6:1,6-pinakon (molecular weight 118, average hydroxyl value is 951mgKOH/g)
(E) the oxirane affixture of Sorbitol Powder
E1: the propylene oxide adduct of Sorbitol Powder (average hydroxyl value is 450mgKOH/g)
E2: the propylene oxide adduct of Sorbitol Powder (average hydroxyl value is 385mgKOH/g)
E3: the propylene oxide adduct of Sorbitol Powder (average hydroxyl value is 550mgKOH/g)
(F) average hydroxyl value is the oxirane affixture of the glycerine of 50～200mgKOH/g
F1: the propylene oxide adduct of glycerine (average hydroxyl value is 168mgKOH/g)
F2: the propylene oxide adduct of glycerine (average hydroxyl value is 112mgKOH/g)
F3: the propylene oxide adduct of glycerine (average hydroxyl value is 56mgKOH/g)
(G) average hydroxyl value is the oxirane affixture of the glycerine of 300～800mgKOH/g
G1: the propylene oxide adduct of glycerine (average hydroxyl value is 400mgKOH/g)
G2: the propylene oxide adduct of glycerine (average hydroxyl value is 480mgKOH/g)
G3: the propylene oxide adduct of glycerine (average hydroxyl value is 561mgKOH/g)
(curing catalysts)
H1: dioctyl two LAURIC ACID 99 MIN tin
In addition, about average hydroxyl value and storage stability, carry out evaluation of measuring through following method.
(average hydroxyl value)
Measure based on JIS K1557-1 (ISO14900:2001).
(storage stability)
Solidifying agent was left standstill under 5 ℃ 24 hours, and visual observations has or not crystallization to separate out and has or not muddiness.
Zero: no crystallization is separated out does not have muddiness yet
*: observe that crystallization is separated out or muddy
Table 1
*: separate out crystallization owing to just made in the after fixing agent, therefore can't measure.
Table 2
Table 3
Table 4
Can know as follows by table 1.
In solidifying agent (II), use 1 of non-propandiols, in the example of 4-butyleneglycol (D5) (II-5), storage stability reduces, and uses 1, and in the example of 6-pinakon (D6) (II-6), solidifying agent does not form uniform solution, can not use as solidifying agent.
On the other hand, use as in the example (II-1) of the dipropylene glycol (D1) of the W 166 of molecular weight 100～300 and tripropylene glycol (D2) and routine (II-2), storage stability is good.
Embodiment 1
(weight ratio, NCO/OH=1.1) the mixing total amount is the amount of 100g, stirs 2 minutes with ratio of mixture 100/68 under 25 ℃ with preparation example 1 host (I-1) for preparing and the solidifying agent (II-1) for preparing example 2 preparations.
Again this mixed solution is left standstill under 25 ℃; Measure viscosity through following method and estimate the investigation usable time in (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes, after 55 minutes, after 60 minutes, after 65 minutes) after the mixed specified time.The result is shown in table 5.
Then; In addition; Will with aforesaid method mix mixed solution after 2 minutes be injected into the metallic mold tool (among 150mm * 150mm * 2mm), 60 ℃ down with 5 hours, made its curing at 25 ℃ times with 72 hours again, obtain the curable urethane resin thing; For this resin cured matter, investigate hardness and mechanical characteristics (elongation, tensile strength) with following method.The result is shown in table 5.
(usable time)
The time that viscosity is reached 10000mPas as usable time (minute).
From making polyurethane resin composition to the abundant viewpoint that waits operation property of the injection activity duration of large-scale plant, preferred usable time is long.But, to solidify the overspending time when long, productivity reduces, and is therefore not preferred.In addition, suitable usable time is according to concrete composition and operating condition etc. and different, but under the composition of present embodiment and comparative example, condition, is about 40～45 minutes.
(hardness)
Use sclerometer (the ASKER D type that polymer gauge Co., Ltd. makes), measure Shore D hardness based on JISK6253-2006.
Suitable hardness is according to purposes and different, but as the Strapping Material that the tubular fibre film module is used, from preventing that hollow-fibre membrane is damaged, improve the weather resistance of curable urethane resin thing and the viewpoint of resistance to pressure, is preferably D50～D80.
(mechanical characteristics)
Use universal testing machine (AUTOGRAPH) (5581 types of ィ Application ス ト ロ Application ジ ャ パ Application manufactured), measure elongation and tensile strength based on JIS K7312-1996.
Suitable elongation is according to purposes and different, but as the Strapping Material that the tubular fibre film module is used, from preventing that hollow-fibre membrane is damaged, improve the weather resistance of curable urethane resin thing and the viewpoint of resistance to pressure, is preferably 20～200%.
Suitable tensile strength is according to purposes and different, but the Strapping Material of using as the tubular fibre film module, from the weather resistance that improves the curable urethane resin thing and the viewpoint of resistance to pressure, is preferably more than the 20MPa.
Embodiment 2～5 and comparative example 1～3
As solidifying agent (II); Using and changing in the preparation example 2 that W 166 (D) composition prepares (II-2) and (II-3)～(II-5) (with reference to table 1) (being respectively embodiment 2 and comparative example 1～3) and append average hydroxyl value is (II-21), (II-22) and (II-23) (with reference to table 4) (being respectively embodiment 3,4 and 5) that the oxirane affixture (G) of the glycerine of 300～800mgKOH/g prepares; In addition; Operate equally with embodiment 1; Mix; (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes, after 55 minutes, after 60 minutes, after 65 minutes) are measured viscosity and are estimated in firm mixed admixture, after the mixed specified time, investigate usable time.Then make its curing again, obtain cured article, investigate hardness, the mechanical characteristics (elongation, tensile strength) of resulting cured article.The result is shown in table 5.
Table 5
Can know as follows by table 5.
Can know from embodiment 1 and 2, when to use molecular weight be 100～300 W 166 (D), can prolong from two liquid and be mixed to the time that viscosity rises, and usable time also can shorten in suitable scope.
In addition; Shown in embodiment 3～5; Be combined with average hydroxyl value when being the oxirane affixture (G) of glycerine of 300～800mgKOH/g, keeping usable time equal when not cooperating, the while can further be reduced the viscosity of mixing of host (I) and solidifying agent (II).
On the other hand, shown in comparative example 1, can know when using molecular weight, be mixed to the time that viscosity rises from two liquid and shorten less than 100 Ucar 35 (D3).In addition, shown in comparative example 2, can know that usable time is slack-off when using molecular weight greater than 300 W 166 (D4), the tensile strength of curable urethane resin thing reduces.
In addition, shown in comparative example 3, can know and use 1 of non-propandiols that during 4-butyleneglycol (D5), the time that is mixed to the viscosity rising from two liquid shortens.
Embodiment 5～8 and comparative example 4～9
As solidifying agent (II); Use each composition that changes solidifying agent (II) in the preparation example 2 to prepare (II-7)～(II-10) and (II-11)～(II-16) (with reference to table 2) (being respectively embodiment 5～8 and comparative example 4～9); In addition; Operate equally with embodiment 1; Mix, (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes, after 55 minutes, after 60 minutes, after 65 minutes) are measured viscosity and are estimated in firm mixed admixture, after the mixed specified time, investigate usable time.Then make its curing again, obtain cured article, investigate hardness, the mechanical characteristics (elongation, tensile strength) of resulting cured article.The result is shown in table 6.In addition, as a reference, the result of embodiment 1 also charges to simultaneously.
Can know as follows by table 6.
Shown in embodiment 1 and embodiment 5～8, when changing each composition within the scope of the invention, the hardness of curable urethane resin thing, elongation and tensile strength are in suitable scope.
But, shown in comparative example 4, when cooperating Viscotrol C (C) as many as 95 weight %; Usable time is elongated, and the reduction of the tensile strength of curable urethane resin thing, on the other hand; Shown in comparative example 5, when not cooperating Viscotrol C (C), it is very long that usable time becomes.
In addition, shown in comparative example 6, when not cooperating W 166 (D), it is very long that usable time becomes, and on the other hand, shown in comparative example 7, when the cooperation molecular weight was 100～300 W 166 (D) as many as 25 weight %, it is very short that usable time becomes.
In addition; Shown in comparative example 8, when not cooperating the oxirane affixture (E) of Sorbitol Powder, the tensile strength of curable urethane resin thing reduces; On the other hand; Shown in comparative example 9, when cooperating oxirane affixture (E) the as many as 25 weight % of Sorbitol Powder, the elongation of curable urethane resin thing reduces.
Embodiment 9～12
As solidifying agent (II); Use each composition that changes solidifying agent (II) in the preparation example 2 to prepare (II-17)～(II-20) (with reference to table 3) (being respectively embodiment 9～12); In addition; Operate equally with embodiment 1; Mix, (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes, after 55 minutes, after 60 minutes, after 65 minutes) are measured viscosity and are estimated in firm mixed admixture, after the mixed specified time, investigate usable time.Then make its curing again, obtain cured article, investigate hardness, the mechanical characteristics (elongation, tensile strength) of resulting cured article.The result is shown in table 7.In addition, as a reference, the result of embodiment 1 also charges to simultaneously.
Table 7
Can know as follows by table 7.
Shown in embodiment 1 and embodiment 9～12, when changing each composition within the scope of the invention, the hardness of curable urethane resin thing, elongation and tensile strength are in suitable scope.
Embodiment 13～16
Use is as (I-2A) and (combination (being respectively embodiment 13 and 14) of I-2B) and solidifying agent (II-1) and host (I-2A) and (combination (being respectively embodiment 15 and 16) of I-2B) and solidifying agent (II-22) of preparation in the preparation of host (I) example 1; In addition; Operate equally with embodiment 1; Mix; (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes, after 55 minutes, after 60 minutes, after 65 minutes) are measured viscosity and are estimated in firm mixed admixture, after the mixed specified time, investigate usable time.Then make its curing again, obtain cured article, investigate hardness, the mechanical characteristics (elongation, tensile strength) of resulting cured article.The result is shown in table 8.In addition, as a reference, the result of embodiment 1 also charges to simultaneously.
Table 8
Can know as follows by table 8.
Shown in embodiment 13～16; Make the reaction of aromatic poly-isocyanate (A) and Viscotrol C (B) and the isocyanate-terminated carbamate prepolymer that obtains during in use as host (I) composition; Firm mixed viscosity improves; But be mixed to time that viscosity rises and embodiment 1 equal extent in proper range from two liquid, the hardness of resulting curable urethane resin thing, elongation and tensile strength are in suitable scope.
The present invention is described in detail or with reference to specific embodiment, but only otherwise break away from the spirit and scope of the present invention, can add various changes and modification, this is conspicuous to those skilled in the art.
The application is based on the Japanese patent application (Japan special hope 2009-141045) of application on June 12nd, 2009, and its content is introduced as reference at this.
The possibility of utilizing on the industry
Two liquid type polyurethane resin composition of the present invention, operation property is good and obtain the cured article that solidify within a short period of time, mechanical characteristics is good, therefore, can be in utilization in the Strapping Material of tubular fibre etc.
Claims (4)
1. two liquid type polyurethane resin composition is made up of host that contains isocyanate prepolymer composition (I) and the solidifying agent (II) that contains polyhydroxy reactant, and wherein, host (I) contains:
(I-1) aromatic poly-isocyanate (A) and/or
(I-2) the isocyanate-terminated carbamate prepolymer that aromatic poly-isocyanate (A) is obtained with Viscotrol C (B) reaction,
And solidifying agent (II) contains in solidifying agent (II) with (C) 10～85 weight %, (D) 1～20 weight %, (E) 0.5～20 weight % and the ratio that (F) surpasses below 10 weight % and the 85 weight %:
(C) Viscotrol C,
(D) dipropylene glycol and/or tripropylene glycol,
(E) average hydroxyl value be 300～800mgKOH/g Sorbitol Powder the oxirane affixture and
(F) average hydroxyl value is the oxirane affixture of the glycerine of 50～200mgKOH/g,
Wherein, host (I) is 0.8～1.3 with the mixture ratio of solidifying agent (II) with the NCO/OH molar ratio computing.
2. two liquid type polyurethane resin composition as claimed in claim 1, wherein, it is oxirane affixture 0.5～20 weight % of the glycerine of 300～800mgKOH/g that said solidifying agent (II) also contains (G) average hydroxyl value.
3. two liquid type polyurethane resin composition as claimed in claim 1, wherein, the average hydroxyl value of said solidifying agent (II) is 200～350mgKOH/g.
4. two liquid type polyurethane resin composition as claimed in claim 1, wherein, polyurethane resin composition is the compsn of tying up usefulness of tubular fibre.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-141045 | 2009-06-12 | ||
| JP2009141045 | 2009-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101921383A CN101921383A (en) | 2010-12-22 |
| CN101921383B true CN101921383B (en) | 2012-12-26 |
Family
ID=43336614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010208813 Active CN101921383B (en) | 2009-06-12 | 2010-06-12 | Two liquid type polyurethane resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5154606B2 (en) |
| CN (1) | CN101921383B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199255B (en) * | 2011-04-07 | 2013-01-09 | 合肥工业大学 | Thermal deblocking type polyurethane-acrylate emulsion and its preparation method |
| JP5797475B2 (en) | 2011-06-23 | 2015-10-21 | 第一工業製薬株式会社 | Polyurethane resin composition and hollow fiber membrane module using the same |
| JP6044161B2 (en) * | 2012-07-31 | 2016-12-14 | 横浜ゴム株式会社 | Two-component curable polyurethane sealant composition and sealant using the same |
| JP6110214B2 (en) * | 2013-05-29 | 2017-04-05 | 旭化成メディカル株式会社 | β-glucan reduction virus removal filter |
| KR101480518B1 (en) * | 2013-09-12 | 2015-01-08 | 켐마트코리아 (주) | Adhesive composite of installing interior for building with excellent restraing effect on noise and vibration |
| JP5761879B1 (en) * | 2014-05-28 | 2015-08-12 | 第一工業製薬株式会社 | Polyurethane resin composition, molded body and electrical / electronic component using the same |
| CN111234161A (en) * | 2020-03-09 | 2020-06-05 | 江苏东邦科技有限公司 | Preparation method of wear-resistant polyurethane primer two-liquid type adhesive for sanding |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680203A (en) * | 1985-05-13 | 1987-07-14 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Protective coating on concrete construction |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61197660A (en) * | 1985-02-27 | 1986-09-01 | Dainippon Toryo Co Ltd | Urethane resin coating composition |
| JP4780738B2 (en) * | 2000-04-28 | 2011-09-28 | 旭化成ケミカルズ株式会社 | Filtration module and manufacturing method thereof |
| JP3959733B2 (en) * | 2000-10-24 | 2007-08-15 | 日本ポリウレタン工業株式会社 | Polyurethane resin-forming composition for casting and sealing material using the composition |
| JP5039535B2 (en) * | 2007-12-25 | 2012-10-03 | 第一工業製薬株式会社 | Two-component polyurethane resin composition |
-
2010
- 2010-06-10 JP JP2010133021A patent/JP5154606B2/en active Active
- 2010-06-12 CN CN 201010208813 patent/CN101921383B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680203A (en) * | 1985-05-13 | 1987-07-14 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Protective coating on concrete construction |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2001-300265A 2001.10.30 |
| JP特开2002-128858A 2002.05.09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5154606B2 (en) | 2013-02-27 |
| JP2011016993A (en) | 2011-01-27 |
| CN101921383A (en) | 2010-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921383B (en) | Two liquid type polyurethane resin composition | |
| CN101151290B (en) | Two-component polyurethane compositions that are especially suitable for use as structural adhesives | |
| CN103476820B (en) | For the tackiness agent of wind generator spinner blade | |
| CN101778877B (en) | Two part polyurethane curable composition having substantially consistent g-modulus across the range of use temperatures | |
| CN103614108B (en) | Flexible packaging composite resin and preparation method thereof | |
| CN104755519B (en) | It is especially suitable for use as the dual-component polyurethane composition of viscoelastic structure adhesive | |
| US5037879A (en) | Polyurethane composition with reduced water to prepolymer mix ratio | |
| CN106459356A (en) | Low-viscosity polyurethane prepolymer with cyclic carbonate end groups and the use thereof in the production of a multi-component adhesive composition | |
| CN102906213A (en) | Liquid coagulant and tire puncture sealing material set | |
| EP2383304A1 (en) | Composition for one-component polyurethane foams | |
| EP2481764A1 (en) | Composition for one-component polyurethane foams having low free monomeric MDI content | |
| CN106459364A (en) | Polyurethane prepolymer with cyclocarbonate end groups of low viscosity and the use thereof in the production of a multi-component adhesive composition | |
| EP3697827A1 (en) | A two-component polyurethane adhesive | |
| CN1986641A (en) | Encapsulating polyurethane material recipe and encapsulating material containing said recipe | |
| CA1115891A (en) | Cartridge for securing stay bars in bore holes | |
| JP5039535B2 (en) | Two-component polyurethane resin composition | |
| CN103328522B (en) | A process for making polyurea particles | |
| CN107771193A (en) | Polyurethane system for the Rotating fields in wind turbine | |
| CN101885828B (en) | Two-fluid polyurethane resin composition | |
| CN111171774B (en) | Reactive hot melt adhesive composition | |
| CN106560499B (en) | Moist rapid curing back mesh glue and preparation method thereof | |
| JP5797475B2 (en) | Polyurethane resin composition and hollow fiber membrane module using the same | |
| AU2003203844B2 (en) | Method for strengthening geological formations | |
| WO2009124680A1 (en) | Polyisocyanate mixtures | |
| US5229453A (en) | Polyurethane composition with reduced water to prepolymer mix ratio |
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 |