CN101870809B - Dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof - Google Patents
Dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof Download PDFInfo
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- CN101870809B CN101870809B CN2010102143393A CN201010214339A CN101870809B CN 101870809 B CN101870809 B CN 101870809B CN 2010102143393 A CN2010102143393 A CN 2010102143393A CN 201010214339 A CN201010214339 A CN 201010214339A CN 101870809 B CN101870809 B CN 101870809B
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Abstract
The invention discloses a dry bonding layer polyurethane resin for pasting double mirror and a preparation method thereof. The formula of the resin mainly comprises raw materials including diisocyanate, a polyalcohol compound, a chain extender, an antioxidant, a catalyst, an aid and a solvent, wherein the raw materials are mixed in a certain ratio to undergo chemical reactions under a set condition so as to generate the polyurethane resin which meets a requirement. The dry bonding layer polyurethane resin for pasting the double mirror produced by the preparation method of the invention has the advantages of fully solving the problem that air bubbles at the bottom of a leather groove of conventional large pattern-pasted double mirror cannot be eliminated fully, improving resin transparency and pattern definition and greatly lifting the grade of a double mirror synthetic leather.
Description
Technical field
The present invention relates to a kind of dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof.
Background technology
The bimirror synthetic leather is with its distinctive pattern level sense, beautiful mirror effect, and processing condition are simple etc., and advantage is favored by deeply in market.But at present because a lot of big-patterns bubble at the bottom of the groove when pasting bimirror can not be eliminated, the minute surface resin is tie layer resins transparent relatively poor particularly, causes the range of application of bimirror limited, and class is not high.
Summary of the invention
The objective of the invention is to prepare a kind of dry bonding layer polyurethane resin for pasting double mirror, paste the groove basis bubble that bimirror class synthetic leather occurs in process of production to solve, decorative pattern is unintelligible, problems such as minute surface transparency difference.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
In urethane (PU) resin building-up process, have the divalent alcohol chainextender of side chain through introducing, destroy polyurethane molecular segmental crystal property to a certain extent, improve the transparency of urethane resin.The divalent alcohol chainextender synthetic molecular resin motion that has side chain in addition is active, has bigger flowability during high temperature, at the bottom of the deep enough groove of ability, eliminates the bubble of bottom of trench.
A kind of subsides bimirror is used dry type polyurethane resin, it is characterized in that: its feed composition proportioning is:
Vulcabond
Polyol compound
Molecular weight is 62～200g/mol small molecules divalent alcohol chainextender
Catalyzer
Auxiliary agent
Solvent
Wherein, polyol compound with the ratio of the molar weight of small molecules divalent alcohol chainextender is: 1: 4～5;
The ratio of the molar weight of hydroxyl sum is in diisocyanate based and polyol compound and the small molecules divalent alcohol chainextender: 1～1.05: 1;
Small molecules divalent alcohol chainextender consumption accounts for 1%～5% of system gross weight;
Catalyst levels is 0.1% of polyol compound weight～1 ‰;
Auxiliary dosage accounts for 0.05%～0.08% of system gross weight;
Solvent load is 69%～71% of a system gross weight.
Described subsides bimirror is used dry type polyurethane resin, it is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate; Described polyol compound is selected from one or both in polyester polyol, the polyether glycol; Described molecular weight is that the small molecules divalent alcohol chainextender of 62～200g/mol is selected from terepthaloyl moietie, 1,4-butyleneglycol, 1, one or both in 2-Ucar 35, the NSC 6366; Described catalyzer is lipid acid bismuth class catalyzer MB20; Described auxiliary agent is selected from one or more in oxidation inhibitor, UV light absorber, weather-proof stablizer, the flow agent; Described solvent is water-soluble organic solvent.
Described subsides bimirror is used dry type polyurethane resin, it is characterized in that: described small molecules divalent alcohol chainextender is a terepthaloyl moietie or/and NSC 6366, and two kinds of alcohol mix when using, and the mol ratio of terepthaloyl moietie and NSC 6366 is 0.1～10: 1.
Described subsides bimirror is used dry type polyurethane resin, it is characterized in that: described polyether glycol is a polytetramethylene ether diol; Described water-soluble organic solvent is N, dinethylformamide (DMF).
Described a kind of preparation method who pastes bimirror with dry type polyurethane resin is characterized in that may further comprise the steps:
(1) in reaction kettle, drops into polyester polyols alkylol cpd, small molecules divalent alcohol chainextender, antioxidant 1010, solvent N; After dinethylformamide fully stirs; Vulcabond is joined in the reaction kettle again and react, the first vulcabond amount that adds is 70%～80% of the prescription add-on;
(2) under the condition that catalyzer exists, continue to add vulcabond and react, along with the continuous increase of system viscosity, progressively add required solvent N, dinethylformamide, final viscosity are controlled at 70～150Pas/25 ℃;
(3) reaction finishes an amount of terminator methyl alcohol of back adding etc., adds UV light absorber, weather-proof stablizer or flow agent at last again, to prolong the shelf lives of resin.
Described preparation method is characterized in that: any water ratio is less than 500ppm in the polyester polyol described in step (1) and (2), vulcabond, small molecules divalent alcohol chainextender, the solvent.
Described preparation method is characterized in that: the temperature of reaction in step (1) and (2) is controlled at 60～80 ℃.
Dry bonding layer polyurethane resin for pasting double mirror of the present invention has solved the problem that present subsides big-pattern bimirror leather ditch basis bubble can not be eliminated fully fully, and the raising of resin transparent degree, decorative pattern sharpness, has improved the class of bimirror leather greatly.
Embodiment:
For technique means, creation characteristic that the present invention is realized, reach purpose and effect easy to understand, below in conjunction with embodiment, further set forth the present invention.
Embodiment 1:
Material name weight (unit K g)
PET-1 200
PET-2 700
1,4-butyleneglycol 110
1,2-Ucar 35 20
4,4-diphenylmethanediisocyanate (MDI) 545
Antioxidant 1010 2.0
UV light absorber UV-328 1.0
Catalyzer MB20 0.2
N, dinethylformamide (DMF) 3700
PET-1 is the polyester polyol of molecular weight 3000.
PET-2 is the polyester polyol of molecular weight 2000.
Prepare according to the following steps:
1, in reaction kettle, drop into various polyol compounds, small molecules divalent alcohol chainextender, antioxidant 1010, N, dinethylformamide stirs, after 10～20 minutes; Drop into 4; 4 '-diphenylmethanediisocyanate, the still temperature control is at 70 ℃～80 ℃, and reaction is more than 2 hours.The first vulcabond amount that adds is 70%～80% of a theoretical add-on.
2, add 4,4 '-the diphenylmethanediisocyanate reaction: react and add catalyzer after 30 minutes again and continue reaction, the still temperature control is at 60～70 ℃ at this moment.
3, along with the continuous increase of system viscosity, progressively add required solvent DMF.Final viscosity is controlled at 80～120Pas/25 ℃, adds UV light absorber UV-328.The still temperature control is at 70～80 ℃.
4, be cooled to and carry out blowdown, metering packing below 60 ℃.
Embodiment 2:
Material name weight (unit K g)
PET-1 200
PET-2 700
Terepthaloyl moietie 160
NSC 6366 25
4,4-diphenylmethanediisocyanate (MDI) 545
Antioxidant 1010 2.0
UV light absorber UV-328 1.0
Catalyzer MB20 0.2
N, dinethylformamide (DMF) 3815
PET-1 is the polyester polyol of molecular weight 3000.
PET-2 is the polyester polyol of molecular weight 2000.
Dry bonding layer polyurethane resin for pasting double mirror of the present invention prepares according to the following steps:
1, the various polyol compounds of input, small molecules divalent alcohol chainextender, antioxidant 1010, DMF stir after 10～20 minutes and drop into MDI in reaction kettle; More than 2 hours, the first vulcabond amount that adds is 70%～80% of a theoretical add-on 70～80 ℃ of reactions in the still temperature control.
2, add the MDI reaction and add catalyzer continuation reaction after 30 minutes again.This moment, the still temperature control was at 60～70 ℃.
3, along with the continuous increase of system viscosity, progressively add required solvent DMF.Final viscosity is controlled at 80～120Pas/25 ℃, adds UV light absorber UV-328.The still temperature control is at 70～80 ℃.
4, be cooled to and carry out blowdown, metering packing below 60 ℃.
Embodiment 3:
In order to verify the premium properties of dry bonding layer polyurethane resin of the present invention, press following prescription and present dry method veneer normal process finished leather to the resin that above-mentioned embodiment is prepared, concrete prescription reaches as follows:
Resin 100
DMF 60
Flow agent 1
Help stripper 0.5
Through detecting, with the Synthetic Leather that the prescription of above-mentioned enforcement is processed, various big-pattern bimirror bottoms of trench all do not have bubble, and the decorative pattern sharpness is high, and the transparency is good, and mirror effect is excellent.
In claims of this specification sheets and the application, so-called system is meant whole reaction system, is exactly the total amount of all materials.That describes in above-mentioned embodiment and the specification sheets just explains principle of the present invention, and the present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improving all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and jljl thereof.
Claims (6)
1. dry bonding layer polyurethane resin for pasting double mirror, it is characterized in that: its feed composition proportioning is:
Vulcabond
Polyol compound
Molecular weight is 62～200g/mol small molecules divalent alcohol chainextender
Catalyzer
Auxiliary agent
Solvent
Wherein, polyol compound with the ratio of the molar weight of small molecules divalent alcohol chainextender is: 1: 4～5;
The ratio of the molar weight of hydroxyl sum is in diisocyanate based and polyol compound and the small molecules divalent alcohol chainextender: 1～1.05: 1;
Small molecules divalent alcohol chainextender, consumption accounts for 1%～5% of system gross weight;
Catalyst levels is 0.1% of polyol compound weight～1 ‰
Auxiliary dosage accounts for 0.05%～0.08% of system gross weight;
Solvent load is 69%～71% of a system gross weight;
Described small molecules divalent alcohol chainextender is terepthaloyl moietie and NSC 6366, and two kinds of alcohol mix use, and the mol ratio of terepthaloyl moietie and NSC 6366 is 0.1～10: 1.
2. subsides bimirror according to claim 1 is used dry type polyurethane resin, it is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate; Described polyol compound is selected from one or both in polyester polyol, the polyether glycol; Described catalyzer is lipid acid bismuth class catalyzer MB20; Described auxiliary agent is selected from one or more in oxidation inhibitor, UV light absorber, weather-proof stablizer, the flow agent; Described solvent is water-soluble organic solvent.
3. subsides bimirror according to claim 2 is used dry type polyurethane resin, it is characterized in that: described polyether glycol is a polytetramethylene ether diol; Described water-soluble organic solvent is N, dinethylformamide.
4. a kind of preparation method who pastes bimirror with dry type polyurethane resin according to claim 1 is characterized in that may further comprise the steps:
(1) in reaction kettle, drops into polyol compound, small molecules divalent alcohol chainextender, antioxidant 1010, solvent N; After dinethylformamide fully stirs; Vulcabond is joined in the reaction kettle again and react, the first vulcabond amount that adds is 70%～80% of the prescription add-on;
(2) under the condition that catalyzer exists, continue to add vulcabond and react, along with the continuous increase of system viscosity, progressively add required solvent N, dinethylformamide, final viscosity are controlled at 70～150Pas/25 ℃;
(3) reaction finishes an amount of terminator methyl alcohol of back adding, adds UV light absorber, weather-proof stablizer or flow agent at last again, to prolong the shelf lives of resin.
5. preparation method according to claim 4 is characterized in that: any water ratio is less than 500ppm in the polyol compound described in step (1) and (2), vulcabond, small molecules divalent alcohol chainextender, the solvent.
6. preparation method according to claim 4 is characterized in that: the temperature of reaction in step (1) and (2) is controlled at 60～80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102143393A CN101870809B (en) | 2010-06-30 | 2010-06-30 | Dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof |
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| CN2010102143393A CN101870809B (en) | 2010-06-30 | 2010-06-30 | Dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof |
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| CN101870809B true CN101870809B (en) | 2012-05-16 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416750B (en) * | 2011-08-15 | 2014-11-05 | 浙江元新实业有限公司 | Spraying type water injection device and water injection type double mirror jointing method |
| CN102533201A (en) * | 2011-12-26 | 2012-07-04 | 合肥安利聚氨酯新材料有限公司 | Preparation method of two-liquid type instant immediately peeled polyurethane resin bonding agent for synthetic leather |
| CN103467691B (en) * | 2013-09-18 | 2015-09-30 | 合肥安利聚氨酯新材料有限公司 | One is colded pressing with dry type polyurethane resin and preparation method thereof |
| CN103555260B (en) * | 2013-10-31 | 2015-07-15 | 淄博德信联邦化学工业有限公司 | One-component polyurethane (PU) wet wood adhesive and preparation method thereof |
| CN104017352B (en) * | 2014-05-30 | 2016-07-20 | 合肥安利聚氨酯新材料有限公司 | A kind of dry type ironing color-changing polyurethane resin and preparation method thereof |
| CN106279599A (en) * | 2015-05-26 | 2017-01-04 | 温州日胜新材料科技有限公司 | A kind of hydrolysis process for preparing resins |
| CN106366290A (en) * | 2016-08-31 | 2017-02-01 | 合肥安利聚氨酯新材料有限公司 | Two-component full-dry adhesive layer polyurethane resin for TPU (thermoplastic polyurethane) film compound synthetic leather and preparation method of resin |
| CN106896443A (en) * | 2017-03-10 | 2017-06-27 | 江苏全真光学科技股份有限公司 | The preparation technology of polarized lenses and its polarized lenses of preparation |
| CN113699804B (en) * | 2021-09-22 | 2023-09-15 | 安徽安利材料科技股份有限公司 | Polyurethane synthetic leather for football shoes and preparation method thereof |
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| CN101481453A (en) * | 2009-01-23 | 2009-07-15 | 合肥安利化工有限公司 | Dry type polyurethane resin for pasting gold-silver film and preparation thereof |
| CN101503498A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet-type high cracking resistance, high wear resistance and high peel strength polyurethane resin and preparation thereof |
| CN101629061A (en) * | 2008-07-14 | 2010-01-20 | 上海新光化工有限公司 | Monocomponent moisture cure urethanes adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629061A (en) * | 2008-07-14 | 2010-01-20 | 上海新光化工有限公司 | Monocomponent moisture cure urethanes adhesive |
| CN101481453A (en) * | 2009-01-23 | 2009-07-15 | 合肥安利化工有限公司 | Dry type polyurethane resin for pasting gold-silver film and preparation thereof |
| CN101503498A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet-type high cracking resistance, high wear resistance and high peel strength polyurethane resin and preparation thereof |
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