CN101870809A - 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 PDF

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Publication number
CN101870809A
CN101870809A CN 201010214339 CN201010214339A CN101870809A CN 101870809 A CN101870809 A CN 101870809A CN 201010214339 CN201010214339 CN 201010214339 CN 201010214339 A CN201010214339 A CN 201010214339A CN 101870809 A CN101870809 A CN 101870809A
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Prior art keywords
polyurethane resin
small molecules
solvent
dibasic alcohol
preparation
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CN 201010214339
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Chinese (zh)
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CN101870809B (en
Inventor
宗军业
武春余
惠坚强
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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  • Polyurethanes Or Polyureas (AREA)

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

A kind of dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof
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 dibasic alcohol chainextender of side chain by introducing, destroy polyurethane molecular segmental crystal property to a certain extent, improve the transparency of urethane resin.The dibasic 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 energy, eliminates the bubble of bottom of trench.
A kind of subsides bimirror dry type polyurethane resin is characterized in that: its feed composition proportioning is:
Vulcabond
Polyol compound
Molecular weight is 62~200g/mol small molecules dibasic alcohol chainextender
Catalyzer
Auxiliary agent
Solvent
Wherein, polyol compound with the ratio of the molar weight of small molecules dibasic 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 dibasic alcohol chainextender: 1~1.05: 1;
Small molecules dibasic 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 dry type polyurethane resin 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 dibasic alcohol chainextender of 62~200g/mol is selected from ethylene glycol, 1,4-butyleneglycol, 1, one or both in 2-propylene glycol, the neopentyl 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.
Described subsides bimirror dry type polyurethane resin is characterized in that: described small molecules dibasic alcohol chainextender is an ethylene glycol or/and neopentyl glycol, and two kinds of alcohol mix when using, and the mol ratio of ethylene glycol and neopentyl glycol is 0.1~10: 1.
Described subsides bimirror dry type polyurethane resin 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 reactor, drops into polyester polyols alkylol cpd, small molecules dibasic alcohol chainextender, antioxidant 1010, solvent N, after dinethylformamide fully stirs evenly, vulcabond is joined in the reactor 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 dibasic 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-propylene glycol 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.
Be prepared according to the following steps:
1, drop into various polyol compounds, small molecules dibasic alcohol chainextender, antioxidant 1010, N in reactor, 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
Ethylene glycol 160
Neopentyl glycol 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 is prepared according to the following steps:
1, the various polyol compounds of input, small molecules dibasic alcohol chainextender, antioxidant 1010, DMF stir after 10~20 minutes and drop into MDI in reactor, 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, the prepared resin of above-mentioned embodiment by following prescription and present dry method veneer normal process finished leather, concrete prescription and as follows:
Resin 100
DMF 60
Flow agent 1
Help stripper 0.5
After testing, with the Synthetic Leather that the prescription of above-mentioned enforcement is made, various big-pattern bimirror bottoms of trench all do not have bubble, decorative pattern sharpness height, 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 substances.That describes in above-mentioned embodiment and the specification sheets just illustrates principle of the present invention, and the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and jljl thereof.

Claims (7)

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 dibasic alcohol chainextender
Catalyzer
Auxiliary agent
Solvent
Wherein, polyol compound with the ratio of the molar weight of small molecules dibasic 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 dibasic alcohol chainextender: 1~1.05: 1;
Small molecules dibasic 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.
2. subsides bimirror dry type polyurethane resin according to claim 1 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 dibasic alcohol chainextender of 62~200g/mol is selected from ethylene glycol, 1,4-butyleneglycol, 1, one or both in 2-propylene glycol, the neopentyl 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 dry type polyurethane resin according to claim 1 is characterized in that: described small molecules dibasic alcohol chainextender is an ethylene glycol or/and neopentyl glycol, and two kinds of alcohol mix when using, and the mol ratio of ethylene glycol and neopentyl glycol is 0.1~10: 1.
4. subsides bimirror dry type polyurethane resin according to claim 2 is characterized in that: described polyether glycol is a polytetramethylene ether diol; Described water-soluble organic solvent is N, dinethylformamide.
5. 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 reactor, drops into polyol compound, small molecules dibasic alcohol chainextender, antioxidant 1010, solvent N, after dinethylformamide fully stirs evenly, vulcabond is joined in the reactor 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.
6. preparation method according to claim 5 is characterized in that: any water ratio is less than 500ppm in the polyol compound described in step (1) and (2), vulcabond, small molecules dibasic alcohol chainextender, the solvent.
7. preparation method according to claim 5 is characterized in that: the temperature of reaction in step (1) and (2) is controlled at 60~80 ℃.
CN2010102143393A 2010-06-30 2010-06-30 Dry bonding layer polyurethane resin for pasting double mirror and preparation method thereof Active CN101870809B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102416750A (en) * 2011-08-15 2012-04-18 浙江科一合成革有限公司 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
CN103467691A (en) * 2013-09-18 2013-12-25 合肥安利聚氨酯新材料有限公司 Dry type polyurethane resin for cold pressing and preparation method thereof
CN103555260A (en) * 2013-10-31 2014-02-05 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
CN104017352A (en) * 2014-05-30 2014-09-03 合肥安利聚氨酯新材料有限公司 Dry-type hot 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
CN113699804A (en) * 2021-09-22 2021-11-26 安徽安利材料科技股份有限公司 Polyurethane synthetic leather for football shoes and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

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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

Cited By (13)

* Cited by examiner, † Cited by third party
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
CN102416750A (en) * 2011-08-15 2012-04-18 浙江科一合成革有限公司 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
CN103467691A (en) * 2013-09-18 2013-12-25 合肥安利聚氨酯新材料有限公司 Dry type polyurethane resin for cold pressing and preparation method thereof
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
CN103555260A (en) * 2013-10-31 2014-02-05 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
CN104017352A (en) * 2014-05-30 2014-09-03 合肥安利聚氨酯新材料有限公司 Dry-type hot 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
CN113699804A (en) * 2021-09-22 2021-11-26 安徽安利材料科技股份有限公司 Polyurethane synthetic leather for football shoes and preparation method thereof
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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