CN111019088A - Preparation method of organic silicon modified polyurethane hot melt adhesive - Google Patents
Preparation method of organic silicon modified polyurethane hot melt adhesive Download PDFInfo
- Publication number
- CN111019088A CN111019088A CN201911363818.9A CN201911363818A CN111019088A CN 111019088 A CN111019088 A CN 111019088A CN 201911363818 A CN201911363818 A CN 201911363818A CN 111019088 A CN111019088 A CN 111019088A
- Authority
- CN
- China
- Prior art keywords
- parts
- hot melt
- melt adhesive
- organic silicon
- polyurethane hot
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of an organic silicon modified polyurethane hot melt adhesive, which comprises the following steps in parts by mass: (1) adding 1-20 parts of dimethyl dimethoxysilane, 1-20 parts of methyl phenyl dimethoxysilane and 1-20 parts of diphenyl dimethoxysilane into a three-necked bottle, adding 1-5 parts of acidic resin catalyst, heating to 40-60 ℃, reacting for 1-2h, then adding 20-40 parts of polyester polyol, and filtering while hot to obtain a block copolymer of organosilicon modified polyester polyol; (2) 20-30 parts of liquid polyester diol, 50-70 parts of the block copolymer of the organic silicon modified polyester polyol synthesized in the step (1), 10-30 parts of isocyanate MDI (diphenyl-methane-diisocyanate), carrying out polymerization reaction for 2-6 hours, and then adding 0.1-2 parts of catalyst to obtain the organic silicon modified polyurethane hot melt adhesive.
Description
Technical Field
The invention belongs to the technical field of structural adhesives, and particularly relates to an organic silicon modified polyurethane hot melt adhesive and a preparation method thereof, which are mainly applied to the structural bonding fields of electronics and electrical appliance industry, display screen industry, lithium battery industry and the like.
Technical Field
The polyurethane hot melt adhesive is a new generation of structural adhesive capable of providing excellent adhesive property, and is prepared by taking a polyurethane prepolymer as a main material and matching with various auxiliary agents. The polyurethane hot melt adhesive is convenient to use and environment-friendly, and the performance of the polyurethane hot melt adhesive can be comparable to that of a solvent type hot melt adhesive. In recent decades, polyurethane hot melt adhesives have been rapidly developed and widely used in high-end fields such as electronic and electrical appliance industry, automobile industry and the like. The polyurethane hot melt adhesive can be divided into thermoplastic polyurethane elastomer hot melt adhesive and reactive polyurethane hot melt adhesive according to different curing forms; reactive polyurethane hot melt adhesives are classified into moisture curing type and closed type according to different curing principles. The moisture-curing type polyurethane hot melt adhesive (PUR) is a single-component hot melt adhesive, is melted after being heated and flows and is dispersedly coated on the surface of a substrate, an adherend is bonded and then is cooled to form excellent initial bonding performance, and then the substrate surface contains trace moisture or other compounds containing active hydrogen and reacts with isocyanate (-NCO) to generate chemical crosslinking reaction, so that the structural bonding hot melt adhesive with high crosslinking network and large cohesive force is generated.
The prior art of moisture-curing type polyurethane hot melt adhesive has been developed unprecedentedly, and the performance optimization adjustment is mainly carried out around high bonding strength, low melt viscosity, open time, repair and curing forms and the like. Chinese patent discloses a reactive hot melt adhesive, application No. 201480080313.0, which produces a removable polyurethane hot melt adhesive with rework, more suitable for high end electronic product applications. Chinese patent discloses a solvent-free moisture-curing polyurethane hot-melt adhesive composition, which has application number of 201180047316.0 and is used for preparing a polyurethane hot-melt adhesive prepared from polyacrylate and polyester with low toxicity and quick adhesive property. In order to improve the curing form of the moisture-curing polyurethane hot melt adhesive, the application number of the organosilicon modified polyurethane sealant disclosed in the Chinese patent is 2017102717258, and the organosilicon modified polyurethane sealant is prepared by substituting isocyanic acid radical (-NCO) with a silane coupling agent and is more suitable for being applied in a high-humidity environment. At present, the research and development technology of the moisture-curing type polyurethane hot melt adhesive is rapidly developed, and the application in the fields of different types of high-end electronic products is met. Although the moisture-curing type polyurethane hot melt adhesive can form a highly crosslinked network after curing, the moisture-curing type polyurethane hot melt adhesive also has the problems of insufficient solvent resistance, aging resistance and water resistance. The main reason for this is that most moisture-curing polyurethane hot melt adhesives incorporate a large amount of non-reactive thermoplastic tackifying resin or a polyacrylic acid copolymer in order to improve their initial adhesive properties. The non-reactive tackifying resins can not participate in curing to generate a cross-linked network, so that the solvent resistance, the aging resistance and the like of the polyurethane hot melt adhesive coating can be easily reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the organic silicon modified polyurethane hot melt adhesive and the preparation method thereof.
In order to achieve the purpose, the technical scheme of the moisture-curing type organic silicon modified polyurethane hot melt adhesive is that the moisture-curing type organic silicon modified polyurethane hot melt adhesive comprises, by mass, 50-70 parts of organic silicon modified crystalline polyester polyol, 20-40 parts of polyester polyol, 10-30 parts of isocyanate, 0.1-2 parts of catalyst and 0.1-1 part of silane coupling agent;
the polyester polyol is one or any combination of more than two of constantly-lasting and highly-rich HJ-0511, HJ-R380 and HJ-7380H;
the isocyanate is MDI;
the catalyst is one or more of triethanolamine, 2-dimorpholinyl diethyl ether and phosphoric acid;
in order to achieve the purpose, the technical scheme of the preparation method of the moisture-curing type organic silicon modified polyurethane hot melt adhesive is realized by the following steps:
the organic silicon modified polyester polyol block copolymer in the step one needs to be prepared by synthesis,
adding 1-20 parts of dimethyl dimethoxysilane, 1-20 parts of methyl phenyl dimethoxysilane and 1-20 parts of diphenyl dimethoxysilane into a three-necked bottle, adding 1-5 parts of acidic resin catalyst, heating to 40-60 ℃ for reaction for 1-2h, then adding 20-40 parts of polyester polyol, uniformly stirring, heating to 100 ℃ and 120 ℃, reacting for 4-6h, and filtering while hot to obtain the block copolymer of the organosilicon modified polyester polyol;
step two of synthesizing organic silicon modified polyurethane hot melt adhesive
20-30 parts of liquid polyester diol, 50-70 parts of the block copolymer of the organic silicon modified polyester polyol synthesized in the step (1), heating to 120 ℃ for 100-70 ℃, vacuumizing for dewatering for 3-5 hours, cooling to 50-70 ℃, adding 10-30 parts of isocyanate MDI under the protection of nitrogen, carrying out polymerization for 2-6 hours, and then adding 0.1-2 parts of catalyst to obtain the organic silicon modified polyurethane hot melt adhesive.
The acid resin catalyst is Lewatit S-100, and the liquid polyester diol is one or a mixture of 7360 or 7380.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention overcomes the defects of poor solvent resistance, aging resistance and the like of the traditional moisture-curing type polyurethane hot melt adhesive; in the technical scheme of the invention, the hydroxyl-terminated organic silicon acrylate copolymer is a block copolymer of hydroxyl-terminated organic silicon modified polyester polyol, which is prepared by copolymerizing an organic silicon monomer and polyester polyol by adopting a hydroxyl-containing free radical initiator. The organic silicon monomer can improve the solvent resistance and the aging resistance of the hot melt adhesive. The hydroxyl-containing end-capped polyorganosiloxane polymer partially participates in the synthesis reaction of the polyurethane prepolymer, has high-efficiency synergistic effect, shows better compatibility, further adjusts the composition and content of other raw materials, and improves water resistance and sweat resistance.
2. According to the invention, hydroxyl-terminated organic silicon is introduced into the prepolymer of polyester polyol, so that the compatibility of organic silicon and polyurethane is improved, and the solvent resistance of the moisture-curing polyurethane hot melt adhesive is further improved;
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The parts referred to in the following examples are parts by mass.
Example 1
(1) Adding 10 parts of dimethyl dimethoxysilane, 10 parts of methyl phenyl dimethoxysilane and 10 parts of diphenyl dimethoxysilane into a three-mouth upper bottle, adding Lewatit S-100, heating to 40 ℃ for reaction for 2 hours, then, stirring uniformly, heating to 100 ℃ for reaction for 4 hours, and filtering while hot to obtain a block copolymer of organic silicon modified polyester polyol;
(2)20 parts of wound 7360, 50 parts of the block copolymer of the organosilicon modified polyester polyol synthesized in the step (1), heating to 100 ℃, vacuumizing to remove water for about 3 hours, cooling to 50 ℃, adding 10 parts of isocyanate MDI under the protection of nitrogen, carrying out polymerization reaction for 2 hours, and then adding 0.1 part of triethanolamine to obtain the organosilicon modified polyurethane hot melt adhesive.
Example 2
(1) Adding 20 parts of dimethyl dimethoxysilane, 20 parts of methyl phenyl dimethoxysilane and 20 parts of diphenyl dimethoxysilane into a three-mouth upper bottle, adding Lewatit S-100, heating to 60 ℃ for reaction for 2 hours, then uniformly stirring 40 parts of HJ-R380, heating to 120 ℃ for reaction for 6 hours, and filtering while hot to obtain a block copolymer of organosilicon modified polyester polyol;
(2)30 parts of wound-winning 7380, 70 parts of the block copolymer of the organosilicon modified polyester polyol synthesized in the step (1), heating at 120 ℃, vacuumizing to remove water for about 5 hours, cooling at 70 ℃, adding 30 parts of isocyanate MDI under the protection of nitrogen, carrying out polymerization reaction for 6 hours, and then adding 2 parts of triethanolamine to obtain the organosilicon modified polyurethane hot melt adhesive.
Example 3
(1) Adding 15 parts of dimethyl dimethoxysilane, 15 parts of methyl phenyl dimethoxysilane and 115 parts of diphenyl dimethoxysilane into a three-opening upper bottle, adding Lewatit S-100, heating to 60 ℃ for reaction for 2 hours, then, stirring uniformly, heating to 100 ℃ for reaction for 6 hours, and filtering while hot to obtain a block copolymer of organic silicon modified polyester polyol;
(2) heating 10 parts of winning 7360+10 parts of winning 7380, 60 parts of the block copolymer of the organic silicon modified polyester polyol synthesized in the step (1), vacuumizing to remove water for about 5 hours, cooling to 70 ℃, adding 25 parts of isocyanate MDI (diphenyl-methane-diisocyanate) under the protection of nitrogen, carrying out polymerization for 3 hours, and then adding 1 part of 2, 2-dimorpholinyl to obtain the organic silicon modified polyurethane hot melt adhesive.
Example 4
(1) Adding 20 parts of dimethyl dimethoxysilane, 10 parts of methyl phenyl dimethoxysilane and 10 parts of diphenyl dimethoxysilane into a three-mouth upper bottle, adding Lewatit S-100, heating to 60 ℃ for reaction for 2 hours, then stirring uniformly and heating to 120 ℃ for reaction for 6 hours, and filtering while hot to obtain a block copolymer of organosilicon modified polyester polyol;
(2)30 parts of wound 7360, 50 parts of the block copolymer of the organosilicon modified polyester polyol synthesized in the step (1), heating at 120 ℃, vacuumizing to remove water for about 4 hours, cooling at 60 ℃, adding 30 parts of isocyanate MDI under the protection of nitrogen, carrying out polymerization for 4 hours, and then adding 0.5 part of phosphoric acid to obtain the organosilicon modified polyurethane hot melt adhesive.
Performance testing
The moisture-curable organosilicon modified polyurethane hot melt adhesive obtained in the four embodiments is subjected to melt viscosity, opening time, shore hardness, elongation at break, shear strength and oil-resistant acidic performance index tests by referring to the current general method of the hot melt adhesive. The melt viscosity was measured according to HG/T3660-1999 standard, using a No. 27 rotor set at 100 ℃. Open time was tested according to ASTM D4497-1994 (2004). The Shore hardness is tested according to the GB-T2411-2008 standard. The elongation at break is tested with reference to the GB/T30776-2014 standard. The shear strength was tested with reference to GB/T7124-2004 standard. The specific test method of the solvent resistance index is to prepare a sample by referring to a shear strength test method, after the sample is placed for 72 hours for solidification, the sample is soaked in an oleic acid (with the purity of 98%) solution for 24 hours, the sample is taken out, placed in an environment with the temperature of 85 ℃ and the relative humidity of 85%, aged for 1000 hours, and then subjected to a shear strength test. The water contact angle is tested with reference to GB/T30693-. All test data are compared in table 1 below.
TABLE 1 comparison of specific Performance tests for each example
As can be seen from the data in Table 1, the moisture-curable silicone modified polyurethane hot melt adhesive synthesized by the invention has excellent solvent corrosion resistance, aging resistance and hydrophobic property.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A preparation method of an organic silicon modified polyurethane hot melt adhesive is characterized by comprising the following steps of:
(1) adding 1-20 parts of dimethyl dimethoxysilane, 1-20 parts of methyl phenyl dimethoxysilane and 1-20 parts of diphenyl dimethoxysilane into a three-necked bottle, adding 1-5 parts of acidic resin catalyst, heating to 40-60 ℃ for reaction for 1-2h, then adding 20-40 parts of polyester polyol, uniformly stirring, heating to 100 ℃ and 120 ℃, reacting for 4-6h, and filtering while hot to obtain the block copolymer of the organosilicon modified polyester polyol;
(2) 20-30 parts of liquid polyester diol, 50-70 parts of the block copolymer of the organic silicon modified polyester polyol synthesized in the step (1), heating to 120 ℃ for 100-70 ℃, vacuumizing for dewatering for 3-5 hours, cooling to 50-70 ℃, adding 10-30 parts of isocyanate MDI under the protection of nitrogen, carrying out polymerization for 2-6 hours, and then adding 0.1-2 parts of catalyst to obtain the organic silicon modified polyurethane hot melt adhesive.
2. The preparation method of the organosilicon modified polyurethane hot melt adhesive according to claim 1, wherein the polyester polyol is one or any combination of more than two of constantly strong HJ-0511, HJ-R380 and HJ-7380H; the catalyst is one or more of triethanolamine, 2-dimorpholinyl diethyl ether and phosphoric acid.
3. The preparation method of the organosilicon modified polyurethane hot melt adhesive according to claim 1, wherein the acidic resin catalyst is Lewatit S-100, and the liquid polyester diol is one or a mixture of 7360 and 7380.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911363818.9A CN111019088A (en) | 2019-12-26 | 2019-12-26 | Preparation method of organic silicon modified polyurethane hot melt adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911363818.9A CN111019088A (en) | 2019-12-26 | 2019-12-26 | Preparation method of organic silicon modified polyurethane hot melt adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111019088A true CN111019088A (en) | 2020-04-17 |
Family
ID=70214486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911363818.9A Pending CN111019088A (en) | 2019-12-26 | 2019-12-26 | Preparation method of organic silicon modified polyurethane hot melt adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111019088A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724906A (en) * | 2020-12-29 | 2021-04-30 | 烟台德邦科技股份有限公司 | Organic silicon modified polyurethane hot melt adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651991A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof |
| CN109679560A (en) * | 2018-12-04 | 2019-04-26 | 顺德职业技术学院 | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof |
| CN109852323A (en) * | 2018-12-04 | 2019-06-07 | 顺德职业技术学院 | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof |
-
2019
- 2019-12-26 CN CN201911363818.9A patent/CN111019088A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651991A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof |
| CN109679560A (en) * | 2018-12-04 | 2019-04-26 | 顺德职业技术学院 | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof |
| CN109852323A (en) * | 2018-12-04 | 2019-06-07 | 顺德职业技术学院 | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724906A (en) * | 2020-12-29 | 2021-04-30 | 烟台德邦科技股份有限公司 | Organic silicon modified polyurethane hot melt adhesive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107987778B (en) | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN108285766A (en) | One kind exempting from pressurize PUR hot melt adhesives and preparation method thereof | |
| CN102010687B (en) | Fast curing reaction type hot melt adhesive and preparation method thereof | |
| CN104449533A (en) | Reactive polyurethane hot melt adhesive for electronic appliance and preparing method thereof | |
| JP2014500360A (en) | Reactive conductive pressure sensitive adhesive tape | |
| CN109679559A (en) | The excellent damp solidifying polyurethane hot melt adhesive and preparation method thereof of oil resistance | |
| EP3778691A1 (en) | Epoxy resin modified with polyurethane in low concentration, production method therefor, epoxy resin composition, and cured object | |
| CN109852320A (en) | Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN103694639A (en) | Halogen-free anti-aging epoxy resin composition and method for preparing cover film by using same | |
| CN109651994A (en) | Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109679561A (en) | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof | |
| CN111019088A (en) | Preparation method of organic silicon modified polyurethane hot melt adhesive | |
| CN113024705B (en) | Adhesion promoter for polyurethane adhesive and polyurethane adhesive | |
| CN109651992A (en) | The excellent moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof of weather resistance | |
| KR20160090290A (en) | Double-sided adhesive sheet and method for producing double-sided adhesive sheet | |
| CN109679564A (en) | Fluorinated silicone modified flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109609078A (en) | Organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type and preparation method thereof | |
| CN109852323A (en) | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN109651991A (en) | Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN106883811B (en) | Epoxy modified polyurethane base adhesive composition and thermosetting laminating sheet | |
| CN109679560A (en) | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof | |
| CN108753241A (en) | Silane modified polyether hot-melt adhesive composition and preparation method thereof | |
| CN109609077A (en) | Organic-silicon-modified reaction-type flame-retarding polyurethane hot melt and preparation method thereof | |
| CN109651995A (en) | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109679563A (en) | Graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No.3-3, Kaifeng Road, Yantai Economic and Technological Development Zone, Shandong Province 264006 Applicant after: Yantai Debang Technology Co.,Ltd. Address before: No.3-3, Kaifeng Road, Yantai Development Zone, Shandong Province 264006 Applicant before: DARBOND TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200417 |
|
| RJ01 | Rejection of invention patent application after publication |