CN112409955A - Nail-free glue and preparation method thereof - Google Patents
Nail-free glue and preparation method thereof Download PDFInfo
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- CN112409955A CN112409955A CN201910766847.3A CN201910766847A CN112409955A CN 112409955 A CN112409955 A CN 112409955A CN 201910766847 A CN201910766847 A CN 201910766847A CN 112409955 A CN112409955 A CN 112409955A
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- Prior art keywords
- nail
- parts
- free glue
- agent
- hydrogenated
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Classifications
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- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nail-free glue and a preparation method thereof, the main components are amorphous alpha-olefin copolymer, hydrogenated styrene-butadiene rubber, ethylene-vinyl acetate copolymer, tackifying resin, mixed solvent, nucleating agent, reinforcing fiber, anti-aging agent, defoaming agent and antifreezing agent; the invention has the advantages that: good stability to foam; 2. the product has high transparency and good cold resistance; 3. the product has good flexibility; 4. the physical and mechanical properties are good, and the nucleating agent can change the crystallization behavior of the resin; 5. the low-temperature constructability of the product is good.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a special transparent nail-free adhesive for foam and a preparation method thereof.
Background
The nail-free adhesive is an adhesive with high solid content, high bonding strength and high curing speed. Has the advantages of convenient carrying and construction. The method is widely applied to industries such as home decoration and decoration, joint filling and edge sealing in furniture manufacturing, advertisement exhibition and display, hardware and the like. At present, nail-free glue is favored by constructors and users by virtue of the advantages of convenience in carrying and construction, high bonding strength, no need of drilling and the like. However, in the advertising industry and the related heat insulation industry, the sticking of the foam material needs to use a transparent nail-free glue which cannot corrode a base material, and meanwhile, the glue film is required to resist yellowing, so that the transparency and the attractiveness of a bonding part are ensured. The nail-free glue which is circulated in the market at present can not meet the bonding requirements of people on foam materials, and the popularization and the application of the nail-free glue are restricted.
There have been few studies on the disclosed transparent nail-free adhesives. CN104293244A discloses a transparent nail-free glue, which comprises 10-25 parts of high molecular polymer, 15-30 parts of transparent tackifier, 5-15 parts of filler, 5-15 parts of thixotropic agent, 0.5-2.5 parts of composite stabilizer and 10-30 parts of organic solvent, wherein the transparent tackifier, the highly transparent filler and the composite stabilizer are added, the transparency of the glue is high, and the weather resistance and the ultraviolet resistance are greatly improved, but the used organic solvent is cyclohexane, methylal, ethyl acetate, acetone and tetrachloroethylene. Practice has shown that the transparent nail-free glue prepared from the solvents can corrode the foam material. Meanwhile, the transparent nail-free glue generates bubbles in the solvent volatilization process, so that the strength of the glue film is damaged, and the final bonding strength is influenced.
In the disclosed technology, the transparent nail-free glue is only used for bonding materials such as glass products, transparent plates, artware and the like, and does not relate to bonding of foam materials. Therefore, the development of the transparent nail-free glue for the foam has great practicability and necessity.
Disclosure of Invention
The invention provides a transparent nail-free adhesive and a preparation method thereof, wherein the adhesive comprises the following components in parts by weight:
10-15% of amorphous alpha-olefin copolymer
5 to 10 parts of hydrogenated styrene-butadiene rubber
5-10% of ethylene-vinyl acetate copolymer
10-20 parts of tackifying resin
20-40 parts of mixed solvent
0.2-0.6 of nucleating agent
1 to 5 reinforcing fibers
0.5 to 3 parts of thickening reinforcing agent
0.3-1.0% of antioxidant
0.1 to 0.5% of defoaming agent
1-2 parts of an antifreezing agent;
the hydrogenated thermoplastic styrene-butadiene rubber is at least one of hydrogenated styrene-butadiene-styrene rubber (SEBS) and hydrogenated styrene-isoprene-styrene rubber (SEPS);
the VA content of the ethylene-vinyl acetate copolymer is 40-80%;
the tackifying resin is at least one of poly-a-methyl styrene resin, hydrogenated terpene resin, hydrogenated petroleum resin, hydrogenated rosin glyceride and hydrogenated rosin pentaerythritol ester;
the mixed solvent comprises the following components in parts by weight: cyclohexane, No. 6 solvent gasoline, propyl acetate and ethanol = 1-3: 2-7: 1-3: 0-2;
the nucleating agent comprises the following components in parts by weight: 2. 2' -methylenebis (4, 6-tert-butylphenol) phosphine aluminum salt (NA-21): bis (P-methylbenzylidene) sorbitol (P-M-DBS) =1-4: 1-3;
the thickening reinforcing agent is at least one of silicon dioxide and organic bentonite;
the reinforcing fiber is prepared from 1-3mm polyethylene fiber: 1-2mm polyethylene fiber = 1-7: 1-6 by weight part;
the antioxidant is at least one of antioxidant 1010, antioxidant 264 and antioxidant 1076;
the defoaming agent is tributyl phosphate;
the antifreezing agent is at least one of ethylene glycol monobutyl ether, propylene glycol monobutyl ether and dichloromethane.
The preparation method of the transparent nail-free glue for the foam comprises the following steps: according to the weight portion, adding amorphous alpha-olefin copolymer, hydrogenated thermoplastic styrene butadiene rubber, ethylene-vinyl acetate copolymer, nucleating agent and tackifying resin into a screw extruder, uniformly mixing, forming and tabletting, wherein the temperature of the screw extruder is controlled at 80-120 ℃; adding the formed tablet, the mixed solvent, the nucleating agent, the thickening reinforcing agent and the reinforcing fiber according to the weight part ratio, and stirring and dispersing uniformly; and adding an anti-aging agent, a defoaming agent and an antifreezing agent, uniformly dispersing, detecting to be qualified, and filtering to obtain the transparent nail-free glue for the foam.
The transparent nail-free glue for foam has the following advantages:
1. good stability to foam and no corrosion to foam;
2. the product has high transparency, good cold resistance, optimized resin, good adhesion, aging resistance and yellowing resistance; the chemical stability is good;
3. the product has good flexibility, and the product added with the reinforced fiber has good crack resistance;
4. the physical and mechanical properties are good, the nucleating agent can change the crystallization behavior of the resin, and the crystallization temperature, rate, crystallization density and the like of the glue film are improved;
5. the product has good low-temperature construction workability, and the adhesive film is smoothly extruded in winter in a low-temperature environment by adding the antifreezing agent in the formula.
Detailed Description
The present invention is illustrated by the following examples, but the present invention is not limited to these examples. Modifications to the embodiments of the invention or equivalent substitutions of parts of technical features without departing from the spirit of the invention are intended to be covered by the scope of the claims of the invention.
Example 1
(1) According to the weight ratio of the formula, 10 parts of amorphous alpha-olefin copolymer, 10 parts of hydrogenated thermoplastic styrene-butadiene rubber, 5 parts of ethylene-vinyl acetate copolymer, 2 parts of poly (a-methylstyrene) resin, 2 parts of hydrogenated terpene resin, 2 parts of hydrogenated rosin glyceride, NA-21: 0.08 parts and P-M-DBS: 0.12 part of the mixture is added into a screw extruder with the temperature of 120 ℃, evenly mixed, discharged and tabletted;
(2) adding 4 parts of cyclohexane, 12 parts of No. 6 solvent oil, 2 parts of propyl acetate and 2 parts of ethanol into a closed reaction kettle with a jacket, starting up to stir, adding 1 part of thickening agent silicon dioxide, uniformly dispersing, adding a tabletting prepared in the step (1), 5 parts of polyethylene fiber with the diameter of 1-3mm, 2 parts of poly-a-methylstyrene resin and 2 parts of hydrogenated rosin glyceride, keeping the temperature of the jacket at 30-40 ℃, and stirring for 1-2 hours until the materials are completely dissolved;
(3) and adding 10100.3 parts of antioxidant, 0.1 part of tributyl phosphate and 1 part of ethylene glycol monobutyl ether, uniformly dispersing, detecting to be qualified, and filtering under the pressure of 0.1MPa to obtain the transparent nail-free adhesive for foam.
Example 2
(1) According to the weight ratio of the formula, the amorphous alpha-olefin copolymer 15 parts, the hydrogenated thermoplastic styrene-butadiene rubber 5 parts, the ethylene-vinyl acetate copolymer 10 parts, the hydrogenated petroleum resin 6 parts, the hydrogenated terpene resin 7 parts, the hydrogenated rosin glyceride 2 parts, the NA-21: 0.16 parts and P-M-DBS: 0.24 part of the raw materials are added into a screw extruder at 100 ℃, uniformly mixed, discharged and tabletted;
(2) putting 4 parts of cyclohexane, 30 parts of No. 6 solvent oil, 3 parts of propyl acetate and 3 parts of ethanol into a closed reaction kettle with a jacket, starting up to stir, then adding 3 parts of organic bentonite, dispersing uniformly, then adding 1 part of tabletting prepared in the step (1), 1-3mm polyethylene fiber: 1-2mm polyethylene fiber, 3 parts of hydrogenated terpene resin and 2 parts of hydrogenated rosin glyceride, keeping the temperature of the jacket at 30-40 ℃, and stirring for 1-2 hours until the materials are completely dissolved;
(3) and adding 2641.0 parts, 0.5 part of tributyl phosphate and 1.5 parts of propylene glycol monobutyl ether, uniformly dispersing, detecting to be qualified, and filtering under the pressure of 0.1MPa to obtain the transparent nail-free adhesive for foam.
Example 3
(1) According to the weight portion ratio of the formula, the amorphous alpha-olefin copolymer 12.5 parts, the hydrogenated thermoplastic styrene-butadiene rubber 7.5 parts, the ethylene-vinyl acetate copolymer 7.5 parts, the poly-a-methyl styrene resin 4 parts, the hydrogenated rosin glyceride 6 parts, the NA-21: 0.12 part and P-M-DBS: 0.18 part of the raw materials are added into a screw extruder at the temperature of 80 ℃, uniformly mixed, discharged and tabletted;
(2) adding 6 parts of cyclohexane, 15 parts of No. 6 solvent oil, 7 parts of propyl acetate and 2 parts of ethanol into a closed reaction kettle with a jacket, starting up to stir, adding 1 part of fumed silica and 1 part of organic bentonite respectively, dispersing uniformly, adding a tackifying resin prepared in the step (1), 3 parts of 1-3mm polyethylene fiber, 2 parts of the rest poly (a-methylstyrene resin) and 3 parts of hydrogenated rosin pentaerythritol ester, keeping the temperature of the jacket at 30-40 ℃, and stirring for 1-2 hours until the materials are completely dissolved;
(3) then 10760.65 parts of antioxidant, 0.3 part of tributyl phosphate and 2 parts of dichloromethane are added to be dispersed evenly,
and (5) detecting to be qualified, and filtering under the pressure of 0.1MPa to obtain the transparent nail-free glue for the foam.
Comparative example 4
In a reaction kettle with a jacket, firstly adding 20 parts of cyclohexane, 10 parts of ethyl acetate and 10 parts of tetrachloroethylene, starting up to stir, adding 3 parts of organic bentonite, uniformly dispersing, then adding 25 parts of styrene-butadiene-styrene triblock copolymer, 11 parts of hydrogenated petroleum resin, 9 parts of hydrogenated rosin pentaerythritol ester and 2640.1 parts of antioxidant, and stirring until the materials are completely dissolved to obtain the transparent nail-free glue.
The related performances of the transparent nail-free glue of the embodiments 1-3 and the comparative example 4 are tested by adopting the following method:
1. and (3) corrosion resistance measurement: the glue is extruded on a 10X 10mm foam plate by a glue gun, and whether the foam substrate collapses or not is observed in comparison.
2. And (3) defoaming effect determination: and extruding the glue on a clean and transparent glass plate by using a glue gun, and comparing and observing whether bubbles exist in the solidified glue film.
3. And (3) extrusion property measurement: reference is made to GB/T13477.3 section 3 of test methods for building sealants: the method for measuring the seal extrudability using a standard instrument. The diameter of the extrusion hole is 4mm, the air pressure is 0.2mMPa, and the weight of the extruded sample in 15S is regulated to be multiplied by 4 and divided by the specific gravity of the mucilage, namely the extrudability of the mucilage is obtained.
4. Determination of initial adhesion and tensile shear strength: taking 2 birch boards with the size of 70mm, the width of 20mm and the thickness of 3.0mm, weighing about 0.1 g of glue solution, uniformly coating the glue solution on one end of the front surface of the polished board by 1.5cm multiplied by 2.0cm, overlapping the two boards, pressurizing for 5min by using a constant pressure device with the pressure of 0.4MPa, releasing the pressure, standing for 30min at room temperature, and performing an initial adhesion strength test by using a tensile machine; after the sample was left at room temperature for 24 hours, a tensile shear strength test was conducted by using a tensile machine.
5. Vicat heat resistance measurement: the method is carried out according to the GB/T1633-2000 method.
The results of the performance tests on the transparent nail-free glue of the examples 1-3 and the comparative example 4 are shown in the following table 1.
As can be seen from the above table, compared with the prior art (comparative example 4), the transparent nail-free glue special for foam of the invention does not corrode foam, has no bubbles after the glue film is cured, and has good adhesion and heat resistance.
Claims (11)
1. The nail-free glue is characterized by comprising the following components in parts by weight:
10-15% of amorphous alpha-olefin copolymer
5 to 10 parts of hydrogenated styrene-butadiene rubber
5-10% of ethylene-vinyl acetate copolymer
10-20 parts of tackifying resin
20-40 parts of mixed solvent
0.2-0.6 of nucleating agent
1 to 5 reinforcing fibers
0.5 to 3 parts of thickening reinforcing agent
0.3-1.0% of antioxidant
0.1 to 0.5% of defoaming agent
1-2 parts of an antifreezing agent.
2. The nail-free glue according to claim 1, wherein: the hydrogenated thermoplastic styrene-butadiene rubber is at least one of hydrogenated styrene-butadiene-styrene rubber (SEBS) and hydrogenated styrene-isoprene-styrene rubber (SEPS), and the VA content of the ethylene-vinyl acetate copolymer is 40-80%.
3. The nail-free glue according to claim 1, wherein: the tackifying resin is at least one of poly-a-methyl styrene resin, hydrogenated terpene resin, hydrogenated petroleum resin, hydrogenated rosin glyceride and hydrogenated rosin pentaerythritol ester.
4. The nail-free glue according to claim 1, wherein: the mixed solvent comprises the following components in parts by weight: cyclohexane, 6# solvent gasoline, propyl acetate and ethanol = 1-3: 2-7: 1-3: 0-2.
5. The nail-free glue according to claim 1, wherein: the nucleating agent comprises the following components in parts by weight: 2. 2' -methylenebis (4, 6-tert-butylphenol) phosphine aluminum salt (NA-21): bis (P-methylbenzylidene) sorbitol (P-M-DBS) =1-4: 1-3.
6. The nail-free glue according to claim 1, wherein: the reinforcing fiber is prepared from 1-3mm polyethylene fiber: 1-2mm polyethylene fiber = 1-7: 1-6 by weight.
7. The nail-free glue according to claim 1, wherein: the thickening reinforcing agent is at least one of silicon dioxide and organic bentonite.
8. The nail-free glue according to claim 1, wherein: the antioxidant is at least one of antioxidant 1010, antioxidant 264 and antioxidant 1076.
9. The nail-free glue according to claim 1, wherein: the defoaming agent is tributyl phosphate.
10. The nail-free glue according to claim 1, wherein: the antifreezing agent is at least one of ethylene glycol monobutyl ether, propylene glycol monobutyl ether and dichloromethane.
11. The nail-free glue according to claim 1, wherein: the preparation method of the transparent nail-free glue for the foam comprises the following steps: according to the weight portion, adding amorphous alpha-olefin copolymer, hydrogenated thermoplastic styrene butadiene rubber, ethylene-vinyl acetate copolymer, nucleating agent and tackifying resin into a screw extruder, uniformly mixing, forming and tabletting, wherein the temperature of the screw extruder is controlled at 80-120 ℃; adding the formed tablet, the mixed solvent, the thickening reinforcing agent and the reinforcing fiber according to the weight part ratio, and stirring and dispersing uniformly; and adding an anti-aging agent, a defoaming agent and an antifreezing agent, uniformly dispersing, detecting to be qualified, and filtering to obtain the transparent nail-free glue for the foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910766847.3A CN112409955A (en) | 2019-08-20 | 2019-08-20 | Nail-free glue and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910766847.3A CN112409955A (en) | 2019-08-20 | 2019-08-20 | Nail-free glue and preparation method thereof |
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| CN112409955A true CN112409955A (en) | 2021-02-26 |
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| CN201910766847.3A Pending CN112409955A (en) | 2019-08-20 | 2019-08-20 | Nail-free glue and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851188A (en) * | 2022-11-21 | 2023-03-28 | 广州立邦涂料有限公司 | Solvent type nail-free glue and preparation method and application thereof |
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| CN103391981A (en) * | 2010-12-27 | 2013-11-13 | 汉高公司 | Hot melt adhesive |
| CN103709960A (en) * | 2013-12-21 | 2014-04-09 | 广东三和化工科技有限公司 | Nail-free rubber and preparation method thereof |
| CN104293244A (en) * | 2014-10-27 | 2015-01-21 | 广东三和化工科技有限公司 | Transparent nail-free glue and preparation method thereof |
| CN107987760A (en) * | 2017-11-15 | 2018-05-04 | 江门保实捷化工有限公司 | A kind of novel environment friendly adhesive and its preparation method and application |
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2019
- 2019-08-20 CN CN201910766847.3A patent/CN112409955A/en active Pending
Patent Citations (5)
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| US20110229721A1 (en) * | 2008-09-11 | 2011-09-22 | Lanxess Deutschland Gmbh | Hotmelt adhesives |
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| CN103709960A (en) * | 2013-12-21 | 2014-04-09 | 广东三和化工科技有限公司 | Nail-free rubber and preparation method thereof |
| CN104293244A (en) * | 2014-10-27 | 2015-01-21 | 广东三和化工科技有限公司 | Transparent nail-free glue and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115851188A (en) * | 2022-11-21 | 2023-03-28 | 广州立邦涂料有限公司 | Solvent type nail-free glue and preparation method and application thereof |
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