CN109385242A - A kind of epoxy gap filler and preparation method thereof - Google Patents
A kind of epoxy gap filler and preparation method thereof Download PDFInfo
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- CN109385242A CN109385242A CN201811276542.6A CN201811276542A CN109385242A CN 109385242 A CN109385242 A CN 109385242A CN 201811276542 A CN201811276542 A CN 201811276542A CN 109385242 A CN109385242 A CN 109385242A
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
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- Chemical & Material Sciences (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention provides a kind of epoxy gap filler and preparation method thereof, by selecting the gap filler product that is fabricated to of the raw materials such as epoxy resin high molecular polymer and nano inorganic filler and modified amine curing agent, the excellent resistance to ag(e)ing of the tridimensional network and nano inorganic material of comprehensive epoxy high molecular material crosslinking and close to the factors such as the linear expansion coefficient of stone lumber class solve existing pointing bad adhesion, it is not resistant to water bear dirty, cracking easy to fall off, color change colour the problems such as.Epoxy gap filler prepared by the present invention is the gap filler product with integrated functions such as joint filling, bonding, U.S. seams, which has the characteristics that water-fast resistance to soiling is good, adhesion strength is high, color is various, cure shrinkage is low, is affected by thermal expansion and contraction that small, ageing-resistant performance is good.
Description
Technical field
The present invention relates to a kind of gap fillers, and in particular to a kind of epoxy gap filler and preparation method thereof belongs to building decoration
Industry field.
Background technique
The stones lumber such as ceramic tile, artificial stone, marble, mosaic is commonly used to the ground in house, wall decoration.It is general
Form of construction work is to select the binding materials such as cement mortar, dry-hang glue, and the stones lumber such as ceramic tile, mosaic is pasted on ground, wall
On face.When paving gap then can be filled and led up with gap filler there are certain gap.Underfill materials are various in style, and superiority and inferiority is different,
It is mainly cement, sandstone, inorganic filler, macromolecule emulsion, the coagulated material that dispersible rubber powder is raw material preparation.Such joint filling
Agent material raw material is easy to get, water-fast resistance to soiling is poor, cure shrinkage is high, it is easy to crack fall off, anti-pollution waterproof it is bad.Occur in the recent period with
Epoxy resin, glitter powder be raw material preparation joint trimming agent, true porcelain cement, it is not aqueous, without volatile solvent, its it is hard as porcelain,
Color multiplicity；But the sides such as easily-deformable cracking, adhesion strength are low after the heat-resisting temperature tolerance of ageing-resistant, colloid, solidification for it, are easy discoloration
There is more problem in face.
Gap filler adhesion is strong, contraction is small, color pull-out capacity is strong, and the flexibility with Anti-cracking, decoration texture is good, compressive resistance
Wear-resistant, antimycotic feature, gap filler can perfectly repair cracking or the breakage of floor surface, and surface can also paint,
With good waterproofness.But from the selection of raw material and the preparation method and application of product analyze, and fill out in ceramic tile gap
In filling, its is water-fast resistance to soiling, resistance to ag(e)ing, heat-resisting temperature tolerance, caking property, keep color persistently etc. and still have it is improved must
It wants.Gap filler in the prior art there are bad adhesion, not resistant to water do not bear dirty, easily black that mouldy, color category is single, it is de- to be easy
Fall cracking, it is ageing-resistant it is poor, the disadvantages of.In addition, the compression shear strength of the gap filler product of the prior art is relatively low.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of epoxy gap filler and its preparation sides
Method, by selecting the raw materials such as epoxy resin high molecular polymer and nano inorganic filler and modified amine curing agent to be fabricated to
Gap filler product, excellent ageing-resistant of the tridimensional network and nano inorganic material of comprehensive epoxy high molecular material crosslinking
Property and the bad adhesion, not resistant to water resistance to that existing pointing is solved close to factors such as the linear expansion coefficients of stone lumber class
It is dirty, it is easy to fall off cracking, color discoloration the problems such as.Epoxy gap filler prepared by the present invention is with one such as joint filling, bonding, U.S. seams
Change function gap filler product, the product have water-fast resistance to soiling is good, adhesion strength is high, color is various, cure shrinkage is low, by
Expanding with heat and contract with cold influences feature small, that ageing-resistant performance is good.
The first embodiment provided according to the present invention provides a kind of epoxy gap filler.
A kind of epoxy gap filler, the epoxy gap filler include component A and B component, and wherein component A includes:
Aqueous epoxy resins 10-50 parts by weight, preferably 12-40 parts by weight, more preferably 15-30 parts by weight,
Nano inorganic filler 1-20 parts by weight, preferably 2-18 parts by weight, more preferably 3-15 parts by weight,
Glass microballoon 40-90 parts by weight, preferably 45-80 parts by weight, more preferably 50-70 parts by weight,
The first diluent I 0.1-10 parts by weight, preferably 0.5-8 parts by weight, more preferably 1-5 parts by weight,
Hollow glass micropearl 0.1-10 parts by weight, preferably 0.3-8 parts by weight, more preferably 0.5-5 parts by weight；
B component includes:
Curing agent 40-150 parts by weight, preferably 50-120 parts by weight, more preferably 60-100 parts by weight,
Promotor 0.1-10 parts by weight, preferably 0.5-8 parts by weight, more preferably 1-5 parts by weight,
Reactive diluent 1-20 parts by weight, preferably 3-18 parts by weight, more preferably 5-15 parts by weight,
Compared with low viscosity epoxy resin 1-40 parts by weight, preferably 3-30 parts by weight, more preferably 5-20 parts by weight,
Second of diluent II 0.1-40 parts by weight, preferably 0.5-30 parts by weight, more preferably 1-20 parts by weight.
Preferably, in component A further include:
Toughener 0.1-10 parts by weight, preferably 0.3-5 parts by weight, more preferably 0.5-3 parts by weight,
Ultraviolet absorbing agent 0.01-2 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.8 parts by weight,
Antioxidant 0.01-2 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.8 parts by weight,
Thixotropic agent 0.1-10 parts by weight, preferably 0.5-5 parts by weight, more preferably 1-3 parts by weight.
Preferably, in component A further include:
Silane coupling agent 0.5-10 parts by weight with guanidine salt group, preferably 1-8 parts by weight, more preferably 2-6 weight
Part.
The silane coupling agent with guanidine salt group is by silane coupling agent (such as γ-glycidyl ether oxygen third
Base trimethoxy silane) with guanidine salt (such as guanidine hydrochloride, guanidine phosphate or guanidine propionate) or polymerize guanidine salt (such as poly- six methylene
Base guanidine salt or cosmocil stearate, such as poly (hexamethylene) hydrochloride or hexamethylene) it is reacted
It is obtained.Generally, the dosage molar ratio of silane coupling agent and guanidine salt is 1-1.8:1, preferably 1.2-1.5:1.Especially, it polymerize
The reaction product of guanidine salt and silane can provide lasting anti-mildew performance for epoxy gap filler, existing at the same time it can also solve
The relatively low problem of the compression shear strength of the gap filler product of technology.
In the present invention, the aqueous epoxy resins are viscosity (cps/25 DEG C) having in>9000 to<13000 ranges
The epoxy resin of moderately viscous self-emulsifying type, preferably 128M type aqueous epoxy resins (national capital chemical industry (Kunshan) limited public affairs
Department).
In the present invention, the nano inorganic filler is nano-titanium dioxide, nano barium sulfate, nano aluminium oxide, He Na
One of rice silica, nanometer calcium carbonate are a variety of.
Preferably, the glass microballoon is calcining glass microballoon.
Preferably, being attached with inorganic pigment on glass microballoon.It is further preferred that the diameter of glass microballoon is 50-500
Mesh, preferably 100-400 mesh, more preferably 120-300 mesh.
In the present invention, the first diluent I is C12-C14 alkyl glycidyl ether, butyl glycidyl ether, ethylene glycol
Diglycidyl ether it is one or more.
Preferably, the specific gravity of the hollow glass micropearl is between 0.1-0.5, preferably specific gravity 0.12-0.4 it
Between, more preferably specific gravity is between 0.15-0.3.
Preferably, the curing agent includes polyethers amine hardener, polyamide curing agent and fatty amine curing agent.
Preferably, polyethers amine hardener additional amount is 20-80 parts by weight in B component, preferably 30-70 parts by weight, more
Preferably 35-60 parts by weight.
Preferably, the additional amount of polyamide curing agent is 10-60 parts by weight in B component, preferably 15-50 parts by weight,
More preferably 20-40 parts by weight.
Preferably, the additional amount of fatty amine curing agent is 1-20 parts by weight in B component, preferably 3-10 parts by weight, more
Preferably 5-10 parts by weight.
In the present invention, the reactive diluent is 2-glycidyl ethers reactive diluent, more preferably ethylene glycol two
Glycidol ether or diethylene glycol diglycidyl glycerin ether.
In the present invention, it is described compared with low viscosity epoxy resin be viscosity (cps/25 DEG C) in>6000 to<11000 ranges
Compared with the bisphenol A type epoxy resin or self-emulsification aqueous epoxy resin of low viscosity.
Preferably, second of diluent II is monofunctional diluent.Preferably benzyl alcohol.
Preferably, the polyethers amine hardener is D-230 and/or D-400.
Preferably, polyamide curing agent is 650 polyamide curing agents.
Preferably, fatty amine curing agent diethylenetriamine curing agent or triethylene tetramine curing agent.
Preferably, the promotor is DMP-30.
In the present invention, the toughener is carboxyl liquid nitrile rubber, polyethers, one in the different certain herbaceous plants with big flowers ester of phthalic acid two
Kind is a variety of.
In the present invention, the ultraviolet absorbing agent is one of UV-26, UV-245, UV-326, UV-328 or more
Kind.
In the present invention, the antioxidant is one of 1076,1010,1098 or a variety of.
In the present invention, the thixotropic agent is hydrophilic fumed silica, organic roc profit is native, any in auxiliary rheological agents
The mixture of kind and hydrophobicity aerosil.
Second of the embodiment provided according to the present invention provides a kind of preparation method of epoxy gap filler.
A kind of preparation method of epoxy gap filler or the method for preparing epoxy gap filler described in the first embodiment, should
Method the following steps are included:
(1) preparation of component A: in a kettle, aqueous epoxy resins, the first diluent I, toughener, ultraviolet are added
Light absorbers, antioxidant stir evenly (mixing time 5-60min, preferably 10-30min), and thixotropic agent is then added, receives
Rice inorganic filler, glass microballoon and the optional above-mentioned silane coupling agent with guanidine salt group are again stirring for uniform (mixing time
For 10-120min, preferably 20-60min), hollow glass micropearl is then added, continuously stirs (mixing time 20-
120min, preferably 30-60min), obtain component A；
(2) preparation of B component: will be uniform compared with low viscosity epoxy resin and second of diluent II mixture, it obtains lower
The mixture of viscosity epoxy and second of diluent II；In a kettle, reactive diluent and polyethers amine hardener is added,
It heats up (being preferably warming up to 40-80 DEG C, preferably 50-60 DEG C), and reaction a period of time (preferably reaction 0.5-4h, preferably
1-2h), fatty amine, polyamide curing agent, promotor is then added, reaction a period of time (preferably reacts 0.2-3h, preferably
0.5-2h), then reaction will be added by the way of being added dropwise compared with the mixture of low viscosity epoxy resin and second of diluent II
In kettle (time for adding 0.2-2h, preferably 0.5-1h), after being added dropwise, temperature of reaction kettle is kept (preferably lower than 70 DEG C
Lower than 65 DEG C), reaction a period of time (preferably reaction 1-6h, preferably 2-4h), obtain B component；
(3) preparation of epoxy gap filler: component A and B component are uniformly mixed, and obtain epoxy gap filler.
In this application, " optional " indicate to be with or without.
Preferably, reaction kettle is warming up to 50-100 DEG C and (is preferably risen after hollow glass micropearl is added in step (1)
Temperature is to 55-80 DEG C, and more preferably 60-70 DEG C), by activation processing (the processing time is 1-12h, preferably 2-10h), obtain A
Component.
Preferably, in step (3) weight ratio of component A and B component be 2-20:1, preferably 5-15:1, more preferably
7-12:1。
In the present invention, main improved formula is to use to consolidate with polyamide curing agent, polyethers amine hardener and fatty amine
The think of that the nano inorganic fillers such as modified aqueous epoxy curing agent and aqueous epoxy resins, glass microballoon be combined with each other based on agent
Road carries out formula design.Solidfied material, should using polyether chain as main chain (polyetheramine hardener dose is maximum) in the formula design system
Polymer is not easy easily to cause aging by factors such as ultraviolet light temperature, inhales in conjunction with a large amount of inorganic filler of addition and uvioresistant
It receives the mode that the auxiliary agents such as agent mutually compound and realizes that ageing-resistant performance is good.
In the present invention, adhesive strength height mainly works: chemistry occurs for aqueous epoxy resins and waterborne curing agent
Reaction, tridimensional network is formed from linearity molecular structure, other small-molecule substances are not generated in reaction process and without go from
Sub- water, so as to realizing adhesion strength height.In addition, fumed silica, nano inorganic filler, be added in resin have increase
The effect of reinforcement degree.
In the present invention, the main reason for cure shrinkage is low is: without deionized water, formula design in waterborne curing agent
It is low to can reach cure shrinkage without not generating other small-molecule substances when addition volatile organic solvent, reaction in scheme
State.
In the present invention, the main reason for small that is affected by thermal expansion and contraction, is: containing its master of a large amount of inorganic filler in product
Wanting ingredient is the materials such as silica, aluminium oxide, magnesia, is hardly affected by temperature, thus is influenced by expansion and contraction small.
In the present invention, the main reason for water-fast resistance to soiling is good is: its surface forms a kind of comparatively dense after product solidification
Tridimensional network, moisture impurity etc. be not easily accessible colloid internal structure and be readily cleaned, so that water-fast anti-pollution characteristic is good.
In a preferred embodiment of the invention, coupling agent uses the silane coupling agent with guanidine salt group.Described has guanidine
The silane coupling agent of salt groups is by silane coupling agent (such as γ-glycidyl ether oxygen propyl trimethoxy silicane) and guanidine salt
(such as guanidine hydrochloride, guanidine phosphate or guanidine propionate) or polymerization guanidine salt (such as poly (hexamethylene) or polyhexamethylene pair
Guanidine salt, such as poly (hexamethylene) hydrochloride or hexamethylene) it carries out reacting obtained.By using having
The silane coupling agent of guanidine salt group, the sterilization idiocratic of, low toxicity efficient using guanidine substance and wide spectrum, by the group modified coupling of guanidine salt
Agent is cleverly introduced into gap filler, is improved epoxy gap filler and is provided the anti-mildew performance of persistently (48 months or more).Meanwhile having
There is the silane coupling agent of guanidine salt group to be reacted with inorganic material and epoxy resin and also reacted with curing agent simultaneously,
Cross-linked structure is formed, the compression shear strength of gap filler product is improved.
In the present invention, the mechanism that the hydrophilic radicals such as more end oxygen hydroxyl are contained at strand both ends in B component be due to
Hydroxyl group and amino group in reactive diluent and curing agent are cross-linked to form the hydrophilic radicals such as end oxygen hydroxyl.Reactive diluent
It is reacted with curing agent such as polyetheramine, polyamide, fatty amines and forms the hydrophilic radicals such as end oxygen hydroxyl at curing agent both ends, compared with low viscosity
Epoxy resin and the adjustable proportion of benzyl alcohol reactive moieties wave hydrogen living and viscosity.
In the present invention, it is using the purpose of glass microballoon and hollow glass micropearl simultaneously in component A: using circular configuration
Glass microballoon and hollow glass micropearl, the resistance of its construction can be reduced convenient for constructing and increasing the additive amount of filler and can reduce
Cost.It reduces its construction resistance, facilitate construction, arrange in pairs or groups more after the more fine and close fine and smooth, construction in solidfied material surface can be made with ceramic tile
Beauty is coordinated.
In the present invention, it is using the purpose of reactive diluent and second of diluent II simultaneously in B component: activity dilution
Agent be in order to it is modified form end oxygen hydroxyl hydrophilic radical, second of diluent II is viscosity in order to adjust curing agent.Activity
Diluent is convenient for a large amount of alcoholic extract hydroxyl group of offer, formation end oxygen hydroxyl group to synthesize waterborne curing agent, second of diluent II
It is easy for adjusting waterborne curing agent viscosity, so as to form suitable Construction State.
In the present invention, the purpose being added in B component compared with low viscosity epoxy resin is: improving fatty amine, polyamide cure
The shock resistance of agent system and the proportion for adjusting product.Compared with low viscosity epoxy resin to the impact resistance side of waterborne curing agent
Face has castering action, convenient for adjusting the proportion of curing agent, so as to keeping the proportion design of product of product more flexible and
The impact strength of product is higher, is not easy embrittlement.
In the present invention, curing agent used in B component includes that polyethers amine hardener, polyamide curing agent and fatty amine are solid
Agent, the purpose is to: be used cooperatively using three kinds of curing agent, the mutual cooperation of three kinds of curing agent be easy for synthesis waterborne curing agent with
And the flexibility of adjustment curing agent speed and raising colloid.
In the present invention, thixotropic agent be hydrophilic fumed silica, organic roc profit soil, any one of auxiliary rheological agents with
The mixture of hydrophobicity aerosil, the purpose is to: prevent inorganic filler sedimentation, product can be made stable paste state,
It is not easy sagging when construction and facilitates construction.The phenomenon that product is not in collapsing and sagging when doing the wider ground in gap and metope.
In the present invention, in the preparation process of component A, in batches, the purpose being added in sequence is raw material: liquid is first added
Body material can be such that ultraviolet absorbing agent, antioxidant is more fully scattered in product, and being eventually adding hollow glass micropearl prevents sky
Heart glass is destructurized when stirring.First be added aqueous epoxy resins, the first diluent I, toughener, ultraviolet absorbing agent,
Then antioxidant is added thixotropic agent, nano inorganic filler, glass microballoon, then adds hollow glass micropearl.
In the present invention, in the preparation process of B component, in batches, the purpose being added in sequence is raw material: solid in order to make
There are more hydrophilic radical and the suitable curing rate of adjustment and viscosity state in agent.
It is now preferentially mixed compared with low viscosity epoxy resin and second of diluent II, the viscosity of its resin is reduced, after convenient
Face carries out dropwise addition work.Reactive diluent and polyethers amine hardener is added, fatty amine, polyamide curing agent, promotion is then added
Then agent will be added in reaction kettle by the way of being added dropwise compared with the mixture of low viscosity epoxy resin and second of diluent II.
In the present invention, in the preparation process of B component, temperature of reaction kettle is kept to be lower than 70 DEG C (preferably less than 65 DEG C)
Purpose is: prevent reaction during temperature it is excessively high cause curing agent colour changed into yellow deepen, make epoxy gap filler when color hold
Easily deepen.
A, two component of B is uniformly mixed using preceding ratio by weight, can be used for the gap fillings such as ceramic tile, stone material, mosaic
And mosaic, the paving of ceramic tile and bonding purposes in interior decoration, method mechanically or manually is full by gap filling,
Remaining material washes with water before glue is not dry on substrate, at room temperature 2-8 hours i.e. just solidification, in 24-96 hours
Realization is fully cured, and allows gap to have more aesthetic appearance in decoration indoors, makes the interior space more environmentally friendly.
In the present invention, raw materials used source is as follows:
Compared with prior art, epoxy gap filler prepared by the present invention has following advantageous effects:
1, the present invention with the fillers such as moderately viscous Self-Emulsified Epoxy and nano inorganic filler, glass microballoon and
The mode that modified amine curing agent combines produce with can scrub water, resistant bear dirty, not easy to crack fall off, be ageing-resistant
Epoxy gap filler；
2, epoxy gap filler prepared by the present invention is by selecting epoxy resin high molecular polymer and nano inorganic filler
And the gap filler product that the raw materials such as modified amine curing agent are fabricated to, combine the three-dimensional netted of epoxy high molecular material crosslinking
Structure and nano inorganic material excellent properties；
3, epoxy gap filler prepared by the present invention have preferable adhesive property, water-fast anti-pollution characteristic, do not black it is mouldy, resistance to
Warm heat resistance keeps color durability, ageing-resistant performance, cracking will not be caused to fall off because expanding with heat and contract with cold, easy to clean and apply
The features such as work is simple.
Specific embodiment
The present invention is described in further detail technical solution by following examples, but the present invention is not restricted to these implement
Example.
Preparation example 1
Hexamethylene (the limited public affairs of industry of upper seamount for being 800 by the viscosity average molecular weigh of 2 parts by weight
Department, PHMB) it is dissolved at 40 DEG C in the tetrahydrofuran of 5.5 parts by weight, obtain guanidinium solution.By γ-shrink of 2.5 parts by weight
Glycerol ether oxygen propyl trimethoxy silicane is dissolved in the tetrahydrofuran of 3 parts by weight, obtains solution of silane.Two kinds of solution are added
It is mixed into reactor, then heats the mixture to 76 DEG C, be stirred to react 3 hours；After reaction, reaction is mixed
Solvent in object removes under reduced pressure, obtains the liquid silane coupling agent product with guanidine salt group, viscosity (25 DEG C,
It cps) is 1570.
Embodiment 1
A kind of epoxy gap filler, the epoxy gap filler include component A and B component, and wherein component A includes: that 128M type is aqueous
Epoxy resin (national capital chemical industry (Kunshan) Co., Ltd) 35 parts by weight, 10 parts by weight of nano barium sulfate, 8 weight of nano silica
Part, calcine 75 parts by weight of glass microballoon, 6 parts by weight of ethylene glycol diglycidylether, 6 parts by weight of hollow glass micropearl；Carboxyl liquid
2 parts by weight of body nitrile rubber, 0.5 parts by weight of UV-26 (BASF), 1076 (BASF) 0.5 parts by weight, hydrophilic gas phase dioxy
2 parts by weight of mixture of SiClx and hydrophobicity aerosil；Wherein: inorganic pigment is attached on glass microballoon, glass is micro-
The diameter of pearl be 200 mesh, the specific gravity of hollow glass micropearl between 0.15-0.3,
B component includes: 60 parts by weight of D-400 (Hensel is graceful), 650 polyamide curing agent, 12 parts by weight, and triethylene tetramine is solid
12 parts by weight of agent, 3 parts by weight of DMP-30 (BASF), 10 parts by weight of diethylene glycol diglycidyl glycerin ether, bisphenol type epoxy tree
Rouge (South Asia company NPEL 127, viscosity (cps/25 DEG C) is in>6000 to<11000 ranges) 12 parts by weight, 10 weight of benzyl alcohol
Part.
Embodiment 2
A kind of preparation method of epoxy gap filler, method includes the following steps:
(1) preparation of component A: in a kettle, 40g 128M type aqueous epoxy resins (national capital chemical industry), 6g butyl is added
Glycidol ether, 4g carboxyl liquid nitrile rubber, 1g UV-26,1076 1g, stir evenly, and 4g hydrophilic gas phase is then added
Silica and the mixture of hydrophobicity aerosil, 24g nano-titanium dioxide, 120g calcine glass microballoon, stir again
It mixes uniformly, then adds 6g hollow glass micropearl, continuously stir, obtain component A；
(2) preparation of B component: by 24g bisphenol A type epoxy resin, (South Asia company NPEL 127, viscosity (cps/25 DEG C) exist
>6000 to<11000 ranges) and 20g benzyl alcohol mixture it is uniform, obtain the mixture of bisphenol A type epoxy resin and benzyl alcohol；
In a kettle, 20g ethylene glycol diglycidylether and 80g D-230 (Hensel is graceful) is added, 55 DEG C are warming up to, when reacting one section
Between, 650 polyamide curing agent of 40g, 40g diethylenetriamine curing agent, 6g DMP-30 (BASF) is then added, reacts one section
Then time adds the mixture of bisphenol A type epoxy resin (South Asia company NPEL 127) and benzyl alcohol by the way of being added dropwise
Enter in reaction kettle, after being added dropwise, keeps temperature of reaction kettle to be lower than 70 DEG C, reaction a period of time, obtain B component；
(3) preparation of epoxy gap filler: component A and B component are uniformly mixed according to the ratio that weight ratio is 6:1,
Obtain epoxy gap filler.
Embodiment 3
A kind of preparation method of epoxy gap filler, method includes the following steps:
(1) preparation of component A: in a kettle, 70g 128M type aqueous epoxy resins (national capital chemical industry), 12g second is added
Hexanediol diglycidyl ether, 4g carboxyl liquid nitrile rubber, 1g UV-26,1076 1g, stir evenly, mixing time is
Then mixture, the 20g nano barium sulfate of 4g hydrophilic fumed silica and hydrophobicity aerosil is added in 20min
10 parts by weight, 16g nano silica, 150g calcine glass microballoon, are again stirring for uniformly, mixing time 40min, then again
12g hollow glass micropearl is added, continuously stirs 40min, obtains component A；
(2) preparation of B component: by 24g bisphenol A type epoxy resin, (South Asia company NPEL 127, viscosity (cps/25 DEG C) exist
>6000 to<11000 ranges) and 20g benzyl alcohol mixture it is uniform, obtain bisphenol A type epoxy resin (South Asia company NPEL 127)
With the mixture of benzyl alcohol；In a kettle, 20g diethylene glycol diglycidyl glycerin ether and 120g D-400 (Hensel is graceful) is added,
60 DEG C are warming up to, 1.5h is reacted, 650 polyamide curing agent of 24g, 24g triethylene tetramine curing agent, 6g DMP-30 is then added
(BASF) reacts 1h, then by the mixture of bisphenol A type epoxy resin (South Asia company NPEL 127) and benzyl alcohol using drop
The mode added is added in reaction kettle, time for adding 1h, after being added dropwise, temperature of reaction kettle is kept to be lower than 65 DEG C, reacts 3h, obtain
Obtain B component；
(3) preparation of epoxy gap filler: component A and B component are uniformly mixed according to the ratio that weight ratio is 10:1,
Obtain epoxy gap filler.
Embodiment 4
A kind of preparation method of epoxy gap filler, method includes the following steps:
(1) preparation of component A: in a kettle, 40g 128M type aqueous epoxy resins (national capital chemical industry), 5g second two is added
Alcohol diglycidyl ether, 2g carboxyl liquid nitrile rubber, 0.8g UV-26,1076 0.8g, stir evenly, mixing time is
Then mixture, the 8g nano aluminium oxide of 2g organic roc profit soil and hydrophobicity aerosil, 6g nanometer two is added in 10min
Silica, 85g calcine glass microballoon, are again stirring for uniformly, then mixing time 30min adds 2g hollow glass micropearl,
20min is continuously stirred, component A is obtained；
(2) preparation of B component: by 6g bisphenol A type epoxy resin (South Asia company NPEL 127, viscosity (cps/25 DEG C) >
6000 to < 11000 ranges) and 3g benzyl alcohol mixture it is uniform, obtain bisphenol A type epoxy resin (South Asia company NPEL 127) and
The mixture of benzyl alcohol；In a kettle, 12g diethylene glycol diglycidyl glycerin ether and 40g D-400 is added, is warming up to 65 DEG C,
1h is reacted, 650 polyamide curing agent of 18g, 8g triethylene tetramine curing agent, 2g DMP-30 is then added, reacts 0.5h, then
Reaction kettle is added by the way of being added dropwise in the mixture of bisphenol A type epoxy resin (South Asia company NPEL 127) and benzyl alcohol
In, time for adding 0.5h after being added dropwise, keeps temperature of reaction kettle to be lower than 65 DEG C, reacts 2h, obtains B component；
(3) preparation of epoxy gap filler: component A and B component are uniformly mixed according to the ratio that weight ratio is 8:1,
Obtain epoxy gap filler.
Embodiment 5 (the preferred solution of the invention)
Embodiment 4 is repeated, only when preparing component A, after 85g calcining glass microballoon is added, is and then additionally added
The silane coupling agent product with guanidine salt group of the preparation example 1 of 6g.
The epoxy gap filler that embodiment 2-5 is prepared is tested for the property, as a result as follows:
As can be seen from the above table, the silane coupling agent with guanidine salt group can be improved the compression shear strength of gap filler.Especially
It is to polymerize guanidine salt and the reaction product of silane to provide the anti-mildew denaturation of lasting (48 months or more) for epoxy gap filler
Energy.
The present invention solidifies with the fillers such as Self-Emulsified Epoxy and nano inorganic filler, glass microballoon and modified amine
The mode that agent combines produce with can scrub water, resistant bear dirty, it is not easy to crack fall off, ageing-resistant epoxy gap filler；
By selecting the raw materials such as epoxy resin high molecular polymer and nano inorganic filler and modified amine curing agent to be fabricated to
Gap filler product combines the tridimensional network and nano inorganic material excellent properties of the crosslinking of epoxy high molecular material；Preparation
Epoxy gap filler have preferable adhesive property, water-fast anti-pollution characteristic, mouldy, the heatproof heat resistance that do not black, keep color
The features such as persistence, will not cause cracking to fall off at ageing-resistant performance because expanding with heat and contract with cold, easy to clean and construction is simple.
Claims (10)
1. a kind of epoxy gap filler, which includes component A and B component, and wherein component A includes:
Aqueous epoxy resins 10-50 parts by weight, preferably 12-40 parts by weight, more preferably 15-30 parts by weight,
Nano inorganic filler 1-20 parts by weight, preferably 2-18 parts by weight, more preferably 3-15 parts by weight,
Glass microballoon 40-90 parts by weight, preferably 45-80 parts by weight, more preferably 50-70 parts by weight,
The first diluent I 0.1-10 parts by weight, preferably 0.5-8 parts by weight, more preferably 1-5 parts by weight,
Hollow glass micropearl 0.1-10 parts by weight, preferably 0.3-8 parts by weight, more preferably 0.5-5 parts by weight；
B component includes:
Curing agent 40-150 parts by weight, preferably 50-120 parts by weight, more preferably 60-100 parts by weight,
Promotor 0.1-10 parts by weight, preferably 0.5-8 parts by weight, more preferably 1-5 parts by weight,
Reactive diluent 1-20 parts by weight, preferably 3-18 parts by weight, more preferably 5-15 parts by weight,
Compared with low viscosity epoxy resin 1-40 parts by weight, preferably 3-30 parts by weight, more preferably 5-20 parts by weight,
Second of diluent II 0.1-40 parts by weight, preferably 0.5-30 parts by weight, more preferably 1-20 parts by weight.
2. epoxy gap filler according to claim 1, it is characterised in that: in component A further include:
Toughener 0.1-10 parts by weight, preferably 0.3-5 parts by weight, more preferably 0.5-3 parts by weight,
Ultraviolet absorbing agent 0.01-2 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.8 parts by weight,
Antioxidant 0.01-2 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.8 parts by weight,
Thixotropic agent 0.1-10 parts by weight, preferably 0.5-5 parts by weight, more preferably 1-3 parts by weight；
Preferably, in component A further include:
Silane coupling agent 0.5-10 parts by weight with guanidine salt group, preferably 1-8 parts by weight, more preferably 2-6 parts by weight.
3. epoxy gap filler according to claim 1 or 2, it is characterised in that: the aqueous epoxy resins are viscosity (cps/
25 DEG C) in the epoxy resin with moderately viscous self-emulsifying type of>9000 to<13000 ranges, preferably 128M type is aqueous
Epoxy resin；And/or
The nano inorganic filler is nano-titanium dioxide, nano barium sulfate, nano aluminium oxide and nano silica, nanometer
Calcium carbonate it is one or more；And/or
Silane coupling agent with guanidine salt group is to carry out reacting obtained with guanidine salt or polymerization guanidine salt by silane coupling agent
Coupling agent.
4. epoxy gap filler according to any one of claim 1-3, it is characterised in that: the glass microballoon is calcining glass
Glass microballon；Preferably, being attached with inorganic pigment on glass microballoon；It is further preferred that the diameter of glass microballoon is 50-500 mesh,
Preferably 100-400 mesh, more preferably 120-300 mesh；And/or
The first diluent I is C12-C14 alkyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidylether
It is one or more.
5. epoxy gap filler described in any one of -4 according to claim 1, it is characterised in that: the ratio of the hollow glass micropearl
It focuses between 0.1-0.5, preferably specific gravity is between 0.12-0.4, and more preferably specific gravity is between 0.15-0.3；And/or
The curing agent includes polyethers amine hardener, polyamide curing agent and fatty amine curing agent；Preferably, gathering in B component
Ether amines curing agent additional amount is 20-80 parts by weight, preferably 30-70 parts by weight, more preferably 35-60 parts by weight；Gather in B component
The additional amount of amide hardener is 10-60 parts by weight, preferably 15-50 parts by weight, more preferably 20-40 parts by weight；In B component
The additional amount of fatty amine curing agent is 1-20 parts by weight, preferably 3-10 parts by weight, more preferably 5-10 parts by weight.
6. epoxy gap filler according to any one of claims 1-5, it is characterised in that: the reactive diluent is two contractings
Water glycerol ethers reactive diluent, more preferably ethylene glycol diglycidylether or diethylene glycol diglycidyl glycerin ether；And/or
It is described compared with low viscosity epoxy resin be the relatively low viscosity of viscosity (cps/25 DEG C) in>6000 to<11000 ranges bisphenol-A
Type epoxy resin or self-emulsification aqueous epoxy resin；And/or
Second of diluent II is monofunctional diluent, preferably benzyl alcohol.
7. epoxy gap filler according to claim 5, it is characterised in that: the polyethers amine hardener is D-230 and/or D-
400；Polyamide curing agent is 650 polyamide curing agents；Fatty amine curing agent diethylenetriamine curing agent or triethylene tetramine are solid
Agent；And/or
The promotor is DMP-30.
8. the epoxy gap filler according to any one of claim 2-7, it is characterised in that: the toughener is carboxyl liquid
One of nitrile rubber, polyethers, the different certain herbaceous plants with big flowers ester of phthalic acid two are a variety of；And/or
The ultraviolet absorbing agent is one of UV-26, UV-245, UV-326, UV-328 or a variety of；And/or
The antioxidant is one of 1076,1010,1098 or a variety of；And/or
The thixotropic agent is any one of hydrophilic fumed silica, organic roc profit soil, auxiliary rheological agents and hydrophobicity gas phase
The mixture of silica.
9. the method for epoxy gap filler described in any one of a kind of preparation method of epoxy gap filler or preparation claim 1-8,
Method includes the following steps:
(1) preparation of component A: in a kettle, aqueous epoxy resins, the first diluent I, toughener, ultraviolet light is added and inhales
Agent, antioxidant are received, (mixing time 5-60min, preferably 10-30min) is stirred evenly, thixotropic agent, nanometer nothing is then added
Machine filler, glass microballoon and the optional silane coupling agent with guanidine salt group are again stirring for uniform (mixing time 10-
120min, preferably 20-60min), hollow glass micropearl is then added, continuously stir (mixing time 20-120min, it is excellent
It is selected as 30-60min), obtain component A；
(2) preparation of B component: will be uniformly mixed compared with low viscosity epoxy resin and second of diluent II, obtain epoxy resin and
The mixture of second of diluent II；In a kettle, reactive diluent and polyethers amine hardener is added, heating (preferably rises
Temperature is to 40-80 DEG C, and preferably 50-60 DEG C), reaction a period of time (preferably reaction 0.5-4h, preferably 1-2h), then it is added
Fatty amine, polyamide curing agent, promotor, then will at reaction a period of time (preferably reaction 0.2-3h, preferably 0.5-2h)
The mixture of epoxy resin and second of diluent II use be added dropwise mode be added in reaction kettle (time for adding 0.2-2h,
Preferably 0.5-1h), after being added dropwise, keep temperature of reaction kettle to be lower than 70 DEG C (preferably less than 65 DEG C), reaction a period of time
(preferably reaction 1-6h, preferably 2-4h), obtains B component；
(3) preparation of epoxy gap filler: component A and B component are uniformly mixed, and obtain epoxy gap filler.
10. according to the method described in claim 9, it is characterized by: will be reacted after hollow glass micropearl is added in step (1)
Kettle is warming up to 50-100 DEG C (being preferably warming up to 55-80 DEG C, more preferably 60-70 DEG C), by activation processing (processing the time be
1-12h, preferably 2-10h), obtain component A；And/or
The weight ratio of component A and B component is 2-20:1, preferably 5-15:1, more preferably 7-12:1 in step (3).
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| CN110723927A (en) * | 2019-10-31 | 2020-01-24 | 栗金超 | Epoxy color bead gap filler, preparation method and construction method |
| CN110819283A (en) * | 2019-12-12 | 2020-02-21 | 湖南柯盛新材料有限公司 | Multi-component sealant and preparation method thereof |
| CN111004599A (en) * | 2019-12-13 | 2020-04-14 | 西安鑫垚陶瓷复合材料有限公司 | Method for filling local gap of ceramic matrix composite material after assembly |
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| CN106700992A (en) * | 2015-11-17 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Underwater curing high-performance epoxy anchoring glue as well as preparation method and application of underwater curing high-performance epoxy anchoring glue |
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| CN110819283A (en) * | 2019-12-12 | 2020-02-21 | 湖南柯盛新材料有限公司 | Multi-component sealant and preparation method thereof |
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| WO2022166825A1 (en) * | 2021-02-08 | 2022-08-11 | Sika技术股份公司 | Curable epoxy resin composition |
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