CN108249821A - A kind of composition and its application for being used to improve artificial shell stone patterns and glossiness - Google Patents
A kind of composition and its application for being used to improve artificial shell stone patterns and glossiness Download PDFInfo
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- CN108249821A CN108249821A CN201810074233.4A CN201810074233A CN108249821A CN 108249821 A CN108249821 A CN 108249821A CN 201810074233 A CN201810074233 A CN 201810074233A CN 108249821 A CN108249821 A CN 108249821A
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- artificial stone
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- stone
- reaction kettle
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a kind of for improving artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:1 resin and Al (OH)3, further include intermediate temperature curing agent that dosage is weight resin 0.5% 1.5% and dosage be 0.5% 1.5% aerosil of weight resin.It is applied the invention also discloses described for improving the composition of artificial shell stone patterns and glossiness in artificial stone and the multifarious artificial stone of a kind of decorative pattern and preparation method thereof.Composition of the present invention is used to be added dropwise in artificial stone raw materials during artificial stone stirs curing molding, using forming different patterns in the artificial stone of cured time difference and temperature difference after hardening, the glossiness of artificial stone is improved, meets the diversified demand of artificial stone.
Description
Technical field
The present invention relates to artificial stone technical fields, are used to improve artificial shell stone patterns and gloss more specifically to one kind
The composition of degree and its application.
Background technology
In building fills sulphur decoration industry, natural marble was once noble luxurious and fashionable in the world with it, but there is also with
Lower insufficient and fatal weakness one is that natural marble belongs to a kind of mineral resources, and the place of production is not many in the world, and
And limits throughput is second is that natural marble rigidity is had a surplus, intensity is insufficient, therefore it is easily broken, damage, cause transport and daily
The difficulty three of maintenance be scientific research in recent years find, natural marble have certain radiativity, can be detrimental to health and
Pollute environment.These reasons are limited by very large its application.So in order to adapt to the demand in market and scientific development,
People switch in the direction of research using waste resource or other low price raw materials, the artificial board that development cost is low, simple for process,
I.e. with certain adhesive, additive and coarse-fine aggregate through certain technical process the manufactured dress with natural marble figue
Exterior material.
After solid surface artificial marble (being commonly called as artificial stone) is developed successfully from the sixties in the U.S., due to defending
Life, style, processing, beauty (can be achieved seamless spliced) etc. have natural marble and incomparable superior of other materials
Property, therefore paid close attention at the very start by market.By the development of more than 30 years and perfect, series of products have been formed.By original used
Material resin if distinguishing, can be divided into following two class：One kind is the artificial stone for adhesives with unsaturated-resin (UPR)
(domestic at present most for this kind of product absolutely).Another kind of is the people with acrylic acid modified resin (Acrylic) for adhesives
Stone is made, there is ultraviolet resistance, can (be with the U.S. " Du Pont's Corian ", South Korea's " Samsung " the features such as arbitrary bending moulding after heated
Main representative).
Using unsaturated-resin as main adhesives, aluminium powder is artificial stone made of main packing material, in forming process
In, using room temperature spontaneous curing, then the cured technique after 80 DEG C.The method condition of molding is simple, and equipment investment is few, during production
With the difference of season temperature, by adjusting the dosage of accelerating agent, curing agent come control solidification time.But obtained artificial stone
Decorative pattern is single, and glossiness, which is difficult to meet, uses diversified requirement.
Invention content
For the drawbacks described above of the prior art, the purpose of the present invention is to provide one kind for improving artificial shell stone patterns and light
The composition of damp degree, the composition are used to be added dropwise in artificial stone raw materials during artificial stone stirs curing molding, utilize
Different patterns is formed in the artificial stone of cured time difference and temperature difference after hardening, improves the glossiness of artificial stone, is met
The diversified demand of artificial stone.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of to be used to improve artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:1 resin
With Al (OH)3, it is weight resin 0.5%- to further include intermediate temperature curing agent that dosage is weight resin 0.5%-1.5% and dosage
1.5% aerosil.
As further embodiment, resin of the present invention is UPR resins or modified unsaturated resin.
As further embodiment, the raw material for preparing the modified unsaturated resin includes the cis-butene as acid starting material
Dicarboxylic anhydride and phthalic acid, as the propylene glycol of raw polyol, diethylene glycol and trimethylolpropane；Wherein acid-alcohol ratio is 1：
Mole total amount of (1-1.2), propylene glycol and diethylene glycol and the molar ratio of trihydroxy methyl are (0.75-0.95)：0.1；It further includes
Styrene and α-methylstyrene and polymerization inhibitor, the styrene dosage are acid starting material and the 30%- of raw polyol gross mass
33%, α-methylstyrene dosage is acid starting material and the 2%-6% of raw polyol gross mass, and the polymerization inhibitor is 0.01-0.05%；
The modified unsaturated resin is prepared by the following method：
Step of esterification：After nitrogen is passed through in reaction kettle, according to proportioning by cis-1 and adjacent benzene two
Formic acid is added in reaction kettle, is added to instead by pipeline after then mixing propylene glycol, diethylene glycol and trimethylolpropane
It answers in kettle, reaction kettle is heated using 220-240 DEG C of conduction oil, started during reactor temperature is raised anti-
The agitating paddle of kettle is answered to be stirred reaction to material, while control heating temperature, when the temperature of charge in reaction kettle reaches 160 DEG C
When, insulation reaction 1-2 hours stops heating after the reaction was complete, obtains carboxylate；
Modified-reaction step：Styrene and α-methylstyrene are added to by pipeline has used nitrogen or vacuumize process
In thinning vessel afterwards, polymerization inhibitor is added in；When above-mentioned carboxylate is cooled to 140-150 DEG C, with negative pressure by the carboxylate of reaction kettle
It is added slowly in thinning vessel, controls the temperature of thinning vessel at 85 DEG C hereinafter, material to the material in stirring thinning vessel is cooled to
48 DEG C hereinafter, obtain semi-finished product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
As further embodiment, intermediate temperature curing agent of the present invention is TBPO, 2-methylimidazole, 2- ethyl -4- first
One kind in base imidazoles.
Another object of the present invention is to provide a kind of composition for being used to improve artificial shell stone patterns and glossiness manufacturing
Application in artificial stone.
A kind of application of composition of the present invention in artificial stone is prepared.
Third object of the present invention is to provide a kind of decorative pattern multifarious artificial stone, which includes above-mentioned be used for
Improve artificial shell stone patterns and the composition of glossiness.
A kind of multifarious artificial stone of decorative pattern, the raw material for preparing the artificial stone include composition of the present invention and people
Stone raw material is made, wherein the mass ratio of composition of the present invention and artificial stone raw materials is (0.2-0.8):1；It is wherein described artificial
Stone raw material is included by percentage to the quality
UPR resins：30%-50%,
Filler：40%-62%,
Curing agent：0.1%-0.5%,
Accelerating agent：0.05%-0.1%
Mill base：5%-10%.
As further embodiment, filler of the present invention is Al (OH)3Or Al (OH)3With CaCO3, MgO, short glass fiber
The mixed fillers of one or more of dimension, cenosphere.
As further embodiment, curing agent of the present invention is MEKP, and accelerating agent is the aphthenic acids containing potassium ion
One kind in cobalt liquor, cobalt octoate solution and cobalt iso-octoate solution.
Fourth object of the present invention is to provide a kind of preparation method of the multifarious artificial stone of decorative pattern, by artificial
It is added dropwise above-mentioned for improving artificial shell stone patterns and the composition of glossiness during stone stirring curing molding, it is more to obtain decorative pattern
Sample, the high artificial stone of glossiness.
A kind of preparation method of artificial stone, including
The step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymerization vacuumized
In kettle, accelerating agent is then added in, is stirred under vacuum, after above-mentioned raw materials stir evenly, this is added dropwise into polymeric kettle in whipping process
The invention composition, treats that the temperature of reaction kettle no longer increases, and stops stirring, after excluding bubble, obtains mixture；
Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, will be mixed with scraper
Material strikes off, and then allows its natural levelling, and the mold for mixture of having cast is sent into vacuum tank, is vacuumized again, after taking-up
It stands, obtains molding artificial stone's semi-finished product；
Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, be placed on reshaping frame after demoulding, be put into drying chamber into
Row curing, obtains artificial stone；
Post-processing step：The above-mentioned irregular part of artificial stone's upper and lower surface is cut off, then using polishing, polish it
Afterwards, artificial stone is obtained.
As further embodiment, the vacuum degree of polymeric kettle of the present invention is 0.09-0.095MPa, and polymerization temperature is
55-80℃；In the curing schedule, first cure 1-2 hours at 52-65 DEG C in drying chamber, then heat to 78-85 DEG C of curing 1-
2 hours.
Compared with prior art, the invention has the advantages that：
1. of the present invention be used to stir curing in artificial stone for improving the composition of artificial shell stone patterns and glossiness
It is added dropwise in artificial stone raw materials during molding, using being formed in the artificial stone of cured time difference and temperature difference after hardening
Different patterns improves the glossiness of artificial stone, meets the diversified demand of artificial stone；
2. artificial stone of the present invention passes through composition by the way that composition of the present invention is added dropwise in preparation process
Time difference and temperature difference between artificial stone raw materials, artificial stone mixture composition in whipping process flow wherein, root
Multiple patterns and decorative pattern can be formed according to the difference of mixing speed, the artificial stone of different pattern and decorative pattern can be obtained.
Specific embodiment
In the following, with reference to specific embodiment, the present invention is described further：
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is the normal of this field unless otherwise instructed
Rule method.
Of the present invention to be used to improve artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:
1 resin and Al (OH)3, it is weight resin to further include intermediate temperature curing agent that dosage is weight resin 0.5%-1.5% and dosage
0.5%-1.5% aerosils.In this scenario, the composition adds in during artificial stone raw materials mixed polymerization,
Due to the temperature difference during artificial stone raw materials mixed polymerization and time difference, by the way that mixing speed is controlled to unify to obtain different figures
The artificial stone of case and decorative pattern meets the multifarious demand of artificial stone, while achievees the purpose that improve artificial stone performance.
As further embodiment, resin of the present invention is UPR resins or modified unsaturated resin；Can also be existing
Somebody makes other unsaturated-resins in stone raw material, can also be the resin identical with resin used in artificial stone.Selection
The purpose of resin between the resin in energy and artificial stone in addition to having good compatibility, it is also contemplated that its flowing in the composition
Property.
In specific embodiment of the present invention, it is preferred that the raw material for preparing the modified unsaturated resin includes conduct
The cis-1 and phthalic acid of acid starting material, as the propylene glycol of raw polyol, diethylene glycol and trimethylolpropane；
Wherein acid-alcohol ratio is 1：Mole total amount of (1-1.2), propylene glycol and diethylene glycol and the molar ratio of trihydroxy methyl are (0.75-
0.95)：0.1；Styrene and α-methylstyrene and polymerization inhibitor are further included, the styrene dosage is acid starting material and raw polyol
The 30%-33% of gross mass, 2%-6% of the α-methylstyrene dosage for acid starting material and raw polyol gross mass, the polymerization inhibitor
For 0.01-0.05%；
The modified unsaturated resin is prepared by the following method：
Step of esterification：After nitrogen is passed through in reaction kettle, according to proportioning by cis-1 and adjacent benzene two
Formic acid is added in reaction kettle, is added to instead by pipeline after then mixing propylene glycol, diethylene glycol and trimethylolpropane
It answers in kettle, reaction kettle is heated using 220-240 DEG C of conduction oil, started during reactor temperature is raised anti-
The agitating paddle of kettle is answered to be stirred reaction to material, while control heating temperature, when the temperature of charge in reaction kettle reaches 160 DEG C
When, insulation reaction 1-2 hours stops heating after the reaction was complete, obtains carboxylate；
Modified-reaction step：Styrene and α-methylstyrene are added to by pipeline has used nitrogen or vacuumize process
In thinning vessel afterwards, polymerization inhibitor is added in；When above-mentioned carboxylate is cooled to 140-150 DEG C, with negative pressure by the carboxylate of reaction kettle
It is added slowly in thinning vessel, controls the temperature of thinning vessel at 85 DEG C hereinafter, material to the material in stirring thinning vessel is cooled to
48 DEG C hereinafter, obtain semi-finished product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
In the present invention, in order to make composition and artificial stone raw materials polymerize and solidification process in form certain temperature difference
With the cured time difference, while ensure the safety used, this hair composition is using intermediate temperature curing agent, as further
Scheme, intermediate temperature curing agent of the present invention is TBPO, 2-methylimidazole, one kind in 2-ethyl-4-methylimidazole.Separately
Outside, in the present invention, it is carried while aerosil can improve transparency, intensity, toughness and the glossiness of artificial stone
The compactness of high artificial stone.
Another object of the present invention is to provide a kind of composition for being used to improve artificial shell stone patterns and glossiness manufacturing
Application in artificial stone.
A kind of application of composition of the present invention in artificial stone is prepared.
Third object of the present invention is to provide a kind of decorative pattern multifarious artificial stone, which includes above-mentioned be used for
Improve artificial shell stone patterns and the composition of glossiness.
A kind of multifarious artificial stone of decorative pattern, the raw material for preparing the artificial stone include composition of the present invention and people
Stone raw material is made, wherein the mass ratio of composition of the present invention and artificial stone raw materials is (0.2-0.8):1；It is wherein described artificial
Stone raw material is included by percentage to the quality
UPR resins：30%-50%,
Filler：40%-62%,
Curing agent：0.1%-0.5%,
Accelerating agent：0.05%-0.1%
Mill base：5%-10%.
In specific embodiment, it is preferred that filler of the present invention is Al (OH)3Or Al (OH)3With CaCO3、MgO、
The mixed fillers of one or more of short glass fibre, cenosphere.Al (OH) is included in filler3, Al (OH)3Using grain
It spends for 200-230 mesh powders, because product water resistance and resistance to soiling that aluminium hydroxide powder as filler is manufactured are good, has good
Flame retardant property and comparatively ideal proportion, and the texture with jade.In addition, in the present invention, the oil resistant of obtained artificial stone
It is influenced by aluminium hydroxide dosage and granularity thickness with durability against pollution, when the dosage of aluminium hydroxide is too low, granularity is excessively thick, can all be led
Its durability against pollution and fuel tolerance capability is caused to reduce.
As further embodiment, curing agent of the present invention is MEKP (methyl ethyl ketone peroxide), and the accelerating agent is
One kind in cobalt naphthenate solution, cobalt octoate solution and cobalt iso-octoate solution containing potassium ion.In the present invention, the promotion
Contain potassium ion in agent, since potassium ion is instead of part cobalt ions, hence it is evident that reduce the coloring effect of cobalt ions, while potassium from
The addition of son can shorten UPR gel times, reduce accelerator dosage.Preferably, in accelerating agent potassium ion and cobalt ions it is dense
Degree is than being (1.8-2)：1.
Fourth object of the present invention is to provide a kind of preparation method of the multifarious artificial stone of decorative pattern, by artificial
It is added dropwise above-mentioned for improving artificial shell stone patterns and the composition of glossiness during stone stirring curing molding, it is more to obtain decorative pattern
Sample, the high artificial stone of glossiness.
A kind of preparation method of artificial stone, including
The step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymerization vacuumized
In kettle, accelerating agent is then added in, is stirred under vacuum, after above-mentioned raw materials stir evenly, this is added dropwise into polymeric kettle in whipping process
The invention composition, treats that the temperature of reaction kettle no longer increases, and stops stirring, after excluding bubble, obtains mixture；
Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, will be mixed with scraper
Material strikes off, and then allows its natural levelling, and the mold for mixture of having cast is sent into vacuum tank, is vacuumized again, after taking-up
It stands, obtains molding artificial stone's semi-finished product；
Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, be placed on reshaping frame after demoulding, be put into drying chamber into
Row curing, obtains artificial stone；
Post-processing step：The above-mentioned irregular part of artificial stone's upper and lower surface is cut off, then using polishing, polish it
Afterwards, artificial stone is obtained.In said program, composition of the present invention adds in artificial stone raw materials whipping process, due to
It is poor with artificial stone raw materials mixed polymerization process existence time, in the artificial stone raw materials of composition upon mixing during stirring
Flowing forms pattern, in the curing process, due to the difference between the mobility of composition and curing agent solidification temperature, figure
Case may send out variation again, therefore can obtain the artificial stone of different pattern.Further, since contain aluminium hydroxide in composition
The glossiness of the artificial stone after curing can be effectively improved with aerosil, while improves the performance of artificial stone.
As further embodiment, the vacuum degree of polymeric kettle of the present invention is 0.09-0.095MPa, and polymerization temperature is
55-80℃；In the curing schedule, first cure 1-2 hours at 52-65 DEG C in drying chamber, then heat to 78-85 DEG C of curing 1-
2 hours.
Embodiment 1
A kind of modified unsaturated resin, the raw material for preparing modified unsaturated polyester resin include cis-1, neighbour
Phthalic acid, propylene glycol, diethylene glycol, trimethylolpropane, styrene, α-methylstyrene, polymerization inhibitor；
Wherein acid-alcohol ratio is 1：1, the molar ratio of mole total amount and trihydroxy methyl of propylene glycol and diethylene glycol is 0.75：
0.1；The styrene dosage is the 30% of acid starting material and raw polyol gross mass, and α-methylstyrene dosage is former for acid starting material and alcohol
Expect the 2% of gross mass, the polymerization inhibitor is 0.01%；
Specific preparation method is as follows：
Step of esterification：To be passed through in reaction kettle after nitrogen vacuumizes, according to proportioning by cis-1 and
Phthalic acid is added in reaction kettle, is added after then mixing propylene glycol, diethylene glycol and trimethylolpropane by pipeline
Enter into reaction kettle, reaction kettle is heated using 220 DEG C of conduction oil, started during reactor temperature is raised
The agitating paddle of reaction kettle is stirred material reaction, while controls heating temperature, when the temperature of charge in reaction kettle reaches 160
DEG C when, insulation reaction 1 hour stops heating after the reaction was complete, obtains carboxylate；
Modified-reaction step：Styrene and α-methylstyrene are added to by pipeline has used nitrogen or vacuumize process
In thinning vessel afterwards, polymerization inhibitor is added in；When above-mentioned carboxylate is cooled to 140 DEG C, with negative pressure by the carboxylate of reaction kettle slowly
It is added in thinning vessel, controls the temperature of thinning vessel at 85 DEG C hereinafter, material to the material in stirring thinning vessel is cooled to 48 DEG C
Hereinafter, obtain semi-finished product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
Embodiment 2
A kind of to be used to improve artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:1 UPR trees
Fat and Al (OH)3, it is UPR weight resins to further include intermediate temperature curing agent TBPO that dosage is UPR weight resins 0.5% and dosage
1.5% aerosil.
Embodiment 3
A kind of to be used to improve artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:1 implementation
Modified unsaturated resin and Al (OH) described in example 13, further include the medium temperature that dosage is modified unsaturated resin weight 1.2% and consolidate
Agent TBPO and dosage are 1.0% aerosil of weight resin.
Embodiment 4
A kind of to be used to improve artificial shell stone patterns and the composition of glossiness, it is 1 that the composition, which includes mass ratio,:1 UPR trees
Fat and Al (OH)3, it is UPR weight resins to further include intermediate temperature curing agent TBPO that dosage is UPR weight resins 1.5% and dosage
0.5% aerosil.
Embodiment 5
A kind of multifarious artificial stone of decorative pattern, the raw material for preparing the artificial stone include composition of the present invention and people
Stone raw material is made, the wherein mass ratio of the composition described in embodiment 2 and artificial stone raw materials is 0.2:1；Wherein described artificial stone is former
Material is included by percentage to the quality
UPR resins：50%th,
Granularity is 220 Al (OH)3：40%th,
MEKP：0.1%th,
Accelerating agent：0.1%th,
Mill base：9.8%；
The accelerating agent is the cobalt naphthenate solution containing potassium ion, and wherein the concentration ratio of potassium ion and cobalt ions is 1.8：
1；
Specific preparation method includes
The step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymerization vacuumized
In kettle, then vacuum degree 0.09MPa adds in accelerating agent, is stirred under vacuum, after above-mentioned raw materials stir evenly, in whipping process
Composition of the present invention is added dropwise into polymeric kettle, polymerization temperature is 65 DEG C, treats that the temperature of reaction kettle no longer increases, stops stirring
It mixes, after excluding bubble, obtains mixture；
Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, will be mixed with scraper
Material strikes off, and then allows its natural levelling, and the mold for mixture of having cast is sent into vacuum tank, is vacuumized again, after taking-up
It stands, obtains molding artificial stone's semi-finished product；
Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, be placed on reshaping frame after demoulding, be put into drying chamber into
Row curing, first cures 2 hours in drying chamber at 52 DEG C, then heats to 78 DEG C and cures 2 hours, obtains artificial stone；
Post-processing step：The above-mentioned irregular part of artificial stone's upper and lower surface is cut off, then using polishing, polish it
Afterwards, artificial stone is obtained.
Embodiment 6
A kind of multifarious artificial stone of decorative pattern, the raw material for preparing the artificial stone include composition of the present invention and people
Stone raw material is made, wherein the mass ratio of composition described in embodiment 3 and artificial stone raw materials is 0.5:1；Wherein described artificial stone is former
Material is included by percentage to the quality
UPR resins：40%th,
Granularity is 230 Al (OH)3：50%th,
MEKP：0.5%th,
Accelerating agent：0.1%th,
Mill base：9.4%；
The accelerating agent is the cobalt iso-octoate solution containing potassium ion, and wherein the concentration ratio of potassium ion and cobalt ions is 2：1；
Specific preparation method includes
The step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymerization vacuumized
In kettle, then vacuum degree 0.092MPa adds in accelerating agent, is stirred under vacuum, after above-mentioned raw materials stir evenly, in whipping process
Composition of the present invention is added dropwise into polymeric kettle, polymerization temperature is 75 DEG C, treats that the temperature of reaction kettle no longer increases, stops stirring
It mixes, after excluding bubble, obtains mixture；
Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, will be mixed with scraper
Material strikes off, and then allows its natural levelling, and the mold for mixture of having cast is sent into vacuum tank, is vacuumized again, after taking-up
It stands, obtains molding artificial stone's semi-finished product；
Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, be placed on reshaping frame after demoulding, be put into drying chamber into
Row curing, first cures 1.5 hours in drying chamber at 60 DEG C, then heats to 80 DEG C and cures 1.5 hours, obtains artificial stone；
Post-processing step：The above-mentioned irregular part of artificial stone's upper and lower surface is cut off, then using polishing, polish it
Afterwards, artificial stone is obtained.
Embodiment 7
A kind of multifarious artificial stone of decorative pattern, the raw material for preparing the artificial stone include composition of the present invention and people
Stone raw material is made, the wherein mass ratio of the composition described in embodiment 4 and artificial stone raw materials is 0.8:1；Wherein described artificial stone is former
Material is included by percentage to the quality
UPR resins：30%th,
Granularity is 200 Al (OH)3：62%th,
MEKP：0.1%th,
Accelerating agent：0.05%th,
Mill base：7.85%；
The accelerating agent is the cobalt octoate solution containing potassium ion, and wherein the concentration ratio of potassium ion and cobalt ions is 2：1；
Specific preparation method includes
The step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymerization vacuumized
In kettle, then vacuum degree 0.093MPa adds in accelerating agent, is stirred under vacuum, after above-mentioned raw materials stir evenly, in whipping process
Composition of the present invention is added dropwise into polymeric kettle, polymerization temperature is 80 DEG C, treats that the temperature of reaction kettle no longer increases, stops stirring
It mixes, after excluding bubble, obtains mixture；
Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, will be mixed with scraper
Material strikes off, and then allows its natural levelling, and the mold for mixture of having cast is sent into vacuum tank, is vacuumized again, after taking-up
It stands, obtains molding artificial stone's semi-finished product；
Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, be placed on reshaping frame after demoulding, be put into drying chamber into
Row curing, first cures 1 hour in drying chamber at 65 DEG C, then heats to 85 DEG C and cures 1 hour, obtains artificial stone；
Post-processing step：The above-mentioned irregular part of artificial stone's upper and lower surface is cut off, then using polishing, polish it
Afterwards, artificial stone is obtained.
Comparative example 1
According to the artificial stone raw materials proportioning and preparation method of embodiment 6, but in the comparative example 1, do not add the present invention
The composition.
Performance test
1. surface topography satin degree detects
The surface topography of the artificial stone of embodiment 5-7 and comparative example 1 is observed under an optical microscope, and uses gloss
The glossiness of instrument detection artificial stone is spent, as a result referring to table 1.
Table 1
2. Mechanics Performance Testing
The mechanical property for the artificial stone that embodiment 5-7 and comparative example 1 obtain is with reference to Mechanics Performance Testing by GB/T 2567-
2008th, the method in GB/T 2570-1995 is tested.Test result is referring to table 2.
Table 2
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 |
| Bending strength (MPa) | 57.14 | 59.01 | 58.37 | 51.89 |
| Compressive strength (strength degree MPa) | 91.71 | 93.56 | 92.84 | 81.62 |
3. corrosion resistant performance is tested
Corrosive medium is respectively 10% sodium hydroxide solution, 20% sulfuric acid solution and toluene, and experiment condition presses B/T 3857-
Sample is immersed in test medium after 30d and takes out by 2005, is dried, and tests bending strength.As a result referring to table 3.
Table 3
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 |
| Bending strength/MPa (toluene reagent) | 29.15 | 37.12 | 29.46 | 26.37 |
| Bending strength/MPa (20%H2SO4) | 31.59 | 41.48 | 34.25 | 27.16 |
| Bending strength/MPa (10%NaOH) | 29.97 | 39.75 | 32.59 | 26.58 |
It will be apparent to those skilled in the art that can technical solution and design as described above, make other various phases
The change and deformation answered, and all these change and deformation should all belong to the claims in the present invention protection domain it
It is interior.
Claims (10)
- It is 1. a kind of for improving artificial shell stone patterns and the composition of glossiness, which is characterized in that the composition is including mass ratio 1:1 resin and Al (OH)3, it is resin weight to further include intermediate temperature curing agent that dosage is weight resin 0.5%-1.5% and dosage Measure 0.5%-1.5% aerosils.
- 2. composition as described in claim 1, which is characterized in that the resin is UPR resins or modified unsaturated resin.
- 3. the composition as described in right wants 2, which is characterized in that the raw material for preparing the modified unsaturated resin is included as acid The cis-1 and phthalic acid of raw material, as the propylene glycol of raw polyol, diethylene glycol and trimethylolpropane；Its Middle acid-alcohol ratio is 1：Mole total amount of (1-1.2), propylene glycol and diethylene glycol and the molar ratio of trimethylolpropane are (0.75- 0.95)：0.1；Styrene and α-methylstyrene and polymerization inhibitor are further included, the styrene dosage is acid starting material and raw polyol The 30%-33% of gross mass, 2%-6% of the α-methylstyrene dosage for acid starting material and raw polyol gross mass, the polymerization inhibitor For 0.01-0.05%；The modified unsaturated resin is prepared by the following method：Step of esterification：After nitrogen is passed through in reaction kettle, according to proportioning by cis-1 and phthalic acid It is added in reaction kettle, reaction kettle is added to by pipeline after then mixing propylene glycol, diethylene glycol and trimethylolpropane In, reaction kettle is heated using 220-240 DEG C of conduction oil, starts reaction kettle during reactor temperature is raised Agitating paddle reaction is stirred to material, while control heating temperature, when the temperature of charge in reaction kettle reaches 160 DEG C, Insulation reaction 1-2 hours stops heating after the reaction was complete, obtains carboxylate；Modified-reaction step：Styrene and α-methylstyrene are added to by pipeline used nitrogen or vacuumize process after In thinning vessel, polymerization inhibitor is added in；When above-mentioned carboxylate is cooled to 140-150 DEG C, with negative pressure by the carboxylate of reaction kettle slowly It is added in thinning vessel, controls the temperature of thinning vessel at 85 DEG C hereinafter, material to the material in stirring thinning vessel is cooled to 48 DEG C Hereinafter, obtain semi-finished product；Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
- 4. composition as described in claim 1, which is characterized in that the intermediate temperature curing agent is TBPO, 2-methylimidazole, 2- second One kind in base -4-methylimidazole.
- 5. a kind of application of composition as described in claim 1 in artificial stone is prepared.
- 6. a kind of multifarious artificial stone of decorative pattern, which is characterized in that the raw material for preparing the artificial stone is included described in claim 1 Composition and artificial stone raw materials, wherein the mass ratio of composition described in claim 1 and artificial stone raw materials be (0.2- 0.8):1；Wherein described artificial stone raw materials are included by percentage to the qualityUPR resins：30%-50%,Filler：40%-62%,Curing agent：0.1%-0.5%,Accelerating agent：0.05%-0.1%Mill base：5%-10%.
- 7. artificial stone as claimed in claim 6, which is characterized in that the filler is Al (OH)3Or Al (OH)3With CaCO3、 The mixed fillers of one or more of MgO, short glass fibre, cenosphere.
- 8. artificial stone as claimed in claim 6, which is characterized in that the curing agent is MEKP, and the accelerating agent is contains potassium One kind in the cobalt naphthenate solution of ion, cobalt octoate solution and cobalt iso-octoate solution.
- It is 9. a kind of such as the preparation method of claim 6-8 any one of them artificial stones, which is characterized in that includingThe step of preparing mixture：UPR resins, filler, curing agent, mill base are proportionally put into the polymeric kettle vacuumized In, accelerating agent is then added in, is stirred under vacuum, after above-mentioned raw materials stir evenly, right is added dropwise into polymeric kettle in whipping process It is required that the composition described in 1, treats that the temperature of reaction kettle no longer increases, stop stirring, after excluding bubble, obtain mixture；Cast molding step：Above-mentioned mixture is poured slowly into the die cavity of pretreated mold, is scraped mixture with scraper It is flat, it then allows its natural levelling, the mold for mixture of having cast is sent into vacuum tank, vacuumizes, is stood after taking-up again, Obtain molding artificial stone's semi-finished product；Curing schedule：By the artificial stone semi-finished product after above-mentioned standing, it is placed on reshaping frame after demoulding, is put into drying chamber and is consolidated Change, obtain artificial stone；Post-processing step：Cut off the above-mentioned irregular part of artificial stone's upper and lower surface, then using polishing, polishing after, Obtain artificial stone.
- 10. the preparation method of artificial stone according to claim 9, which is characterized in that the vacuum degree of the polymeric kettle is 0.09-0.095MPa, polymerization temperature are 55-80 DEG C；In the curing schedule, in drying chamber 52-65 DEG C first curing 1-2 it is small When, it then heats to 78-85 DEG C and cures 1-2 hours.
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