CN110819155A

CN110819155A - Anti-adhesion and easy-demolding ultrathin rock slice and preparation process thereof

Info

Publication number: CN110819155A
Application number: CN201911137894.8A
Authority: CN
Inventors: 陈启智
Original assignee: Ji'an Tiansheng New Materials Co Ltd
Current assignee: Ji'an Tiansheng New Materials Co Ltd
Priority date: 2019-11-19
Filing date: 2019-11-19
Publication date: 2020-02-21

Abstract

The invention relates to an anti-adhesion and easy-demolding ultrathin rock slice and a preparation process thereof. The raw materials comprise the following components in percentage by weight: 30-50 parts of acrylic resin, 1-5 parts of fluorocarbon resin, 0.001-0.01 part of cellulose, 0.02-0.1 part of cross-linking agent, 0.5-5 parts of release agent, 30-60 parts of filler and 5-15 parts of water, wherein the thickness of the ultrathin rock slice is 30-70 mu m. The ultrathin rock slice obtained by the application has the advantages of excellent stone imitation effect, uniform thickness, obvious improvement on the demolding efficiency, labor cost saving, capacity and speed improvement, and improvement on the market competitiveness of ultrathin rock slice production.

Description

Anti-adhesion and easy-demolding ultrathin rock slice and preparation process thereof

Technical Field

The invention relates to the field of building coatings, in particular to an anti-adhesion and easy-demolding ultrathin rock slice and a preparation process thereof.

Background

The stone-like paint is a kind of building paint which is made up by using colour materials of natural colour sand, etc. and matching with special resin and high-grade raw material, and can be sprayed on stone sample plate to obtain colorful and bright coating surface. The stone-like paint has strong adhesive force, high hardness, rich texture, economic cost and good weather resistance. Meanwhile, the wall has the characteristics of fire prevention, water resistance, acid and alkali resistance, pollution resistance, no toxicity, no odor, strong bonding force, no fading and the like, and the natural macadam is adopted to show the color and keep the long-term beautiful texture of the wall. The stone-like paint has good adhesive force and freeze-thaw resistance, so the stone-like paint is particularly suitable for being used in cold regions, can effectively prevent corrosion of a severe environment outside to buildings and prolongs the service life of the buildings. Meanwhile, the real stone paint is simple and convenient to construct. In order to ensure the real effect and quality of the spraying of the conventional real stone paint, a large amount of the conventional real stone paint is often sprayed on a stone sample plate, and the spraying amount reaches 4 kilograms per square. If the coating is used as a coating of an outer wall of a building, the bearing of the wall is overweight, the building fatigue is accelerated, the cracking, deformation and falling of the wall are slowly caused, the appearance is influenced, and the safety of downstairs pedestrians is threatened.

Therefore, the real stone paint has the requirements of small spraying amount per unit area and no influence on the beautiful texture. The prior art finds that the use amount of the real stone paint coating can be reduced by using dry rock slices in the real stone paint coating, and the thinner the rock slices are, the smaller the use amount of the real stone paint coating is. CN105907213A adds irregular dry flake structure color chips into the coating of the marble-imitated color chips, which is soft and elastic, is not easy to adhere, and can embody the colorful patterns and textures of natural stones to the maximum extent. Meanwhile, the thickness of the color sheet is controlled to be 0.05mm-0.15mm, so that the spraying thickness of the coating of the marble-imitated color sheet is reduced. CN105505221A adopts the formula combination of high-elasticity weather-resistant resin, cellulose, film-forming agent and the like to ensure that the rock slice product has excellent mechanical property and simultaneously reduces the thickness of the ultrathin rock slice to 180 +/-40 mu m.

However, the prior art can not obtain thinner rock slices because the dry film rock slices are directly stripped off in the conventional demolding process, and because the resin has certain adhesive force to the carrier in the drying process, the direct stripping efficiency is slow, and time and labor are wasted. And the lighter the weight per unit area during peeling, the thinner the thickness, the more difficult it is to perform direct peeling. The effect of leveling and homogenizing appearance cannot be achieved in the prior art, if the base material carrier is coated with lubricating oil or silicone oil, although a certain effect can be achieved on stripping, the oiliness is too strong, the oil shrinkage of the coating of the rock slice slurry is easily caused, the thickness is not uniform, the appearance is not smooth, and the stone-imitating effect is not ideal.

Therefore, the anti-adhesion and easy-demolding ultrathin rock slice is needed to be provided, the thickness can be maintained to be thin on the one hand, so that the obtained stone-like paint is reduced in material cost, the bearing pressure of building paint is improved, on the other hand, a good stone-like effect is presented, more importantly, the demolding process is simple and easy to operate, and the output efficiency of the whole ultrathin rock slice can be improved.

Disclosure of Invention

The invention aims to provide an anti-adhesion and easy-demolding ultrathin rock slice, which has the advantages that the demolding process is simple and easy to operate, the overall output efficiency of the ultrathin rock slice can be improved, meanwhile, the thickness of the rock slice can be controlled to be 30-70 mu m, namely 3-7 wires, which is lower than the 10 wires of the thinnest rock slice in the market, and the ultrathin rock slice still has good water resistance, weather resistance, high toughness, cracking resistance, high strength and other physical and chemical properties and a good stone imitation effect.

The purpose of the invention is realized by the following modes:

1. raw material formula selection

The formula of the raw materials of the ultrathin rock slice comprises the following components in percentage by weight: 30 to 50 parts of acrylic resin, 1 to 5 parts of fluorocarbon resin, 0.001 to 0.01 part of cellulose, 0.02 to 0.1 part of cross-linking agent, 0.5 to 5 parts of release agent, 30 to 60 parts of filler, 5 to 15 parts of water and other auxiliary agents.

The acrylic resin is any polymer resin containing (meth) acrylic acid derivative monomers, preferably a combination of polymerization, copolymerization or polymer blending of one or more monomers selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or isobutyl methacrylate as a main component of the ultra-thin rock slice;

the fluorocarbon resin is a polymer resin with C-F bond as skeleton, and can be selected from Polytetrafluoroethylene (PTFE), modified PTFE, tetrafluoroethylene and perfluoropropyl vinyl ether copolymer (PFA), tetrafluoroethylene and hexafluoropropylene copolymer (FEP), or Polytetrafluoroethylene (PTFE), or a mixture of PTFE and PFA (PTFE/PFA), or a mixture of PTFE and FEP (PTFE/FEP), or a mixture of PTFE, PFA and FEP (PTFE/PFA/FEP). The fluorocarbon resin can improve the water resistance of the rock slices in the base material and is not easy to be back-adhered.

The cross-linking agent comprises one or more of methyl silicate, silane coupling agent, isocyanate and polyamine, the formula slurry is cross-linked in the drying process on the substrate carrier, the cross-linking strength among resins can be improved, the toughness and the water resistance of the rock slice are improved, and the rock slice film cannot be broken even if the rock slice is calendered and stretched under the condition of ultrathin thickness.

The cellulose may be selected from one or more of cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose or carboxymethyl cellulose. The cellulose can improve the uniform drying stability of the rock slices, prevent the rock slices from cracking caused by too fast drying, and improve the toughness of the rock slices.

The release agent is selected from emulsion of one or more of methyl silicone oil, modified silicone oil, hydroxyl silicone oil, phenyl silicone oil, amino silicone oil, mineral oil and alkyl silicone oil, and after the release agent is compounded in the rock slice raw material, the release agent is beneficial to demolding after drying.

The filler is an inorganic filler commonly used in the field, can be selected from one or a combination of calcium carbonate, quartz sand, kaolin, titanium dioxide, silicon dioxide and bentonite, and has the functions of increasing the granular layering of the rock slices, presenting stone-like lines and reducing the cost. Preferred are precipitated calcium carbonate and precipitated silica. The preferred particle size of the filler is 500-1000 mesh.

The formula of the ultrathin rock slice raw material also contains other conventional necessary auxiliary agents, including: 0.5 to 2.5 portions of film forming additive, 0.1 to 1.0 portion of wetting and leveling agent, 0.1 to 0.6 portion of dispersant, 0.1 to 0.5 portion of defoamer, 0.1 to 0.5 portion of water-based thickener and 0.1 to 1.0 portion of color paste. These adjuvants are essential raw material components that are routinely added to obtain rock chips in the art. Those skilled in the art can select the conventional types according to actual needs, and examples of the film-forming assistant include, but are not limited to, alcohol ester twelve, benzyl alcohol, 22413-monoisobutyrate, ethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipentene, turpentine, and the like. Examples of the wetting and leveling agent include, but are not limited to, silicone-based, fluorocarbon-based, and vinyl acetate-based leveling agents. The dispersant may be exemplified by, but not limited to, carboxylic acid salt type anionic surfactant or sulfonate type anionic surfactant or sulfate type anionic surfactant or phosphate type anionic surfactant. Defoaming agents may be exemplified by, and not limited to, GPE type defoaming agents, GPES type defoaming agents, polydimethylsiloxanes, ethylene glycol siloxanes, or polyether modified silicone defoaming agents. Aqueous thickeners include polyacrylic acids, such as PTF aqueous thickeners or special hand finishes Appretan Thiickener 2710. The color paste is at least one of water-based paint color pastes.

The ultrathin rock slice raw material formula can also contain other conventional auxiliary functional additives, and the additives are added according to specific use scenes and requirements, and comprise 0.1-1.0 part of optional processing additive, 0.1-0.5 part of antioxidant, 0.1-0.5 part of ultraviolet absorber and 0.1-0.5 part of antistatic agent. The processing aid is one or a combination of paraffin, polyethylene wax, polypropylene wax, stearic acid and naphthenic oil. The processing aid mainly plays roles of lubricating, reducing rheological viscosity, increasing softness, improving surface and the like. Antioxidants may be exemplified by, but not limited to: zinc dialkyldithiophosphates, zinc dialkyldithiocarbamates, dioctyldiphenylamines, 2, 6-di-tert-butyl-p-cresol (BHT), and the like. Ultraviolet light absorbers include, but are not limited to, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates/acrylolates (propenoates), aromatic propanediones, benzimidazoles, cycloaliphatic ketones, formanilides (including oxamides), cyanoacrylates, benzopyranones, salicylates, and the like. Because the obtained rock slices are thin, the rock slices are easy to generate electrostatic adsorption in the transmission and drying processes, the adsorption between the rock slices or between the rock slices and a carrier belt can be avoided to the greatest extent by adding the antistatic agent, and the antistatic agent is an anionic or nonionic antistatic agent commonly used in the field.

According to the raw material formula design of the invention, the fluorocarbon resin and the release agent are added, so that the dried film can be easily separated from the matrix carrier tape, the blocking resistance is good, and the curing effect of the cross-linking agent and the reinforcing effect of the cellulose can keep the toughness of the rock slices from breaking, thereby laying a foundation for the application of the thin rock slices in paint for durable storage and difficult crushing. The four components are added in a matching manner, so that the rock slice keeps toughness and cannot be cracked or curled without peeling when the ultra-thin rock slice is in an ultra-thin state by roller coating, and meanwhile, the anti-adhesion performance is achieved, and the aim that the ultra-thin rock slice cannot be continuously produced or cannot be continuously produced all the time when the ultra-thin rock slice is considered in the past is fulfilled.

2. Preparation process of ultrathin rock slice

Mixing and dispersing a raw material formula with water to form slurry, coating the slurry on a carrying belt by a spraying or three-roller coating process, then drying, and adjusting the thickness of a wet film of the slurry by adjusting a gap between two rollers to obtain the anti-adhesion and easy-demolding ultrathin rock slice;

the spraying process specifically comprises the steps of spraying the slurry on a carrying belt by using a spraying device before the slurry enters a double-roller calendering device;

the three-roll coating is characterized in that one or more three-roll coating machines are used, coating slurry is adhered through rollers, the coating slurry is transferred among the rollers, and finally the coating slurry is adhered and transferred onto a carrier belt.

Preferably, a three-roll coater is used, the amount of the supplied slurry can be controlled by adjusting the pressure between the rolls by using the metering roll 10 according to the viscosity and viscosity of the upper slurry, and the metering roll 10 and the material taking roll 9 are reversely rotated to stir the slurry for the second time, so that the slurry can be more uniformly transferred to the coating roll 11, and after the coating slurry is adhered by the coating roll 11, the slurry is transferred between the rolls and finally adhered to and transferred onto a carrying belt, and then the drying treatment at 80-110 ℃ is carried out, and the thickness of the wet slurry film is adjusted by adjusting the gap between the two rolls. The slurry has stable physical and chemical properties, can produce stable and uniform ultrathin rock slices, and has tensile strength, toughness and demolding property, so that the thickness of the rock slices is allowed to be controlled to be 30-70 mu m, namely 3-7 filaments, and finally the anti-adhesion and easy-demolding ultrathin rock slices are obtained.

Preferably, the substrate carrier tape is made of Teflon leather or Teflon steel tape, and the sizing agent with the specific formula is not easy to stick to the tape after being dried on the Teflon belt or the Teflon steel tape carrier tape.

Therefore, when the ultrathin rock slice raw material with specific components is used and matched with a corresponding anti-adhesion Teflon belt or steel belt carrier, on one hand, high-temperature drying can be further carried out to volatilize moisture, and on the other hand, a better demolding effect can be achieved.

3. Rock slice collecting material

After being dried and solidified on the substrate carrying belt, the slurry is continuously conveyed to a material receiving position, and a rolling rotating shaft is arranged at the material receiving position. The dried large rock slices directly fall into a material receiving frame through a rolling rotating shaft to obtain the ultrathin rock slice, and the process is different from the traditional process of receiving materials in a scraper mode by a specially-assigned person.

Further, the ultrathin rock slice obtained according to the invention is used for preparing the stone-like paint. The method specifically comprises the following steps:

1. and (4) crushing and screening the ultrathin rock slices to obtain fragmented rock slices.

2. Mixing the water-based resin, the fragmented ultrathin rock slices, the fine sand, the water and the auxiliary agent, and adjusting the pH value to 8-9 and the viscosity to 130KU-140KU to obtain the stone-like paint.

The ultrathin rock slice obtained by the invention has thin thickness of 30-70 mu m, namely 3-7 silks, excellent stone imitation effect, obviously improved demoulding efficiency, labor cost saving, capacity and speed improvement, and market competitiveness of ultrathin rock slice production is improved.

Drawings

FIG. 1 is a schematic diagram of a spraying device for preparing ultrathin rock slices and a material collecting process

FIG. 2 is a schematic diagram of a preparation process and a material receiving process of the ultrathin rock slice by using a three-roller coating device

1-a heating device;

2-a material receiving device;

3-calendering rolls;

4-rolling the rotating shaft;

5-a turning roll;

6-matrix carrier tape

7-three-roller coater

8-slurry tank

9-Material taking roller

10-metering roll

11-coating roller

12-spraying device

Detailed Description

The invention is further illustrated by the following specific examples.

Example 1

30 parts of polymethyl acrylate, 3 parts of Polytetrafluoroethylene (PTFE), 0.005 part of methyl cellulose, 0.05 part of a silane coupling agent, 1 part of methyl silicone oil, 20 parts of light calcium carbonate, 20 parts of bentonite, 0.1 part of a nonionic antistatic agent, 0.5 part of a film forming additive, 0.5 part of a wetting leveling agent, 0.1 part of a dispersing agent, 0.2 part of a defoaming agent, 0.3 part of an aqueous thickening agent and 0.5 part of color paste are mixed and dispersed with water to form slurry, the slurry is coated on a calendering roller 3 through a three-roller coating machine 7, the slurry is subjected to double-side roller coating through the calendering roller 3 and a steering roller 5, the slurry is transferred and coated on a carrier tape 6, meanwhile, the drying treatment at 110 ℃ is carried out, the distance between two rollers is adjusted to control the thickness of a rock slice to be 30 mu m, the carrier tape 6 of a substrate is a Teflon leather tape, the substrate carrier tape 6 is dried and solidified and then is continuously conveyed to a material receiving position, and a. The dried large rock slices directly fall into the material receiving device 2 through the rolling rotating shaft 4, and the crushed ultrathin fragmented rock slices are obtained.

Example 2

50 parts of poly (n-butyl acrylate), 4 parts of tetrafluoroethylene and perfluoropropyl vinyl ether copolymer (PFA), 0.008 part of hydroxypropyl methyl cellulose, 0.02 part of methyl silicate, 3 parts of hydroxyl silicone oil, 10 parts of titanium dioxide, 30 parts of quartz sand, 0.5 part of anionic antistatic agent, 1 part of film-forming additive, 0.3 part of wetting and leveling agent, 0.5 part of dispersing agent, 0.3 part of defoaming agent, 0.5 part of water-based thickening agent and 0.4 part of color paste are mixed and dispersed by water to form slurry, coating the slurry on a calendering roll 3 by a three-roll coater 7, carrying out double-side roll coating by the calendering roll 3 and a turning roll 5, transferring and coating the slurry on a carrier tape 6, at the same time, drying treatment is carried out at 130 ℃, the distance between two rollers is adjusted to control the thickness of the rock slice to be 40 mu m, the substrate carrier band 6 is a Teflon steel band, after being dried and solidified, the substrate carrier tape 6 is continuously conveyed to a material receiving position, and a rolling rotating shaft 4 is arranged at the material receiving position. The dried large rock slices directly fall into the material receiving device 2 through the rolling rotating shaft 4, and the crushed ultrathin fragmented rock slices are obtained.

Example 3

40 parts of poly ethyl methacrylate, 2 parts of a mixture of PTFE and FEP, 0.01 part of carboxymethyl cellulose, 0.1 part of isocyanate, 5 parts of mineral oil, 30 parts of light calcium carbonate, 30 parts of kaolin, 0.25 part of an anionic antistatic agent, 2 parts of a film forming auxiliary agent, 1 part of a wetting leveling agent, 0.3 part of a dispersing agent, 0.3 part of an antifoaming agent, 0.1 part of an aqueous thickening agent, 0.8 part of color paste and 0.5 part of an antioxidant BHT are mixed and dispersed with water to form slurry, the slurry is coated on a calender roll 3 through a three-roll coater 7, the slurry is roll-coated on a carrier tape 6 through the calender roll 3 and a turning roll 5, the slurry is transferred and coated on the carrier tape 6, the drying treatment at 125 ℃ is carried out at the same time, the distance between two rolls is adjusted to control the thickness of a rock slice to be 50 mu m, the carrier tape 6 is a Teflon leather tape, the carrier tape 6 is dried and solidified and then is continuously conveyed to a material receiving. The dried large rock slices directly fall into the material receiving device 2 through the rolling rotating shaft 4, and the crushed ultrathin fragmented rock slices are obtained.

Example 4

The raw material ratio is the same as that of the example 1, except that the substrate carrier tape 6 is a rubber conveyer belt.

Comparative example 1

The raw materials were not added with Polytetrafluoroethylene (PTFE), and the rest of the component ratios were the same as in example 1.

Comparative example 2

Hydroxypropyl methylcellulose is not added into the raw materials, and the rest of the component proportion is the same as that of the example 2.

Comparative example 3

The raw materials were not added with isocyanate, and the rest of the component ratios were the same as in example 3.

Performance test method

The performance test of the ultrathin rock slice comprises the tests of demolding performance, stone-like appearance, rock slice damage condition, flexibility and adhesion, wherein the test is partially carried out according to the content of national standard HG/T4345-.

And (3) testing the demolding property:

1. the evaluation method comprises the following steps: the large piece of rock slice passing through the drying tunnel can not be automatically stripped from the carrier substrate.

2. Evaluation criteria:

a-will peel off automatically;

b-slightly tearing the material with a little force by hand during material receiving;

c-the material can be torn off only by applying great effort.

The appearance is stone-like:

1. the evaluation method comprises the following steps: comparing the size ratio and the shade of the design color with the simulated stone

2. Evaluation criteria:

a-similarity > 95%;

b-similarity is 80-95%;

the C-similarity is less than or equal to 80 percent.

And (3) rock fragment breakage condition:

1. the evaluation method comprises the following steps: the appearance of the dried and formed rock piece was observed to see if it was torn, broken or damaged due to poor mold release.

2. Evaluation criteria:

a-breakage degree of 0%;

b-breakage degree is less than or equal to 10%;

c-degree of breakage > 10%;

flexibility test:

1. the evaluation method comprises the following steps: sample 3 pieces with a diameter greater than 3mm were selected and folded 180 ° with thumb and forefinger and the bend was observed immediately.

2. Evaluation criteria:

a-has no cracks and no fracture phenomenon;

the B-2 sheets have no cracks and no fracture phenomenon;

the C-1 sheet or 0 sheet has no crack and no fracture phenomenon.

And (3) testing the adhesion:

1. the evaluation method comprises the following steps: the 4 samples were stacked and placed under a load of 100 g (40. + -. 2 ℃ C.) for 2 hours, and the samples were separated by hand to observe the adhesion between the samples.

2. Evaluation criteria:

a-is substantially non-blocking;

b-partial adhesion;

c-complete adhesion and blocking.

TABLE 1 Performance test of examples 1-4 and comparative examples 1-3

Claims

1. The anti-adhesion and easy-demolding ultrathin rock slice is characterized by comprising the following raw materials in percentage by weight: 30-50 parts of acrylic resin, 1-5 parts of fluorocarbon resin, 0.001-0.01 part of cellulose, 0.02-0.1 part of cross-linking agent, 0.5-5 parts of release agent, 30-60 parts of filler and 5-15 parts of water, wherein the thickness of the ultrathin rock slice is 30-70 mu m.

2. The ultra-thin rock slice of claim 1, further comprising other conventional necessary aids, including: 0.5 to 2.5 portions of film forming additive, 0.1 to 1.0 portion of wetting and leveling agent, 0.1 to 0.6 portion of dispersant, 0.1 to 0.5 portion of defoamer, 0.1 to 0.5 portion of water-based thickener and 0.1 to 1.0 portion of color paste.

3. The ultra-thin rock laminate as claimed in claim 1, wherein the fluorocarbon resin is selected from the group consisting of Polytetrafluoroethylene (PTFE), modified PTFE, tetrafluoroethylene and perfluoropropylvinylether copolymer (PFA), tetrafluoroethylene and hexafluoropropylene copolymer (FEP), a mixture of PTFE and PFA (PTFE/PFA), a mixture of PTFE and FEP (PTFE/FEP) or a mixture of PTFE, PFA and FEP (PTFE/PFA/FEP).

4. The ultra-thin rock laminate of claim 1, wherein the cross-linking agent is one or more of a methyl silicate, a silane coupling agent, an isocyanate, a polyamine.

5. The ultra-thin rock laminate of claim 1, wherein the cellulose is selected from one or more of cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, or carboxymethyl cellulose.

6. The ultra-thin rock slice as claimed in any one of claims 1 to 5, which is prepared by mixing and dispersing raw materials with water in proportion to form a slurry, coating the slurry on a carrying belt by a spray coating or three-roll coating process, and then drying, and adjusting the thickness of the wet film of the slurry by adjusting the gap between two rolls;

7. The ultra-thin rock slice as claimed in claim 6, wherein the substrate carrier tape is selected from a Teflon belt or a Teflon steel tape.

8. A preparation method for preparing the anti-adhesion and easy-demolding ultrathin rock slice comprises the steps of proportioning the components and the content according to the claims 1-5, mixing and dispersing the components with water to form slurry, coating the slurry on a carrying belt through a spraying or three-roll coating process, drying, and adjusting the thickness of a wet film of the slurry by adjusting a gap between two rolls to obtain the anti-adhesion and easy-demolding ultrathin rock slice;

9. The method of claim 8, wherein, in receiving, a rolling shaft is installed at the receiving place, and the rock fragments directly fall into the receiving frame via the rolling shaft.

10. A stone-like paint, characterized in that it comprises the ultra-thin rock laminate according to any one of claims 1 to 7.