CN114318943A - Surface treatment method and object obtained by using same - Google Patents
Surface treatment method and object obtained by using same Download PDFInfo
- Publication number
- CN114318943A CN114318943A CN202011061002.3A CN202011061002A CN114318943A CN 114318943 A CN114318943 A CN 114318943A CN 202011061002 A CN202011061002 A CN 202011061002A CN 114318943 A CN114318943 A CN 114318943A
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- fluorine
- free
- agent
- surface treatment
- treatment method
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Landscapes
- Paper (AREA)
Abstract
The present invention relates to a surface treatment method and an object obtained by using the method. The invention provides a surface treatment method, which comprises the following steps: step A: spraying a fluorine-free treatment agent on the surface of the base material; and a step B: drying the base material treated in the step A; wherein the fluorine-free treatment agent is an aqueous emulsion and comprises 10-70 wt% of acrylate copolymer or a mixture thereof, the glass transition temperature of the acrylate copolymer is-30-40 ℃, and 0.5-5.0 wt% of rheology modifier is based on the total weight of the fluorine-free treatment agent. The fluorine-free treating agent adopted by the invention can be coated on the surface of the substrate, especially the paper substrate, by a simple spraying mode, the method is convenient and fast to implement, has no requirement on the shape of the substrate, and is easier to popularize and apply.
Description
Technical Field
The invention relates to the field of waterproof and oil-proof agents, in particular to a spraying method of a fluorine-free oil-proof agent and an object obtained by using the method.
Background
The 'paper replacing plastic' is one of the most effective ways to solve the increasingly serious 'white' pollution problem at present. For paper packaging, paper has the advantages of biodegradability and recycling, but for paper products used in the fields of food, catering and the like, an impermeable barrier layer is required for contacting with food containing oil, fat and/or water, and the technical key of how to endow the paper packaging with waterproof and oil-proof functions is 'paper-for-plastic'. The development of the oil-proof agent for paper has great market potential and is a key field of the current technological innovation.
At present, the oil-proof treatment of paper materials is mainly divided into two types: the first method is to coat oil-proof plastic (commonly called as film coating or plastic coating) on the surface of paper, and the method can only reduce the pollution of the plastic but can not radically treat the pollution of the plastic; the second method is to add an oil-repellent agent into the paper pulp or to coat the paper surface with the oil-repellent agent to achieve the water-repellent and oil-repellent effects. The method greatly retains the advantages of paper biodegradation and recycling.
The mainstream products of the current oil-repellent agents are fluorine-containing oil-repellent agents, particularly perfluoroalkyl phosphate esters (salts) and perfluoroalkyl copolymers, and such polymers have excellent oil-repellent properties mainly due to the presence of C-F bonds which have high bond energy and a small fluorine atom radius, so that-CF3The groups have extremely low surface tension, so that the perfluoroalkyl compounds have excellent properties of being hydrophobic and oleophobic. The fluorine-containing oil-proofing agent is available in various ways, and can be added in the pulp or in the size press or in the coating process.
Research shows that C8-PFCs (perfluorocarbons containing 8 carbons) are gradually exiting the market due to the fact that the C8-PFCs are unsafe in toxicology, have bioaccumulation and potential systemic and developmental toxicity, and the like. Taking perfluorooctylsulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) as examples, the reaction raw materials of various fluorine-containing compounds or the final products of conversion in the environment are perfluorooctylsulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Since 1999, it is continuously discovered that these substances belong to the most difficult-to-decompose organic pollutants, which are not only not degraded by various heat, chemical and microbial actions, but also enter into the organism through respiratory tract inhalation and food intake, and are difficult to be discharged by the organism through metabolism, so that these substances will accumulate and persist in the environment and organism, thus leading to the ubiquitous existence of these pollutants in the global environment and affecting the blood, liver, newborn development, immune system and hormone level of the organism. In view of the great threat to the environment and the human health, various policies for forbidding the use of the PFOS and the PFOA are developed in various countries in the world, and products related to the PFOS and the PFOA are produced in large enterprises. Although most of the C8 series fluorine-containing oil-proof agents select C6 series fluorine-containing oil-proof agents as substitutes, the data of C6 series fluorine-containing substances on a plurality of toxicological nodes such as chronic and reproductive development toxicity and the like are still lacked, and the data show that PFHxA (undecafluorohexanoic acid, C6) and PFOA (perfluorooctanoic acid and salts thereof, C8 and above) have similar toxicological properties aiming at the chronic toxicity, but the accumulation in the liver is not observed, so that the damage action level (NOEAL) value is higher by several orders of magnitude relatively than that of long-chain PFCs.
In addition to fluorine-containing oil-repellent agents, fluorine-free oil-repellent agents have attracted attention in recent years. The fluorine-free oil-proof agent fundamentally avoids the harm of the fluorine-containing oil-proof agent or the film to the environment or organisms, and better meets the pursuit of people for green environmental protection. The 1997 Hangzhou chemical research institute develops an oil-proof agent HOR special for food packaging paper, which is a non-fluorine-containing copolymer aqueous composite emulsion with a core-shell structure. The Khaoula Khwaldia et al studies mentioned that natural polymers used as oil repellents are dispersed whey protein, zein, isolated soy protein, chitosan, etc. Ham-pichovant makes careful research on chitosan as an oil repellent, and although the chitosan can achieve the oil-proof effect of a fluorine-containing oil repellent, the viscosity of the chitosan at the concentration is too high, the chitosan is not easy to coat, the cost is too high, the cost is 3 times of that of the fluorine-containing oil repellent, and even if the chitosan is compounded with other natural polymer materials, the chitosan still has the problems of high viscosity, high price, inconvenience in operation and narrow application range. At present, other kinds of fluorine-free oil-proof agents are constructed by adopting a blade coating mode basically, the cost is overhigh, and the space for further improving the coating quality, the construction efficiency and the oil resistance exists.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the above problems of the prior art, the present invention provides a surface treatment method, which uses a fluorine-free treatment agent that can be applied to the surface of a substrate, especially a paper substrate, by a simple spraying method, and the method is easy to implement, has no requirement on the shape of the substrate, and is easier to popularize and apply.
Furthermore, it is also an object of the present invention to provide an object obtained using this method, which has excellent oil-repellent properties. Further, the object of the present invention also includes a method for improving the oil repellency of food-contactable paper materials.
Means for solving the problems
The invention comprises the following technical scheme:
[1] a surface treatment method, wherein the method comprises:
step A: spraying a fluorine-free treatment agent on the surface of the base material;
and a step B: drying the base material treated in the step A;
wherein the fluorine-free treating agent is an aqueous emulsion comprising:
10-70 wt% of an acrylic copolymer or a mixture thereof, wherein the glass transition temperature of the acrylic copolymer is-30-40 ℃ based on the total weight of the fluorine-free treating agent;
and 0.5 to 5.0 wt% of a rheology modifier,
based on the total weight of the fluorine-free treatment agent.
[2] The surface treatment method according to [1], wherein the fluorine-free treatment agent has a viscosity of 10 to 40 seconds as measured at 25 ℃ by a rock viscosity cup NK-2.
[3] The surface treatment method according to [1] or [2], wherein the fluorine-free treatment agent further comprises:
surfactant (b): 0 to 2 wt%
Dispersing agent: 0 to 5 wt%
pH regulator: 0 to 3 wt.%
The balance being water, based on the total weight of the fluorine-free treating agent.
[4] The surface treatment method according to any one of claims 1 to 3, wherein the rheology modifier is selected from the group consisting of povidone type, acrylic emulsion, styrene-acrylic emulsion, silicon dioxide, alkali-swellable emulsion, and/or nonionic polyurethane-associated rheology modifiers.
[5] The surface treatment method according to any one of the above aspects 1 to 4, wherein the spraying in the step A is performed by using a spray gun having a spray air pressure of 0.1 to 0.4 MPa.
[6]According to [5]]The surface treatment method described above, wherein the fluorine-free treatment agent is sprayed in an amount of 0.006g/cm in the step A2～0.02g/cm2Spraying the mixture on the surface of the substrate.
[7] The surface treatment method according to any one of the technical schemes [1] to [6], wherein the drying temperature is 75-120 ℃ and the time is 5-30 min.
[8] The surface treatment method according to any one of claims 1 to 7, wherein the substrate is a paper substrate.
[9] An object, wherein at least a part of the surface of the object is treated by the surface treatment method according to any one of [1] to [8 ].
[10] The object according to [9], characterized in that it is a paper-like product.
[11] A method for improving the oil repellency of a paper material which can be contacted with food, wherein the method comprises the step of treating the surface of the paper substrate by using the surface treatment method according to any one of the technical schemes [1] to [8 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The invention provides a surface treatment method, wherein the adopted fluorine-free treatment agent can be coated on the surface of a substrate, particularly a paper substrate, in a simple spraying manner, and the method is convenient to implement, has no requirement on the shape of the substrate, and is easier to popularize and apply. The fluorine-free treating agent used in the invention can eliminate the influence on fluorine supply source, environment and the like, has wide sources of preparation raw materials, low preparation cost, excellent water and oil proofing performance, controllable viscosity, good moldability and easy operation, can prepare high-performance oil-proof paper products by a spraying mode, greatly saves the use amount and the process time, and reduces the oil proofing cost of packaging materials. In some preferred embodiments of the present invention, the fluorine-free treatment agent of the present invention also has good water resistance and stability. The above description does not disclose all embodiments of the present invention and all advantages of the present invention.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims, and embodiments and examples obtained by appropriately combining the technical means disclosed in the respective embodiments and examples are also included in the technical scope of the present invention. All documents described in this specification are incorporated herein by reference.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
The range of values indicated by "value a to value B" or "value a to value B" in the description and claims of the present invention is intended to include the endpoint value A, B.
The meaning of "may" used in the specification and claims of the present invention includes both the meaning of performing a certain treatment and the meaning of not performing a certain treatment. "optional" or "optionally" in the description and claims of the invention means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. Such as "optionally added" means that it may or may not be added.
The term "comprises" and any variations thereof in the description and claims of the invention are intended to cover non-exclusive inclusions. For example, a process, method, or system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
The term "predominantly" in the present description and claims means that the substance or substances make up more than 60% by weight, preferably more than 80% by weight, of the total amount of such substances. For example, "the fluorine-free polymer is obtained by copolymerizing the following monomers mainly" means that the following monomers account for 60 wt% or more, preferably 80 wt% or more of the total amount of the copolymer monomers.
Reference throughout this specification to "some particular/preferred embodiments," "other particular/preferred embodiments," "some particular/preferred aspects," "other particular/preferred aspects," or the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
"grease-proof paper" in the specification and claims of the present invention refers to a paper or article that is rendered resistant to penetration and absorption of grease using an oil-repellent treatment added in the pulp or applied to the surface. "paper product" refers to products made from paper, including but not limited to paper, cartons, bags, trays, and the like.
By "treating" in the present specification and claims is meant applying the treatment of the present invention to a substrate, such as a paper substrate, by dipping, spraying, painting or the like. By the treatment, the effective component in the treatment agent is impregnated into the interior of the base material and/or attached to the surface of the base material.
By "food accessible" in the description and claims of the present invention is meant that the product is in contact with food in normal use, meeting GB9685 and us FDA registration requirements.
The surface treatment method of the present invention comprises:
step A: spraying a fluorine-free treatment agent on the surface of the base material;
and a step B: drying the base material treated in the step A;
wherein the fluorine-free treating agent is an aqueous emulsion comprising:
10-70 wt% of an acrylate copolymer or a mixture thereof, wherein the glass transition temperature of the acrylate copolymer is-30-40 ℃;
and 0.5 to 5.0 wt% of a rheology modifier,
based on the total weight of the fluorine-free treatment agent.
The inventor adjusts the formula of the fluorine-free treating agent to regulate and control the viscosity, thereby realizing good spraying operation, greatly improving the construction efficiency and simultaneously ensuring that the treated surface of the base material has excellent oil resistance.
The fluorine-free treating agent, the surface treatment method, the treated article and the like of the present invention will be described in order below.
< fluorine-free treating agent >
The invention firstly provides a fluorine-free treating agent, which means that the treating agent does not contain fluorine atoms.
The fluorine-free treating agent is an aqueous emulsion, the aqueous emulsion is an emulsion taking an aqueous medium (or aqueous liquid medium) as a dispersion medium, and the emulsion comprises 10-70 wt% of an acrylate copolymer or a mixture thereof, and further 15-55 wt%, wherein the glass transition temperature of the acrylate copolymer is-30-40 ℃, and further-25-30 ℃ based on the total weight of the fluorine-free treating agent. The acrylic copolymer or a mixture thereof is used as the oil-repellent component in the present invention.
In some embodiments of the present invention, the acrylate-based copolymer of the present invention is a fluorine-free polymer, and is formed by copolymerizing:
(I) (meth) acrylic acid;
(II) one or more acrylate monomers having the general formula (1):
CH2＝CX-C(＝O)-O-Y (1)
in the general formula (1), X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms or a halogen atom other than a fluorine atom, and Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms.
In the present invention, the above-mentioned monomers (I) and (II) account for 60 wt% or more, further 80 wt% or more, and further 100 wt% of the total amount of the acrylic copolymer monomers. The comonomers of the acrylate copolymers of the present invention optionally also include (iii) one or more vinyl aromatic monomers and/or (IV) a crosslinking monomer. The acrylic copolymer has the advantages of simple preparation and wide raw material source, and the acrylic copolymer with the structure has excellent water and oil resistance which is comparable to fluorine-containing oil-proof agents. In some embodiments of the present invention, the acrylic copolymer is obtained by copolymerizing the above-mentioned two monomers (i) and (ii). In other embodiments of the present invention, the acrylic copolymer is obtained by copolymerizing the above-mentioned three monomers (I), (II) and (III).
In the present invention, (i) (meth) acrylic acid includes acrylic acid and/or methacrylic acid, and in some embodiments of the present invention, the (i) monomer is selected from acrylic acid for better water and oil repellency.
In the present invention, (II) is one or more acrylate monomers having the general formula (1). Examples of the substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms in the general formula (1) include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and the like, and those substituted with an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen atom (except for a fluorine atom), an epoxy group-containing group such as a glycidoxy group, an epoxycyclohexyl group, an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group, and an isocyanate group, and if the carbon atom is more than 10, the oil repellency of the fluorine-free polymer is adversely affected. In some embodiments of the present invention, the substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms is a saturated alkyl group having 1 to 10 carbon atoms, further a saturated alkyl group having 1 to 5 carbon atoms, and further a saturated alkyl group having 1 to 4 carbon atoms. The halogen atom in the general formula (1) includes a chlorine atom, a bromine atom and/or an iodine atom. Examples of the substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms in the general formula (1) include cyclopentyl, cyclohexyl, tert-butylcyclohexyl, adamantyl, cycloheptyl, cyclopentenyl, cyclohexenyl, and the like, and groups substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom (except a fluorine atom), an epoxy group-containing group such as a glycidoxy group, an epoxycyclohexyl group, an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group, and an isocyanate group. In some embodiments of the present invention, X is selected from a hydrogen atom, Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, further X is selected from a hydrogen atom, and Y is a substituted or unsubstituted saturated alkyl group having 1 to 5 carbon atoms. The (II) monomer may be selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate and 2-ethylhexyl methacrylate. For better water and oil repellency and gloss requirements, the (II) monomer is selected from one or more of methyl acrylate, butyl acrylate, methyl methacrylate and/or butyl methacrylate.
In the present invention, (III) is optionally one or more vinyl aromatic monomers. Vinyl aromatic monomers include, but are not limited to, styrene, ethylvinylbenzene, alpha-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinyltoluene, methoxystyrene, t-butoxystyrene, and the like. In some embodiments of the invention, the vinyl aromatic monomer comprises styrene or ethylvinylbenzene or a mixture thereof. The addition of the monomer (III) can properly reduce the dosage of the monomer (II), and the monomer (III) belongs to a hard monomer, so that a core/shell structure is easily formed in emulsion polymerization, and the improvement of mechanical properties is facilitated.
In the present invention, it may optionally further contain (IV) a crosslinking monomer selected from a monomer having at least two reactive groups, a monomer having at least two carbon-carbon double bonds, or a monomer having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups include, but are not limited to, hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl, and the like. Examples of the crosslinking monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, methylol (meth) acrylate, hydroxyethyl (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like, but is not limited to these monomers.
The above monomers of the present invention may be used alone or in combination of two or more. Alternatively, the monomer of the present invention may be a single compound or a mixture of two or more compounds.
In some embodiments of the present invention, in order to obtain better water and oil repellency, (i) the monomer may be 30 wt% to 60 wt%, further 35 wt% or more, or 40 wt% or more, and further 55 wt% or less or 50 wt% or less based on the total weight of all monomers of the fluorine-free polymer. The amount of the (II) monomer may be 5 to 50 wt% based on the total weight of all the monomers of the fluorine-free polymer. In some embodiments of the present invention, the weight ratio of the monomers (I), (II) and (III) is 1:1 to 1.5:0 to 0.5, and further 1:1 to 1.5:0.1 to 0.5.
The acrylic copolymer of the present invention can be produced by a conventional polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, preferably by emulsion polymerization. In the emulsion polymerization, the monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier and stirred for 1 to 12 hours at a temperature of 50 to 80 ℃ to copolymerize the monomers. As the polymerization initiator, a peroxide initiator such as benzoyl peroxide or the like, or an azo initiator such as azobisisobutyronitrile or the like can be used. The polymerization initiator is used in an amount ranging from 0.01 to 5 parts by weight relative to 100 parts by weight of the total polymerizable monomers. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the amount of the emulsifier is in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. In the polymerization, a chain transfer agent may be used. The molecular weight of the acrylate copolymer may be varied depending on the amount of the chain transfer agent used. Examples of the chain transfer agent include lauryl mercaptan, thiol group-containing compounds such as mercaptoethanol and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium hydrogen phosphite. The amount of the chain transfer agent to be used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers. The polymerization may be random copolymerization or segmented polymerization. The addition of the comonomer can be carried out in one batch or can be carried out continuously. The acrylate copolymers of the present invention may be commercially available or may be self-made.
In some embodiments of the invention, the weight average molecular weight (M) of the acrylate copolymerw) Usually 10 to 70 ten thousand, and further 15 to 55 ten thousand, and usually measured by GPC (gel permeation chromatography).
The fluorine-free treating agent of the present invention comprises an aqueous liquid medium in addition to an acrylate copolymer or a mixture thereof as an oil repellent, and is an aqueous emulsion.
In the present specification, the "aqueous liquid medium" includes a medium composed of only water and a medium containing an organic solvent (usually a water-soluble organic solvent) in addition to water. Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, and the water-soluble organic solvent can be used in an amount of 0.1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of water. The amount of the aqueous liquid medium is 30 to 90 wt%, for example 40 to 85 wt%, based on the total mass of the oil-repellent agent. In some embodiments of the invention, the "aqueous liquid medium" is selected from deionized water.
To facilitate spraying, in some embodiments of the invention, the fluorine-free treating agent has a viscosity of 10 seconds to 40 seconds, further 15 seconds to 25 seconds, as measured at room temperature (e.g., 25 ℃) using a rockwell viscosity cup NK-2.
In order to better control the viscosity of the fluorine-free treatment agent, the fluorine-free treatment agent also comprises 0.5-5.0 wt% of a rheological regulator (also called rheological agent and thickening agent) based on the total weight of the fluorine-free treatment agent. The inventors have found that the addition of rheology modifiers can also increase the oil repellency in certain circumstances. In some embodiments of the invention, the rheology modifier is present in an amount of 0.5 to 2.0 wt%. It has been found by the present inventors that povidone, acrylic, styrene-acrylic, silica, alkali-swellable emulsions and/or nonionic polyurethane associated rheology modifiers can be used in the present invention, combining film-forming, oil-repellent and spray-coating considerations, and further that silica, alkali-swellable emulsions (including non-associated ASE and associated HASE) and nonionic polyurethane associated rheology modifiers are preferred for use in the present invention for better water-repellency and stability. Among them, the alkali-swellable emulsion contains a hydrophilic (meth) acrylic monomer and a hydrophobic (meth) acrylate monomer, and is an anionic acrylate copolymer emulsion that relies on a change from low pH to high pH (neutralization) to trigger thickening.
The fluorine-free treatment agent of the present invention further comprises one or more auxiliary agents of optionally added surfactants, dispersants and/or pH adjusters. The foaming property, the wettability and the permeability of the surfactant have certain influence on the film-forming property of the product, and compared with other types of surfactants, the nonionic surfactant adopted in the invention can enable the product to obtain better film-forming property. In the present invention, the nonionic surfactant is selected from one or more of polyoxyethylene sorbitan fatty acid ester, sugar ester, polyether surfactant, acetylene glycol surfactant, polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylate, and copolymer of silicone and polyether. The invention optionally adds a certain amount of dispersant for stabilizing the suspension, the dispersant is one or more dispersing aids, which can be inorganic nano-particles, polyamide dispersant and the like. In order to better control the pH, the fluorine-free treating agent of the present invention may further comprise a pH adjusting agent such as ammonia, etc. The pH value of the fluorine-free treating agent is adjusted by a pH adjusting agent. In some embodiments of the present invention, the pH of the fluorine-free treatment agent is in the range of 3 to 10, further in the range of 4 to 9, and further in the range of 6 to 9.
In some embodiments of the invention, the fluorine-free treatment agent of the invention comprises:
the aforementioned acrylate-based copolymer or mixture thereof: 10-70 wt%
Thickening agent: 0.5-5.0 wt%
Surfactant (b): 0 to 2 wt%
Dispersing agent: 0 to 5 wt%
pH regulator: 0 to 3 wt.%
The balance being water, based on the total weight of the fluorine-free treating agent.
In addition, if necessary, a certain amount of preservative may be optionally added to the fluorine-free treating agent of the present invention, and the preservative is used for inhibiting the growth of the bacterial species of the fluorine-free treating agent. In some embodiments of the present invention, the amount of the preservative in the present invention is 0 to 3.0 wt%, further 0.1 to 1.5 wt%, with respect to the total mass of the fluorine-free treatment agent. In order to improve the physical properties of the paper, other additives, such as plasticizers, water repellents, and the like, can be added to the fluorine-free treating agent to modify the properties of the pattern. In some embodiments of the invention, the invention adds an environment-friendly auxiliary agent, preferably an additive which can be contacted with food and/or an additive in food, so that the fluorine-free treatment agent (also called a fluorine-free oil-proof agent) in the invention has no harm to the environment and organisms, and the harm of the fluorine-containing oil-proof agent is radically avoided.
The preparation method of the fluorine-free treating agent of the invention is not particularly limited, and the fluorine-free treating agent can be prepared by adding the acrylic ester copolymer or the mixture thereof, the rheology modifier and other auxiliary agents into a liquid medium containing water in sequence in a common mode and mixing.
< method of surface treatment >
The invention provides a surface treatment method, which comprises the following steps:
step A: spraying the fluorine-free treating agent on the surface of the base material;
and a step B: and (D) drying the base material treated in the step (A).
In some embodiments of the present invention, a single spray and a single bake are used. In other embodiments of the present invention, two or more spraying and two or more drying may be performed, i.e., two or more times of the process of the present invention are circulated. The method of the invention is beneficial to large-area spraying or further improving the spraying uniformity after being circulated for multiple times.
In some embodiments of the invention, process step A is spray coating using a spray gun, said spray gun being adapted to spray coating material onto a substrateThe spraying air pressure of the spray gun is 0.1-0.4 MPa, and further 0.2-0.3 MPa. If a multi-time spraying mode is adopted, one or more spray guns can be selected according to actual needs. The spray width of the spray gun is not particularly limited, and may be, for example, 100mm or 180 mm. The spraying distance is 100-300 mm. In some embodiments of the invention, the fluorine-free treating agent is sprayed in process A in an amount of 0.006g/cm2～0.02g/cm2The paint is sprayed on the surface of the base material, so that the production cost is reduced as far as possible on the premise of ensuring the oil resistance and the spraying property. Further, in some preferred embodiments of the present invention, the thickness of the sprayed film is 0.004mm or more, further 0.008mm or more, and further 0.01 to 0.05mm, and the thickness of the film can be measured by a micrometer.
In some embodiments of the present invention, the drying temperature in the step (B) is 75 to 120 ℃, further 80 to 115 ℃, and the time is 5 to 30 min. There is no particular limitation on the apparatus for drying and the like.
In some embodiments of the present invention, the substrate to which the surface treatment method of the present invention relates may be exemplified by textile, stone, filters, dust covers, parts of fuel cells, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramics, plastics, painted surfaces, plaster, and the like. Examples of the fiber product include natural fibers of animals and plants such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, and polyacrylonitrile, semi-synthetic fibers such as acetate fibers, inorganic fibers such as asbestos fibers, and mixed fibers thereof. Preferably, the substrate is a paper substrate.
< object >
The invention further provides an object, wherein at least part of the surface of the object is treated by the surface treatment method according to the invention. The object of the invention has excellent oil-repellent properties. In some embodiments of the invention, the object is a paper-like article, further an oil-resistant paper-like article. The paper product substrate to which the oil-repellent agent of the present invention is applied can be manufactured by a conventional paper-making method. The following materials may be used as starting pulp materials for paper: bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high yield pulp such as high grade (grand) pulp, mechanical pulp or thermomechanical pulp, and the like. Mixtures may also be used between the pulp material described above and any of the synthetic fibers such as polyamides, polyimides, polyesters, polyolefins and polyvinyl alcohols. When the surface application method and the internal application method are employed, a sizing agent may be optionally added in addition to the fluorine-free treatment agent to improve the water resistance of the paper. Examples of the sizing agent are a cationic sizing agent, an anionic sizing agent, and a rosin sizing agent (e.g., an acidic rosin sizing agent, a neutral rosin sizing agent). Among them, styrene-acrylic acid copolymers, alkenyl succinic anhydrides, and alkyl ketene dimers are preferable. The amount of the sizing agent may be 0.001 to 5 wt% based on the amount of the pulp. In the surface application method, the present invention applies the fluorine-free treatment agent to the surface of the paper substrate by means of the aforementioned spray coating.
The invention also provides a method for improving the oil resistance of food-contactable paper materials, which comprises the step of treating the surface of a paper substrate or base paper by using the surface treatment method. The base paper is paper which has not been subjected to oil-repellent treatment. In some preferred embodiments of the present invention, the food-contactable paper material of the present invention has excellent oil repellency and water repellency and is simple to construct and easy to popularize and apply.
The invention is further illustrated, but not limited, by the following examples.
The present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
In the following, parts or% or ratios represent parts by weight,% by weight or ratios by weight, unless otherwise specifically noted.
Examples
Production example 1
4/5, OP-10, sodium dodecyl sulfate, ammonium persulfate and all monomers (acrylic acid, methyl acrylate, methyl methacrylate and butyl methacrylate) of the total amount of water are put into a container in a 1L reaction kettle, the mass ratio of the monomers of the acrylic acid, the methyl acrylate, the methyl methacrylate and the butyl methacrylate is 4:2:1:3 (the concrete mixture ratio is shown in Table 1), and the mixture is rapidly stirred and emulsified for 30min at room temperature; then the pre-emulsion of 1/3 and water of 1/5 are put into a reactor to be stirred; heating to the polymerization temperature of 60 ℃, reacting for 0.5-1 h, dropwise adding the rest pre-emulsion and a chain transfer agent lauryl mercaptan, and completing dropwise adding within 3 h; keeping the temperature for reaction until the conversion rate is more than 98 percent, cooling, adjusting the pH value, and discharging. Through testing, the acrylic ester copolymer 1 is prepared, and the glass transition temperature is-15 ℃, and the weight average molecular weight is about 30 ten thousand (measured by GPC).
The evaluation in examples and comparative examples was performed as follows.
(apparent viscosity)
Apparent viscosity (or apparent viscosity) at 25 deg.C as measured using a rockwell viscosity cup NK-2. In the following tables, the viscosity evaluation "low" indicates a residence time of < 15s, "medium" indicates a residence time of 15-45s, and "high" indicates a residence time of > 45 s.
(sprayability)
The surface appearance of the paper product after spraying was visually confirmed to evaluate the sprayability. Criteria for determining sprayability are as follows:
o: can be evenly sprayed, and the surface has no sagging phenomenon after spraying.
And (delta): can be sprayed, and the surface coating after spraying sometimes has uneven thickness
X: the viscosity of the fluorine-free treatment agent is too high to be sprayed.
(oil repellency)
A2X 4cm strip of fluorine-free oil-repellent paper was immersed in hot oil at 90 ℃ for 15min, and then the penetration was observed. The criteria for determining oil repellency are as follows:
o: no infiltration.
And (delta): by point or local penetration
X: there is a majority or total penetration.
(Water-repellency)
A2X 4cm strip of fluorine-free oil-proof paper was immersed in 80 ℃ hot water for 15min, and then the penetration was observed. The criteria for determining water repellency are as follows:
o: the paint film has no obvious change.
X: the paint film turns white when meeting water.
(stability)
The fluorine-free treating agent was placed in an oven at 54 ℃ and heat-stored for 7 days, and then the appearance and fluidity thereof were observed. The criteria for determining stability are as follows:
o: no obvious change in appearance.
X: there is delamination or precipitation or a significant increase in viscosity.
Examples 1 to 3 and comparative examples 1 to 5
The acrylic copolymer obtained in production example 1 and the rheology modifier were sequentially added to water to prepare a fluorine-free treatment agent in the following weight parts in table 1, and ammonia was added to adjust the pH to 8.5, and the viscosity was measured.
The obtained fluorine-free treating agent is sprayed by a rock field spray gun in an amount of 0.01g/cm2Spraying the base paper on the surface of the base paper, wherein the spraying air pressure of a spray gun is 0.2-0.3 MPa, and the spraying distance is 100-300 mm; and drying after spraying, and drying for 20min at 80 ℃ to obtain the fluorine-free oil-proof paper.
The stability and sprayability of the fluorine-free treatment agent were evaluated, and the oil repellency and water repellency of the fluorine-free oil-repellent paper were evaluated, and the results are shown in table 2.
The test formulations are shown in table 1:
TABLE 1 formulation of fluorine-free treating agent
| Name of ingredient | Content (wt.) | Remarks for note |
| Acrylic copolymer | 35％ | |
| Rheology modifier | Adding on demand | Variables of |
| Deionized water | Complement |
Table 2 results of performance investigation
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as limitations of the present invention, and modifications, variations and changes of the above embodiments are within the scope of the present invention as long as they are within the spirit and scope of the present invention.
Claims (10)
1. A surface treatment method, characterized in that the method comprises:
step A: spraying a fluorine-free treatment agent on the surface of the base material;
and a step B: drying the base material treated in the step A;
wherein the fluorine-free treating agent is an aqueous emulsion comprising:
10-70 wt% of an acrylate copolymer or a mixture thereof, wherein the glass transition temperature of the acrylate copolymer is-30-40 ℃;
and 0.5 to 5.0 wt% of a rheology modifier,
based on the total weight of the fluorine-free treatment agent.
2. The surface treatment method according to claim 1, wherein the fluorine-free treatment agent has a viscosity of 10 seconds to 40 seconds as measured at 25 ℃ using a rockfield viscosity cup NK-2.
3. The surface treatment method according to claim 1 or 2, wherein the fluorine-free treatment agent further comprises:
surfactant (b): 0 to 2 wt%
Dispersing agent: 0 to 5 wt%
pH regulator: 0 to 3 wt.%
The balance being water, based on the total weight of the fluorine-free treating agent.
4. The surface treatment process according to claim 3, wherein the rheology modifier is selected from the group consisting of povidone type, acrylic emulsion, styrene-acrylic emulsion, silicon dioxide, alkali-swellable emulsion and/or nonionic polyurethane-associative rheology modifiers.
5. The surface treatment method according to any one of claims 1 to 4, wherein the spraying in the step A is performed by using a spray gun having a spray air pressure of 0.1 to 0.4 MPa.
6. The surface treatment method according to claim 5, wherein the fluorine-free treatment agent is sprayed in an amount of 0.006g/cm in the step A2～0.02g/cm2Spraying the mixture on the surface of the substrate.
7. The surface treatment method according to any one of claims 1 to 6, wherein the drying temperature is 75 to 120 ℃ and the time is 5 to 30 min.
8. An object, characterized in that at least a part of the surface of the object is treated by the surface treatment method according to any one of claims 1 to 7.
9. The object according to claim 8, characterized in that it is a paper product.
10. A method of improving the oil repellency of a food-contactable paper material, which comprises treating the surface of a paper substrate with a surface treatment process as claimed in any one of claims 1 to 7.
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