KR20150062595A - Curing hwangchil composition, preparing method for the same, and manufacturing method of hwangchil coating film - Google Patents

Abstract

The present invention relate to a Dendropanax morbifera polymer material having excellent hardening time reduction, scratch resistance, heat resistance, solvent resistance, base resistance, and acid resistance. Dendropanax morbifera which is a natural resin expressing golden light is combined with a light (electron beams or gamma rays) or heat hardening monomer to chemically bind a Dendropanax morbifera component, capable of having a radical reaction, and a cross-linked polymer chain or physically isolate a component, that is impossible to participate in a chemical reaction, in a polymer net, thereby maintaining the properties of Dendropanax morbifera. The developed light hardening Dendropanax morbifera polymer has excellent film properties, may adjust a concentration of a Dendropanax morbifera color, and reduces hardening time to a minute scale, thereby ensuring economical feasibility in work. Moreover, a coating process is simple, so that the same may be used for handles, cellular phones, acrylic products, glass containers, nail reinforcing coating materials, cosmetic containers, tea cups, electronic products, packing materials, foods, and storing materials, and a dim golden color thereof may be used when a product needs to be gentrified.

Description

TECHNICAL FIELD The present invention relates to a curing yellowing chemical composition, a method for producing the same, and a method for producing a yellowing coating film. BACKGROUND ART [0002]

The present invention relates to a paint composition for forming a paint film having excellent physical properties such as shortening of curing time, improvement of content dissolution, improvement of scratch resistance, heat resistance and improvement of heat resistance by blending a Korean traditional natural resin showing golden color with a photocurable or thermosetting compound A chemical composition thereof, a process for producing the same, and a cured hard coat film produced by light (ultraviolet ray, electron beam, gamma ray, etc.) of the composition or a thermosetting reaction.

It is also known as a traditional paint, which is obtained by extracting a milky white or golden high viscosity gel obtained by applying a small scratch on a dendropanax morbifera Lev. (Dendropanax morbifera Lev.) Belonging to Araliaceae. The milky white, high viscosity gel has a peculiar property that turns into golden color over time. However, it grows only in the temperate forests and grows only in some parts of the south coast including Jeju Island, which is a hot and humid region in Korea. Hwangchil has a similar ecology to other trees, and it has been used as a natural traditional paint on the surface of a product that has a natural flavor for a long time after drying the hwachil in the sunlight.

The natural whitish paint has a long drying time until it exhibits proper hardness and the dried whitish paint film is weak in mechanical properties, water resistance, alkali resistance and solvent resistance and is partially applied to the surface of some artworks or decorative products Has come. There have been prior art techniques for improving the characteristics of such a hardening time and coating film.

Previous studies have shown that the addition of a small amount of thermal initiator and photoinitiator to the natural whitening process reduces the drying or curing time by using a combination of heat and light. [Registration No. 10-1170387, Patent No. 10-2011-0135601]. Mixed organic solvents were used to improve the solubility of natural yellowgrass and it was mixed with oily artificial coatings (lacquer, varnish, cellak, cashew) and vegetable oil (extracts of corn, soybean, rice bran, olive, coconut, etc.) There is also a case in which a coating composition having a composition is developed [Registration No. 10-0199689].

It is an object of the present invention to provide a paint which has golden unique characteristic of Korean traditional natural paint which is golden, and which has improved workability and quick curing speed within a few minutes to shorten the curing time and is excellent in heat resistance, alkali resistance, acid resistance, (Or electron beam, gamma ray) or a thermosetting chemical composition capable of forming a yellowish coating film having improved scratch resistance and the like, a method for producing the chemical composition, a method for forming a greyish coating film using the composition, and a method for forming the same .

The sulfuric acid chemical composition according to an embodiment of the present invention may contain 0.01 to 99 parts by weight of refined yellowing, 0.01 to 99 parts by weight of a compound capable of crosslinking or linear bonding, 0.001 to 10 parts by weight of an initiator and 0 to 70 parts by weight of an additive; Wherein the compound capable of crosslinking or linear bonding is selected from the group consisting of an ene compound having at least one carbon-carbon double bond in the compound, a thiol compound containing a thiol group in the compound, an oligomer of the ene compound, , And the additive includes any one selected from the group consisting of a diluent, a defoaming agent, a leveling agent, and a combination thereof.

The initiator may include any one selected from the group consisting of photoinitiators, thermal initiators, and combinations thereof.

The photoinitiator may be selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, acetophenone, 2-hydroxy-2-methyl- 2-methyl-1-phenyl-1-propanone, benzaldehyde, benzoin propyl ether, triphenylamine, 3-methylacetophenone, 4-phenylbenzophenone, benzyl ketal, alpha-hydroxyalkylphenone, alpha -aminoalkylphenone, acetylphosphine oxide, and combinations thereof.

Wherein the thermal initiator is selected from the group consisting of ROO-R 'wherein R and R' are each independently selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms (Wherein R is any one selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms), benzoyl peroxide Organic peroxides including seeds; Hydroperoxides, mixtures of persulfate and a reducing agent, oxidation-reduction agents comprising a mixture of hydroperoxides and iron (II); RN = N-R 'wherein R and R' are each independently selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms ), And azobisisobutyronitrile (AIBN); And a metal compound containing alkylated silver (R-Ag, wherein R is an alkyl group having 1-20 carbon atoms).

The compound capable of crosslinking or linear bonding may be a mixture of two different compounds.

The crosslinking compound _{is, - (CH 2) a -CH} = CH 2, - (CH 2) a -O-CH = CH 2, - (CH 2) a -O-CH = CH-CH 3, _{- (CH 2) a -O- (} CH 2) b -CH = CH 2, - (CH 2) a -OCO-CH = CH 2, - (CH 2) a-CH = CH 2 -H, - ( _{CH 2) a - (CH =} CH 2) b -H, - (C 6 H 6) a -CH = CH 2, - (C 6 H 6) a -O-CH = CH 2, - (C 6 H _{6) a -O-CH = CH} -CH 3, - (C 6 H 6) a -O- (CH 2) b -CH = CH 2, - (C 6 H 6) a -OCO-CH = CH 2 _{, - (C 6 H 6)} a -CH = CH 2 -H, - (C 6 H 6) a - (CH = CH 2) b -H, - (C n H m) a -CH = CH 2, _{- (C n H m) a} -O-CH = CH 2, - (C n H m) a -O-CH = CH-CH 3, - (C n H m) a -O- (CH 2) b _{-CH = CH 2, - (C} n H m) a -OCO-CH = CH 2, - (C n H m) a -CH = CH 2 -H, - (C n H m) a - (CH = _{CH 2) b -H, - (} CH 2 - CH 2 -O) a -CO-CR = CH 2, -R (CH) a -NH-CO-CH = CH 2, - (CH 2 - CH 2 - O, _a , b, n and m are each independently selected from the group consisting of _a -CO-CR = CH ₂ , -R (CH ₂ ) _a -NH-CO-CH═CH ₂ , from 1 to 100, and a natural number, wherein R is -H, -CH _3, - a (CH _{2) n} CH _3, or -OH) of the compound 1 < / RTI > to 100 < RTI ID = 0.0 >

The crosslinkable compound may be at least one selected from the group consisting of ethylene glycol dimethyl acrylate derivatives, methylene bisacrylamide derivatives, polyester acrylates, epoxy acrylates, urethane acrylates, polyester acrylates, ) Acrylate Any one functional group selected from the group consisting of allyl ether, allylamine, vinyl ether, unsaturated esters, styrene, maleimides, and combinations thereof may be present in the compound in an amount of 1 to 100 It may be included.

The thiol compound may be selected from the group consisting of alkane dithiol, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptobutyrate), trimethylolpropane butanediol bis (2-mercaptobutyrate), butanediol bis (3-mercaptopropionate), butanediol bis (2-mercaptobutyrate), butanediol bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptobutyrate), 1,3,5-triazine, and the like. (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (3-mercaptopropionate) Triazine-2,4,6-trione tris (3-mercaptopropionate), 1,3,5-tri (2-hydroxyethyl) -1,3,5-triazine- , 6-trionetris (2- (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (2-mercaptobutyrate) and combinations thereof. It can be one.

The above-mentioned ene compound is preferably selected from the group consisting of (meth) acrylate, allyl ether, allylamine, vinyl ether, and the like, including polyester acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, , Unsaturated esters, styrene, maleimides, and combinations thereof.

The cross-linkable compound is selected from the group consisting of diurethane dimethacrylate (DUDMA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol divinyl ether 1,4-butanediol divinylether, BDVE), bisphenol A glycerol, glycerol / phenol diacrylate (BPAGD), trimethylolpropane trimethacrylate (TMPTMA), trimethylol (TMPTA), 2,4,6-triallyloxy-1,3,5-triazine (TAOTA), 1, 2,4,6-triazine , 3,5-triallyl-1,3,5-triazine-2,4,6-trione, 1,3,5- TANTA), tri (ethylene glycol) divinyl ether (TEGDVE), and combinations thereof.

The cross-linkable compound is a monomer having a viscosity of 0.01 to 500,000 cps or less, and the sulfuric acid chemical composition may not further contain an organic solvent.

The sulfuric acid chemical composition may include the compound capable of crosslinking and the purified sulfuric acid in a weight ratio of 10: 1 to 40.

The refined yellowing can be lyophilized to a freeze-dried refined yellowish having a liquid or solid form.

According to another embodiment of the present invention, there is provided a method for producing a cured yellowish coating film, comprising: (1) preparing a yellowish coating solution by mixing a sulfuric acid chemical composition; (2) coating the above-described yellowish coating liquid on a substrate to produce a yellowish coating film; And (3) curing the yellowish coating film by light irradiation treatment or heat treatment to obtain a yellowish coating film.

In the step (3), the time (curing time) of the light irradiation treatment or the heat treatment may be within 30 minutes.

In the step (3), the light irradiation treatment may be performed using ultraviolet light at a light amount of 5,000 mW or less per unit area of the peroxide coating film, or by using gamma rays or electron beams.

The heat treatment may be to treat the yellowish coating film at a temperature of 40 to 200 ° C.

The refined yellowtail may be an organic extraction-purified yellowtail refined by an extraction method using an organic solvent, or a freeze-dried refined yellowtail refined by using a freeze drying method.

The freeze-drying method may include a step of freezing the organic extraction-refined yellowtail and then drying it for at least 8 hours at a vacuum or a low pressure of minus 10 ° C or less and 10 mTorr or less.

Hereinafter, the present invention will be described in more detail.

Unless otherwise defined in the present invention, the term "yellowish liquor" refers to a liquid of yellowgrass which is used for a traditional paint, such as a yellowish lacquer, and refers to a yellowish state before being collected and purified.

Unless defined otherwise in the present invention, refined yellowing refers to natural yellowing in which the yellowing liquid is refined and the foreign material is removed from the yellowing liquid and the excessive water content contained in the yellowing liquid is reduced. The refined yellowish crust may be in a viscous liquid state according to the purification method, and may be in gel or solid form. Unless otherwise specified in the present invention, refined yellowing refers to refined yellowing without special suggestions for its shape.

Unless defined otherwise in the present invention, the wollastonite film means a coating film formed and cured by using a composition including a sulfuric acid solution or refined yellowing. The cured yellowish coating film means a coating film obtained by curing a coating film by light (or electron beam, gamma ray) or heat, by mixing yellowish or refined yellowish with photocurable or thermosetting monomers.

The cerium oxide chemical composition according to one embodiment of the present invention can produce a cured hard coat film which is cured by light irradiation or heat treatment within a period of several minutes to several tens of minutes, and has improved heat resistance, scratch resistance, solvent resistance, acid resistance, 0.01 to 99 parts by weight of refined yellowing, 0.01 to 99 parts by weight of a compound capable of crosslinking or linear bonding, 0.001 to 10 parts by weight of an initiator, and 0 to 70 parts by weight of an additive.

Unlike the conventional method of forming a coating film by drying the refractory yellow crust, the above sulfuric acid chemical composition is prepared by mixing a compound capable of crosslinking with an initiator to form a coating film formed only by refined yellowing, It is possible to improve physical properties such as gender. Further, by using a compound capable of crosslinking, it is possible to appropriately use the compound of the present invention so as to determine whether the yellowish tint of the hardened yellowish coat, the transparency of the hardened yellowish coat, the smooth or rough appearance of the hardened yellowish coat, Can be adjusted.

The compound capable of cross-linking or linear bonding is preferably a compound having at least one carbon-carbon double bond in the compound, a thiol compound having a thiol group in the compound, an oligomer of the ene compound, an oligomer of the thiol compound, It is selected from the group.

For example, the crosslinkable compound may be - (CH ₂ ) _a -CH═CH ₂ , - (CH ₂ ) _a -O-CH═CH ₂ , - (CH ₂ ) _a -O-CH═CH _{-CH 3, - (CH 2)} a -O- (CH 2) b -CH = CH 2, - (CH 2) a -OCO-CH = CH 2, - (CH 2) a-CH = CH 2 - _{H, - (CH 2) a} - (CH = CH 2) b -H, - (C 6 H 6) a -CH = CH 2, - (C 6 H 6) a -O-CH = CH 2, - _{(C 6 H 6) a -O} -CH = CH-CH 3, - (C 6 H 6) a -O- (CH 2) b -CH = CH 2, - (C 6 H 6) a -OCO- _{CH = CH 2, - (C} 6 H 6) a -CH = CH 2 -H, - (C 6 H 6) a - (CH = CH 2) b -H, - (C n H m) a -CH _{= CH 2, - (C n} H m) a -O-CH = CH 2, - (C n H m) a -O-CH = CH-CH 3, - (C n H m) a -O- ( _{CH 2) b -CH = CH 2} , - (C n H m) a -OCO-CH = CH 2, - (C n H m) a -CH = CH 2 -H, - (C n H m) a _{- (CH = CH 2) b} -H, - (CH 2 - CH 2 -O) a -CO-CR = CH 2, -R (CH) a -NH-CO-CH = CH 2, - (CH 2 _{- CH 2 -O) a -CO-} CR = CH 2, -R (CH) a -NH-CO-CH = CH 2 and mixtures thereof of any one of functional groups selected from the group consisting of combinations (the a, b, n , m each independently it is 1 to 100 of a natural number, wherein R is _{-H, -CH 3, - (CH} 2) _n is CH _3, or -OH ) May be contained in the compound in an amount of 1 to 100.

The compound capable of crosslinking or linear bonding may be selected from the group consisting of ethylene glycol dimethyl acrylate derivatives, methylene bisacrylamide derivatives, polyester acrylates, epoxy acrylates, urethane acrylates, polyester acrylates, silicone acrylates (Meth) acrylate having at least one functional group selected from the group consisting of allyl ether, allylamine, vinyl ether, unsaturated esters, styrene, maleimides, and combinations thereof. 1 < / RTI > to 100 < RTI ID = 0.0 >

For example, the ene compound may be selected from the group consisting of allyl ether, allylamine, vinyl ether, (meth) acrylate, unsaturated esters, styrene, maleimide, norbornene and pentaerythritol But are not limited to, pentaerythritol triallyl ether, triallyloxy triazine, triallyl isocyanurate, alkane divinyl ether, trimethylolpropane triallyl ether, multi (dimethylsiloxane) dinorbornene, and the like, and combinations thereof.

The oligomer of the above-mentioned ene compound may also be an epoxy acrylate, a polyester acrylate, a urethane acrylate, a polyether acrylate, a polybutadien acrylate, (degree of polymerization) of from 2 to 20 repeating structural units in the polymer between 8 and 12 carbon atoms such as acrylate, silicone acrylate, unsaturated polyester, and non-acrylate.

For example, the thiol compound may be selected from the group consisting of alkane dithiol, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercapto tris Butanediol bis (2-mercaptobutyrate), butanediol bis (3-mercaptopropionate), butanediol bis (2-mercaptobutyrate), butanediol bis (2-mercaptobutyrate) , Pentaerythrytal tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptobutyrate), 1,3 (1,3-mercaptopropionate) Tri (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (3-mercaptopropionate) 3-mercaptopropionate}, 1,3,5-tri (2-hydroxyethyl) -1,3,5-triazine -2,4,6-triione (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (2-mercaptobutyrate) and combinations thereof May be any one selected from the group consisting of

The crosslinkable compound is preferably selected from the group consisting of diurethane dimethacrylate (DUDMA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol divinyl 1,4-butanediol divinylether (BDVE), bisphenol A glycerol, glycerol / phenol diacrylate (BPAGD), trimethylolpropane trimethacrylate (TMPTMA) Trimethylolpropane triacrylate (TMPTA), 2,4,6-triallyloxy-1,3,5-triazine (TAOTA), 2,4,6- , 1,3,5-triallyl-1,3,5-triazine-2,4,6-triene, trione, TANTA), tri (ethylene glycol) divinyl ether, TEGDVE, and combinations thereof.

For example, when the compound capable of crosslinking includes 1,6-hexanediol diacrylate (HDDA), the scratch resistance of the cured hard coat can be further improved, and 1 And 1,4-butanediol divinylether (BDVE), it is possible to improve the solvent resistance, and in the case of containing diurethane dimethacrylate (DUDMA), the cured hard coat film It has some elasticity and can have characteristics such as impact reduction and slip prevention.

The compound capable of crosslinking may include two or more compounds capable of different crosslinking, and a mixture of two or more compounds capable of different crosslinking may be used to control the physical properties of the cured hard coat film.

The crosslinkable compound allows the initiator to be used together to quickly cure when forming the greyish coating.

Refined yellowcurrant is produced by removing impurities from natural yellow crust and removing moisture and the like, and has the characteristics of natural yellow crust.

In recent literature, the phenomenon that the double bond (IR peak 1600 ~ 1700cm ^-1 ) disappears in the natural yellowish crust during curing, the natural yellowish crust grows in part Crosslinking is observed. [H.-J.Dark and H.-J. Kim, Wood Sci. 48, 346-347 (2002).

Natural whiting is a chemical compound of a small molecule whose components are dissolved in n-hexane (β-cubebene, δ-cadinene, β-selinene, α-Cubebene, Ylangene, α-elemene, δ-elemene, germacrene-d (II), Aromadendrene oxide, etc.), which are known to be composed of α-Muurolene, α-Humulene, α-selinene, α-calacorene, spathulenol, tau-Cadinol, tau-Muurolol, Epiglobulol, Other chemical compounds that can form double linear polymers are reported to contain trace amounts (Octadeca-3Z, 16E-dien-5,7-diynoic acid, ethyl ester and alcohol). (Han, Jongsoo, Dongbang Journal, Vol. 3, No. 1, 1-14, February 2010)

Thus, the multifunctional monomer component that can cause crosslinking appears to be present only in a smaller amount in natural whitening, and therefore, when the real coating is formed, the crosslinking density is considerably reduced. The inventors of the present invention decided that the poor solvent resistance and poor physical properties of the coating film were attributable to the fact that too little crosslinking was possible in the coating film, so that a compound capable of crosslinking was introduced into the paint film, And to obtain a cured hard coat layer having excellent physical and chemical stability by chemically bonding the ingredients of natural whitish with the coating or physically fixing the whitish component by the dense crosslinking of the coating film.

In order to increase the crosslinking rate in the cured yellowish coating film, it is preferable to remove the components such as moisture contained in the refining yellowish oil from the body odor process of the organic solvent or the yellowing oil introduced during the removal process of the impurities. Therefore, in order to remove the impurities, for example, a process of mixing and filtering the organic solvent and the solution of the sulfuric acid solution may be performed, and the organic solvent may be removed from the sulfuric acid solution subjected to the filtering process. The removal of the organic solvent can be carried out, for example, using a reduced-pressure circulating still or a heated vacuum method.

The yellowish liquid from which the impurities, organic solvent, moisture and the like have been removed is referred to as refined yellowing, and the case where no further treatment by the freeze-drying method described below is carried out according to the degree of removal is called organic extraction-refining yellowing.

The organic extraction-refined yellowtail is obtained in the form of a gel or a high-viscosity solution, and can be directly applied to the sulfuric acid chemical composition.

The refined yellowing that is included in the yellowing chemical composition may include the freeze-dried refined yellowing which further reprecipitates the organic extraction-congealing yellowing and secondly removes the water and the organic solvent capable of partially remaining. When freeze-drying-refined yellowing is used in the above-mentioned sulfuric acid chemical composition, the degree of crosslinking of the yellowing coat can be increased, which is a method of further improving physical properties of the yellowing coating film.

The lyophilization-refined yellowish lime can be prepared in the form of a liquid or a solid, thereby providing convenience in storage and transportation of the refined yellowish lime.

The term " initiator " means a radical initiator which is a compound that generates radicals by breaking bonds of weak chemical bonds by light, heat, chemical reaction or radiation.

For example, the thermal initiator may be selected from the group consisting of ROO-R 'wherein R and R' each independently represent an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, (Wherein R is any one selected from the group consisting of an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms) ), Organic peroxides including benzoyl peroxide; Hydroperoxides, mixtures of persulfate and a reducing agent, oxidation-reduction agents comprising a mixture of hydroperoxides and iron (II); RN = N-R 'wherein R and R' are each independently selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms ), And azobisisobutyronitrile (AIBN); And a metal compound containing alkylated silver (R-Ag, wherein R is an alkyl group having 1-20 carbon atoms).

The initiator may be one comprising a photoinitiator.

Examples of the photoinitiator applied to the ultraviolet curing type sulfuric acid compound of the present invention include 1-Hydroxy-Cyclohexyl-Phenyl-Ketone (trade name Irgacure 184, Ciba Co.), acetophenone, 2- Hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy- Benzophenones such as propyl ether, triphenylamine, 3-methylacetophenone and 4-phenylbenzophenone, benzyl ketals, α-dialkoxy acetophenenes, It may be used in combination with one or more kinds of α-hydroxy alkyl phenones, α-amino alkyl phenones, and acetyl phosphine oxides.

Preferably, the photoinitiator is selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, acetophenone, 2-hydroxy-2-methyl- Benzene ketal, alpha -dialkoxy, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzaldehyde, benzoin propyl ether, triphenylamine, 3- Acetophenone,? -Hydroxyalkylphenone,? -Aminoalkylphenone, acetylphosphine oxide, and combinations thereof.

When the photoinitiator is included as the initiator, the curing time can be drastically shortened in the production of the hardened painted film using the above-described pain relief chemical composition. The coatings prepared from natural wild grasses required a considerably long drying time to take a few days to cure or dry. However, in the present invention, the curing time is shortened to several tens of minutes, and it can be applied differently depending on the thickness of the coating film manufactured using the sulfuric acid chemical composition, the kind of light to be irradiated, the temperature at the heat treatment, Can be completed. When the thickness of the coating film applied once is about 100 m or less, curing can be performed within a period of about 30 minutes so that the curing of the coating film can be completed. It is possible to control the thickness of the coating film to be painted and the composition contained in the chemical composition so that the hardening of the film can be performed even in the first time within about 10 minutes and within 180 seconds.

The sulfuric acid chemical composition may include the crosslinkable compound and the purified sulfuric acid in a weight ratio of 10: 1 to 40. Depending on the relative amount of the compound capable of crosslinking and the amount of refined yellowing, the yellow coloring of the cured yellowing film produced using the Huangchil chemical composition can be controlled.

Considering that sulfuric acid itself is limited in harvesting the sulfuric acid solution, the collected sulfuric acid solution is expensive, and the physical properties of the coated film formed only by the purified sulfuric acid solution are weak, it is necessary to minimize the amount of sulfuric acid solution used, , And it is preferable that the compound capable of crosslinking and the above-mentioned purified yellow crudes are contained in a weight ratio of 10: 1 to 40. [ In addition, when the compound capable of crosslinking and the purified yellowing are contained in a weight ratio of 10: 1 to 10, a cured yellowish coating film having excellent coating properties can be obtained even without application of an additional additive in a short time.

The sulfuric acid chemical composition may or may not further include a solvent. When a solvent is required in the form of the purified yellowish gel or the liquid having a high viscosity, an additional solvent may be used. However, when a compound capable of crosslinking is selected to have a low viscosity, the use of a solvent can be reduced, Ease of formation, ease of storage of the coating solution, and the like. Preferably, the cross-linkable compound may have a viscosity of 0.01 to 500,000 cps.

The additive may include any one selected from the group consisting of a diluent, a defoaming agent, a leveling agent, and a combination thereof. The additive may or may not be included in the above-mentioned sulfuric acid chemical composition, if necessary.

The diluent is a material mixed to improve the ease of work in the process of preparing a yellowish coating solution prepared by mixing a sulfuric acid chemical composition and using the same to prepare a yellowish coating film. Examples of the diluent include heptane, hexane, But are not limited to, pentane, cyclohexane, trichloroethylene, carbon tetrachloride, Di-Iso-Propyl Ether, toluene, methyl- Methyl-t-butyl ether, xylene, benzene, diethyl ether, dichloromethane, 1,2-dichloroethane, N-butanol, n-propanol, chloroform, ethylacetate, isopropanol, n-butanol, isobutanol, butylacetate, iso-propanol, n-butanol, tetrahydrofuran, 2-butanone, dioxane, acetone It can be used in a wide variety of applications such as acetone, methanol, ethanol, acetonitrile, acetic acid, dimethylformamide, dimethylsulfoxide, water, methyl ether ketone methyl-ether-keton), ketones, and organic solvents such as sesame oil, terpine oil, and oil.

The antifoaming agent is a substance to be added to remove bubbles generated during mixing of the sulfuric acid compound or to inhibit the formation of bubbles. The antifoaming agent may be selected from the group consisting of fatty acids, alcohols, esters, amines, polyhydric alcohols, Oxyamides are used or diluted in water or solvent.

The leveling agent is an additive for improving the fluidity of a coating film. Examples of the additives include polyalkyl acrylate, polyalkyl vinyl ether, cellulose acetate butylate, dimethyl polysiloxane (Di methyl polysiloxane, Methyl phenyl polysiloxane, Organic modified polysiloxane, and a fluorine surfactant.

Additional additives used in other coating formulations may be used.

When the sulfuric acid chemical composition is used, it can be mixed without phase separation between the purified sulfuric acid and the compound capable of crosslinking at the time of preparing the sulfuric acid coating solution, and can be mixed with ultraviolet (UV), electron beam, A crosslinkable compound (such as a monomer) is grown as a polymer of a network by a crosslinking chemical reaction to form a hardened film.

As illustrated in FIG. 1, in the crosslinked yellowish coating film, the yellowish component is physically fixed between the chemical bonds or the network in the polymer chain. (A) chemically cross-linked to a chain of crosslinked polymers having at least two double or triple bonds, or (b) chemically attached to only one side of the crosslinked polymer chain, or (C) a yellowish coating may be formed in a state (d) in which all of the above three cases (a), (b) and (c) are included.

According to another embodiment of the present invention, there is provided a method for manufacturing a cured yellowish coating film, comprising the steps of: (1) preparing a yellowish coating solution by mixing the above-described sulfuric acid chemical composition; (2) coating the above-described yellowish coating liquid on a substrate to produce a yellowish coating film; And (3) curing the yellowish coating film by light irradiation treatment or heat treatment to obtain a yellowish coating film. Specific details of the above-described sulfuric acid chemical composition are the same as those described above, and thus the description thereof will be omitted.

In the present invention, the time (curing time) of the light irradiation treatment or the heat treatment in step (3) is within a few tens of minutes, and the fast curing time is characterized by the invention. The curing time depends on the kind of crosslinkable compound used, the content of refined yellowish crushed, the thickness of the yellowish coating film formed in step (2), the amount of light per light type or the unit area in the light irradiation treatment, The curing can be completed within about 30 minutes. This is a remarkably short time considering that it takes a few days to harden or dry the existing yellowish paint film. Preferably, the curing time can be within 10 minutes, 30 seconds to 6 minutes.

The light irradiation treatment in the step (3) may be a treatment using ultraviolet light at a light intensity of 5,000 mW or less per unit area of the peroxide coating film, a treatment using a gamma ray or an electron beam, a light intensity of 100 to 5,000 mW or less , Or by using ultraviolet rays. If the light amount per unit area is less than 100 mW, the curing reaction may not be sufficiently performed or may proceed slowly. If the light amount per unit area is more than 5,000 mW, the physical properties of the coating film may be deteriorated due to the difference in reaction speed between the surface and the inside of the coating film.

For example, when the thickness of the yellowish coating film is 100 탆 or less, a lightly cured yellowish coating film can be obtained by irradiating light with a light intensity of 5,000 mW or less for 30 minutes or less.

The heat treatment in the step (3) may be a step of heat-treating the burnt coating film at a temperature of 40 to 200 ° C. If the temperature of the heat treatment is less than 40 占 폚, the effect of the heat treatment may be insignificant. If the temperature exceeds 200 占 폚, the physical properties of the cured painted film may be deteriorated due to damage to the cured yellowish coating film. Preferably, the heat treatment may be performed at a temperature ranging from 40 to 150 ° C.

The refined yellowtail may be an organic extraction-refined yellowtail refined by an extraction method using an organic solvent, or a freeze-dried refined yellowtail refined using the freeze-drying method, or a mixture thereof .

The organic extraction method may be applied to a method of organic extraction generally used, and may be applied to a method of filtering the organic solvent after mixing with an organic solvent. The organic solvent includes, for example, tetrahydrofuran (THF) Can be applied.

The freeze-drying method can be applied to a freeze-drying method capable of removing moisture and residual organic extraction solvent while minimizing the volatilization of the sulfuric acid component of the organic extraction-refined yellowtail.

For example, the freeze-drying method may include a step of freezing the organic extraction-refined yellowtail at a freezing temperature of minus 10 ° C or less and then drying the organic extraction-refined yellowtail for a drying time of 8 hours or more at a vacuum or a low pressure of 10 mTorr or less ≪ / RTI >

The freezing temperature may preferably be in the range of minus 10 to minus 100 ° C, and the pressure in the vacuum or low pressure state may be preferably 0.01 mTorr to 10 mTorr, and the freeze-drying time may preferably be 12 to 200 hours. The freeze-dried tablets of the present invention can be prepared by freeze-drying-refined yellowing for distinguishing them from the organic extracted tablets of the present invention. The freeze-dried tablets of the present invention can be produced in the form of a liquid or solid having a high viscosity, This is easier.

The method for producing a cured yellowish coating film is a method for curing a yellowish coating film which is capable of shortening the curing time so that the curing can proceed within a few minutes and curing (ultraviolet ray, electron beam, gamma ray) hardening with improved heat resistance, scratch resistance, solvent resistance, A yellowish paint film can be produced. In addition to this, it is possible to control the transparency and surface texture of the yellow color coat by adjusting the composition and content of the yellowish chemical composition, and improve the physical properties such as scratch resistance, such as chemical resistance and heat resistance . In addition, it is possible to reduce the use amount of the expensive raw material (or the refined yellow rust), and also to shorten the curing time drastically, thereby improving the economical efficiency and the compatibility of the cured yellowish coating film and facilitating the mass production of the hollowing resin.

The sulfuric acid chemical composition of the present invention and the method for producing the sulfuric acid film can be cured in a short time of several tens of minutes or less by using photo-curing, thereby providing a sulfuric acid composition having workability and quick drying property. The whitening film formed by using the above-described whitening composition has excellent physical properties such as alkali resistance, acid resistance, organic solvent resistance and heat resistance, and the formation of the coating film is improved. By adjusting the compounding ratio of the whitening chemical composition, Scratch resistance can also be given. Further, it is possible to control the shade of color of the existing yellowish paint film and to manufacture the yellowish paint film having improved physical properties in a short time. By adjusting the amount of yellowing, it is possible to tune the color and the characteristics of the coating film, and a small amount of yellowing can be used to obtain a hardened yellowing film, thereby improving the economical efficiency and compatibility.

In addition, the coating process is simple, and it can be used for handle, mobile phone, acrylic product, glass container, nail reinforced coating material, cosmetics container, multimedia, electronic product, packaging material, food and storage material, Can be used where required.

FIG. 1 is a conceptual diagram showing a method in which refined yellowhatch is physically, chemically, or both bonded to a greyish coating film.
FIG. 2 is a graph showing the results of a comparison between purified natural whitening film Comparative Example 1 (a yellowish paint film sample prepared by natural hardening of refined yellowtail refined using THF) and thiol-ene yellowing chemical Example 4-1 The mixture of the refined sulfuric acid was adjusted to 18 mW / cm < ² > (A yellowish paint film sample produced by UV curing for 180 seconds in an ultraviolet exposure machine of the present invention).
Fig. 3 is a graph showing the results obtained when the present invention is prepared by immersing the surface of Comparative Example 1 (refined yellow crust) in an acidic solution (sulfuric acid aqueous solution of pH 1.26) and a basic solution (aqueous sodium hydroxide solution of pH 12.70) This is the result of observing the degree of emergence.
FIG. 4 is a graph showing the results of a comparison between the results of Example 5-2 of the present invention after coating a glass plate with a composition obtained by mixing triethylol propane triacrylate (TMPTA), 1,4-butanediol divinyl ether (BDVE) and photoinitiator (HCPK) ² (A sample prepared by UV curing for 180 seconds in an ultraviolet exposure apparatus of the present invention) for 16 hours in an acidic solution (aqueous solution of sulfuric acid of pH 1.26) and a basic solution (aqueous solution of sodium hydroxide of pH 12.70) The results of observing the degree of melting out.
FIG. 5 is a graph showing the results of measurement of the optical density of 18 mW / cm ² after coating a glass plate using a composition obtained by mixing Example 4-2 (TriMethylol Propane Trithol, TMPSH), 1,4-Butanediol divinyl ether (BDVE) (A sample prepared by UV curing for 180 seconds in an ultraviolet exposure apparatus of the present invention) for 16 hours in an acidic solution (aqueous solution of sulfuric acid of pH 1.26) and a basic solution (aqueous solution of sodium hydroxide of pH 12.70) The results of observing the degree of melting out.
6 is a graph showing the results of the thermogravimetric analysis (TGA) of Comparative Example 1 and Example 3-10 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

One. Refined yellowtail and The sulfuric acid chemical composition  Manufacture of coated film

Example  One: Solution phase Refined yellowtail  Produce

In order to remove impurities contained in the sulfuric acid solution collected from Hokutogi, 20 parts by weight of the crude sulfuric acid solution was dissolved in 200 parts by weight of tetrahydrofuran (THF) as a solvent and filtered to obtain a sulfuric acid solution from which impurities were removed. The sulfuric acid solution from which the impurities were removed was partially removed by heating vacuum method using a rotary evaporator to obtain 12.0917 parts by weight of refined sulfuric acid as a viscous solution.

Example  2: By freeze-drying method Refined yellowtail  Produce

The experiment was performed by immersing the yellowish liquor prepared in Example 1 in liquid nitrogen and further freeing water using a freeze dryer (Freeze Dryer, Ilshin; FDA8508) to obtain lyophilized tablets of powdery form. The freeze dryer was applied under the conditions of -40 ℃ and 5mTorr, and the weight change of the refined yellowtail was evaluated based on the weight of the yellowtail during the lyophilization process.

Sample 1
Weight parts (% by weight) Sample 2
Weight parts (% by weight) Sample 3
Weight parts (% by weight) Average
(weight%) 0 hours 14.5957
(100) 18.6606
(100) 14.6229
(100) - 12 hours elapsed 14.5161
(99.45) 18.5356
(99.33) 14.5645
(99.6) 99.46 24 hours elapsed 14.5160
(99.45) 18.4181
(98.7) 14.5230
(99.31) 99.15 48 hours elapsed 14.4203
(98.8) 18.2472
(97.78) 14.5169
(99.27) 98.62 100 hours elapsed 14.3323
(98.2) 18.0916
(96.65) 14.4356
(98.71) 97.95

Through the above-described freeze-drying process, it was confirmed that the water and residual solvents contained in the refined yellow crust of Example 1 such as water were further removed.

Comparative Example  One: Burnt  Produce

The purified yellow rust prepared according to Example 1 was coated on a glass plate to an average thickness of 40 μm and then naturalized for about 12 days in the shade to prepare a natural hardened yellowish coating film sample of Comparative Example 1.

Comparative Example  2-1 to 2-4: Acrylate  Monomer Photocuring Coating Production

The coating solutions prepared in Comparative Examples 2-1 to 2-4 were prepared by mixing acrylate monomers with the compositions shown in Table 2 below. Each of the prepared coating solutions was coated on a glass plate to an average thickness of 40 μm, and then coated with 40 mW / cm ² And then irradiated with ultraviolet light onto a conveyor exposure machine at a rate of 10 m / min for 20 times to cure the photocured coating films of Comparative Examples 2-1 to 2-4.

Furtherance Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Comparative Example 2-1 D + I D = 100 - I = 5 Comparative Example 2-2 D + B + I D = 77 B = 23 I = 5 Comparative Example 2-3 D + P + I D = 49 P = 51 I = 5 Comparative Example 2-4 D + H + I D = 90 H = 10 I = 5

In Table 2, i) D represents diurethane dimethacrylate (DUDMA), which is an acrylate monomer, ii) B represents 1,4-butanediol divinylether (BDVE) iii) H is 1,6-hexanediol diacrylate (HDDA), iv) P is bisphenol A glycerol / glycerol / phenol diacrylate [glycerol / phenol] diacrylate, BPAGD) and v) I means 1-Hydroxy-Cyclohexyl-Phenyl-Ketone (HCPK) which is a photoinitiator.

Example  3-1 to 3-20: Acrylate  Monomer-based Photocuring Burnt  Produce

The purified yellow rust prepared according to Example 1 and the acrylate monomers shown in Table 3 were mixed to prepare coating solutions of Examples 3-1 to 3-20. Each coating solution was coated on a glass plate with an average thickness of 40 μm And then cured 20 times at a speed of 10 m / min in a conveyor exposure machine emitting ultraviolet light of 40 mW / cm ² intensity to prepare a photocured yellowish coating film using the yellowing chemical compositions of Examples 3-1 to 3-20.

Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content
(weight%*) Example
3-1 Hw + D + I Hw = 1 D = 99 - I = 5 One Example
3-2 Hw + D + B + I Hw = 1 D = 76 B = 23 I = 5 One Example
3-3 Hw + D + P + I Hw = 1 D = 49 P = 50 I = 5 One Example
3-4 Hw + D + H + I Hw = 1 D = 89 H = 10 I = 5 One Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content Example
3-5 Hw + D + I Hw = 10 D = 90 - I = 5 10 Example
3-6 Hw + D + B + I Hw = 10 D = 70 B = 20 I = 5 10 Example
3-7 Hw + D + P + I Hw = 10 D = 45 P = 45 I = 5 10 Example
3-8 Hw + D + H + I Hw = 10 D = 80 H = 10 I = 5 10 Furtherance Refined yellowtail
(Colonial Department) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content Example
3-9 Hw + D + I Hw = 30 D = 70 - I = 5 30 Example
3-10 Hw + D + B + I Hw = 30 D = 54 B = 16 I = 5 30 Example
3-11 Hw + D + P + I Hw = 30 D = 35 P = 35 I = 5 30 Example
3-12 Hw + D + H + I Hw = 30 D = 63 H = 7 I = 5 30 Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content Example
3-13 Hw + D + I Hw = 50 D = 50 - I = 5 50 Example
3-14 Hw + D + B + I Hw = 50 D = 38 B = 12 I = 5 50 Example
3-15 Hw + D + P + I Hw = 50 D = 25 P = 25 I = 5 50 Example
3-16 Hw + D + H + I Hw = 50 D = 45 H = 5 I = 5 50

* The amount of sulfuric acid means the weight percentage of sulfuric acid contained in the whole, when the sum of monomer and sulfuric acid is 100 (total), excluding the content of photo-curing agent and other additives.

Ii) D is a diurethane dimethacrylate (DUDMA) which is an acrylate monomer; iii) B is 1,4-butanediol divinyl ester (1,4-butanediol divinyl ester Iv) H is 1,6-hexanediol diacrylate (HDDA); v) P is bisphenol A glycerolate (glycerol / phenol) diacrylate [diacrylate bisphenol A glycerolate (glycerol / phenol) diacrylate, BPAGD), and vi) I means 1-Hydroxy-Cyclohexyl-Phenyl-Ketone as a photoinitiator.

Example  4-1 to 4-7: Thiol - Using the Yen hardening system Photocuring Burnt  Produce

The coating solutions of Examples 4-1 to 4-7 were prepared by mixing the purified yellow rust prepared according to Example 1 with the monomers having thiol groups and the monomers having double bonds as shown in Table 4 below, Coated onto a glass substrate to form a coating layer and photo-cured to prepare the photocured yellowish coating films of Examples 4-1 to 4-7.

The coating layers of Examples 4-1 and 4-2 were coated with 18 mW / cm < ² > The coating layers of Examples 4-3 to 4-7 were passed through a conveyor exposure machine emitting ultraviolet rays of 40 mW / cm ² intensity at a speed of 5 m / min, irradiated with ultraviolet light 10 times, .

Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Monomer 3
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content
(weight%*) Example
4-1 Hw + S + I Hw = 100 S = 100 - - I = 10 50 Example
4-2 Hw + S + B + I Hw = 103.26 S = 67.26 B = 36 - I = 10.3 50 Example
4-3 Hw + S + O + I Hw = 500 S = 300 O = 50 - I = 50 58.82 Example
4-4 Hw + S + N + I Hw = 500 S = 300 N = 50 - I = 50 58.82 Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Monomer 3 (parts by weight) Light curing agent
(Parts by weight) Yellow crust content
(weight%*) Example
4-5 Hw + S + B + O + I Hw = 600 S = 300 B = 188 O = 112 I = 107 50 Example
4-6 Hw + S + N + B + I Hw = 600 S = 300 N = 112 B = 188 I = 107 50 Example
4-7 Hw + S + D + I Hw = 273 S = 775 D = 827 - I = 53 14.56

* The content of sulfuric acid means the weight percentage of sulfuric acid contained in the total amount of the monomer and the sulfuric acid excluding the content of the photocuring agent and other additives, when the total of the monomer and the sulfuric acid is 100 (total).

Ii) S is a monomer having a thiol group (TriMethylol Propane Trithol, TMPTSH, a monomer having a thiol group); iii) B is 1,4-butanediol divinyl Ether, 1,4-butanediol divinyl ether, BDVE, monomer containing carbon-carbon double bond, iv) O is 2,4,6-triallyloxy-1,3,5-triazine (2,4, 6-triallyloxy-1,3,5-triazine, TAOTA, monomers containing three carbon-carbon double bonds), v) N is 1,3,5-triallyl-1,3,5-triazine- Triene-1,3,5-triazine-2,4,6-trione , TANTA, a monomer containing three double bonds), vi) D is a diurethane Di-dimethacrylate (DUDMA, a monomer containing two carbon-carbon double bonds), and vii) I is a photoinitiator, 1-Hydroxy-Cyclohexyl-Phenyl- Ketone).

The IR of the sample 4-1 (Hw: S: I, 100: 100: 10 parts by weight, after removal of the I content: the sulfur content Hw of 50% by weight) before and after the UV curing was measured in the production of the samples, Is shown in Fig. In FIG. 2, the cured compound (solid line) and refined yellowing (dotted line, comparative example 1) were compared, and the arrow shows that the carbon double bond characteristic peak in the region of the infrared frequency of 1600 to 1700 cm ^-1 disappears after curing have. It can be seen that the carbon double bond peak in the coating decreases with the UV curing time, which is a result of the fact that some of the sulfur compounds are participating in the photocuring reaction with the monomers by ultraviolet rays .

Example  5-1 to 5-5: 3 Functional group  Using a monomer curing system Photocuring Burnt  Produce

The coating solution of Examples 5-1 to 5-5 was prepared by mixing the purified whitening prepared in Example 1 and the monomers having three functional groups described in the following Table 5, and coating them on a glass substrate to form a coating layer And photocured to prepare the photocured yellowish coating films of Examples 5-1 to 5-5.

The coating layers of Examples 5-1 to 5-3 were coated with 18 mW / cm < ² > The coating layers of Examples 5-4 and 5-5 were passed through a conveyor exposure machine emitting ultraviolet rays of 40 mW / cm ² intensity at a speed of 5 m / min, irradiated with ultraviolet light 50 times, .

Furtherance Refined yellowtail
(Parts by weight) Monomer 1
(Parts by weight) Monomer 2
(Parts by weight) Light curing agent
(Parts by weight) Yellow crust content
(weight%*) Example
5-1 Hw + A + I Hw = 70 A = 70 - I = 7 50 Example
5-2 Hw + A + B + I Hw = 120 A = 70 B = 50 I = 12 50 Example
5-3 Hw + A + H + I Hw = 147 A = 63 H = 48 I = 12 56.98 Example
5-4 Hw + N + H + I Hw = 122 N = 100 H = 22 I = 12 50 Example
5-5 Hw + N + B + I Hw = 157 N = 100 B = 57 I = 15.7 50

* The content of sulfuric acid means the weight percentage of sulfuric acid contained in the total amount of the monomer and the sulfuric acid excluding the content of the photocuring agent and other additives, when the total of the monomer and the sulfuric acid is 100 (total).

Ii) A is trimethylolpropane triacrylate (TMPTA, a monomer having three functional groups); iii) B is 1,4-butanediol divinyl ether (1 , 4-butanediol divinyl ether, BDVE, a monomer containing a carbon-carbon double bond), iv) H is a monomer containing 1,6-hexanediol diacrylate, HDDA, ), v) N is 1,3,5-triallyl-1,3,5-triazine-2 , 4,6-trione , TANTA, a monomer containing three double bonds), and vi) 1 means a photoinitiator, 1-Hydroxy-Cyclohexyl-Phenyl-Ketone do.

2. Characterization of coating film

(One) The sulfuric acid chemical composition  Used hardening Burnt  Surface observation

The surface of the coating films of Examples 3-1 to 3-20, Examples 4-1 to 4-7, and Examples 5-1 to 5-5 were observed and shown in Table 6 below. In the evaluation items shown in the following Table 6, i) A: cured, surface smooth and transparent, ii) B: cured, surface is transparent but surface is not smooth, iii) C: cured but surface is opaque, iv ) D: The surface was sticky with only a little hardening.

division Furtherance evaluation division Furtherance evaluation Example
3-1 Hw + D + I A Example
3-15 Hw + D + P + I B Example
3-2 Hw + D + B + I A Example
3-16 Hw + D + H + I B Example
3-3 Hw + D + P + I A Example
4-1 Hw + S + I C Example
3-4 Hw + D + H + I A Example
4-2 Hw + S + B + I C Example
3-5 Hw + D + I A Example
4-3 Hw + S + O + I C Example
3-6 Hw + D + B + I A Example
4-4 Hw + S + N + I C Example
3-7 Hw + D + P + I A Example
4-5 Hw + S + B + OI C Example
3-8 Hw + D + H + I A Example
4-6 Hw + S + N + B + I C Example
3-9 Hw + D + I A Example
4-7 Hw + S + D + I C Example
3-10 Hw + D + B + I A Example
5-1 Hw + A + I D Example
3-11 Hw + D + P + I A Example
5-2 Hw + A + B + I B Example
3-12 Hw + D + H + I A Example
5-3 Hw + A + H + I B Example
3-13 Hw + D + I B Example
5-4 Hw + N + H + I D Example
3-14 Hw + D + B + I B Example
5-5 Hw + N + B + I D

The abbreviations denoting the respective compositions in Table 6 are the same as those used in Tables 4 to 5, and thus the description thereof will be omitted. The results of Table 6 above confirm that hardened film of various compositions is cured under a constant light irradiation dose to form a hardened whitish film having respective characteristics. In the case of Example 5-1, Examples 5-4 and 5-5 evaluated as D, however, it was confirmed that the coating film hardening was not sufficiently performed with the light amount applied above, and the surface was tacky It was possible to go to such a degree.

(2) The sulfuric acid chemical composition  Used hardening Burnt Content-based  evaluation

Comparative Example  1 and Example  3-5 hardening Thick film  Solvent extraction experiment using

The solvent resistance of the greyish coat and cured greyish coat prepared in Comparative Example 1 and Example 3-5 was tested for the following eight solvents. The glass plate on which the whitish coating film of Comparative Example 1 was fully cured and the hardened whitish coating film (including 10% by weight of purified whitening) prepared in Example 3-5 were immersed in the respective solvents shown in Table 7 for 16 hours, The solvent resistance was evaluated on the basis of the state of the yellowish paint film on the taken-out glass plate and whether or not yellowish water was present in the solution in which the yellowish paint film was immersed, and is shown in Table 7 below.

Yellowish paint film Cured yellow paint film menstruum Whether surface changes Content-based surface
Change Content-based Dimethyl sulfoxide Deteriorated none No change has exist water
(Water) Deteriorated has exist No change has exist Aqueous solution of sulfuric acid
(Sulfuric acid, 5 wt%) No change has exist No change has exist An aqueous solution of sodium hydroxide (Sodium hydroxide, 5 wt%) Deteriorated none No change has exist Hexane
(Hexane) No change has exist No change has exist toluene
(Toluene) No change has exist No change has exist chloroform
(Chloroform) Deteriorated none No change has exist

Referring to Table 7, in the sample of Comparative Example 1, in the aqueous sulfuric acid solution as the acidic aqueous solution, It was confirmed that the surface was deteriorated by the use of water, an aqueous solution of sodium hydroxide, chloroform, dimethylsulfoxide, hexane, toluene or the like, or melted yellow crust was observed. However, it was confirmed that the cured yellow paint film according to Example 3-5 has solvent resistance to all of the eight tested solvents.

FIG. 3 is a photograph showing the state of the coating film and the state of the solution after the experiment in which the samples prepared in Comparative Example 1 were immersed in an acidic aqueous solution, an aqueous sulfuric acid solution and an aqueous sodium hydroxide solution, respectively, for 16 hours. It can be seen from the results that even though the greyish coating film prepared by the conventional method of Comparative Example 1 has a certain solvent resistance to the acidic solution, it has a very weak characteristic to the basic solution.

Example  4-2 hardening Thick film  For acidic and basic aqueous solutions Content-based  Experiment

The surface of each of the surface and each solution after immersing in an acidic solution (aqueous solution of sulfuric acid having a pH of 1.26) and a basic solution (aqueous solution of sodium hydroxide having a pH of 12.70) for 16 hours, The degree of appearance is shown in FIG. 4 and FIG.

4 and 5, regardless of the content of the yellowing that is contained in the yellowish coating film, the yellowish yellowish component did not dissolve in both the acidic solution and the basic solution. Thus, in Comparative Example 1, The comparative results indicate that the solvent resistance of the cured painted film is improved.

(3) Gel content ( Come Contents ) Experiment

THF Using Comparative Example  And Example Crosslinking density evaluation

The gel content test was carried out using Comparative Example 1 in which a yellowish paint film was formed with refined yellowtone alone and some samples in the Examples, and the crosslinking density of the yellowish paint film was evaluated based on the gel content test. The samples of the examples were tested using two samples (Example 5-2 and Example 5-3) that were sufficiently cured to the same light dose in Examples 5-1 to 5-5. THF was used as a solvent and the components of non-crosslinked components were dissolved by immersing each of the yellowish paint film and the hardened sulfuric acid samples in a solvent at 60 ° C. for 6 hours. After that, the yellowish paint film which did not melt was dried at 50 ° C. for 24 hours and then weighed , And this was compared with the initial weight to evaluate the degree of crosslinking.

Furtherance Before processing
(g) After processing
(g) The crosslinking ratio (% by weight) evaluation Comparative Example
One Hw 0.0448 0.0205 45.8 - Example
5-2 Hw + A + B + I 0.0851 0.0627 73.68 Great Example
5-3 Hw + A + H + I 0.1001 0.0594 59.34 usually

Referring to Table 8, it was confirmed that the cured yellowish coating film stably exists without being dissolved in the solvent due to the components trapped between the crosslinked or cured mesh.

THF Using Example  Curing of 3-5 to 3-12 Burnt Crosslinking density evaluation

The samples of Examples 3-5 to 3-12 were loaded in a THF solvent for 24 hours, and the change in weight was observed. At this time, the THF solvent was tested while maintaining the temperature at room temperature, and the weight after drying was evaluated in the same manner as in the evaluation of the crosslinking density, and the results are summarized in Table 9 below.

Furtherance Before processing
(g) After processing
(g) The crosslinking ratio (% by weight) evaluation Example
3-5 Hw + D + I 0.00233 0.00228 97.8 Very good Example
3-6 Hw + D + B + I 0.00248 0.00244 98.3 Very good Example
3-7 Hw + D + P + I 0.00256 0.00227 88.6 Very good Example
3-8 Hw + D + H + I 0.00252 0.0025 99.2 Very good Example
3-9 Hw + D + I 0.00232 0.00174 75.0 Great Example
3-10 Hw + D + B + I 0.00225 0.00172 g 76.4 Great Example
3-11 Hw + D + P + I 0.00232 0.00164 70.6 Great Example
3-12 Hw + D + H + I 0.00223 0.00178 79.8 Great

Referring to Table 9, it was confirmed that the samples of Examples 3-5 to 3-12 were all excellent in the degree of crosslinking, and showed excellent results regardless of the kinds of monomers used. The samples of Examples 3-5 to 3-8, each containing 10% by weight of refined yellowtail, exhibited a very good degree of crosslinking, and in particular, excellent results of more than 99% in Examples 3-8 . In the case of Examples 3-9 to 3-12 containing 30% by weight of refined yellowtail, but less than 70% by weight, which is lower than Examples 3-5 to 3-8 containing 10% by weight I can confirm the point.

Curing for acidic, neutral and basic aqueous solutions Burnt Crosslinking density evaluation

The samples (photocured acrylate monomers) of Comparative Example 2 and the samples of Examples (3-1 to 3-12) (yellowish polymers crosslinked with acrylate monomers) were subjected to the crosslinking density in aqueous solution The results are shown in Table 10 below. The pH of each solution was adjusted to 1, 4, 7, 10, and 13, respectively, and the cured film was immersed for 48 hours or more.

pH 1 pH 4 pH 7 pH 10 pH 13 Comparative Example 1
(Hw: 100%) 0.8 One 0.99 0.82 0.70 Comparative Example 2-1
(Hw: 0%) 0.99 0.98 0.98 0.98 0.99 Comparative Example 2-2
(Hw: 0%) 0.99 0.82 0.96 One One Comparative Example 2-3
(Hw: 0%) 0.99 0.97 One 0.94 One Comparative Example 2-4
(Hw: 0%) 0.97 One One 0.97 0.98 Example 3-1
(Hw: 1%) 0.99 One 0.95 0.98 One Example 3-2
(Hw: 1%) 0.69 0.98 One 0.98 One Example 3-3
(Hw: 1%) 0.96 0.96 0.98 0.96 0.89 Example 3-4
(Hw: 1%) 0.98 0.98 0.93 0.98 0.87 Example 3-5
(Hw: 10%) 0.99 0.99 0.99 0.95 One Examples 3-6
(Hw: 10%) 0.98 0.99 0.97 0.90 0.91 Examples 3-7
(Hw: 10%) 0.98 One 0.98 0.99 0.90 Examples 3-8
(Hw: 10%) 0.98 0.99 0.99 One 0.97 Examples 3-9
(Hw: 30%) 0.97 0.96 0.97 0.83 0.72 Examples 3-10
(Hw: 30%) 0.95 0.94 0.97 0.87 0.73 Examples 3-11
(Hw: 30%) 0.99 0.99 0.97 0.91 0.88 Examples 3-12
(Hw: 30%) 0.96 0.98 0.95 0.88 0.85

Referring to Table 10, it was confirmed that, even though the pH was changed, the bonding ratio was 0.7 or more as a whole, and thus the degree of crosslinking was excellent. However, it was confirmed that the weight decrease in the strong basic aqueous solution was increased as the content of the sulfuric acid increased. However, if the kinds of the monomers to be used and the curing system were appropriately selected, it was possible to manufacture the coating film free from any damage until 10% by weight of the film was used.

(4) hardening Burnt My Scratchy Castle  evaluation

The cured hard coat films of Comparative Example 1, Comparative Examples 2-1 to 2-4, and Examples 3-1 to 3-16 were subjected to pencil hardness test to evaluate the scratch resistance. The results are shown in Table 11 below.

The pencil hardness was measured according to ASTM D 3363 using a Pencil hardness tester 2210 with a load of 1 kg and a pencil angle of 45 ^° C. The pencil was rubbed on a sandpaper to make it flat. The coated portion was scratched 5 times, then erased with an eraser, and hardness was evaluated by hardly recognizing hardness of the hard coat layer when scratches were observed more than 2 times.

In the following, the larger the number H, the larger the hardness and the better the scratch resistance. For reference, the hardness of pencil 9H is the hardest and 9B is the hardest.

Hulkhill content (0wt%) Pencil hardness Hulkhill content (0wt%) Pencil hardness Comparative Example 2-1 8H Comparative Example 2-2 8H Comparative Example 2-3 8H Comparative Example 2-4 8H Bulk content (1wt%) Pencil hardness Huulchil content (10wt%) Pencil hardness Example 3-1 8H Example 3-5 7H Example 3-2 7H Examples 3-6 3H Example 3-3 8H Examples 3-7 7H Example 3-4 8H Examples 3-8 6H Huulchil content (30wt%) Pencil hardness Huulchil content (50wt%) Pencil hardness Examples 3-9 3H Examples 3-13 3H Examples 3-10 3H Examples 3-14 2H Examples 3-11 HB or less Examples 3-15 HB or less Examples 3-12 4H Examples 3-16 1H Huulchil content (100wt%) Pencil hardness - - Comparative Example 1 1H - -

Referring to Table 11, the scratch resistance of the coating film of the cured natural yellowish crust (Comparative Example 1) was the weakest, and the scratch resistance was different according to the types of the monomers among the examples. When the content of the sulfuric acid (the content of the refined sulfuric acid or the sulfuric acid solution) is large, the scratch resistance of the cured coating film is weak. On the other hand, when the content of sulfuric acid in the composition is small, scratch resistance tends to be strong. Therefore, I can confirm that there is a considerable difference in the scratch resistance. Therefore, it can be confirmed that the scratch resistance can be controlled by the kind of the monomer or the blending ratio of the composition when the content of the yellow crush is small.

(5) Heat resistance test

Samples of the yellowish coating film of Comparative Example 1 (100% of refined yellowing) and the sample of Example 3-14 (yellowing coating film crosslinked with acrylate monomer) were subjected to thermogravimetric analysis and the results are shown in FIG.

Referring to FIG. 6, the sample of Comparative Example 1 which is spontaneously cured with sulfuric acid shows a rapid decrease in weight from around 150 ° C., but the sample of Example 3-14 (a yellowish macromolecule crosslinked with an acrylate monomer), which is an ultraviolet- Shows a weight reduction rate of 20% up to 300 ° C. This is a result of showing that the photocurable, yellowing polymer coating is thermally more stable than the conventional cured natural yellowing coating, which means that the heat resistance is improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

1: Polymer chain of cured resin
2: Cross-linking point between the curing resin polymer chains
3: Bulk-litter that participated in crosslinking by covalent bonding with the curing resin chain
4: Cross-linking point between cured resin chain and refined yellowing
5: refined bristles physically isolated in the bridging space between the resins

Claims (16)

0.01 to 99 parts by weight of refined sulfuric acid, 0.01 to 99 parts by weight of a compound capable of crosslinking or linear bonding, 0.001 to 10 parts by weight of an initiator, and 0 to 70 parts by weight of an additive,
The compound capable of cross-linking or linear bonding is preferably a compound having at least one carbon-carbon double bond in the compound, a thiol compound having a thiol group in the compound, an oligomer of the ene compound, an oligomer of the thiol compound, Lt; / RTI >
Wherein the additive comprises any one selected from the group consisting of diluents, defoamers, leveling agents, and combinations thereof. The method of claim 1, wherein
Wherein the initiator comprises any one selected from the group consisting of photoinitiators, thermal initiators, and combinations thereof. The method according to claim 2, wherein
The photoinitiator may be selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, acetophenone, 2-hydroxy-2-methyl- 2-methyl-1-phenyl-1-propanone, benzaldehyde, benzoin propyl ether, triphenylamine, 3-methylacetophenone, 4-phenylbenzophenone, benzyl ketal, ? -hydroxyalkylphenone,? -aminoalkylphenone, acetylphosphine oxide, and combinations thereof.
Wherein the thermal initiator is selected from the group consisting of ROO-R 'wherein R and R' are each independently selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms (Wherein R is any one selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms), benzoyl peroxide Organic peroxides including seeds; Hydroperoxides, mixtures of persulfate and a reducing agent, oxidation-reduction agents comprising a mixture of hydroperoxides and iron (II); RN = N-R 'wherein R and R' are each independently selected from an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 1-20 carbon atoms, an aryl group having 1-20 carbon atoms, and an allyl group having 1-20 carbon atoms ), And azobisisobutyronitrile (AIBN); And an alkylated silver (R-Ag, wherein R is an alkyl group having 1-20 carbon atoms). The method according to claim 1,
Wherein the compound capable of crosslinking or linear bonding is a mixture of two different compounds. The method according to claim 1,
The crosslinking compound _{is, - (CH 2) a -CH} = CH 2, - (CH 2) a -O-CH = CH 2, - (CH 2) a -O-CH = CH-CH 3, _{- (CH 2) a -O- (} CH 2) b -CH = CH 2, - (CH 2) a -OCO-CH = CH 2, - (CH 2) a-CH = CH 2 -H, - ( _{CH 2) a - (CH =} CH 2) b -H, - (C 6 H 6) a -CH = CH 2, - (C 6 H 6) a -O-CH = CH 2, - (C 6 H _{6) a -O-CH = CH} -CH 3, - (C 6 H 6) a -O- (CH 2) b -CH = CH 2, - (C 6 H 6) a -OCO-CH = CH 2 _{, - (C 6 H 6)} a -CH = CH 2 -H, - (C 6 H 6) a - (CH = CH 2) b -H, - (C n H m) a -CH = CH 2, _{- (C n H m) a} -O-CH = CH 2, - (C n H m) a -O-CH = CH-CH 3, - (C n H m) a -O- (CH 2) b _{-CH = CH 2, - (C} n H m) a -OCO-CH = CH 2, - (C n H m) a -CH = CH 2 -H, - (C n H m) a - (CH = _{CH 2) b -H, - (} CH 2 - CH 2 -O) a -CO-CR = CH 2, -R (CH) a -NH-CO-CH = CH 2, - (CH 2 - CH 2 - O, _a , b, n and m are each independently selected from the group consisting of _a -CO-CR = CH ₂ , -R (CH ₂ ) _a -NH-CO-CH═CH ₂ , from 1 to 100, and a natural number, wherein R is -H, -CH _3, - a (CH _{2) n} CH _3, or -OH) of the compound And 1 to 100 carbon atoms. The method according to claim 1,
The compound capable of crosslinking or linear bonding includes an ethylene glycol dimethyl acrylate derivative, a methylene bisacrylamide derivative, a polyester acrylate, an epoxy acrylate, a urethane acrylate, a polyester acrylate, and a silicone acrylate (Meth) acrylate having at least one functional group selected from the group consisting of allyl ether, allylamine, vinyl ether, unsaturated esters, styrene, maleimide, and combinations thereof, 0.0 > 100, < / RTI > The method according to claim 1,
The thiol compound may be selected from the group consisting of alkane dithiol, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptobutyrate), trimethylolpropane butanediol bis (2-mercaptobutyrate), butanediol bis (3-mercaptopropionate), butanediol bis (2-mercaptobutyrate), butanediol bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptobutyrate), 1,3,5-triazine, and the like. (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (3-mercaptopropionate) Triazine-2,4,6-trione tris (3-mercaptopropionate), 1,3,5-tri (2-hydroxyethyl) -1,3,5-triazine- , 6-trionetris (2- (2-hydroxyethyl) -1,3,5-triazine-2,4,6-trione tris (2-mercaptobutyrate)}, and combinations thereof. One,
The above-mentioned ene compound is preferably selected from the group consisting of (meth) acrylate, allyl ether, allylamine, vinyl ether, and the like, including polyester acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, , Unsaturated esters, styrene, maleimides, and combinations thereof. The method according to claim 1,
The cross-linkable compound is selected from the group consisting of diurethane dimethacrylate (DUDMA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol divinyl ether 1,4-butanediol divinylether, BDVE), bisphenol A glycerol, glycerol / phenol diacrylate (BPAGD), trimethylolpropane trimethacrylate (TMPTMA), trimethylol (TMPTA), 2,4,6-triallyloxy-1,3,5-triazine (TAOTA), 1, 2,4,6-triazine , 3,5-triallyl-1,3,5-triazine-2,4,6-trione, 1,3,5- (Ethylene glycol) divinyl ether, TEGDVE), and combinations thereof. ≪ / RTI > The method according to claim 1,
Wherein the cross-linkable compound is a monomer having a viscosity of 0.01 to 500,000 cps or less, and the sulfuric chemical composition further does not contain an organic solvent. The method according to claim 1,
Wherein the sulfuric acid chemical composition comprises the crosslinkable compound and the purified sulfuric acid in a weight ratio of 10: 1 to 40. The method according to claim 1,
The refined yellowing is freeze-dried to have a liquid or solid form. (1) a step of preparing a sulfuric acid coating solution by mixing the sulfuric acid chemical composition according to claim 1; (2) coating the above-described yellowish coating liquid on a substrate to produce a yellowish coating film; And (3) curing the yellowish coating film by light irradiation treatment or heat treatment to obtain a yellowish coating film. 13. The method of claim 12,
Wherein the time (curing time) of the light irradiation treatment or the heat treatment is within 30 minutes in the step (3). 13. The method of claim 12,
In the step (3), the light irradiation treatment is performed by using ultraviolet rays at a light quantity of 5,000 mW or less per unit area of the yellowish coating film, or by using a gamma ray or electron beam,
Wherein the heat treatment is to treat the yellowish coating film at a temperature of 40 to 200 占 폚. 13. The method of claim 12,
The refined yellowtail may be either an organic extract-refined yellowtail refined by an extraction method using an organic solvent, or a freeze-dried refined yellowtail refined refined yellowtail refined using the freeze drying method, Gt; 16. The method of claim 15,
Wherein the freeze-drying method comprises a step of freezing the organic extraction-refined yellowhook, followed by drying for at least 8 hours at a vacuum or a low pressure of minus 10 ° C or less and 10 mTorr or less.

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