Primer composition

Abstract

The present invention relates to a primer composition which can be used for both glass and plastic materials, the primer composition according to the present invention comprising: a first silane-modified urethane polymer; a second silane-modified urethane polymer; a phosphate-based polyisocyanate; a polyisocyanate which does not include a phosphate group; and an additive.

Description

Primer composition

[0001] This application claims the benefit of priority from Korean Patent Application No. 10-2024-0030826, filed March 4, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a primer composition, and more particularly, to a urethane primer composition having excellent adhesion to glass and plastic materials.

[0003] During automobile manufacturing, painting is performed to enhance the exterior appearance of the vehicle body and protect the surface from external influences. Typically, a primer is applied before painting to improve adhesion between the painted surface and the vehicle body. Primers for plastic materials are commonly used as body primers.

[0004] Meanwhile, when bonding glass to a painted surface, such as a sunroof, the adhesive strength between the dissimilar materials can be insufficient, causing the glass to shift or detach from the painted surface. To prevent this, a method is used in which a glass primer is first applied to the painted surface and / or glass, a moisture-hardening adhesive is applied over the primer, and then the glass is bonded.

[0005] Because car bodies and glass are made of different materials, different types of primers are required. However, automotive inline and sunroof manufacturers use both glass primers and body-specific primers. This leads to frequent instances of defective products due to worker confusion and incorrect use of primers. Measures such as separating work lines and strengthening primer can identification are being taken to prevent this. However, quality issues due to primer misuse persist, necessitating a solution.

[0006] The present invention is intended to solve the above problems, and to provide a urethane primer composition that has excellent adhesion to both glass and plastic materials, can be used for both glass and car bodies, and can prevent defects and quality deterioration due to incorrect use of the primer.

[0007] According to one embodiment, the primer composition of the present invention comprises: a first silane-modified urethane polymer; a second silane-modified urethane polymer; a phosphate-based polyisocyanate; a polyisocyanate not containing a phosphate group; and an additive.

[0008] The above first silane-modified urethane polymer may be a reaction product of an amino group-containing silane compound and an isocyanate compound, and the above second silane-modified urethane polymer may be a reaction product of a mercapto group-containing silane compound, a (meth)acrylic compound, and an isocyanate compound.

[0009] The above phosphate-based polyisocyanate may be represented by the following [chemical formula 1].

[0010] [Chemical Formula 1]

[0011]

[0012] In the above chemical formula 1, X is S or O, and L1, L2 and L3 are each independently C 1~10 Alkyl group of C 5~10 aryl group or a combination thereof.

[0013] The polyisocyanate not including the above phosphate group and the phosphate-based polyisocyanate may be included in a weight ratio of 1:3 to 1:8.

[0014] The additive may include a moisture absorbent, a film former, a pigment, or a combination thereof.

[0015] Specifically, the primer composition may include 5 to 20 parts by weight of a first silane-modified urethane polymer; 10 to 20 parts by weight of a second silane-modified urethane polymer; 10 to 25 parts by weight of a phosphate-based polyisocyanate; 2 to 10 parts by weight of a polyisocyanate not containing a phosphate group; and additives such as 3 to 10 parts by weight of a pigment, 1 to 5 parts by weight of a moisture absorbent, and 1 to 5 parts by weight of a film forming agent.

[0016] The primer composition according to the present invention exhibits excellent adhesion to both glass and plastic materials by including a silane-modified urethane polymer with excellent adhesion to glass and a phosphate-based polyisocyanate with excellent adhesion to plastic materials. Therefore, the primer composition of the present invention can be used for both automotive bodies and glass. In other words, the use of the primer composition of the present invention eliminates the need for two types of primers, thereby preventing defects due to incorrect primer use.

[0017] Hereinafter, the present invention will be described in detail.

[0018] In the present invention, “(meth)acrylic” of the resin means “acrylic” and / or “methacrylic”.

[0019] In the present invention, functional groups such as 'content of unreacted NCO (NCO%)', 'acid value' and 'hydroxyl value' can be measured by methods well known in the art, and may be values ​​measured by, for example, titration.

[0020] In the present invention, “part by weight” means the weight ratio between each component.

[0021]

[0022] The present inventors have conducted repeated research to develop a primer that can be used for both glass and plastic materials in order to prevent quality deterioration due to incorrect use of the primer. As a result, they have discovered that when two types of silane-modified urethane polymers having different reactors and two types of specific polyisocyanates are used together, excellent adhesion can be achieved for both glass and plastic materials, and have completed the present invention.

[0023] Specifically, the primer composition according to the present invention comprises a first silane-modified urethane polymer, a second silane-modified urethane polymer, a phosphate-based polyisocyanate, a polyisocyanate not containing a phosphate group, and an additive.

[0024]

[0025] Hereinafter, each component of the primer composition according to the present invention will be described in detail.

[0026]

[0027] (1) Silane-modified urethane polymer

[0028] The primer composition according to the present invention comprises a first silane-modified urethane polymer and a second silane-modified urethane polymer having different reactive groups. The silane-modified urethane polymer forms a siloxane bond with a silicon compound on the glass surface, thereby imparting adhesion and bonding properties to the glass. When two types of silane-modified urethane polymers having different reactive groups are mixed and used, the effect of improving adhesion to glass and plastic materials can be obtained, and in particular, the effect of significantly improving adhesion to glass can be obtained.

[0029] The above first silane-modified urethane polymer is intended to provide adhesion and bonding properties between the coating film and the adherend surface (substrate), and may be a reaction product of an amino group-containing silane compound and an isocyanate compound.

[0030] At this time, the amino group-containing silane compound may be a silane compound containing one or more amino groups, for example, an alkoxy silane compound containing an amino group. Specific examples of the amino group-containing silane compound include, but are not limited to, N-Phenyl-3-aminopropyltrimethoxysilane, N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, or combinations thereof. In terms of reactivity with isocyanate, adhesion to glass, and water resistance, it is particularly preferable that the amino group-containing silane compound is N-phenyl-3-aminopropyltrimethoxysilane.

[0031] The above isocyanate compound is for forming a urethane bond by reacting with an amino group-containing silane compound, and the isocyanate compound used in the production of the first silane-modified urethane polymer includes, for example, hexamethylene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,2-diisocyanate, hexahydroxylylene diisocyanate, dicyclohexyl-4,4-diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, It may include at least one selected from the group consisting of aromatic-aliphatic polyisocyanates such as, but not limited to, l-methyl-2,6-diisocyanatocyclohexane, bis(4-isocyanatocyclohexyl)methane, 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, m-xylene diisocyanate, and 1,3-diisocyanato-2-methylbenzene-1,6-diisocyanatohexane (CAS NO 63368-95-6). Preferably, the isocyanate compound used in the production of the first silane-modified urethane polymer may be hexahydroxylylene diisocyanate.

[0032] The first silane-modified urethane polymer can be manufactured by adding an isocyanate compound dropwise to an amino group-containing silane compound and reacting the same for a predetermined period of time. Preferably, the first silane-modified urethane polymer can be manufactured by reacting the amino group-containing silane compound and the isocyanate compound in a weight ratio of 50:45 to 45:40, 40:35 to 38:33, or 35:30 to 30:27. When the weight ratio of the amino group-containing silane compound and the isocyanate compound satisfies the above range, the adhesion to the substrate and the water resistance are excellent.

[0033] At this time, the reaction temperature is preferably 30°C to 50°C, and the reaction time is preferably 2 to 5 hours. Meanwhile, the first silane-modified urethane polymer may have a proportion of unreacted isocyanate groups (NCO) of 4 to 7 wt%, preferably 4.5 to 6.5 wt%. When the content of unreacted NCO in the first silane-modified urethane polymer satisfies the above range, the adhesion to the substrate and storage properties are excellent.

[0034]

[0035] Meanwhile, the first silane-modified urethane polymer may be included in an amount of 5 to 20 parts by weight, 5 to 15 parts by weight, or 7 to 15 parts by weight, based on 100 parts by weight of the primer composition. When the content of the first silane-modified urethane polymer satisfies the above range, excellent adhesion to the substrate and storability are exhibited.

[0036]

[0037] Next, the second silane-modified urethane polymer may be a reaction product of a mercapto group-containing silane compound, an acrylic compound, and an isocyanate compound to improve the weather resistance of the primer layer and prevent pigment sedimentation to improve the storage stability of the composition.

[0038] At this time, the mercapto group-containing silane is used to provide adhesion between the coating film and the adherend surface, for example, mercapto C 1-5 Alkyl C 1-5 It may be an alkoxysilane, specifically, mercapto C 1-5 AlkyltriC 1-5 It may be an alkoxysilane. More specifically, the mercapto group-containing silane may include, but is not limited to, mercaptomethyltrimethoxy silane, mercaptoethyltrimethoxy silane, mercaptopropyltrimethoxy silane, mercaptomethyltriethoxy silane, mercaptoethyltriethoxy silane, mercaptopropyltriethoxy silane, mercaptomethyltripropoxy silane, mercaptoethyltripropoxy silane, mercaptopropyltripropoxy silane, and the like.

[0039] The above acrylic compound is intended to impart weather resistance to the manufactured coating film, and may be, for example, an aryloxy-alkylacrylate, C 6-12 Aryloxy-C 1-6 It may be an alkyl acrylate. Specifically, the acrylate compound may include 2-hydroxy-3-phenoxypropyl acrylate.

[0040] The above isocyanate-based compound is for forming a urethane bond by reacting with the mercapto group-containing silane and acrylic compound, and the isocyanate-based compound used in the production of the second silane-modified urethane polymer includes, for example, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4'-methylene diphenyl diisocyanate (4,4'-MDI), 2,4'-diphenylmethylene diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate, bis(4-isocyanatecyclohexyl)methane, It may include at least one selected from the group consisting of 1-methyltrimethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, triphenylmethane triisocyanate, tris(isocyanatephenyl) thiophosphate, 1,6,10-undecane triisocyanate, and 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene and isocyanurates derived therefrom, but is not limited thereto. Preferably, the isocyanate compound used in the production of the second silane-modified urethane polymer may be TDI / HDI isocyanurate.

[0041] The above second silane-modified urethane polymer can be manufactured by adding a mixture of a mercapto group-containing silane compound and a solvent dropwise to a mixture of an isocyanate compound and a solvent, allowing a first reaction for a certain period of time, and then adding an acrylic compound thereto and allowing a second reaction to occur.

[0042] At this time, the isocyanate compound: mercapto group-containing silane compound: acrylic compound may be added in a weight ratio of 60:30:20 to 55:25:18, 50:20:15 to 48:18:15, or 45:15:15 to 45:12:13. When the weight ratio of the reactants for producing the second silane-modified urethane polymer satisfies the above range, the adhesion to glass and plastic and weather resistance are excellent. Specifically, if the content of the acrylic compound is too low, the effect of improving the weather resistance of the primer layer is reduced, and if the contents of the mercapto group-containing silane compound and the isocyanate compound are out of the above range, the silanol group that implements adhesion to glass is reduced, so that the adhesion to glass may be deteriorated.

[0043] Additionally, the solvent may be ethyl acetate, dimethyl carbonate, butyl acetate, methyl ethyl ketone or a combination thereof, preferably ethyl acetate.

[0044] Meanwhile, in the first reaction, the reaction temperature may be 40°C to 60°C, and the reaction time may be 1 to 2 hours, and in the second reaction, the reaction temperature may be 50°C to 70°C, and the reaction time may be 2 to 4 hours.

[0045] Meanwhile, the second silane-modified urethane polymer may have a proportion of unreacted isocyanate groups (NCO) of 1 wt% or less. If the content of unreacted NCO in the second silane-modified urethane polymer is high, a crosslinking reaction may occur between the second silane-modified urethane polymer and polyisocyanate due to moisture, which may increase viscosity and reduce storage properties.

[0046] Meanwhile, the second silane-modified urethane polymer may be included in an amount of 10 to 20 parts by weight, 10 to 18 parts by weight, or 10 to 15 parts by weight, based on 100 parts by weight of the primer composition. When the content of the second silane-modified urethane polymer satisfies the above range, the adhesion to ceramic glass and plastic materials is more excellent. When the content of the second silane-modified urethane polymer is less than the above range, the adhesion to glass may be reduced, and when it exceeds the above range, the adhesion to plastic may be reduced.

[0047]

[0048] (2) Polyisocyanate

[0049] The primer composition according to the present invention comprises two types of polyisocyanates, specifically a phosphate-based polyisocyanate and a polyisocyanate that does not contain a phosphate group.

[0050] The above phosphate-based polyisocyanate is a component for improving adhesion to plastic materials, and may be represented by the following [chemical formula 1].

[0051] [Chemical Formula 1]

[0052]

[0053] In the above chemical formula 1, X is S or O, and L1, L2 and L3 are each independently C 1~10 Alkyl group of C 5~10 aryl group or a combination thereof. Preferably, the X may be S, and the L1, L2 and L3 are each independently C 5~10 It may be an aryl group, and more preferably, L1, L2 and L3 may be a phenyl group.

[0054] More preferably, the phosphate-based polyisocyanate may be represented by the following [Chemical Formula 1-1].

[0055] [Chemical Formula 1-1]

[0056]

[0057] The above phosphate-based polyisocyanate may be included in an amount of 10 to 30 parts by weight, preferably 15 to 30 parts by weight, and more preferably 15 to 25 parts by weight, relative to 100 parts by weight of the primer composition. When the content of the phosphate-based polyisocyanate satisfies the above range, excellent adhesion to both plastic materials and glass materials can be achieved. If the content of the phosphate-based polyisocyanate is too low, adhesion to plastic materials may be reduced, and if it is too high, adhesion to glass materials may be reduced.

[0058] When the above phosphate-based polyisocyanate and silane-modified urethane polymer are applied simultaneously, the chlorobenzene component, which is a byproduct of the phosphate-based polyisocyanate, more actively promotes the coupling reaction (siloxane reaction) of silane, thereby improving the adhesion to the glass material, and at the same time, the phosphate-based polyisocyanate component penetrates into the interior of the porous plastic material and forms a strong physical bond with the matrix resin within the plastic material, thereby improving the adhesion to the plastic material, thereby having the effect of improving the adhesion to both the glass material and the plastic material.

[0059]

[0060] Meanwhile, the primer composition according to the present invention uses a polyisocyanate that does not contain a phosphate group together with the phosphate-based polyisocyanate.

[0061] The polyisocyanate not containing the above phosphate group is for improving the adhesion with the coating or sealant layer disposed on the upper part of the primer layer, for example, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4'-methylene diphenyl diisocyanate (4,4'-MDI), 2,4'-diphenylmethylene diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate, bis(4-isocyanatecyclohexyl)methane, 1-methyltrimethylene diisocyanate, 1,3-cyclopentene Diisocyanate, 1,4-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, triphenylmethane triisocyanate, tris(isocyanatephenyl) thiophosphate, 1,6,10-undecane triisocyanate and 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene, an isocyanurate derived therefrom or a mixture thereof. Preferably, the polyisocyanate not including a phosphate group may be TDI / HDI isocyanurate, and more preferably, it may be a compound represented by the following [Chemical Formula 2].

[0062] [Chemical Formula 2]

[0063]

[0064] The polyisocyanate not containing a phosphate group may be included in an amount of 2 to 10 parts by weight, preferably 3 to 8 parts by weight, and more preferably 3 to 7 parts by weight, based on 100 parts by weight of the primer composition. When the content of the polyisocyanate not containing a phosphate group satisfies the above range, excellent adhesion with the coating film and / or sealant layer disposed on the upper part of the primer layer is exhibited. If the content of the polyisocyanate not containing a phosphate group is too low, the adhesion with the upper layer may be weakened, resulting in damage to the coating film and peeling, and if too high, the adhesion with glass may be reduced.

[0065]

[0066] Meanwhile, the weight ratio of the polyisocyanate not including a phosphate group to the phosphate-based polyisocyanate may be 1:3 to 1:8, 1:3 to 1:7, or 1:3 to 1:6. When the ratio of the phosphate-based polyisocyanate to the polyisocyanate not including a phosphate group satisfies the above range, excellent adhesion to both glass and plastic materials can be realized, so that one primer can be applied to both car bodies and glass.

[0067]

[0068] (3) Additives

[0069] Meanwhile, the primer composition according to the present invention may additionally include additives such as pigments, moisture absorbents, film forming agents, etc. in addition to the above components to improve viscosity, stability, and durability of the primer layer.

[0070] The above pigment is intended to improve the properties of the primer layer, such as weather resistance, durability, and strength, by preventing the primer layer from being damaged by UV rays or other factors that cause the primer layer's links to break.

[0071] The pigment may be any pigment that does not deteriorate the properties and functions of the primer composition and the primer layer, and its type is not particularly limited. For example, the pigment may include an extender pigment, a white pigment, a black pigment, a yellow pigment, a red pigment, a blue pigment, a green pigment, a metal powder pigment, a pearl pigment, and a metallic pigment. Specifically, the pigment may include an extender pigment such as barium sulfate (Ba2SO4) (barite), barite, calcium carbonate (CaCO3), clay (Clay, Al2O3·2SiO2·2H2O), bone powder (3MgO·4SiO2·H20), silica powder (SiO2), diatomaceous earth (SiO2·nH2O), silica, bentonite, talc, and aluminum silicate; White pigments such as titanium oxide (TiO2), zinc oxide (ZnO), lithopon, zinc sulfide, lead white (2PbCO3·Pb(OH)2), and antimony oxide (Sb2O3); black pigments such as carbon black, graphite, and iron black (Fe3O4); yellow pigments such as lead chromium (PbCrO3), zinc chromate, cadmium yellow (CdS), lead cyanamide (PbCN2), titanium yellow (TiO2-NiO-Sb2O3), and strontium yellow (SrCrO4); Red pigments such as iron red (Fe2O3), lead (Pb3O4), silver (HgS), cadmium red (mixed crystal of CdS and HgS), molybdenum red (mixed crystal of PbCrO4, PbMoO4, PbSO4), cuprous oxide (Cu2O); prussian blue (MFe[Fe(CN)6], M=K, NH4, Na), ultramarine (2(Al2Na2Si3O 10)·Na2S4), cobalt blue (CoO·nAl2O3), etc.; green pigments such as chrome green (a mixture of PbCrO4 and prussian blue KFe[Fe(CN)6]), chromium oxide (Cr2O-3), chromium hydroxide (Cr2O3·2H2O); metal powder pigments such as silver powder (Alluminium powder), gold powder (Bronze powder), etc.; and pearl pigments such as natural pearl essence, synthetic pearl pigment, etc. Preferably, carbon black can be used as a pigment to improve the color and weather resistance of the primer composition of the present invention, and more preferably, two kinds of carbon blacks having different average particle sizes can be used. When two kinds of carbon blacks having different average particle sizes are used, the ultraviolet ray blocking effect is more excellent than when one kind of carbon black is used.

[0072] The above pigment may be included in an amount of 3 to 10 parts by weight, 3 to 8 parts by weight, or 4 to 7 parts by weight, based on 100 parts by weight of the primer composition. When the pigment content satisfies the above range, the durability of the primer layer is excellent. If the pigment content is too low, the durability of the primer layer may be reduced, and if it is too high, the dispersibility of the pigment within the primer composition is reduced, resulting in poor storage stability.

[0073]

[0074] Next, the moisture absorbent is intended to control moisture in the primer composition to improve the stability of the primer composition and the primer layer. Any moisture absorbent may be used as long as it does not deteriorate the properties and functions of the primer composition and the primer layer, and its type is not particularly limited. Specific examples of the moisture absorbent include, but are not limited to, sodium / calcium aluminosilicate, zeolite, aldimine, oxazolidine, trimethoxyvinylsilane, and the like.

[0075] The above moisture absorbent may be included in an amount of 1 part by weight to 5 parts by weight, or 1 part by weight to 3 parts by weight, based on 100 parts by weight of the primer composition.

[0076]

[0077] Next, the film forming agent is a component for improving workability by increasing the viscosity of the composition. If the film forming agent is not included, the viscosity of the primer composition may become too low, forming the primer layer too thin, and reducing workability.

[0078] The film-forming agent may be any agent that does not impair the properties and functions of the primer composition and primer layer, and its type is not particularly limited. For example, the film-forming agent may be a thermoplastic polyurethane resin. The thermoplastic polyurethane resin may be directly synthesized using a known method, or a commercially available product may be used.

[0079] The film forming agent may be included in an amount of 1 to 5 parts by weight, 1 to 4 parts by weight, or 2 to 4 parts by weight, based on 100 parts by weight of the primer composition. When the content of the film forming agent satisfies the above range, the viscosity of the composition can be appropriately maintained. If the content of the film forming agent is too small, the viscosity of the composition may be too low, resulting in a primer layer thickness that is formed too thin, and if the content of the film forming agent is too large, the viscosity of the composition may be excessively high, resulting in poor workability.

[0080]

[0081] Meanwhile, the primer composition according to the present invention may further include other additives such as a dispersant or a storage stabilizer, in addition to a pigment, a moisture absorbent, and a film forming agent, as needed. The storage stabilizer can improve workability by extending the working life of the primer composition, and can improve storage stability by preventing the sedimentation of pigments in the composition. In addition, the storage stabilizer is not particularly limited as long as it can be commonly applied to glass primers, and examples thereof include, but are not limited to, diethyl malonate, trimethyl orthoacetate, methanol, ethanol, isopropyl alcohol, and trimethyl orthoformate.

[0082] The above dispersant can improve the storage stability of the composition by uniformly and stably dispersing the pigment within the composition. In addition, the dispersant is not particularly limited as long as it does not deteriorate the physical properties when commonly applied to glass primers, and commercially available products include, but are not limited to, EFKA PU 4061, LUBRIZOL 2063, DISPERBYK-180, DISPERBYK-110, DISPERBYK-2152, etc.

[0083]

[0084] (4) Solvent

[0085] The above primer composition may additionally include a solvent. In this case, the solvent can control the viscosity and drying properties of the composition.

[0086] The above solvent is not particularly limited as long as it can be added to a typical primer composition, and examples thereof include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and isoparaffin, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and isobutyl acetate, ethers such as diisopropyl ether and 1,4-dioxane, or carbonates such as dimethyl carbonate and diethyl carbonate.

[0087] The solvent may be included in an amount of 30 to 60 parts by weight, or 30 to 50 parts by weight, based on 100 parts by weight of the primer composition. If the content of the solvent is too small, the viscosity of the primer composition may become excessively high, which may result in a decrease in the storage stability and workability of the composition. If the content of the solvent is too large, the viscosity of the primer composition may become excessively low, which may result in the composition flowing down during the formation of the primer layer, or the film of the primer layer may be formed unevenly, and problems may arise in which the adhesion to the adherend surface or adhesive and the weather resistance of the primer layer are insufficient.

[0088]

[0089] Hereinafter, the present invention will be described in more detail through specific examples. However, these examples are provided solely to aid understanding of the present invention and are not intended to limit the scope of the present invention in any way.

[0090]

[0091] The specific specifications of each component used in the examples and comparative examples of the present invention are as follows.

[0092] (1) Urethane polymer (A)

[0093] 1) A1: A first silane-modified urethane polymer synthesized according to the following method was used.

[0094] 3.09 parts by weight of phenylaminopropyl trimethoxysilane (Y-9669, CAS No. 3068-76-6) was added to a reaction flask. Then, 2.37 parts by weight of hydrogenated xylylene diisocyanate (Tankenate® 600, hydrogenated XDI-H6XDI, CAS No. 42170-25-2) was added to a dropping tank, and the mixture was added dropwise to the reaction flask over 30 minutes, followed by reaction at 40°C for 3 hours. Then, 3.26 parts by weight of ethyl acetate was added to the reaction flask, and the reaction was terminated when the proportion of unreacted isocyanate groups (NCO groups) reached 4.5 to 6.5 wt%, thereby producing a first silane-modified urethane polymer.

[0095] 2) A2: A second silane-modified urethane polymer synthesized according to the following method was used.

[0096] 5.28 parts by weight of TDI / HDI isocyanurate (Desmodur HL, CAS No. 26426-91-5) and 1.97 parts by weight of ethyl acetate were charged into a reaction flask. Then, 3.86 parts by weight of ethyl acetate and 1.29 parts by weight of 3-mercaptopropyl trimethoxysilane (KBM-803, CAS No. 4420-74-0) were charged into a dropping tank, and the mixture was dropped into the reaction flask over 15 minutes, followed by reaction at 50°C for 1 hour. Then, 1.46 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate (ARONIX M5700, CAS No. 116969-10-1) and ethyl acetate were added to the reaction flask, and the reaction was allowed to proceed at 60°C for 3 hours. When the proportion of unreacted isocyanate groups (NCO groups) reached 1% by weight, the reaction was terminated to produce a second silane-modified urethane polymer.

[0097] 3) A3: An unmodified urethane polymer synthesized according to the following method was used.

[0098] 64.25 parts by weight of TDI / HDI isocyanurate (Desmodur HL, CAS No. 26426-91-5), 34.31 parts by weight of ethyl acetate, and 1.45 parts by weight of 1,4-butanediol were added to a reaction flask, and the reaction was allowed to proceed at 70°C for 6 hours. When the proportion of unreacted isocyanate groups (NCO groups) reached 5.0 to 5.7 wt%, the reaction was terminated, thereby producing an unmodified urethane polymer.

[0099] (2) Polyisocyanate (B)

[0100] 1) B1: Desmodur HL (TDI / HDI isocyanurate, CAS No. 26426-91-5) from Covestro was used.

[0101] 2) B2: Desmodur RFE (tris-(p-isocyanatophenyl) thiophosphate, CAS No. 4151-51-3) from Covestro was used.

[0102] (3) Film former (C): Pandex T5205-65K, a thermoplastic polyurethane (TPU) manufactured by DIC Corporation, was used.

[0103] (4) Moisture absorbent (D): Zeolite was used.

[0104] (5) Pigment (E)

[0105] 1) E1: Ashahi Kasei's Thermal FT (carbon black) was used.

[0106] 2) E2: MITSUBISHI's MA600 (carbon black) was used.

[0107]

[0108] Experimental example

[0109] The components described in Tables 1 and 2 below were mixed in the amounts (parts by weight) described in Tables 1 and 2 below to prepare primer compositions of Experimental Examples 1 to 12.

[0110] Specifically, a solvent and a film-forming agent were added to a dispersion tank and mixed for 3 hours to completely dissolve the film-forming agent. Then, a pigment and a moisture absorbent were added to the dispersion tank and mixed for 30 minutes. The mixing was performed at 400 rpm until the particle size of the mixture became 10 μm or less. Then, a urethane polymer and an isocyanate were sequentially added to the mixture to prepare a primer composition.

[0111]

[0112] Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Experimental Example 6 Experimental Example 7 Urethane polymer (A) A 18.7 27.2 10.5 4.5 12.1 18.7 28.72 A 211.8 9 13.4 110.1 16.1 18.5 11.8 9 11.89 Isocyanate (B) B 14.3 64.0 9 5.3 24.3 64.3 6.5 2.36 B 220.1 321.3 19.17 20.1 320.1 317.9 22.13 Film former (C) TPU 2.3 6 ... Absorbent (D) Zeolite 1.161.161.161.161.161.161.16 Pigment (E) E14.724.724.724.724.724.724.72E21.451.451.451.451.451.451.451.45 Solvent (F) DMC 45.2145.2145.2145.2145.2145.2145.21

[0113] Experimental Example 8 Experimental Example 9 Experimental Example 10 Experimental Example 11 Experimental Example 12 Urethane polymer (A) A1-20.618.728.728.72A220.61--11.8911.89A3--11.89--Isocyanate (B) B14.364.364.364.364.36-B220.1320.1320.13-20.13Film former (C)TPU2.362.362.362.362.36Moisture Absorbent (D) Zeolite 1.161.161.161.161.16 Pigment (E) E14.724.724.724.724.72 E21.451.451.451.451.451.45 Solvent (F) DMC 45.2145.2145.2165.3449.57

[0114]

[0115] The properties of the primer compositions manufactured by the above Experimental Examples 1 to 12 were evaluated using the following methods. The evaluation results are shown in [Table 3] and [Table 4] below.

[0116]

[0117] (1) Adhesiveness

[0118] The primer compositions of the examples and comparative examples were applied to ceramic glass and plastic substrates (Carbon fiber reinforced plastic, CFRP) in a 120 mm (length) X 10 mm (width) X 5 mm (thickness) thickness, respectively, and cured for 7 days under conditions of 20°C and 65% relative humidity to form a primer layer. After cutting the primer layer at one end with a 15 mm knife, the substrate was held with one hand and peeled off using the knife at a 30° angle. Thereafter, the adhesion was evaluated by calculating the non-peeled area as a % of the total area of ​​the primer layer.

[0119]

[0120] (2) Storage

[0121] For each primer composition of the examples and comparative examples, the viscosity was measured using a Ford Cup No. 4 at 20°C, stored at 60°C for 10 days, and then the viscosity was measured again. Thereafter, the viscosity increase rate (%) was measured based on the initial viscosity.

[0122]

[0123] (3) Shear strength

[0124] Each primer composition of the examples and comparative examples was applied and cured for 7 days under conditions of 20°C and 65% relative humidity to produce a 5 mm thick dogbone-shaped specimen, and then the shear strength was measured using a UTM (Universal Testing Machine).

[0125]

[0126] Evaluation ItemsExperimental Example 1Experimental Example 2Experimental Example 3Experimental Example 4Experimental Example 5Experimental Example 6Experimental Example 7AdhesionCeramicGlass100%100%100%85%80%100%90%Plastic100%100%97%100%95%88%90%Storageability10%15%8%12%18%8%25%Shear Strength4.153.853.973.883.203.514.20

[0127]

[0128] Evaluation ItemsExperimental Example 8Experimental Example 9Experimental Example 10Experimental Example 11Experimental Example 12AdhesionCeramicGlass70%70%40%100%80%Plastic100%95%75%20%90%Storage12%14%12%8%16%Shear Strength4.003.974.114.002.80

[0129]

[0130] Through the above [Table 3], it can be confirmed that the primer compositions of Experimental Examples 1 to 7 that satisfy the composition of the present invention have excellent adhesion to both ceramic glass and plastic, and also exhibit excellent storage stability and shear strength. In particular, the primer compositions of Experimental Examples 1 to 3 that satisfy the content of the first silane-modified urethane of 5 to 20 parts by weight, the content of the second silane-modified urethane of 10 to 20 parts by weight, and the content of the phosphate-based polyisocyanate of 10 to 25 parts by weight were found to have very excellent adhesion to both ceramic glass and plastic.

[0131] In comparison, as shown in the above [Table 4], the primer compositions of Experimental Examples 8 and 9 using only one type of urethane polymer showed inferior adhesion to ceramic glass, and in the case of the primer composition of Experimental Example 10 using the first silane-modified urethane polymer and the unmodified urethane polymer, the adhesion to both ceramic glass and plastic materials was found to be significantly reduced.

[0132] In addition, in the case of the primer composition of Experimental Example 11 that does not include phosphate-based polyisocyanate, the adhesion to the plastic substrate was significantly reduced, and in the case of Experimental Example 12 that used phosphate-based polyisocyanate alone, the adhesion to ceramic glass and plastic materials was shown to be reduced compared to the examples, and the shear strength was significantly reduced, so it is expected that the coating properties will be inferior.

Claims

1. First silane-modified urethane polymer; Secondary silane modified urethane polymer; Phosphate polyisocyanate; Polyisocyanates that do not contain phosphate groups; and A primer composition comprising an additive.

2. In paragraph 1, A primer composition wherein the above phosphate-based polyisocyanate is represented by the following [chemical formula 1]. [Chemical Formula 1] In the above chemical formula 1, X is S or O, and L1, L2 and L3 are each independently C 1~10 Alkyl group of C 5~10 aryl group or a combination thereof.

3. In paragraph 1, A primer composition wherein the polyisocyanate not containing the phosphate group and the phosphate-based polyisocyanate are included in a weight ratio of 1:3 to 1:

8.

4. In paragraph 1, The above first silane-modified urethane polymer is a reaction product of an amino group-containing silane and an isocyanate, The above second silane-modified urethane polymer is a primer composition which is a reaction product of a mercapto group-containing silane, an isocyanurate, and an acrylic compound.

5. In paragraph 1, A primer composition wherein the additive comprises a moisture absorbent, a film former, a pigment or a combination thereof.

6. In paragraph 1, The above primer composition, 5 to 20 parts by weight of the first silane-modified urethane polymer; 10 to 20 parts by weight of the second silane-modified urethane polymer; 10 to 25 parts by weight of the above phosphate-based polyisocyanate; 2 to 10 parts by weight of polyisocyanate not containing the above phosphate group; A primer composition comprising 3 to 10 parts by weight of a pigment, 1 to 5 parts by weight of a moisture absorbent, and 1 to 5 parts by weight of a film forming agent as the above additives.

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