Glass adhesive primer composition

Abstract

A glass adhesive primer composition according to the present invention comprises: a silane polymer; an acrylic polymer; a first adhesion promoter; a second adhesion promoter; and an additive, wherein the first adhesion promoter includes a silane monomer, and the second adhesion promoter includes a polyester polymer having an acid group.

Description

Primer composition for glass adhesives

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2025-0050169 filed April 17, 2025, and all contents disclosed in the document of said Korean Patent Application are incorporated herein as part of this specification.

[0002] The present invention relates to a primer composition for glass adhesives. Specifically, it relates to a primer composition for glass adhesives having excellent initial adhesion performance even at low temperatures.

[0003] When bonding glass to the painted surface of a vehicle body, in order to prevent the glass from sliding or detaching from the painted surface due to insufficient adhesion between the dissimilar materials of the painted surface and the glass, a primer is generally applied first to the painted surface and / or the glass surface, and then a moisture-curing adhesive is applied over the primer to bond them.

[0004] In the case of conventional primer compositions for glass adhesives, while there were no significant issues in high-temperature and high-humidity environments, there is a problem where the reaction does not proceed smoothly in low-temperature and dry environments, such as during the winter, resulting in reduced adhesion performance.

[0005] Therefore, there is a need to develop a primer for glass adhesives with improved adhesion performance at low temperatures.

[0006] The present invention aims to solve the above-mentioned problems by providing a primer composition for glass adhesives that includes an adhesion promoter capable of fast reaction speed and physical bonding with glass, thereby providing excellent initial adhesion even at low temperatures.

[0007] [1] The present invention provides a primer composition for glass adhesive comprising a silane polymer; an acrylic polymer; a first adhesion promoter; a second adhesion promoter; and an additive, wherein the first adhesion promoter comprises a silane monomer and the second adhesion promoter comprises a polyester polymer having an acid group.

[0008] [2] The present invention provides a primer composition for glass adhesive in which, in [1] the second adhesion promoter has an amine value of 20 to 35 mgKOH / g and an acid value of 20 to 35 mgKOH / g.

[0009] [3] The present invention provides a primer composition for glass adhesive in which, in [1] or [2], the first adhesion promoter and the second adhesion promoter are included in a weight ratio of 1:0.02 to 3.

[0010] [4] The present invention provides a primer composition for glass adhesives in which, in at least one of [1] to [3], the silane polymer comprises epoxy groups and amino groups.

[0011] [5] The present invention provides a primer composition for glass adhesive, wherein, in at least one of [1] to [4], the additive comprises a pigment, a storage stabilizer, a dispersant, a moisture absorbent, and a solvent.

[0012] [6] The present invention provides a primer composition for glass adhesive, wherein, in at least one of [1] to [5], the primer composition comprises: 30 to 40 parts by weight of the silane polymer; 10 to 30 parts by weight of the acrylic polymer; 1 to 5 parts by weight of the first adhesion promoter; 0.1 to 3 parts by weight of the second adhesion promoter; and as additives, 6 to 8 parts by weight of pigment, 0.1 to 2 parts by weight of storage stabilizer, 0.5 to 3 parts by weight of dispersant, 0.1 to 1 part by weight of moisture absorbent and 20 to 55 parts by weight of solvent.

[0013] The primer composition for glass adhesive according to the present invention comprises a first adhesion promoter with a fast reaction rate and a second adhesion promoter that physically bonds glass and a silane polymer, and can have excellent initial adhesion performance and storage stability with glass in a wide temperature range (about -10°C to 40°C).

[0014] FIG. 1 is a schematic diagram illustrating the adhesion mechanism of the primer composition for glass adhesive of the present invention.

[0015] The present invention will be described in more detail below.

[0016] Meanwhile, in this specification, "comprising" is an open description having an equivalent meaning to expressions such as "comprising," "containing," "having," or "characterizing," and does not exclude elements, materials, or processes not additionally listed.

[0017] Additionally, units used in this specification without special mention are based on weight, and, for example, units of % or ratio mean weight % (wt%) or weight ratio.

[0018] In this specification, the “weight-average molecular weight” and “number-average molecular weight” of the resin can be measured by methods well known in the art, and, for example, values ​​measured by the method of gel permeation chromatograph (GPC).

[0019] In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic," and "acrylate-based" means "acrylate" and / or "methacrylate."

[0020] In this specification, functional groups such as "acid value" and "hydroxyl value" are measured by conventional methods known in the art, for example, by titration.

[0021] In this specification, the unit "parts by weight" refers to the ratio of weight between each component.

[0022] In this specification, "glass transition temperature" is measured by conventional methods known in the art, for example, by differential scanning calorimetry (DSC).

[0023] In this specification, “viscosity” is measured by conventional methods known in the art, for example, using a Brookfield viscometer at room temperature (25°C).

[0024] Primer composition for glass adhesives

[0025] A primer composition for glass adhesive according to the present invention comprises a silane polymer; an acrylic polymer; a first adhesion promoter; a second adhesion promoter; and an additive, wherein the first adhesion promoter comprises a silane monomer and the second adhesion promoter comprises a polyester polymer having an acid group.

[0026]

[0027] Conventional primer compositions for glass adhesives have a problem in that their adhesion to glass decreases at low temperatures. Accordingly, the inventors have completed the present invention by discovering that, in order to devise a primer composition for glass adhesive with excellent initial adhesion in a variety of temperature ranges (about -10°C to 40°C), applying a silane monomer as a first adhesion promoter can improve the reaction rate compared to a silane polymer as an adhesion promoter, and applying a polyester polymer having an acid value as a second adhesion promoter can physically bond the glass and the silane polymer to improve initial adhesion.

[0028]

[0029] Below, each component of the primer composition for glass adhesive is described in detail.

[0030]

[0031] Silane polymer

[0032] Silane polymers can impart adhesion and bonding properties to the manufactured coating film with the adhesive and glass, which serve as the attachment surfaces.

[0033] The above silane polymer comprises an epoxy group or an amino group and can be prepared from an epoxy-based silane and an amino-based silane. Specifically, the above silane polymer can be prepared by mixing and reacting an epoxy-based silane and an amino-based silane at 40 to 60°C for 20 to 50 hours.

[0034] In this case, the epoxy silane is, for example, glycidoxy C 1-5 Alkyl C 1-5 It may be an alkoxysilane, specifically, glycidoxy C 1-5 AlkyltriC 1-5 It may be an alkoxysilane. More specifically, the epoxy silane may include, but is not limited to, glycidoxymethyltrimethoxysilane, glycidoxyethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxyethyltriethoxysilane, glycidoxypropyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxyethyltripropoxysilane, glycidoxypropyltripropoxysilane, etc.

[0035] In addition, the above amino-based silane may be, for example, a silane comprising one or more amino groups, and may be, for example, an aliphatic silane comprising two or more amino groups. Specifically, the above amino-based silane is amino C 1-5 Alkyl-triC 1-5 It may be an alkoxysilane, for example, aminomethyl-trimethoxy-silane, aminoethyl-trimethoxy-silane, aminopropyl-trimethoxy-silane, aminoethyl-aminopropyl-trimethoxy-silane, etc., but is not limited thereto.

[0036] A first solvent may be used when reacting the above epoxy-based silane and amino-based silane, and the first solvent may include methyl ethyl ketone, ethyl acetate, dimethyl carbonate, methanol, n-butanol, and mixtures thereof.

[0037] The above epoxy-based silane and amino-based silane may react in a weight ratio of 1:0.1 to 1.0, 1:0.2 to 0.8, or 1:0.3 to 0.5. If the reaction weight ratio of the epoxy-based silane and amino-based silane is less than the above range, that is, if a small amount of amino-based silane is used relative to the epoxy-based silane, the adhesion strength with the adhesive may be reduced due to a lack of adhesive functional groups; if it exceeds the above range, that is, if an excessive amount of amino-based silane is used relative to the epoxy-based silane, an excessive amount of unreacted amino groups may be present in the composition, which may reduce the weather resistance and water resistance of the coating film and worsen storage stability during storage.

[0038] In addition, the silane polymer may have an epoxy equivalent (EEW) of 2,000 to 9,000 g / eq or 3,000 to 5,000 g / eq and a weight-average molecular weight (Mw) of 700 to 5,000 g / mol or 700 to 3,000 g / mol. When the epoxy equivalent and weight-average molecular weight of the silane polymer are within the above ranges, there is an effect of excellent storage stability and adhesion. If the epoxy equivalent of the silane polymer is below the above range, the dispersibility of pigment and / or additive particles is reduced due to the low epoxy equivalent, which may cause a problem of reduced storage stability; if the epoxy equivalent is high, it may react with the isocyanate groups of the urethane adhesive applied later to form microbubbles, which may cause a problem of reduced adhesion. Furthermore, if the weight-average molecular weight of the silane polymer is below the above range, there is a problem of poor storage stability, and if it exceeds the above range, there may be a problem of poor adhesion.

[0039] The above silane polymer may be included in the primer composition for the glass adhesive in an amount of 30 to 40 parts by weight, 32 to 38 parts by weight, or 34 to 36 parts by weight. When the content of the above silane polymer is within the above range, the long-term storage stability of the primer and its adhesion to glass may be improved. If the content of the above silane polymer is included below the above range, a problem of reduced storage stability may occur, and if it is included above the above range, a problem of reduced adhesion may occur due to a lack of adhesion functional groups with the adhesive.

[0040]

[0041]

[0042] acrylic polymer

[0043] Acrylic polymers can impart tackiness and adhesion to the primer composition.

[0044] The above acrylic polymer may be one that is directly synthesized according to a known method, or a commercially available product may be used. In this case, the acrylic polymer may be prepared, for example, from an alkyl group-containing (meth)acrylate monomer and a hydroxyl group and aromatic ring-containing (meth)acrylate monomer.

[0045] The above alkyl group-containing (meth)acrylate monomer improves the adhesion and bonding properties of the acrylic polymer. In addition, the above hydroxyl group and aromatic ring-containing (meth)acrylate monomer forms bonding sites (-OH) with the adhesive, thereby improving the adhesion of the composition and improving the weather resistance of the primer.

[0046] For example, the above acrylic polymer is C 1-3 Alkyl group-containing (meth)acrylate monomer, C 4-10 Alkyl group-containing (meth)acrylate monomer and hydroxyl group and C 6-12 It can be manufactured from aromatic ring-containing (meth)acrylates.

[0047] For example, the above acrylic polymer is C1-3 Alkyl group-containing (meth)acrylate monomer, C 4-10 Alkyl group-containing (meth)acrylate monomer and hydroxyl group and C 6-12 It may contain aromatic ring-containing (meth)acrylate in a weight ratio of 1:0.1 to 10:0.1 to 10 or 1:1 to 5:0.15 to 3.

[0048] If the weight ratio of each of the above monomers satisfies the above range, film-forming properties, tackiness, and adhesion may be improved. The above C 4-10 If the content of the alkyl group-containing (meth)acrylate monomer is less than the above range, i.e., C 1-3 A small amount of C with respect to alkyl group-containing (meth)acrylate monomers 4-10 If it contains an alkyl group-containing (meth)acrylate monomer, film-forming properties and adhesion may be inferior, and if it exceeds the above range, i.e., C 1-3 Excess C with respect to alkyl group-containing (meth)acrylate monomers 4-10 If it contains (meth)acrylate monomers containing alkyl groups, storage stability may be reduced.

[0049] The above hydroxyl group and C 6-12 If the content of aromatic ring-containing (meth)acrylate is less than the above range, i.e., C 1-3 A small amount of hydroxyl groups and C for (meth)acrylate monomers containing alkyl groups 6-12 If it contains (meth)acrylates containing aromatic rings, there is a problem where the curing reaction is insufficient and film formation is reduced, and if it exceeds the above range, i.e., C 1-3 With respect to alkyl group-containing (meth)acrylate monomers, excess hydroxyl groups and C 6-12 If it contains (meth)acrylates containing aromatic rings, a problem with poor storage stability may occur.

[0050] Meanwhile, the above acrylic polymer may have a weight-average molecular weight (Mw) of 50,000 to 300,000 g / mol, 100,000 to 250,000 g / mol, or 100,000 to 200,000 g / mol. When the weight-average molecular weight of the acrylic polymer is within the above range, excellent adhesion and workability are achieved. Additionally, if the weight-average molecular weight of the acrylic polymer is below the above range, adhesion to the substrate may decrease, and if it exceeds the above range, storage stability may decrease.

[0051] In addition, the acrylic polymer may have a glass transition temperature (Tg) of 30 to 70 ℃, 35 to 60 ℃, or 45 to 50 ℃. When the glass transition temperature of the acrylic polymer is within the above range, excellent adhesion and workability are achieved. In addition, if the glass transition temperature of the acrylic polymer is below the above range, adhesion to the substrate may decrease, and if it exceeds the above range, storage stability may decrease.

[0052] The above acrylic polymer may have a viscosity of 10 to 500 cps, 50 to 400 cps, or 50 to 300 cps at 25°C. When the viscosity of the acrylic polymer at 25°C is within the above range, excellent adhesion and workability are achieved. Additionally, if the viscosity of the acrylic polymer is below the above range, the adhesion to the substrate may decrease, and if it exceeds the above range, storage stability may decrease.

[0053] The above acrylic polymer may be included in an amount of 10 to 30 parts by weight, 12 to 25 parts by weight, or 15 to 20 parts by weight with respect to the primer composition for glass adhesive. When the content of the above acrylic polymer is within the above range, excellent adhesion and workability may be achieved. Additionally, if the content of the above acrylic polymer is below the above range, there is a problem of reduced adhesion to the substrate, and if it exceeds the above range, there may be a problem of reduced storage stability.

[0054]

[0055] 1st adhesion promoter

[0056] The first adhesion promoter includes a silane monomer, which can improve adhesion by rapidly coupling to the glass surface through silane groups and has higher reactivity than polymer-type adhesion promoters, thereby increasing the adhesion speed with the glass at low temperatures. Additionally, it can rapidly react with the second adhesion promoter described later to promote adhesion with the glass.

[0057] The above silane monomer may be a silane compound containing at least one of an amine group and an alkoxy group, or a silane compound containing both an amine group and an alkoxy group. For example, the above amine group-containing silane compound may include one or more selected from the group consisting of N-3-(trialkoxysilylalkyl)benzeneamine, N-phenyl-gamma-aminoalkyltrialkoxysilane, and 3-aminoalkyltrialkoxysilane. The "alkoxy" of each of the above components may have 1 to 5 carbon atoms or 1 to 3 carbon atoms, and examples include methoxy, ethoxy, propoxy, butoxy, etc. Additionally, the "alkyl" of each of the above components may have 1 to 5 carbon atoms or 2 to 4 carbon atoms, and examples include methyl, ethyl, propyl, butyl, etc.

[0058] In addition, the first adhesion promoter may be included in an amount of 1 to 5 parts by weight, 1.3 to 3 parts by weight, or 1.5 to 2.5 parts by weight with respect to the primer composition for glass adhesive. If the first adhesion promoter is below the above range, the initial adhesion performance with glass may be reduced. If the first adhesion promoter exceeds the above range, the long-term adhesion performance may be reduced.

[0059]

[0060] 2nd adhesion promoter

[0061] The second adhesion promoter comprises a polyester polymer having an acid group, and when the primer composition is applied to glass, the polyester polymer is positioned on the glass surface and physically bonds with the glass surface and the silane polymer to improve initial adhesion performance.

[0062] The above polyester polymer has acid groups, and the acid groups impart an acid value. The types are not specifically limited as long as they can be applied to a primer composition, but examples include carboxyl groups, sulfonic acid groups, acetic acid groups, hydroxyl groups, and phosphate groups. For example, the above polyester polymer may be the commercial product BYK-4509.

[0063] Meanwhile, the second adhesion promoter may have an amine value of 20 to 35 mgKOH / g and an acid value of 20 to 35 mgKOH / g. Alternatively, the amine value of the second adhesion promoter may be 23 to 32 mgKOH / g or 25 to 30 mgKOH / g, and the acid value may be 23 to 32 mgKOH / g or 25 to 30 mgKOH / g. If the second adhesion promoter is below the above amine value range, the interaction with the glass decreases, and the adhesion strength may decrease. If the amine value exceeds the above amine value range, uneven curing of the coating film may occur. If the second adhesion promoter is below the above acid value range, hydrogen bonding with the glass and ionic bonding with the silane polymer or the first adhesion promoter decrease, and the adhesion strength may decrease. If the acid value exceeds the above acid value range, the acid groups in the primer composition increase, which may hinder the formation of the coating film and reduce the stability of the composition.

[0064] The second adhesion promoter may be included in an amount of 0.1 to 3 parts by weight, 0.3 to 2.5 parts by weight, or 0.5 to 2 parts by weight with respect to the primer composition for glass adhesive. If the second adhesion promoter is included in an amount less than the above range, the adhesion strength between the glass and the silane polymer may decrease. If the second adhesion promoter exceeds the above range, the acid groups in the primer composition increase, which may hinder the formation of the coating film.

[0065] The above-described first adhesion promoter and second adhesion promoter may be included in a weight ratio of 1:0.02 to 3, 1:0.1 to 0.9, or 1:0.3 to 0.6. When the composition includes the first adhesion promoter and the second adhesion promoter in a weight ratio within the above ranges, the acid value and amine value contained in the second adhesion promoter can promote the silane coupling reaction between the first adhesion promoter and the glass, thereby improving adhesion to the glass, and the second adhesion promoter can also improve physical adhesion due to the etching effect on the glass surface.

[0066]

[0067] additives

[0068] The above primer composition for glass adhesive may include a pigment, a storage stabilizer, a dispersant, a moisture absorbent, and a solvent as additives.

[0069]

[0070] The above pigment provides color to the primer composition and can improve physical properties such as weather resistance, durability, and strength.

[0071] The above pigments may generally be used without special restrictions as long as they do not degrade physical properties and functions when included in the paint composition. Examples include extender pigments, white pigments, black pigments, yellow pigments, red pigments, blue pigments, green pigments, metal powder pigments, pearl pigments, and metallic pigments.

[0072] The above pigments are, for example, extender pigments such as barium sulfate (Ba2SO4) (barite), barite, calcium carbonate (CaCO3), clay (Al2O3·2SiO2·2H2O), bone powder (3MgO·4SiO2·H2O), silica powder (SiO2), diatomite (SiO2·nH2O), silica, bentonite, talc, and aluminum silicate; white pigments such as titanium oxide (TiO2), zinc oxide (ZnO), lithopone, zinc sulfide, lead white (2PbCO3·Pb(OH)2), and antimony oxide (Sb2O3); and black pigments such as carbon black, graphite, and iron black (Fe3O4). Yellow pigments such as yellow lead (PbCrO3), zinc chromate, cadmium yellow (CdS), lys cyanamide (PbCN2), titanium yellow (TiO2-NiO-Sb2O3), and strontium yellow (SrCrO4); red pigments such as ferrous red (Fe2O3), lead red (Pb3O4), silver vermilion (HgS), cadmium red (mixed crystals of CdS and HgS), molybdenum red (mixed crystals of PbCrO4, PbMoO4, and PbSO4), and cuprous oxide (Cu2O); ultramarine (MFe[Fe(CN)6], M=K, NH4, Na) and ultramarine (2(Al2Na2Si3O2) 10 Examples include blue pigments such as )·Na2S4), cobalt blue (CoO·nAl2O3); green pigments such as chrome ochre (a mixture of PbCrO4 and ultramarine KFe[Fe(CN)6]), chromium oxide (Cr2O3), and chromium hydroxide (Cr2O3·2H2O); metal powder pigments such as silver powder (alluminium powder) and gold powder (bronze powder); and pearl pigments such as natural pearl essence and synthetic pearl pigment, and carbon black may be used to improve the color and weather resistance of the primer composition of the present invention.

[0073] The above pigment may be included in the composition in an amount of 6 to 8 parts by weight, or 6.3 to 7.7 parts by weight, or 6.5 to 7.5 parts by weight, relative to the primer composition for glass adhesive. If the pigment content is below the above range, the opacity and appearance characteristics of the cured primer film may be reduced, and if it is included above the above range, the dispersibility of the pigment in the primer composition may be reduced, resulting in a long time required for dispersion or sedimentation occurring during storage of the manufactured primer composition, which may cause problems such as reduced storage stability and product reliability of the primer.

[0074]

[0075] The above storage stabilizer can improve workability by extending the pot life of the primer composition and improve storage stability by preventing the settling of pigments within the composition.

[0076] The above storage stabilizer is not particularly limited as long as it is generally applicable to glass primers, and examples include, but are not limited to, diethyl malonate, trimethyl orthoacetate, methanol, ethanol, isopropyl alcohol, trimethyl orthoformate, etc.

[0077] The above storage stabilizer may be included in an amount of 0.1 to 2 parts by weight, 0.1 to 1.8 parts by weight, or 0.3 to 1.5 parts by weight with respect to the primer composition for glass adhesive. If the above storage stabilizer is too abundant, the hardness, durability, and adhesion of the primer film may be compromised. If the above storage stabilizer is too scarce, changes in viscosity or phase separation may occur during the storage of the primer composition, leading to a decrease in quality.

[0078]

[0079] The above-mentioned dispersant can improve the storage stability of the composition by dispersing the pigment in a uniform and stable state within the composition.

[0080] The above-mentioned dispersant is not particularly limited as long as it is not applied to a primer for glass and does not degrade physical properties. Examples of commercially available products include BYK-2152, EFKA PU 4061, LUBRIZOL 2063, DISPERBYK-180, DISPERBYK-110, DISPERBYK-2152, etc., but are not limited thereto.

[0081] The above-mentioned dispersant may be included in an amount of 0.5 to 3 parts by weight, 0.7 to 2.7 parts by weight, or 1 to 2.5 parts by weight with respect to the primer composition for glass adhesive. If the amount of the above-mentioned dispersant is too high, the physical properties of the primer film may deteriorate. If the amount of the above-mentioned dispersant is too low, the pigment may not be uniformly distributed, which may result in a decrease in color quality, and particles may aggregate and precipitation may occur.

[0082]

[0083] The above moisture absorbent is intended to improve the stability of the primer composition and the primer layer by controlling moisture within the primer composition, and it only needs not degrade the physical properties and functions of the primer composition and the primer layer, and its type is not particularly limited. Specific examples of the above moisture absorbent include sodium / calcium aluminosilicate, zeolite, aldimin, oxazolidine, trimethoxyvinylsilane, etc., but are not limited thereto.

[0084] The above moisture absorbent may be included in an amount of 0.1 to 1 part by weight or 0.15 to 0.7 parts by weight with respect to the primer composition for glass adhesive. If the amount of the moisture absorbent is too high, the viscosity of the primer composition may increase, thereby reducing workability. If the amount of the moisture absorbent is too low, it may react with moisture remaining in the primer composition, thereby reducing storage stability.

[0085]

[0086] The above solvent can control the viscosity and drying properties of the composition.

[0087] The above solvent is not particularly limited as long as it can be added to a conventional primer composition, and examples include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane, and isoparaffin, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, acetate solvents such as ethyl acetate and isobutyl acetate, ether solvents such as diisopropyl ether and 1,4-dioxane, or carbonate solvents such as dimethyl carbonate and diethyl carbonate, or mixtures thereof.

[0088] The above solvent may be included in an amount of 20 to 55 parts by weight, 25 to 50 parts by weight, or 30 to 45 parts by weight with respect to the primer composition for glass adhesive. If the content of the solvent is too low, the viscosity of the primer composition may become excessively high, which may reduce the storage stability and workability of the composition; if the content of the solvent is too high, the viscosity of the primer composition may become excessively low, which may cause it to run down during the formation of the primer layer, or the film of the primer layer may be formed unevenly, and problems may arise regarding the adhesion to the substrate or adhesive and the weather resistance of the primer layer.

[0089]

[0090] The primer composition for glass adhesive of the present invention includes the first adhesion promoter and the second adhesion promoter, and thus can have excellent adhesion ability even at low temperatures, and the adhesion mechanism of the primer composition for glass adhesive including the first adhesion promoter and the second adhesion promoter can be explained through FIG. 1.

[0091] When the above-mentioned primer composition for glass adhesive is applied to glass (10) to form a primer film (20), the silane polymer (230) is chemically bonded and attached to the glass, but time is required for the bonding to be completed. On the other hand, the first adhesion promoter (210) is in the form of a monomer and has higher reactivity than the silane polymer (230), so the bonding speed can be increased. Meanwhile, when the second adhesion promoter (220) is applied to the primer composition for glass adhesive, the first adhesion promoter (210) and the second adhesion promoter (220) do not chemically bond, but are positioned on the surface of the glass (10) to physically bond with the glass (10), and at the same time, can promote the bonding between the first adhesion promoter (210) and the glass (10). That is, the second adhesion promoter (220) can provide an adhesion site on the surface of the glass (10) and, at the same time, combine with the first adhesion promoter (210) to improve the initial adhesion ability, and the primer film (20) can be formed as the silane polymer (230) chemically combines with the first adhesion promoter (210).

[0092]

[0093] The present invention will be explained in more detail below through specific embodiments. However, these embodiments are intended only to aid in understanding the invention and do not limit the scope of the invention in any way to these embodiments.

[0094]

[0095] Synthesis Example 1. Preparation of Silane Polymer

[0096] 3.6 g of N-(beta-aminoethyl)-gamma-aminopropyl-trimethoxy-silane, 9 g of gamma-glycidoxypropyltrimethoxysilane, 7 g of methyl ethyl ketone (MEK), 15 g of dimethyl carbonate (DMC), and 1 g of methanol were added to a reaction vessel and reacted at 40–50°C for 20–25 hours to prepare a silane polymer.

[0097]

[0098] Synthesis Example 2. Preparation of acrylic polymer

[0099] 10 g of methyl ethyl ketone (MEK), 2 g of methyl methacrylate (MMA), 2.5 g of butyl methacrylate (BMA), 0.5 g of 2-hydroxy-3-phenoxypropylacrylate (HPPA), and 0.05 g of tert-butyl peroxide were added to a reaction vessel, and an acrylic polymer was prepared by reacting at 75–85 °C for 10–15 hours.

[0100]

[0101] Experimental Example 1. Preparation of a Primer Composition for Glass Adhesives

[0102] The above silane polymer, the above acrylic polymer, 2.0 g of the first adhesion promoter, 1.0 g of the second adhesive, 7.0 g of carbon black as a pigment, 0.35 g of a moisture absorbent, 1.5 g of a dispersant, 0.5 g of a storage stabilizer, 17 g of ethyl acetate, and 20 g of dimethyl carbonate were placed in a reaction vessel, and a primer composition for glass adhesive was prepared using a high-speed stirrer.

[0103]

[0104] Experimental Examples 2 to 16

[0105] A primer composition for glass adhesive was prepared in the same manner as in Experimental Example 1, except that the content of each component listed in Tables 1 and 2 below was used.

[0106]

[0107]

[0108] The product name, ingredients, physical properties, etc. of each component used in the experimental example are shown in Table 3 below.

[0109] Name of component compound, or manufacturer and product name Physical properties 1st Adhesion Promoter - 1 N-[3-(trimethoxysilyl)propyl]benzeneamine (Momentive, Silquest Y-9669) - 1st Adhesion Promoter - 2 Aqueous 3-aminopropylsilane hydrolysate (Dynasylan hydrosol 1151, EVONIK)) - 2nd Adhesion Promoter - 1 BYK, BYK-4509 Amine value: 29 mgKOH / g, Acid value: 29 mgKOH / g 2nd Adhesion Promoter - 2 EFKA PU 4010 Amine value: ~6 mgKOH / g, Acid value: ~13 mgKOH / g 2nd Adhesion Promoter - 3 BYK-9076 Amine value: 44 mgKOH / g, Acid value: 38 mgKOH / g 2nd Adhesion Promoter - 4 BYK-2152 - Storage stabilizer Diethyl malonate - Moisture Absorbent: Sodium / Calcium Aluminosilicate - Dispersant: Hyperbranched Polyester (BYK, BYK-2152) - Pigment: Carbon Black (Birla, Raven 425)

[0110]

[0111] Physical property evaluation

[0112] The physical properties of the primer compositions for glass adhesives of Experimental Examples 1 to 16 above were measured by the following method, and the results are shown in Table 4 below.

[0113] (1) Initial adhesion

[0114] A primer composition was applied to a glass plate measuring (25) mm (length) x (150) mm (width) x (5) mm (thickness), and an adhesive (PU9510, KCC P2P product) was pressed onto it to prepare a specimen.

[0115] Test specimens were cured at temperatures of 20°C, 40°C, and -10°C under conditions of 40% or less relative humidity. An adhesion test was conducted three days after the adhesive application date to observe the condition of the adhesive interface. Subsequently, the primer layer at one end of the specimen was cut with a 15mm knife; the coated substrate was then held with one hand, and the cut was peeled off using the knife at a 30° angle. After curing, adhesion was evaluated by calculating the percentage of the area of ​​the adhesive that did not adhere to the primer (interfacial delamination between the primer layer and the adhesive) relative to the total area of ​​the adhesive layer. In this case, adhesion was evaluated as better when the adhered area was higher.

[0116]

[0117] (2) Storage

[0118] For each primer composition, the viscosity was measured using a No. 4 Ford cup at 20°C, and then the viscosity was measured again after storing at 40°C for 10 days. Subsequently, the viscosity increase rate (%) was measured based on the initial viscosity. If the viscosity increase rate was less than 20%, it was evaluated as good; if it was between 20% and 50%, it was evaluated as poor; and if it exceeded 50%, it was evaluated as poor.

[0119]

[0120] Classification Experiment Example 1 Experiment Example 2 Experiment Example 3 Experiment Example 4 Experiment Example 5 Experiment Example 6 Experiment Example 7 Experiment Example 8 Adhesion (20℃) 100% Cf 100% Cf 100% Cf 100% Cf 100% Cf 100% Cf 100% Cf 75% Cf Adhesion (40℃) 100% Cf 90% Cf 85% Cf 100% Cf 100% Cf 100% Cf 100% Cf 80% Cf Adhesion (-10℃) 100% Cf 100% Cf 80% Cf 80% Cf 80% Cf 90% Cf 100% Cf 100% Cf Storage Depth Good Good Good Good Good Good Good Classification Experiment Example 9 Experiment Example 10 Experiment Example 11 Experiment Example 12 Experiment Example 13 Experiment Example 14 Experiment Example 15 Experimental Example 16 Adhesion (20℃) 80% Cf 85% Cf 100% Cf 100% Cf 100% Cf 30% Cf 70% Cf 65% Cf Adhesion (40℃) 75% Cf 40% Cf 100% Cf 30% Cf 100% Cf 30% Cf 65% Cf 60% Cf Adhesion (-10℃) 80% Cf 55% Cf 0% Cf 0% Cf 0% Cf 0% Cf 50% Cf 40% Cf Storage stability Good Good Good Good Good Good Good Good

[0121] Referring to Table 4 above, it can be seen that Experimental Examples 1 to 9 have excellent adhesion and storage properties at different temperatures. On the other hand, Experimental Examples 10 to 15, which do not include some components among the silane polymer, acrylic polymer, first adhesion promoter, and second adhesion promoter having acid groups, have inferior low-temperature adhesion properties.

[0122] Experimental Example 16, in which a silane polymer (polyfunctional aminopolymer silane) rather than a silane monomer was applied as the first adhesion promoter, was found to have inferior low-temperature adhesion.

Claims

1. comprising a silane polymer; an acrylic polymer; a first adhesion promoter; a second adhesion promoter; and an additive, A primer composition for a glass adhesive, wherein the first adhesion promoter comprises a silane monomer, and the second adhesion promoter comprises a polyester polymer having an acid group.

2. In Paragraph 1, The above second adhesion promoter is a primer composition for glass adhesive having an amine value of 20 to 35 mgKOH / g and an acid value of 20 to 35 mgKOH / g.

3. In Paragraph 1, A primer composition for glass adhesive comprising the first adhesion promoter and the second adhesion promoter in a weight ratio of 1:0.02 to 3.

4. In Paragraph 1, The above silane polymer is a primer composition for glass adhesives comprising epoxy groups and amino groups.

5. In Paragraph 1, The above additive is a primer composition for glass adhesive comprising a pigment, a storage stabilizer, a dispersant, a moisture absorbent, and a solvent.

6. In Paragraph 1, The above-mentioned primer composition for glass adhesive is, 30 to 40 parts by weight of the above silane polymer; 10 to 30 parts by weight of the above acrylic polymer; 1 to 5 parts by weight of the first adhesion promoter above; 0.1 to 3 parts by weight of the second adhesion promoter; and A primer composition for glass adhesive comprising, as the above additives, 6 to 8 parts by weight of pigment, 0.1 to 2 parts by weight of storage stabilizer, 0.5 to 3 parts by weight of dispersant, 0.1 to 1 part by weight of moisture absorbent, and 20 to 55 parts by weight of solvent.

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