KR20180092756A - Adhesive compositions for ingot and the manufacturing method thereof - Google Patents

Abstract

The present invention relates to an adhesive composition for ingots and a method for manufacturing the same. The composition comprises: a main agent mixture comprising a resin mixture comprising an epoxy resin and a modified rubber and a filler; a curing agent mixture comprising a mercaptan-based compound and a tertiary amine-based compound; a urea-modified amine; and a C4 to C30 linear or branched, saturated or unsaturated fatty acid. The adhesive composition for ingots according to the present invention suppresses or weakens the bad smell even if a mercaptan-based compound is included.

Description

TECHNICAL FIELD [0001] The present invention relates to an adhesive composition for an ingot, and an adhesive composition for an ingot,

The present invention relates to an ingot adhesive composition capable of temporarily fixing an ingot to a supporting means and a method for producing the same. More specifically, the present invention relates to an ingot adhesive composition having improved smell, surface skinning, and storage stability of the composition and a method for producing the same.

It is common to use a massive inorganic raw material such as silicon, glass, ceramic, gadolinium, gallium, garnet, arsenic, phosphorus, sapphire, , Hereinafter referred to as an "ingot"), the ingot is fixed or temporarily fixed to a supporting means such as a beam, a zig, or the like, processed, and the finished workpiece is separated from the supporting means shall. An ingot adhesive is used as a means for fixing the ingot uniformly to the support means.

The ingot adhesives may be thermosetting resins such as thermoplastic resins and epoxy resins selected from vinyl resins, petroleum resins, natural resins such as rosin, oligomer waxes such as paraffin wax, A resin is mixed with a curing agent. Such an ingot adhesive should be easily detachable without damaging the ingot or the supporting means when the ingot is separated from the supporting means after processing the ingot.

The adhesive composition for ingots contains a mercapane compound as a curing agent to improve the low-temperature curing performance, but has a disadvantage in that it has a strong smell during storage and skinning of the surface. The above-mentioned mercaptan-type compounds are not preferable from the viewpoints of environmental pollution and hygiene in operation and practical use due to headache or discomfort when the human body is inhaled, irrespective of the mechanism of odor generation. .

From this point of view, the inventors of the present invention have developed an adhesive composition for ingots and a method for producing the same, which improves the skinning of the surface while suppressing or reducing the odor during storage even when the composition contains a mercaptan-based compound and has excellent storage stability.

DISCLOSURE OF THE INVENTION In order to solve the above problems, the present invention provides a method for producing an adhesive composition for ingots which is excellent in storage stability by improving the skinning which suppresses odor during storage even when a mercapanic compound is contained and the surface is dried The purpose.

The present invention also relates to a composition comprising a main mixture comprising an epoxy resin and a modified rubber; Curing agent mixture; Urea-modified amines; And a linear or branched saturated or unsaturated fatty acid of C ₄ to C ₃₀ , the ingot is firmly fixed to the supporting means, and is easily peeled off from the room-temperature peeling liquid or middle-temperature water (50 to 75 ° C) And an object of the present invention is to provide an adhesive composition for ingots that improves odor and surface drying phenomenon and a method for producing the same.

As a result of research to achieve the above object, the adhesive composition for ingots of the present invention comprises a main mixture comprising a resin mixture comprising an epoxy resin and a modified rubber and a filler; A curing agent mixture comprising a mercaptan-based compound and a tertiary amine-based compound; Urea-modified amines; And C ₄ to C ₃₀ linear or branched, saturated or unsaturated fatty acids.

The epoxy resin may be a phenolic novolak type epoxy resin.

The modified rubber may be an acrylic rubber containing at least one functional group selected from a carboxyl group, an amine group and a hydroxyl group.

The fatty acid may be selected from the group consisting of 2-ethylhexanoic acid, isononanoic acid, oleic acid, palmitic acid, stearic acid and linolenic acid. Or a mixture of two or more thereof.

The subject mixture may contain 50 to 85% by weight of the resin mixture and 15 to 50% by weight of the filler.

The resin mixture may include an epoxy resin and a modified rubber in a weight ratio of 1: 1 to 1: 2.

The curing agent mixture may further include any one or a mixture of two or more selected from amine-based compounds having two or more primary amino groups and amine-containing phenolic resins.

The mixture of the subject mixture and the curing agent may be mixed in a weight ratio of 1: 1 to 3: 1.

The adhesive composition for ingots may contain 0.1 to 10 parts by weight of a urea-modified amine and 0.1 to 10 parts by weight of a fatty acid based on 100 parts by weight of the mixture of the subject mixture and the curing agent.

The method for producing an ingot adhesive of the present invention comprises the steps of: a) mixing a resin mixture comprising an epoxy resin and a modified rubber with a curing agent mixture and heating; And b) further adding a filler, a urea-modified amine and a C ₄ to C ₃₀ linear or branched saturated or unsaturated fatty acid after the heating.

In the step a), 1 to 10% by weight of the resin mixture and the curing agent mixture may be mixed and heated in the entire resin mixture, and then the remaining 90 to 99% by weight of the resin mixture may be further mixed.

In the step a), one or more of the antioxidants and fragrances may be further mixed and heated.

The adhesive composition for ingots according to the present invention has an advantage that the storage stability can be improved by improving the skinning of the outer surface during storage while suppressing or weakening the bad smell even if a mercapanic compound is included.

In addition, the adhesive composition for ingots according to the present invention not only has excellent adhesion when the ingot is fixed to the supporting means, but also improves productivity by shortening the fixing time and can be easily peeled off with stability against warm water and moderate temperature There are advantages.

Hereinafter, the adhesive composition for ingots and the method for producing the same according to the present invention will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In order to attain the above object, the present invention relates to an adhesive composition for ingots and a method for producing the same.

The present invention will be described in detail,

The adhesive composition for ingots of the present invention comprises a main mixture comprising a resin mixture comprising an epoxy resin and a modified rubber and a filler; A curing agent mixture comprising a mercaptan-based compound and a tertiary amine-based compound; Urea-modified amines; And C ₄ to C ₃₀ linear or branched, saturated or unsaturated fatty acids.

The adhesive composition for ingots according to the present invention is an adhesive composition for fixing or tacking an ingot on a supporting means, which increases productivity by shortening the fixing or temporary fixing time, and is easily peeled off with stability against warm water and moderate temperature . In addition, the above-mentioned adhesive composition for ingots can improve the storage stability and workability by suppressing or weakening the bad smell even if it contains a mercaptan-type compound, and it is possible to improve the storage stability due to drying of the surface in contact with air during storage.

According to one embodiment of the present invention, the epoxy resin may be a phenolic novolak type epoxy resin. The phenolic novolac epoxy resin may be any one or more selected from phenol novolak epoxy resin and bisphenol novolac resin. Preferably, the phenolic novolac epoxy resin may be an epoxy resin represented by the following general formula (1).

[Chemical Formula 1]

In the formula 1, the linking group L is a linear or branched alkylene group having ₁ to ₁₀ carbon atoms, n is an integer of 1 or more, may have a weight average molecular weight of 500 g / mol or more, But may be, but not limited to, greater than 100,000 g / mol.

When the phenolic novolak type epoxy resin is used, the water absorbency of air and moisture is low, so that the mercapanic compound reacts with the mercapanic compound to neutralize the unpleasant odor generated due to the reaction with air and moisture . In addition, when the ingot is fixed to the support means or when the ingot is fixed, the adhesion is excellent.

According to an embodiment of the present invention, the modified rubber may be an acrylic rubber containing at least one functional group selected from a carboxyl group, an amine group and a hydroxyl group. Preferably, the functional group may be contained in the end of the main chain or the side chain of the acrylic rubber, but is not limited thereto. Specific examples of the modified rubber include ATBN (Amine Terminated Butadiene Acrylonitrile Copolymer), CTBN (Carboxylated Terminated Butadiene Acrylonitrile Copolymer), HTBN (Hydroxyl Terminated Butadiene Acrylonitrile Copolymer), and the like. But is not limited to, a carboxyl terminated butadiene acrylonitrile copolymer (CTBN). The modified rubber is uniformly combined with the epoxy resin and the curing agent at low temperatures when mixed with the epoxy resin and the curing agent so that the elastic region dispersed in the network structure of the epoxy resin interferes with the progress of the crack and can provide long term stability. Further, the modified rubber is preferable because the gas permeability of the ingot adhesive composition is lowered so that moisture, gas, and the like contained in the air can not be transmitted.

The resin mixture of the present invention may contain epoxy resin and modified rubber at a weight ratio of 1: 1 to 1: 2. When mixed in the above-mentioned range, the gas permeability of the adhesive composition for ingots may be lowered to contact with the gas to improve odor and surface drying phenomenon during storage, which is preferable. In addition, the glass transition temperature of the above-mentioned ingot adhesive composition can be adjusted to 35 to 50 DEG C, which is preferable because the ingot can be easily fixed at low temperature when it is peeled from the support means after fixing or temporarily fixing the ingot.

The fillers of the present invention can be used in accordance with an embodiment of the invention in the form of fused silica, fumed silica, crystalline silica, alumina, calcium carbonate, titanium dioxide, clay, magnesium carbonate, talc, aluminum hydroxide, magnesium hydroxide, aluminum silicide, Barium, and scorching, or a mixture thereof. Preferably fused silica, but is not limited thereto. The filler is preferable because it can suppress the thermal expansion of the adhesive and shorten the peeling time. The filler may have an average particle diameter of 1 to 30 mu m, preferably 5 to 10 mu m, but is not limited thereto. When the filler having an average particle diameter is used, the viscosity of the adhesive can be easily controlled, the surface can be made uniform after application of the adhesive, and the adhesion strength between the ingot and the support means can be improved.

According to an embodiment of the present invention, the subject mixture may contain 50 to 85% by weight of a resin mixture and 15 to 50% by weight of a filler. The above-mentioned amount of the subject mixture is preferable because it can have excellent adhesive strength and adhesion strength. It is preferable that the gas permeability is lowered so that there is little contact with air or the like, so odor and surface drying phenomenon occurring during storage are improved to secure storage stability and long- .

In addition, by mixing the resin mixture and the filler, the subject mixture maximizes the control of the interfacial penetration force, thereby preventing the ingot from falling off the supporting means due to the weakening of the adhesive force due to the processing and washing process at a temperature of 40 ° C or lower. Lt; 0 > C or more because the peeling can be easily performed in a shorter time.

According to one embodiment of the present invention, the curing agent mixture may include a mercaptan-based compound and a tertiary amine-based compound to improve adhesive strength, impact strength, hot water peelability, reaction curability, and mechanical properties. The above mercaptan-based compound is preferably mixed with a tertiary amine-based compound because it can exhibit excellent adhesive strength and reaction curability.

When a curing temperature is lowered, a curing time of a conventional adhesive is greatly increased, and in some cases, complete curing may become difficult. Since the increase in the curing time leads to an increase in the production time, development of a low temperature fast curing type adhesive which can lower the curing temperature without deteriorating the productivity has been demanded.

Thus, in order to improve the low-temperature fast curing performance, a mercaptan-type compound containing -SH group was included in the curing agent mixture. However, since the -SH group has a strong odor, it has a problem in application as an adhesive. In order to solve such a problem, the combination of the adhesive composition for ingots of the present invention remarkably suppresses or weakens the bad smell, and the surface drying phenomenon during storage is reduced, so that storage stability and long-term stability can be remarkably improved.

According to one embodiment of the present invention, the curing agent mixture may include 85 to 99.9% by weight of a mercaptan-based compound and 0.1 to 15% by weight of a tertiary amine-based compound, but is not limited thereto. The curing agent mixture within the above range is preferable because it has excellent bonding strength and can be cured within a short time even at a low temperature.

According to one aspect of the present invention, the mercaptan-based compound may include polythiol or polymercaptan. Specific examples thereof include methanedithiol, propanedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimercapto-succinate, 2,3-dimercapto-1-propanol (2-mercapto Acetate), diethylene glycol bis (2-mercaptoacetate), 1,2-dimercaptopropyl methyl ether, bis (2-mercaptoethyl) ether, trimethylolpropane tris (thioglycolate), pentaerythritol tetra (Mercaptopropionate), pentaerythritol tetra (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (beta-thiopropionate), dipentaerythritol poly (beta-thiopropionate ), Di-mercaptobenzene, tri-mercaptobenzene, tetra-mercaptobenzene, bis (mercaptoalkyl) benzene, tris (mercaptoalkyl) benzene, tetrakis (mercaptoalkyl) benzene, dimercaptobiphenyl , Toluene dithiol and naphthalene di (Mercaptoalkylthio) alkane, tris (mercaptoalkylthio) benzene, tris (mercaptoalkylthio) benzene, tetra (mercaptoalkylthio) benzene, bis (Mercaptoalkylthio) alkane, bis (mercaptoalkyl) disulfide, hydroxyalkyl sulfide bis (mercaptopropionate), hydroxyalkyl sulfide bis (mercaptoacetate), mercaptoethyl ether bis 4-dithiane bis (mercaptoacetate), thiodiglycolic acid bis (mercaptoalkyl ester), thiodipropionic acid bis (2-mercaptoalkyl ester), 4 , 4-thiobutyrate bis (2-mercaptoalkyl ester), 3,4-thiopentothiol, bismuththiol and 2,5-dimercapto-1,3,4-thiadiazole, or But are not limited to, mixtures of two or more.

According to an embodiment of the present invention, the tertiary amine compound may include, for example, triethanolamine, trisdiethylaminomethylphenol, benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, 2-2- Dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and the like, or a mixture of two or more thereof.

According to one embodiment of the present invention, the curing agent mixture may further include any one or a mixture of two or more selected from an amine compound having two or more primary amino groups and an amine group-containing phenolic resin.

The curing agent mixture of the present invention further contains 5 to 100 parts by weight of a mixture of an amine-based compound having two or more primary amine groups and an amine group-containing phenolic resin per 100 parts by weight of a mixture of a mercaptan-based compound and a tertiary amine- And preferably 10 to 50 parts by weight, but is not limited thereto. When it is further included in the above range, it is preferable to increase the chemical bonding force of the subject compound to increase the bonding strength, heat resistance and chemical resistance.

According to one embodiment of the present invention, the amine compound having two or more primary amino groups includes, for example, 1,3-bis (aminomethyl) benzene, diethylenetriamine, 1,3-bis Any one selected from hexane, isophoronediamine, triethylene tetramine, tetraethylene pentamine, polyoxypropylene diamine, polyoxypropylene triamine, bis (4-aminophenyl) methane and bis (4-aminocyclohexyl) Or a mixture of two or more thereof.

According to one embodiment of the present invention, the amine group-containing phenol resin may be, for example, phenol resin synthesized from phenols, aldehydes and primary amines, but is not limited thereto. Examples of the phenol include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromo Phenol, resorcin, catechol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpene phenol, Pentadiene, and the like. The aldehydes may be, for example, formaldehyde. The primary amines may be aliphatic or aromatic primary amines having at least one functional group. But is not limited to, an aliphatic or aromatic primary amine having preferably two or more functional groups.

According to one embodiment of the present invention, the mixture of the subject mixture and the curing agent may be mixed at a weight ratio of 1: 1 to 3: 1 for curing the adhesive composition for ingots. Preferably, the subject mixture and the curing agent mixture may be mixed in a weight ratio of 1: 1 to 2: 1. When the above-mentioned mixing is carried out, it is preferable to shorten the fixing or temporary fixing time through room temperature or heat curing, and also to improve the bonding strength. The mixing ratio may be one in which the equivalent ratio of the subject compound and the curing agent compound is calculated and mixed.

More preferably, the amount of the curing agent mixture to be used is such that the reactive reactive group in the curing agent is 0.5 to 1.5 equivalents, more preferably 0.7 to 1.2 equivalents to 1 equivalent of the epoxy group in the epoxy resin of the subject mixture, in accordance with one embodiment of the present invention It can be used as a ratio. In this range, the curing rate is appropriate, and the excellent properties of the shear strength can be exhibited.

According to an embodiment of the present invention, the adhesive composition for ingots may contain 0.1 to 10 parts by weight of a urea-modified amine and 0.1 to 10 parts by weight of a fatty acid based on 100 parts by weight of a mixture of a subject mixture and a curing agent. As the urea-modified amine and the fatty acid are mixed in the adhesive composition, the adhesive composition for ingots of the present invention is particularly preferable because it can remarkably improve the odor of the mercaptan-type compound and the surface drying phenomenon during storage.

According to one embodiment of the present invention, the urea-modified amine may be any one or more selected from N, N'-bis (3-dimethylaminopropyl) urea, N, N-dimethylaminopropyl urea and the like. When the urea-modified amines are mixed together with the fatty acid in the mixture of the subject mixture and the curing agent, the specific odor of the mercaptan-type compound and the effect of improving the surface drying phenomenon during storage are remarkably improved.

According to one embodiment of the present invention, the fatty acid may be a linear or branched, saturated or unsaturated fatty acid of C ₄ to C ₃₀ . Preferably C ₅ to C ₂₀ straight-chain or may be a saturated or unsaturated fatty acids of the crushing. The fatty acid is specific, for example, 2-ethyl hexanoate acid (2-Ethylhexanoic acid), isophthalic acid furnace nm (Isononanoic acid) Oleic acid, palmitic acid, stearic acid, linolenic acid, and the like, or a mixture of two or more thereof. When the fatty acid of the present invention is mixed with a mixture of a subject mixture and a curing agent together with a urea-modified amine, the specific odor of the mercaptan-type compound and the effect of improving the surface drying phenomenon during storage are improved remarkably.

The adhesive composition for ingots according to the present invention having the above-described constitution of the present invention exhibits a remarkably excellent odor elimination or inhibitory effect by including both the composition of the subject mixture, the curing agent mixture, the urea-modified amine and the fatty acid, The surface of the adhesive composition for ingots can be remarkably improved in surface skinning due to air, moisture and the like.

According to an embodiment of the present invention, the adhesive composition for ingots may include a silane coupling agent for improving adhesion, defoamers for removing air bubbles, a leveling agent for increasing surface smoothness, ), And an organic solvent. If necessary, various additives known in the art may be added.

Hereinafter, a method for producing an ingot adhesive of the present invention will be described in detail.

The method for producing an ingot adhesive of the present invention comprises the steps of: a) mixing a resin mixture comprising an epoxy resin and a modified rubber with a curing agent mixture and heating; And b) further adding a filler, a urea-modified amine and a C ₄ to C ₃₀ linear or branched saturated or unsaturated fatty acid after the heating.

INDUSTRIAL APPLICABILITY The method for producing an ingot adhesive of the present invention can improve the storage stability and workability by suppressing or weakening the bad odor even if it contains a mercaptan-type compound, and it is possible to improve the storage stability, have.

According to an embodiment of the present invention, in step a), 1 to 10% by weight of the resin mixture and the curing agent mixture may be mixed and heated in the entire resin mixture, and then the remaining 90 to 99% by weight of the resin mixture may be further mixed. As described above, mixing of a part of the whole resin mixture with the curing agent mixture is preferable since the mixing of the metal ions of the filler is prevented to suppress or weaken the smell of the mercaptan-based compound, and the surface drying phenomenon during storage can be improved.

According to an embodiment of the present invention, one or more of the antioxidants and fragrances may be further mixed and heated in step a). When the antioxidant and the flavoring agent are further included as described above, it is possible to further improve the odor suppression and the surface drying phenomenon of the mercaptan-based compound, but the present invention is not limited thereto.

The antioxidant may be any one selected from phenol-based antioxidants, phosphite-based antioxidants, sulfur-based antioxidants, and hindered amine-based antioxidants, or a mixture thereof, though not particularly limited.

Specific examples of the phenolic antioxidant include 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) isocyanuric acid, 1,1,3-tris (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionic acid-n-octadecyl, 3- (3-t-butyl-4-hydroxy-5-tert-butylphenyl) propionic acid-n-octadecyl, Methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5.5] undecane, 2-t-butyl-4-methoxyphenol, 3- -Methoxyphenol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylene-bis (4-methyl- Butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methane, and the like.

The phosphite antioxidant may be at least one selected from the group consisting of triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis (3-methyl- ) Cyclic neopentane tetraylbis (nonylphenyl) phosphite, cyclic neopentane tetraylbis (dinonylphenyl) phosphite, cyclic neopentane tetrayltris (nonylphenyl) phosphite, cyclic neopentane (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2-methylenebis Di-t-butylphenyl) octyl phosphite, diisodecyl pentaerythritol, tris (2,4-di-t-butylphenyl) phosphite, and the like.

The sulfur-based antioxidant may be selected from the group consisting of tetrakis [methylene-3- (dodecylthio) propionate] methane, dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, N-cyclohexylthiophthalimide, N-n-butylbenzenesulfonamide, and the like.

The hindered amine antioxidant may be bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, N-methyl-3-dodecyl- 2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1- (2,2,6,6- Pyridyl) pyrrolidine-2,5-dione, poly {(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine- ({2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} But the present invention is not limited thereto.

The perfume of the present invention is not particularly limited, but may be a synthetic material of aldehyde, alcohol, ester, ether, ketone and hydrocarbon. Specific examples thereof include esters such as benzyl acetate and benzyl formate; Ethers such as benzyl ethyl ether; Aldehydes such as citronellal; ketones such as? -isomethylionone; Alcohols such as citronellal, eugenol, geraniol and linalool; Hydrocarbons such as limonene and pinene, and mixtures of any two or more thereof. But may also include, but is not limited to, natural fragrance mixtures selected from pine oil, citrus oil, lavender oil, mint oil or oils obtained from orange peel.

In addition, it is preferable to add a process such as water removal and oxygen barrier hermetic packaging after the step a), because it is more effective in removing odor and improving surface drying phenomenon.

According to one embodiment of the present invention, the heating of the ingot adhesive may be performed at a temperature of 0 to 300 캜, preferably 50 to 200 캜, more preferably 100 to 150 캜. The time required for curing the ingot adhesive may depend on the temperature to be applied. The higher the curing temperature, the shorter the time required to complete the reaction, and the lower the curing temperature, the longer the time required to complete the reaction. Specifically, the curing time may be 1 minute to 48 hours, preferably 5 minutes to 24 hours, more preferably 30 minutes to 12 hours, but is not limited thereto.

The ingot adhesive according to the present invention as described above can be used to temporarily fix the ingot to the support means as described above, and the temporarily fixed ingot can be easily peeled from the support means even at room temperature or at low temperature. A fast and effective adhesive detachment solution of low toxicity can be used to more effectively separate it.

The most effective peeling solution for an adhesive made of the composition of the present invention may be an acid or an alkali mixed with water, and the acid or alkali may be mixed in an amount of 5 to 20% by weight based on the total weight of the peeling solution. The acid may be at least one selected from sulfuric acid, nitric acid, hydrochloric acid, sulfuric acid, and sulfonic acid, and the alkali may be at least one selected from sodium hydroxide, potassium hydroxide, ammonia, and the like.

In a high glass transition temperature product having a glass transition temperature of 50 DEG C or higher in an adhesive, de-bonding is hardly achieved at a temperature lower than the glass transition temperature, and even in the case of a toxic release liquid such as acetone or a low- de-bonding is difficult or not easy.

In addition, a low glass transition temperature product having a general glass transition temperature of 35 DEG C or lower is capable of de-bonding due to softening of the adhesive at a temperature higher than the glass transition temperature, but the release speed is low. In addition, there is a disadvantage in that it is relatively slowly de-bonded even in a toxic release liquid such as acetone or a low-toxicity release liquid of the present invention. On the other hand, the adhesive composition for ingots according to the present invention has a glass transition temperature of 35 to 50 캜, and is easily peeled even at a low temperature of 35 to 50 캜, and the control of interfacial penetration is maximized, It is possible to prevent the ingot from falling off the support means and breaking. Further, in an actual peeling step of 50 占 폚 or more, peeling can be easily performed in a shorter time, which is preferable.

Hereinafter, the adhesive composition for ingots and the method for producing the same according to the present invention will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Measurement of physical properties]

1) Adhesive strength

Measured according to KSM 3705: 2015.

The adhesive composition was applied by overlapping two specimens of 25 mm x 100 mm x 1.6 mm by 12.7 mm and cured at 25 DEG C for 24 hours to prepare test pieces. A universal testing machine (Instron) was used and the test speed was 1.3 mm / min.

2) Curing time and peeling time

The curing temperature was measured at room temperature (25 ° C) and the curing time was measured. The exfoliation solution was mixed with lactic acid and water at a weight ratio of 5:95, and the exfoliating temperature was 50 ° C.

3) Glass transition temperature (Tg)

Was measured with a differential scanning calorimeter (DSC, manufactured by TA Corporation, Q1000).

The measurement was carried out by raising the temperature to 200 DEG C at a temperature raising rate of 20 DEG C / min. In a nitrogen atmosphere.

4) Odor improvement effect

After mixing each of the compositions obtained above, the effect of improving the odor of mercaptans was confirmed and qualitatively evaluated according to the following criteria.

◎: Extremely weak mercaptan odor (slight or unrecognized level)

○: Weak mercaptan odor (weak odor level)

△: Normal odor of mercaptan (level of smell and feeling of discomfort)

X: Strong mercaptan odor (strong smell and high discomfort)

5) Storage stability and surface drying phenomenon

Each composition obtained above was filled in a hermetically sealed container, followed by nitrogen substitution. After standing for 6 months in an atmosphere at room temperature (25 ° C), the viscosity was measured, and the increase rate (%) with respect to the initial viscosity and the occurrence of the surface drying phenomenon were visually confirmed and quantitatively evaluated according to the following criteria.

◎: Viscosity increase rate less than 10%, no surface drying phenomenon.

○: Viscosity increase rate is 10 to 20% or less, and some surface drying phenomenon (less than 10%) occurs.

Δ: Viscosity increase rate is 20 to 25% or less, and surface drying phenomenon is 50% or more.

X: Viscosity increase rate exceeds 25%, surface drying occurs.

[Example 1]

1. Total mixture 120.5g

: 100 g of a resin mixture obtained by mixing 50 g of a phenol novolac resin (Cas No. 9003-36-5) and 50 g of a carboxyl-terminated butadiene acrylonitrile copolymer (CTBN)

20 g of fused silica mixed with 0.5 g of titanium dioxide,

2. Total 60 g of hardener mixture

55 g of polymercaptan (Toray, QM-340M, Thiol content 12 wt%),

5 g of 2,4,6-tris (dimethylaminomethyl) phenol

3. Urea-modified amines

: 1,3-Bis [3- (dimethylamino)] propyl] urea 5 g

4. Fatty acids

: 5 g of 2-ethylhexanoic acid

5 g of the resin mixture and 60 g of the curing agent mixture were added to a reactor connected to a vacuum pump and a stirrer, followed by stirring under a vacuum for 60 minutes at 800 rpm, followed by heating and reacting. 95 g of the resin mixture and 20.5 g of the filler were added to the above linear reactant and mixed. 5 g of 1,3-bis [3- (dimethylamino)] propyl] urea and 5 g of 2-ethylhexanoic acid were added thereto, The mixture was stirred at 1,600 rpm.

[Example 2]

Except that 110 g of the polymeric compound and 10 g of 2,4,6-tris (dimethylaminomethyl) phenol were used as the curing agent mixture in Example 1 above.

[Example 3]

Except that 34 g of the phenolic novolac resin (Cas No. 9003-36-5) and 68 g of the carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) were mixed in the resin mixture in Example 1 above.

[Example 4]

The same procedure was performed as in Example 1 except that the curing agent mixture was mixed as follows.

- hardener mixture

: 30 g of Polymer (Toray, QM-340M, Thiol content 12 wt%),

5 g of 2,4,6-tris (dimethylaminomethyl) phenol

15 g of 1,3-bis (aminomethyl) benzene,

Phenol resin (Cas No. 57214-10-5) 10 g

[Example 5]

Except that an antioxidant (triphenylphosphite) and a flavoring agent were further mixed in Example 1 above.

[Example 6]

In Example 1, the subject mixture was mixed with 80 g of a resin mixture obtained by mixing 40 g of a phenolic novolac resin and 40 g of a carboxyl terminated butadiene acrylonitrile copolymer (CTBN), 40 g of a filler obtained by mixing 40 g of fused silica and 0.5 g of titanium dioxide Was used in place thereof.

[Example 7]

Except that bisphenol A diglycidyl ether (Momentiva, DGEBA, EPIKOTE 828, EEW 187 eq / g) was used in place of the phenol novolak type resin in Example 1.

[Example 8]

The procedure of Example 1 was repeated except that stearic acid was used instead of 2-ethylhexanoic acid.

[Comparative Example 1]

Except that the urea-modified amine and the fatty acid were not included in Example 1, and the mixture of the subject mixture and the curing agent was added to the reactor at once and the mixture was mixed without heating.

[Comparative Example 2]

In Example 1, except that the subject mixture, the curing agent mixture, the urea-modified amine and the fatty acid were charged into the reactor at once and mixed without heating the reaction.

[Comparative Example 3]

In the same manner as in Example 1, except that the urea-modified amine was not used.

[Comparative Example 4]

Except that the fatty acid was not used in Example 1 above.

[Comparative Example 5]

Except that only 60 g of polymeric compound (Toray, QM-340M, Thiol content 12 wt%) was used as the curing agent mixture in Example 1 above.

[Comparative Example 6]

Except that only 100 g of the phenolic novolak type resin was used as the resin mixture in Example 1 above.

The physical properties of the examples and comparative examples were measured and reported in the following Table 1.

Improving odor Save
stability Glass transition temperature
(° C) Adhesive strength
(kg / cm2)
Glass + Si Functional curing time
(25 DEG C) Peeling time
(Adhesion area: 180x180um, peeling solution: 55C hot water) Example 1 ◎ ◎ 45 280 180 minutes 10 minutes Example 2 ○ ◎ 40 210 120 minutes 5 minutes Example 3 ◎ ◎ 35 250 200 minutes 6 minutes Example 4 ◎ ◎ 50 310 210 minutes 25 minutes Example 5 ◎ ◎ 45 280 180 minutes 10 minutes Example 6 ◎ ◎ 45 280 180 minutes 8 minutes Example 7 ○ ○ 40 260 210 minutes 6 minutes Example 8 ◎ ◎ 45 260 180 minutes 10 minutes Comparative Example 1 X X 45 260 180 minutes 10 minutes Comparative Example 2 △ △ 45 270 180 minutes 10 minutes Comparative Example 3 ○ △ 40 200 160 minutes 8 minutes Comparative Example 4 △ ○ 45 260 180 minutes 10 minutes Comparative Example 5 △ ○ 30 60 840 minutes 1 minute Comparative Example 6 ○ ○ 75 220 150 minutes 130 minutes

As shown in Table 1, it was confirmed that the examples showed improved odor, surface drying, and storage stability. In addition, in the case of the example using the ingot adhesive of the present invention, not only the adhesive strength was excellent but also the curing time was short, and it was confirmed that the peeling proceeded even in the medium temperature water (50 to 60 ° C) in a short time.

On the contrary, in the case of Comparative Example 1, the composition was simultaneously supplied without heating line reaction, and it was confirmed that the smell was strong due to the absence of the urea-modified amine and fatty acid of the composition, In the case of Comparative Example 2, it was confirmed that the odor of the mercaptan-type compound was excessively generated by the simultaneous introduction of the composition and the mixing without the heating-line reaction, and the storage stability was poor and the surface was dried. In the case of Comparative Examples 3 to 4, it was confirmed that odor was excessively generated due to the absence of the urea-modified amine or fatty acid of the composition for ingots, and storage stability was poor and surface drying phenomenon occurred. In the case of Comparative Example 5, it was confirmed that the adhesive strength was remarkably lowered due to the absence of the tertiary amine compound, the curing time was increased at room temperature, and the glass transition temperature was remarkably low due to incomplete curing. In the case of Comparative Example 6, it was confirmed that the glass transition temperature did not include the modified rubber and thus the peeling time was drastically increased due to the difficulty in peeling in the medium temperature water (50 to 60 ° C).

Therefore, the adhesive composition for ingots of the present invention is excellent in the improvement of odor of the mercaptan-based compound, improves the surface drying phenomenon during storage, and is excellent in storage stability. Further, it can be easily peeled from a room-temperature peeling liquid to medium-temperature water (50 to 60 ° C), and can be peeled off in a short time.

As described above, in the present invention, the adhesive composition for ingots and the method of manufacturing the same have been described through the specified items and the limited embodiments. However, the present invention is not limited to the above- It is to be understood that the invention is not limited to those precise embodiments, and various modifications and changes may be made thereto by those skilled in the art.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (12)

A subject mixture comprising a resin mixture comprising an epoxy resin and a modified rubber and a filler;
A curing agent mixture comprising a mercaptan-based compound and a tertiary amine-based compound;
Urea-modified amines; And
C ₄ to C ₃₀ linear or branched, saturated or unsaturated fatty acids. The method according to claim 1,
Wherein the epoxy resin is a phenolic novolak type epoxy resin. The method according to claim 1,
Wherein the modified rubber is an acrylic rubber containing at least one functional group selected from a carboxyl group, an amine group and a hydroxyl group. The method according to claim 1,
The fatty acid may be selected from the group consisting of 2-ethylhexanoic acid, isononanoic acid, oleic acid, palmitic acid, stearic acid and linolenic acid. Or a mixture of two or more thereof. The method according to claim 1,
Wherein the subject mixture comprises 50 to 85% by weight of a resin mixture and 15 to 50% by weight of a filler. The method according to claim 1,
Wherein the resin mixture comprises an epoxy resin and a modified rubber in a weight ratio of 1: 1 to 1: 2. The method according to claim 1,
Wherein the curing agent mixture further comprises any one or a mixture of two or more selected from an amine-based compound having at least two primary amino groups and an amine group-containing phenol-based resin. The method according to claim 1,
Wherein the mixture of the subject mixture and the curing agent is mixed in a weight ratio of 1: 1 to 3: 1. The method according to claim 1,
Wherein said ingot adhesive composition comprises 0.1 to 10 parts by weight of a urea-modified amine and 0.1 to 10 parts by weight of a fatty acid based on 100 parts by weight of a mixture of a main mixture and a curing agent. a) mixing and heating a resin mixture comprising an epoxy resin and a modified rubber and a curing agent mixture; And
b) further adding a filler, a urea-modified amine and a C ₄ to C ₃₀ linear or branched saturated or unsaturated fatty acid after the heating;
Wherein the method comprises the steps of: 11. The method of claim 10,
Wherein the resin mixture and the curing agent mixture are mixed in an amount of 1 to 10% by weight of the total resin mixture in the step (a), heated and mixed with the remaining 90 to 99% by weight of the resin mixture. 11. The method of claim 10,
Wherein at least one of the antioxidant and the perfume is further mixed and heated in the step a).