KR102223542B1 - Sealant - Google Patents

Abstract

The present invention relates to a sealant composition for sealing gaps in automobile parts, construction, windows and runways. More particularly, an object of the present invention is to provide a new sealant having high mechanical strength and excellent elongation, and having further improved adhesiveness and elastic recovery rate by adding hydrophilic modified elastic particles.

Description

Silylated polyurethane-based sealant for automobile industry with added elastic particles{Sealant}

The present invention relates to a sealant composition for sealing gaps in automobile parts, buildings, windows, and runways, and more particularly, by adding hydrophilic modified elastic particles, adhesion and elastic recovery rate are further improved, mechanical strength is high, and elongation is improved. It is to provide a good new sealant.

Materials filled to maintain watertightness and airtightness for spaced or cracked gaps, such as between automobile bodies and parts, between windows and window frames, between building materials and structures, between blocks and blocks of runways, are commonly referred to as sealing materials, and to a certain degree of strength. And it is used for the purpose of improving the durability of the building by fixing the member with elasticity.

In particular, a sealing material having elasticity is also referred to as a sealant, and such a sealant must have sufficient physical properties such as extrusion workability and curable adhesion. In addition, when fixing the gap between the window frame and the window of a building structure, there is a characteristic that physical properties, such as destruction or elasticity restoration properties, such as external temperature change, wind or long-term vibration, must be satisfied.

In addition, automotive sealants are used to prevent deformation due to vibration or expansion and contraction of members in addition to air-tight and watertight functions in parts such as tail lights, headlights, wand shields, and windows. Physical properties such as absorption, relaxation of the above properties, and prevention of breakage are required.

In addition, as a sealant property, the hardened filling sealant must satisfy the elasticity, which is the resistance to rupture and peel, even when the joint is moved, and it can maintain the movement resistance under natural conditions outdoors, and the durability performance is weather resistance, cold resistance, and heat resistance. , Water resistance and chemical resistance must be satisfied, and at the same time, it is required to develop a sealant that is more excellent in flexibility, elastic recovery rate, and adhesion to adherends even under external impacts or harsh conditions.

Korean Registered Patent Publication No. 10-1045297 (2011.06.23)

In order to solve the above problems, the present invention has a high elongation of 400% or more, preferably 1,000% or more, has an adhesive property of 3Kg/m or more, preferably 4kg/m or more, and a remarkable increase in the elastic recovery rate. This is to provide a new sealant.

In order to achieve the above object, the present invention is to provide a sealant composition comprising a modified polyurethane resin, a curing catalyst, and a hydrophilic modified rubber particle having a specific structure of silane endcapped, and a moisture-cured sealant using the same.

In addition, the present invention provides a sealant composition for providing a sealant capable of sufficient elasticity and elasticity recovery in places subject to extreme stress strain, such as in the field of automobiles and aircraft runways.

As a result of doing a lot of research to solve the above problems,

The present inventor solves the above problems by providing a sealant composition comprising a siloxane-modified polyurethane resin, hydrophilic modified rubber particles, fillers, and a curing catalyst in which both ends of a polyurethane diol are end-capped with trialkoxysilane or dialkoxyalkylsilane. Thus, the present invention was completed.

One aspect of the present invention is any one selected from a first modified polyurethane resin in which both ends of the polyurethane diol are endcapped with trialkoxysilane and a second modified polyurethane resin in which both ends of the polyurethanediol are endcapped with alkyldialkoxysilane. It provides a sealant composition comprising one or two components of a modified polyurethane resin, a hydrophilic modified rubber particle, a curing catalyst, and a filler.

In one aspect of the present invention, the polyurethane diol is a polyurethane diol prepared by reacting a polyester-based diol and a diisocyanate to provide a sealant composition or a sealant prepared using the same.

In one aspect of the present invention, the polyurethane diol is a polyurethane diol prepared including a polyester-based diol and a cyclic aliphatic diisocyanate, and thus has the best elongation and elastic restoration properties, and thus has excellent mechanical properties. Unlike other aspects, I prefer it more.

In one aspect of the present invention, the first modified polyurethane resin is _{capped with isocyanatoalkyltrialkoxysilane (NCO-R'-Si(OR 2} ) ₃ ) at both ends of the polyurethane diol, and the The second modified polyurethane resin may be capped at both ends of the polyurethane diol with isocyanate alkyldialkoxyalkylsilane (NCO-R'-Si(R″)(OR ₂ ) _{2 ).} Of R, R'and R″ are each independently a C1-C8 alkyl group.)

The hydrophilicity-modified rubber particles of the present invention are not particularly limited as long as they are produced by copolymerization with a carboxylic acid group, but for example, a styrene group-containing monomer and a butadiene group-containing monomer are polymerized in a weight ratio of 1:99 to 99:1, and It is preferable to contain monomers such as acrylic acid, methacrylic acid, maleic acid and maleic anhydride in an amount of 0.1 to 5% by weight of the total monomers. Although their molecular weight is not particularly limited, for example, a rubber having a weight average molecular weight of 10,000 to 1,000,000 and a glass transition temperature (Tg) of 25° C. or less may be exemplified, that is, preferably styrene-butadiene ( Although it is recommended to use SBR: styrene butadiene rubber) series rubber, it is not limited thereto as long as the glass transition temperature is satisfied. The rubber component according to the present invention is not particularly limited as long as it is a polymerization method known in this field such as an emulsion polymerization method and a suspension polymerization method, and the rubber polymer may be prepared as single particles or core-shell particles. The hydrophilic rubber particles are monomers that impart hydrophilicity, and are not particularly limited, and non-limiting examples thereof include maleic acid, acrylic acid, acrylate, carboxylic acid, nitrile group, hydroxy group, acetate group, or one or more hydrophilicity thereof. And monomers containing a functional group. Preferably, a monomer having a carboxylic acid group is preferred. The particle size is not limited, but preferably a size of 0.1 to 30 µm is preferred, but is not limited thereto.

In addition, in one aspect of the present invention, the sealant composition further comprises one or more additives selected from additives such as plasticizers, antioxidants, UV inhibitors, lubricants, pigments, dyes, dehydrating agents, long-term property stabilizers and adhesion imparting agents. can do.

In one aspect of the present invention, the long-term property stabilizer may be one or two or more components selected from mono, di, or trialkoxysilane compounds having a reactive group selected from vinyl group, allyl group, methacrylic group, and acrylic group. .

In one aspect of the present invention, the adhesion-imparting agent may be a silane compound containing an amine group.

In one aspect of the present invention, the curing catalyst may be a tin (Tin)-based catalyst. In addition, the capping may be capping in the presence of a tin-based catalyst.

In one aspect of the present invention, the sealant composition may include 0.1 to 10 parts by weight of hydrophilic modified rubber particles, 0.01 to 5 parts by weight of a curing catalyst, and 1 to 300 parts by weight of a filler, based on 100 parts by weight of the modified polyurethane diol. .

In addition, the sealant composition may include 1 to 80 parts by weight of a plasticizer based on 100 parts by weight of the modified polyurethane diol.

In addition, the sealant composition may include 1 to 20 parts by weight of a long-term property stabilizer and 1 to 10 parts by weight of an adhesion-imparting agent based on 100 parts by weight of the modified polyurethane diol.

In one aspect of the present invention, the silane end-capped modified polyurethane resin is 1 to 50 parts by weight based on 100 parts by weight of a trialkoxy end-capped modified polyurethane resin and/or a dialkoxy end-capped modified polyurethane resin. Monoalkoxyendcapped modified polyurethane resins may also be included.

The sealant according to the present invention has excellent strain resistance characteristics of 400% or more, preferably 700% or more, very preferably 1,000% or more, and 90% or more of elastic resilience, and has excellent adhesion on the adhesive surface, and is also excellent on the runway of automobiles and aircraft. It can serve as a sealant for a long time even in harsh environments such as, etc.

Preferably, the present invention provides a new sealant that has a high elongation of 400% or more, preferably 1,000% or more, has an adhesive property of 3Kg/m or more, preferably 4kg/m or more, and has a remarkable increase in the elastic recovery rate. To provide.

In the case of having a sealant having a high elongation rate as described above, it is possible to improve the adhesion of the part sealed to the vehicle in winter and reduce the occurrence of cracks, reduce the occurrence of cracks and damage due to external impact, and also increase the elongation rate in sealants for the aviation industry. This is good because it can prevent distortion of the concrete flat plate.

1 is an aspect of a specimen for measuring the elongation of the sealant of the present invention.
Figure 2 shows a method of measuring the elastic resilience of the present invention.

Hereinafter, the present invention will be described in more detail through specific examples or examples including the accompanying drawings. However, the following specific examples or examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

In addition, 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 the present invention belongs. The terms used in the description in the present invention are merely for effectively describing specific embodiments and are not intended to limit the present invention.

In addition, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.

In addition, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

Hereinafter, the components of the present invention will be described in detail.

The present invention is a sealant comprising at least one silane-modified polyurethane resin selected from silane-modified polyurethane resins encapsulated with trialkoxysilane or dialkoxysilane at both ends of a polyurethane diol, hydrophilic modified rubber particles, fillers, and curing catalyst It relates to compositions and cured (eg, cured by moisture curing, etc.) sealants prepared therefrom.

In the present invention, the polyurethane diol is prepared by reacting a polyester diol and a diisocyanate, and the molar ratio of the polyester diol and diisocyanate is not particularly limited as long as the structure of the prepared polyurethane diol is a terminal diol. For example, it can be prepared by preparing the molar ratio of the diisocyanate to the polyester-based diol in a molar ratio of 1:1.01 to 1.2.

In the present invention, the polyester-based diol is not particularly limited as long as it achieves the object of the present invention, but may have a number average molecular weight of 50 to 10,000.

The diisocyanate compound of the present invention is not particularly limited as long as it is a conventional one,

It is preferable to include an aliphatic diisocyanate or an alicyclic isocyanate, and more preferably, an alicyclic diisocyanate is more preferable because it has a more remarkable effect in elongation and elasticity restoration.

Examples of the aliphatic diisocyanate include butane diisocyanate, pentane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, but the present invention is not particularly limited thereto.

In addition, the alicyclic isocyanate of the present invention refers to a compound having a cyclic aliphatic hydrocarbon that does not have aromaticity in the molecule, and is not particularly limited, but, for example, isophorone diisocyanate, hydrogenated xylylene isocyanate, hydrogenated diphenyl Methane diisocyanate, 1,4-cyclohexane diisocyanate, etc. are mentioned. Among the alicyclic diisocyanates, isophorone diisocyanate, hydrogenated xylylene isocyanate, hydrogenated diphenylmethane diisocyanate, or a mixture thereof or containing these is preferable. It is preferred because it is excellent.

The hydrophilicity-modified rubber particle of the present invention is not particularly limited as long as it is a rubber produced by copolymerization with a hydrophilic monomer. In the present invention, the rubber particles having hydrophilicity are monomers that impart hydrophilicity, and there is no particular limitation, and non-limiting examples thereof include maleic acid, acrylic acid, acrylate, carboxylic acid, nitrile group, hydroxy group, acetate group, or 1 And monomers containing more than one type of hydrophilic functional group. Preferably, monomers such as acrylic acid, methacrylic acid, and maleic acid, which are monomers having a carboxylic acid group, are preferred.

In addition, in the present invention, the hydrophilic modified rubber particles more preferably have a glass transition temperature of 25°C or less, more preferably -10°C or less, which exhibits physical properties such as elastic recovery rate and adhesive strength of the sealant of the present invention, and This is because sufficient physical properties can be maintained even at low temperatures.

For example, a styrene group-containing monomer and a butadiene group-containing monomer are polymerized in a weight ratio of 1:99 to 99:1, and a monomer such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. It is preferable to contain 0.1 to 5% by weight of the total monomer. Although their molecular weight is not particularly limited, for example, a rubber having a weight average molecular weight of 10,000 to 1,000,000 and a glass transition temperature (Tg) of 25° C. or less may be exemplified, that is, preferably styrene-butadiene ( Although it is recommended to use SBR: styrene butadiene rubber) series rubber, it is not limited thereto as long as the glass transition temperature is satisfied. The rubber component according to the present invention is not particularly limited as long as it is a polymerization method known in this field such as an emulsion polymerization method and a suspension polymerization method, and the rubber polymer may be prepared as single particles or core-shell particles. The hydrophilic rubber particles are monomers that impart hydrophilicity, and are not particularly limited, and non-limiting examples thereof include a monomer including a carboxylic acid, a nitrile group, and a hydroxy group or at least one hydrophilic functional group thereof. Preferably, a monomer having a carboxylic acid group is preferred. The particle size is not limited, but preferably a size of 0.1 to 30 µm is preferred, but is not limited thereto.

By using the hydrophilic modified rubber particles as the sealant component of the present invention, the present invention has a high elongation of 400% or more, preferably 1,000% or more, and has an adhesive property of 3Kg/m or more, preferably 4kg/m or more. In addition, it is possible to provide a new sealant having a remarkable increase in the elastic recovery rate.

The content of the hydrophilic modified rubber particles may be 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the modified polyurethane diol. It has a high elongation rate of 400% or more, preferably 1,000% or more, adhesion properties of 3Kg/m or more, preferably 4 kg/m or more, and a new sealant with a remarkable increase in the elastic recovery rate can be provided. .

The following describes the curing catalyst of the present invention.

The curing catalyst of the present invention may be used without limitation as long as the alkoxysilane end groups are condensed to react with each other to cure. As the condensation reaction catalyst, for example, a tin-based catalyst may be exemplified, but is not limited to a dialkyltindialkylate-based catalyst, and specifically, dibutyltindilaurate may be used. It is not limiting. The content of the curing catalyst may be 0.01 to 5 parts by weight based on 100 parts by weight of the modified polyurethane diol, but is not limited thereto.

In the present invention, the polyurethane diol can be prepared by reacting the polyester-based diol and diisocyanate in the presence of a catalyst. The reaction catalyst of the present invention may be used in the same manner as the alkoxysilane curing catalyst, or may be used differently, so it is not necessary to specifically specify it in the present invention. When considering the raw material cost, it is more preferred to use the tin-based catalyst.

The molecular weight of the polyurethane diol of the present invention is not particularly limited in terms of weight average molecular weight, but when using a material having a weight average molecular weight of 5000 to 50,000, sufficient mechanical strength can be provided, and it has elastic resilience, and at the same time, it has an elongation of 400% higher than 700. %, more preferably, an elongation of 1,000% or more can be given, so it is more preferred in the present invention, but is not necessarily limited thereto.

In addition, in the present invention, the alkoxysilane cappingdin-modified polyurethane resin has isocyanate alkyltrialkoxysilane (NCO-R-Si(OR ₂ ) ₃ ) or/and isocyanate alkyldialkoxy at both ends of the polyurethane diol. It may be capped by reacting with an alkylsilane (NCO-R-Si(R)(OR ₂ ) _{2 ).} (In the above, each of R, R'and R″ is independently a C1-C8 alkyl group.)

When the sealant composition containing the above components of the present invention is cured using the same (for example, moisture curing), as measured by ASTM D412, the elongation is 400% or more, preferably 700% or more, more preferably 1,000% or more. An elastic sealant can be provided, and a remarkable increase in adhesion and an elastic recovery rate can be further increased.

In addition, the present invention provides a sealant composition comprising a mixed modified polyurethane resin of a modified polyurethane resin end-capped with trialkoxy salane and a modified polyurethane resin end-capped with dialkoxysilane, and a sealant prepared using the same.

In addition, the present invention provides a sealant composition or a sealant prepared using the polyurethane diol is a polyurethane diol prepared by reacting a polyester-based diol and a diisocyanate.

In addition, the polyurethane diol of the present invention has the best elongation and elastic restoration properties in the case of a polyurethane diol prepared including a polyester diol and an aliphatic cyclic diisocyanate, and thus has excellent mechanical properties. I prefer it otherwise.

In addition, the sealant composition in the present invention may further include a filler. The filler is not particularly limited, and for example, components such as calcium carbonate, metal chloride, metal oxide, metal nitride, zeolite, tac, metal carbonate, or a filler containing these components may be used, and hard coal heavy carbon, dioxide Since various things such as titanium can be used, it is not limited thereto. In the present invention, the filler may be used in an amount of 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the modified polyurethane resin, but is not limited thereto.

In addition, the present invention may further include a plasticizer in the sealant composition.The plasticizer of the present invention increases the viscosity stability of the sealant composition, imparts excellent properties to the long-term elongation characteristics of the sealant, and significantly increases the extrudability during construction. It is preferred because it can improve construction stability. In the aspect of achieving the object of the present invention, it is preferred to use 10 to 80 parts by weight of the plasticizer in the sealant composition of the present invention based on 100 parts by weight of the modified polyurethane resin. The plasticizer used in the present invention is not particularly limited as long as it is a plasticizer used for processing of ordinary PVC (PVC), for example, phthalic acid, hydrogenated phthalic acid, trimellitic acid, epoxy, polyester, etc. DOP (PHTHALIC ACID DI-2 ETHYL-HEXYL), DIDP (PHTHALIC ACID DI-ISO DECYL), DINP (PHTHALIC ACID DI-ISO NONYL), DBP (PHTHALIC ACID DI-BUTYL), TOTM ( TRI-MERITIC ACID TRI-2 ETHYL HEXYL), DOA (ADIPINIC ACID DI-2 ETHYL HEXYL), DINCH (1,2-cyclohexanedicarboxylic acid diisononyl ester), etc. can be used. no.

In addition, the sealant composition of the present invention may further add a long-term property stabilizer. The long-term property stabilizer reacts with the alkoxysilane-capped modified polyurethane resin of the present invention and also contains a reactive group, so that curing gradually progresses with time change, preventing deterioration of elongation and elastic restoration performance due to deterioration during long-term use. I give you. The long-term property stabilizer of the present invention may be a mono, di, or trialkoxysilane compound having a reactive group selected from a radically polymerizable vinyl group, allyl group, methacrylic group, and acrylic group. Specifically, vinyl triethoxy Compounds such as silane may be exemplified.

The long-term property stabilizer of the present invention may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the modified polyurethane resin, but is not limited thereto.

In addition, the present invention may further add a silane compound having a mono or diamino group as an adhesion-imparting agent for increasing the adhesion of the surface of the adherend such as concrete, glass, or metal or wood by using the sealant composition of the present invention. . The amino silane compound of the present invention is more preferable because the amino group participates in curing while water crosslinking and strengthens hydrogen bonds to increase adhesion to an adherend, which is a substrate, thereby having an adhesive effect and a waterproof effect. The adhesion-imparting agent is used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the modified polyurethane resin, but is not limited thereto.

In addition, the present invention may further include one or more additives selected from additives such as plasticizers, antioxidants, UV inhibitors, lubricants, pigments, dyes, dehydrating agents, and adhesion-imparting agents in the sealant composition of the present invention. Each of the additives may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the modified polyurethane resin, but is not limited thereto.

In the present invention, the curing catalyst may be a tin (Tin)-based catalyst.

In the present invention, the sealant composition may include 1 to 80 parts by weight of a plasticizer, 10 to 300 parts by weight of a filler, and 0.01 to 5 parts by weight of a curing catalyst based on 100 parts by weight of the modified polyurethane resin.

In the present invention, the silane end-capped modified polyurethane resin is 1 to 50 parts by weight of monoalkoxy end capped based on 100 parts by weight of the trialkoxy end-capped modified polyurethane resin and/or the dialkoxy end-capped modified polyurethane resin. Modified polyurethane resins may also be included.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for describing the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Production Example 1] SLPU polymer

100 parts by weight of Polyester diol (Songwon Industrial SS-20N, OH value; 57.33 mgKOH/g) was added to the reactor and mixed. After raising the reaction temperature to 70°C, 0.01 parts by weight of dibutyl tin dilaurate was added, followed by mixing. 11 parts by weight of isophorone diisocyanate (IPDI, NCO/OH=0.95) was added and stirred while maintaining a reaction temperature of 82°C. If the NCO peak (2,267 ~ 2,270 cm ^-1 ) is not confirmed using FT-IR, it is set as the end point of the first step reaction. The reaction temperature was lowered to 70°C, and 3.1 parts by weight of 3-Isocyanatopropyl trimethoxysilane (ICPTMS, NCO/OH=0.05) was added, followed by stirring while maintaining the temperature at 80°C. If the NCO peak is not confirmed using FT-IR, it is used as the end point of the second step reaction. The temperature was lowered to room temperature, about 1 g of a sample was taken, dried in a 150°C convection oven for 1 hour, and the solid content was measured, confirming that it was 99.5%. The weight average molecular weight was 23,100 g/mol.

[Production Example 2] SLPU-M polymer

100 parts by weight of Polyester diol (Songwon Industrial SS-20N, OH value; 57.33 mgKOH/g) was added to the reactor and mixed. After raising the reaction temperature to 70°C, 0.01% by weight of dibutyl tin dilaurate was added, followed by mixing. Add 10 parts by weight of Isophorone diisocyanate (IPDI,NCO/OH=0.95) and stir while maintaining the reaction temperature at 82℃. If the NCO peak (2,267 ~ 2,270 cm ^-1 ) is not confirmed using FT-IR, it is set as the end point of the first step reaction. The reaction temperature was lowered to 70°C, 2.9 parts by weight of 3-Isocyanatopropylmethyl dimethoxysilane (ICPMDMS, NCO/OH=0.05) was added and stirred while maintaining the temperature at 80°C. If the NCO peak is not confirmed using FT-IR, it is used as the end point of the second step reaction. After lowering the temperature to room temperature, about 1g of a sample was taken and the solid content was measured in a 150℃ convection oven for 1 hour, and it was confirmed that it was 99.4%. The weight average molecular weight was 25,320 g/mol.

[Production Example 3] SLPU-A polymer

100 parts by weight of Polyester diol (Songwon Industrial SS-20N, OH value; 57.33 mgKOH/g) was added to the reactor and mixed. After raising the reaction temperature to 70°C, 0.01% by weight of dibutyl tin dilaurate was added, followed by mixing. MDI (Methylene diphenyl diisocyanate) was added at a molar ratio of NCO/OH=0.95 and stirred while maintaining a reaction temperature of 82°C. If the NCO peak (2,267 ~ 2,270 cm ^-1 ) is not confirmed using FT-IR, it is set as the end point of the first step reaction. The reaction temperature was lowered to 70°C, 2.9 parts by weight of 3-Isocyanatopropylmethyl dimethoxysilane (ICPMDMS, NCO/OH=0.05) was added and stirred while maintaining the temperature at 80°C. If the NCO peak is not confirmed using FT-IR, it is used as the end point of the second step reaction. After lowering the temperature to room temperature, about 1g of a sample was taken, and the solid content was measured in a 150℃ convection oven for 1 hour, and as a result, it was confirmed that it was 99.7%. The weight average molecular weight was 25,880 g/mol.

[Example 1]

SLPU polymer 100 parts by weight, 3 μm SBR (styrene:butadiene = 1:1.3 weight ratio) copolymerized with 3.2 wt% acrylic acid as hydrophilic modified rubber particles 4.5 parts by weight, plasticizer (DINCH) 7.9 parts by weight, UV stabilizer (Prosorb UV-292) 1.1 parts by weight, antioxidant (Songnox2450) 1.1 parts by weight, titanium dioxide (R5566) 16.4 parts by weight, and thickener (RHEOTHIX SG 705P) 2.3 parts by weight are added to the mixing tank, and the tank is mounted on a stirrer and stirred for 30 minutes. . Subsequently, 200 parts by weight of calcium carbonate and 0.6 parts by weight of calcium oxide were added, and after mixing, the vacuum pump was operated, followed by stirring at 90° C. for 30 minutes. Next, put 46.3 parts by weight of DINCH again and proceed with cooling and stirring. Subsequently, after vacuum release, 6.2 parts by weight of a long-term property stabilizer (vinyltrimethoxysilane, VTMS) was added and stirred for 30 minutes after operation of the vacuum pump. Further, 2.3 parts by weight of dibutyltindilaurate was added as a curing catalyst at 60° C. or lower and stirred for 30 minutes. After the vacuum is released, the mixing tank is quickly removed, the contents are covered with a plastic cover, and packaged within 30 minutes to seal/package the sealant composition in the prescribed cartridge.

The sealed sealant composition was put into a jig as shown in Fig. 1 according to ASTM D412 Die C, water-crosslinked and cured to prepare a 25.0mm±0.25mm specimen, and then inserted into a tensile tester using this, and then elongation at a rate of 500mm/min Was measured. After preparing the elastic resilience test body as shown in FIG. 2, the elastic resilience was measured by the test method of KS F 4910. In addition, adhesion was measured according to the method of ASTM C794. The results are listed in Table 1.

[Example 2]

It was carried out in the same manner as in Example except that 50 parts by weight of SLPU polymer and 50 parts by weight of SLPU-M polymer were used.

[Example 3]

It was carried out in the same manner as in Example 2, except that 50 parts by weight of SLPU polymer and 50 parts by weight of SLPU-A polymer were used.

[Example 4]

The same procedure was carried out except that 4.5 parts by weight of aminosilane (DAS) was used as the adhesion imparting agent in Example 2. The results are listed in Table 1.

[Comparative Example 1]

In Example 1, except that the carboxylic acid-modified SBR, which is a hydrophilic modified rubber particle, was not used, it was carried out in the same manner. The results are listed in Table 1.

Adhesion Elasticity Elongation Comparative Example 1 1.9N/m 71% 411% Example 1 3.1N/m 91% 534% Example 2 3.4N/m 96% 1,210% Example 3 4.5N/m 92% 1010% Example 4 4.6N/m 97% 1260%

As can be seen from the above table, the product of the present invention has an elastic restoring force of 80% or more, preferably 90% or more, and at the same time, exhibits excellent properties in adhesion, as well as an elongation of 500% and better. Showed excellent elongation of more than 1000%.

In addition, in the case of using the hydrophilic modified rubber particles in adhesion, it showed a remarkable increase in adhesion as compared to Comparative Example 1, which did not use it, and showed physical properties of 3N/m or more, more preferably 4N/m or more as a whole.

In addition, compared to Example 1 in which the modified polyurethane resin endcapped with trialkoxysilane was used alone in the present invention, the modified polyurethane resin endcapped with trialkoxysilane and the modified polyurethane resin endcapped with dialkoxysilane. In the case of Example 2, which is a sealant composition containing a mixed-modified polyurethane resin, it showed more remarkable improvement in elastic restoration and elongation, and some loss in adhesion showed excellent physical properties.

In addition, in the present invention, in the case of Example 3 using an aromatic diisocyanate instead of the cyclic isocyanate, compared to the case of Examples 1 to 2 using the cyclic isocyanate, the elastic restoration rate and elongation were more excellent in the elastic restoration property.

In addition, in the case of using aminosilane as an adhesion-imparting agent in Example 4, it was found that compared to Example 2 in which it was not used, physical properties in elastic restoration and elongation were increased, and at the same time, an effect of increasing adhesion was obtained.

As described above, in the present invention, specific matters and limited embodiments and drawings have been described, but this is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is Those of ordinary skill in the relevant field can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (12)

Modified polyurethane resin mixed with a first modified polyurethane resin in which both ends of a polyurethane diol are endcapped with trialkoxysilane and a second modified polyurethane resin in which both ends of a polyurethane diol are endcapped with alkyldialkoxysilane, hydrophilic modification It is manufactured including rubber particles, curing catalyst and filler,
A sealant composition having an elongation of 500% or more according to ASTM D412 Die C, 90% or more of elastic restoration according to KS F 4910, and an adhesion of 3N/m or more according to ASTM C794. The method of claim 1,
The polyurethane diol is a sealant composition that is a polyurethane diol prepared by reacting a polyester diol and a diisocyanate. The method of claim 1,
The first modified polyurethane resin is capped at both ends of the polyurethane diol with isocyanatoalkyltrialkoxysilane (NCO-R'-Si(OR ₂ ) ₃ ), and the second modified polyurethane resin is The sealant composition that the both ends of the polyurethane diol are capped with isocyanate alkyldialkoxyalkylsilane (NCO-R'-Si(R″)(OR ₂ ) _{2 ).}
(In the above, each of R, R'and R″ is independently a C1-C8 alkyl group.) The method of claim 3,
The capping is a sealant composition that is capped in the presence of a tin-based catalyst. The method of claim 1,
The hydrophilicity of the hydrophilicity-modified rubber particles is a sealant composition obtained by copolymerizing a monomer including a carboxylic acid, a nitrile group, and a hydroxy group as a monomer or at least one hydrophilic functional group thereof during rubber polymerization. The method of claim 1,
The sealant composition further comprises a plasticizer. The method according to any one of claims 1 to 6,
The sealant composition further comprises any one or more components selected from a long-term property stabilizer and an adhesion-imparting agent. The method of claim 7,
The long-term property stabilizer is one or two or more components selected from mono, di, or trialkoxysilane compounds having a reactive group selected from vinyl group, allyl group, methacrylic group, and acrylic group. The method of claim 7,
The adhesion-imparting agent is a sealant composition comprising an amine group. The method of claim 1,
The sealant composition is a sealant composition comprising 0.1 to 10 parts by weight of hydrophilic modified rubber particles, 0.01 to 5 parts by weight of a curing catalyst, and 1 to 300 parts by weight of a filler, based on 100 parts by weight of the modified polyurethane diol. The method of claim 7,
The long-term property stabilizer is 1 to 20 parts by weight based on 100 parts by weight of the modified polyurethane resin, and the adhesion-imparting agent is 1 to 10 parts by weight of the sealant composition. The method of claim 2,
The diisocyanate is a sealant composition comprising a cyclic aliphatic diisocyanate.

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