Pumpable, thermoblastable filler composition with extended open time

Abstract

The present application is directed to pumpable, thermally foamable filler compositions based on a combination of a liquid epoxy resin, a polyvinyl chloride resin and / or an acrylic resin powder, and at least one alkali metal salt of a fatty acid containing 16 or 18 carbon atoms, where the alkali metal is calcium or zinc. These pumpable filler materials have the advantage that they can be expanded to give foams with high expansion ratio values, even after wet exposure / storage. The present invention also describes a method for filling enclosed spaces with the pumpable, thermally foamable filler composition, and vehicle parts obtained using the method described.

Description

Technical Field

[0001] The present invention relates to a heat-expandable filler composition that can be pumped, and particularly to a heat-expandable filler composition that can be pumped and is suitable for forming a sound insulation material for blocking noise during vehicle operation when it is filled into a closed portion of a vehicle body element, for example, inside a vehicle pillar and then foamed by heating using a baking method.

Background Art

[0002] Hitherto, in order to improve the sound insulation performance against vehicle noise, particularly to block wind noise, two-component pumpable polyurethanes and other materials have been used. They are foamed in a pre-determined shape in advance and then filled into closed portions, for example, the front pillar (A pillar), center pillar (B pillar), rear pillar (C pillar), wheel arch (tire house), or side sill. However, this method is difficult to implement by automotive OEMs because the equipment and processes used are complex. In some cases, the applicator may not be able to access some of the small-area cavities.

[0003] Another type of sound insulation / acoustic material is a partial baffle, which can be manually attached to vehicle parts in an unfoamed state and then foamed and expanded during the OEM baking process. Examples of these thermoplastic plastic baffles include commercially available products such as SikaBaffle 255 or SikaBaffle 450, which can expand their volume up to about 1000 - 2000% before foaming.

[0004] A further type of isolation / acoustic material is a tape baffle, such as SikaBaffle 229, which shows a volume expansion of about 800%. The disadvantage of the above-mentioned component baffle or tape baffle technology is that their materials have to be attached manually. In OEMs, robotic attachment is more desirable.

[0005] A novel approach to overcome the difficulties associated with pre-foamed sound-insulating baffles is to use pumpable baffle materials, which can be applied and metered by means of an injection nozzle and thus can be easily used "on request." For example, European Patent No. 3281970 discloses pumpable, thermoplastic filler compositions based on a combination of liquid epoxy resin and polyvinyl chloride resin and / or acrylic resin powder. These pumpable filler materials have the advantage of being applicable using conventional injection devices as needed and being expanded to obtain a foam with good physical strength, high expandability, and good adhesion to oil-covered metal substrates. [Overview of the project] [Problems that the invention aims to solve]

[0006] However, if the filler composition is exposed to moisture after being applied to the substrate, the raw materials may absorb that moisture before it can finally harden. The time between application and hardening is called the open time. The water absorbed into the reactants adversely affects the expansion of those compositions.

[0007] This application addresses these issues. [Means for solving the problem]

[0008] In a first embodiment, the present application relates to a pumpable, thermoblastable filler composition comprising: - A liquid epoxy resin in an amount of preferably 8-30% by weight, 10-25% by weight, and preferably 15-20% by weight, based on the total weight of the pumpable, heat-expandable filler composition; - Based on the total weight of the pumpable, heat-expandable filler composition, preferably 5-40% by weight, 8-30% by weight, preferably 10-20% by weight of polyvinyl chloride resin and / or acrylic resin powder, preferably polyvinyl chloride resin; - A blowing agent in an amount of preferably 1-10% by weight, 2-8% by weight, and preferably 3-6% by weight, based on the total weight of the pumpable, heat-expandable filler composition; and - Based on the total weight of the pumpable, heat-expandable filler composition, it contains 1 to 5% by weight of 16 or 18 carbon atoms. A little At least one type of fatty acid Calcium or zinc Salt AMS.

[0009] The pumpable, heat-expandable filler composition contains, based on the total weight of the pumpable, heat-expandable filler composition, 1 to 5% by weight of at least one fatty acid containing 16 or 18 carbon atoms. Calcium or zinc Salt AM S It is included.

[0010] Surprisingly, as mentioned above Contains 16 or 18 carbon atoms fatty acids Calcium or zinc It was found that using salt AMS in the indicated amount yields a high expansion value even after storage in humid conditions. At amounts less than 1% by weight, the expansion value is insufficient. This can be seen, for example, by comparing Examples 1-3 with Examples 4-9 with Examples 10-11. Calcium carbonate coated with different metal ions, and even different fatty acids, each using stearic acid, does not achieve a satisfactory expansion value after storage in humid conditions, as can be seen, for example, by comparing Examples 4-11 with Examples 12-17.

[0011] The fatty acid containing at least one of the 16 or 18 carbon atoms Calcium or zinc Salt AM S Preferably, the following are selected from the group: - Calcium salts of saturated fatty acids containing 16 carbon atoms, calcium salts of unsaturated fatty acids containing 16 carbon atoms, calcium salts of saturated fatty acids containing 18 carbon atoms, calcium salts of unsaturated fatty acids containing 18 carbon atoms, - Zinc salts of saturated fatty acids containing 16 carbon atoms, zinc salts of unsaturated fatty acids containing 16 carbon atoms, zinc salts of saturated fatty acids containing 18 carbon atoms, and zinc salts of unsaturated fatty acids containing 18 carbon atoms.

[0012] More preferably, at least one fatty acid containing 16 or 18 carbon atoms. Calcium or zinc Salt AM S , selected from the following group: - Calcium salts of palmitic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid, alpha-linoleic acid, - Zinc salts of palmitic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid, and alpha-linoleic acid.

[0013] Most preferably, at least one fatty acid containing 16 or 18 carbon atoms Calcium or zinc Salt AM S , selected from the group consisting of the following: calcium salt of palmitic acid, calcium salt of stearate, calcium salt of oleic acid, calcium salt of linoleic acid, zinc salt of palmitic acid, zinc salt of stearate, zinc salt of oleic acid, and zinc salt of linoleic acid.

[0014] Most preferably, at least one fatty acid containing 16 or 18 carbon atoms Calcium or zinc Salt AM S, selected from the group consisting of: calcium stearate and zinc stearate, most preferably calcium stearate.

[0015] At least one salt AMS of a fatty acid containing 16 or 18 carbon atoms Calcium or zinc If the salt AMS is a calcium metal salt, it can be advantageous. Preferably, this calcium salt is selected from the group consisting of calcium palmitate, calcium stearate, calcium oleate, and calcium linoleate, most preferably calcium stearate. This is advantageous in terms of the buckling-free and sealed pore structure of the foamed filler after storage in a humid environment, as can be seen in the comparison of Examples 4 to 9 with Examples 10 to 11 in Table 3.

[0016] At least one salt AMS of a fatty acid containing 16 or 18 carbon atoms Calcium or zinc If the salt AMS is a zinc metal salt, this can also be advantageous. Preferably, this zinc salt is selected from the group consisting of zinc palmitate, zinc stearate, zinc oleate, and zinc linoleate, most preferably zinc stearate.

[0017] This is advantageous in that, as can be seen in the comparison of Examples 10 to 11 with Examples 4 to 9 in Table 3, the expansion value after storage in a humid environment is higher.

[0018] Preferably, Contains 16 or 18 carbon atoms of the fatty acid Calcium or zinc The amount of salt AMS is 1.25 to 4% by weight, preferably 1.5 to 3% by weight, more preferably 1.75 to 2.5% by weight, most preferably 1.85 to 2.25% by weight, based on the total weight of the pumpable thermally foaming filler composition.

[0019] This is advantageous in that, as can be seen in Table 3, the expansion value after storage in a humid environment is higher.

[0020] The liquid epoxy resin is a substance that is liquid or at least has fluidity at ambient temperature (23°C). Those skilled in the art know that polyepoxides known as "reactive diluents" are also referred to as liquid epoxy resins in this specification.

[0021] Examples of liquid epoxy resins suitable for use in the compositions of the present invention include liquid resins of formula (I):

Chemical formula

[0022] The liquid epoxy resin of formula (I) is a diglycidyl ether of bisphenol A, bisphenol F, and bisphenol A / F, where A represents acetone and F represents formaldehyde, and they function as reactants for preparing these bisphenols. Therefore, as R' and R" in formula (I), bisphenol A liquid resin has a methyl group, bisphenol F liquid resin has a hydrogen atom, and bisphenol A / F liquid resin has both a methyl group and a hydrogen atom. In the case of bisphenol F, it can exist as positional isomers particularly derived from 2,4'- and 2,2'-hydroxyphenylmethane.

[0023] Such liquid epoxy resins are commercially available, for example, as follows: Araldite® GY204, Araldite® GY250, Araldite® GY260, Araldite® GY281, Araldite® GY282, Araldite® GY285, Araldite® PY304, Araldite® PY720 (manufactured by Huntsman); DER® 330, DER® 331, DER® 332, DER® 336, DER® 354, DER® 351, DER® 352, DER® 356 (Dow); Epikote® 162, Epikote® 827, Epikote® 828, Epikote® 158, Epikote® 862, Epikote® 169, Epikote® 144, Epikote® 238, Epikote® 232, Epikote® 235 (Hexion), Epalloy® 7190, Epalloy® 8220, Epalloy® 8230, Epalloy® 7138, Epalloy® 7170, Epalloy® 9237-70 (CVC), Chem Res(registered trademark) E20, Chem Res(registered trademark) E30 (manufactured by Cognis), Beckopox(registered trademark) EP 1 16, Beckopox(registered trademark) EP140 (manufactured by Cytec), Epiclon EXA-4850 (manufactured by Sun Chemical).

[0024] Further preferred liquid epoxy resins are glycidylation reaction products of the following: dihydroxybenzene derivatives, e.g., resorcinol, hydroquinone, and catechol; further bisphenols or polyphenols, e.g., bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propanehydroxyphenyl)propane Su(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 3,3-bis(4-hydroxyphenyl)pentane, 3,4-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane , 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol P), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 4,4'-dihydroxydiphenyl (DOD), 4 ,4'-dihydroxybenzophenone, bis(2-hydroxynaphthi-1-yl)methane, bis(4-hydroxynaphthi-1-yl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl)sulfone; condensates of phenol and formaldehyde (these are obtained under acidic conditions), e.g., phenol novolac or cresol novolac;Aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine (MDA), 4,4'-methylenediphenyldi(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline P), and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline M).

[0025] In further embodiments, the liquid epoxy resin is an aliphatic or alicyclic polyepoxide, for example: diglycidyl ethers; saturated or unsaturated, branched or unbranched, cyclic or open-chain C2-C3 diols, such as glycidyl ethers of ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, and neopentyl glycol; trifunctional or tetrafunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyoxyols. For example, castor oil, trimethylolpropane, trimethylolethane, penta-erythritol, sorbitol, or glycerol, and glycidyl ethers of alkoxylated glycerol or alkoxylated trimethylolpropane; hydrogenated bisphenol A, F, or A / F liquid resins, or glycidyl reaction products of hydrogenated bisphenol A, F, or A / F; amides or heterocyclic nitrogen bases, such as N-glycidyl derivatives of triglycidyl cyanurate and triglycidyl isocyanurate, and reaction products of epichlorohydrin and hydantoin.

[0026] Aliphatic or alicyclic liquid epoxy resins are commercially available, for example, as follows: Araldite® DY-C, Araldite® DY-F, Araldite® DY-H, Araldite® DY-T, Araldite® DY0397, Araldite® DY3601 (manufactured by Huntsman), DER® 732, DER® 736 (manufactured by Dow); Heloxy® BD, Heloxy® HD, Heloxy® TP, Epikote® 877 (manufactured by Hexion), Beckopox® EP075 (manufactured by Cytec). Mixtures of aliphatic or alicyclic polyepoxides and aromatic epoxides of formula (I), for example, particularly mixtures of diglycidyl ethers of bisphenol A, bisphenol F, and bisphenol A / F, and diglycidyl ethers of α,ω-alkanediols (where the α,ω-alkanediol preferably contains 2 to 10 carbon atoms), can also be used. Such mixtures are commercially available, for example, from Dow as DER358.

[0027] In further embodiments, the liquid epoxy resin is a polyepoxide prepared by oxidizing an olefin, such as vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene, or divinylbenzene.

[0028] The liquid epoxy resin is preferably the liquid resin of formula (I) mentioned above, and the one listed above as preferred is even more preferred.

[0029] In relation to this application, particularly preferred liquid epoxy resins are bisphenol A diglycidyl ether-based epoxy resins having an epoxy equivalent weight of 156 to 250 g / eq, such as DER® 331 (manufactured by Dow).

[0030] Preferably, the liquid epoxy resin is contained in the composition in an amount of 5 to 40% by weight, based on the total weight of the composition. In a more preferred embodiment, the liquid epoxy resin is contained in the composition in an amount of 8 to 30%, 10 to 25%, and particularly 15 to 20% by weight.

[0031] The polyvinyl chloride (PVC) resin in the composition of this application may be a homopolymer or copolymer of polyvinyl chloride, preferably a copolymer of polyvinyl chloride. If the polyvinyl chloride is a copolymer, it is preferable that it contains a vinyl ester, such as vinyl acetate or vinyl propionate, as a comonomer to the vinyl chloride. The amount of the comonomer is preferably in the range of 1 to 25%, more typically 2 to 20%, 2 to 15%, 2 to 10%, and most preferably 3 to 7%, based on the total weight of the copolymer.

[0032] A preferred PVC homopolymer in relation to this application is Formolon KVH (manufactured by Formosa). A particularly preferred PVC copolymer in relation to this application is Formolon F40, also manufactured by Formosa.

[0033] There are no particular restrictions on the acrylic resin powder that can be used in place of or in addition to polyvinyl chloride resin, however, it is preferable that it is solid at ambient temperature (23°C). The acrylic resin powder has a glass transition temperature Tg in the range of 50°C to 120°C, and even more preferably in the range of 70°C to 90°C. The glass transition temperature is measured by DSC. In addition, it is preferable that the acrylic resin powder can form a plastisol.

[0034] The acrylic resin in the acrylic resin powder may be a homopolymer or a copolymer. Preferred acrylic resins are methyl methacrylate-based resins, such as those commercially available as Diana LP-3106 or Diana LP-3202 (manufactured by Diana America Inc.). Another commercially available acrylic resin that can be advantageously used in this application is Kane Ace U506 (manufactured by Kaneka).

[0035] It is preferable that the composition contains one or more polyvinyl chloride resins and / or one or more acrylic resin powders in an amount ranging from 5 to 40% by weight, preferably 8 to 30% by weight, and most preferably 10 to 20% by weight.

[0036] As a third essential component, the pumpable, heat-expandable filler composition of the present invention includes a blowing agent. Any substance may be used as the blowing agent for use in the present invention, as long as it decomposes upon heating and generates gas. Suitable blowing agents include azo compounds such as azo-dicarbonamide, nitroso compounds such as N,N-dinitrosopentamethylenetetraamine, and hydrazine derivatives such as diphenylsulfone-3,3'-disulfohydrazide. These blowing agents may be used individually or as a mixture of two or more. In relation to this application, dicyandiamide is particularly preferred, at least as part of the blowing agent, because its decomposition reaction product (ammonia) contributes to the curing and crosslinking of the liquid epoxy resin.

[0037] The amount of foaming agent in the pumpable, heat-expandable filler composition of the present invention is typically in the range of 1 to 10% by weight, 2 to 8% by weight, and preferably in the range of 3 to 6% by weight.

[0038] The "pumpable" characteristic of the thermoplastic filler composition of this application should be understood as meaning that the filler has a viscosity suitable for pumping at ambient temperature (20°C), preferably a paste-like viscosity. The viscosity of the pumpable thermoplastic filler composition is measured using a rheometer with a heatable plate (MCR301, manufactured by Anton Paar) (gap 1000 μm, measuring plate diameter: 25 mm (plate / plate), deformation 0.01-10%, 5 Hz, temperature: 20°C), and is usually in the range of 50-500 Pa·s, preferably 100-300 Pa·s. If the viscosity is lower than 50 Pa·s, dripping may easily occur, and the shape may not be adequately maintained during processing. On the other hand, if the viscosity exceeds 500 Pa·s, the processability of the material becomes extremely poor.

[0039] In addition to the components listed above, the pumpable, heat-expandable filler composition may contain further components.

[0040] Therefore, in preferred embodiments, the pumpable, thermoblastable filler composition includes rubber, particularly synthetic rubber, preferably partially crosslinked synthetic rubber. Examples of partially crosslinked rubber for use in the filler composition of the present invention include, preferably, partially crosslinked diene rubber, more preferably selected from the group consisting of: acrylonitrile-isoprene copolymer rubber (NIR), acrylonitrile-butadiene copolymer rubber (NBR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), and isoprene rubber (IR). The crosslinking may be the result of adding a crosslinking agent, such as divinylbenzene or sulfur. The addition of rubber provides the advantages of improved rheological properties, sag resistance, wash-off resistance, and higher volume expansion of the resulting filler composition.

[0041] The rubber is incorporated into the filler composition of the present invention in an amount typically of 1-20%, preferably 3-15% by weight, and more preferably 5-10% by weight, based on the total weight of the composition.

[0042] A further component that can be advantageously used in the pumpable, thermoplastic filler composition of this application is a plasticizer. Therefore, the pumpable, thermoplastic filler composition of this application preferably includes at least one plasticizer. The combination of a low-viscosity plasticizer with PVC and / or acrylic resin powder is advantageous for a stable paste-like state and is particularly advantageous for obtaining a cured material with good physical strength and good expansion rate after storage in humid conditions.

[0043] Any substance may be used as a plasticizer, provided that polyvinyl chloride swells and dissolves in it. Examples of plasticizers include: phthalates, for example, di(2-ethylhexyl) phthalate, butyl benzyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate, ditridecyl phthalate (DTDP), diheptyl phthalate, and butylphthalyl butyl glycolate; aliphatic dibasic acid esters, for example, dioctyl adipate, didecyl adipate, and dioctyl sebacate; polyglycol benzoates, for example, polyoxyethylene glycol dibenzoate and polyoxypropylene glycol dibenzoate; phosphate esters, for example, tributyl phosphate and tricresyl phosphate; hydrocarbons, for example, alkyl-substituted diphenyl, alkyl-substituted terphenyl, partially hydrogenated terphenyl, aromatic process oils, and pile oils. These plasticizers may be used individually or as a mixture of two or more of them. In relation to this application, preferred plasticizers among those described above are phthalate esters, particularly diisononyl phthalate (DINP), ditridecyl phthalate (DTDP), and diisodecyl phthalate (DIDP).

[0044] In relation to this application, the preferred amount of plasticizer is 5 to 40% by weight, preferably 10 to 30% by weight, 15 to 25% by weight, and particularly 10 to 20% by weight, based on the total weight of the composition.

[0045] The pumpable, heat-expandable filler composition of this application preferably also includes a curing agent for liquid epoxy resin. Preferably, a latent curing agent is used, which cures by heating and can usually be activated at temperatures between 80 and 250°C. Specific examples of latent curing agents include: dicyandiamide, 4,4'-diaminodiphenylsulfone, imidazole derivatives such as 2-N-heptadecylimidazole, isophthaldihydrazide, N,N-dialkylurea derivatives, N,N-dialkylthiourea derivatives, and melamine derivatives. These curing agents may be used independently or as a mixture of two or more, depending on the curing conditions and their properties. A particularly preferred curing agent for use in connection with this application is dicyandiamide. In one preferred embodiment, dicyandiamide is used as the sole epoxy curing agent in the composition because it has been observed that combining liquid epoxy resin with dicyandiamide results in a mixture with extremely high storage stability.

[0046] The amount of curing agent is preferably in the range of 0.05 to 2.0% by weight, 0.1 to 1.5% by weight, 0.2 to 1.2% by weight, 0.4 to 1.0% by weight, and more preferably 0.5 to 0.8% by weight, based on the total weight of the composition. It has been observed that when a large amount of liquid epoxy resin is combined with a small amount of curing agent, a substance is obtained that crosslinks to an appropriate level upon curing and provides good adhesion even to oil-covered metal substrates. In addition, this system also provides good physical strength.

[0047] In addition to the components described above, the pumpable, thermoblastable filler composition of this application preferably further comprises a filler, particularly an inorganic filler. Suitable inorganic fillers include, for example, calcium carbonate, silica, clay, and fly ash. These inorganic fillers may be used individually or as a mixture of two or more of them. It is also possible to use two or more modified fillers, such as calcium carbonate with different modifications.

[0048] There are no particular restrictions on the amount of filler, especially inorganic filler, in relation to this application, but it depends on the viscosity of the composition without filler, while maintaining the composition's pumpability (i.e., if the viscosity is low, a larger amount of filler can be incorporated, while if the viscosity is high without filler, only a small amount of filler can be incorporated). Therefore, the amount of filler is typically in the range of 10 to 55% by weight, preferably 15 to 45% by weight, and more preferably 20 to 35% by weight, based on the total weight of the composition.

[0049] The pumpable, thermoblastable filler composition of this application may further contain, if necessary, other additives in appropriate amounts, such as: thixotropy imparters such as organic bentonite, fumed silica, castor oil derivatives; pigments such as carbon black, titanium dioxide, zinc dioxide, or other inorganic pigments; dehydrating agents such as calcium oxide and powdered silica gel; and / or PVC stabilizers.

[0050] There are no particular restrictions on the amount of these additional additives, however, it is preferable that the content does not exceed 15% by weight, more preferably 10% by weight or less, and even more preferably 8% by weight or less.

[0051] In a particularly preferred embodiment of this application, the pumpable, thermoblastable filler composition of this application includes the following: - Based on the total weight of the pumpable, heat-expandable filler composition, 1-5% by weight, 1.25-4% by weight, 1.5-3% by weight, 1.75-2.5% by weight, preferably 1.85-2.25% by weight, of at least one fatty acid containing 16 or 18 carbon atoms. Calcium or zinc Salt AM S、 Preferably selected from the group consisting of calcium palmitate, calcium stearate, calcium oleate, calcium linoleate, zinc palmitate, zinc stearate, zinc oleate, and zinc linoleate; more preferably selected from the group consisting of calcium stearate and zinc stearate; most preferably calcium stearate; - 8-30% by weight, 10-25% by weight, preferably 15-20% by weight of liquid epoxy resin, preferably liquid resin of formula (I); - 5-40% by weight, 8-30% by weight, preferably 10-20% by weight of polyvinyl chloride resin and / or acrylic resin powder, preferably polyvinyl chloride resin; - 1-20%, 3-15% by weight, preferably 5-10% by weight of rubber, preferably synthetic rubber, more preferably diene rubber; - 1-10% by weight, 2-8% by weight, preferably 3-6% by weight of a foaming agent; - 5-40% by weight, 10-30% by weight, 15-25% by weight, preferably 10-20% by weight of a plasticizer, preferably a phthalate ester; - A curing agent in an amount of 0.05-2.0% by weight, 0.1-1.5% by weight, 0.2-1.2% by weight, 0.4-1.0% by weight, preferably 0.5-0.8% by weight, preferably a latent curing agent; - A filler in an amount of 10-55% by weight, 15-45% by weight, preferably 20-35% by weight, preferably an inorganic filler.

[0052] The weight percentages mentioned above are based on the total weight of the composition.

[0053] The pumpable, heat-expandable filler composition of the present invention can be manufactured by mixing the above-mentioned components in a mixer. There are no particular restrictions on the mixer used, but examples of various mixers include planetary mixers and kneaders.

[0054] In a second embodiment, the present invention aims to provide a foamed filler that can be obtained by heating a pumpable, heat-expandable filler composition to a temperature higher than the activation temperature of the foaming agent, as described above. Preferably, the temperature at which the pumpable, heat-expandable filler composition is heated should not exceed 210°C, and should be in the range of 140 to 200°C, more preferably 155 to 200°C. It is preferable to heat the composition at the above temperature for 10 to 60 minutes, preferably 15 to 15 minutes, more preferably 20 to 40 minutes.

[0055] In addition, it is preferable that the foamed filler, when cured in UB at 160°C for 25 minutes as described in the experimental section, has an expansion rate of 400% to 1000%, preferably 450% to 900%, based on its volume in the unfoamed state after storage in high humidity (3 days, 40°C, 99% relative humidity), and / or preferably, when cured in OB at 200°C for 40 minutes as described in the experimental section, has an expansion rate of 300% to 1000%, preferably 320% to 900%, more preferably 340% to 900%, based on its volume in the unfoamed state after storage in high humidity (3 days, 40°C, 99% relative humidity).

[0056] The pumpable, thermoplastic filler composition can be conveniently used to apply (for example, by extrusion) into a confined space using a robot and expand within it to provide a noise-isolating foam. Thus, in one embodiment, the present invention also aims to provide a pumpable, thermoplastic filler composition as a filler for confined spaces, as described above, and in particular for confined spaces in vehicle components. The pumpable, thermoplastic filler composition is suitably used to form isolation walls in confined spaces where noise, such as wind noise, occurs while the vehicle is in motion. Such confined spaces include, in particular, the front pillars (A-pillars), center pillars (B-pillars), rear pillars (C-pillars), wheel arches (wheel wells), and side sills.

[0057] In a further embodiment, the present application also aims to provide a method for filling a sealed space, comprising the following steps: - (a) Applying a pumpable, heat-expandable filler composition into a sealed space as described above, and - (b) Heating a sealed space containing a pumpable, heat-expandable filler composition to a temperature higher than the activation temperature of the foaming agent to cause the filler to foam.

[0058] In step (b), it is preferable that the pumpable, heat-expandable filler composition is heated to a temperature of 140 to 200°C, more preferably 155 to 200°C. It is preferable to heat the composition at the above temperature for 10 to 60 minutes, more preferably 15 to 15 minutes, more preferably 20 to 40 minutes.

[0059] After step (a), it is preferable to expose the applied pumpable, heat-expandable filler composition to a temperature of 30°C or higher and a relative humidity of 80% or higher, more preferably 40°C or higher and a relative humidity of 90% or higher, for a period of 2 days, 10 days or longer, and more preferably 30 days or longer, before carrying out step (b).

[0060] In preferred embodiments of the pumpable, thermoplastic filler composition and sealed space in this method, the above description applies in the same manner.

[0061] Since this method is particularly useful in automobile assembly, it is preferable that the sealed space is a sealed space in a vehicle component. Furthermore, it is preferable that the sealed space is a metal surface, particularly a metal surface to which oil is attached.

[0062] In a further embodiment, the present application aims to provide a vehicle component that can be obtained by the method described above.

[0063] The pumpable, thermo-expandable filler composition of this application provides a good expansion rate even after storage in humid conditions, thereby significantly improving the severity of noise and vibration in vehicles. [Examples]

[0064] Each component was compounded according to the compounding amounts (basic formulations) shown in Table 1. The premix contained 12.9% by weight of styrene-butadiene rubber, 26.8% by weight of DIDP plasticizer, 39.9% by weight of calcium carbonate filler, and 20.4% by weight of liquid epoxy resin (based on bisphenol A / epichlorohydrin at an epoxy equivalent weight of 180-190 g / eq). In Examples 2 to 17 of the compositions shown in Table 3, the indicated amounts of metal salts or coated calcium carbonate were added, and an equivalent amount of calcium carbonate was removed from the basic formulation. For example, in Example 8 of the composition, 2.0% by weight of CaSt was added to the basic formulation based on the total amount of the basic formulation, and at the same time, 2.0% by weight of calcium carbonate was removed from the basic formulation based on the total amount of the basic formulation. Therefore, each of the compositions in Example 8 contains 0.5% by weight of calcium carbonate and 2.0% by weight of CaSt based on the total weight of the composition in Example 8.

[0065] [Table 1]

[0066] [Table 2]

[0067] The volume change of the paste-like filler composition obtained in this manner was evaluated under various baking conditions.

[0068] Expansion rate (in %) For each sample, the expansion rate was quantified by measuring the density of a test material bead with a radius of approximately 5 mm and a length of 50 mm before and after expansion. The density was determined using the water immersion method in deionized water (Archimedes' principle) according to DIN EN ISO 1183, and a precision balance was used for mass measurement. To measure the expansion rate before storage in high humidity (initial expansion rate), the test materials were expanded at 160°C for 25 minutes (underbake = UB), 180°C for 20 minutes (normal bake = NB), and 200°C for 40 minutes (overbake = OB), respectively.

[0069] In parallel, the samples were stored at 40°C in 99% relative humidity for 3 days (3 days, 40°C / 99%rh). The stored samples were then stored at 23°C in 50% relative humidity for 1 hour, and the expansion rate was determined (expansion after 3 days, 40°C, 99%rh). These test materials were similarly expanded at 160°C for 25 minutes (underbake = UB), at 180°C for 20 minutes (normal bake = NB), and at 200°C for 40 minutes (overbake = OB).

[0070] [Table 3]

[0071] As shown in Table 3, the pumpable, heat-expandable filler compositions of the present invention exhibit good expansion values ​​even after storage in humid conditions. Furthermore, it was found that compositions 10 and 11 containing ZnSt exhibited an open pore structure on the surface of their cured compositions after expansion following storage in humid conditions.

[0072] Furthermore, in Composition Examples 2, 10, and 11, it was found that slight twisting and strain (known as "buckling") were observed in the expanded material after expansion following storage in a humid environment. This disclosure includes the following embodiments of the invention: <Aspect 1> A pumpable, heat-expandable filler composition comprising the following: - A liquid epoxy resin in an amount of preferably 8-30% by weight, 10-25% by weight, and preferably 15-20% by weight, based on the total weight of the pumpable, heat-expandable filler composition; - Based on the total weight of the pumpable, heat-expandable filler composition, preferably 5 to 40% by weight, 8 to 30% by weight, and preferably 10 to 20% by weight of polyvinyl chloride resin and / or acrylic resin powder, preferably polyvinyl chloride resin; - A blowing agent in an amount of preferably 1 to 10% by weight, 2 to 8% by weight, and preferably 3 to 6% by weight, based on the total weight of the pumpable, heat-expandable filler composition; and - Based on the total weight of the pumpable, heat-expandable filler composition, 1 to 5% by weight of at least one calcium or zinc salt AMS of a fatty acid containing 16 or 18 carbon atoms. <Aspect 2> The pumpable, heat-expandable filler composition according to Embodiment 1, wherein the amount of the calcium or zinc salt AMS of the fatty acid containing 16 or 18 carbon atoms is 1.25 to 4% by weight, preferably 1.5 to 3% by weight, more preferably 1.75 to 2.5% by weight, and most preferably 1.85 to 2.25% by weight, based on the total weight of the pumpable, heat-expandable filler composition. <Aspect 3> The pumpable, heat-expandable filler composition according to embodiment 1 or 2, wherein the calcium or zinc salt AMS of a fatty acid containing 16 or 18 carbon atoms is selected from the group consisting of calcium salt of palmitic acid, calcium salt of stearate, calcium salt of oleic acid, and calcium salt of linoleic acid, and is preferably calcium salt of stearate. <Aspect 4> The pumpable, heat-expandable filler composition according to embodiment 1 or 2, wherein the calcium or zinc salt AMS of a fatty acid containing 16 or 18 carbon atoms is selected from the group consisting of zinc salt of palmitic acid, zinc salt of stearic acid, zinc salt of oleic acid, and zinc salt of linoleic acid, and is preferably zinc salt of stearic acid. <Aspect 5> A pumpable, heat-expandable filler composition according to any one of embodiments 1 to 4, characterized in that the liquid epoxy resin is of formula (I): [ka] In the formula, R' and R'' are each independently a hydrogen atom or a methyl group, and s has an average value of 0 to 1, preferably less than 0.2. <Aspect 6> A pumpable, heat-expandable filler composition according to any one of embodiments 1 to 5, further comprising rubber, preferably synthetic rubber, more preferably partially crosslinked synthetic rubber, more preferably diene rubber, in an amount preferably 1 to 20%, preferably 3 to 15% by weight, more preferably 5 to 10% by weight, based on the total weight of the composition. <Aspect 7> A pumpable, heat-expandable filler composition according to any one of embodiments 1 to 6, further comprising at least one plasticizer, preferably a phthalate ester, in an amount preferably 5 to 40% by weight, preferably 10 to 30% by weight, 15 to 25% by weight, and particularly 10 to 20% by weight, based on the total weight of the pumpable, heat-expandable filler composition. <Aspect 8> A pumpable, heat-expandable filler composition according to any one of embodiments 1 to 7, further comprising a curing agent for the liquid epoxy resin, preferably a latent curing agent, more preferably dicyandiamide, in an amount preferably within the range of 0.05 to 2.0% by weight, 0.1 to 1.5% by weight, 0.2 to 1.2% by weight, 0.4 to 1.0% by weight, more preferably 0.5 to 0.8% by weight, based on the total weight of the pumpable, heat-expandable filler composition. <Pattern 9> A pumpable, heat-expand <Aspect 10> A foamed filler obtained by heating a pumpable, heat-expandable filler composition according to any one of embodiments 1 to 9 to a temperature higher than the activation temperature of the foaming agent. <Aspect 11> The filler according to embodiment 10, wherein, after humid storage at 99% relative humidity and 40°C for 3 days, curing at 160°C for 25 minutes results in an expansion rate of 400% to 1000%, preferably 450% to 900%, based on its volume in the unfoamed state; and after humid storage at 99% relative humidity and 40°C for 3 days, curing at 200°C for 40 minutes results in an expansion rate of 300% to 1000%, preferably 320% to 900%, more preferably 340% to 900%, based on its volume in the unfoamed state. <Aspect 12> Use of a pumpable, thermoplastic filler composition according to any one of embodiments 1 to 9 as a filler for enclosed spaces, particularly as a filler for enclosed spaces in vehicle components. <Aspect 13> A method for filling a sealed space, including the following steps: - A pumpable, heat-expandable filler composition according to any one of embodiments 1 to 9 is placed inside a sealed space, and - Heating the sealed space containing the pumpable, heat-expandable filler composition to a temperature higher than the activation temperature of the foaming agent to cause the filler to foam. <Aspect 14> The method according to embodiment 13, wherein the sealed space is a sealed space in a vehicle component. <Aspect 15> A vehicle component obtained by the method described in embodiment 13 or 14.

Claims

1. A pumpable, heat-expandable filler composition including the following: - A liquid epoxy resin in an amount of 8 to 30% by weight, based on the total weight of the pumpable, heat-expandable filler composition; - 5 to 40% by weight of polyvinyl chloride resin and / or acrylic resin powder, based on the total weight of the pumpable, heat-expandable filler composition; - A blowing agent in an amount of 1 to 10% by weight, based on the total weight of the pumpable, heat-expandable filler composition; and - Based on the total weight of the pumpable, heat-expandable filler composition, 1.25 to 4% by weight of at least one calcium or zinc salt of a fatty acid containing 16 or 18 carbon atoms.

2. The pumpable, heat-expandable filler composition according to claim 1, wherein the amount of calcium or zinc salt of the fatty acid containing 16 or 18 carbon atoms is 1.5 to 3% by weight, based on the total weight of the pumpable, heat-expandable filler composition.

3. The pumpable, heat-expandable filler composition according to claim 1 or 2, wherein the calcium or zinc salt of the fatty acid containing 16 or 18 carbon atoms is selected from the group consisting of calcium salt of palmitic acid, calcium salt of stearic acid, calcium salt of oleic acid, and calcium salt of linoleic acid.

4. The pumpable, heat-expandable filler composition according to claim 1 or 2, wherein the calcium or zinc salt of the fatty acid containing 16 or 18 carbon atoms is selected from the group consisting of zinc salt of palmitic acid, zinc salt of stearic acid, zinc salt of oleic acid, and zinc salt of linoleic acid.

5. A pumpable, heat-expandable filler composition according to any one of claims 1 to 4, characterized in that the liquid epoxy resin is of formula (I): 【Chemistry 1】 In the formula, R' and R'' are independently a hydrogen atom or a methyl group, and s has an average value between 0 and 1.

6. A pumpable, heat-expandable filler composition according to any one of claims 1 to 5, further comprising rubber.

7. A pumpable, heat-expandable filler composition according to any one of claims 1 to 6, further comprising at least one plasticizer.

8. A pumpable, thermoplastic filler composition according to any one of claims 1 to 7, further comprising a curing agent for the liquid epoxy resin.

9. A pumpable, heat-expandable filler composition according to any one of claims 1 to 8, further comprising one or more fillers.

10. A foamed filler obtained by heating a pumpable, heat-expandable filler composition according to any one of claims 1 to 9 to a temperature higher than the activation temperature of the foaming agent.

11. The filler according to claim 10, wherein after humid storage at 99% relative humidity and 40°C for 3 days, curing at 160°C for 25 minutes results in an expansion rate of 400% to 1000% relative to its volume in the unfoamed state; and after humid storage at 99% relative humidity and 40°C for 3 days, curing at 200°C for 40 minutes results in an expansion rate of 300% to 1000% relative to its volume in the unfoamed state.

12. Use of the pumpable, thermoplastic filler composition according to any one of claims 1 to 9 as a filler for enclosed spaces, particularly as a filler for enclosed spaces in vehicle components.

13. A method for filling a sealed space, including the following steps: - A pumpable, heat-expandable filler composition according to any one of claims 1 to 9 is placed inside a sealed space, and - Heat the sealed space containing the pumpable, heat-expandable filler composition to a temperature higher than the activation temperature of the foaming agent to cause the filler to foam.

14. The method according to claim 13, wherein the sealed space is a sealed space in a vehicle component.

15. A vehicle component obtained by the method described in claim 13 or 14.

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