JP5344876B2 - UV pre-curing sealant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet ray precuring sealant which is used for cover panels and the like produced by the Heming method and can effectively prevent blister due to thermal expansion of internal minute spaces or air bubbles in baking and heating. <P>SOLUTION: The ultraviolet ray precuring sealant includes 50 pts.wt. of an acryl resin, 35 pts.wt. of DINP (diisononyl phthalate) as a plasticizer, 35 pts.wt. of OBzP (octylbenzil phthalate), a bulking agent comprising 35 pts.wt. of calcium carbonate (small grain) and 70 pts.wt. of calcium carbonate (large grain), 22 pts.wt. of a cohesiveness-imparting agent, 5 pts.wt. of a bubble inhibitor, and 31 pts.wt. of an ultraviolet curing resin material. An opening is coated with the ultraviolet ray precuring sealant and then exposed to ultraviolet ray for 1 second or 10 seconds for precuring. Even when the resultant is then placed under conditions where it is heated and then minute spaces or air bubbles contained therewithin are thermally expanded, no blister is generated. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an ultraviolet pre-curing sealing material containing an ultraviolet-curing resin material and having a sealing function such as water-tightness and air-tightness, and in particular, can suppress the occurrence of blistering during heating for paint baking. The present invention relates to an ultraviolet pre-curing sealant that can be produced. Here, in the present specification, claims, drawings, and abstract, the “ultraviolet curable resin material” is an organic material that is cured by irradiation of ultraviolet rays, and includes not only a polymer but also an oligomer. , Monomers, and mixtures thereof.

  Heat-curing type sealing materials are applied to joints such as lid panels of vehicles such as automobiles to provide a sealing function (watertight, airtight, etc.). As such sealing materials, vinyl chloride resin is used. A heat-sealing type vinyl chloride resin-based sealing material is mainly used from the viewpoints of cost and ease of handling. This vinyl chloride resin-based sealing material is in the form of a paste at room temperature, and is simultaneously cured into an elastomer during heating and baking in the subsequent coating process.

  On the other hand, lid panels such as doors and hoods (bonnets) are constructed by a hemming method in which the end of the outer panel is bent and fixed after applying a rust-proof adhesive to the mating part. Microscopic spaces and bubbles are likely to be generated, and the paste-like sealing material applied from above the folded part will cause a swelling phenomenon due to thermal expansion of the internal microscopic spaces and bubbles during heat curing, and it will look good in appearance. Not only did it worsen, but when the swelling increased, bubbles were broken and water tightness could not be secured, causing water leakage and rusting.

  Therefore, in the vinyl chloride resin-based sealing material, for example, there is an invention of a hem portion adhesive sealing method for a vehicle body panel described in Patent Document 1 as an object to solve such a problem. In the invention described in this Patent Document 1, it is possible to press at a lower pressure than before by adding glass beads of 100 μm to 300 μm in the adhesive used in the hemming process, and the sealing used for the plate joining portion If 3% or more of a thermosetting material is added to the material so that the strength at 150 ° C. is 50 kPa or more, swelling or the like can be effectively prevented or reduced.

Moreover, in the invention of the photocurable sealing agent for automobiles described in Patent Document 2 and the construction method using the same, a photocurable resin, a monomer, a filler, a thermoplastic resin or polyisobutylene, a photoreaction initiator, Disclosed is a photo-curing sealing agent for automobiles containing a thermal reaction initiator, and this sealing material can be confirmed in a short time by applying UV light after coating and correcting, and by subsequent heating. It is said that it will further harden and become excellent in adhesion to the electrodeposition coated plate.
JP 2004-026070 A Japanese Patent Laid-Open No. 06-116546

  However, in the technique described in the above-mentioned Patent Document 1, since the swelling phenomenon due to the thermal expansion of the internal minute space and bubbles is generally generated in the temperature rising process of 40 ° C. or higher, the strength at 150 ° C. is 50 kPa or higher. However, since the swelling phenomenon has already occurred before that, the swelling cannot be reliably prevented. In addition, since the technique described in Patent Document 2 is intended only for confirming the finished state in a short time, it effectively and reliably prevents the bulging phenomenon caused by thermal expansion of the minute internal spaces and bubbles. There was a problem that could not be done.

  Accordingly, the present invention has been made to solve such problems, and in a sealing material used for a lid panel or the like manufactured by a hemming method, an internal minute space or air bubble caused by heating during paint baking is used. It is an object of the present invention to provide an ultraviolet pre-curing sealing material that can effectively and reliably prevent blistering caused by thermal expansion.

  The ultraviolet curable sealing material according to the invention of claim 1 contains an ultraviolet curable resin material, and the content of the ultraviolet curable resin material is in the range of 5 wt% to 25 wt%, more preferably 5 wt%. % To 15% by weight of a sealing material having a hardness of 20 to 60 as measured by an Asker C-type rubber hardness tester after being cured by irradiation with ultraviolet light or light containing ultraviolet light. Within the range, more preferably within the range of 30-60.

  Here, the “hardness measured with an Asker C-type rubber hardness meter” is a value measured using an Asker C-type rubber hardness meter, which is a type of durometer, and is “SRIS0101”, a standard of the Japan Rubber Association. The hardness by.

Further, it contains an acrylic resin and / or vinyl chloride resin, a plasticizer, a filler, and an anti-bubble agent, and the content of the acrylic resin and / or vinyl chloride resin is from 15% by weight to 20%. The plasticizer content is in the range of 20 wt% to 30 wt%, the filler content is in the range of 30 wt% to 45 wt%, and the bubbles The content of the inhibitor is in the range of 1.0% to 2.0% by weight.

  As used herein, “acrylic resin” broadly includes acrylic resin and methacrylic resin, and means a single polymer or copolymer of a monomer selected from acrylic acid alkyl ester, methacrylic acid alkyl ester, and the like. Specific examples of these monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. As such, various monomers can be used.

  Further, the “vinyl chloride resin” refers to a homopolymer of vinyl chloride, a copolymer with vinyl acetate, and a mixture thereof. Furthermore, as the “plasticizer”, diisononyl phthalate (DINP), octylbenzyl phthalate (OBzP), dioctyl phthalate (DOP), and the like can be used. As the “filler”, calcium carbonate, barium sulfate, calcium sulfate, talc, diatomaceous earth, clay, mica, and the like can be used. Furthermore, calcium oxide (CaO), magnesium oxide (MgO), or the like can be used as the “anti-bubble agent”.

The ultraviolet pre-curing sealant according to the invention of claim 2 further comprises an adhesion imparting agent in the configuration of claim 1 . Here, as the “adhesion imparting agent”, a block urethane prepolymer, a polyamidoamine, or the like can be used. Adeka Resin QR-1636-2, Adeka Hardener EH4070S, Adeka Hardener EH4358S, and the like can be used.

The ultraviolet pre-curing sealing material according to the invention of claim 3 is the structure of claim 1 or claim 2 , wherein the ultraviolet curable resin material contains a urethane-modified acrylic oligomer and does not contain a polyester-modified acrylic oligomer. Is. Here, more specifically, “ADEKA RESIN QR9299 manufactured by ADEKA Corporation” or the like can be used as the “urethane-modified acrylic oligomer”.

  The ultraviolet pre-curing sealing material according to the invention of claim 1 contains an ultraviolet curable resin material, the content of which is in the range of 5 wt% to 25 wt%, and includes ultraviolet irradiation or light containing ultraviolet light. The surface is cured by irradiation, and the hardness measured with an Asker C-type rubber hardness meter after surface curing is in the range of 20-60. The inventors of the present invention have conducted extensive experimental research on methods for effectively preventing blistering due to heating during paint baking in sealing materials used for lid panels manufactured by the hemming method. It has been found that swelling can be effectively prevented by blending an appropriate amount of resin material, and the present invention has been completed based on this finding.

  That is, by including the ultraviolet curable resin material in the range of 5 wt% to 25 wt% in the sealing material, the surface hardness according to “SRIS0101” after the ultraviolet precuring becomes in the range of 20 to 60. Even when coated and heated and baked from above, the surface hardness is 20 or more, so that it has sufficient strength, it is possible to suppress swelling due to thermal expansion of internal bubbles, and since the surface hardness is 60 or less, sufficient It has flexibility and does not crack.

  Here, when the content of the ultraviolet curable resin material is in the range of 5% by weight to 15% by weight, the surface hardness according to “SRIS0101” after the ultraviolet preliminary curing is more surely in the range of 20-60. More preferable. Further, it is more preferable that the surface hardness according to “SRIS0101” after ultraviolet pre-curing is in the range of 30 to 60, because it is possible to more reliably suppress the expansion due to the thermal expansion of the internal bubbles.

  In this way, in sealing materials used for lid panels and the like manufactured by the hemming method, it is possible to effectively and reliably prevent bulging caused by thermal expansion of microscopic spaces and bubbles due to heating during paint baking. It becomes an ultraviolet pre-curing sealant that can be used.

An acrylic resin and / or a vinyl chloride resin is contained within a range of 15 wt% to 20 wt%, a plasticizer is contained within a range of 20 wt% to 30 wt%, and a filler is 30 wt%. In addition to the effect of the invention according to claim 1, ultraviolet preliminarily cured since it contains in the range of ˜45 wt% and the antifoaming agent is contained in the range of 1.0 wt% to 2.0 wt%. It is possible to maintain the swelling suppression, flexibility, and adhesion of the subsequent sealing material coating film.

In the ultraviolet pre-curing sealant according to the invention of claim 2 , in addition to the effect of claim 1 by further containing an adhesion-imparting agent, a large amount of ultraviolet curable resin material (5 wt% to 25 wt%). Even when blended (within a range of% by weight), the adhesion of the sealant coating film can be reliably maintained. In addition, it is preferable to make content of an adhesive provision agent into the range of 5 weight%-8 weight%.

In the ultraviolet pre-curing sealing material according to the invention of claim 3 , the ultraviolet curable resin material contains a urethane-modified acrylic oligomer and does not contain a polyester-modified acrylic oligomer . In addition to the effect , the flexibility when the urethane-modified acrylic oligomer is UV-cured is utilized, and the surface hardness according to “SRIS0101” after UV pre-curing can be more reliably reduced to 60 or less. The film has sufficient flexibility.

  Hereinafter, an embodiment of the present invention will be described with reference to FIG. FIG. 1 is an explanatory diagram showing a method for evaluating swelling suppression of an ultraviolet curable sealing material according to an embodiment of the present invention. First, the blending components and blending ratio of the ultraviolet curable sealing material according to the embodiment of the present invention will be described.

  In the ultraviolet curable sealing material according to the present embodiment, an acrylic monomer, urethane-modified acrylic oligomer, hydroxyalkylphenone, bisacylphosphine oxide is used as the “ultraviolet curable resin material”, and Shin Nakamura is used as the acrylic monomer. NK ester APG400 manufactured by Chemical Industry Co., Ltd., Adeka Resin QR9299 manufactured by ADEKA Co., Ltd. as urethane-modified acrylic oligomer, Irgacure 184 manufactured by Ciba Japan Co., Ltd. as hydroxyalkylphenone, and bisacylphosphine oxide Used Irgacure 819 manufactured by Ciba Japan Co., Ltd.

  Also, “Dainar LP-3105 manufactured by Mitsubishi Rayon Co., Ltd.” as “acrylic resin”, PCH-22 manufactured by Kaneka Co., Ltd. as “vinyl chloride resin (copolymer type)”, and vinyl chloride resin (homo “Polymer type” as P-100 manufactured by Vitec Corporation, and “plasticizer” as diisononyl phthalate (DINP) manufactured by J Plus Co., Ltd. and octylbenzyl phthalate (OBzP) manufactured by J Plus Co., Ltd. , Respectively.

  Furthermore, as a “filler”, a mixture of fine calcium carbonate and coarse calcium carbonate is used, Viscolite OS manufactured by Shiraishi Kogyo Co., Ltd. is used as fine calcium carbonate, and Takehara Chemical Industry is used as coarse calcium carbonate. Heavy calcium carbonate manufactured by Co., Ltd. was used. Further, QC-X manufactured by Inoue Lime Industry Co., Ltd., which is calcium oxide (CaO), was used as the “foam inhibitor”, and D-80 manufactured by ExxonMobil Co., Ltd. was used as the “thickening agent”.

  Furthermore, as an “adhesion imparting agent”, a block urethane prepolymer and a polyamidoamine are used, Adeka Resin QR9428 manufactured by ADEKA Co., Ltd. as Block Urethane Prepolymer A, and Adeka Resin manufactured by ADEKA Co., Ltd. as Block Urethane Prepolymer B QR-1636-2I was used as ADEKA Hardener EH4070 manufactured by ADEKA Corporation as polyamideamine A, and ADEKA HARDNER EH4358S manufactured by ADEKA Corporation was used as polyamideamine B, respectively.

  These blends were mixed to prepare three types of ultraviolet pre-curing sealants from Example 1 to Example 3. For comparison, four types of comparative sealing materials from Comparative Example 1 to Comparative Example 4 were prepared. In Comparative Example 3, Aronix A8060 manufactured by Toa Synthetic Chemical Co., Ltd. was used as the polyester-modified acrylic oligomer as the “ultraviolet curable resin material”. Table 1 shows the blending components and blending ratios of the seven types of sealing materials of Examples 1 to 3 and Comparative Examples 1 to 4.

  As shown in Table 1, the compounding amount of the plasticizer is unified at a total of 70 parts by weight (DINP 35 parts by weight, OBzP 35 parts by weight) in the ultraviolet pre-curing sealants of Examples 1 to 3, and the viscosity is reduced. The blending amount of the agent D-80 was changed to 15 parts by weight in Examples 1 and 2 and 8 parts by weight in Example 3. Similarly, regarding the blending amount of calcium carbonate as a filler, Examples 1 and 2 total 105 parts by weight (35 parts by weight of fine particles, 70 parts by weight of coarse particles), and Example 3 has a total of 118 parts by weight (78 parts by weight of fine particles). Part and 40 parts by weight of coarse particles).

  The UV pre-curing sealing material according to Examples 1 and 2 is mainly composed of an acrylic resin, the blending amount of the acrylic resin is 50 parts by weight, and a block as an adhesion imparting agent for the acrylic resin. The amount of urethane prepolymer A is 20 parts by weight, and the amount of polyamidoamine A is 2 parts by weight. On the other hand, the ultraviolet pre-curing sealant according to Example 3 is mainly composed of vinyl chloride resin, and the total amount of vinyl chloride resin is 48 parts by weight (copolymer type 28 parts by weight, homopolymer type 20 parts by weight), The blending amount of the block urethane prepolymer B as an adhesion-imparting agent for the vinyl chloride resin is 20 parts by weight, and the blending amount of the polyamidoamine B is 2 parts by weight.

  The blending amount of the anti-bubble agent QC-X is standardized at 5 parts by weight in the ultraviolet precured sealing materials of Examples 1 to 3. On the other hand, the acrylic monomer, urethane-modified acrylic oligomer, hydroxyalkylphenone, and bisacylphosphine oxide as the “ultraviolet curable resin material” were 5 parts by weight, 25 parts by weight, and 0.5 parts by weight in Examples 1 and 3, respectively. In the second embodiment, 3 parts by weight, 12 parts by weight, 0.5 parts by weight, and 0.5 parts by weight (16 parts by weight in total) are used. ) And less.

  As described above, the ultraviolet pre-curing sealing material of Example 1 is mainly composed of an acrylic resin, and an acrylic monomer, a urethane-modified acrylic oligomer, a hydroxyalkylphenone, and a bisacylphosphine oxide are combined as an ultraviolet curable resin material. About 10.4% by weight is used. In comparison with this, the ultraviolet pre-curing type sealing material of Example 2 was obtained by reducing the amount of the ultraviolet curable resin material by about half (about 5.65% by weight). The sealing material is mainly composed of vinyl chloride resin instead of acrylic resin.

  On the other hand, in the sealing material according to the comparative example, the comparative example 1 is obtained by removing the ultraviolet curable resin material from the blending mainly of the acrylic resin of the first example, and the comparative example 2 is the third example. UV curable resin material is excluded from the composition mainly composed of vinyl chloride resin. Therefore, Comparative Examples 1 and 2 are not ultraviolet pre-curing sealing materials.

  Comparative Example 3 has the same blending ratio as Example 1, but uses a polyester-modified acrylic oligomer instead of a urethane-modified acrylic oligomer as an acrylic oligomer that is an ultraviolet curable resin material. Furthermore, in Comparative Example 4, the amount of the ultraviolet curable resin material was increased based on the formulation of Example 3 as compared with Example 3.

  About seven kinds of sealing materials of Examples 1 to 3 and Comparative Examples 1 to 4 having such a composition, ultraviolet (UV) curability, UV curing hardness, swelling suppression, flexibility and adhesion The performance evaluation about was carried out.

  As a UV curable evaluation method, an inner diameter of 30 mm, a depth of five kinds of sealing materials of Examples 1 to 3 and Comparative Examples 3 and 4 excluding Comparative Examples 1 and 2 not containing an ultraviolet curable resin material were used. An excess sealing material was removed using a spatula or the like in which a 15 mm thick Aznole petri dish was filled to a depth or more and the end face was linear so that the surface layer was constant. The surface layer of the sample thus prepared was subjected to UV irradiation using a UV irradiation apparatus at a distance from the UV lamp of 20 cm and irradiation times of 1 second and 10 seconds.

As the UV irradiation device, a UV irradiation device manufactured by Eye Graphics Co., Ltd. (metal halide lamp, output 1.5 kW, illuminance 192 mW / cm ² (when the irradiation distance is 20 cm, center wavelength 365 nm)) was used. Therefore, when the irradiation time is 1 second, the integrated light amount is 192 mJ / cm ² , and when the irradiation time is 10 seconds, the integrated light amount is 1920 mJ / cm ² . After irradiation, the cured portion of the surface layer of the sealing material was cut out and the uncured portion was removed, and then the cured film thickness was measured using calipers or the like.

  In addition, as an evaluation method of the UV curing hardness, the UV cured parts produced by the above method are overlapped so that the thickness becomes 10 mm or more, and the hardness (by Japan Rubber Association) is measured using an Asker C type rubber hardness meter. Hardness based on the standard “SRIS0101” was measured.

  Next, a method for evaluating swelling suppression will be described with reference to FIG. First, as shown in FIG. 1 (a), a thermosetting epoxy adhesive 4 is applied to a steel plate 3 of 70 mm × 150 mm × 0.8 mm subjected to electrodeposition coating, as shown in FIG. It was applied so as to have a thickness of 0.2 mm to 0.3 mm in the pattern shown. Then, a 35 mm × 150 mm × 0.8 mm steel plate 2 that has also been subjected to electrodeposition coating is bonded together and heated to cure the epoxy adhesive 4, and the opening as shown in FIG. A specimen 1 having a space of a predetermined size inside 5 was prepared.

  With respect to this specimen 1, seven kinds of sealing materials of Examples 1 to 3 and Comparative Examples 1 to 4 were respectively closed so as to close each opening 5 from above each opening 5. It applied to the dimension of 10 mm and thickness 2mm. And after performing UV irradiation as it is or, after putting into the dryer adjusted to 140 degreeC for 30 minutes, it took out from the dryer and evaluated the presence or absence and the magnitude | size of swelling. As evaluation criteria, those having a bulge size of 10 mm or more in diameter or a bulge height of 0.5 mm or more x, those having a bulge size of less than 10 mm in diameter and bulge height of less than 0.5 mm The case where the occurrence of blistering was not observed was rated as ◯.

  In addition, as a method for evaluating flexibility, seven types of sealing materials of Examples 1 to 3 and Comparative Examples 1 to 4 were formed on a 70 mm × 150 mm × 0.8 mm steel plate subjected to electrodeposition coating. Were applied so as to have a width of 10 mm, a length of 100 mm, and a thickness of 2 mm, respectively. And after performing UV irradiation as it is or after being put into a drier adjusted to 140 ° C. for 30 minutes, after taking out from the drier and allowing to cool to room temperature, the specimen is wrapped around a round steel tube having a diameter of 1 inch, When cracking occurred in the sealing material, it was evaluated as x, and when cracking did not occur in the sealing material, it was evaluated as ○.

  Furthermore, as a method for evaluating adhesion, seven kinds of sealing materials of Examples 1 to 3 and Comparative Examples 1 to 4 are formed on a 70 mm × 150 mm × 0.8 mm steel plate subjected to electrodeposition coating. Are applied so that the width is 10 mm, the length is 100 mm, and the thickness is 2 mm, respectively, or after being irradiated with UV, the mixture is put into a dryer adjusted to 140 ° C. for 30 minutes, taken out from the dryer and brought to room temperature. After standing to cool, a peel test was conducted with nails and the like. Then, the destruction state was observed with an optical microscope, and the case where the destruction state was interfacial failure was evaluated as x, the case where trace destruction was caused was evaluated as Δ, and the case where aggregation destruction was observed was evaluated as ○. The above evaluation results are summarized in Table 2.

  As shown in Table 2, there is no significant difference between the five types of sealing materials of the evaluated Examples 1 to 3 and Comparative Examples 3 and 4 with respect to the cured UV film thickness. As for UV curing hardness, Examples 1 to 3 and Comparative Example 4 all have a hardness measured with an Asker C-type rubber hardness meter in the range of 20 to 60, whereas a polyester-modified acrylic oligomer. In Comparative Example 3 using Aronix A8060 manufactured by Toa Gosei Chemical Co., Ltd., the hardness exceeds 60 in both cases of irradiation time of 1 second and 10 seconds.

  As a result, the sealing material of Comparative Example 3 was cracked in the evaluation of flexibility and was evaluated as x. Therefore, in order to ensure sufficient flexibility in the UV pre-curing sealant, the hardness measured with an Asker C-type rubber hardness tester, which is a type of durometer (a hardness based on the “SRIS0101” standard of the Japan Rubber Association) ) Is required to be 60 or less.

  In addition, as for swelling suppression, in the case of “no UV irradiation”, since any sealing material remains in a paste state, it naturally becomes blistering and is evaluated as x. However, when UV irradiation is performed for 10 seconds The UV pre-curing sealants of Examples 1 to 3 were all evaluated as ◯, and no blistering occurred. Further, when UV irradiation was carried out for only 1 second, Example 1 was evaluated as “Good”, but Examples 2 and 3 were evaluated as “Good”, and small swelling occurred.

  Therefore, it is clear that among the ultraviolet pre-curing sealing material according to the present embodiment, it is more preferable to use a certain amount or more (10% by weight or more) of the ultraviolet curable resin material mainly composed of acrylic resin. became. In Comparative Examples 3 and 4, even when UV irradiation was carried out for only 1 second, no blistering occurred, so the hardness (hardness based on “SRIS0101”) measured with an Asker C-type rubber hardness meter was 20 In addition to being in the range of ˜60, it has become clear that it is more preferably 30 or more.

  Further, regarding the adhesion, in all of Examples 1 to 3, the fracture state in the peel test was cohesive failure, and the adhesion was excellent. On the other hand, about the comparative example 4 which used many ultraviolet curable resin materials, the destruction state in a peeling test was trace destruction or interface destruction, and adhesiveness was insufficient. Therefore, it has become clear that it is more preferable that the amount of the ultraviolet curable resin material used is a certain amount or less (25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less).

  When the above evaluation results were combined, it was found that the sealing materials of Comparative Examples 1 to 4 had problems in any of swelling suppression, flexibility, and adhesion, and could not be practically used as a sealing material. On the other hand, the ultraviolet precuring type sealing material 1 of Examples 1 to 3 has passed all the tests of swelling suppression, flexibility and adhesion, and has excellent characteristics as a sealing material. It became clear.

  Therefore, the content of the ultraviolet curable resin material is within the range of 5% by weight to 25% by weight in the sealing material that is used for the cover panel manufactured by the hemming method and has a minute space or bubbles inside. More preferably, the hardness is in the range of 5 to 15% by weight, the surface is cured by irradiation with ultraviolet rays or light containing ultraviolet rays, and the hardness measured by an Asker C-type rubber hardness meter after surface curing is 20 to It has been proved that the condition of being in the range of 60, more preferably in the range of 30-60, has to be met.

  As described above, in the ultraviolet pre-curing type sealing materials of Examples 1 to 3 according to the present embodiment, in the sealing material used for the lid panel manufactured by the hemming method, the interior by heating at the time of coating baking is used. It is possible to effectively prevent swelling caused by the minute space and thermal expansion of bubbles.

  That is, the ultraviolet pre-curing sealant of Examples 1 to 3 according to the present embodiment is applied to a construction part containing a minute space or bubbles inside, such as a lid panel manufactured by a hemming method. Then, after pre-curing by irradiating with ultraviolet rays, paint is applied from above, for example, by heating to 140 ° C., for example, a blister due to thermal expansion of minute internal spaces and bubbles is generated. It can be cured while maintaining flexibility and adhesion, and the construction part can be sealed.

  Therefore, in this specification, not only the inventions according to claims 1 to 5 of the claims are described but also the “ultraviolet rays described in any one of claims 1 to 5”. There is also described an invention of a “sealing material construction method characterized in that a pre-curing type sealing material is applied to a construction part and pre-cured by irradiating ultraviolet rays and then heated to seal the construction part” .

  In the present embodiment, the case where an acrylic resin or a vinyl chloride resin is blended alone has been described, but an acrylic resin and a vinyl chloride resin can be mixed and used. Moreover, although the case where the copolymer type and the homopolymer type were mixed and used as the “vinyl chloride resin” was described, the copolymer type or the homopolymer type can also be used alone.

  Furthermore, in the present embodiment, the case of using the dialal LP-3105 manufactured by Mitsubishi Rayon Co., Ltd. as the “acrylic resin” has been described, but the “acrylic resin” is not limited thereto. A single polymer or copolymer of monomers widely selected from alkyl acrylates and alkyl methacrylates can be used. Specific examples of these monomers include methyl acrylate, ethyl acrylate, and acrylic acid. Various monomers such as n-butyl, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like can be used.

  In the present embodiment, the case where calcium carbonate is used as the “filler” has been described. However, the present invention is not limited to this, and barium sulfate, calcium sulfate, talc, diatomaceous earth, clay, mica, Etc. can be used. Furthermore, in the present embodiment, the case where calcium oxide (CaO) is used as the “anti-bubble agent” has been described, but magnesium oxide (MgO) or the like can also be used.

  In this embodiment, the case where diisononyl phthalate (DINP) and octylbenzyl phthalate (OBzP) are mixed and used as the “plasticizer” has been described. However, these plasticizers may be used alone. In addition, dioctyl phthalate (DOP) or the like can also be used.

  In carrying out the present invention, the configuration, composition, blending, components, shape, quantity, material, size, manufacturing method, etc. of other parts of the UV pre-curing sealing material are also described in the present embodiment and each example. It is not limited to. Note that the numerical values given in the embodiments of the present invention are not all critical values, and certain numerical values indicate preferred values suitable for implementation, so even if the numerical values are slightly changed. The implementation is not denied.

FIG. 1 is an explanatory diagram showing a method for evaluating swelling suppression of an ultraviolet curable sealing material according to an embodiment of the present invention.

Claims (3)

After containing the ultraviolet curable resin material, the content of the ultraviolet curable resin material is in the range of 5% by weight to 25% by weight, and the surface is cured by irradiation with ultraviolet rays or light including ultraviolet rays. In the ultraviolet pre-curing type sealing material having a hardness measured by an Asker C-type rubber hardness meter in the range of 20 to 60,
The content of acrylic resin and / or vinyl chloride resin is in the range of 15 wt% to 20 wt%, the content of plasticizer is in the range of 20 wt% to 30 wt%, and the inclusion of filler An ultraviolet precuring type sealing material, wherein the amount is in the range of 30 wt% to 45 wt%, and the content of the antifoaming agent is in the range of 1.0 wt% to 2.0 wt%. The ultraviolet pre-curing sealing material according to claim 1, further comprising an adhesion-imparting agent. The ultraviolet curable resin material according to claim 1 or 2, wherein the ultraviolet curable resin material contains a urethane-modified acrylic oligomer and does not contain a polyester-modified acrylic oligomer.

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