WO2009128157A1 - Composition adhésive photodurcissable pour application sur une surface huileuse - Google Patents

Composition adhésive photodurcissable pour application sur une surface huileuse Download PDF

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Publication number
WO2009128157A1
WO2009128157A1 PCT/JP2008/057500 JP2008057500W WO2009128157A1 WO 2009128157 A1 WO2009128157 A1 WO 2009128157A1 JP 2008057500 W JP2008057500 W JP 2008057500W WO 2009128157 A1 WO2009128157 A1 WO 2009128157A1
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WO
WIPO (PCT)
Prior art keywords
meth
adhesive composition
oil surface
photocurable
surface adhesive
Prior art date
Application number
PCT/JP2008/057500
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English (en)
Japanese (ja)
Inventor
杉木　孝至
真起 岡田
新史 渡邊
Original Assignee
ニチバン株式会社
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Publication date
Application filed by ニチバン株式会社 filed Critical ニチバン株式会社
Priority to PCT/JP2008/057500 priority Critical patent/WO2009128157A1/fr
Publication of WO2009128157A1 publication Critical patent/WO2009128157A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • the present invention relates to a photocurable oil surface adhesive composition that exhibits high adhesiveness when applied to an adherend to which an oil component such as press oil or rust preventive oil is adhered and cured by light irradiation. More specifically, the present invention has a high degree of freedom in designing the viscosity of the composition before curing, and is cured in seconds by light irradiation, and the physical properties of the cured product can be freely designed from soft rubbery to hard.
  • the present invention relates to a photocurable oil surface adhesive composition that exhibits excellent adhesion to various oil surface adherends after curing, and is excellent in rust resistance, corrosion resistance, dust resistance, and waterproof properties.
  • Applications include coating agents (for example, bodies of automobiles, railway vehicles, ships, aircraft, etc., engine parts, metal building materials such as metal roofs and walls, and steel plates of home appliances (body panel materials, etc.) Primer, paint), sealing agent, damping material, reinforcing material, soundproofing material and the like.
  • a large amount of a sealing agent is used in an automobile body manufacturing process for rust prevention and corrosion prevention.
  • Auto bodies, doors, trunks, etc. are usually cold-rolled steel sheets, zinc phosphate steel sheets, aluminum alloys, etc., to which press oil, rust-preventing oil, etc. are attached, and then pressed with structural adhesives, spot welding, etc.
  • the base coat is applied.
  • a sealing agent is applied, and in order to cure it, it is usually heated at 100 to 120 ° C. for about 10 to 20 minutes in a dedicated oven. After that, it is completed by intermediate coating and top coating.
  • the sealing agent can be applied to the oil surface before the degreasing (oil cleaning) process, the process can be greatly rationalized.
  • the sealant can be applied before attaching the door, trunk, etc. before degreasing to the body, not only will it be unnecessary to remove them again after the undercoating, but there will be no manual operation after the undercoating. There is no risk of contamination.
  • a conventional thermosetting sealing agent can be cured with light in a short period of time, a dedicated oven is not required, resulting in significant energy savings.
  • thermosetting types and do not peel off in the subsequent degreasing process, and are cured in a drying furnace for undercoating. Since it flows in the degreasing process in the liquid state, it needs to be in the form of a sheet. Therefore, it has a drawback that it floats when it is pasted or air bubbles are easily involved.
  • installing an oven before the degreasing process requires equipment costs and enormous energy. Therefore, if there is a photo-curing liquid material that can be applied to the oil surface, the process can be greatly rationalized and the quality improved. Furthermore, if it is a light irradiation apparatus, it can be installed relatively inexpensively and uses much less energy.
  • the object of the present invention is to provide a material that can be applied even to a steel plate in which oil before the cleaning process is applied, to contribute to rationalization and quality improvement of the process, to eliminate the cleaning process and to reduce the environmental burden. Furthermore, it is to provide a photo-curing material instead of a thermosetting material, thereby contributing to a reduction in utility cost and time.
  • the present inventors have already used a (meth) acrylate monomer having a phenyl group as means for solving these problems in JP-A No. 2001-049237, JP-A No. 2002-226509, and PCT / JP2001 / 010529. Proposes a photocurable sealing agent composition having excellent oil surface adhesion. By these compositions, it is possible to remarkably save energy and increase productivity as compared with conventional thermosetting sealing agents.
  • the line may stop due to a holiday or abnormal process. Especially in the summer, it may be left for a long time under conditions of high temperature and humidity. After that, when the heating process was performed in the drying process of coating, a phenomenon was observed in which foaming occurred at the interface with the adherend or adhesiveness was lowered. This is presumably because, although the adhesiveness to the oil surface after photocuring is high, the slightly absorbed water moves to the interface by heating and decreases the adhesiveness of the interface. Therefore, intensive research was conducted to obtain a photocurable oil surface adhesive composition that can reduce the hygroscopicity after photocuring and further improve the adhesion to the oil surface.
  • the present invention provides (A) a (meth) acrylic acid ester having an alicyclic hydrocarbon group, (B) a diene elastomer, and (C) a polymerizable phosphoric acid having at least one (meth) acryloyl group.
  • the present invention relates to a photocurable oil surface adhesive composition containing an ester and (D) a photoradical polymerization initiator.
  • the diene elastomer (B) is a homopolymer of butadiene or isoprene, a hydrogenated polymer thereof, a copolymer of butadiene and isoprene, a hydrogenated polymer thereof, isoprene or butadiene and styrene. Or a hydrogenated polymer thereof, and the photocurable oil surface adhesive composition having a styrene content of 0 to 50% by weight.
  • the weight ratio of (A) (meth) acrylic acid ester having an alicyclic hydrocarbon group and (B) diene elastomer is 95/5 to 5/95, and (A) and ( (C) 0.1 to 20 parts by weight of a polymerizable phosphate ester having at least one (meth) acryloyl group, and (D) a radical photopolymerization initiator 0.01 to 10 parts per 100 parts by weight of B) It is related with the said photocurable oil surface adhesive composition containing a weight part.
  • the photocurable oil surface adhesive composition of the present invention can easily control the viscosity and hardness after curing depending on the composition ratio, and since it adheres strongly to the oil surface after curing, it can be used for oil surface steel plates. It can be used as a coating agent, sealing agent, damping material, reinforcing material, soundproofing material, etc. with excellent antirust, anticorrosion, dustproof and waterproof properties. And since it hardens
  • the component (A) according to the present invention is a (meth) acrylic acid ester having an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group is a hydrocarbon group containing a ring structure, and is a saturated or unsaturated monocyclic or polycyclic (for example, 2 to 4 ring) hydrocarbon group having 4 to 20 carbon atoms in total. possible.
  • (meth) acrylic acid ester which has an alicyclic hydrocarbon group of a component (A)
  • a component (A) For example, isobornyl (meth) acrylate, isophoronyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl ( (Meth) acrylate, menthyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (Meth) acrylate, tetracyclododecanylmethyl (meth) acrylate, adamantyl (meth) acrylate, dimethylol tricyclodecane diacrylate, trimethylol tricyclodecane diacrolein
  • (meth) acrylate monomers are commercially available.
  • isobornyl acrylate is manufactured by Kyoeisha Chemical Co., Ltd. under the trade name of light acrylate IB-XA
  • dicyclopentanyl acrylate is funcryl FA- It is available from Hitachi Chemical Co., Ltd. under the trade name 513A.
  • Those not commercially available can be easily synthesized by dehydration condensation reaction or transesterification reaction between (meth) acrylic acid and the corresponding alicyclic alcohol.
  • Examples of the diene elastomer of component (B) according to the present invention include homopolymers of dienes such as butadiene and isoprene or hydrogenated polymers thereof, copolymers of dienes or hydrogenated polymers thereof, or dienes.
  • styrene, butylene, propylene or ethylene and other hydrogenated polymers thereof are not particularly limited, but SBS (styrene-butadiene-styrene copolymer), SIS (styrene-isoprene- Styrene copolymer), SBBS (styrene-butadiene-butylene-styrene copolymer), SEBS (styrene-ethylene-butylene-styrene copolymer), SEPS (styrene-ethylene-propylene-styrene copolymer), SEP ( Styrene-ethylene-propylene copolymer), SEB (styrene-ethylene-butyl copolymer) Hydrogenated or non-hydrogenated styrene thermoplastic elastomer (diblock type, triblock type, side chain type), SBR (styrene-butadiene rubber), SIR (styrene-is
  • a butadiene or isoprene homopolymer a hydrogenated polymer thereof, a copolymer of butadiene and isoprene, a hydrogenated polymer thereof, a copolymer of butadiene or isoprene and styrene, or a hydrogenated polymer thereof, etc.
  • a styrene content of 0 to 50% by weight is preferred because of high oil surface adhesion.
  • the diene elastomer of component (B) absorbs oil applied to the steel sheet and can affect physical properties such as elastic modulus and elongation after curing.
  • Component (C) is a polymerizable phosphoric acid ester having at least one (meth) acryloyl group.
  • Such polymerizable phosphoric acid esters are commercially available, and for example, JPA-514 (Johoku Chemical Co., Ltd.), Light Acrylate P-1A (Kyoeisha Chemical Co., Ltd.) and the like are available.
  • Component (C) can impart adhesion to the steel sheet.
  • the radical photopolymerization initiator of component (D) is not particularly limited, and generally used, for example, organic peroxides, benzoin compounds, acetophenones, benzophenones, thioxanthones, ⁇ -acyloxime esters , Phenyl glyoxylates, benzyls, azo compounds, diphenyl disulfide compounds, acyl phosphine oxide compounds, organic dye compounds, iron-phthalocyanine compounds, etc., in particular, benzoin compounds, acetophenones, Preferred examples include benzophenones and acylphosphine oxide compounds. These may be used in combination.
  • the photocurable oil surface adhesive composition according to the present invention is not limited to other polymerizable monomers and oligomers as long as the photoreactivity and oil surface adhesion are not hindered in order to adjust Tg, viscosity, and impart hardness and elongation.
  • organic and inorganic fillers such as silica, talc, calcium carbonate, mica, diatomaceous earth, apatite, cross-linked acrylic beads, and cross-linked polystyrene beads may be added to impart impact resistance and flexibility at low temperatures.
  • Plasticizers such as phthalate esters, liquid resins, and oils may be added.
  • flame retardants such as aluminum hydroxide, surfactants, oil-absorbing resins, organic / inorganic pigments, light stabilizers, light absorbers, antioxidants, and other parts where light is difficult to reach or thick coatings as necessary
  • a thermal reaction initiator such as an organic peroxide may be contained.
  • the viscosity of the photocurable oil surface adhesive composition according to the present invention varies depending on the intended application method, and it is necessary to make the viscosity as low as it is necessary to apply thinly.
  • the coating agent or paint to be applied is preferably about 0.1 to 20 Pa ⁇ s (1 s ⁇ 1 , 20 ° C.), preferably when used as a sealing agent, a damping material or a reinforcing material to be applied in a thickness of millimeters. 10 to 1000 Pa ⁇ s (1 s ⁇ 1 , 20 ° C.).
  • the viscosity of the photocurable oil surface adhesive composition according to the present invention is greatly influenced by the weight ratio of the component (A) and the component (B), and increases as the molecular weight of the component (B) increases and as the amount increases. Sticky.
  • the viscosity was measured at 20 ° C. and a shear rate of 1 s ⁇ 1 using a Physica MCR301, 25 mmf cone plate type probe manufactured by Anton Paar.
  • the contents of the component (A) and the component (B) are set depending on the amount of oil of the adherend and desired physical properties in addition to the viscosity.
  • the weight ratio of the component (A) to the component (B) is preferably 5/95 to 95/5, more preferably 20/80 to 80/20.
  • the photocurable oil surface adhesive composition according to the present invention preferably contains 0.1 to 20 parts by weight of component (C) with respect to 100 parts by weight of the total of components (A) and (B). More preferably, 1 to 10 parts by weight, and component (D) is contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, depending on the coating thickness.
  • the photocurable oil surface adhesive composition according to the present invention can be usually produced by stirring, dissolving or dispersing, and degassing the above components with a high-speed stirrer or the like.
  • the photocurable oil surface adhesive composition according to the present invention is applied to an adherend according to the same method of use as known sealing agents and coating agents, and cured by light irradiation with an appropriate light source.
  • the light source used in the present invention may be any device that generates light such as UV, electron beam, infrared, etc.
  • Low-pressure mercury lamp chemical lamp, germicidal lamp, health line fluorescent lamp, black lamp, excimer laser, LED, and the like. You may combine these several light sources.
  • the composition shown in Table 1 was uniformly stirred and dispersed with a high-speed stirrer and vacuum degassed. In either case, a transparent or translucent paste or liquid was obtained. This was applied to a zinc phosphate steel plate coated with 3 g / m 2 of a rust preventive oil (Platinol B804 / 3, manufactured by Oest), and 5 by a Fusion F600V, D bulb (2.5 W / cm 2 , UVA). Irradiated for 2 seconds. As a result, all the blend compositions were cured within 5 seconds. Immediately after that, the case of heating at 180 ° C. for 30 minutes was compared with the case of heating at 180 ° C. for 30 minutes after standing for 1 week in an atmosphere of 35 ° C. ⁇ 80% RH after photocuring. As a result, as shown in Table 1, none showed foaming after heating, showed good adhesion, and almost no rust was observed even in a 1000 h salt spray test (cross cut).
  • Photocurability ⁇ Completely cured, no surface tack, ⁇ Surface tack, ⁇ Uncured part, Oil surface adhesion: ⁇ Strongly adhered, ⁇ Easy to peel, ⁇ Almost non-adhesive salt spray test: ⁇ Rust Almost no occurrence (within 0.5 mm from the cut part), ⁇ slightly rusted (within 1 mm from the cut part), ⁇ rusted within 3 mm from the cut part, and rust generated at 3 mm or more from the cut part
  • Light Acrylate IB-XA Kyoeisha Co., Ltd. Funkrill FA-513A: Hitachi Chemical Co., Ltd.
  • Light Acrylate DCP-A Kyoeisha Co., Ltd. Clayton G1657: Clayton Japan Co., Ltd.
  • Tuftec 126 Asahi Kasei Co., Ltd.
  • LIR310 Kuraray Co., Ltd.
  • LIR390 Kuraray Co., Ltd.
  • Light Acrylate P-1A Kyoeisha Co., Ltd.
  • Darocur 1173 Ciba Specialty Chemicals Co., Ltd.
  • Photocurability ⁇ Completely cured, no surface tack, ⁇ Surface tack, ⁇ Uncured part, Oil surface adhesion: ⁇ Strongly adhered, ⁇ Easy to peel, ⁇ Almost non-adhesive salt spray test: ⁇ Rust Almost no occurrence (within 0.5 mm from the cut part), ⁇ slightly rusted (within 1 mm from the cut part), ⁇ rusted within 3 mm from the cut part, and rust generated at 3 mm or more from the cut part
  • Light Acrylate IB-XA Kyoeisha Co., Ltd. Fankrill FA-513A: Hitachi Chemical Co., Ltd.
  • Light Acrylate LA Kyoeisha Co., Ltd.
  • Light Acrylate P200A Kyoeisha Co., Ltd. Clayton G1657: Clayton Japan Co., Ltd. : Nippon Zeon Co., Ltd.
  • Light acrylate P-1A Kyoeisha Co., Ltd.
  • Darocur 1173 Ciba Specialty Chemicals Co., Ltd.
  • the photocurable oil surface adhesive composition of the present invention is a coating agent, sealing agent, vibration damping material, reinforcing material, and soundproofing material with excellent rust, corrosion resistance, dust resistance, and waterproof properties that can be used for oil surface steel sheets. Can be used as etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition adhésive photodurcissable pour application sur des surfaces huileuses, dont l'hygroscopicité peut être réduite et qui présente une meilleure adhésion aux surfaces huileuses après photodurcissement. Elle comprend (A) un ester (méth)acrylique contenant un groupe hydrocarboné alicyclique, (B) un élastomère diénique, (C) un ester phosphorique polymérisable contenant au moins un groupe (méth)acryloyle, et (D) un initiateur de photopolymérisation par les radicaux libres.
PCT/JP2008/057500 2008-04-17 2008-04-17 Composition adhésive photodurcissable pour application sur une surface huileuse WO2009128157A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/057500 WO2009128157A1 (fr) 2008-04-17 2008-04-17 Composition adhésive photodurcissable pour application sur une surface huileuse

Applications Claiming Priority (1)

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PCT/JP2008/057500 WO2009128157A1 (fr) 2008-04-17 2008-04-17 Composition adhésive photodurcissable pour application sur une surface huileuse

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634765A (zh) * 2016-12-16 2017-05-10 深圳市华星光电技术有限公司 黑色封口胶与lcd异形屏及其制作方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05125329A (ja) * 1991-11-06 1993-05-21 Daihachi Chem Ind Co Ltd 活性エネルギー線硬化型接着剤組成物
JPH07138332A (ja) * 1993-11-19 1995-05-30 Nippon Zeon Co Ltd 紫外線硬化性組成物、該組成物を用いた接着剤層を有する成形品、および成形品の接着方法
JP2002226509A (ja) * 2001-02-05 2002-08-14 Nichiban Co Ltd 光硬化型油面接着性組成物
JP2007056119A (ja) * 2005-08-24 2007-03-08 Nichiban Co Ltd 光遅延硬化型油面用接着剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05125329A (ja) * 1991-11-06 1993-05-21 Daihachi Chem Ind Co Ltd 活性エネルギー線硬化型接着剤組成物
JPH07138332A (ja) * 1993-11-19 1995-05-30 Nippon Zeon Co Ltd 紫外線硬化性組成物、該組成物を用いた接着剤層を有する成形品、および成形品の接着方法
JP2002226509A (ja) * 2001-02-05 2002-08-14 Nichiban Co Ltd 光硬化型油面接着性組成物
JP2007056119A (ja) * 2005-08-24 2007-03-08 Nichiban Co Ltd 光遅延硬化型油面用接着剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634765A (zh) * 2016-12-16 2017-05-10 深圳市华星光电技术有限公司 黑色封口胶与lcd异形屏及其制作方法

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