JP2012121981A - Repairing material - Google Patents

Repairing material Download PDF

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JP2012121981A
JP2012121981A JP2010273375A JP2010273375A JP2012121981A JP 2012121981 A JP2012121981 A JP 2012121981A JP 2010273375 A JP2010273375 A JP 2010273375A JP 2010273375 A JP2010273375 A JP 2010273375A JP 2012121981 A JP2012121981 A JP 2012121981A
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JP5358552B2 (en
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Kenji Muto
憲二 武藤
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Abstract

PROBLEM TO BE SOLVED: To provide an easily handleable and storable repairing material which can perform easily a repair work to an object to be repaired.SOLUTION: This repairing material 1 includes a solid sheet body 7 formed by sticking a powder agent 3 containing polymer powder of (meth)acrylate and a polymerization initiator causing polymerization of a (meth)acrylate monomer onto a reinforcing cloth body 2 by a synthetic resin emulsion adhesive 4. The repairing material 1 is constituted of the solid sheet body 7 and (meth)acrylate monomer liquid 8 to be polymerized by being added to the solid sheet body 7. The synthetic resin emulsion adhesive 4 is a vinyl acetate resin emulsion adhesive or the like. The reinforcing cloth body 2 is a glass fiber fabric or the like. The repairing material 1 also includes a material formed by adding a liquid-impermeable sheet not allowing passage of (meth)acrylate monomer liquid onto the bottom surface of the solid sheet body 7.

Description

本発明は、メタクリレートまたはアクリレート(以下、これらを(メタ)アクリレートと略称する)を主剤として含むものであって、被補修物の接着、肉盛り、造形などの補修に使用される補修材に関するものである。   The present invention relates to a repair material used for repair such as adhesion, build-up, and modeling of a repair object, which contains methacrylate or acrylate (hereinafter, abbreviated as (meth) acrylate) as a main agent. It is.

従来、この種の補修材としては、重合開始剤および(メタ)アクリレートポリマーを共に含有している粉剤と、(メタ)アクリレートモノマーの液剤とから成る補修材が知られている。
そして、下記の特許文献1には、過酸化ベンゾイルが併存しているメタクリル酸メチルのポリマー粉末と、ポリ酢酸ビニルを添加したメタクリル酸メチルのモノマー液とから成る成型材料が記載されている。この成型材料は、ポリマー粉末とモノマー液を混合して所望形状に成形し、重合・硬化させて歯科用の成型材料を得るようにしたものである。
Conventionally, as this type of repair material, a repair material comprising a powder containing both a polymerization initiator and a (meth) acrylate polymer and a liquid agent of a (meth) acrylate monomer is known.
Patent Document 1 below describes a molding material comprising a polymer powder of methyl methacrylate coexisting with benzoyl peroxide and a monomer liquid of methyl methacrylate to which polyvinyl acetate is added. This molding material is obtained by mixing a polymer powder and a monomer liquid to form a desired shape, and polymerizing and curing to obtain a dental molding material.

特開平11−140128号公報(明細書の段落[0015]〜[0024])JP 11-140128 A (paragraphs [0015] to [0024] of the specification)

上記した特許文献1記載の成型材料は、(メタ)アクリレートのポリマー粉末と重合開始剤とを含んで成る粉剤と、(メタ)アクリレートのモノマー液と、酢酸ビニルとを備えているが、この成型材料で使用されるポリ酢酸ビニルは粉末側でなくモノマー液側に添加されている。その使用目的は硬化時の成形体収縮率を所定値以下に下げて成型寸法誤差を小さく抑えることであり、補強用布体へ粉剤を付着させるためではない。そして、この成型材料は補修・補強を行なうために使用されるものでないから、補強用布体は用いない。従って、粉剤は必ず型内に入れなければならないが、粉剤を入れる際に散らばったり手指が触れて汚れたりするおそれがあって、取扱いと保管に多大な注意を必要としていた。   The molding material described in Patent Document 1 includes a powder containing a polymer powder of (meth) acrylate and a polymerization initiator, a monomer liquid of (meth) acrylate, and vinyl acetate. Polyvinyl acetate used in the material is added not to the powder side but to the monomer liquid side. The purpose of use is to reduce the shrinkage ratio of the molded body at the time of curing to a predetermined value or less to suppress a molding dimensional error, and not to adhere the powder to the reinforcing cloth body. And since this molding material is not used for repair and reinforcement, a reinforcing cloth body is not used. Therefore, the powder must be put in the mold. However, when the powder is put, it may be scattered or get dirty by touching with fingers, and handling and storage are required with great care.

本発明は、上記した従来の問題点に鑑みてなされたものであって、取扱いや保管がしやすく、被補修物への補修作業を容易に行なうことのできる補修材の提供を目的とする。   The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a repair material that is easy to handle and store and can easily perform repair work on a repaired object.

上記目的を達成するために、本発明に係る補修材は、(メタ)アクリレートのポリマー粉末と(メタ)アクリレートモノマーの重合を引き起こす重合開始剤とを含んで成る粉剤を合成樹脂エマルジョン接着剤により補強用布体に付着させた固形シート体を備えている構成にしてある。   In order to achieve the above object, the repair material according to the present invention reinforces a powder comprising a (meth) acrylate polymer powder and a polymerization initiator causing polymerization of a (meth) acrylate monomer with a synthetic resin emulsion adhesive. It is set as the structure provided with the solid sheet body adhered to the cloth body.

また、前記構成において、固形シート体の底面に、(メタ)アクリレートのモノマー液を通さない不通液シートが添付されているものである。   Moreover, the said structure WHEREIN: The liquid impervious sheet which does not let the monomer liquid of (meth) acrylate pass is attached to the bottom face of a solid sheet body.

そして、前記した各構成において、合成樹脂エマルジョン接着剤が、酢酸ビニル樹脂エマルジョン接着剤であるものである。   And in each above-mentioned structure, a synthetic resin emulsion adhesive is a vinyl acetate resin emulsion adhesive.

更に、前記した各構成において、補強用布体が、ガラス繊維を原料として織成された織布であるものである。   Further, in each of the above-described configurations, the reinforcing cloth body is a woven cloth woven using glass fibers as a raw material.

また、前記した各構成において、(メタ)アクリレートのポリマー粉末と(メタ)アクリレートモノマーの重合を引き起こす重合開始剤とを含んで成る粉剤を合成樹脂エマルジョン接着剤により補強用布体に付着させた固形シート体と、当該固形シート体に添加されて重合する(メタ)アクリレートのモノマー液と、から成るものである。   Further, in each of the above-described constitutions, a solid comprising a powder comprising (meth) acrylate polymer powder and a polymerization initiator causing polymerization of the (meth) acrylate monomer attached to the reinforcing fabric with a synthetic resin emulsion adhesive. It consists of a sheet body and a monomer liquid of (meth) acrylate which is added to the solid sheet body and polymerizes.

本発明に係る補修材によれば、ポリマー粉末と重合開始剤とを含んで成る粉剤を合成樹脂エマルジョン接着剤により補強用布体に付着させた固形シート体を使用するので、固形シート体が定形性を有していることから、粉剤が補強用布体からポロポロ落ちて散らばるということがなく、商品として取扱いや保管がしやすい。また、ハサミやカッターナイフでカットしても型崩れしにくく、必要な時に必要な分だけ使用できるので無駄がない。無論、補強用布体を有しているので、被補修部位の機械的強度を高くすることができる。そして、補強用布体に均一に粉剤を分配させた場合、被補修物の表面に粉剤を万遍なく広く分布させることができる。また、モノマー液も万遍なく添加しやすく添加量の調整が楽である。そして、固形シート体はモノマー液の添加により柔軟化して自在に変形できるため、被補修部位の形状に拘束されることなく、補修、および肉盛りなどの造形を容易に行なうことができる。また、被補修部位に馴染みやすいから、補修跡の表面が滑らかであり、補修跡は見た目に自然で美しく被補修物の基体と一体化したような外観を呈する。   According to the repair material according to the present invention, since the solid sheet body in which the powder containing the polymer powder and the polymerization initiator is adhered to the reinforcing cloth body with the synthetic resin emulsion adhesive is used, the solid sheet body has a fixed shape. Therefore, it is easy to handle and store as a product without the powder falling from the reinforcing cloth and scattered. In addition, even if it is cut with scissors or a cutter knife, it is hard to lose its shape, and it can be used as much as necessary, so there is no waste. Of course, since the reinforcing cloth body is provided, the mechanical strength of the repaired portion can be increased. When the powder is evenly distributed on the reinforcing cloth body, the powder can be uniformly and widely distributed on the surface of the repair object. In addition, it is easy to add the monomer solution evenly and the adjustment of the addition amount is easy. Since the solid sheet body can be flexibly deformed by the addition of the monomer liquid and can be freely deformed, it is possible to easily perform repairing and shaping such as overlaying without being restricted by the shape of the repaired part. In addition, since the surface of the repaired track is smooth because it is easy to become familiar with the repaired part, the repaired track has a natural and beautiful appearance that is integrated with the base of the repaired object.

また、固形シート体の底面に、(メタ)アクリレートのモノマー液を通さない不通液シートが添付されているものでは、固形シート体の保管および陳列時において破損や型崩れを抑制でき、ハサミなどで固形シート体をカットする際も型崩れの抑制ができる。従って、固形シート体の下に敷く合成樹脂シートやテーブルを別途準備しなくても、モノマー液を固形シート体に含浸させた後に、指先を汚すことなくそのまま被補修部位に貼り付けて補修作業ができる。固形シート体に添加して含浸したモノマー液は不通液シート上で収受されて漏れないので、固形シート体内に留まって無駄なく使用される。また、不通液シートが固形シート体の片面に密着している状態でモノマーが重合し硬化するので、仕上り面に光沢が得られてきれいになるという効果もある。   In addition, when a liquid-impervious sheet that does not allow the (meth) acrylate monomer liquid to pass through is attached to the bottom of the solid sheet body, it is possible to suppress breakage and loss of shape during storage and display of the solid sheet body. Even when the solid sheet body is cut, the deformation of the shape can be suppressed. Therefore, even if a synthetic resin sheet or table laid under the solid sheet body is not separately prepared, after the monomer liquid is impregnated into the solid sheet body, the repair work can be performed by directly applying it to the repaired site without soiling the fingertip. it can. Since the monomer liquid added and impregnated into the solid sheet body is received on the liquid-impervious sheet and does not leak, it remains in the solid sheet body and is used without waste. In addition, since the monomer is polymerized and cured in a state where the liquid-impervious sheet is in close contact with one side of the solid sheet body, there is an effect that gloss is obtained on the finished surface and the surface is clean.

そして、合成樹脂エマルジョン接着剤として酢酸ビニル樹脂エマルジョン接着剤を用いた固形シート体は、当該接着剤が入手容易で安価であり、補強用布体の繊維表面にポリマーの粉剤を付着させる付着力も大である。また、酢酸ビニル樹脂エマルジョン接着剤は、モノマー液を添加された固形シート体が被補修部分に接着されたのち、モノマーの重合により硬化して得られたポリマーの機械的強度、表面光沢、耐候性が高く、他の種類の合成樹脂エマルジョン接着剤を用いた場合よりも格段に優れていた。   The solid sheet body using the vinyl acetate resin emulsion adhesive as the synthetic resin emulsion adhesive is readily available and inexpensive, and has an adhesive force for attaching the polymer powder to the fiber surface of the reinforcing fabric. It ’s big. In addition, the vinyl acetate resin emulsion adhesive is the mechanical strength, surface gloss, and weather resistance of the polymer obtained by curing the monomer by polymerizing the solid sheet after adding the monomer liquid to the repaired part. It was much higher than when other types of synthetic resin emulsion adhesives were used.

更に、前記した各構成において、補強用布体としてガラス繊維を原料として織成された織布を用いたものでは、当該ガラス繊維織布が入手容易で安価であり機械的強度および耐候性も比較的大きい。また、ガラス繊維織布で構成されているFRPに馴染みやすいので、FRPの補修・補強に好適となる。   Further, in each of the above-described configurations, when the woven fabric woven from glass fiber is used as the reinforcing fabric, the glass fiber woven fabric is easily available and inexpensive, and the mechanical strength and weather resistance are also compared. Big. Moreover, since it is easy to become familiar with FRP comprised with the glass fiber woven fabric, it becomes suitable for repair and reinforcement of FRP.

本発明の一実施形態に係る補修材の固形シート体を構成する材料を示す概略外観図である。It is a schematic external view which shows the material which comprises the solid sheet body of the repair material which concerns on one Embodiment of this invention. 前記補修材を示しA部拡大部分を有する側面図である。It is a side view which shows the said repair material and has an A section enlarged part. 底面に不通液シートを添付された補修材の側面図である。It is a side view of the repair material which attached the liquid-impervious sheet to the bottom.

次に、本発明の実施形態を説明するが、以下に述べる実施形態は本発明を具体化した一例に過ぎず、本発明の技術的範囲を限定するものでない。
本発明に用いるポリマー粉末を構成する「(メタ)アクリレート」の種類は、CH2=C(−R)COOX(RはHまたはMe)で表される(メタ)アクリル酸エステルであってXがアルキル基であるものであれば、特に限定されない。そのうち、アクリル酸アルキルエステルとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n−ブチル、アクリル酸t−ブチル、アクリル酸シクロヘキシル、アクリル酸2−エチルヘキシルなどが挙げられる。また、メタクリル酸アルキルエステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−ブチル、メタクリル酸t−ブチル、メタクリル酸シクロヘキシル、メタクリル酸2−エチルヘキシルなどが例示される。これらのうち、入手容易な点で汎用のメタクリル酸メチルやメタクリル酸エチルが、本発明において最も好ましく使用される。また、これらの(メタ)アクリレートは単独でも、もしくは2種類以上の混合物であってもよい。
Next, embodiments of the present invention will be described. However, the embodiments described below are merely examples embodying the present invention, and do not limit the technical scope of the present invention.
The kind of “(meth) acrylate” constituting the polymer powder used in the present invention is a (meth) acrylic acid ester represented by CH 2 ═C (—R) COOX (R is H or Me), and X is If it is an alkyl group, it will not specifically limit. Among them, examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and the like. Of these, general-purpose methyl methacrylate and ethyl methacrylate are most preferably used in the present invention because they are easily available. In addition, these (meth) acrylates may be used alone or as a mixture of two or more.

本発明に用いる(メタ)アクリレートの「ポリマー粉末」は、(メタ)アクリレートモノマーの重合により得られたポリマーを粉砕手段により微粉化させたものである。ポリマー粉末の粒径は、取扱いが容易であること、モノマー液との混合によりスラリー状になりやすいこと、モノマー重合後はその重合体と強固に結合することを満たすものであれば特に限定されないが、粉末の取り扱いやすさおよび粉末の製造容易性の観点から、例えば50〜100μmの平均粒径であることが好ましい。ポリマーを粉砕する手段としては特に限定されないが、例えば破砕機と粉砕機が挙げられる。   The “polymer powder” of (meth) acrylate used in the present invention is obtained by pulverizing a polymer obtained by polymerization of a (meth) acrylate monomer by a pulverizing means. The particle diameter of the polymer powder is not particularly limited as long as it is easy to handle, easily becomes a slurry by mixing with the monomer liquid, and firmly bonds to the polymer after the monomer polymerization. From the viewpoint of ease of handling the powder and ease of production of the powder, the average particle size is preferably, for example, 50 to 100 μm. The means for pulverizing the polymer is not particularly limited, and examples thereof include a crusher and a pulverizer.

上記したポリマー粉末の原材料として、例えば(メタ)アクリレート樹脂製品の成形不良品など廃プラスチックを粉砕化して用いると、資源の有効利用と原料コストの低下を図ることができる。このような廃プラスチックを破砕してポリマー粉末を得る場合は、破砕対象物の形状、材質などに応じて、それらに適合する破砕・粉砕手段を選択することが望ましい。前記した破砕化および粉砕化を行なう場合は、まず2軸破砕機で粗砕きして大粒の粒体を得、次に1軸破砕機で細粒化するとよい。続いて、粉砕機により所望粒径のポリマー粉末が得られる。ここで用いる粉砕機としては特に限定されないが、例えばハンマーミル、ローラーミル、ディスクミル、ボールミルなどが挙げられる。それらのうち、ハンマーミルを用いて平均粒径50〜100μmの粉体が得られる。   For example, when waste plastic such as a molding failure product of a (meth) acrylate resin product is pulverized and used as the raw material of the above-described polymer powder, it is possible to effectively use resources and reduce raw material costs. When polymer powder is obtained by crushing such waste plastic, it is desirable to select a crushing and crushing means suitable for the shape and material of the crushing object. When the above-mentioned crushing and pulverization are performed, it is preferable to first roughly crush with a biaxial crusher to obtain large particles, and then to refine with a uniaxial crusher. Subsequently, a polymer powder having a desired particle diameter is obtained by a pulverizer. Although it does not specifically limit as a grinder used here, For example, a hammer mill, a roller mill, a disk mill, a ball mill etc. are mentioned. Among them, a powder having an average particle size of 50 to 100 μm is obtained using a hammer mill.

本発明に用いる「重合開始剤」は、(メタ)アクリレートモノマーのラジカル重合を引き起こす触媒であって安定性の高いものであれば特に限定されない。この重合開始剤は、重合後の例えば(メタ)アクリレートポリマーに併存している。かかる重合開始剤としては、例えば過酸化ベンゾイル(BPO)、ジ−tert−ブチルペルオキシド、tert−ブチルヒドロペルオキシド、メチルエチルケトンペルオキシドなどの有機過酸化物や、アゾビスイソブチロニトリル(AIBN)、1,1'-アゾビス(シクロヘキサンカルボニトリル(ABCN)などのアゾ化合物、またはジハロゲンなどが挙げられる。これらのうち、過酸化ベンゾイルとアゾビスイソブチロニトリルが、安価で入手容易ならびに高い安定性の観点から、本発明において望ましく使用される。重合開始剤を用いてラジカル重合を終えた(メタ)アクリレートのポリマーには重合開始剤が安定に残存している。従って、そのポリマーの成型品を用いることにより、重合開始剤を新たに添加することなく、ポリマーに併存していたものをそのまま再利用することができる。但し、重合開始剤が足りない場合は、新たな重合開始剤を追加してもよい。   The “polymerization initiator” used in the present invention is not particularly limited as long as it is a catalyst that causes radical polymerization of a (meth) acrylate monomer and has high stability. This polymerization initiator coexists in, for example, (meth) acrylate polymer after polymerization. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide (BPO), di-tert-butyl peroxide, tert-butyl hydroperoxide, and methyl ethyl ketone peroxide, azobisisobutyronitrile (AIBN), 1, Examples thereof include azo compounds such as 1′-azobis (cyclohexanecarbonitrile (ABCN)), dihalogen, etc. Among these, benzoyl peroxide and azobisisobutyronitrile are inexpensive, easily available, and from the viewpoint of high stability. In the present invention, the polymerization initiator remains stable in the polymer of (meth) acrylate that has been radically polymerized using the polymerization initiator. Without adding a new polymerization initiator What was present together can be reused. However, if the polymerization initiator is insufficient, it may add new polymerization initiators.

本発明の「粉体」は、上記のように(メタ)アクリレートのポリマーから得られたポリマー粉末と、このポリマー粉末に付随している重合開始剤との混合物、または、この混合物に新たな重合開始剤を加えた混合物を主成分として含むものである。本発明の粉体には、例えばシリカ、炭酸カルシウム、アスベストロービングなどの充填材を適量加えることも可能である。   The “powder” of the present invention is a mixture of a polymer powder obtained from a polymer of (meth) acrylate as described above and a polymerization initiator attached to the polymer powder, or a new polymerization in this mixture. A mixture containing an initiator is included as a main component. An appropriate amount of a filler such as silica, calcium carbonate or asbestos roving can be added to the powder of the present invention.

本発明に用いる「補強用布体」としては、モノマー重合後の補修部分の機械的強度を高く保持できる基体となり得るものであれば特に限定されないが、例えばガラス繊維織布、炭素繊維織布、アラミド繊維織布、ビニロン繊維織布、繊維織布などが挙げられる。   The “reinforcing fabric” used in the present invention is not particularly limited as long as it can be a substrate capable of maintaining a high mechanical strength of the repaired portion after monomer polymerization. For example, a glass fiber woven fabric, a carbon fiber woven fabric, Examples include aramid fiber woven fabric, vinylon fiber woven fabric, and fiber woven fabric.

本発明に用いる「合成樹脂エマルジョン接着剤」としては、前記した粉体を補強用布体の繊維表面にしっかり付着させて担持できるものであって、且つ、補修時にモノマーの重合により得られたポリマー構造の機械的強度を損なわせることのないものであれば特に限定されない。このような合成樹脂エマルジョン接着剤としては、例えば酢酸ビニル樹脂エマルジョン接着剤、アクリル樹脂エマルジョン接着剤、エチレン−酢酸ビニル樹脂エマルジョン接着剤、エポキシ樹脂エマルジョン接着剤などが挙げられる。前記の粉体と合成樹脂エマルジョン接着剤の使用割合は、例えば粉体100重量部に対し合成樹脂エマルジョン接着剤20〜25重量部である。   As the “synthetic resin emulsion adhesive” used in the present invention, the above-mentioned powder can be firmly attached to the fiber surface of the reinforcing fabric and supported, and the polymer obtained by polymerization of monomers at the time of repair There is no particular limitation as long as the mechanical strength of the structure is not impaired. Examples of such synthetic resin emulsion adhesives include vinyl acetate resin emulsion adhesives, acrylic resin emulsion adhesives, ethylene-vinyl acetate resin emulsion adhesives, and epoxy resin emulsion adhesives. The use ratio of the powder and the synthetic resin emulsion adhesive is, for example, 20 to 25 parts by weight of the synthetic resin emulsion adhesive with respect to 100 parts by weight of the powder.

補強用布体の繊維表面にポリマーの粉剤を合成樹脂エマルジョン接着剤で付着させると、補修用の「固形シート体」が得られる。このように(メタ)アクリレートのポリマー粉を接着剤で補強用布体に付着させたものはこれまでに開発されていない。
この補修材の固形シート体について図を参照して説明する。図1に示すように、繊維2A,2Aで平織りされた補強用布体2にポリマーの粉剤3を付着させる態様としては、例えば粉剤3と合成樹脂エマルジョン接着剤4の液を混合し、この混合物をスプレーガンで補強用布体2に吹き付けた後に乾燥、またはロールや刷毛で塗布した後に乾燥させる態様、あるいは補強用布体2の表面に粉剤3をまぶし、これを合成樹脂エマルジョン接着剤4の液中にドブ漬けして取り出した後に乾燥させる態様などが挙げられる。これらの場合、合成樹脂エマルジョン接着剤4には予め水5などの分散媒を加え適度な粘度の水溶液として用いることが好ましい。
When a polymer powder is adhered to the fiber surface of the reinforcing fabric with a synthetic resin emulsion adhesive, a “solid sheet” for repair is obtained. Thus, the thing which adhered the polymer powder of (meth) acrylate to the reinforcing cloth body with the adhesive agent has not been developed so far.
The solid sheet body of the repair material will be described with reference to the drawings. As shown in FIG. 1, as a mode in which the polymer powder 3 is adhered to the reinforcing fabric 2 plain-woven with the fibers 2A and 2A, for example, a mixture of the powder 3 and the synthetic resin emulsion adhesive 4 is mixed, and this mixture Is sprayed onto the reinforcing cloth body 2 with a spray gun and dried, or applied with a roll or brush, and then dried, or the surface of the reinforcing cloth body 2 is coated with the powder 3, and this is coated with the synthetic resin emulsion adhesive 4. The aspect etc. which are made to drip in a liquid and take out after drying are mentioned. In these cases, it is preferable to add a dispersion medium such as water 5 to the synthetic resin emulsion adhesive 4 in advance and use it as an aqueous solution having an appropriate viscosity.

前記のように得られた固形シート体7は、図2に示すように、(メタ)アクリレートのモノマー液8で湿潤すると柔軟化して自由に変形し得る。一方、固形シート体7の粉剤3中には重合開始剤が含まれている。そこで、固形シート体7にモノマー液8が添加されると、粉剤3中の重合開始剤の触媒作用によりモノマーの重合反応が始まり、室温で短時間のうちに重合が進み、重合して得られたポリマーが各種素材に接着しながら硬化する。
かかる(メタ)アクリレートのモノマー液としては、常温で液体のものであれば特に限定されないが、そのうち、アクリル酸アルキルエステルとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n−ブチル、アクリル酸t−ブチル、アクリル酸シクロヘキシル、アクリル酸2−エチルヘキシルなどが挙げられる。また、メタクリル酸アルキルエステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−ブチル、メタクリル酸t−ブチル、メタクリル酸シクロヘキシル、メタクリル酸2−エチルヘキシルなどが例示される。これらのうち、入手容易な点で汎用のメタクリル酸メチルやメタクリル酸メチルが、本発明において最も好ましく使用される。また、これらのモノマーは単独でも、もしくは2種類以上の混合物であってもよい。これらのモノマー液には、適宜の副資材を加えることができる。かかる副資材としては、ヒドロキノン、フェノチアジン、ヒドロキノン誘導体、フェノチアジン誘導体などの重合禁止剤、ジアルキルフタレート、エポキシ系フタレート、ジオクチルセバケート、塩素化パラフィンなどの可塑剤、BHT,MDP,DLTDT,TNTなどの抗酸化剤、フェニルサリチレートなどの紫外線吸収剤、または着色剤などが挙げられる。
すなわち、前記したモノマー液8と、上記した固形シート体7とから、本実施形態の補修材1が構成される。
As shown in FIG. 2, the solid sheet body 7 obtained as described above can be softened and freely deformed when wetted with the monomer liquid 8 of (meth) acrylate. On the other hand, a polymerization initiator is contained in the powder 3 of the solid sheet body 7. Therefore, when the monomer liquid 8 is added to the solid sheet body 7, the polymerization reaction of the monomer starts by the catalytic action of the polymerization initiator in the powder 3, and the polymerization proceeds and polymerizes in a short time at room temperature. The polymer is cured while adhering to various materials.
The monomer liquid of (meth) acrylate is not particularly limited as long as it is liquid at room temperature. Among them, examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, and acrylic acid. Examples include t-butyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and the like. Of these, general-purpose methyl methacrylate and methyl methacrylate are most preferably used in the present invention because they are easily available. These monomers may be used alone or as a mixture of two or more. Appropriate auxiliary materials can be added to these monomer solutions. Examples of such auxiliary materials include polymerization inhibitors such as hydroquinone, phenothiazine, hydroquinone derivatives, and phenothiazine derivatives, plasticizers such as dialkyl phthalates, epoxy phthalates, dioctyl sebacate, and chlorinated paraffin, and anti-resins such as BHT, MDP, DLTDT, and TNT. Examples thereof include an oxidizing agent, an ultraviolet absorber such as phenyl salicylate, and a coloring agent.
That is, the repair material 1 of this embodiment is composed of the monomer liquid 8 and the solid sheet body 7 described above.

また、本実施形態では、図3に示すように、(メタ)アクリレートのモノマー液を通さない「不通液シート6」を、固形シート体7の底面7Aに添付することも可能である。かかる不通液シートとしては、例えば、ポリ塩化ビニリデン、ポリ塩化ビニル、低密度ポリエチレン、低密度ポリプロピレン、延伸ポリプロピレン、またはポリエチレンテレフタレートなどの材質から成るシートまたはフィルムが挙げられる。当該不通液シートは、モノマー液と反応せずモノマー液に溶解することなく、かつ、手の力で容易に変形するものであれば十分である。この不通液シートの厚さは特に限定されないが、取扱いやすさおよび入手容易の観点から例えば厚さ0.01〜0.03mm程度のものが好ましい。   In the present embodiment, as shown in FIG. 3, a “non-liquid-permeable sheet 6” that does not allow the monomer liquid of (meth) acrylate to pass can be attached to the bottom surface 7 </ b> A of the solid sheet body 7. Examples of the liquid-impervious sheet include a sheet or film made of a material such as polyvinylidene chloride, polyvinyl chloride, low density polyethylene, low density polypropylene, stretched polypropylene, or polyethylene terephthalate. The liquid-impervious sheet is sufficient if it does not react with the monomer liquid, does not dissolve in the monomer liquid, and can be easily deformed by hand force. The thickness of the liquid-impervious sheet is not particularly limited, but is preferably about 0.01 to 0.03 mm in thickness from the viewpoint of ease of handling and availability.

上記のように固形シート体7およびモノマー液8から成る補修材1を用いて被補修物に補修作業を行なう作業例を説明する。まず、被補修物における被補修部位およびその周辺の表面を粗目のサンドペーパーなどで削って、汚れ、塗装、及び油分を十分に落としておく。一方で、被補修部位の大きさに合わせて、固形シート体7および不通液シート6をハサミやカッターナイフで必要な大きさにカットする。そして、固形シート体7を載せるために別途用意した、モノマー液と反応しないポリエチレン製などの合成樹脂シート、あるいは皿の上に、不通液シート6を下にした状態の固形シート体7を置く。この場合、不通液シート6を取り外した後の固形シート体7を合成樹脂シートや皿の上に直に置いても構わない。次に、固形シート体7の上面7Bにモノマー液8を滴下し、シート全体に万遍なく浸透させるように十分な量を振りかけていく。すると、固形シート体7は変形自在に柔らかくなる。気温が高いと重合硬化反応が促進されるので、前記の作業は素早く行うことが好ましい。固形シート体7および不通液シート6を合成樹脂シートごと手にとって、固形シート体7を被補修部位に湿布のように貼り付ける。合成樹脂シートの表面を指先で押さえて、固形シート体7全体を被補修部位に馴染ませる。固形シート体7が固まるのを待って合成樹脂シートおよび不通液シート6を固形シート体7から剥がすと、補修作業が完了する。尚、被補修部位の強度を更に持たせたい時は、複数の固形シート体7,7,7,・・・を重ねて貼り付けることで、強力な補強を行なうことができる。   A working example of performing repair work on a repaired object using the repair material 1 composed of the solid sheet body 7 and the monomer liquid 8 as described above will be described. First, the part to be repaired and the surface around the part to be repaired are shaved with a coarse sandpaper or the like to sufficiently remove dirt, paint, and oil. On the other hand, the solid sheet body 7 and the liquid-impervious sheet 6 are cut into a necessary size with scissors or a cutter knife in accordance with the size of the repaired part. Then, the solid sheet body 7 in a state where the liquid-impervious sheet 6 is placed down is placed on a synthetic resin sheet or the like made of polyethylene that does not react with the monomer liquid, or a dish prepared separately for mounting the solid sheet body 7. In this case, the solid sheet body 7 after removing the liquid-impervious sheet 6 may be placed directly on a synthetic resin sheet or a dish. Next, the monomer liquid 8 is dropped on the upper surface 7B of the solid sheet body 7, and a sufficient amount is sprinkled over the entire sheet so as to penetrate evenly. Then, the solid sheet body 7 becomes soft and deformable. Since the polymerization curing reaction is promoted when the temperature is high, the above operation is preferably performed quickly. The solid sheet body 7 and the liquid-impervious sheet 6 are put together with the synthetic resin sheet, and the solid sheet body 7 is affixed to the repair site like a compress. The surface of the synthetic resin sheet is pressed with a fingertip, and the entire solid sheet body 7 is made to conform to the repaired part. When the solid sheet 7 is solidified and the synthetic resin sheet and the liquid-impervious sheet 6 are peeled off from the solid sheet 7, the repair work is completed. In addition, when it is desired to further increase the strength of the repaired portion, it is possible to perform strong reinforcement by stacking a plurality of solid sheet bodies 7, 7, 7,.

上記したように、本発明の補修材において、固形シート体は商品としての定形性を確保することができる。合成樹脂エマルジョン接着剤によってポリマー粉末を補強用布体に付着させているので、粉剤が補強用布体からポロポロ落ちたりせず、ハサミやカッターナイフでカットしても型崩れしない。また、必要な時に必要な分だけ使用できるので無駄がない。すなわち、この固形シート体は取り扱い方法が単純で煩わしさがなく、誰でも簡単にFRP製品などの補修を個人差のバラツキなく行える。また、固形シート体長期間の保存が可能で、開封後も特別な管理が不要である。固形シート体は平面状に成型されたものであっても切れ込みを入れておきモノマー液をかけると曲面が得られるので、容易に曲面の補修・補強ができる。この場合、切れ込みを入れるための型紙を予め作っておくと便利である。モノマー硬化後は、その表面に塗装やメッキなどの仕上げ処理を行なうができる。モノマー硬化後は(メタ)アクリレート樹脂になるから毒性が無く安全である。上記のスプレー方式は、従来の刷毛や塗布ロールを用いるハンドレイアップ方式と比べ、種々材料・ツールの準備、材料の計量、混合、含浸などの手間が省けるので、トータルコストが安く済む。一方、食品衛生法上では、ガラス繊維が露出しないことを条件としてFRPの使用が食品を扱う機械に認められている。従って、本発明に係る固形シート体も同じ条件下で食品用機械への使用が認められるものと考えられる。また、本発明に係る固形シート体は安全性が高いことから、食品を扱う機械類の補修にも適用可能である。   As described above, in the repair material of the present invention, the solid sheet body can ensure regularity as a product. Since the polymer powder is adhered to the reinforcing fabric by the synthetic resin emulsion adhesive, the powder does not fall off from the reinforcing fabric, and does not lose its shape even if it is cut with scissors or a cutter knife. In addition, there is no waste because it can be used only when necessary. That is, this solid sheet body is simple in handling method, and anyone can easily repair FRP products and the like without variation among individuals. Moreover, the solid sheet body can be stored for a long time, and no special management is required even after opening. Even if the solid sheet body is formed into a flat shape, a curved surface can be obtained by applying a monomer solution with a notch, and the curved surface can be easily repaired and reinforced. In this case, it is convenient to make a pattern for making a cut in advance. After the monomer is cured, the surface can be subjected to finishing treatment such as painting or plating. After the monomer is cured, it becomes a (meth) acrylate resin and is safe without toxicity. Compared to the conventional hand lay-up method using a brush or coating roll, the spray method described above can save the total cost because it eliminates the trouble of preparing various materials and tools, weighing materials, mixing and impregnation. On the other hand, under the Food Sanitation Law, the use of FRP is permitted for machines that handle food, provided that the glass fibers are not exposed. Therefore, it is considered that the solid sheet according to the present invention can be used for food machinery under the same conditions. Moreover, since the solid sheet body according to the present invention has high safety, it can be applied to repair of machinery for handling food.

そして、不通液シートを固形シート体の片面に添付した場合は、次のような利点が考えられる。固形シート体の保管および陳列時においても、破損・型崩れを抑制でき、ハサミなどで固形シート体を切断する際も型崩れの抑制ができる。また、固形シート体を載せる合成樹脂シートやテーブルを別途準備しなくても、モノマー液を固形シート体に含浸させた後に、指先を汚すことなくそのまま被補修部位に貼り付けて補修作業ができる。不通液シートが固形シート体の片面に密着している状態でモノマーが重合して硬化するので、仕上り面に光沢が得られてきれいになるという効果がある。   And when a liquid-impervious sheet is attached to one side of the solid sheet body, the following advantages can be considered. Even at the time of storage and display of the solid sheet body, it is possible to suppress breakage and loss of shape, and also when the solid sheet body is cut with scissors or the like, the deformation of shape can be suppressed. Further, even if a synthetic resin sheet or a table on which the solid sheet body is placed is not separately prepared, after the solid liquid sheet is impregnated with the monomer liquid body, the repair work can be performed by attaching it to the repaired part without staining the fingertip. Since the monomer is polymerized and cured in a state where the liquid-impervious sheet is in close contact with one side of the solid sheet body, there is an effect that gloss is obtained on the finished surface and the surface is clean.

続いて、本発明を以下の実施例により更に詳しく説明する。
この実施例1の固形シート体の原材料は、1)粉剤:重合開始剤を併有しているメタクリル酸エチル樹脂の粉末、2)補強用布体:厚さ0.25mmで平織りのガラス繊維織布、3)合成樹脂エマルジョン接着剤:酢酸ビニル樹脂エマルジョン接着剤、4)接着剤希釈用の水、5)不通液シート:ポリエチレンフィルム、を用いた。前記のガラス繊維織布は、株式会社エポック製の商品名ガラスクロステープを用いた。このガラス繊維織布は19本のタテ糸と19本のヨコ糸を平織りして幅100mm、厚さ0.25mmに織成されたものであり、嵩密度18.7g/m3で標準引張強さ110kgf/25mmである。そして、酢酸ビニル樹脂エマルジョン接着剤は、コニシ株式会社製の木工用速乾水性形接着剤(商品名コニシボンド、品番#40007)を用いた。この酢酸ビニル樹脂エマルジョン接着剤(以下、接着剤と略称する)は、懸濁重合により水(45wt%)中に酢酸ビニル樹脂(55wt%)の微粒子が分散したエマルジョンである。また、前記の不通液シートは、厚さ0.02mmのポリエチレンフィルム(GCデンタルプロダクツ社製)を用いた。
Subsequently, the present invention will be described in more detail with reference to the following examples.
The raw material of the solid sheet body of Example 1 was 1) powder: ethyl methacrylate resin powder having both polymerization initiators, 2) reinforcing cloth: plain woven glass fiber weave with a thickness of 0.25 mm Cloth, 3) Synthetic resin emulsion adhesive: Vinyl acetate resin emulsion adhesive, 4) Water for diluting the adhesive, and 5) Liquid-impervious sheet: Polyethylene film were used. As the glass fiber woven fabric, a trade name glass cloth tape manufactured by Epoch Corporation was used. This glass fiber woven fabric is made by plain weaving 19 warp yarns and 19 weft yarns into a width of 100 mm and a thickness of 0.25 mm, and has a bulk density of 18.7 g / m 3 and a standard tensile strength. 110 kgf / 25 mm. As the vinyl acetate resin emulsion adhesive, a quick-drying water-based adhesive for woodwork (trade name Konishi Bond, product number # 40007) manufactured by Konishi Co., Ltd. was used. This vinyl acetate resin emulsion adhesive (hereinafter abbreviated as an adhesive) is an emulsion in which fine particles of vinyl acetate resin (55 wt%) are dispersed in water (45 wt%) by suspension polymerization. In addition, a polyethylene film (manufactured by GC Dental Products) having a thickness of 0.02 mm was used as the liquid-impervious sheet.

そこで、まず接着剤1重量部に対して水5重量部を加え、十分に撹拌して混合し、「接着剤希釈液」を得た。次に、ポリメチルメタクリレートの成型物を粉砕して粉剤(平均粒径約21μm)を得た。この粉剤中には、その重合時に加えた過酸化ベンゾイルが0.3wt%程度含まれている。粉剤中の過酸化ベンゾイルは安定である。前記の接着剤希釈液1重量部に対して粉剤0.75重量部を加え、撹拌して十分に混練し、「シート成型素材」を得た。   Therefore, first, 5 parts by weight of water was added to 1 part by weight of the adhesive, and the mixture was sufficiently stirred and mixed to obtain an “adhesive diluent”. Next, the molded product of polymethyl methacrylate was pulverized to obtain a powder (average particle diameter of about 21 μm). This powder contains about 0.3 wt% of benzoyl peroxide added during the polymerization. Benzoyl peroxide in the powder is stable. 0.75 part by weight of a powder was added to 1 part by weight of the adhesive diluent, and the mixture was stirred and sufficiently kneaded to obtain a “sheet molding material”.

上記のようにして得たシート成型素材をスプレーガンのカップに入れる。そして、予め用意した平らなプレート上にガラス繊維織布を置き、ガラス繊維織布の上面にシート成型素材をスプレーガンで吹き付ける。シート成型素材の吹き付け量はガラス繊維織布表面の単位面積当たり0.15〜0.18g/cm2とすることが好ましい。不通液シートが貼り付いた下側プレートを準備し、成型素材を吹き付けたガラス繊維織布を上下反転して、吹き付け面が不通液シートの上になるようにセットする。ゴムへラなどで撫でて、成型素材を吹き付けたガラス繊維織布と不通液シートを馴染ませて密着させる。ガラス繊維織布の大きさに合わせたシート体成型用の角穴を開けた上側プレートを下側プレート上に重ねる。ガラス繊維織布の反対側の面にも、スプレーガンでシート成型素材を吹き付ける。上側プレートを下側プレート上に重ねた状態で、乾燥器により固形シート体を乾燥させながら角穴内で成型する。乾操器の設定温度は、不通液シートの収縮などの変形を極力防ぐために60℃とする。90分間ほど加熱して乾燥させた後、固形シート体が型崩れしないように注意しながら、上側プレートを下側プレート上から取り外す。更に、上側プレートの角穴から乾燥物を取り出すと、不通液シート(この例ではポリエチレンフィルム)が片面に貼り付いた状態の固形シート体が得られた。このようにして得た固形シート体は、実施形態で述べたような被補修物の補修に有効に使用できた。 The sheet molding material obtained as described above is placed in a spray gun cup. Then, a glass fiber woven fabric is placed on a previously prepared flat plate, and a sheet molding material is sprayed onto the upper surface of the glass fiber woven fabric with a spray gun. The amount of sheet molding material sprayed is preferably 0.15 to 0.18 g / cm 2 per unit area of the surface of the glass fiber woven fabric. Prepare the lower plate to which the liquid-impervious sheet is attached, turn the glass fiber woven fabric sprayed with the molding material upside down, and set the spray surface to be on the liquid-impervious sheet. Boil with a rubber spatula, etc., blend the glass fiber woven fabric sprayed with the molding material and the liquid-impervious sheet, and adhere to them. An upper plate having a square hole for molding a sheet body in accordance with the size of the glass fiber woven fabric is overlaid on the lower plate. Spray the sheet molding material on the opposite side of the glass fiber woven fabric with a spray gun. With the upper plate stacked on the lower plate, the solid sheet is dried in a square hole while being dried by a dryer. The preset temperature of the dryer is 60 ° C. in order to prevent deformation such as shrinkage of the liquid-impervious sheet as much as possible. After heating and drying for about 90 minutes, the upper plate is removed from the lower plate, being careful not to lose the shape of the solid sheet. Further, when the dried product was taken out from the square hole of the upper plate, a solid sheet body in which a liquid-impervious sheet (in this example, a polyethylene film) was adhered to one side was obtained. The solid sheet body thus obtained could be used effectively for repairing the repair object as described in the embodiment.

この実施例2は、メタクリル酸エチル樹脂および過酸化ベンゾイルを含むポリマー粉末に替えて、「アクリル酸メチル」および過酸化ベンゾイルを含むポリマー粉末を用いたこと以外は、実施例1と同様に処理して固形シート体(厚さ約1mm)を製作し、その固形シート体の片面に不通液シートが貼り付いたものを得た。この不通液シート付き固形シート体も被補修物の補修に有効に使用できた。   This Example 2 was treated in the same manner as in Example 1 except that polymer powder containing “methyl acrylate” and benzoyl peroxide was used instead of the polymer powder containing ethyl methacrylate resin and benzoyl peroxide. Thus, a solid sheet body (thickness of about 1 mm) was produced, and a liquid-impermeable sheet adhered to one side of the solid sheet body was obtained. This solid sheet body with a liquid-impervious sheet could also be used effectively for repairing the repair object.

本発明の補修剤は、FRPをはじめ各種素材に化学結合あるいは物理的付着により接着するので、補修材料、補強材料、造形材料、絶縁材料として幅広く利用でき、例えば鉄、アルミニウム、銅、マグネシウム、チタンなどの金属およびそれらの合金類、ポリエステル樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリフェニレンスルフィド樹脂などのプラスチック類、ガラス、モルタル、石英などの無機物など、幅広い材料に接着可能であり、それらの補修に適用できる。   Since the repair agent of the present invention adheres to various materials including FRP by chemical bonding or physical adhesion, it can be widely used as repair material, reinforcement material, modeling material, insulating material, for example, iron, aluminum, copper, magnesium, titanium It can be bonded to a wide range of materials such as metals and their alloys, plastics such as polyester resin, acrylic resin, polycarbonate resin and polyphenylene sulfide resin, and inorganic materials such as glass, mortar and quartz, and can be applied to repair them. .

1 補修材
2 補強用布体
3 粉剤
4 合成樹脂エマルジョン接着剤
6 不通液シート
7 固形シート体
8 モノマー液
DESCRIPTION OF SYMBOLS 1 Repair material 2 Reinforcing cloth body 3 Powder agent 4 Synthetic resin emulsion adhesive 6 Impervious liquid sheet 7 Solid sheet body 8 Monomer liquid

Claims (5)

(メタ)アクリレートのポリマー粉末と(メタ)アクリレートモノマーの重合を引き起こす重合開始剤とを含んで成る粉剤を合成樹脂エマルジョン接着剤により補強用布体に付着させた固形シート体を備えていることを特徴とする補修材。 It is provided with a solid sheet body in which a powder comprising a polymer powder of (meth) acrylate and a polymerization initiator causing polymerization of a (meth) acrylate monomer is attached to a reinforcing cloth body with a synthetic resin emulsion adhesive. Characteristic repair material. 固形シート体の底面に、(メタ)アクリレートのモノマー液を通さない不通液シートが添付されていることを特徴とする請求項1に記載の補修材。 The repair material according to claim 1, wherein a liquid-impervious sheet that does not allow the monomer liquid of (meth) acrylate to pass through is attached to the bottom surface of the solid sheet body. 合成樹脂エマルジョン接着剤が、酢酸ビニル樹脂エマルジョン接着剤であることを特徴とする請求項1または請求項2に記載の補修材。 The repair material according to claim 1 or 2, wherein the synthetic resin emulsion adhesive is a vinyl acetate resin emulsion adhesive. 補強用布体が、ガラス繊維を原料として織成された織布であることを特徴とする請求項1から請求項3のいずれか一項に記載の補修材。 The repair material according to any one of claims 1 to 3, wherein the reinforcing fabric body is a woven fabric made of glass fiber as a raw material. (メタ)アクリレートのポリマー粉末と(メタ)アクリレートモノマーの重合を引き起こす重合開始剤とを含んで成る粉剤を合成樹脂エマルジョン接着剤により補強用布体に付着させた固形シート体と、当該固形シート体に添加されて重合する(メタ)アクリレートモノマーのモノマー液と、から成ることを特徴とする請求項1から請求項4のいずれか一項に記載の補修材。 A solid sheet body in which a powder comprising a polymer powder of (meth) acrylate and a polymerization initiator causing polymerization of a (meth) acrylate monomer is attached to a reinforcing cloth body with a synthetic resin emulsion adhesive, and the solid sheet body The repair material according to claim 1, comprising a monomer liquid of a (meth) acrylate monomer that is added to and polymerizes.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0321385A (en) * 1989-06-16 1991-01-30 Mitsubishi Petrochem Co Ltd Absorbing material for stagnation water in pipe
JPH06313270A (en) * 1993-04-23 1994-11-08 Gunze Ltd Graft polymerization on fiber
JPH09184304A (en) * 1995-11-01 1997-07-15 Mitsubishi Rayon Co Ltd Method of repairing and reinforcing existent construction and repairing and reinforcing member
JPH09239853A (en) * 1996-03-12 1997-09-16 Sekisui Chem Co Ltd Method for repairing decorative molding
JP2007198093A (en) * 2006-01-30 2007-08-09 Denki Kagaku Kogyo Kk Method of repairing and reinforcing structure
WO2008053817A1 (en) * 2006-10-30 2008-05-08 National University Corporation Gunma University Composite material composed of natural vegetable fiber and synthetic polymer, and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0321385A (en) * 1989-06-16 1991-01-30 Mitsubishi Petrochem Co Ltd Absorbing material for stagnation water in pipe
JPH06313270A (en) * 1993-04-23 1994-11-08 Gunze Ltd Graft polymerization on fiber
JPH09184304A (en) * 1995-11-01 1997-07-15 Mitsubishi Rayon Co Ltd Method of repairing and reinforcing existent construction and repairing and reinforcing member
JPH09239853A (en) * 1996-03-12 1997-09-16 Sekisui Chem Co Ltd Method for repairing decorative molding
JP2007198093A (en) * 2006-01-30 2007-08-09 Denki Kagaku Kogyo Kk Method of repairing and reinforcing structure
WO2008053817A1 (en) * 2006-10-30 2008-05-08 National University Corporation Gunma University Composite material composed of natural vegetable fiber and synthetic polymer, and method for producing the same

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