JP2018100345A - Two-part adhesive, and structure comprising cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-part adhesive which has excellent water resistance and exhibits high adhesive strength to a fluororesin substrate under a high temperature.SOLUTION: A two-part adhesive comprises a main agent, which contains a methyl methacrylate and an acid amide having an ethylenic unsaturated bond, and an initiator, which contains organoborane. The main agent contains, based on the mass of polymerizable components, 50 mass% to 75 mass% of the methyl methacrylate, and 25 mass% to 50 mass% of the acid amide having the ethylenic unsaturated bond.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a structure including a two-component adhesive and a cured product thereof, and particularly relates to a reactive two-component adhesive for a fluororesin substrate and a structure including the cured product thereof.

  There is a need for efficient and effective means for bonding fluororesin substrates with adhesives. When a fluororesin base material is bonded, surface treatment such as flame treatment, ittro treatment, corona discharge, plasma treatment, oxidation with ozone or an oxidizing acid, or sputter etching is often required. Although the surface of the fluororesin substrate may be coated with a primer containing a high surface energy material, the surface treatment may be required to sufficiently adhere the primer. As described above, the adhesion of the fluororesin base material often requires a complicated and expensive process, and even if such a process is performed, a sufficient adhesive force may not be obtained.

  A reactive two-component adhesive composed of an initiator (curing agent) containing organoborane, which is an aerobic initiator acting in the presence of air or oxygen, and a main agent containing a (meth) acrylic monomer is a fluororesin It is known to exhibit excellent adhesion to substrates.

  Patent Document 1 (Japanese Patent Publication No. 2001-502689) describes “a composition containing an organoborane amine complex and an aziridine functional substance”.

〔式中、ｎは、１以上の値を有する整数であり、ｘは、１以上の値を有する整数であり、ｙは、０以上の値を有する整数であり、Ａｒは、置換アリール基であり、Ｒ^３１、Ｒ^３２、およびＲ^３３は、独立して、水素、アルキル、アリール、およびハロゲンからなる群より選択され、Ｒ^３４は、有機基であり、Ｒ^３４は、それぞれ独立して、アルキル、アルコキシ、アルカノイル、アルカノイルオキシ、アリールオキシ、アロイル、アロイルオキシ、およびハロゲンからなる群より選択され、Ｘは、２価有機基または共有結合であり、Ｒ^３０は、有機基であり、ここで、それぞれのＸとＲ^３０とを合わせた合計分子量は、１００以上である。〕と、を含んでなる結合性組成物」が記載されている。 Patent Document 2 (Japanese Patent Publication No. 2003-526729) discloses that “(i) organoborane, (ii) at least one polymerizable monomer, and (iii) a vinyl aromatic represented by the general formula (1)”. Compound:

[Wherein, n is an integer having a value of 1 or more, x is an integer having a value of 1 or more, y is an integer having a value of 0 or more, and Ar is a substituted aryl group. R ³¹ , R ³² , and R ³³ are independently selected from the group consisting of hydrogen, alkyl, aryl, and halogen, R ³⁴ is an organic group, and each R ³⁴ is independently Selected from the group consisting of alkyl, alkoxy, alkanoyl, alkanoyloxy, aryloxy, aroyl, aroyloxy, and halogen, wherein X is a divalent organic group or a covalent bond, and R ³⁰ is an organic group, wherein The total molecular weight of each X and R ³⁰ combined is 100 or more. And a binding composition comprising

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2015-157888) includes “(A) (1) isobornyl methacrylate and (2) at least selected from the group consisting of phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, and cyclohexyl methacrylate. A two-component adhesive comprising a main agent containing one kind of monocyclic methacrylate and an initiator containing (B) an organoborane, wherein the monocyclic methacrylate is added to 100 parts by mass of the isobornyl methacrylate. A "two-component adhesive" containing 40 to 200 parts by mass is described.

  Patent Document 4 (Japanese Patent Application Laid-Open No. 2006-047901) discloses “(A) an initiator containing an organoborane, and (B) a two-component type comprising a main component containing a polymerizable component, a metal halide and a metal carboxylate. "Adhesive" is described.

JP-T-2001-50289 Special table 2003-526729 gazette Japanese Patent Laying-Open No. 2015-157888 JP, 2006-047901 A

  However, the adhesive strength of the cured product of the two-component adhesive described in the above-mentioned patent document may decrease at a high temperature, for example, 120 ° C., which is used in applications where the high heat resistance of a fluororesin is utilized. It is disadvantageous. In addition, since fluororesin exhibits water repellency, it is often used in applications where moisture resistance or water resistance is required, so that cured adhesives also have excellent water resistance, for example, soaked in warm water for a long period of time. It is desirable to maintain the necessary adhesion strength even after being applied.

  The present disclosure provides a two-component adhesive exhibiting high adhesive strength at high temperatures and excellent water resistance with respect to a fluororesin substrate.

  According to one embodiment of the present disclosure, a two-component adhesive comprising a main agent containing methyl methacrylate and an acid amide having an ethylenically unsaturated bond, and an initiator containing an organoborane, the main agent comprising: Provided is a two-component adhesive containing 50% by mass to 75% by mass of the methyl methacrylate and 25% by mass to 50% by mass of the acid amide having an ethylenically unsaturated bond based on the mass of the polymerizable component. .

  According to another embodiment of the present disclosure, a structure including a first fluororesin base material, a second base material, and a cured product of the two-component adhesive, the two-component type There is provided a structure in which the first fluororesin substrate and the second substrate are bonded via a cured product of an adhesive.

  According to the present disclosure, high adhesive strength is exhibited at a high temperature with respect to a fluororesin base material, and the water resistance is also excellent. For example, the necessary adhesive strength can be maintained even after being immersed in warm water for a long time. A liquid adhesive can be obtained.

  The above description should not be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.

It is sectional drawing of the structure of one embodiment of this indication.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  In the present disclosure, “(meth) acryl” means “acryl” or “methacryl”, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acryloyl” means “acryloyl” or Each means “methacryloyl”.

  The “polymerizable component” in the present disclosure refers to other (meta) contained in the main agent and / or the initiator as necessary in addition to the methyl methacrylate and the acid amide having an ethylenically unsaturated bond contained in the main agent. It means a component capable of reacting or polymerizing with acrylic monomer or oligomer, other polymerizable monomer or oligomer, other methyl methacrylate and acid amide having an ethylenically unsaturated bond. When “polymerizable component” is used in terms of parts by weight, it means the total amount of these components.

  The two-part adhesive of one embodiment of the present disclosure comprises a main agent and an initiator. The main agent contains methyl methacrylate and an acid amide having an ethylenically unsaturated bond. The initiator includes an organoborane that is an aerobic initiator. The main component of the two-component adhesive is, based on the weight of the polymerizable component, about 50% to about 75% by weight of methyl methacrylate and about 25% to about 50% of the acid amide having an ethylenically unsaturated bond. % Is included. Since methyl methacrylate has a glass transition temperature higher than 100 ° C., it can impart high adhesive strength to the cured adhesive at high temperatures, but has a relatively low boiling point. It volatilizes at the time of curing and tends to cause a decrease in adhesive strength due to a decrease in the adhesive volume. The present inventor forms a cured product exhibiting high adhesive strength even at high temperatures with respect to a fluororesin substrate by combining a predetermined amount of an acid amide having an ethylenically unsaturated bond as a polymerizable component with a predetermined amount of methyl methacrylate. And found that the cured product has high water resistance. Since the acid amide having an ethylenically unsaturated bond is hydrophilic, its use is considered disadvantageous for water resistance. By using an acid amide having an ethylenically unsaturated bond in combination with methyl methacrylate, It was unpredictable by those skilled in the art that not only high adhesive strength can be obtained by suppressing volume reduction of the adhesive due to volatilization of methyl methacrylate during curing, but also excellent water resistance can be imparted to the cured product.

  In some embodiments, the base agent comprises no more than about 75 wt.% Or no more than about 70 wt.% Methyl methacrylate, based on the weight of the polymerizable component. In preferred embodiments, the base agent comprises from about 50% to about 75%, or from about 60% to about 70% by weight methyl methacrylate, based on the weight of the polymerizable component. By setting the content of methyl methacrylate in the above range, a cured product having excellent water resistance and higher adhesive strength can be obtained.

  In some embodiments, the base agent comprises about 25% by weight or more or about 30% by weight or more of an acid amide having an ethylenically unsaturated bond, based on the weight of the polymerizable component. In a preferred embodiment, the base agent comprises from about 25% to about 50%, or from about 30% to about 40% by weight of acid amide having an ethylenically unsaturated bond, based on the weight of the polymerizable component. By setting the content of the acid amide having an ethylenically unsaturated bond in the above range, a cured product having excellent water resistance and higher adhesive strength can be obtained.

  In some embodiments, the acid amide having an ethylenically unsaturated bond is a compound whose homopolymer has a glass transition temperature of about 100 ° C. or higher, or about 120 ° C. or higher and about 200 ° C. or lower. By selecting the acid amide so that the glass transition temperature of the homopolymer of acid amide having an ethylenically unsaturated bond falls within the above range, a cured product having higher adhesive strength can be obtained.

  As an acid amide having an ethylenically unsaturated bond, various acid amides having a vinyl group, an allyl group, a (meth) acryloyl group, or the like can be used. An acid amide having a (meth) acryloyl group as an acid amide having an ethylenically unsaturated bond can be suitably used because of its excellent miscibility and reactivity with methyl methacrylate. Examples of the acid amide having a (meth) acryloyl group include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N- ((Meth) acryloyl) morpholine, N-((meth) acryloyl) piperidine and the like. The acid amide having an ethylenically unsaturated bond is preferably an acrylamide having a substituent on the nitrogen atom of the amide bond, and more preferably an acrylamide having no active hydrogen on the nitrogen atom of the amide bond. By using acrylamide having a substituent on the nitrogen atom of the amide bond, the curing rate can be further increased, and the water resistance of the cured product can be further increased. In some embodiments, the acid amide having an ethylenically unsaturated bond is at least one selected from the group consisting of N, N-dimethylacrylamide and acryloylmorpholine.

  The main agent may further contain other (meth) acrylic monomers or oligomers as optional components. As such (meth) acrylic monomers or oligomers, for example, linear or branched alkyl (meth) acrylates having 1 to about 12, 1 to about 8, or 1 to about 4 carbon atoms in the alkyl moiety, such as methyl acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate; ) Acrylic esters, such as 2-ethoxyethyl (meth) acrylate; partial or complete esters of polyhydric alcohols and (meth) acrylic acid, such as ethylene glycol, diethylene glycol, polyethylene glycol, trimethylolpropane, triethyleneglycol , Tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, polypropylene glycol, ethoxylated or propoxylated diphenylolpropane, hydroxy-terminated polyurethane (meth) acrylate, aliphatic polyester And urethane-based (meth) acrylates. When these (meth) acrylic monomers or oligomers are used, for example, about 0.1% by weight or more, about 1% by weight or more, or about 2% by weight or more, about 20% by weight, based on the weight of the polymerizable component. Hereinafter, it is used in an amount of about 10% by mass or less or about 5% by mass or less.

  Since linear or branched alkyl (meth) acrylates having a large number of carbon atoms may reduce the cohesive strength and interfacial adhesive strength of the cured adhesive due to the low Tg of their homopolymers, In an embodiment, the main agent does not contain a linear or branched alkyl (meth) acrylate having 5 or more carbon atoms in the alkyl moiety.

  The main agent is, as an optional component, further other polymerizable monomers or oligomers such as vinyl acetate, vinyl chloride, vinyl fluoride, vinyl bromide, styrene, divinylbenzene, crotonic acid ester, maleic acid ester, styrenated unsaturated polyester. Resins, amino group-containing polymerizable monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and combinations thereof may also be included. These polymerizable monomers or oligomers can be used in amounts that do not significantly affect the desired properties of the cured adhesive.

  In some embodiments, the base agent is about 95% or more total of methyl methacrylate and acid amide having an ethylenically unsaturated bond, based on the weight of the polymerizable component, and about 97% or more, Or about 99 mass% or more is included. In some embodiments, the polymerizable component comprises methyl methacrylate and an acid amide having an ethylenically unsaturated bond.

によって表すことができる。式中、Ｒ^１は炭素数１〜約１０のアルキル基であり、Ｒ^２及びＲ^３は、同じでも異なってもよく、独立に炭素数１〜約１０のアルキル基、及び炭素数６〜１０のアリール基から選択される。好ましくは、Ｒ^１、Ｒ^２、及びＲ^３は独立に、１〜約５個の炭素原子を有するアルキル基から選択される。Ｒ^１、Ｒ^２、及びＲ^３は全て異なってもよく、Ｒ^１、Ｒ^２、及びＲ^３の中の２つ以上が同じであってもよい。Ｒ^１、Ｒ^２、及びＲ^３と、これらが結合しているホウ素原子（Ｂ）とが１つになって開始剤が形成される。具体的なオルガノボランとして、例えば、トリメチルボラン、トリエチルボラン、トリ−ｎ−プロピルボラン、トリイソプロピルボラン、トリ−ｎ−ブチルボラン、トリイソブチルボラン、及びトリ−ｓｅｃ−ブチルボランが挙げられる。 The initiator includes an organoborane. Organoborane initiates free radical polymerization of polymerizable monomers to produce the polymer necessary to function as an adhesive. Organoborane has the following general formula:

Can be represented by In the formula, R ¹ is an alkyl group having 1 to about 10 carbon atoms, and R ² and R ³ may be the same or different, and are independently an alkyl group having 1 to about 10 carbon atoms, and 6 to 10 carbon atoms. Selected from the aryl groups. Preferably, R ¹ , R ² , and R ³ are independently selected from alkyl groups having 1 to about 5 carbon atoms. R ¹ , R ² , and R ³ may all be different, and two or more of R ¹ , R ² , and R ³ may be the same. R ¹ , R ² , and R ³ and the boron atom (B) to which they are bonded together form an initiator. Specific examples of organoborane include trimethylborane, triethylborane, tri-n-propylborane, triisopropylborane, tri-n-butylborane, triisobutylborane, and tri-sec-butylborane.

で表すことができる。式中、Ｒ^１、Ｒ^２、及びＲ^３は前述のとおりであり、Ｃｘは錯化剤である。 The organoborane can be stabilized by complexing with a complexing agent. The organoborane complex has the following general formula:

Can be expressed as In the formula, R ¹ , R ² , and R ³ are as described above, and Cx is a complexing agent.

  Useful complexing agents (Cx) include, for example, amine complexing agents, amidine complexing agents, hydroxide complexing agents, and alkoxide complexing agents. The ratio of boron atom to complexing agent (Cx) in the complex is represented by “v” and is preferably selected so that the complexing agent and boron atom are in an effective ratio. The ratio of the boron atom in the complex to the complexing site of the complexing agent is preferably about 1: 1. Free organoborane which tends to have pyrophoric properties when the ratio of complexing sites of boron atom and complexing agent exceeds 1: 1, that is, when the boron atom is excessive with respect to the complexing site of the complexing agent May occur.

  As the amine complexing agent, various compounds having at least one amino group or a mixture thereof can be used. The amine complexing agent may be a monoamine or a polyamine (ie, a compound having two or more amino groups, for example, 2 to 4 amino groups). In polyamine, a plurality of amino groups can each function as a complex-forming site, so that two or more organoboranes can be complexed with respect to one molecule of polyamine.

  In some embodiments, the amine complexing agent is a primary or secondary monoamine. Such monoamines include, for example, ammonia, ethylamine, butylamine, hexylamine, octylamine, benzylamine, morpholine, piperidine, pyrrolidine, and polyoxyalkylene monoamines (eg, JEFFAMINE ™ M715 and M2005, Huntsman PetroChemical Corp., Available from Vermont, Texas).

  In another embodiment, the amine complexing agent is a polyamine. Such polyamines include alkane diamines such as 1,2-ethanediamine, 1,3-propanediamine, 1,5-pentadiamine, 1,6-hexanediamine, 1,12-dodecanediamine, 2-methyl-1 , 5-pentanediamine, and 3-methyl-1,5-pentanediamine; alkyl polyamines such as triethylenetetraamine and diethylenetriamine; polyoxyalkylene polyamines such as polyethylene oxide diamine, polypropylene oxide diamine, polypropylene oxide triamine, and diethylene glycol Dipropylamine, triethylene glycol dipropylamine, polytetramethylene oxide diamine, poly (ethylene oxide-co-propylene oxide) diamine, and poly (ethylene oxide) De -co- propylene oxide) triamine; and isomers thereof.

  As the amidine complexing agent, for example, those described in WO 01/32717 can be used. Examples of such amidine complexing agents include N, N, N ′, N′-tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4. 3.0] nona-5-ene, 2-methylimidazole, 2-methylimidazoline, and 4- (N, N-dimethylamino) pyridine.

As the hydroxide complexing agent and the alkoxide complexing agent, for example, those described in WO 01/32716 can be used. Examples of such hydroxide complexing agents and alkoxide complexing agents include, for example, the general formula: M ^{m +} (R ⁴ O ⁻ ) _n (wherein R ⁴ is independently hydrogen or an organic group (for example, an alkyl group or an alkylene group). M ^{m +} represents a counter cation (eg, sodium ion, potassium ion, tetraalkylammonium, or a combination thereof), m is an integer of 1 or more, and n is an integer of 1 or more. There is one represented by.

  The organoborane complex can be easily prepared using a known technique. Generally, the complexing agent is mixed with the organoborane with stirring in an inert atmosphere. Since an exotherm is often observed, it is desirable to cool the mixture and / or slowly add the organoborane to the complexing agent. If the vapor pressure of the component is high, it is desirable to maintain the reaction temperature below about 70 ° C to 80 ° C. The material is mixed well before the complex is cooled to room temperature. Although special storage conditions are not required, it is preferable to store the complex in a sealed container in a cool and dark place.

  The organoborane is used in an amount effective so that the main polymerizable monomer produces a polymer having a desired degree of polymerization and the cured adhesive has the desired properties. If the amount of organoborane is too small, polymerization may not proceed completely and the adhesiveness of the cured adhesive product may be insufficient. On the other hand, if the amount of organoborane is too large, the progress of the polymerization may be too rapid and the working time required for the work may not be secured, or the degree of polymerization of the resulting polymer will be low, and the cohesive force required for adhesion May not be obtained.

により計算することができる。 The amount of organoborane used is based on the total mass of the adhesive (mass of the main agent and initiator) minus the mass of filler, non-reactive diluent, and other non-reactive materials. When converted as boron, it is generally about 0.003% by mass or more and about 1.5% by mass or less, preferably about 0.008% by mass or more and about 0.5% by mass or less, more preferably about 0.01% by mass. % Or more and about 0.3% by mass or less. In the present disclosure, “non-reactive” with respect to organoborane is used for materials or components that are free of abstractable hydrogen atoms or unsaturated bonds. The mass% of boron in the adhesive is given by the following formula:

Can be calculated.

  The initiator may include a suitable diluent such as an aziridine compound or a combination thereof to dissolve or dilute the organoborane complex. Such diluents are described, for example, in WO 98/17694. The diluent is not reactive with the organoborane or organoborane complex and functions as a bulking agent for the organoborane or organoborane complex.

  Aziridine compounds used as diluents can be, for example, short chain alkyl groups (eg, organic groups having 1 to about 10 carbon atoms, preferably methyl, for example) to form a methyl, ethyl or propylaziridine moiety. , Ethyl or propyl) and having at least one aziridine ring or group. In some embodiments, the aziridine compound is polyaziridine.

  Examples of useful commercially available polyaziridines include trade name CX-100 (available from Akzo Nobel Polymer Chemicals LLC, Chicago, Illinois, USA).

  The aziridine compound is advantageously soluble in the organoborane complex, and a two-part adhesive having excellent storage properties can be provided using such an aziridine compound. The aziridine compound is advantageously soluble in the monomer contained in the main agent, and a uniform mixture can be easily formed using such an aziridine compound, and the workability of the adhesive can be improved. The amount of the aziridine compound used is generally about 50% by mass or less, preferably about 25% by mass or less, more preferably about 10% by mass or less, based on the total mass of the adhesive. The organoborane complex may be dissolved in an aziridine compound in a considerable amount (for example, about 75% by mass or more, up to about 100% by mass).

  When an organoborane complex is included in the initiator, the main agent further includes a decomplexing agent. In the present disclosure, the “decomplexing agent” is, for example, a compound capable of dissociating organoborane from the complexing agent by reacting with an amino group, amidine group, hydroxide group or alkoxide group in the complexing agent. Means. The reaction of the polymerizable monomer contained in the main agent can be initiated by the decomplexing agent.

  When the organoborane is complexed with an amine complexing agent, the preferred decomplexing agent is an amine reactive compound. General types of useful amine-reactive compounds include acids, acid anhydrides, aldehydes, and β-ketone compounds. As the amine-reactive compound, isocyanate, acid chloride, sulfonyl chloride and the like, for example, isophorone diisocyanate, toluene diisocyanate, and methacryloyl chloride can be used.

Useful acids include Lewis acids _(e.g., SnCl 4, etc. TiCl _4), and Bronsted acids (e.g., aliphatic carboxylic acids having straight-chain or branched saturated or unsaturated alkyl group of from 1 to about 8 carbon atoms, Or an aromatic carboxylic acid having a substituted or unsubstituted aromatic ring having 6 to 10 carbon atoms, such as acrylic acid, methacrylic acid, acetic acid, benzoic acid, and p-methoxybenzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acid, Phosphinic acid, silicic acid, etc.). Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid; and 1,2-ethylenebismaleate, 1,2-propylenebis Carboxylic acid esters such as maleate, 2,2′-diethylene glycol bis-maleate, 2,2′-dipropylene glycol bis-maleate, trimethylolpropane trimaleate can also be used.

  A chain or cyclic acid anhydride can also be used as the amine-reactive compound. When a free radical polymerizable group such as an ethylenically unsaturated group is present in the acid anhydride, it may be possible to copolymerize with a polymerizable monomer contained in the main agent. Useful acid anhydrides include, for example, acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and the like.

  Useful aldehydes include, for example, benzaldehyde, o-, m-, and p-nitrobenzaldehyde, 2,4-dichlorobenzaldehyde, p-tolylaldehyde, 3-methoxy-4-hydroxybenzaldehyde, and the like. Aldehydes blocked with acetal or the like can also be used.

  As useful β-ketone compounds, for example, those described in WO2003 / 057743 can be used. Examples of such β-ketone compounds include methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, 2-methacryloyloxyethyl acetoacetate, diethylene glycol bis (acetoacetate), polycaprolactone tris (acetoacetate), propylene glycol bis ( Acetoacetate), poly (styrene-co-allyl acetoacetate), N, N-dimethylacetoacetamide, N-methylacetoacetamide, acetoacetanilide, ethylene bis (acetoacetamide), propylene glycol bis (acetoacetamide), acetoacetamide, Acetoacetonitrile and the like can be used.

  The decomplexing agent is used in an effective amount, that is, an amount effective to dissociate the organoborane from the complexing agent to accelerate the polymerization but does not substantially affect the desired properties of the cured adhesive. Is done. As can be understood by those skilled in the art, if the amount of the decomplexing agent used is too large, the progress of the polymerization may be too rapid to ensure the usable time required for the work, or the degree of polymerization of the resulting polymer. The cohesive force required for adhesion may not be obtained. On the other hand, when the amount of the decomplexing agent used is too small, the polymerization does not proceed completely, and the adhesiveness of the cured adhesive product may be insufficient. The decomplexing agent generally includes an amine reactive group, an amidine reactive group, a hydroxide reactive group, or an alkoxide reactive group in the decomplexing agent and an amino group, an amidine group, water in the complexing agent. Used in an amount such that the molar ratio with the oxide group or alkoxide group is in the range of 0.1: 1.0 to 10.0: 1.0, preferably an amine reactive group in the decomplexing agent, amidine The molar ratio of the reactive group, hydroxide reactive group, or alkoxide reactive group to the amino group, amidine group, hydroxide group, or alkoxide group in the complexing agent is 0.2: 1.0 to Used in an amount in the range of 4.0: 1.0, or about 1.0: 1.0.

  The base agent and / or initiator may include at least one metal salt that can adjust the cure kinetics of the adhesive to provide a suitable balance of pot life and polymerization rate.

  Examples of the metal cation of the metal salt include vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, antimony, platinum, and cerium cations. Among metal cations, vanadium, chromium, manganese, iron, cobalt, nickel, copper, ruthenium, palladium, and antimony cations are preferred, and because of low cost, high activity, and good hydrolysis stability, Iron, cobalt, and copper cations are more preferred, and copper and iron cations are even more preferred. Metal cations include water, ammonia, σ electron donating ligands such as amines, or carbonyl (carbon monoxide), isonitriles, phosphines, phosphites, arsines, nitrosyl (nitrogen oxide), ethylene, etc. You may have a pi electron donating ligand.

  Examples of the counter ion (anion) of the metal salt include halide ion, borate ion, sulfonate ion, and carboxylate ion, and include chloride ion, bromide ion, tetrafluoroborate ion, trifluoromethanesulfonic acid. Ions, naphthenate ions, and 2-ethylhexanoate ions are preferred.

  Examples of suitable metal salts include copper (II) bromide, copper (II) chloride, copper (II) 2-ethylhexanoate, iron (III) bromide, vanadium (III) bromide, chromium bromide (III ), Ruthenium (III) bromide, copper (II) tetrafluoroborate, copper (II) trifluoromethanesulfonate, copper (II) naphthenate, copper (I) bromide, iron (II) bromide, bromide Examples include manganese (II), cobalt (II) bromide, nickel (II) bromide, antimony (III) bromide, and palladium (II) bromide.

  The metal salt is used in an effective amount, that is, an amount that affects the cure kinetics of the adhesive but does not substantially affect the desired properties of the cured adhesive. The metal salt is generally up to about 40,000 ppm, preferably about 60 ppm or more and about 20,000 ppm or less, more preferably about 100 ppm or more and about 4,000 ppm or less, based on the total mass of the adhesive. Advantageously, the metal salt is soluble in the main agent or at least partially soluble in the adhesive in use.

  The two-component adhesive of the present disclosure may further include an optional additive. Such additives are generally added to the main agent, but can be added to the initiator as long as the function of the initiator is not impaired.

  One useful additive is a thickening agent such as polybutyl methacrylate having a molecular weight of about 10,000 to about 40,000. By using a thickener, the viscosity of the adhesive can be increased to a consistency like a viscous syrup with better coatability. Such thickeners can generally be used in amounts up to about 50% by weight, based on the total weight of the adhesive.

  Another useful additive is an elastomeric material. The elastomeric material can improve the fracture toughness of the cured adhesive. For example, it may be beneficial when bonding rigid, high yield strength materials (eg, metal substrates that do not mechanically absorb energy as easily as other materials such as flexible polymeric substrates). Such additives can be used in amounts generally up to about 50% by weight relative to the total weight of the adhesive.

  Core-shell polymers can also be used to improve adhesive applicability and flow characteristics. Improved coatability and flow characteristics reduce unwanted stringing or sag after adhesive is applied to a vertical surface when the adhesive is dispensed from a syringe type applicator Can be confirmed. The core-shell polymer is generally about 5% or more, about 10% or more, or about 20% or more, about 50% or less, about 40% or less, or about 30% by weight, based on the total weight of the adhesive. It can be added in the following amounts.

  A reactive diluent may be added to the main agent and / or initiator. Suitable reactive diluents include 1,4-dioxo-2-butene functional compounds as described in US Pat. No. 6,252,023, and US Pat. No. 5,935,711. And aziridine compounds as described in the literature.

  A vinyl aromatic compound as described in WO 01/68783 is added to the initiator and / or main agent to substantially affect the polymerization rate, curing time and desired properties of the adhesive cured product. It is also possible to lengthen the pot life.

  Useful vinyl aromatic compounds include, for example, 3-isopropenyl-α, α-dimethylbenzyl isocyanate (available under the trade designation “TMI” from Cytec Industries, Inc., Woodland Park, NJ, USA) Or the polyfunctional reactive hydrogen compound, Preferably, the (alpha) -methylstyrene group containing oligomer prepared by making it react with a monofunctional or polyfunctional amine, alcohol, or those combination is mentioned. Particularly preferred monofunctional or polyfunctional amines include Huntsman PetroChemical Corp. Amine-terminated polyethers commercially available under the trade name JEFFAMINE, such as JEFFAMINE ™ ED600 (a diamine-terminated polyether with a nominal molecular weight of 600), JEFFAMINE ™ D400 (with a nominal molecular weight of 400, available from Vermont, Texas, USA) Diamine-terminated polyether), JEFFAMINE ™ D2000 (diamine-terminated polyether having a nominal molecular weight of 2000), JEFFAMINE ™ T3000 (a triamine-terminated polyether having a nominal molecular weight of 3000), and JEFFAMINE ™ M2005 (nominal molecular weight of 2000). Monoamine-terminated polyethers). Suitable alcohol-containing compounds include, for example, polypropylene glycol, polycaprolactone triol, and diethylene glycol. The vinyl aromatic compound is generally about 1% or more, about 2% or more, or about 5% or more, about 30% or less, about 20% or less, or about 10%, based on the total weight of the adhesive. It can be added in amounts up to mass%.

  A small amount of an inhibitor such as hydroquinone monomethyl ether or tris (N-nitroso-N-phenylhydroxylamine) aluminum salt can be added to the main agent to prevent or reduce deterioration of the polymerizable monomer during storage, for example. Inhibitors can be added in amounts that do not substantially reduce the rate of monomer polymerization or the desired properties of the cured adhesive. Inhibitors can generally be used in an amount of about 100 ppm or more and about 10,000 ppm or less, based on the mass of the polymerizable component.

  Other optional additives include non-reactive diluents or solvents (eg, acetone, methyl ethyl ketone, ethyl acetate, N-methyl caprolactam, etc.), non-reactive colorants, fillers (eg, carbon black, hollow glass / ceramics) Bead, silica, titanium dioxide, solid glass / ceramic microspheres, silica alumina ceramic microspheres, conductive and / or thermally conductive particles, antistatic compounds, chalk, etc.). The various optional additives can be added in amounts that do not substantially reduce the polymerization rate of the monomer or the desired properties of the cured adhesive.

  The two-part adhesive of the present disclosure is particularly useful when adhering a fluororesin base material including polytetrafluoroethylene (PTFE), a fluoroelastomer, and the like, which are hardly adhesive materials. In one embodiment, the fluororesin substrate comprises polytetrafluoroethylene. When using the two-component adhesive of the present disclosure, surface treatment techniques such as flame treatment, itro treatment, corona discharge, and primer treatment may be used. However, in a preferred embodiment, the surface treatment technique is not used. A two-component adhesive is used.

  The main component and initiator of the two-part adhesive of the present disclosure are mixed as is usually done when handling such materials. Part or all of the two-component adhesive of the present disclosure is mixed before applying the adhesive to the substrate.

  When two-part adhesives are used in commercial and industrial environments, the ratio of the main agent and initiator mixed is a simple integer, indicating that the application of adhesives using conventional commercial feeders This is advantageous because it becomes easier. Such supply devices include double syringe applicators such as those described in US Pat. Nos. 4,538,920 and 5,082,147, such as the trade name “Mixpack” (MIXPAC) ( ConProTec, Inc., available from Salem, NH, USA).

  Typically, the dispensing device comprises a set of tubular containers arranged side by side, and each tube is designed to receive one of the adhesive base and initiator. Two plungers, one in each tube, are moved simultaneously (eg, moved by hand or using a manual gear mechanism) and the contents of the tubes are fed into a common elongated mixing chamber. The mixing chamber may include a static mixer for promoting mixing of the two liquids. The mixed adhesive is supplied onto the substrate from the mixing chamber. When the tube is empty, it can be replaced with a new tube and the application process can continue.

  The ratio at which the adhesive base and initiator are mixed can be adjusted by the tube diameter. At this time, each plunger has dimensions adapted to the inside of a constant diameter tube, and the plunger moves in the tube at the same speed. The dispensing device is often intended to use a variety of different two-part adhesives, and the plunger is sized to deliver the adhesive base and initiator in a suitable mixing ratio. In some embodiments, the mixing ratio of base agent to initiator is generally 1: 1, 2: 1, 4: 1, and 10: 1.

  When the adhesive base and initiator are mixed in a fractional mixing ratio (eg, 100: 3.5), the user will manually weigh the two liquids of the adhesive. Therefore, the two liquids of adhesive can be mixed at a general integer mixing ratio such as 10: 1 or less, more preferably 4: 1, 3: 1, 2: 1, or 1: 1, It is advantageous to increase the commercial and industrial utility of the adhesive and to facilitate the use of currently available supply equipment. Adjust the mixing ratio of the two liquids of the adhesive to an integer mixing ratio (for example, 20: 1, 15: 1, 12: 1, 10: 1, 4: 1, 3: 1, 2: 1, or 1: 1). For the purpose, the vinyl aromatic compounds already described can advantageously be added to the initiator.

  After the two liquids are mixed, the adhesive is preferably used within the pot life. Adhesive is applied to one or both substrates, then pressure is applied to the substrates to bond the substrates together and excess adhesive is pushed out of the bond line. If it does in this way, the adhesive agent which is exposed in the air and may harden | cure too much can also be removed. In general, the bonding is preferably performed in a short time after the adhesive is applied to the substrate, and is preferably performed within the usable time of the adhesive. The thickness of the adhesive layer is generally about 0.01 mm or more and about 0.3 mm or less, but may exceed 1.0 mm when filling the gap between the substrates is required. The bonding step can be easily performed at room temperature, and the adhesive can be post-cured at a high temperature as required.

  As an embodiment using the two-component adhesive of the present disclosure, for example, a first fluororesin substrate 12, a second substrate 16, and a cured product of the two-component adhesive as shown in FIG. 14, a structure 10 is provided in which a first fluororesin substrate 12 and a second substrate 16 are bonded via a cured product 14 of a two-component adhesive. As the second substrate, a fluororesin such as polytetrafluoroethylene (PTFE), an olefin material such as polyethylene (PE) and polypropylene (PP), a polyester such as polyvinyl chloride (PVC) and polyethylene terephthalate (PET), Silicone rubbers such as polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), polyphenylene oxide, dimethyl silicone rubber, vinyl methyl silicone rubber, phenyl methyl silicone rubber, or elastomer-modified products of these materials Or those containing polymer blends of these materials with elastomers such as ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM). In some embodiments, the second substrate is a fluorine resin such as polytetrafluoroethylene (PTFE), an olefin-based material such as polyethylene (PE), polypropylene (PP), which are all hard-to-adhere materials, Alternatively, silicone rubber such as dimethyl silicone rubber, vinyl methyl silicone rubber, and phenyl methyl silicone rubber is included. According to these embodiments, the first fluororesin base material and the second base material, which are hardly adhesive materials, can be used without using an adhesive containing a special material such as an acrylic-modified silicone resin or a fluororesin. A joined structure can be obtained.

  In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.

  The reagents and raw materials used in this example are shown in Table 1 below.

<Peel test>
An adhesive composition was prepared by mixing a main component and an initiator of a two-component adhesive, and the obtained adhesive composition was applied on a polytetrafluoroethylene (PTFE) test piece. Immediately thereafter, the adhesive composition was coated with another PTFE specimen so that the coated area was 1 cm × 2 cm and the thickness was 1 mm. The adhesive composition was cured at room temperature for 1 day. Using a tensile tester RTC-1325A (A & D Co., Ltd., Toshima-ku, Tokyo, Japan) at a temperature of 25 ° C. or 120 ° C. and a crosshead speed of 5 cm / min, the adhesion test piece is in the direction of 180 degrees. The peeling force when peeling (T-shaped peeling) was recorded in kN / m. Moreover, after immersing the adhesive test piece in 40 ° C. warm water for one week, the peel strength when peeling the adhesive test piece in the direction of 180 degrees (T-peeling) at a temperature of 25 ° C. and a crosshead speed of 5 cm / min. Recorded at kN / m.

<Examples 1-5 and Comparative Examples 1-23>
<Synthesis of α-methylstyrene group-containing oligomer (AMSPU)>
120.60 g of TMI and 600.00 g of JEFFAMINE ™ D2000 were mixed and reacted at room temperature overnight without temperature adjustment. As a result of IR spectrum measurement, the peak due to the isocyanate having a wave number of 2265 cm ⁻¹ disappeared, so that it was confirmed that the reaction was complete. In this way, an α-methylstyrene group-containing oligomer (AMSPU) was obtained.

<Initiator>
Table 1 shows the materials used for the initiator, and Table 2 shows the initiator composition. Each component is weighed into a 200 mL glass bottle so that the total mass of the initiator is 50 g, and is 2000 rpm using “Awatori Nertaro” ARE-500 (Spinning Revolving Mixer, Sinky Corporation, Chiyoda-ku, Tokyo, Japan). To obtain an initiator. The obtained initiator was used in Examples 1 to 5 and Comparative Examples 1 to 23.

<Main agent>
Table 1 shows the materials used for the main agent. Table 3 shows the compositions of the main agents of Examples 1 to 5 and Comparative Examples 1 to 23. A 25% DMAA solution (CuBr ₂ / DMAA) of copper (II) bromide was prepared by dissolving copper (II) bromide in DMAA so that the concentration was 25% by mass. First, PMMA added to the monomer mixture was placed in an 80 ° C. oven to dissolve the PMMA. Each component was weighed in a 200 mL glass bottle so that the total mass of the main agent was 50 g, and allowed to stand at 70 ° C. for 20 minutes. The mixture was stirred at 2000 rpm for 2 minutes to obtain the main agent.

<Adhesive>
After filling the initiator on the volume ratio 1 side and the main agent on the volume ratio 10 side of the 10: 1 volume ratio dual syringe applicator (Mixpack CD050-10-PP, ADW Corporation, Osaka, Osaka, Japan) Static mix nozzle by installing 17cm static mix nozzle (MX5.4-17-S, ADI Corporation, Osaka, Osaka, Japan) of 10cm length and extruding main agent and initiator simultaneously. The adhesive mixed in was applied. Table 4 shows the evaluation results of the cured adhesive by the peel test.

  As can be seen from Table 4, the cured adhesives of Examples 1 to 5 exhibited a peel strength of 2 kN / m or more at both 25 ° C and 120 ° C. Further, the cured adhesives of Examples 1 to 5 exhibited a peel strength of 2 kN / m or more even after being immersed in warm water at 40 ° C. for 1 week.

  On the other hand, in Comparative Examples 1 to 3, the peel strength after immersion in warm water decreased to less than 2 kN / m. This decrease can be attributed to the high hydrophilicity of DMAA. Comparative examples 7-9 also had peel strength after warm water immersion reduced to less than 2 kN / m, probably due to the high hydrophilicity of ACMO. Comparative Examples 4-6 and 10-13 had a peel strength of less than 2 kN / m at 120 ° C. The low peel strength of these comparative examples may be attributed to the glass transition temperature of the homopolymers PhEMA, THFMA, BZMA and CHMA being lower than the glass transition temperature of the MMA homopolymer. In Comparative Example 14, the peel strength was less than 2 kN / m even at 25 ° C. This low peel strength is believed to be due to the volume being reduced by volatilization of MMA during curing due to the low boiling point of MMA. Comparative Examples 15 to 23 had a peel strength of less than 2 kN / m at 120 ° C. The low peel strength of these comparative examples is that the glass transition temperature of the homopolymer of PhEMA, THFMA, BZMA and CHMA is lower than the glass transition temperature of the homopolymer of MMA, as in Comparative Examples 4-6 and 10-13. It is thought to be caused.

DESCRIPTION OF SYMBOLS 10 Structure 12 1st fluororesin base material 14 Hardened | cured material of 2 liquid type adhesive agent 16 2nd base material

Claims (8)

A two-component adhesive comprising a main agent containing methyl methacrylate and an acid amide having an ethylenically unsaturated bond, and an initiator containing an organoborane, wherein the main agent is based on the mass of the polymerizable component, A two-component adhesive comprising 50% by mass to 75% by mass of methyl methacrylate and 25% by mass to 50% by mass of the acid amide having an ethylenically unsaturated bond.   The two-component adhesive according to claim 1, wherein the main agent contains 95% by mass or more of the methyl methacrylate and the acid amide having an ethylenically unsaturated bond in total based on the mass of the polymerizable component. Agent.   The two-component adhesive according to claim 1, wherein the homopolymer of acid amide having an ethylenically unsaturated bond has a glass transition temperature of 100 ° C. or higher.   The two-component type according to any one of claims 1 to 3, wherein the acid amide having an ethylenically unsaturated bond is at least one selected from the group consisting of N, N-dimethylacrylamide and acryloylmorpholine. adhesive.   The two-component adhesive according to any one of claims 1 to 4, which is used for adhesion of a fluororesin substrate.   The two-component adhesive according to claim 5, wherein the fluororesin base material contains polytetrafluoroethylene. A first fluororesin substrate;
A second substrate;
It is a structure containing the hardened | cured material of the 2 liquid adhesives as described in any one of Claims 1-6, Comprising: A said 1st fluororesin base material through the hardened | cured material of the said 2 liquid adhesives, A structure formed by bonding the second base material.   The structure according to claim 7, wherein the second base material includes a fluororesin, an olefin-based material, or silicone rubber.

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