JP2010229199A - Reactive hot melt resin composition and reactive hot melt adhesive agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive hot melt resin composition that exhibits the same heat resistance as one comprising a boron halide and/or a boron halide complex and substantially contains neither halogen compounds nor organic tin compounds. <P>SOLUTION: The reactive hot melt resin composition comprises a curable resin (A) bearing a hydrolyzable silicon group in the molecule and a carboxylic acid metal salt (B). The carboxylic acid metal salt (B) is preferably contained in an amount of 0.01-10 pts.mass based on 100 pts.mass of the curable resin (A). The carboxylic acid metal salt (B) is preferably at least one compound selected from carboxylates of calcium, vanadium, iron, titanium, zirconium, cerium, aluminum, potassium, bismuth, barium and zinc. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a reactive hot melt resin composition and a reactive hot melt adhesive using the same, and in particular, prepared using a curable resin having a hydrolyzable silicon group and a specific organometallic salt, and heated. The present invention relates to a reactive hot melt adhesive that melts and is applied and bonded to an adherend and then rapidly cured at room temperature.

  There are various types of curable resins used for bonding / bonding formation, and their curing forms also differ depending on the molecular structure of the resin, and they react and cure by contact with heat curing agents, catalysts, moisture in the atmosphere, etc. Various types of cured products can be used depending on the application.

  The hot melt adhesive bonds the adherend by heating and melting a solid thermoplastic resin at room temperature and applying it to an adhesive surface, followed by cooling and solidification. On the other hand, reactive hot melt adhesives, such as the above-mentioned hot melt adhesives, are bonded by cooling and solidification (primary adhesion), and then a curing catalyst acts in the resin constituting the adhesive layer to cause crosslinking and the like. It hardens while the reaction proceeds, and adheres the adherend more firmly, and at the same time improves the heat resistance of the adhesive layer (secondary bonding). Therefore, with a reactive hot melt adhesive, the resin curing reaction does not proceed during the melting, coating, and bonding stages (primary bonding stage), and the resin is cured in the secondary bonding stage, that is, the resin applied on the adherend surface. In order to proceed, the curing catalyst needs to act in a state where there is no heat supply and the temperature drops (typically close to room temperature).

  In conventional reactive hot melt adhesives, resins with terminal isocyanate groups are widely used as curable resins, but those with a fast curing speed that quickly develops adhesive strength in minutes. There is no.

  In addition, although not general-purpose, the resin having a hydrolyzable silicon group such as a hydrolyzable silicon group was used by paying attention to the characteristics such as heat resistance, weather resistance, and electrical insulation of the resin having a hydrolyzable silicon group. Reactive hot melt adhesives are commercially available. This reactive hot melt adhesive uses an organotin compound such as dibutyltin dilaurate or dibutyltin diacetate as a curing catalyst. For example, in Patent Document 1 below, a silylated urethane resin is used as a curable resin. As an example, a compound containing an organic tin compound is described. However, a reactive hot melt adhesive using a resin having such a hydrolyzable silicon group also has a very slow reaction rate and requires one day or longer for curing. In addition to organic tin compounds, organic acids and amine compounds are well known. However, even when these curing catalysts are used, since they are insufficient in terms of curing speed, they have not been widely used as reactive hot melt adhesives.

  Therefore, the present inventors have studied for the purpose of providing a fast-curing reactive hot-melt resin composition using a resin having a hydrolyzable silicon group, a reactive hot-melt adhesive using the same, and the like. And a reactive hot melt resin composition containing a curable resin having a hydrolyzable silicon group in the molecule and at least one boron compound selected from the group consisting of a boron halide and / or a boron halide complex. Invented that the intended purpose was achieved and filed a patent application (Patent Document 2).

JP 2003-055555 A WO 2006/016568

When the present inventors have achieved the intended purpose as described above and introduced the reactive hot melt adhesive using the above-mentioned fast-curing reactive hot melt resin composition into the market, there are further new problems. It was found.
Due to recent trends in laws and regulations concerning chemical substances, halogenated compounds containing chlorine, bromine, fluorine and the like tend to be avoided in some industries, and so-called “halogen-free” products may be required. From such an industry situation, it is said that even in a trace amount of boron halide and / or boron halide complex, which is a component showing a curing catalytic action in the above-mentioned fast-curing reactive hot-melt resin composition, it is worrisome. There was a user.

  The problem to be solved by the present invention is a reactive hot having substantially the same halogen-free and organotin compounds as the above-mentioned boron halide and / or boron halide complex. An object of the present invention is to provide a melt resin composition and a reactive hot melt adhesive containing the same.

  In order to solve such problems, the present inventors, as a result of intensive research, have developed a reactive hot melt adhesive prepared using a curable resin having a hydrolyzable silicon group and a specific organometallic salt. It has been found that the above-mentioned problems can be solved by the composition, and the present invention has been completed. The present invention comprises the following first to thirteenth inventions.

That is, the first invention relates to a reactive hot melt resin composition comprising a curable resin (A) having a hydrolyzable silicon group in the molecule and a carboxylic acid metal salt (B). Is.
Moreover, 2nd invention concerns on 1st invention which contains a carboxylic acid metal salt (B) in the ratio of 0.01 mass part-10 mass parts with respect to 100 mass parts of curable resin (A). The present invention relates to a reactive hot melt resin composition.
In the third invention, the carboxylic acid metal salt (B) is a carboxylic acid calcium salt, a carboxylic acid vanadium salt, a carboxylic acid iron salt, a carboxylic acid titanium salt, a carboxylic acid zirconium salt, a carboxylic acid cerium salt, or an aluminum carboxylate. The present invention relates to a reactive hot melt resin composition according to the first or second invention, which is one or more compounds selected from a salt, a potassium carboxylate, a bismuth carboxylate, a barium carboxylate, and a zinc carboxylate. is there.
By using carboxylic acid metal salt (B) for curable resin (A) having a hydrolyzable silicon group, it has the same heat resistance as when boron halide and / or boron halide complex is used. A reactive hot melt resin composition substantially free of halogen compounds and organotin compounds is obtained. The carboxylic acid metal salt (B) is preferably within a predetermined blending range, and is preferably a specific metal salt.

The fourth invention further relates to a reactive hot melt resin composition according to any one of the first to third inventions, which contains a tackifier resin (C) having compatibility with the curable resin (A). It is.
Moreover, 5th invention is reactive hot melt which concerns on 4th invention which contains tackifying resin (C) in the ratio of 5 mass parts-1000 mass parts with respect to 100 mass parts of curable resin (A). The present invention relates to a resin composition.
By blending a tackifier resin (C) that is compatible with the curable resin (A), the cooling and solidifying characteristics of the reactive hot melt resin composition can be adjusted, the viscosity can be adjusted during melting, and the adhesive. It is possible to adjust the adhesiveness when used as.

The sixth invention further relates to the reactive hot melt resin composition according to any one of the first to fifth inventions, which contains a thermoplastic resin (D) having compatibility with the curable resin (A). Is.
Moreover, 7th invention is a reactive hot melt which concerns on 6th invention which contains a thermoplastic resin (D) in the ratio of 5 mass parts-1000 mass parts with respect to 100 mass parts of curable resin (A). The present invention relates to a resin composition.
The eighth invention relates to the reactive hot melt resin composition according to the sixth or seventh invention, wherein the thermoplastic resin (D) is polyethylene wax.
By blending a thermoplastic resin (D) that is compatible with the curable resin (A), the cooling and solidifying characteristics of the reactive hot melt resin composition can be adjusted, the viscosity can be adjusted during melting, and the adhesive. It is possible to adjust the adhesiveness when used as. Moreover, since the adhesive strength with respect to polyethylene of hardened | cured material will improve significantly that a thermoplastic resin (D) is polyethylene wax, the resin composition suitable for the use which requires adhesion | attachment of polyethylene is obtained.

The ninth aspect of the invention is any one of the first to eighth aspects, further comprising a reactive diluent (E) that is compatible with the curable resin (A) and has a hydrolyzable silicon group and is liquid at room temperature. The present invention relates to a reactive hot melt resin composition according to the present invention.
Moreover, 10th invention is reactive hot melt resin which concerns on 9th invention which contains a reactive diluent (E) in the ratio of 3-75 mass parts with respect to 100 mass parts of curable resin (A). It relates to a composition.
By blending a reactive diluent (E) that is compatible with the curable resin (A) and has a hydrolyzable silicon group at room temperature, the cooling and solidification characteristics of the reactive hot melt resin are adjusted. In addition, the viscosity at the time of melting can be adjusted, and the heat resistance performance of the film after reaction hardening can be kept high in the secondary adhesion stage.

The eleventh invention relates to a reactive hot melt resin composition according to any one of the first to tenth inventions, wherein the main chain of the curable resin (A) is substantially polyolefin.
In the twelfth invention, the hydrolyzable silicon group of the curable resin (A) has the formula: —SiR ¹ X ¹ X ² or the formula: —SiX ¹ X ² X ³ (wherein X ¹ , X ² and X ³ each represent a hydrolyzable group selected from the group consisting of a hydride group, an alkoxyl group, an acyloxyl group, a ketoximate group, an amino group, an amide group, an aminooxyl group, a mercapto group, and an alkenyloxyl group. The inventions according to any one of the first to eleventh inventions, which may be the same or different, and R ¹ represents a hydrolyzable silicon group represented by a substituted or unsubstituted organic group having 1 to 6 carbon atoms) The reactive hot melt resin composition according to the present invention.
The curable resin preferably has a specific main chain skeleton, and also preferably has a specific hydrolyzable silicon group.

  The thirteenth invention relates to a reactive hot melt adhesive containing the reactive hot melt resin composition according to any one of the first to twelfth inventions.

  If the reactive hot melt resin composition according to the present invention and the reactive hot melt adhesive containing the same are used, while having the same heat resistance as when boron halide and / or boron halide complex is used, A reactive hot melt resin composition substantially free of halogen compounds and organotin compounds, and a reactive hot melt adhesive containing the same are obtained.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

  The reactive hot melt resin composition of the present invention contains a curable resin (A) having a hydrolyzable silicon group in the molecule and a curing catalyst, and a carboxylic acid metal salt (B) is used as the curing catalyst. The hydrolyzable silicon group of the curable resin is a hydrolyzable silicon group or a silanol group, and the curing catalyst functions as a catalyst for hydrolysis of the silyl group and dehydration / crosslinking reaction of the silanol group. Since the curing catalyst is a carboxylic acid metal salt (B), the resin after application is very fast, and the resin stabilizes very quickly in the initial stage of adhesion, so that the joined state can be maintained. Efficiency is greatly improved.

  When the carboxylic acid metal salt (B) is used as the curing catalyst, the curable resin (A) cures extremely fast, which is a fact found from trial and error using various compounds. However, it is considered that one reason is that the carboxylic acid metal salt (B) is likely to be localized in the vicinity of the hydrolyzable silicon group in the curable resin composition. That is, the carboxylic acid metal salt is caused by intramolecular polarization due to the electron withdrawing property of the oxygen atom of the carbonyl group, and the metal atom forming the salt with the carboxylic acid is highly inorganic. However, the details are not clear.

  Hereafter, each element which comprises the reactive hot melt resin composition in this invention is demonstrated in detail.

[Curable resin (A)]
In the present invention, the curable resin (A) having a hydrolyzable silicon group is not basically limited as long as it is a curable resin having a hydrolyzable group in its molecule, but a reactive hot melt resin composition. From the viewpoint of obtaining a product, it is preferable to be a solid at room temperature in an uncured state. When the main chain of such a room temperature solid curable resin (A) is substantially polyolefin, it is difficult to adhere not only to adherends such as ABS, PET, and hard vinyl chloride, but also PP and PE. It is further preferable from the viewpoint of exhibiting excellent adhesion to an adherend.
The hydrolyzable silicon group of the curable resin (A) has the formula: —SiR ¹ X ¹ X ² or the formula: —SiX ¹ X ² X ³ (wherein X ¹ , X ² and X ³ Each represents a hydrolyzable group selected from the group consisting of a hydride group, an alkoxyl group, an acyloxyl group, a ketoximate group, an amino group, an amide group, an aminooxyl group, a mercapto group, and an alkenyloxyl group. R ¹ is preferably a group represented by a substituted or unsubstituted organic group having 1 to 6 carbon atoms. Among these, a hydrolyzable silicon group in which the hydrolyzable group is an alkoxyl group is preferable from the viewpoints of high reactivity and low odor.
Also, since the trifunctional hydrolyzable silicon group is more reactive with the curing catalyst (B) than the bifunctional hydrolyzable silicon group, the resin having a trifunctional hydrolyzable silicon group The curing rate is faster when using. When the trifunctional hydrolyzable silicon group coexists with the trifunctional hydrolyzable silicon group, the reactivity is improved as compared with the case of the bifunctional hydrolyzable silicon group alone. The curable resin (A) in which a part of the group is difunctional and the other part is trifunctional is one of preferred forms, and a resin having a bifunctional hydrolyzable silicon group and trifunctional You may mix and use resin which has a hydrolysable silicon group.

  The curable resin (A) having a hydrolyzable silicon group further includes a urethane bond (—NHC (═O) O—), a urea bond (—NHC (═O) NH—), and a substituted urea bond (—NHC). (= O) NR− / where R is a monovalent organic group), a secondary amino group (—NRH), a tertiary amino group (—NRR ′), etc. Since the rate of curing by the curing catalyst (B) tends to be faster, a curable resin having at least one polar element selected from the above bonds and groups is preferable. The reason why such a polar element is effective in improving the curing rate is not clear, but it is hydrolyzed due to the relationship with these bonds or groups, particularly electronic coordination with nitrogen atoms or oxygen atoms having lone pairs. This is presumably because the reaction of the functional silicon group is activated. Among the polar elements, a substituted urea bond is particularly effective. The improvement in the curing rate by introducing a polar element is greater when the hydrolyzable silicon group is trifunctional than when it is difunctional.

  The curable resin (A) that does not have a polar element can be classified into an oxyalkylene polymer, a saturated hydrocarbon polymer, a vinyl polymer, and the like depending on the main chain skeleton. It can be appropriately selected and used.

  Examples of the curable resin (A) in which the main chain skeleton is an oxyalkylene polymer include, for example, JP-B Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, and 51. -73561, 54-6096, 55-82123, 55-123620, 55-125121, 55-131022, 55-135135, 55-137129, etc. The proposed resin (generally a resin called a modified silicone) can be mentioned.

  As a method for producing the oxyalkylene polymer type curable resin (A), an addition reaction of a hydrogenated silicon compound having a hydrolyzable silicon group in the molecule to an alkenyl group of a polyoxyalkylene having an alkenyl group. Or a method of radically adding a mercapto group to an alkenyl group by reacting a mercaptosilane compound having a mercapto group and the hydrolyzable silicon group in the molecule with a polyoxyalkylene having an alkenyl group. It has been.

  Alternatively, as the oxyalkylene polymer type curable resin (A), a commercially available oxyalkylene polymer may be selected and used. Examples of usable resin products include Kaneka Chemical Co., Ltd. Products (trade names: S203, S303, S810, SAT010, SAT030, SAT070, SAT200, SAT350, SAT400, MA903, MA904, MAX923, S911, S943, EST200, EST250, ESX 280, SAX720, SAX725, SAX770, MA430, MA430 MA440A, MA447, MAX610), products manufactured by Asahi Glass Co., Ltd. (trade names: ES-S2410, ES-S2420, ES-S3430, ES-S3630, ES-GX3440ST).

  Examples of the curable resin (A) whose main chain skeleton is a saturated hydrocarbon polymer include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, and Japanese Patent Application Laid-Open No. 64-22904. And reactive silyl group-containing saturated hydrocarbon polymers described in Japanese Patent Publication No. 2539445 and the like. Moreover, as a saturated hydrocarbon polymer type curable resin (A), you may select and use the suitable thing from a commercially available saturated hydrocarbon polymer, for example, the product (brand name: Kaneka Chemical Co., Ltd.). Epion series), products manufactured by Evonik Degussa Japan (trade names: VESTOPLAST 206, VESTOPLAST EP204, VESTOPLAST EP2303, VESTRLAST EP2403, VESTOPLAST EP2606, VSTPLAST EP2412, VESTRLAST EP2315, etc. It is done.

  Examples of the curable resin (A) whose main chain skeleton is a vinyl polymer include, for example, JP-A-9-272715, JP-A-9-272714, JP-A-11-080249, JP-A-11-080250, and the like. 11-005815, etc., JP-A-11-116617, etc., JP-A-11-116606, etc., JP-A-11-080571, etc., JP-A-11-080570, etc., JP-A-11-130931, etc., JP-A-11-100433, etc. -116763, etc., JP2003-82192A, JP2003-119339, JP2003-171416, JP2003-246661, JP2003-327852, JP2003-327620, JP2004. And reactive silyl group-containing vinyl polymers described in No. 002835 and the like.

The curable resin (A) having the polar element in the molecule can be produced using a known method, and the polar element is introduced as a linking group generated when a plurality of raw materials are chemically reacted. Alternatively, a curable resin may be produced by reacting a compound that already has the polar element. Moreover, you may prepare curable resin (A) containing multiple types of polar elements using both methods. For the introduction of hydrolyzable silicon groups, known methods can also be used, for example, a method of adding a hydrosilane compound or a radical addition of a mercaptosilane compound to a polymer having an end alkenylated, hydrolyzable silicon group A method of introducing a hydrolyzable silicon group together with polymerization using a copolymerizable monomer having a method, a method of synthesizing a vinyl polymer having an alkenyl group and introducing a hydrolyzable silicon group by hydrosilylation, and an aminosilane compound Examples thereof include a method of introducing a hydrolyzable silicon group into the urethane prepolymer. About a preparation method, what is necessary is just to refer description of patent 3313360 gazette, special table 2004-518801 gazette, special table 2004-536957 gazette, special table 2005-501146, etc.
The number average molecular weight of the curable resin (A) is preferably about 1000 to 50000 in order to have physical properties that allow hot melt application.

  In addition, a compound described as a curable resin having a hydrolyzable silicon group in the specification of International Application No. PCT / JP2004 / 010549, which is the prior application of the present applicant, is appropriately used as the curable resin (A) in the present application. Can be used. However, since the resin described in the above international application is liquid at room temperature, the molecular weight of the main chain skeleton is increased and a solid resin is used, or the tackifying resin (C) and / or heat described later in the present application is used. It is necessary to devise such as applying a prescription that gives a composition that is solid at room temperature and exhibits a property that can be handled as a hot melt by adding the plastic component (D).

[Carboxylic acid metal salt (B)]
In the present invention, the carboxylic acid metal salt (B) is used as a curing catalyst for proceeding with hydrolysis of hydrolyzable silicon groups by moisture in the atmosphere and subsequent condensation crosslinking reaction. Carboxylic acid metal salts (B) may be used singly or in combination of two or more. As the carboxylic acid metal salt (B), carboxylic acid calcium salt, carboxylic acid vanadium salt, carboxylic acid iron salt, carboxylic acid titanium salt, carboxylic acid zirconium salt, carboxylic acid cerium salt, carboxylic acid aluminum salt, carboxylic acid potassium salt, One or more compounds selected from a carboxylic acid barium salt, a carboxylic acid bismuth salt, and a carboxylic acid zinc salt are preferable because good curability can be secured. Among these, carboxylic acid potassium salt, carboxylic acid barium salt, and carboxylic acid bismuth salt are particularly preferable because they provide better curability.

  The blending ratio of the carboxylic acid metal salt (B) is preferably 0.01 to 10 parts by mass, and particularly preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the curable resin (A). When using 2 or more types of compounds together, it is preferable that the total amount is the said range. When the blending ratio of the carboxylic acid metal salt (B) is less than 0.01 parts by mass, inconveniences such as marked decrease in curability tend to occur, and when it exceeds 10 parts by mass, the cured product after the reaction has sufficient cohesive strength. Inconvenience that it cannot be obtained easily occurs.

  In addition to the curable resin (A) and the carboxylic acid metal salt (B), the reactive hot melt resin composition of the present invention includes a tackifier resin (C), a thermoplastic component (D), a reaction, as necessary. A diluent (E) may be added. As the tackifying resin (C), the thermoplastic component (D) and the reactive diluent (E), those having compatibility with the curable resin (A) are used.

[About tackifying resin (C)]
The tackifying resin (C) can adjust the cooling and solidification characteristics of the reactive hot melt resin composition, adjust the viscosity at the time of melting, and adjust the adhesiveness when used as an adhesive. Therefore, it contributes to shortening the working time of assembling and joining and ensuring workability. As long as the tackifier resin (C) is compatible with the curable resin (A), any commonly used one can be used without particular limitation, and it is asked whether it is solid or liquid at room temperature. Absent. Specific examples include phenol resins, modified phenol resins (for example, cashew oil modified phenol resin, rosin phenol resin, polymerized rosin, polymerized rosin ester, tall oil modified phenol resin, etc.), terpene phenol resin, xylene-phenol resin, cyclopentadiene. -Phenol resin, coumarone indene resin, DCPD resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin) C9 hydrocarbon resin, C5 / C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin and the like. These may be used alone or in combination of two or more.

  As for the compounding ratio of tackifying resin (C), 5-1000 mass parts is preferable with respect to 100 mass parts of curable resin (A), and especially 20-200 mass parts with respect to 100 weight parts of curable resin (A). Is preferred.

[Thermoplastic resin (D)]
As the thermoplastic resin (D), a thermoplastic resin or elastomer having compatibility with the curable resin (A) is used. For example, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylate copolymer resin , Propylene copolymer resin, acrylic copolymer resin, polyamide resin, polyester resin, polyolefin resin, polyurethane resin, polycarbonate resin, styrene-isoprene-styrene copolymer resin, styrene-butadiene-styrene copolymer resin, styrene-ethylene- Butylene-styrene copolymer resin, styrene-ethylene-propylene-styrene copolymer resin, ethylene-propylene copolymer resin, butyl rubber, isobutylene rubber, acrylic rubber, urethane rubber, wax (PE wax, PP wax, paraffin wax) Microcrystalline wax, Fischer-Tropsch waxes) and the like. One of these can be used alone or in combination of two or more. In addition to this, a block copolymer of a polymer block mainly composed of styrene and a polymer block mainly composed of a conjugated diene such as butadiene and isoprene, and a styrene elastomer such as a hydrogenated product thereof, ethylene and α -Thermoplastic elastomers such as ethylene-α-olefin copolymer rubber obtained by copolymerization with olefin or subsequent copolymerization with diene compound can be used. When PE (polyethylene) wax is used as the thermoplastic resin (D), the adhesive strength of the cured product to polyethylene is greatly improved, so that a resin composition suitable for applications requiring the adhesion of polyethylene can be obtained.

  The blending ratio of the thermoplastic resin (D) is preferably 3 to 1000 parts by weight with respect to 100 parts by weight of the curable resin (A), particularly 5 to 100 parts by weight of the curable resin (A). A range of ˜200 parts by mass is preferred.

[Reactive diluent (E)]
The reactive diluent (E) is preferably used for the purpose of extending / controlling the open time of the reactive hot melt resin composition. Specifically, the reactive diluent (E) is a hydrolyzable silicon group (2 or A compound having a trifunctionality and having a compatibility with the curable resin (A) at room temperature is used. When a diluent having no reactive group is used, the heat resistance of the cured resin composition is lowered even if the open time can be extended. Examples of the compound having compatibility with the curable resin (A) as described above include acrylic compounds and the like, particularly those having a molecular weight of 1000 to 5000 are preferable, and combinations or polymerization compositions of two or more kinds of compounds. (The molecular weight in the case of a polymer is based on the weight average). Practical examples of the reactive diluent (E) include acrylic polymers having a glass transition temperature Tg of 0 ° C. or lower, preferably −20 ° C. or lower and having hydrolyzable silicon groups. When the reactive diluent (E) is used, the blending ratio is preferably 3 to 70 parts by weight, and most preferably 5 to 40 parts by weight with respect to 100 parts by weight of the curable resin (A). The open time can be suitably extended by about 10 to 90 seconds without deteriorating the adhesive properties and the like, and the open time can be adjusted by the blending ratio. When a plurality of types of compounds are used, the blending ratio is defined by the total amount.

  As a reactive diluent (E) available as a commercial product, a reactive plasticizer XPR series product (trade name: XPR-15, XPR-22, etc.) manufactured by Toagosei Co., Ltd., which is a liquid silyl group-containing acrylic oligomer , Products manufactured by Soken Chemical Co., Ltd. (trade names: Actflow AS-300, Actflow AS-301, Actflow ASM-4001), Kaneka Corporation products (trade name: SA100S), and the like. It is not a thing.

  The reactive hot melt resin composition of the present invention prepared using the above-mentioned components is excellent in rapid curing at ordinary temperature, and is used for adhesives, sealants, paints, coating agents, sealants (for example, repairing cracks in concrete). Can be used for a variety of applications such as casting materials and coating materials, and is particularly useful for bonding automotive parts and structural members for construction and construction. is there. When used in these applications, silane coupling agents, fillers, various additives, and the like can be appropriately blended according to the performance required for each application. In particular, silane coupling agents and fillers are often blended. Examples of various additives include a dehydrating agent, a plasticizer, an anti-aging agent or an ultraviolet absorber, a pigment, a titanate coupling agent, and an aluminum coupling agent.

  Examples of silane coupling agents include so-called vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, β- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl trimethoxy silane, and γ-glycid. So-called epoxy silanes such as xylpropylmethyldiethoxy silane and γ-glycidoxy propyl triethoxy silane, and other known ones such as so-called mercaptosilanes and isocyanate silanes may be used. These silane coupling agents may be used alone or in combination of two or more.

  The reaction of the present invention is carried out by heating and melt-mixing the curable resin (A), the carboxylic acid metal salt (B), and the optional component added as necessary in an environment where moisture is blocked. Reactive hot melt resin composition is obtained, which is suitably used as a reactive hot melt adhesive or the like. The reactive hot melt resin composition is prepared by hydrolyzing a hydrolyzable silicon group by contacting the heat-melted curable resin (A) with moisture in the atmosphere in the presence of the carboxylic acid metal salt (B). Condensation and cross-linking reactions are initiated and cure rapidly even at room temperature.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

[Procurement of raw materials]
As a curable resin (A) having a hydrolyzable silicon group, VESTLAST EP2412 (product of Evonik Degussa Japan Co., Ltd.) / Normal temperature white solid whose main chain is a polyolefin skeleton and a trimethoxysilyl group in a side chain / softening point before curing A thermoplastic resin having a temperature of 100 ° C. was prepared.
As the carboxylic acid metal salt (B), bismuth octylate, barium octylate, potassium octylate, zinc octylate, and calcium octylate were prepared. For comparative experiments, boron trifluoride piperidine complex, which is a boron trifluoride complex, and dioctyltin diversate, which is an organotin compound (manufactured by Nitto Kasei Co., Ltd./tetravalent dioctyltin compound / room temperature yellow liquid) Prepared.
As a tackifier resin (C), Alcon M100 (Arakawa Chemical Industries, Ltd./C9 series partially hydrogenated hydrocarbon resin / softening point 100 ° C.) was prepared.
As the thermoplastic resin (D), Recommont PE830 (manufactured by Clariant Japan Ltd./polyethylene wax) was prepared.
As a reactive diluent (E), SA100S (manufactured by Kaneka Corporation / normal temperature liquid silyl group-containing acrylic polymer) was prepared.

[Preparation of Reactive Hot Melt Resin Composition]
Resin compositions (1) to (8) were prepared according to the following.

<Example 1: Resin composition (1)>
Into the reaction vessel, 100 parts by mass of a silane-modified amorphous-poly-α-olefin resin (trade name: VESTPLAST EP2412) was added and heated to 150 ° C. under reduced pressure to dehydrate the resin for 30 minutes. The resin composition (1) was obtained by adding 0.2 parts by mass of bismuth octylate to the resin and stirring and mixing at 150 ° C. for 30 minutes.

<Example 2: Resin composition (2)>
A resin composition (2) was obtained in the same manner as in the resin composition (1) except that the bismuth octylate salt was changed to the same amount of barium octylate salt.

<Example 3: Resin composition (3)>
A resin composition (3) was obtained in the same manner as in the resin composition (1) except that the bismuth octylate salt was changed to the same amount of potassium octylate.

<Example 4: Resin composition (4)>
Resin composition (4) was obtained in the same manner as in resin composition (1) except that bismuth octylate was changed to zinc octylate having the same amount.

<Example 5: Resin composition (5)>
A resin composition (5) was obtained in the same manner as in the resin composition (1) except that the bismuth octylate salt was changed to the same amount of calcium octylate salt.

<Reference Example 1: Resin composition (6)>
A resin composition (6) was obtained in the same manner as in the resin composition (1) except that the bismuth octylate salt was changed to the same amount of boron trifluoride piperidine complex.

<Reference Example 2: Resin composition (7)>
A resin composition (7) was obtained in the same manner as in the resin composition (1) except that the bismuth octylate salt was changed to the same amount of dioctyltin diversate.

[Evaluation of curability (Measurement of softening temperature of cured film)]
The heat resistance of the resin composition was evaluated by measuring the heat resistance creep resistance of the reactive hot melt resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2. The results are shown in Table 1.
The measurement method of heat-resistant creep resistance is as follows. In a 23 ° C. and 50% relative humidity atmosphere, a molten resin composition is applied to a 2.5 cm wide canvas and the other canvas is immediately bonded (bonded area: 2.5 cm × 2.5 cm ² ) and left for 1 or 7 days. After that, according to JIS K 6833, one canvas fixed and a 500 gf weight attached to the other canvas is suspended in an oven capable of controlling the temperature rise, and the ambient temperature is gradually increased. The dropped temperature was defined as the softening temperature. In addition, the measurement was performed 3 times and the average value was described in the table.
The following criteria were used as evaluation criteria.
As the initial heat resistance rising speed, if the value after 1 day in the heat resistance creep resistance test exceeds 50 ° C., it can be judged that it can be used depending on the application, and if it is 70 ° C. or higher, it is almost practical. No problem.
As the film heat resistance of the final cured product, if the value after 7 days in the heat-resistant creep resistance test exceeds 60 ° C, it can be judged that it can be used depending on the application, and if it is 85 ° C or higher It can be determined that there is no practical problem as the final heat resistance.

Table 1 shows the measurement results of heat resistance creep resistance of each resin composition. From the results of the table, it can be seen that the reactive hot melt resin composition according to the present invention exhibits a practically sufficient initial heat resistance rise, and there is no practical problem with respect to the final film heat resistance. Especially, about what used the carboxylic acid metal salt of Examples 1-3, the start of heat resistance equivalent to boron trifluoride and / or a boron trifluoride complex, and final heat resistance were expressed, and it is favorable. Results are shown.
Moreover, since the reactive hot melt resin composition according to the present invention does not contain a halogen compound and an organotin compound, it can sufficiently cope with uses in which these compounds are disliked and laws and regulations that will become stricter in the future.

[Preparation of reactive hot melt adhesive]
Reactive hot melt adhesives (8) to (11) were prepared according to the following.

<Example 6: Reactive hot melt adhesive (8)>
Silane-modified amorphous-poly-α-olefin resin (trade name: VESTPLAST EP2412) 100 parts by mass in a reaction vessel, tackifier resin (trade name: Alcon M100) 30 parts by weight, which is a C9 partially hydrogenated hydrocarbon resin, polyethylene wax 15 parts by mass of a thermoplastic resin (trade name: Recommont PE 830) and 30 parts by mass of a reactive diluent (trade name: SA100S) which is a silyl group-containing acrylic polymer at room temperature are charged, and 150 ° C. under reduced pressure. And the resin was dehydrated for 30 minutes. Thereafter, 0.2 parts by mass of potassium octylate was added, and the mixture was further stirred and mixed at a temperature of 150 ° C. for 30 minutes to obtain a reactive hot melt adhesive (8).

<Example 7: Reactive hot melt adhesive (9)>
In Example 6, the same operation as in the case of the reactive hot melt adhesive (8) was performed except that the thermoplastic resin (trade name: Recommon PE830), which is a polyethylene wax, was not added. An adhesive (9) was obtained.

<Example 8: Reactive hot melt adhesive (10)>
In Example 6, the same operation as in the case of the reactive hot melt adhesive (8) was performed except that the tackifying resin (trade name: Alcon M100) which is a C9-based partially hydrogenated hydrocarbon resin was not added. Thus, a reactive hot melt adhesive (10) was obtained.

<Reference Example 3: Reactive hot melt adhesive (11)>
A reactive hot melt adhesive (11) was obtained by performing the same operation as in the case of the reactive hot melt adhesive (8) except that the potassium octylate was changed to the same amount of boron trifluoride piperidine complex. It was.

[Evaluation of properties and performance (melt viscosity, softening point, heat-resistant creep resistance, peel adhesion strength)]
The performance of the reactive hot melt adhesive was evaluated by measuring the performance of each of the reactive hot melt adhesives obtained in Examples 6 to 8 and Reference Example 3. The results are shown in Table 2.
The melt viscosity was measured in accordance with the Japan Adhesive Industry Association Standard (JAI-7) by measuring the melt viscosity at 180 ° C. using a Brookfield viscometer.
The measuring method of the softening point was measured by the R & B method according to the Japan Adhesive Industry Association Standard (JAI-7). In addition, the softening point measured here shows the softening point of the hot-melt adhesive when uncured.
The measurement of heat-resistant creep property was tested 7 days after bonding by the same method as the heat-resistant creep property evaluation of the resin composition described above. As an evaluation standard, if the final heat resistance is 85 ° C. or higher, it can be determined that there is no practical problem.
The peel adhesion strength is measured by uniformly applying 1 g of each reactive hot melt adhesive on one entire surface of a polyethylene flat plate (thickness 3 mm, width 25 mm, length 100 mm), and the width of the bonded portion is 25 mm. A canvas (width 25 mm, length 200 mm) was immediately pasted to a length of 80 mm to obtain a test specimen. Each specimen was cured at a temperature of 23 ° C. and a relative humidity of 50 ± 5% for 7 days, and then the 180 ° peel adhesion strength (N / 25 mm) was measured according to JIS K 6854. The 180 degree peel adhesion strength was measured in an atmosphere of 0 ° C, 23 ° C, and 40 ° C.

Table 2 shows the measurement results of properties and performance of each hot melt adhesive.
From the results shown in Table 2, it can be seen that the reactive hot melt resin according to the present invention has good film heat resistance and has no practical problem. Also, the peel strength was sufficient at low temperatures (0 ° C.) and at high temperatures (40 ° C.), and good results were obtained without any practical problems.
In addition, since the reactive hot melt according to the present invention does not contain a halogen compound or an organotin compound, the reactive hot melt can sufficiently cope with the use in which these compounds are avoided and the laws and regulations that are expected to become increasingly severe in the future. It is.

Taking advantage of the heat resistance, light resistance, and electrical insulation of the resin having a hydrolyzable silicon group, it has substantially the same heat resistance as when a boron halide and / or a boron halide complex is used. A reactive hot melt resin composition that does not contain a tin compound can be provided, and is highly useful in fields such as adhesives, sealing materials, and coating materials.

Claims (13)

  A reactive hot melt resin composition comprising a curable resin (A) having a hydrolyzable silicon group in the molecule and a carboxylic acid metal salt (B).   The reactive hot-melt resin composition of Claim 1 which contains a carboxylic acid metal salt (B) in the ratio of 0.01 mass part-10 mass parts with respect to 100 mass parts of said curable resins.   Carboxylic acid metal salt (B) is carboxylic acid calcium salt, carboxylic acid vanadium salt, carboxylic acid iron salt, carboxylic acid titanium salt, carboxylic acid zirconium salt, carboxylic acid cerium salt, carboxylic acid aluminum salt, carboxylic acid potassium salt, carboxylic acid The reactive hot melt resin composition according to claim 1 or 2, which is at least one compound selected from a bismuth acid salt, a barium carboxylate, and a zinc carboxylate.   The reactive hot melt resin composition according to any one of claims 1 to 3, further comprising a tackifying resin (C) having compatibility with the curable resin (A).   The reactive hot-melt resin composition of Claim 4 which contains tackifying resin (C) in the ratio of 5 mass parts-1000 mass parts with respect to 100 mass parts of curable resin (A).   Furthermore, the reactive hot melt resin composition in any one of Claims 1-5 containing the thermoplastic resin (D) which has compatibility with curable resin (A).   The reactive hot-melt resin composition of Claim 6 which contains a thermoplastic resin (D) in the ratio of 5 mass parts-1000 mass parts with respect to 100 mass parts of curable resin (A).   The reactive hot melt resin composition according to claim 6 or 7, wherein the thermoplastic resin (D) is polyethylene wax.   The reactivity according to any one of claims 1 to 8, further comprising a reactive diluent (E) that is compatible with the curable resin (A) and has a hydrolyzable silicon group and is liquid at room temperature. Hot melt resin composition.   The reactive hot-melt resin composition of Claim 9 which contains a reactive diluent (E) in the ratio of 3-70 mass parts with respect to 100 mass parts of curable resin (A).   The reactive hot melt resin composition according to any one of claims 1 to 10, wherein the main chain of the curable resin (A) is substantially a polyolefin. The hydrolyzable silicon group of the curable resin (A) has the formula: —SiR ¹ X ¹ X ² or the formula: —SiX ¹ X ² X ³ (wherein X ¹ , X ² and X ³ are Each represents a hydrolyzable group selected from the group consisting of a hydride group, an alkoxyl group, an acyloxyl group, a ketoximate group, an amino group, an amide group, an aminooxyl group, a mercapto group, and an alkenyloxyl group, which may be the same or different. The reactive hot melt according to any one of claims 1 to 11, wherein R ¹ is a hydrolyzable silicon group represented by a substituted or unsubstituted organic group having 1 to 6 carbon atoms. Resin composition.   A reactive hot melt adhesive containing the reactive hot melt resin composition according to claim 1.