WO2003066772A1

WO2003066772A1 - Curable adhesive and method of bonding with the same

Info

Publication number: WO2003066772A1
Application number: PCT/JP2003/001323
Authority: WO
Inventors: Yukiko Fujita; Takashi Tomiyama
Original assignee: Dainippon Ink And Chemicals, Inc.
Priority date: 2002-02-08
Filing date: 2003-02-07
Publication date: 2003-08-14

Abstract

An excellent adhesive which is excellent in surface-drying properties during cold setting and in such tenacious adhesion that no peeling occurs at the interface between an adherend and the adhesive and the curability of which is not influenced by moisture or water content of the adherend; and a method of bonding a fiber-reinforced plastic with the adhesive. The adhesive is a curable adhesive which comprises (A) a urethane resin having polymerizable unsaturated groups, (B) a resin having polymerizable unsaturated groups which is dryable with air, (C) an unsaturated monomer having a (meth)acryloyl group, (D) a coupling agent, and (E) a filler, and gives a cured article having a tensile elongation of 1 to 33%. The bonding method comprises the step of bonding a fiber-reinforced plastic molding with the curable adhesive.

Description

Description Curable adhesive and bonding method using the same

The present invention has excellent surface drying properties and adhesiveness when cured at room temperature. In particular, the curing properties and adhesive strength are not affected by the working environment such as temperature and humidity, and the bonding of large molded products of fiber reinforced plastic (FRP). The present invention relates to a cold-setting adhesive and a method for bonding a fiber-reinforced plastic using the same. Background art

In recent years, fiber reinforced plastics (FRP) such as unsaturated polyester resin, vinyl ester resin, and epoxy resin, which are lightweight, high strength, and excellent in corrosion resistance, have been used for honeycomb structural members. There is an increasing demand for adhesives used as adhesives and coating materials for the purpose of preventing the deterioration of concrete and steel used in buildings, structures and equipment and preventing the collapse of tunnels. This coating material is a material that does not require heating and pressurization, such as hot melt adhesives or epoxy resin, which requires a large capital investment for the bonding operation, or a material in the air or base, such as a two-liquid polyurethane resin. Materials in which the curability and adhesiveness are not affected by the moisture content of the materials are particularly desired, and in particular, a curing system in which the curing time can be adjusted according to the work content and scale is desirable. In response to such demands, studies have been conducted on a lumber with a room-temperature curing type with excellent adhesiveness and a hardening time that can be adjusted by workability. However, no satisfactory one has been proposed.

As an energy ray-curable resin composition with excellent adhesion and durability to a substrate, for example, a glass fiber, as a coating material application, urethane (meth) acrylate, a monofunctional or polyfunctional monomer, a silane coupling agent (Japanese Unexamined Patent Publication No. 3-1992 17) has been proposed. However, when such a resin thread is used as an adhesive for molded articles such as FRP by radical curing at room temperature, curing in the air is inhibited by oxygen in the air, and the surface is not sticky. is there. As an active energy ray-curable resin composition for a coating material, an aromatic polyether polyol is used. Containing at least one of ethylenic unsaturated monomers, urethane acrylates, air-drying type unsaturated polyesters, unsaturated polyesters, and epoxy acrylates using ethyl acetate (JP-A-10-3) No. 0 0 1 2) has been proposed. However, since the ethylenically unsaturated monomer of the resin composition is a styrene monomer, satisfactory adhesive strength such as peeling off at the interface between the adhesive and the base material cannot be obtained. Furthermore, for civil engineering and building materials, reactive oligomers (urethane acrylates), polymers containing unsaturated groups that are air-dry and crosslinkable by radical polymerization, and have phenyl groups and a molecular weight of 18 A composition comprising a monomer having 0 or more (meth) acrylate groups, paraffin wax, and a dispersant having an ability to disperse paraffin wax (Japanese Patent Application Laid-Open No. 11-209628) has been proposed. ing. However, it could not be used as an adhesive because it contained paraffin wax.

In addition, all of these resin cured products had a tensile elongation of 35% or more, and were flexible and easily distorted, so they were not suitable as adhesives for rigid products. Disclosure of the invention

An object of the present invention is excellent in surface drying property at room temperature curing, strong adhesion without interfacial delamination between a substrate to be bonded and an adhesive, and excellent in curability not affected by humidity or moisture of the substrate. It is an object of the present invention to provide an adhesive and a method for bonding a fiber-reinforced plastic using the same.

The present inventors have conducted intensive studies on these problems, and as a result, have completed the present invention.

The present invention relates to (A) a urethane resin having a polymerizable unsaturated group, (B) a resin containing an air-dryable polymerizable unsaturated group, and (C) an unsaturated resin having a (meth) acryloyl group. A curable adhesive containing a monomer, (D) a coupling agent and (E) a filler, wherein the cured product of the curable adhesive has a tensile elongation of 1 to 33%. The present invention relates to a curable adhesive and a method of bonding a fiber-reinforced plastic using the same. BEST MODE FOR CARRYING OUT THE INVENTION

[Tensile elongation]

The term "tensile elongation" used in the present invention refers to a cured product of the curable adhesive of the present invention comprising the above (A), (B), (C), (D) and (E). It is measured in an atmosphere of ° C according to JIS K7113 by the following measurement method.

Measuring method>

(1) 55% methyl ethyl ketone peroxide (polymerization initiator) 1.0% and 6% cobalt naphthenate (polymerization accelerator) 0.1% are added to the adhesive consisting of (Α) to (〜) above. By adding an appropriate amount of hydroquinone monomethyl ether (a polymerization inhibitor) to the mixture obtained by mixing, the gel time of the mixture at 25 ° C (based on Japanese Industrial Standard JISK-6901) becomes 30 minutes. Adjust as follows. After defoaming, the mixture is poured into the gap between two glass plates facing each other with a spacer of 3 mm in thickness, and then left at 25 ° C for one week to cure.

② One week later, from a 3 mm thick plate-like cured product, a No. 1 test piece specified in JI SK71 13 (total length: 175 mm, width at both ends: 20 ± 0.5 mm, length of parallel part: 60 ± 0.5 mm, width of parallel part 10 ± 0.5 mm, radius of shoulder roundness (minimum) 60 mm, thickness 3 mm, distance between reference lines 50 soil 0.5 mm, distance between grips 1 1 5 Soil 5 mm) is mechanically cut out, and this test piece is attached and fixed to a tensile tester (“Autograph AG 100 KNG” manufactured by Shimadzu Corporation).

③ Maintain the test piece at 25 ° C for 10 minutes. The test piece was pulled at a tensile speed of 5 mm / min by the tensile tester until it broke, the elongation at that time was measured, and the percentage of the elongation to the distance between the reference lines was defined as the tensile elongation.

In the adhesive of the present invention, the tensile elongation of the cured product is controlled to 1 to 33%, preferably 2 to 30%. By controlling the tensile elongation of the cured product within this range, even when the substrate bonded with the adhesive is subjected to a large external stress, the substrate is not deformed by the adhesive layer. In addition, the adhesive layer absorbs stress, preventing internal rupture, and as a result, the adhesive acquires a strong adhesive force. Examples of the urethane resin having a polymerizable unsaturated group as the component (A) of the present invention include: And a polyol, preferably a polyester polyol or a polyether polyol, and a urethane resin having a polymerizable unsaturated group at a molecular terminal obtained by reacting a hydroxyl group-containing (meth) atalyl compound. a hydroxyl group-containing (meth) acrylic compound, or a hydroxyl group-containing (meth) acrylic compound and a hydroxyl group-containing (meth) aryl ether compound in a urethane prepolymer having an isocyanate group at a terminal obtained by reacting z or a polyether polyol with a polyisocyanate; Is a urethane resin containing a (meth) atalyloyl group at the molecular end.

The urethane resin (A) having a polymerizable unsaturated group is preferably a urethane resin having a (meth) acryloyl group, and particularly preferably a polyether urethane resin using a polyether polyol. Further, such a resin (A) is obtained by reacting the above polyisocyanates with a polyether polyol having a (meth) acryloyl group, a polyester polyol having a (meth) acryloyl group, and those further having an aryl ether group added thereto. Those obtained by using can also be used. Incidentally, a diamine may be used as a reaction raw material, if necessary.

The polyether polyol has a number average molecular weight of 200 or more, preferably 300 to 300, and particularly preferably 400 to 150. Specifically, for example, polyoxypropylene dione (hereinafter abbreviated as PPG), polyoxytetramethylene diol (hereinafter abbreviated as PTMG), polyoxyethylene diol, polyoxyethylene monopropylene diol, and the like can be given.

The polyester polyol has a number average molecular weight of 200 or more, preferably 300 to 500, particularly preferably 400 to 300, and a diol (glycol) component and an acid component. And obtained by reacting

The diol component includes, for example, ethylene glycol, propylene dalycol, butylene glycolone, pentylene glycolone, hexylene glycol, dimethylolcyclohexane, 2,4,4-trimethyl-1,3-pentanediol, and the like. Representative alkylene glycols; poly'alkylene glycols represented by diethylene glycol, polyethylene glycol, dipropylene glycol Λ ^, polypropylene glycolone, and polybutylene glycol; bisphenol フ It is an addition reaction product of a divalent phenol represented by Sphenoleno F, Bisphenole S, Tetrabromobisphenol A and an alkylene oxide represented by ethylene oxide-propylene oxide. Such diols include glycerin, trimethylonolepropane, trimethylolethane, and 1,2,6-hexanetriol. As a tetraol unit, a trile such as pentaerythritol, diglycerol, 1,2-3,4-butanetetriol can be used in combination. Polycarbonate diol, polypropylene triol, polytetramethylene triol, polyoxyethylene triol, polycarbonate triol, polypropylene tetraol, polytetramethylene tetraanol, polyoxyethylene tetraol, polycarbonate tetraol, etc. It can also be used by adding.

The acid component may be an α, / 3-unsaturated dibasic acid or an acid anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and esters thereof. Such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, and halogenated phthalic anhydride; And aliphatic esters or alicyclic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, gnoletanoleic acid and hexahydrophthalic anhydride. And esters thereof, etc., which are used alone or in combination. Tribasic acids such as trimellitic acid, trimesic acid, aconitic acid, butanetricarboxylic acid, 6-carboxy-13-methyl-1,2-3,6-hexahydrophthalic acid, pyromellitic acid, butanetetracarboxylic acid A tetrabasic acid such as an acid can be used in combination with the dibasic acid.

Examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomers or heterogeneous mixtures (hereinafter abbreviated as TDI), diphenyl methane diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, trizine diisocyanate, naphthalindi Socyanate, Trifenylmethanetriisocyanate, "Barnock D-7500", "Chrisbon NX" (product of Dainippon Ink & Chemicals, Inc.), "Desmodur" (product of Sumitomo Bayer), "Coronate LJ" (Manufactured by Nippon Polyurethane Co., Ltd.), "Takenate D102" (manufactured by Takeda Pharmaceutical Co., Ltd.), "Coronate HX" (manufactured by Nippon Polyurethane Co., Ltd.), etc. Disocyanurate isocyanate, etc., but diisocyanate is preferred. Particularly, TDI is preferably used.

As the hydroxyl group-containing (meth) acrylic compound, hydroxyalkyl (meth) acrylate is preferable, for example, 2-hydroxyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl. (Meta) hydroxyalkyl (meth) acrylate such as atarilate, polyethylene daricol (meth) acrylate, polyoxyalkylene mono (meth) acrylate such as polypropylene glycol (meth) acrylate, 2-Hydroxy-1-3 phenoxypropyl (meth) acrylate, diisocyanuric acid ethylene oxide-modified di (meth) acrylate, trimethylolpropane di (meth) atalylate trimethylol ethanedi (meth) acrylate , Pentaerythritau Rutoli

Poly (alcohol) such as (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like. Or two or more of them may be used in combination.

In the urethane resin (A) having a polymerizable unsaturated group, an aryl ether group can be introduced into the urethane resin (A) in order to improve anaerobic property during curing. It is preferably introduced using a hydroxyl group-containing aryl ether compound from the viewpoint of the synthesis method. As the hydroxyl group-containing aryl ether compound, known and commonly used ones can be used, and typical examples thereof include ethylene glycol monoallyl ether ether, diethylene glycol monooleyl ether ether ether, triethylene glycol mono allyl ether ether, and polyethylene. Glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, triple-mouth pyrendalicole monoallyl ether, polypropylene dallycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1, 3 —Butylene Polyhydric alcohols such as glycolone monoaryl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropanediaryl ether, glycerin diarynoether, pentaerythritol tonoreto alcohol Aryl ether compounds and the like. Preferably, it is an aryl ether compound having one hydroxyl group.

As a method for producing the urethane resin (A) having a polymerizable unsaturated group, preferably, first, a polyisocyanate and a polyester polyol or a polyether polyol are mixed with NC OZOH = 2 to l (Equivalent ratio) to produce a urethane prepolymer having a terminal isocyanate group, and then reacting a 2 mole ratio of hydroxyl group-containing '(meth) acrylic compound with respect to 1 mole of the polymer, The resin is manufactured. In addition, first, a hydroxyl group-containing (meth) acrylic compound is reacted with diisocyanate, and then the obtained unsaturated monoisocyanate is optionally reacted with polyester polyol or Z and polyether polyol in the presence of diisocyanate. There is also a method of producing the luster of the tree. When isocyanurate isocyanate is used, a compound in which diisocyanate is isocyanurated may be used, or an adduct of diisocyanate and an active hydrogen atom-containing (meth) acrylate is isocyanurated, and then polyol and The reaction may be carried out, or the diisocyanate and the polyol may be reacted and then isocyanurated. These reactions may be carried out together with the reaction for synthesizing the urethane resin having a polymerizable unsaturated group (A).

As a method for producing the urethane resin having a (meth) acryloyl group as the urethane resin having a polymerizable unsaturated group (A), first, a polysocyanate and a polyester polyol or a polyether polyol are preferably used. Is reacted at 1 ^ 〇0 / 0 «[= 2 to 1.5 (equivalent ratio) to produce a urethane prepolymer containing terminal isocyanate groups, and then the hydroxyl group-containing (meth) acrylic compound and This is a method in which a hydroxyl group-containing aryl ether compound is reacted with an isocyanate group such that the hydroxyl group is substantially equivalent to the isocyanate group. At this time, the molar ratio of the hydroxyl group-containing (meth) ataryl compound / hydroxyl group-containing aryl ether compound is preferably 90 to 10/20/80, more preferably 70/30 to 40/60. so is there. As another method, first, a hydroxyl group-containing (meth) acrylic compound and a hydroxyl group-containing arylene ether compound are reacted with a polyisocyanate, and then the obtained isocyanate group-containing compound is reacted with a polyester polyol or z and polyether polyol. To produce an allyl ether group-containing polyether urethane resin having a (meth) acryloyl group at the end or an aryl ether group-containing polyester resin urethane having a (meth) atalyloyl group at the end.

The number average molecular weight of the urethane resin (A) having a polymerizable unsaturated group is preferably from 650 to 500,000, more preferably from 800 to 500, when only a (meth) atalyloyl group is present at the terminal. When it contains a (meth) acryloyl group and an arylester group, it is preferably 800 to 500,000, and more preferably 100 to 2000. It is. The urethane resin (A) is preferably polyether urethane.

The urethane resin (A) having a polymerizable unsaturated group may be used by mixing an unsaturated monomer having a (meth) acryloyl group as a component (C) in advance. The mixture ratios (wt ^_0/0), the urethane榭脂(A) 1 0 to 9 0%, preferably from 3 0-7 and 0% unsaturated monomer (C) 9 0 to: 1 0 %, Preferably 70 to 30%. To the mixture of the resin (A) and the unsaturated monomer (C), a polymerization inhibitor can be added preferably in an amount of 100 to 900 ppm.

The adhesive of the present invention contains, as a reactive component, an air-drying polymerizable unsaturated group-containing resin (hereinafter referred to as an air-drying imparting resin) (B) as an essential component. When the adhesive of the present invention contains the air-drying property-imparting resin (B), when used as an adhesive, not only the surface drying property at the time of curing is improved, but also the adhesive property is improved. Can be.

The air-drying property-imparting resin (B) is preferably one in which the adhesive of the present invention can be cured even in the air, and contains a resin such as a saturated polyester resin, an unsaturated polyester resin, or a vinyl ester resin as an essential component. It is obtained by introducing a drying property imparting component, that is, a compound imparting air drying property, into these resin skeletons. A preferable example of the air-drying property-imparting resin (B) is an air-drying unsaturated polyester resin from the viewpoint of adhesive strength. . The unsaturated polyester resin as the air-drying-imparting resin (B) refers to a polyester component and a -3-unsaturated dibasic acid, or an acid component composed of a saturated dibasic acid used in combination therewith and air-drying property. And a compound that imparts The polyol component comprises a diol used in the polyester polyol as a main component and a triol or the like in combination.

Examples of the acid component include: H, 3-unsaturated dibasic acid or an acid anhydride thereof, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof. And aromatic saturated dibasic acids or anhydrides thereof, such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, and halogen. Phthalic anhydride and esters thereof; aliphatic or alicyclic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, daltaric acid, and hexahydrophthalic anhydride; There are acids and esters thereof, and these are used alone or in combination. Tribasic acids such as trimellitic acid, trimesic acid, aconitic acid, butanetricarboxylic acid, 6-carboxy-3-methyl-1,2,3,6-hexahydrophthalic acid, pyromellitic acid, butanetetracarboxylic acid, etc. Can be used in combination with the dibasic acid.

The vinyl ester resin of the air-drying resin (B) is, for example, an unsaturated epoxy resin, a polyester (meth) acrylate resin, or the like.

The unsaturated epoxy resin is preferably a bisphenol-type epoxy resin alone or a mixture of a bisphenol-type epoxy resin and a nopolak-type epoxy resin, and the average epoxy equivalent is preferably Is obtained by reacting an epoxy resin in the range of 150 to 450 with an unsaturated monobasic acid at an equivalent ratio of epoxy group to carboxyl group of about 1/2 in the presence of an esterification catalyst. is there.

The bisphenol type epoxy resin is a glycidyl ether type epoxy resin having substantially two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin with bisphenol A or bisphenol F. , Methyl Epichlorohydrin or dimethyldaricidyl ether type epoxy resin obtained by the reaction of epichloronohydrin with bisphenol A or bisphenol A or alkylene oxide adduct of bisphenol A with epichlorohydrin or methylepichlorohydrin Epoxy luster obtained from the same. Representative examples of the novolak type epoxy resin include epoxy resin obtained by reacting phenol nopolak or cresol novolac with epichlorohydrin or methylepiclonorehydrin.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, oxalic acid, monomethylmalate, monopropinolemalate, monobutenemalate, sorbic acid and mono (2-ethylhexyl) Malate and the like. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out at a temperature of 60 to 140 ° C, particularly preferably 80 to 120 ° C, using an ester ester catalyst. As the esterification catalyst, for example, a known catalyst such as tertiary amine, such as triethylamine, N, N-dimethylbenzinoleamine, N, N-dimethylaniline or diazavic octane, or a known catalyst such as getylamine hydrochloride can be used as it is. it can.

The number average molecular weight of the unsaturated epoxy resin is preferably from 900 to 250, particularly preferably from 130 to 220. When the molecular weight is 900 to 250, there is no stickiness of the cured product, excellent strength physical properties, excellent curing time and excellent productivity. As the polyester (meth) acrylate resin described above, Saturated polyester resin or unsaturated polyester resin A resin containing at least one (meth) atalyloyl group in one molecule, and a polymerizable unsaturated monomer having these resin and (meth) atalyloyl group The polyester (meth) acrylate resin is exemplified by those represented by the following chemical formulas 1 to 10. General formula 1

M— G- D— G½- General formula 2

—General formula 3

General formula 4

General formula 5

General formula 6

M 'MMM -General formula 7

General formula 8

MH-J—— D 1 no a -J- Η

General formula 9

M-i-J—— D, m-X

-General formula 1 o

M "~ J— hD— J- a-1 -Y

However, M: (meth) acrylic acid residue, G: glycol residue, T r: Trio one Le residues, T e: tetraol residues, dibasic acid residue, D _2: tribasic acid residue , D ₃ : Tetraacid residue, J: Dalicol residue based on monoepoxyside, X: m-valent organic residue based on reaction with carboxyl group of m-valent epoxy compound, Y: n-valent isocyanate A, b, c, d: an integer of 1 or more, p: 0 or 1, m: an integer of 2 to 10, n: 2 to 5 When each represents an integer and a plurality of groups in parentheses are returned, the constituent components may be different for each repeating unit. The saturated polyester resin is a resin obtained without using an α, β monounsaturated dibasic acid or its anhydride in the production of the unsaturated polyester resin. The polyester (meth) acrylate resin is preferably obtained by reacting a (meth) acryloyl group-containing glycidyl compound with a saturated polyester resin or an unsaturated polyester resin having a carboxyl group. In addition, those obtained by reacting a hydroxyl group-containing saturated polyester resin or unsaturated polyester resin with an acrylic acid, methacrylic acid, or (meth) acrylic compound having an isocyanate group can also be used.

Examples of the (meth) acryloyl group-containing glycidyl compound include glycidyl esters of unsaturated monobasic acids such as acrylic acid and methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate. Glycidyl acrylate is preferable as the (meth) atalylyl group-containing daricidinole compound. The number average molecular weight of such a polyester (meth) acrylate resin is preferably from 800 to 300, particularly preferably from 100 to 280. When the molecular weight is from 800 to 300, the cured product has no tackiness, has high strength physical properties, has a short curing time, and has excellent productivity.

Examples of the compound imparting air drying property used in the production of the resin (B) for imparting air drying property include: 1) an alcoholysis compound obtained by a transesterification reaction between a polyhydric alcohol and a fatty oil such as a drying oil; ) Fatty acid fatty acids obtained by saponifying drying oils and the like, 3) polyols having an aryl ether group, 4) alicyclic dibasic acids, and 5) dicyclopentagenes.

Examples of the alcoholysis compound of the above 1) include, for example, polyhydric alcohols such as glycerol, trimethylolethane, trimethylolpropane, trihydric alcohols such as trishydroxymethylaminoaminomethane, pentaerythritol, and tetrahydric alcohols such as dipentaerythritol; Fatty oils, preferably dry decaying oils, especially fats and oils having an iodine value of at least 130, such as polyol compounds obtained by an ester exchange reaction with linseed oil, soybean oil, cottonseed oil, peanut oil, coconut oil, etc. is there.

As the fatty acid of the above 2), the above fatty oil, preferably a fatty oil fatty acid obtained by saponifying the drying oil or the like is used. As the above-mentioned 3), an aryl ether group-containing polyol can be used. The alicyclic dibasic acid of the above 4) includes, for example, tetrahydro (anhydride) phthalic acid, 4-methyl-tetrat Lahydro (anhydride) phthalic acid, 3-methyl-tetrahydro (anhydride) phthalic acid, and the like.

The method of introducing the compound imparting air-drying property is as follows. The method of producing the resin (B) which imparts air-drying property is as follows: 1) The alcoholysis obtained by transesterification of polyhydric alcohol with fatty oil such as drying oil. A method of using the compound as an alcohol component of the above-mentioned ginseng; a method of using a fatty oil fatty acid obtained by saponifying a drying oil as an acid component; and a method of using a polyol containing an aryl ether group as an alcohol component. 4) a method using an alicyclic dibasic acid as the acid component, and 5) a method in which a dicyclopentene is reacted with an acid or dalicol and used as an acid component or an alcohol component. At this time, the compound imparting air drying property is preferably used in combination with another alcohol component or acid component, and in some cases, it can be used alone as the alcohol component or acid component.

The content of the air-drying compound (air-drying component) is not particularly limited as long as air-drying can be imparted to the composition of the present invention without adding wax or the like. during the air-drying-imparting resin (B), preferably 3.0 to 7 0 molar% (at the total resin component), more preferably 3 0-6 0 mol ^_0/0.

The mixing ratio of the urethane resin (A) having a polymerizable unsaturated group used in the present invention and the air-drying-imparting resin (B) is preferably 95/5 to 5% by weight in the ratio of (A) / (B). 50/50, more preferably 90 to 60 Z40. With such a weight ratio, the surface drying property of the adhesive is good, and properties such as tensile strength, tear strength, water resistance, and heat and moisture resistance of the cured adhesive are also desirable.

The unsaturated monomer having a (meth) atalyloyl group as the component (C) of the adhesive of the present invention includes a urethane resin (A) having a polymerizable unsaturated group at a molecular terminal and an air-drying resin (B). And a monomer or oligomer having a (meth) atalyloyl group. As such an unsaturated monomer (C), a (meth) acrylic acid ester monomer is preferable, and a (meth) acrylic acid ester monomer containing an active hydrogen atom is particularly preferable since it has excellent adhesion to a substrate. . The amount of the unsaturated monomer (C) used is preferably from 20 to 60% by weight, more preferably from 30 to 60% by weight based on the total weight of the components (A), (B) and (C). 50% by weight. Incidentally, the unsaturated monomer (C) containing a (meth) acryloyl group may be used in combination with another polymerizable monomer, but the content of the other polymerizable monomer may be 5 or less. It is preferable to keep it at 0% by weight or less. If the amount is large, the copolymerizability with the urethane resin (A) having a polymerizable unsaturated group may be deteriorated, and disadvantages such as a longer curing time may occur.

As the (meth) acrylic acid ester monomer containing an active hydrogen atom, those having a (meth) acryloyl group, a hydroxyl group, a carboxyl group, or an amino group are preferable, and specific examples of the monomer containing a hydroxyl group include Specific examples of the above-mentioned hydroxyalkyl (meth) acrylates and the above-mentioned monomers containing a carboxyl group include (meth) acrylic acid, 2_ (meth) acrylic acid kissille succinic acid, and 2-(meth) Specific examples of the above-mentioned monomers containing an amino group, such as acryloyloxechinolehexahydrophthalic acid, 2- (meth) acrylic oxicetylphthalic acid, and ω-carboxy-polycaprolactone mono (meth) acrylate, include (meth) ) Acrylamide, diacetone (meth) acrylamide, - There are methylol (meth) Akuriruamaido like, not limited to those listed here, these may be used singly or in combination of two or more.

Specific examples of the monomer (C) having a (meth) atalyloyl group other than the above include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid η-butyl, (meth) acrylic acid Isobutyl, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n_otatyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , (Meth) acrylic acid 2_hide mouth quichetyl, (meth) acrylic acid β-ethoxyxyl, (meth) acrylic acid 2-cyanoethyl, (meth) cyclohexyl acrylate, (meth) methyl ethyl acrylate, fu Nilcarbitol (meta) atalylate, nonylphenol Nylcarbitol (meta) atalylate, nonifenoki Propyl (meth) acrylate, Ν-bulpyrrolidone, (meth) atalyloyloxyshetyl phthalate, (meth) acryloyloxysuccinate, phenol ethylene oxide ((Ο) modification (η = 2 to 4) ) ( (T) Acrylate, noyulphenol EO modified (n = 1 to 4) (meth) acrylate, nonylphenol propylene oxide (PO) modified (n = 2.5) (meta) acrylate, 21-ethyl Hexyl carbitol (meth) atalylate, tris (2-hydroxyxethyl) isocyanuric (meth) acrylate, and the like.

Although the copolymerizability at the time of the crosslinking reaction is slightly inferior, a small amount of other ethylenically unsaturated monomers may be used in combination with the monomer (C) having a (meth) acryloyl group. For example, allyl monomers such as styrene, vinylinole acetate, vinyl toluene, α-methinolestyrene, diaryl phthalate, diaryl isophthalate, triaryl isocyanurate, diaryl tetrabrom phthalate; acrylic nitrile, glycidyl methacrylate, η Hard monomers such as —methylolacrylamide butyl ether, η-methylmethylacrylamide, and acrylamide.

As the unsaturated monomer (C) having a (meth) atalyloyl group, a compound having at least two (meth) atalyloyl groups in one molecule can also be used. It is preferably used for the purpose of improving scratch resistance, inflammation resistance, chemical resistance, and the like. A compound having at least two (meth) acryloyl groups in one molecule, that is, a plurality of (meth) atalyloyl group-containing monomers, preferably a polyfunctional (meth) acrylate monomer, for example, Ethylene glycol di (meth) acrylate, 1,2-propylene propylene glycol di (meta) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) Alkanediol di (meth) atalylate such as atarilate, dipropylene glycol di (meth) atalylate, triethylene glycol (meth) atalylate, tetraethylene glycol di (meta) atalylate, polyethylene glycol (meth) acrylate Polyoxanorylene-glycol such as rate Di (meth) acrylate, dibutylbenzene, diallyl phthalate, triallyl phthalate, triaryl cyanurate, triaryl isocyanurate, aryl (meth) atalylate, diaryl fumarate, etc., which are used alone or Used in combination of two or more.

Further, as the unsaturated monomer (C) having a (meth) acryloyl group, Unsaturated monomers which impart drying property can also be used. For example, acrylic acid derivatives such as dicyclopentagen and tricyclodecane, dicyclopenturoxyshetyl acrylate, tricyclo [5-2-1- 02, 6] decanyl acrylate and epoxy-reactive diluent.

The coupling agent (D) used in the present invention generally refers to a compound which is used for an unsaturated polyester resin molding material and improves the adhesion between a matrix resin and an inorganic material. The strong coupling agent is typically an organic silicon compound or an organic chromium compound. Examples of the organic silicon-based compound include a compound represented by the general formula RS i X ₃ (wherein R is a monovalent hydrocarbon group containing an unsaturated unsaturated group or an amino group, an epoxy group, or a mercapto group, or a hydride-type carbonoxy group. And the group X represents chlorine or a hydrolyzable organic group, for example, an alkoxy group). Examples of the organic chromium compound, general formula RC r X ₂ (where, R represents Orefin unsaturated group or an amino group in the formula, an epoxy group, monovalent charcoal hydrocarbon group containing a mercapto group, or hide port And X represents a chlorine or alkoxy group or a hydroxy group.) An organic chromium-based compound represented by the formula:

Specific examples of the coupling agent (D) include (meth) atalylate chromic chloride or a hydrolyzate thereof, burtrichlorosilane, vininoletrimethoxysilane, biertriethoxysilane, bultris (—methoxyethoxy) silane, γ- ( (Methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ-aminopropyltrimethoxysilane, Ν-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β — ( 3, 4 epoxycyclohexyl) Echirutorime Tokishishiran, .gamma. glycidic xylo pro built Increment Tokishishiran, gamma one mercaptopropyltrimethoxysilane main Tokishishira _down, Ί - (methacryloxypropyl) Mechirujime _{Tokishishiran,} Ί - (Metatari proxy Ropyl) Methyl ethoxy silane, γ- (Atari xy propyl) trimethoxy silane, 71 (Atalyloxy propyl) methyl dimethoxy silane, y- (methacryloxy propyl) 11-Pindecyl trimethoxy silane, 4- (1-methacryloxy 4-1) Methyl 2-phenyl) · 1-ethyltrimethoxysilane, Examples thereof include methacrylate chromic chloride and methacrylate chromic hydride.

The more preferable coupling agent (D) used in the present invention is a compound having a silyl group having an alkoxy group such as a methoxy group and an ethoxy group, an acetyl group and a phenoxy group, and a (meth) acryloyl group. Specific examples include (meth) ataryloxymethinoletriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and the like. These may be used alone. But you can use them together. Further, a silane coupling agent having an epoxy group, an isocyanate group, a hydroxyl group or an amino group may be used in combination.

The amount of the coupling agent (D) used is preferably 0.5 to 15 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). Department.

The filler (E) is used as a bulking agent and a viscosity modifier. For example, carbonate, silicic acid, silicate, hydroxide, sulfate, borate, titanate, metal oxide, carbonaceous matter, organic matter and the like can be mentioned. Specific examples of such a filler (E) include calcium carbonate, silica, myriki, force olin clay, talc, organic bentonite, sericite, synthetic magnesium hydroxide, glass flakes, powdered glass, metal whiskers, and ceramics Examples include whiskers and calcium sulfate whiskers. These may be used in combination of two or more as necessary. The amount of the filler is preferably 5 to 300 parts by weight based on 100 parts by weight of the total amount of the resin (A) component, the resin (B) component, and the unsaturated monomer (C) − component. Parts by weight, more preferably 25 to 200 parts by weight.

Polymerization inhibitors are preferably used in the adhesive of the present invention, for example, trihydric benzene, tonolehydroquinone, 1,4-naphthoquinone, and phenol. Labenzoquinone, tonole hydroquinone, noidroquinone, benzoquinone, noidroquinone monomethynorethenoate, p-tert-butylcatecholone, 2,6-z-tert-butynoley 4-methylphenol, and the like can be added. Preferably, 100 to 100 parts by weight of the total of the component (A), the component (B) and the component (C); 900 ppm can be added.

To the adhesive of the present invention, a thermoplastic resin can be added as a low-shrinking agent for the purpose of improving the air-drying property (air-curing property) of the adhesive and reducing the curing shrinkage. Specific examples of such a thermoplastic resin include lower alkyl esters of acrylic acid or methacrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, styrene, butyl chloride, vinyl acetate, and the like. Homopolymers or copolymers of monomers, at least one of the above-mentioned vinyl monomers, lauryl methacrylate, isobutyl methacrylate, (meth) acrylamide, hydroxyalkyl (meth) acrylate, In addition to (meth) acrylic nitrile, (meth) acrylic acid, at least one copolymer of cetylstearyl (meth) acrylate, and the like, cellulose acetate butylate and cellulose acetate propionate, polyethylene, Poli Propylene, mention may be made of a saturated polyester and the like. When such a low-shrinking agent is added, the amount of addition is preferably 2 to 50 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the components (A), (B) and (C) in total. 35 parts by weight are particularly preferred. The adhesive of the present invention may be used in combination with a viscosity modifier (thixotropic agent) in order to impart structural viscosity (thixotropic property) in consideration of its handling property. Examples of such a thixotropic agent include fumed silica, colloidal calcium carbonate, talc powder, my powder, glass flakes, metal whiskers, ceramic whiskers, calcium sulfate whiskers, asbestos, smectite, and the like. Two or more types may be used in combination. The amount of the thixotropic agent to be added is preferably 100 parts by weight based on a total amount of 100 parts by weight of the resin (A), the resin (B), and the unsaturated monomer (C). 0.2 to 10.0 parts by weight, more preferably 1.5 to 5.0 parts by weight.

The adhesive of the present invention is used by adding an organic peroxide as a radical polymerization initiator when used. Specifically, di-silver oxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxyside type, peroxyketanore type, a / lequinolenoester type And known ones such as Parkerponate type. The amount of the radical polymerization initiator to be added depends on the component (A), It is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the components (B) and (C). The above radical polymerization initiators may be used in combination of two or more.

Further, a polymerization accelerator is preferably added to the adhesive of the present invention. Examples of such a polymerization accelerator include metal stones such as cobalt naphthenate, cobalt octoate, vanadyl octoate, and copper naphthenate. And barium naphthenate. Examples of the metal chelate compound include vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetyl acetonate. Also, amines include N, N-dimethylamino p-venzanoledialdehyde, N, N-dimethinorea diphosphorus, N, N-diethinorea diphosphorus, N, N-dimethyl-p-tonolidine, N-ethynolein m-tonolidine, and Lietanomonoamine, m-tonolidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolanolaniline and the like. The polymerization accelerator is used in an amount of preferably 0.001 to 5 parts by weight based on 100 parts by weight of the total of (A), (B), (C) and (D). The polymerization accelerator may be added to the resin in advance, or may be added at the time of use.

In the adhesive of the present invention, an organic acid metal such as cobalt, vanadium or manganese may be used in combination for the purpose of improving the surface drying property. It is an organic acid salt. The amount added is preferably from 0.1 to 3 parts by weight, more preferably from 0.3 to 1 part by weight, per 100 parts by weight of the total of components (A), (B), (C) and (D). It is.

The adhesive of the present invention is a mixture of (A), (B), (C), (D) and (E), but is used to prevent sagging when used for bonding slopes and vertical surfaces. It is preferably a liquid having a high viscosity, and more preferably a paste. Its viscosity is preferably between 800 dPa · s and 20000 dPa · s (25 ° C.), more preferably between 1000 and: l O O O O dPa · s. The measurement is a value measured with a B8U viscometer (East: manufactured by Kiki Sangyo Co., Ltd.) and a spindle T-B5 rpm.

Further, in addition to the above additives, a coloring agent such as a fiber reinforcing material, an aggregate, a pigment, a dye, or the like may be added to the adhesive of the present invention.

Examples of the fiber-reinforced material include glass fiber, amide, aramide, vinylon, Organic fibers such as polyester and phenol, carbon fibers, metal fibers, ceramic fibers, or a combination thereof are used. In consideration of workability and economy, glass fibers and organic fibers are preferable. The form of the fiber is plain weave, satin weave, non-woven fabric, matte shape, etc., but the matte shape is preferred due to the construction method, thickness maintenance, etc., and the glass mouth bing is 5 to 10 Omm. It is also possible to cut it into chopped strands for use.

The bonding method of the present invention comprises applying a mixture of the adhesive of the present invention and the radical polymerization initiator to a fiber-reinforced plastic (FRP) molded product and Z or a base, and joining the molded product and a base material. I do. At that time, it does not prevent the physical and chemical treatment of the base material in advance. The thickness of the adhesive layer can usually be 0.5 mm or more. The thickness of the adhesive layer is preferably 1 to 1 Omm. The adhesive of the present invention is particularly useful when a thick adhesive layer is required when bonding an FRP molded product to a substrate. The substrate includes, for example, FRP molded products, metal, wood, concrete, rubber and the like. The FRP molded product is composed of a known matrix resin such as an unsaturated polyester resin, a polyester acrylate resin, an epoxy acrylate resin, an epoxy resin, a phenol resin, and the fiber reinforced material. . Example

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, where “parts” and “%” are on a weight basis unless otherwise specified. In addition, the composition in Tables 1-3 is "part". Synthetic Example 1 [Preparation of (meth) atarylonole group-containing urethane resin (UA-1)] Four-port, three-liter equipped with thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser A flask was charged with 2.0 mol of tolylene disocyanate (TDI) and 1.0 mol of polypropylene glycol (PPG) having a number average molecular weight of 700, and reacted at 80 ° C for 5 hours under a nitrogen atmosphere. Since the NCO equivalent became almost the same as the theoretical value and stabilized, it was cooled to 40 ° C, then 2.1 mol of 2-hydroxyethyl methacrylate was added, and the mixture was reacted at 80 ° C for 4 hours in an air atmosphere. . NCO% is 0. After confirming that the content was 1% or less, 0.19 parts of toluhydroquinone was added to the mixture to obtain a polyether (meth) acryloyl group-containing urethane resin (UA-1). Synthesis Example 2 [Preparation of (meth) acryloyl group-containing urethane urea (UA-2)] Number average in a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser 1.0 mol of polypropylene glycol (PPG) having a molecular weight of 400 was charged, and 2 mol of tolylene disocyanate (TDI) was added, and the mixture was reacted at 80 ° C for 5 hours while suppressing heat generation. Since the NCO equivalent became almost the same as the theoretical value and became stable, it was cooled to 40 ° C, and 0.5 mol of pentaerythritol triallyl ether (manufactured by Daiso Co., Ltd., neoallyl P-30) in 2-hydroxyhexyl was added. 1.6 mol of methacrylate was added, and the mixture was reacted at 90 in an air atmosphere for 7 hours. Since the NCO% became 0.1% or less, 0.067 parts of toluhydroquinone was added to obtain an acrylyl group-containing polyether (meth) acryloyl group-containing urethane resin (UA-2). Synthesis Example 3 [Preparation of (meth) acryloyl group-containing urethane resin (UA-3)] A 4-liter, 3-liter equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser A flask was charged with 3.0 moles of TDI and 2.0 moles of a polyester polyol having a number average molecular weight of 700, and reacted at 80 ° C for 5 hours under a nitrogen atmosphere. Since the NCO equivalent became almost the same as the theoretical value and stabilized, it was cooled to 40 ° C, then 2.1 mol of 2-hydroxyethyl methacrylate was added, and the mixture was reacted at 80 in an air atmosphere at 80 for 4 hours. . After confirming that the NCO% was 0.1% or less, 0.19 parts of tolhai'droquinone was added to the mixture to obtain a polyester-based (meth) acryloyl group-containing urethane resin (UA-3). Was. Synthesis Example 4 [Preparation of (meth) atalyloyl group-containing urethane resin (UA-4)] In a three-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser 2.0 mol of TDI and 1.0 mol of PPG having a number average molecular weight of 700 were charged and reacted at 80 in a nitrogen atmosphere for 5 hours. NCO equivalent is theoretical After cooling to 40 ° C, 1.0 mol of 2-hydroxyhexyl methacrylate was added, and N, N, N-trimethyl-N-2-hydroxyethylammonium p_t After adding -butylbenzoate and reacting at 60 ° C for 2 hours in an air atmosphere, 0.5 mol of 2-hydroxyshethyl methacrylate was added and reacted at 80 ° C for 2 hours under an air atmosphere. After confirming that the NC〇% was 0.1% or less, 0.19 parts of toluhydroquinone was added to the mixture, and a polyether (meth) acryloyl group-containing urethane resin (UA-4) was added. I got Synthesis Example 5 [Preparation of air-drying type unsaturated polyester resin (UPE-1)] 2.9 mol of maleic anhydride, 2.0 monoles of dicyclopentadiene and 2.0 mol of water were charged, and a nitrogen gas atmosphere was used. The reaction was carried out within a temperature range of 100 to 125 ° C. while stirring under the conditions, and the acid value of the reactant was measured at any time. When the acid value reached 360, 1.8 mol of diethylene glycol was mixed with the above reaction product. Thereafter, the mixture was reacted at 200 ° C. for 7 to 8 hours with stirring under a nitrogen gas atmosphere to obtain an air-drying unsaturated polyester resin having an acid value of .30 (UPE-1, air-drying component of 30 mol%). ). Synthesis Example 6 [Preparation of air-drying type unsaturated polyester resin (UPE-2)] 1.33 mol of glycerin and 0.67 mol of amayu oil were 180 to 200. The reaction was continued for 4 hours to obtain alcoholysis. Next, 4 moles of diethylene glycol, 4 moles of dipropylene glycol, 5.0 moles of fumaric acid, and 5.0 moles of phthalic anhydride are subjected to heat dehydration condensation under known conditions to obtain an air-drying type unsaturated polyester resin having an acid value of 25 ( UP E-2, an air-drying component of 4.5 mol%). Synthesis Example 7 [Preparation of air-drying type unsaturated polyester resin (UPE-3)] 2.2 mol of maleic anhydride, 2.0 mol of dicyclopentadiene, and 2.0 mol of water were charged, and a nitrogen gas atmosphere was used. The reaction was carried out within a temperature range of 100 to 125 ° C. while stirring under the conditions, and the acid value of the reactant was measured at any time. When the acid value reached 360, pentaerythritol triallyl ether was added to the reaction product. (Deoso Co., Ltd., Neoallyl P-30) 1.95 mol were mixed. Thereafter, the mixture was reacted at 180 ° C. for 10 to 13 hours while being stirred in a nitrogen gas atmosphere, and an air-drying imparting unsaturated polyester resin having an acid value of 30 (UPE-3, air-drying component of 64 mol) was used. ./.). Comparative Synthesis Example 1 [Preparation of Epoxyacrylate Jujutsu (VE-1)]

In a three-neck flask equipped with a thermometer, a stirrer, and a condenser, 3850 g (equivalent to 10 epoxy groups) of an epoxy resin having an epoxy equivalent of 385 obtained by the reaction of bisphenol A and epichlorohydrin, and methacrylic acid were added. 860 g of the acid (equivalent to 10 carboxyl groups), 1.36 g of hydroquinone and 10.8 g of triethylamine were charged and heated to 120 ° C, and the reaction was continued for 10 hours at the same temperature. A liquid epoxy acrylate (VE-1) with a pH of 3.5 was obtained. Comparative Synthesis Example 2 [Preparation of (meth) acryloyl group-containing urethane resin (UA-5)] Four 3-liter units equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser 2.0 mol of tolylene diisocyanate (TDI) and 1.0 mol of PPG having a number average molecular weight of 1000 were charged into a neck flask, and reacted at 80 under a nitrogen atmosphere for 5 hours. Since the NCO equivalent became almost the same as the theoretical value and stabilized, it was cooled to 40 ° C, then 2.1 mol of 2-hydroxyshethyl methacrylate was added, and the reaction was carried out at 80 ° C for 4 hours in an air atmosphere. I let it. After confirming that the NCO% was 0.1% or less, 0.23 parts of toluhydroquinone was added to obtain a urethane resin (UA-5) containing a polyether (meth) atalylol group. Test method>

The adhesive peel strength was evaluated in accordance with JISK-6850. The base material used for the test is a FRP molded plate and SMC molded plate as test substrate pieces with a thickness of 3 mm. The molded plates were prepared by cutting them. (Preparation of test substrate)

As the adhesion test substrate, an FPR molded plate and an SMC molded plate were used.

The FRP molded plate is made of unsaturated polyester resin Polylite PC-110 (manufactured by Dainippon Ink and Chemicals, Inc.), glass mat Nittobo # 450 is laminated in three plies, and a 3 mm thick plate I got The radical polymerization initiator used was 1% of Permec N (55% methyl ethyl ketone peroxide, manufactured by NOF CORPORATION), left for 24 hours at room temperature, and post-cured at 60 for 8 hours. did.

The SMC molded plate was pressed at 145 ° C. using Dickmat GM-230 (SMC manufactured by Dainippon Ink and Chemicals, Inc.) to obtain a plate having a thickness of 3 mm.

The adhesive surface of the two test substrate pieces was sanded with a # 80 sandpaper, and subjected to air blowing and degreasing with acetone before applying the adhesive. The thickness of the adhesive layer between the test substrate pieces was adjusted with a spacer so as to be 1 mm. Tensile shear adhesive strength was measured after preparing an adhesion test substrate piece and allowing it to stand at 25 ° C for one week. Surface dryness test method>

An adhesive was applied to the test piece for evaluation of adhesive peel strength at a thickness of 5. Omm, left at 25 ° C for 12 hours, and the dryness of the surface was evaluated by a finger touch test. The evaluation method was as follows: absorbent cotton was pressed against the adhesive surface, and the condition was examined.

It was measured by the method described above.

(Examples 1-5, Comparative Examples 1-2)

The resins shown in Tables 1 to 3 were blended with the resins and the like obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 and 2 to form a uniform resin solution. The resin solution ((A) + (B) + (C)) Add 0.4 parts of cobalt octoate to 100 parts, and add The thixotropic agent, the filler (E), and the coupling agent (D) shown in the table were mixed using a mixer or a high-speed rotating disperser to obtain an adhesive.

The obtained adhesive was adjusted with hydroquinone monomethyl ether (polymerization inhibitor) so that the curing time at the time of adding 1.5% of Permec N (radical polymerization initiator) at 25 ° C was 30 minutes. . The measurement of the curing time in this case is a method of judging the pot life of the adhesive. The method for measuring the curing time is as follows: After the adhesive is kept at 25 ° C in a constant temperature water bath, the time from the point when Permec N 1.5% is added until the adhesive loses fluidity to the extent that the adhesive cannot be applied is measured. The “curing time 30 minutes” was determined by the measurement method. Actually, when an adhesive is used, the curing time can be adjusted from about 10 minutes to 2 hours or more according to the work content, so the curing properties are not evaluated in the table. The above test (tensile shear bond strength test, surface drying property) was performed on the adhesive, and the evaluation results are shown in Tables 1 to 3.

Example 1, Example 2 Example 3

(A) Having a polymerizable unsaturated group

Tree U A- 1 58.5 U A— 2 52 U A— 3 58.5

Fat

(B) Air-drying resin U P E- 18 U P E- 1 14 U P E- 28

(C) H EMA having a (meth) acryloyl group 33.5 H EMA 15.8 solution H EMA 34

Unsaturated monomer D EMA 31.5 P h EMA 15.8

(D) or; furinge agent MPMS 5 MPMS 5 MPMS 5 Silica 2.5 Silica 2.5

(E) Filler Charcoal 45.0

Talc 40 talc 40

F RP Tensile shear bond strength 1 1. 9MPa 1 2. 3MPa 1 2. OMPa substrate Fracture surface FRP substrate F RP substrate F RP substrate

SMC Tensile shear bond strength 7. 7MPa 8. OMPa 7.2MPa Substrate Fracture surface SMC substrate SMC substrate SMC substrate Surface drying No absorbent cotton attached No absorbent cotton attached No absorbent cotton attached Tensile elongation (%) 6.6 2.1 28.3 Viscosity (d Pa-s) 950 2455 2900 Table 2

The composition of each raw material in the above table is “parts” −. Abbreviations in the above tables are as follows.

H EMA: Hydroxyshetyl methacrylate P h EMA: Huenoxyshetyl methacrylate D EMA: Dispensing mouth penteninoleoxymethyl methacrylate n— BA: n-butyl phthalate

MPMS: 3—methacryloxypropyltrimethoxysilane

MC H: methacrylate mouth mixed hydroxyide As can be seen from the above table, the results of the tensile shear bond strengths of Examples 1 to 5 indicate that the test substrate was broken, whereas Comparative Example 2 In this case, since the tensile elongation was out of the range, it was ruptured in the adhesive layer. From this, it is understood that the adhesive of the present invention exhibits excellent adhesive strength. Furthermore, it can be seen that Comparative Example 1 is poor in adhesiveness because it is an epoxy acrylate resin that is not a urethane resin having a polymerizable unsaturated group.

From these Examples and Comparative Examples, it can be seen that the adhesive of the present invention is excellent in surface dryness and adhesiveness. Industrial applicability

The adhesive of the present invention adopts the constitutions of (A), (B), (C), (D) and (E), and has a specific tensile elongation, so that the surface drying property and the room temperature curability can be achieved. It has excellent adhesive properties to the extent that the substrate breaks, and cures at room temperature even in the presence of air, so it can be used for various purposes. Utilizing such properties, the adhesive of the present invention can be used in various situations, but is particularly preferably used for bonding a FRP molded article to a substrate. It is also useful as an adhesive for bonding the same molding materials.

Claims

The scope of the claims

1. (A) a urethane resin having a polymerizable unsaturated group, (B) an air-drying resin having a polymerizable unsaturated group, (C) an unsaturated monomer having a (meth) acryloyl group,

A curable adhesive containing (D) a coupling agent and (E) a filler, wherein the cured product of the curable adhesive has a tensile elongation of 1% to 33 ° / _0. Curable adhesive.

2. Urethane resin having a polymerizable unsaturated group (A) Strength A urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyester polyol or z or a polyether polyol with a polyisocyanate has a hydroxyl group-containing (meth 2. The curable adhesive according to claim 1, wherein the curable adhesive is a (meth) atalyloyl group-containing urethane resin obtained by reacting an acrylic compound.

3. The curable adhesive according to claim 1, wherein the resin (B) is an air-drying polymerizable unsaturated group-containing resin, and is an air-drying unsaturated polyester resin.

4. The compound that imparts air-drying property, which is a constituent of the polymerizable unsaturated group-containing resin (B) that is air-drying, is obtained by 1) transesterification reaction between polyhydric alcohol and fatty oil such as drying oil. The alcoholysis compound obtained is selected from the group consisting of 2) a fatty oil fatty acid obtained by saponifying a drying oil, 3) an aryl ether group-containing polyol, 4) an alicyclic dibasic acid, and 5) a dicyclopentene. Curing according to claim 3

5. The curable adhesive according to claim 4, wherein the content of the component for imparting air-drying property in the air-drying polymerizable unsaturated group-containing resin (B) is 3.0 to 70 mol%. .

6. The hardener according to claim 1, wherein the viscosity is 800 dPas to 20,000 dPas. Adhesive. .

7. The curable adhesive according to claim 1, wherein the unsaturated monomer (C) having a (meth) acryloyl group is a (meth) acryloyl group-containing compound containing an active hydrogen atom.

8. Coupling agent (D), general formula RS i X ₃ (wherein R is a monovalent hydrocarbon group containing an olefinic unsaturated group or an amino group, an epoxy group, a mercapto group, or a hydride) And X represents a chlorine or alkoxy group.) Or an organic silicon-based compound represented by the general formula RC r X ₂ (where R is a olefinic unsaturated group or an amino group, An organic chromium compound represented by a monovalent hydrocarbon group containing an epoxy group or a mercapto group, or a hydroxycarbonyl group, or a hydroxy group, and X represents a chlorine or alkoxy group or a hydroxy group.) The curable adhesive according to claim 1, which is:

9. The curable adhesive according to claim 1, wherein the coupling J (D) is a silane coupling agent having a (meth) acryloyl group.

10. A method for bonding a fiber-reinforced plastic, comprising joining a fiber-reinforced plastic molded product using the adhesive according to any one of claims 1 to 9.