JP2007002108A - Resin composition and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and an adhesive which are most suitable for use in the fixation of a rod and a reel in a fishing rod and has the good surface curability and high adhesive strength and which are curable by ultraviolet rays at ordinary temperatures. <P>SOLUTION: The resin composition comprises (1) a urethane oligomer, (2) a polyene, (3) a polythiol, (4) a photopolymerizaton initiator, (5) a reducing agent, (6) a multifunctional polymerizable vinyl monomer and (7) an oxidizing agent, wherein the above resin composition is such a composition that is blended after (2) the polyene and (3) the polythiol has been previously reacted; and the adhesive comprises said resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a composition (hereinafter simply referred to as “resin composition”) that provides a resin by being cured with ultraviolet rays and at room temperature, and an adhesive. More specifically, the present invention relates to a two-material resin composition and an adhesive that are cured at room temperature under ultraviolet light, which is optimal for fixing rods and reels of fishing rods.

Conventionally, epoxy fixing agents, ultraviolet curable fixing agents, and the like have been used as curable resin compositions for fixing rods and reels of fishing rods. However, (1) the epoxy-based fixing agent is used by mixing two liquids, but has a disadvantage that the viscosity increases from about 10 minutes after mixing, the curing time is long, and the workability is poor. (2) Among the UV curable fixing agents, the polyene and polythiol-based resins may have insufficient adhesive strength, which requires higher adhesive strength and cannot be irradiated with ultraviolet rays. The site has the disadvantage of not curing. In addition, (3) the acrylic curable resin composition has been requested to be improved, for example, because it is anaerobic, consideration must be given to curing in the air and curing the surface (see Patent Document 1). .

JP-A-62-236809

In view of the circumstances of the prior art, the present inventor has a resin composition that has a good surface curability and a high adhesive strength and is cured at room temperature under ultraviolet light, and is particularly suitable for fixing rods and reels of fishing rods. The present inventors have studied for the purpose of providing an adhesive and have arrived at the present invention.

In other words, the present invention has been made to solve the above-described problems of the prior art, and more specifically, the working time can be taken sufficiently to be suitable for fixing rods and reels of fishing rods. Unlike conventional UV-curable resin compositions, it has high adhesive strength to the adherend and is not easily affected by oxygen. It is cured in a short time from a few seconds to a few minutes by UV irradiation. Is a resin composition having a characteristic that it is good, and is an adhesive.

The present invention includes (1) urethane oligomer, (2) polyene, (3) polythiol, (4) photopolymerization initiator, (5) reducing agent, (1) urethane oligomer, (6) polyfunctional polymerizable vinyl monomer, (4) A resin composition containing a photopolymerization initiator and (7) an oxidant, preferably (2) a polyene and (3) a polythiol previously reacted and then blended The above resin composition.

The present invention is an adhesive comprising the above resin composition, and as a more preferred embodiment, (1) urethane oligomer, (2) polyene, (3) polythiol, (4) photopolymerization initiator , (5) a first resin composition containing a reducing agent, (1) a urethane oligomer, (6) a polyfunctional polymerizable vinyl monomer, (4) a photopolymerization initiator, and (7) an oxidizing agent. The adhesive is a two-material type comprising a second resin composition. In addition, the present invention is the adhesive described above, which is used for fixing rods and reels of fishing rods.

The resin composition of the present invention is cured without being affected by oxygen, and therefore has a good surface curability and gives a cured product having a high pencil hardness. For example, an adhesive applied to a rod or reel of a fishing rod. Can provide. Moreover, since the said resin composition can be made into a prepolymer, when it applies to uses, such as an adhesive agent, a viscosity can be adjusted easily and there exists the characteristic which can improve workability | operativity.

Since the adhesive of the present invention is composed of the specific resin composition, it is an adhesive suitable for, for example, fishing rods and reels, reflecting the above characteristics.

In the present invention, (1) a urethane oligomer is used. (1) Urethane oligomers that can be used in the present invention include divinylbenzene derivatives, UN-9000PEP, F-6023 (manufactured by Cognis Japan), aliphatic acrylates, F-6008, F-6210 (manufactured by San Nopco) ) And other commonly used urethane compounds (isophorone diisocyanate-2-hydroxyethyl acrylate adduct), among which F-6008 is fast in curing speed, low in skin irritation, and excellent in abrasion. Are preferably selected.

In the present invention, the composition ratio of (1) urethane oligomer is 1: 9 to 9: 1 (mass ratio) with respect to the total amount of (2) polyene described later and (3) polythiol described later. It is preferably 8: 2 to 9: 1 (mass ratio).

(2) Polyene used in the present invention refers to a polyfunctional compound having two or more carbon-carbon double bonds in one molecule.

(2) Examples of polyenes include allyl alcohol derivatives, esters of (meth) acrylic acid and polyhydric alcohols, urethane (meth) acrylates, divinylbenzene derivatives, and the like. These 1 type (s) or 2 or more types can be used in combination.

Here, as allyl alcohol derivatives, triallyl isocyanurate, triallyl cyanurate, diallyl maleate, diallyl fumarate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl ether, triaryl ether Examples include methylolpropane diallyl ether, pentaerythritol diallyl ether, and sorbitol diallyl ether.

Examples of esters of (meth) acrylic acid and polyhydric alcohol include, as polyhydric alcohols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane. , Pentaerythritol and sorbitol.

(2) About the compounding quantity of a polyene, 5-50 mass parts is preferable with respect to a total of 100 mass parts with (1) urethane oligomer, (3) polythiol, and (6) polyfunctional polymerizable vinyl monomer, 15-15. More preferred is 25 parts by mass.

The (3) polythiol used in the present invention refers to a polyfunctional compound having two or more thiol groups in one molecule. Examples of such polythiols include esters of mercaptocarboxylic acid and polyhydric alcohols, aliphatic polythiols, and aromatic polythiols. These 1 type (s) or 2 or more types can be used.

Here, among esters of mercaptocarboxylic acid and polyhydric alcohol, examples of mercaptocarboxylic acid include thioglycolic acid, α-mercaptopropionic acid, and β-mercaptopropionic acid.

Among the esters of mercaptocarboxylic acid and polyhydric alcohol, polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol and Examples include sorbitol.

Aliphatic polythiols and aromatic polythiols include ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol and xylenedithiol.

Among these polythiols, esters of mercaptocarboxylic acid and a polyhydric alcohol are preferable from the viewpoint of low odor.

(3) About the compounding quantity of polythiol, 10-60 mass parts is preferable with respect to a total of 100 mass parts with (1) urethane oligomer, (2) polyene, and (6) polyfunctional polymerizable vinyl monomer, 25- 35 parts by mass is more preferred. In the present invention, the ratio of (2) polyene and (3) polythiol is such that the double bond in the polyene and the thiol group in the polythiol have a molar ratio of 5: 1 to 1: 5, 1: 1 is more preferred.

(4) Photopolymerization initiators used in the present invention include benzophenone, benzophenone ultraviolet initiators such as benzophenone, methyl orthobenzoylbenzoate and 4-benzoyl-4′-methyldiphenyl sulfide, 1-hydroxycyclohexyl phenyl ketone, acetophenone, benzyl Acetophenone-based ultraviolet polymerization initiators such as dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; Benzoin ether UV polymerization initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, thioxanthone acyl such as isopropylthioxanthone and diethylthioxanthone Scan fins oxide, benzyl, camphorquinone, and anthraquinone and Mihirateton the like. These 1 type (s) or 2 or more types can be used. Among these, from the viewpoint of surface curability, benzophenone-based ultraviolet initiators are preferable, and benzyldimethyl ketal is more preferable.

(4) About the compounding quantity of a photoinitiator, it is 0.1 with respect to a total of 100 mass parts of (1) urethane oligomer, (2) polyene, (3) polythiol, and (6) polyfunctional polymerizable vinyl monomer. 01-10 mass parts is preferable, and 0.5-5 mass parts is more preferable.

Examples of (5) reducing agents used in the present invention include thiourea derivatives, amines, condensation products of aldehyde and amine, organic salts, and the like. Examples of thiourea derivatives include diethylthiourea, dibutylthiourea, ethylenethiourea, tetra And thioamide compounds such as methylthiourea and mercaptobenzimidazole. Examples of amines include triethylamine, tripropylamine, ethylenediamine, tributylamine, and N, N-dimethylparatoluidine. Examples of the metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. One or more of these may be used. Among these, thiourea derivatives are preferable and ethylenethiourea is preferable in terms of acceleration of curing.

(5) The use amount of the reducing agent is preferably 0.01 to 10 parts by mass, and preferably 0.5 to 5 with respect to 100 parts by mass in total of (1) urethane oligomer, (2) polyene, and (3) polythiol. Part by mass is more preferable.

(6) Polyfunctional polymerizable vinyl monomers used in the present invention include dimethylol-tricyclodecane diacrylate, neopentyl glycol alkoxy diacrylate, pivalate ester neopentyl glycol diacrylate, neopentyl glycol diacrylate, bisphenol A. Examples include alkoxy diacrylate, trimethylolpropane (meth) acrylate, triacrylate of tris (2-hydroxyethyl) isocyanuric acid, isophorone diisocyanate-2-hydroxyethyl acrylate, and the like.

(6) Regarding the blending ratio of the polyfunctional polymerizable vinyl monomer, the blending ratio of (1) urethane oligomer, (2) polyene, (3) polythiol, and (6) polyfunctional polymerizable vinyl monomer is 10: 90-90: 10 are preferable and 30: 70-70: 30 are especially preferable.

(7) As the oxidizing agent used in the present invention, cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide and tertiary butyl peroxide Examples thereof include oxybenzoate, and one or more of these may be used. Among these, cumene hydroperoxide is preferable in terms of reactivity.

(7) The usage-amount of an oxidizing agent has a preferable 0.01-10 mass part with respect to a total of 100 mass parts with (1) urethane oligomer and (6) polyfunctional polymerizable vinyl monomer, and is 1-5 mass parts. Is more preferable.

Further, in the present invention, it is preferable that (2) polyene and (3) polythiol are reacted in advance, and then a prepolymer is blended. By this operation, it is possible to easily provide a resin composition and an adhesive having a preferable viscosity according to the end use, thereby improving workability in the end use.

As a method of producing a prepolymer by reacting in advance, (2) a method of simply heating a mixture of polyene and (3) polythiol, a method of heating by adding a small amount of peroxide, etc., a small amount of (4) light Examples include a method of adding a polymerization initiator and irradiating ultraviolet rays, but from the viewpoint of controlling the reaction rate, a method of simply heating a mixture of (2) polyene and (3) polythiol is preferable. The reaction temperature is preferably 5 to 70 ° C. from the viewpoint of controlling the reaction rate.

Moreover, (2) polyene and (3) polythiol which are usually marketed usually contain impurities, and it is easier to control the reaction rate by converting these impurities into chelate compounds and removing them. Become.

Furthermore, for the adhesive of the present invention, (1) urethane oligomer, (2) polyene, (3) polythiol, (4) photopolymerization initiator, (5) a first resin composition containing a reducing agent, A two-material type comprising (1) a urethane oligomer, (6) a polyfunctional polymerizable vinyl monomer, (4) a photopolymerization initiator, and (7) a second resin composition containing an oxidizing agent is preferable.

By using the two-material type as described above, it is possible to exhibit a feature that enables long-term storage (one year or more). In addition, the working time can be sufficiently secured when the members are bonded to each other, and the bonding strength can be increased in a short time at the time of bonding, so that the workability can be further improved.

In the adhesive of the present invention, the composition ratio of the first resin composition and the second resin composition is preferably 3: 7 to 7: 3 (mass ratio), and 1/1 (mass ratio) is More preferred.

In addition, the resin composition and adhesive of the present invention, when irradiated with ultraviolet rays, (2) polyene, (3) polythiol, (1) urethane oligomer, and (6) polyfunctional polymerizable vinyl monomer are polymerized for several seconds. Can be cured in a few minutes. As the ultraviolet light source, for example, ultraviolet light from an ultra high pressure, high pressure, low pressure mercury lamp and metal halide lamp is used. In addition, since it is a redox curing system, the part which cannot be irradiated with ultraviolet rays is cured at room temperature.

The resin composition and adhesive of the present invention include, as necessary, adhesion improvers such as organophosphorus compounds and organosilicon compounds, polymerization inhibitors, fillers, colorants, thixotropic agents, curing accelerators, and plasticizers. In addition, various commonly used compounding agents such as surfactants may be added.

In addition, the viscosity of the resin composition and adhesive of the present invention can be adjusted, for example, to a range of 100 cps to 700,000 cps at 25 ° C. For example, when suitably applied to rods, reels, etc. of fishing rods From the viewpoint of workability, it is preferable to adjust to 600 cps to 800 cps. Further, the adhesive adjusted to the viscosity can be preferably used for fixing rods and reels of fishing rods.

(Example 1, Comparative Examples 1-4)

(Experimental example 1) When the diallyl maleate and tris-2hydroxyethyl-isocyanurate-tris-β-mercaptopropionate have a molar ratio of carbon-carbon double bond group in polyene to thiol group in polythiol is 1 / 1 so as to be mixed. When the reaction is carried out with stirring at 40 ° C. and the viscosity becomes about 300 (mPa / s), the N-nitrosophenyl-hydroxyamine ammonium salt is added to the total of 100 parts by mass of polyene and polythiol. 0005 parts by weight are added. After confirming the termination of the reaction, 0.002 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol and 0.50 part by mass of benzyldimethyl ketal are added and dissolved at 60 ° C. for 1 hour. After confirming dissolution, add 20 parts by mass of isophorone diisocyanate-2-hydroxyethyl acrylate adduct and stir under natural cooling to dissolve.After dissolution, add 0.5 parts by mass of ethylenethiourea and dissolve by stirring. Thus, a resin composition (B) was obtained.

(Experimental example 2) 30 parts by mass of a polyurethane acrylate oligomer previously heated and dissolved in 5 parts by mass of neopentyl glycol alkoxy diacrylate, 13 parts by mass of bisphenol A alkoxy diacrylate, and 40 parts by mass of bivalic acid ester neopentyl glycol alkoxy diacrylate, Add 12 parts by mass of triacrylate of tris (2-hydroxyethyl) isocyanuric acid and stir. Add 0.5 parts by mass of benzyl dimethyl ketal and dissolve at 60 ° C. for 1 hour. After cooling, 3 parts by mass of cumene hydroperoxide was added, stirred and dissolved to obtain a resin composition (A).

(Experimental example 3) 5 mass parts of neopentyl glycol alkoxy diacrylate, 13 mass parts of bisphenol A alkoxy diacrylate, 40 mass parts of bivalic acid ester neopentyl glycol alkoxy diacrylate, tris-2 hydroxyethyl-isocyanurate-tris-β- 30 parts by mass of a polyurethane-based acrylate oligomer preliminarily heated and dissolved in mercaptopropionate and 12 parts by mass of triacrylate of tris (2-hydroxyethyl) isocyanuric acid are added and stirred. Add 0.5 parts by mass of benzyl dimethyl ketal and dissolve at 60 ° C. for 1 hour. After cooling, 3 parts by mass of cumene hydroperoxide and 0.5 parts by mass of ethylenethiourea were added and dissolved by stirring to obtain a resin composition.

(Experimental example 4) Polyurethane acrylate oligomer preliminarily heated and dissolved in 5 parts by mass of neopentyl glycol alkoxy diacrylate, 13 parts by mass of bisphenol A alkoxy diacrylate, 40 parts by mass of bivalic acid ester neopentyl glycol alkoxy diacrylate, diallyl maleate 30 parts by mass and 12 parts by mass of triacrylate of tris (2-hydroxyethyl) isocyanuric acid are added and stirred. Add 0.5 parts by mass of benzyl dimethyl ketal and dissolve at 60 ° C. for 1 hour. After cooling, 3 parts of cumene hydroperoxide and 0.5 parts by mass of ethylenethiourea were added and dissolved by stirring to obtain a resin composition.

The obtained resin composition (B) (Experimental Example 1) and the resin composition (A) (Experimental Example 2) were blended so that the mass ratio was 1, and the resin composition of Experimental Example 1 (B ), The resin composition (A) of Experimental Example 2 and the resin compositions of Experimental Examples 3 and 4 were evaluated as follows. The results are shown in Table 1. In Table 1, each case is represented by the composition ratio of the experimental example as real 1 / real 2 = 1/1, real 1, real 2, and real 4 (hereinafter, the same is displayed).

<Evaluation 1: Surface Curability> Each sample is applied to a real carbon candy (with nylon thread winding) using a brush, and cured by irradiating with ultraviolet rays under the following conditions to evaluate the tackiness of the surface. However, coating / curing was performed twice and curing was performed in an oxygen atmosphere.
-UV irradiation dose: 3000 mJ / cm ²
・ Ultraviolet irradiation device: Toscuer 400
The evaluation of the surface tack state was performed with a fingertip, and the following evaluation results were obtained.
0: No tack 1: Degree of fingerprint 2: Tack

<Evaluation 2; Under-thread curability> A sample was prepared by the method of Evaluation 1, and after standing in a 23 ° C. × 50% RH atmosphere for 24 hours, the nylon thread was peeled off, and the surface was observed with the naked eye. The rating was attached.
0: There is a thread on the carbon surface
1: There are some threads on the carbon surface. 2: No threads on the carbon surface.

<Evaluation 3: Adhesive strength> Each sample was applied to a real carbon gutter (with a guide) using a brush, cured by irradiating with ultraviolet rays, and after curing, a pushable gauge was used to place the guide in a perpendicular direction. Pull and measure strength. The curing conditions were in accordance with Evaluation 1. The strength was ranked according to the following score.
0:30 kg or more 1:20 kg or more and less than 30 kg 2:20 kg or less

<Evaluation 4: Pencil hardness> The hardness was evaluated according to JIS K 5400.

(Examples 2 to 4)

(Experimental example 5) The molar ratio of the carbon-carbon double bond group in polyene and the thiol group in polythiol is 1 for diallyl maleate and tris-2hydroxyethyl-isocyanurate-tris-β-mercaptopropionate. / 1 to mix. And it is made to react at 40 degreeC, stirring, and when it will be about 300 (mPa / s), N-nitrosophenyl-hydroxylamine ammonium salt 0.0005 with respect to a total of 100 mass parts of polyene and polythiol. Add parts by weight. After confirming the termination of the reaction, 0.005 parts by mass of 2,2-methylenebis (4-methyl-6-tertiary butylphenol and 0.50 parts by mass of benzyldimethyl ketal were added and dissolved for 1 hour at 60 ° C. After confirmation of dissolution Then, 20 parts by mass of isophorone diisocyanate-2-hydroxyethyl acrylate adduct was added, and the mixture was stirred and dissolved under natural cooling to obtain a resin composition (B).

(Experimental Example 6) 5 parts by mass of neopentyl glycol alkoxy diacrylate, 13 parts by mass of bisphenol A alkoxy diacrylate, 30 parts by mass of a polyurethane-based acrylate oligomer previously dissolved in 40 parts by mass of bivalic acid ester neopentyl glycol alkoxy diacrylate, Add 12 parts by mass of triacrylate of tris (2-hydroxyethyl) isocyanuric acid and stir. 0.5 part by mass of benzyl dimethyl ketal was added and dissolved at 60 ° C. for 1 hour to obtain a resin composition (A).

(Experimental example 7) Diallyl maleate and tris-2hydroxyethyl-isocyanurate-tris-β-mercaptopropionate have a molar ratio of carbon-carbon double bond group in polyene to thiol group in polythiol is 1. / 1 to mix. And it is made to react at 40 degreeC, stirring, and when it will be about 300 (mPa / s), N-nitrosophenyl-hydroxylamine ammonium salt 0.0005 with respect to a total of 100 mass parts of polyene and polythiol. Add parts by weight. After confirming the termination of the reaction, 0.005 parts by mass of 2,2-methylenebis (4-methyl-6-tertiarybutylphenol and 0.50 parts by mass of benzyldimethyl ketal were added and dissolved for 1 hour at 60 ° C. After cooling, 0.5 parts by mass of ethylenethiourea was added and dissolved by stirring to obtain a resin composition (B).

Using the resin compositions (A) and resin compositions (B) of Experimental Examples 1, 2, and 5-7, a resin composition was prepared with the formulation shown in Table 2, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 2.

The resin composition and adhesive of the present invention are characterized by good surface curability and a cured product with high pencil hardness, and further, the viscosity can be easily adjusted according to the intended use. For example, it can be used in various fields, for example, it can be used for fishing rods, reels, etc., and its workability can be greatly improved.

Claims (5)

(1) Urethane oligomer, (2) polyene, (3) polythiol, (4) photopolymerization initiator, (5) reducing agent, (6) polyfunctional polymerizable vinyl monomer, and (7) oxidizing agent. A resin composition characterized by the above. The resin composition according to claim 1, wherein (2) polyene and (3) polythiol are reacted in advance and then blended. An adhesive comprising the resin composition according to claim 1. (1) urethane oligomer, (2) polyene, (3) polythiol, (4) photopolymerization initiator, (5) first resin composition containing a reducing agent, (1) urethane oligomer, (6) many The adhesive according to claim 3, wherein the adhesive is a two-material type comprising a functional polymerizable vinyl monomer, (4) a photopolymerization initiator, and (7) a second resin composition containing an oxidizing agent. The adhesive according to claim 3 or 4, wherein the adhesive is used for fixing rods and reels of fishing rods.