JP5405001B2 - Resin composition and adhesive - Google Patents

Description

The present invention relates to an adhesive having a plastic resin foam as an adherend, and more particularly to a polyene / polythiol resin composition and an adhesive that cure at room temperature.

Conventionally, as a casting method for producing a casting, a wooden mold method, a disappearance model casting method (also called a full mold casting method or a lost foam method), a shrink mold method, and the like are known.

A typical example of the synthetic resin foam that is the base material of the casting disappearance model is a polystyrene resin foam (EPS). Examples of adhesives that have been used to join model parts of polystyrene resin foam include two-component epoxy-based, one-component urethane-based, and urea-based adhesives.

Since these adhesives have a slow curing rate and take a long time for the adhesive strength to develop, it is necessary to leave the joint to stand before moving to the next step. Furthermore, since the two-component epoxy adhesive is cured by an addition polymerization reaction, it is essential to mix the two components well, and in the case of poor mixing, there is a disadvantage that the adhesive strength is not improved. One-component urethane adhesives and urea adhesives cure more slowly than epoxy adhesives and have slightly weaker adhesive strength.

In addition, these adhesives have a drawback that a large amount of combustion residue remains when burned. If there are many combustion residues of the adhesive used in the manufacture of the disappearance model for casting, when the casting is manufactured using the disappearance model for casting, the combustion residue enters the interior of the casting or adheres to the surface. Cheap. If the combustion residue enters the inside of the casting or adheres to the surface, the strength of the casting is reduced or the workability is deteriorated. Accordingly, this combustion residual has been a problem particularly in the case of producing castings that require high accuracy such as automobile and ship engines and precision machine tools (see Patent Document 1).

Japanese Patent Laid-Open No. 05-212491

Conventionally, residual combustion of adhesives such as two-part epoxy, one-part urethane, and urea that have been used in the manufacture of disappearance models for casting made of polystyrene and methacrylic (hereinafter simply referred to as plastic) resin foams Specifically, a certain amount of a cured product of these adhesives is heated from 20 ° C. to 800 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the weight of the remaining residue is measured. When the amount of combustion residue is calculated and the combustion residue of polystyrene foam is 1.0, the combustion residue of the two-part epoxy adhesive is 9.0, and the one-part urethane adhesive is 5. 2. The combustion residue of urea adhesive is 17.9, and the combustion residue of any adhesive is much more than that of polystyrene foam.

The present invention has been made to solve the above-mentioned problems of the prior art, and more specifically, in the production of a disappearance model for casting made of a plastic resin foam, the occurrence of a combustion residue of the cured product is generated. An object of the present invention is to provide a resin composition and an adhesive that are reduced, have a weak property of dissolving an adherend, and can be strongly bonded in a short time.

The present invention is, (1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] polyenes comprising propane, (2) trimethylol propane -β- mercaptopropionate It is a resin composition for adhering a resin foam, comprising a polythiol containing (3) a reducing agent, (4) an oxidizing agent, and (5) an antioxidant.

The present invention is, (1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] polyenes comprising propane, (3) a reducing agent, (5) an antioxidant A second resin composition containing a first resin composition containing, (2) a polythiol containing trimethylolpropane-β-mercaptopropionate, (4) an oxidizing agent, and (5) an antioxidant. is said resin composition, which is a dual-material type consisting of an object, comprising (1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane A polyene comprising (3) a reducing agent, (5) a first resin composition containing an antioxidant, and (1) a polyene comprising PO-modified neopentyl glycol diacrylate, 2) A two-material type comprising a polythiol containing trimethylolpropane-β-mercaptopropionate, (4) an oxidizing agent, and (5) a second resin composition containing an antioxidant. The above-mentioned resin composition, which is an adhesive comprising the above-mentioned resin composition.

The present invention is the above-mentioned adhesive, and the mass of the combustion residue of the cured product cured at 23 ° C. and 50% RH (combustion condition: 800 ° C. in a nitrogen atmosphere) is the mass of the cured product before combustion. It is an adhesive characterized by being 3% or less, and is an adhesive for adhering model parts constituting the disappearance mold for casting made of polystyrene or methacrylic resin foam. is there.

Because of the composition of the resin composition of the present invention, it is possible to provide a polyene / polythiol adhesive that hardly dissolves the plastic resin foam and has improved curability. Moreover, the said resin composition can manufacture the vanishing model for casting which made the base material the polystyrene-type resin foam in which the smoke and combustion residue which were emitted when it combusted were reduced.

Since the adhesive of this invention consists of the said specific resin composition, it reflects the said characteristic, for example, is an adhesive suitable for joining of a plastic resin foam.

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

(1) Examples of the polyene include allyl alcohol derivatives, esters of (meth) acrylic acid and polyhydric alcohols, and pivalic acid esters. 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 can be used. Examples of the compound include dimethylol / tricyclodecane diacrylate, neopentyl glycol alkoxy diacrylate, pivalate ester neopentyl glycol diacrylate, neopentyl glycol diacrylate, bisphenol A alkoxy diacrylate, trimethylol propane ( meth) acrylate, tris (2-hydroxyethyl) triacrylate isocyanuric acid, isophorone diisocyanate wetting over preparative-2-hydroxyethyl acrylate, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane .

Examples of pivalate esters include hydroxypivalate neopentyl glycol (meth) acrylate, PO-modified (n mol) neopentyl glycol diacrylate, EO-modified (n mol) neopentyl glycol diacrylate, neopentyl glycol diacrylate, and the like. Is mentioned.

(1) One type of polyene may be used, but a combination of two or more types may be used.

It is preferable that the polyene has a weak or substantially no property of dissolving the polystyrene resin foam. Further, triallyl cyanurate over DOO as 100 wt% on the total amount of (1) and (2), 40 to 60 wt%, more preferably selected from 45 to 55 weight%.

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

Among the 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.

(2) The polythiol may be one of the above, but may be used in combination of two or more.

It is preferable that the polythiol has weak or substantially no property of dissolving the polystyrene resin foam. Therefore, the polythiol that does not dissolve the polystyrene resin foam is selected to be 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, with the total amount of (1) and (2) being 100% by mass. Is done.

(3) Examples of the reducing agent include thiourea derivatives, amines, condensation products of aldehydes and amines, and organic salts. Examples of thiourea derivatives include diethylthiourea, dibutylthiourea, ethylenethiourea, tetramethylthiourea, mercapto. And thioamide compounds such as benzimidazole. 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. In these, an organic salt is preferable and vanadyl acetylacetonate is preferable at the point of hardening acceleration.

(3) The amount of the reducing agent used is preferably 0.01 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of (1) and (2).

(4) Examples of the oxidizing agent include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide and tertiary butyl peroxybenzoate. One or more of these may be used. Among these, cumene hydroperoxide is preferable in terms of reactivity.

(4) As for the usage-amount of an oxidizing agent, 0.01-10 mass parts is preferable with respect to 100 mass parts and the total amount of (1) and (2), and 1-5 mass parts is more preferable.

(5) Antioxidants include hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiarybutyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-tertiarybutylphenol), triphenyl phosphite , Phenothiazine, N-isopropyl-N′-phenyl-p-phenylenediamine, and the like. One or more of these may be used.

(5) As for the usage-amount of antioxidant, 0.001-3 mass parts is preferable with respect to 100 mass parts for the total amount of (1) and (2). If it is 0.001 part by weight or more, the effect of addition can be obtained, and if it is 3 parts by weight or less, the curing strength does not decrease.

The resin composition of the present invention can contain a carboxylic acid amide compound as an optional component for the purpose of improving curability in air. Examples of the carboxylic acid amide compounds include fatty acid amides such as oleic acid amide, erucic acid amide, lauric acid amide, palmitic acid amide, myristic acid amide, caproic acid amide, and stearic acid amide, and acrylic acid amides. These may be contained alone or in combination of two or more.

The content of the carboxylic acid amide compound is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of (1) and (2). The addition effect is obtained at 0.1 parts by mass or more, and it is not difficult to dissolve in (1) polyene or (2) polythiol at 3 parts by mass or less.

For the resin composition and adhesive of the present invention, if necessary, adhesion improvement of a monofunctional polymerizable monomer having one carbon-carbon double bond in one molecule, an organic phosphorus compound, an organosilicon compound, etc. Various commonly used compounding agents such as an agent, a polymerization inhibitor, a filler, a colorant, a thixotropic agent, a curing accelerator, a plasticizer, and a surfactant may be added.

As a preferred embodiment, the resin composition and adhesive of the present invention can be stored in two parts until they are used. (Hereinafter, these two agents are abbreviated as “agent A and agent B”). (3) The reducing agent is included only in the B agent, and (4) the oxidizing agent is included only in the A agent. This is to prevent the curing reaction from starting during storage.

Example 1
(Manufacture of A agent) Trimethylolpropane-β-mercaptopropionate (manufactured by Sakai Chemical Co., “TP”) 75 parts by mass, PO-modified neopentyl glycol diacrylate (manufactured by Cognis Japan, “F-4127”) 25 Part by mass, 0.5 part by mass of 2,6-ditallybutyl-4-methylphenol (manufactured by Sumitomo Chemical Co., Ltd., “BHT”) is mixed and stirred, and further 3 parts by mass of lactic acid (commercial product) And dissolve at 80 ° C. for 1 hour. After confirmation of dissolution, the mixture is cooled and 0.5 part by mass of oleic amide (commercial product) is added and dissolved. After dissolution, 5 parts by mass of cumene hydroperoxide (manufactured by NOF Corporation, “CHP”) was added, stirred, and dissolved to obtain a resin composition (A).

(Production of B agent) triallyl cyanurate over preparative (Hitachi Chemical Co., Ltd., "TAIC") to 50 parts by weight of 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd., " BPE-1300N ") 50 parts by mass and 0.5 parts by mass of 2,6-ditallybutyl-4-methylphenol (manufactured by Sumitomo Chemical Co.," BHT ") are added and dissolved at 60 ° C for 1 hour. After cooling, 0.4 part by mass of vanadyl acetyl acetate (manufactured by Shinsei Chemical Co., Ltd., “VoAA”) was added and dispersed by stirring, and (2-hydroxyethyl) methacrylate acid phosphate (manufactured by Johoku Chemical Industry Co., Ltd., “JPA-514”) was added. ]) The resin composition (B) was obtained by adding 1.5 mass parts, stirring and dissolving.

The following evaluation was performed using the resin composition (A) and the resin composition (B) obtained above. The results are shown in Table 1.

<Storage stability>
A resin composition (A) or a resin composition (B) is put into a test tube (diameter 16 mm, length 150 mm) to a height of about 5 cm. A sensor equipped with a polyethylene cover with a cork stopper is inserted into a test tube, sealed, and placed in a constant temperature water bath at 70 ° C. The thing without a temperature change in 120 minutes is set as a pass.

<Combustion residual>
About the hardened | cured material obtained from the equal mass mixture of the resin composition (A) and the resin composition (B) in a thermostatic chamber at 23 ° C. and 50% RH, in accordance with JIS K7120, the difference is as follows. Thermal analysis was performed and the weight of the combustion residual was measured. Moreover, 3% or less was set as the pass.

Measuring device: TG / DTA220 manufactured by Seiko Electronics Industry Co., Ltd.
Sample: Measured at 10 mg in a platinum open-type sample container having a diameter of 5 mm Measurement temperature: 20 to 800 ° C., temperature increase speed = 10 ° C./min, measurement completed at 800 ° C. Nitrogen flow: 300 ml / min

<Confirmation of adhesiveness to polystyrene resin foam>
At a temperature of 20 ° C., an adherend composed of a polystyrene-based resin was used. After applying the resin composition (A) on one side and applying the resin composition (B) on the other side, the resin composition (A) and The resin composition (B) is bonded to each other, and is weighted (100 g / 25 cm ² ) and clamped until the initial strength is obtained. The test was repeated 5 times, and after 20 minutes from the pasting, the strength test was conducted, and if the material destruction was 3 (60%) or more, the test was accepted.

(Comparative Example 1)
(Manufacture of agent A)
75 parts by mass of trimethylolpropane-β-mercaptopropionate (“TP” manufactured by Sakai Chemical Co., Ltd.), 25 parts by mass of PO-modified neopentyl glycol diacrylate (“F-4127” manufactured by Cognis Japan), lactic acid (commercially available) Product) 3 parts by mass are mixed and dissolved at 80 ° C. for 1 hour. After confirmation of dissolution, the mixture is cooled and 0.5 part by mass of oleic amide (commercial product) is added and dissolved. After dissolution, 5 parts by mass of cumene hydroperoxide (manufactured by NOF Corporation, “CHP”) was added, stirred, and dissolved to obtain a resin composition (A).

(Manufacture of B agent)
Triallyl cyanurate over preparative (Hitachi Chemical Co., Ltd., "TAIC") to 50 parts by weight of 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-500") 50 A part by mass was added and dissolved at 40 ° C. for 1 hour. After cooling, 0.4 parts by mass of vanadyl acetylacetate (manufactured by Shinsei Chemical Co., Ltd., “VoAA”) was added and stirred and dispersed, (2-hydroxyethyl) methacrylate acid phosphate (Johoku Chemical Industry Co., Ltd., “JPA-514”). The resin composition (B) was obtained by adding 1.5 mass parts, stirring and dissolving.
The same evaluation as Example 1 was performed using the obtained resin composition (A) and resin composition (B), and the results are shown in Table 1.

(Examples 2 and 3, Comparative Examples 2 to 6)
Except that the composition was changed, a resin composition (A), a resin composition (B), and a cured body comprising both were prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. These results are shown in Table 1.

The resin composition of the present invention is characterized by the fact that it can provide a polyene / polythiol-based adhesive that is difficult to dissolve the plastic resin foam and has improved curability due to its composition. Since a casting disappearance model based on a polystyrene resin foam with reduced smoke and combustion residuals can be produced, it is industrially useful.

Claims (6)

(1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] polyenes comprising propane, containing (2) trimethylol propane -β- mercaptopropionate A resin composition for adhering a resin foam, comprising: a polythiol, (3) a reducing agent, (4) an oxidizing agent, and (5) an antioxidant. (1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] polyenes comprising propane, (3) a reducing agent, first containing (5) antioxidant And (2) a polythiol containing trimethylolpropane-β-mercaptopropionate, (4) an oxidizing agent, and (5) a second resin composition containing an antioxidant. The resin composition according to claim 1, wherein the resin composition is a two-material type. (1) triallyl cyanurate over preparative and 2,2-bis [4- (methacryloxy polyethoxy) phenyl] polyenes comprising propane, (3) a reducing agent, first containing (5) antioxidant (1) polyene containing PO-modified neopentyl glycol diacrylate, (2) polythiol containing trimethylolpropane-β-mercaptopropionate, (4) oxidizing agent, 5) The resin composition according to claim 1, which is a two-material type comprising a second resin composition containing an antioxidant. An adhesive comprising the resin composition according to claim 1. 5. The adhesive according to claim 4, wherein the mass of the combustion residue of the cured product cured at 23 ° C. and 50% RH (combustion condition: 800 ° C. under a nitrogen atmosphere) is the mass of the cured product before combustion. Adhesive characterized by being 3% or less. The adhesive according to claim 1, wherein the adhesive is used to bond model parts constituting a casting mold made of polystyrene or methacrylic resin foam.