JP2003026784A - Curable resin composition and method for easily dismantling joint member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-pack type curable resin composition which excels in heat curability and storage stability, and can be softened or liquefied after curing by heating without involving the generation of a harmful gas, and a method for dismantling a joint member by using the heat-curable resin composition. SOLUTION: The curable resin composition comprises (A) a compound having two or more hydroxyl groups in the molecule, (B) a compound having one or more acid anhydride groups in the molecule, and (C) a compound having two or more vinyl ether groups and/or vinyl thioether groups in the molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a one-part thermosetting curable resin composition in which a cured product can be softened or liquefied by heating after curing. The present invention also relates to a method for easily disassembling a joining member using the curable resin composition.

[0002]

2. Description of the Related Art In recent years, recyclability is required in various fields from the viewpoint of being environmentally friendly and reducing costs. In the automotive field as well, in order to recycle the members, disassembling the members bonded with urethane adhesives is being considered, but to soften or liquefy the urethane adhesives, heat above 200 ° C. Must be
There are problems such as generation of toxic gas. On the other hand, if a thermoplastic adhesive is used, generation of toxic gas can be suppressed during disassembly, but since a heating device is required at the time of application,
Workability was poor. In addition, since thermoplastic resin products gradually begin to soften at relatively low temperatures, their physical properties at high temperatures are low,
It had the drawback that it could not be used in hot areas.

By the way, a hemiacetal ester bond (or hemiacetal thioester bond) consisting of a vinyl ether group or a vinyl thioether group and a carboxyl group dissociates at a temperature lower than the thermal decomposition temperature, and below the dissociation temperature, the bond. Is known to be stable (Chemical Abstract 43,6576d, 1949). In addition, JP-A-4-72324 describes a thermosetting resin composition containing a compound having a vinyl ether group and a compound having a carboxyl group. But,
The thermosetting resin composition is a two-pack type, and the vinyl ether group and the carboxyl group have extremely high reactivity, so in a composition in which these groups coexist in the container, they react during storage. However, it cannot be used as a one-pack type because it causes gelation and shortens the pot life. Further, the publication does not mention that the cured product can be easily softened or liquefied.

[0004]

DISCLOSURE OF THE INVENTION The present invention has excellent thermosetting property and storage stability, and has good workability since it is in a liquid state before curing. After heating, it produces a toxic gas by heating. An object of the present invention is to provide a one-pack type curable resin composition that can be softened or liquefied without involving, and a method for easily disassembling a joining member using the thermosetting resin composition.

[0005]

The first aspect of the present invention is as follows.
A compound (A) having two or more hydroxyl groups in the molecule, and a compound (B) having one or more acid anhydride groups in the molecule,
A curable resin composition comprising a compound (C) having two or more vinyl ether groups and / or vinyl thioether groups in the molecule. The compound (B) is preferably a compound having one acid anhydride group in the molecule. Moreover, it is preferable that the total of the number of moles of the hydroxyl group of the compound (A) with respect to the total of the number of acid anhydride groups of the compound (B) is 4 or less.

A second aspect of the present invention provides a cured product obtained by curing the curable resin composition according to any one of the above 15
It is a method for easily disassembling a joined member, characterized in that it is softened or liquefied by heating at 0 to 200 ° C. to disassemble members joined by the cured product.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition according to the first aspect of the present invention comprises a compound (A) having two or more hydroxyl groups in the molecule (hereinafter also referred to as "compound (A)"). A compound (B) having one or more acid anhydride groups in the molecule (hereinafter also referred to as "compound (B)") and a compound (B) having two or more vinyl ether groups and / or vinyl thioether groups in the molecule ( C) (hereinafter also referred to as “compound (C)”).

The compound (A) is a compound having two or more hydroxyl groups in one molecule (hereinafter referred to as "polyol compound").
Also called. ). When one molecule has two or more hydroxyl groups, the crosslink density is high and the physical properties of the cured product are excellent. When a high molecular weight polyol compound is used, the number of hydroxyl groups can be arbitrarily set according to the application, required physical properties of the cured product, and the like. The compound having a plurality of hydroxyl groups in one molecule is not particularly limited, and a low molecular weight compound or a high molecular compound (hereinafter, including prepolymer) can be used.

Examples of such polyol compounds include polyols, alkanolamines, epoxy polyols and the like. As polyols,
Ethylene glycol, 1,3-butanediol, 1,4
-Butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerin, sorbitol, neopentyl glycol, 1,2- and 1,3
-Propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 1,8-octanediol, cyclohexanedimethanol, 1,4-bis-
Hydroxymethyl-cyclohexane, 2-methyl-1,
Low-molecular-weight functional polyols such as 3-propanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane and pentaerythritol; polyester resin, polyacrylic resin, polyvinyl Examples thereof include alcohol resins, epoxy resins, phenol resins, polyoxyalkylene glycol resins, urethane resins and the like, or polymer polyols such as prepolymers thereof. The alkanolamines include ethanolamine, propanolamine and the like, and the polyhydric phenols include resorcin, bisphenols (eg, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F) and the like. .

Among these polyol compounds, glycerin, 1,6-hexanediol, 1,2- and 1,3-propylene glycol, 1,4-bis-hydroxymethyl-cyclohexane, trimethylolpropane or any of the above-mentioned various compounds. The high molecular weight polyols are preferably used. Low molecular weight functional polyols or polyester resins of glycerin or trimethylolpropane,
Polymer polyols such as polyvinyl alcohol resin, polyoxyalkylene glycol resin or urethane resin are more preferably used. Particularly, polytetramethylene ether glycol, polypropylene glycol and polyester polyol are preferably used.

When the above-mentioned polymer polyols are used as the polyol compound, the molecular weight of the main chain of the polymer polyols is not particularly limited, and can be any molecular weight depending on the performance of the composition, the application and the like. . From the viewpoint of curability, the molecular weight of the main chain of polymer polyols is 100 to 1
10,000 is preferable, 120-8,000 is more preferable, 150-6,000 is especially preferable. This is because if the molecular weight is too high, the reactivity becomes low and the curing speed becomes slow. Moreover, the said polyol compound can be used individually by 1 type or in combination of 2 or more types. In this case, the mixing ratio can be any ratio depending on the required physical properties of the cured product, the application, and the like.

The compound (B) is a compound having at least one acid anhydride group in the molecule. The acid anhydride group is not particularly limited as long as it is an acid anhydride group of an aliphatic or aromatic carboxylic acid. The compound (B) is not particularly limited as long as it is a compound having one or more such acid anhydride groups in the molecule, but is preferably a compound having one acid anhydride group in the molecule. This is because by using a compound having one acid anhydride group in the molecule, the crystallinity does not increase and many of them are liquid at room temperature, and the reaction between the hydroxyl group and the acid anhydride group easily occurs.

Examples of the compound (B) include the following compounds. 1) Saturated or unsaturated aliphatic dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, and polysebacic anhydride, 2) tetrahydrophthalic anhydride (4-cyclohexene-
1,2-dicarboxylic anhydride), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), methylhexahydrophthalic anhydride, methylhymic acid anhydride, methylcyclohexenedicarboxylic anhydride , 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride, saturated or unsaturated alicyclic polyvalent carboxylic acid anhydride such as het anhydride, trialkyltetrahydrophthalic anhydride, 3) Phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride, methylcyclohexene tricarboxylic acid anhydride, pyrolimetic anhydride, mellitic anhydride, 1,8; 4,
Aromatic polyvalent carboxylic acid anhydrides such as 5-naphthalene tetracarboxylic acid dianhydride. In addition, these compounds have a substituent such as an alkyl group, an alkenyl group, or an alkoxyl group.
You may have one piece or two or more pieces.

Among these compounds (B), from the viewpoint of reactivity with the above-mentioned compound (A), alicyclic polyvalent carboxylic acid anhydride is preferable, and particularly, the following general formula (1) Hexahydrophthalic anhydride, which may have a substituent, represented by

[0015]

[Chemical 1] R in the general formula (1) is a hydrogen atom or a carbon number of 1 to 10.
Is an alkyl group, an alkenyl group or an alkoxyl group.

Here, the alkyl group is a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group are preferred. As the alkenyl group, alkenyl groups corresponding to these are preferable. As the alkoxyl group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group are preferable. Above all, as R,
A methyl group and an ethyl group are preferred because they are easily available.

Especially preferred as compound (B) are:
Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhymic acid anhydride, and trialkyltetrahydrophthalic anhydride. These compounds (B) can be used alone or in combination of two or more. In this case, the mixing ratio can be any ratio depending on the required physical properties of the cured product, the application, and the like.

The compound (C) is not particularly limited as long as it has two or more vinyl ether groups and / or vinyl thioether groups in the molecule. Such a compound (C) is preferably a compound having two or more functional groups represented by the following general formula (2).

[0019]

[Chemical 2]

R ^{1 to} R ⁵ in the general formula (2) are each a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹ or R ² and R ⁴ or R ⁵ are bonded to each other to contain X. It may form a heterocycle. X including R ⁴ or R ⁵
It includes compounds having a ring structure not containing. X is an oxygen atom or a sulfur atom. Here, the organic group is
Substituted with or without at least one atomic group selected from the group consisting of a cycloalkyl group, an alkoxyl group, a cycloalkoxy group, an aryl group, an aryloxy group, an alkanoyloxy group, an aralkyloxy group and a halogen atom. An alkyl group, which need not be present,
It is a cycloalkyl group, an aryl group, an alkylene group, a cycloalkylene group or an arylene group.

The functional group represented by the general formula (1) is not particularly limited, and examples thereof include methyl vinyl ether group, ethyl vinyl ether group, isopropyl vinyl ether group, n-propyl vinyl ether group, n-butyl vinyl ether group and isobutyl. Vinyl ether groups such as vinyl ether group, 2-ethylhexyl vinyl ether group, cyclohexyl vinyl ether group and vinyl thioether groups corresponding thereto; 2,3-dihydrofuranyl group,
3,4-dihydro-2H-pyranyl group, 3,4-dihydro-2-methoxy-2H-pyranyl group, 3,4-dihydro-2-ethoxy-2H-pyranyl group, 2,3-dihydrobenzopyranyl group , 2,3-dihydrobenzofuranyl group and other cyclic vinyl ether groups bonded at the 2-position, and corresponding cyclic vinyl thioether groups.

In the above general formula, R¹~ R³Are hydrogen
An atom or an alkyl group having 1 to 10 carbon atoms is preferable, and R is
^FourOr R^FiveAre each a hydrogen atom or a carbon number of 1 to 1, respectively.
Alkyl or alkylene groups of 0 are preferred. (R
¹Or R²And R^FourOr R ^FiveBinds each other to X
It may form a heterocycle containing. Also, R^FourOr R
^FiveAnd a compound having a ring structure containing no X. ) In particular, R¹~ R³Are each preferably a hydrogen atom
Well, R^FourOr R^FiveOne of is a hydrogen atom
Is preferred. Is the reactivity improved and it is easy to obtain raw materials?
It is.

When two or more functional groups are contained in one molecule, the crosslink density is high and the physical properties of the cured product are excellent. When using a polymer compound (including a prepolymer) described below,
The number of functional groups can be arbitrarily set according to the application, the required physical properties of the cured product, and the like.

Compound (b) having two or more of the above functional groups
Is not particularly limited, and a low molecular weight (monomer) compound or a high molecular compound (including a prepolymer) can be used. Specific examples include the compounds shown below. 1) ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, butanediol diisopropenyl ether, pentanediol divinyl ether, hexanediol divinyl ether, Neopentyl glycol diisopropenyl ether, nonanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether,
Pentaerythritol tetravinyl ether, 2,2-
Low molecular weight polyvalent vinyl ethers such as bis [p- (2-vinyloxyethoxy) phenyl] propane, cyclohexanediol divinyl ether, cyclohexanemethanol diol divinyl ether, and acetic acid diisocyanate ester, and low molecular weight polyvalent vinyl ethers corresponding thereto. Examples include divalent vinyl thioethers.

2) A vinyl ether and / or a vinyl thioether compound obtained by reacting the polyvalent vinyl ether or vinyl thioether described in 1) above and a polyol with an excess of a vinyl ether group or the like. Here, the polyols specifically include ethane diol, propane diol, butane diol, pentane diol, octane diol or their homologues, and corresponding oligomer ethers; glycerin, trimethylol ethane, trimethylol propane, hexane triol,
Pentaerythritol, dipentaerythritol, sorbitol, polyvinyl alcohol, bisphenol A,
Examples include polyols such as resorcin, hydroquinone or derivatives thereof; trishydroxyethyl isocyanurate; hydroxyl group-containing epoxide; hydroxyl group-containing polyether; hydroxyl group-containing polyester; hydroxyl group-containing polyacryl;

3) Adducts of hydroxyl group-containing monovinyl ether and / or monovinyl thioether with polyisocyanate compounds, such as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, 1,4-butylene glycol monovinyl ether, methanol dihydropyran, and the like. Vinyl thioether compounds corresponding to these, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
1,12-dodecane diisocyanate, cyclohexane-1,3- or -1,4-diisocyanate, isophorone diisocyanate, perhydro-2,4'- or -4,4'-diphenylmethane diisocyanate, 1,
3- and -1,4-phenylene diisocyanate,
2,4- and -2,6-tolylene diisocyanate,
Diphenylmethane-2,4'- or -4,4'-diisocyanate, 3,2- or -3,4-diisocyanate-4'-methyldiphenylmethane, naphthalene-
1,5-diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, norbornane diisocyanate, triphenylmethane-4,
Examples thereof include adducts of 4 ′, 4 ″ -triisocyanate or low molecular weight polyvalent isocyanates with isocyanurate type, buret type, and polyol addition type polyisocyanates.

Among these compounds (C), low molecular weight polyvalent vinyl ethers and corresponding low molecular weight polyvalent vinyl thioethers; hydroxyl group-containing monovinyl ethers and / or adducts of monovinyl thioethers with polyvalent isocyanate compounds; Is preferably used. In particular, low molecular weight polyvalent vinyl ethers and low molecular weight polyvalent vinyl thioethers corresponding thereto are used from the viewpoint of cost reduction, and hydroxyl group-containing monovinyl ethers and / or adducts of monovinyl thioethers with polyvalent isocyanate compounds are used for adjusting physical properties. It is preferably used because it is easy.

The molecular weight of the main chain when the above-mentioned high molecular weight vinyl ether compound (or vinyl thioether compound) is used as the compound (C) is not particularly limited, and may be any molecular weight depending on the performance of the composition, application and the like. be able to. From the viewpoint of easy disassembly, the molecular weight of compound (C) is 1
00 to 20,000 is preferable, 120 to 10,000
Is more preferable, and 150 to 5,000 is particularly preferable.
When the molecular weight is too low, the reactivity with the compound (A) becomes high, and the hemiacetal ester bond or the hemiacetal thioester bond in the cured product (hereinafter, these are collectively referred to as “hemiacetal (thio) ester bond”). The content rate of may decrease. On the other hand, when the molecular weight is too high, the crosslink density becomes low, and the strength of the cured product may decrease. These vinyl ether compounds or vinyl thioether compounds may be used alone or in combination of two or more. The mixing ratio in this case is
The ratio can be set arbitrarily according to the physical properties required for the cured product, the application, and the like.

The curable resin composition of the present invention is a one-component thermosetting type, which is cured by heating during use to cause a crosslinking reaction. The heating temperature during curing is 80 ° C.
It is preferably at least 100 ° C, more preferably at least 100 ° C, even more preferably at least 120 ° C. This is because if the temperature is lower than 80 ° C, it takes a long time to cure. In order to further improve the physical properties of the cured product, it is preferable that the heating temperature be equal to or lower than the thermal dissociation temperature of the generated hemiacetal (thio) ester bond. The cured product obtained by curing the curable resin composition of the present invention is an easily dismantled cured product that softens or liquefies in a short time by heating. The temperature required for softening or liquefying depends on the types and composition ratios of compound (A), compound (B), and compound (C), but is preferably 150 to 200 ° C, more preferably 160 to 19 ° C.
It is adjusted to be 0 ° C. If it is higher than 200 ° C, a toxic gas may be generated, and if it is lower than 150 ° C, the heat resistance of the cured product may be lowered. Thus, the curable resin composition of the present invention is softened or liquefied after curing because the cured product forms a thermally dissociable hemiacetal (thio) ester bond and is crosslinked. it is conceivable that. In the curable resin composition of the present invention, the reaction mechanism in which this hemiacetal (thio) ester bond is formed is not clear, but the present inventors consider as follows.

First, the curable resin composition of the present invention is heated to a predetermined temperature to react the hydroxyl group of the highly reactive compound (A) with the acid anhydride group of the compound (B). To do. By this reaction, the compound (A) and the compound (B) form an ester bond, and the produced compound (hereinafter referred to as “compound (D)”) has a carboxyl group. The number of carboxyl groups contained in the compound (D) is considered to be almost the same as the number of moles of the reacted hydroxyl group or acid anhydride group. The carboxyl group of the compound (D) produced by this reaction then reacts with the vinyl ether group and / or the vinyl thioether group of the compound (C) to form a thermally dissociable hemiacetal (thio) ester bond. To crosslink.

As described above, the cured product obtained by curing the curable resin composition of the present invention is considered to form a crosslink by forming a heat dissociable hemiacetal (thio) ester bond. Since the hemiacetal (thio) ester bond is dissociated by heating to a predetermined temperature as described above, the cured product, once cured, is softened or softened at a temperature lower than the thermal decomposition temperature. Since it can be liquefied, it can be easily disassembled.

The vinyl ether group and / or the vinyl thioether group can also react with a hydroxyl group to form an acetal bond, but this bond cannot be dissociated at a temperature below the thermal decomposition temperature of the cured product. Therefore, when the reaction between the compound (A) and the compound (B) is delayed and the reaction between the compound (A) and the compound (C) proceeds, the content of hemiacetal (thio) ester bond in the cured product becomes low, There may be a case where desired ease of dismantling cannot be obtained.

Therefore, when the content of the hemiacetal (thio) ester bond is increased to make the cured product particularly easy to disassemble, 1) the compound (B) is used as an alicyclic polycarboxylic acid. A highly reactive compound such as an acid anhydride is used. 2) As the compound (C), a high molecular weight vinyl ether compound such as an adduct of a hydroxyl group-containing monovinyl ether and / or a monovinyl thioether and a polyvalent isocyanate compound can be used. preferable.

In the curable resin composition of the present invention, the composition ratio of compound (A), compound (B) and compound (C) is not particularly limited. From the viewpoint of easy dismantling, the compound (B)
The total number of moles of hydroxyl groups of the compound (A) (hereinafter abbreviated as “hydroxyl group / acid anhydride group”) with respect to the total number of moles of acid anhydride groups is preferably 4 or less, more preferably Is 3 or less. When it is larger than 4, the content of the heat dissociative hemiacetal ester bond in the cured product becomes low, and therefore the cured product may become difficult to be softened or liquefied when heated to a predetermined temperature.

The content of the compound (C) is such that the molar ratio of the contained vinyl ether group and / or vinyl thioether group to the hydroxyl group of the compound (A) is 1.5 / 1 to
It is preferably set to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When the content is set within this range, the reaction product has little residual tack and good physical properties.

The curable resin composition of the present invention may contain other polymers, reinforcing agents, antioxidants, antioxidants, pigments (dyes), if necessary, within the range not impairing the object of the present invention. ,
Plasticizer, thixotropic agent, ultraviolet absorber, flame retardant, solvent,
Surfactants (including leveling agents), dispersants, dehydrating agents,
Additives such as a rust preventive agent, an adhesion imparting agent, an antistatic agent, and a filler can be contained. The kind and content of the additive are appropriately selected depending on the desired physical properties and the like.

The method for producing the curable resin composition of the present invention is as follows:
No particular limitation is imposed, and the compound (A), the compound (B), the compound (C) and, if necessary, an additive are added, and the mixture is sufficiently kneaded under normal temperature and normal pressure or reduced pressure to be uniformly dispersed. To be done.

The curable resin composition of the present invention cures rapidly when heated to a predetermined temperature, but below the temperature mentioned above, the reactivity is low and the composition can be stably retained. . That is, the curable resin composition of the present invention can satisfy both thermosetting property and storage stability. Further, a bonding member obtained by bonding a member to be bonded and a member to be bonded using the curable resin composition of the present invention is heated to a predetermined temperature to soften or harden the cured product. By making it possible, it can be easily disassembled in a short time. At this time, since the cured product can be disassembled at a temperature lower than the thermal decomposition temperature of the cured product, no toxic gas is generated and workability is excellent. The curable resin composition of the present invention having such characteristics is suitably used for adhesives and sealing materials in the fields of automobiles and civil engineering and construction.

Next, the second aspect of the present invention will be described. A second aspect of the present invention is to soften or liquefy a cured product obtained by curing a curable resin composition at 150 to 200 ° C., and disassemble members joined by the cured product. It is a method for easily disassembling a joining member. The curable resin composition used in the easy disassembly method of the present invention is the curable resin composition of the first aspect. The member joined with the cured product of the curable resin composition is not particularly limited, and may be a cured product made of glass, metal, wood, or another resin composition. As described in the first aspect, the cured product obtained by curing the curable resin composition of the present invention forms a thermally dissociable hemiacetal (thio) ester bond and is crosslinked. And 150 ~
By heating to 200 ° C., the hemiacetal (thio) ester bond is dissociated, whereby the cured product can be softened or liquefied.

Therefore, according to the second aspect of the present invention, the joining member obtained by joining the members with the cured product is softened or liquefied by heating the cured product to 150 to 200 ° C. As a result, it can be easily disassembled in a short time. Moreover, since no toxic gas is generated during disassembly, workability is excellent, and the recycling of the members can be facilitated. Further, according to the second aspect of the present invention, by using the curable resin composition of the present invention as an adhesive for temporarily adhering a member and a reinforcing material, the reinforcing material is easily removed. be able to.

[0041]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. (Example 1) 100 parts by weight of a compound having three hydroxyl groups in the molecule (an ester type triol having a molecular weight of 500, "Plaxel 305" manufactured by Daicel Chemical Industries Ltd., hereinafter "triol"), 1 in the molecule A compound having one acid anhydride group (“B650” manufactured by Dainippon Ink and Chemicals, Inc.,
Hereinafter referred to as "acid anhydride 1". ), And 56 parts by weight of a compound having two vinyl ether groups in the molecule (“CHDVE” manufactured by Nippon Carbide Co., Ltd., hereinafter referred to as “divinyl ether”) are mixed until homogeneous in a flask. Then, the composition was prepared. (Hydroxyl group /
The acid anhydride group) is 1.0.

(Example 2) Instead of the acid anhydride 1, a compound having one acid anhydride group in the molecule ("YH306" manufactured by Japan Epoxy Resin Co., hereinafter referred to as "acid anhydride 2"). A composition was prepared in the same manner as in Example 1 except that 101 parts by weight of was used. (Hydroxyl group /
The acid anhydride group) is 1.4.

Example 3 A composition was prepared in the same manner as in Example 2 except that the addition amount of the acid anhydride 2 was changed to 50 parts by weight. The (hydroxyl group / acid anhydride group) of this composition is
2.8.

(Comparative Example 1) Instead of the acid anhydride 1, ethyl acid phosphate ("JP50" manufactured by Johoku Chemical Industry Co., Ltd.) was used.
2 ", hereinafter referred to as" acidic phosphate ester ". A composition was prepared in the same manner as in Example 1 except that 1 part by weight of (4) was used.

(Comparative Example 2) 214 parts by weight of a compound having 3 carboxyl groups in the molecule (hereinafter referred to as "tricarboxylic acid") synthesized by the following method instead of triol and acid anhydride 1 was used. A composition was prepared in the same manner as in Example 1 except that was used. <Synthesis of tricarboxylic acid> Triol and acid anhydride 1 were mixed so that (hydroxyl group / acid anhydride group) became 1, and 12
After stirring at 0 ° C. for 5 hours, the target product was obtained.

Next, the thermosetting property, easy dismantling property and storage stability of the obtained composition were evaluated. (1) Time to cure the thermosetting test composition by leaving it at 150 ° C. (m
in) was measured. The time when the surface tack disappeared was defined as the curing time. (2) The easily dismantling test composition was heated at 150 ° C. for 15 to 30 minutes to be cured, and then heated at 190 ° C. for 10 minutes to be liquefied and flowed, and the shape was maintained. Was evaluated as x. (3) Storage stability test The composition was allowed to stand at room temperature for 1 week and evaluated as ◯ when it did not gel and as x when it gelled. The results are shown in Table 1.
Summarized in.

[0047]

[Table 1]

[0048]

The curable resin composition of the present invention is excellent in thermosetting property and storage stability, and the cured product can be softened or liquefied in a short time by heating. A joining member obtained by joining members using the curable resin composition of the present invention can be easily disassembled without generating toxic gas.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/1539 C08K 5/372 5/372 C08L 101/06 C08L 101/06 B09B 3/00 ZABZ F term ( (Reference) 4D004 AA07 AA18 AA21 CA02 4F301 AA30 BF04 BF15 CA24 4J002 AA051 CF001 CF181 CH021 ED027 EL136 EL146 EV047 GJ00 GN00 GT00 4J029 AA01 AB07 AC01 AE13 AE18 J02E02 AE18 AE18B02 BA02 BA02 BA02 BA01 BA02 BA10 BA02 BA10 BA07 BA02 BA10 BA07 BA02 BA02 BA10 BA02 BA07 BA02 BA02 BA10 BA08 JE152 JE162 JE182 JE192 KE17 KJ08

Claims (4)

[Claims] 1. A compound (A) having two or more hydroxyl groups in the molecule, a compound (B) having one or more acid anhydride groups in the molecule, two or more vinyl ether groups in the molecule, and / Or compound having vinyl thioether group (C)
And a curable resin composition. 2. The compound (B) is a compound having one acid anhydride group in the molecule.
The curable resin composition according to. 3. The total number of moles of hydroxyl groups of the compound (A) with respect to the total number of moles of acid anhydride groups of the compound (B) is 4 or less. The curable resin composition according to item 2. 4. A cured product obtained by curing the curable resin composition according to claim 1 at 150 to 200 ° C.
A method for easily disassembling a joined member, characterized in that the members joined by the cured product are disassembled by heating to soften or liquefy.