JP2003020333A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component curable resin composition which is excellent in storage stability and thermal curability and can be produced at a reduced cost. SOLUTION: This resin composition contains a compound having at least two hydroxyl groups and a compound having at least two specific vinyl(thio) ether groups provided these functional groups are at least partly blocked by a carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a heat latent curing agent.
Regarding the curable resin composition to be contained, more specifically,
Specific (thio) acetal ester as a permanent curing agent
One-part curing with excellent storage stability and thermosetting properties
The present invention relates to a water-soluble resin composition. [0002] BACKGROUND OF THE INVENTION Hydroxyl compounds and vinyl ethers
Compound or vinyl thioether compound (hereinafter referred to as “vinyl
Abbreviated as "ether ether compound")
The composition is known, for example a coating comprising this composition
Compositions are disclosed (European Patent Application No. 29
6,507A2). The thermosetting composition is comparable
Gives cured products with excellent chemical and physical performance at very low temperatures
However, in the presence of an acid catalyst,
Vinyl ether group or vinyl thioether group (hereinafter, referred to as
The reactivity of "vinyl ether group etc." is extremely high
High, in a composition where these three components coexist,
During the reaction, they react and gel, shorten the pot life, etc.
Cause problems. [0003] As a means for solving this problem, for example, acid
A method for neutralizing the catalyst with volatile amines is described in the patent.
Have been proposed. However, this method requires room temperature
Effective at improving storage stability at nearby temperatures
The storage stability at temperatures between 40 and 50 ° C
Is not always enough, and as a result,
As a result, the composition cannot be used.
Japanese Patent No. 3041897 discloses a proton acid group.
Low molecular weight (monomer)
That the vinyl group portion of the vinyl ether compound
Do not block the active protons of the acid catalyst
Heat latent acid catalysts. But this
Heat latent acid catalyst, the acid functions as a catalyst when heated
It only describes what to do. [0004] Also, Japanese Patent No. 3041945 discloses that
One-pack type with improved storage stability at temperatures over 50 ° C
Are described. The composition
Is a compound having at least two hydroxyl groups in one molecule
And at least two specific vinyl ethers in one molecule
Group-containing compounds and specific sulfonic acid esters
Thermal potential that is active during heat curing and shows storage stability
Contains an acid catalyst. However, this thermal latent acid catalyst does not
Is difficult to produce industrially due to the complicated synthesis of
There is a disadvantage that the cost increases. [0005] DISCLOSURE OF THE INVENTION The present invention has a hydroxyl group.
Compounds and vinyl ether compounds (derivatives)
Thermosetting composition with excellent storage stability and thermosetting properties
To provide a one-part curable resin composition
You. In addition, the number of manufacturing processes can be reduced, and
To provide a one-pack type curable resin composition
You. [0006] Means for Solving the Problems The present inventors have proposed a vinyl ether
Compounds such as acetal esters or thioacetals
Esters (hereinafter abbreviated as "acetal esters, etc.")
Will prevent reaction with the polyol compound during storage.
High storage stability.
That the one-part curable resin composition
Done. [0007] That is, the present invention provides two or more molecules per molecule.
A compound having a hydroxyl group of the formula:
The above-mentioned compound having two or more functional groups represented by (1)
All or some of the functional groups are blocked with carboxylic acid
And a curable resin composition containing the compound
I will provide a. Here, in the general formula (1), “R^FourAlso
Is R^FiveIs a ring not containing X together with the carbon to which they are attached.
May be formed. Is defined as shown in the following equation (2).
When a vinyl ether group or the like is directly
Compounds are also included in the vinyl ether compounds of the present invention.
Means that. The cyclic compound is represented by the following formula (2).
The substituent is not limited to the 6-membered ring described above, but may be a 5-membered ring.
You may have. [0008] Embedded image (R^1-3And X are as defined above. ) The latent thermosetting agent of the present invention is easy to synthesize.
Manufacturing costs can be reduced. Further, the composition of the present invention comprises water
Consists of compounds with acid groups and vinyl ether compounds
Keeping the excellent chemical and physical properties of the cured product
Storage stability and heat curing as prepolymer
It is a one-pack type curable resin composition having excellent properties. Further
In comparison with urethane resin compositions, two or more
Once the above compound having a hydroxyl group is
To form a urethane prepolymer.
Compared to when used as a liquid curable composition,
The present invention which can be used as a main component of a one-part composition
The composition can reduce the manufacturing process and the manufacturing cost
Can be reduced. [0010] BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention
Although described in detail below, the present invention is not limited to this.
Not something. In the present specification, "vinyl ether compound"
Is a compound containing at least one vinyl ether group.
And compound (b) of the present invention. Similarly, "vinylthio
“Ether compound” means one or more vinyl thioether groups.
Containing the compound (b) of the present invention.
No. In addition, "vinyl ether compounds" and "vinylthio
Ether compounds "include vinyl ether groups and vinyl
May contain compounds containing both thioether groups
No. The curable resin composition of the present invention has one molecule
Compound (A) having two or more hydroxyl groups, and one molecule
A compound having two or more functional groups represented by the general formula (1)
All or a part of the functional groups in the compound (b) is a carboxylic acid
And the compound (B) blocked with
Is a curable resin composition. First, the compound (A) will be described. Conversion
Compound (A) is a compound having two or more hydroxyl groups in one molecule.
(Hereinafter abbreviated as “polyol compound”).
The crosslink density is high if there are two or more hydroxyl groups in one molecule.
And the physical properties of the cured product are excellent. Hydroxyl group of polyol compound
The number is optional depending on the application, required physical properties of the cured product, etc.
Can be set to Such multiple molecules have multiple hydroxyl groups in one molecule.
Is not particularly limited as long as it is a compound having a low molecular weight.
Products, high-molecular compounds (including prepolymers)
Can also be used. Also, besides hydroxyl group, amino group,
Use compounds with other substituents such as epoxy groups
Can be. Examples of such polyol compounds include:
For example, ethylene glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
Diethylene glycol, pentanediol, dimethylbut
Tandiol, glycerin, sorbitol, neo pliers
Glycol, 1,2- and 1,3-propylene glycol
Cole, 1,4-butylene glycol, 2,3-butylene
Glycol, 1,8-octanediol, cyclohexyl
Sandimethanol, 1,4-bis-hydroxymethyl-
Cyclohexane, 2-methyl-1,3-propanediol
1,2,6-hexanetriol, 1,2,4-butane
Tantriol, trimethylolethane, trimethylol
Low-molecular-weight functional ports such as lupropane and pentaerythritol
Riols; polyester polyols, polyacrylic polyesters
Riol, polyvinyl alcohol, phenolic resin,
Lioxyalkylene glycol or their poly
All and polyisocyanate compound isocyanate
The molar ratio of the hydroxyl groups to the hydroxyl groups (NCO / OH) is less than 1
Polymer polyols mixed and reacted as described above;
Amine, dipropanolamine; resorcinol, bis
Phenols (for example, bisphenol A, bispheno
F, hydrogenated bisphenol A, hydrogenated bisphenol
F) and the like. [0015] Among these polyol compounds,
Lyserine, 1,6-hexanediol, 1,2- and
1,3-propylene glycol, 1,4-bis-hydro
Xymethyl-cyclohexane, trimethylolpropane
Alternatively, various polymer polyols described above are preferably used.
You can. Glycerin or trimethylolpropane
Low molecular functional polyols or polyester polio
, Polyvinyl alcohol, polyoxyalkylene
Recall or the above-mentioned polymer polyols are more preferable.
It is often used. In particular, polytetramethylene ether
Recall, polypropylene glycol, polyester po
Riol is preferably used. The above-mentioned polymer poly is used as a polyol compound.
When using alls, the amount of the main chain of the polymer polyols
The amount of particles is not particularly limited, and depends on the performance, use, etc. of the composition.
To any molecular weight. Also, the poly
All compounds are used alone or in combination of two or more
Can be used. The mixing ratio in this case is
The ratio can be set arbitrarily according to the physical properties, use, etc.
Can be. Next, the compound (B) will be described. Conversion
Compound (B) is represented by the following general formula (1) in one molecule.
All of the functional groups of the compound (b) having two or more functional groups
A compound whose part or part is blocked with a carboxylic acid
You. Embedded image (R^1-5Is a hydrogen atom or a carbon number of 1 to 18, respectively.
An organic group of R¹Or R^TwoAnd R^FourOr R^FiveAre each other
To form a heterocyclic ring containing X.^Four
Or R^FiveDoes not include X with the carbon to which they are attached.
May be formed. X is an oxygen atom or a sulfur atom
It is. ) Here, the organic group is a cycloalkyl group, an alkoxyl
Group, cycloalkoxy group, aryl group, aryloxy
Group, alkanoyloxy group, aralkyloxy group and
At least one member selected from the group consisting of halogen atoms
Whether substituted or unsubstituted by an atomic group
Good, alkyl group, cycloalkyl group, aryl group,
With a alkylene group, cycloalkylene group or arylene group
is there. The functional group represented by the general formula (1)
Is not particularly limited, for example, methyl vinyl ether
Group, ethyl vinyl ether group, isopropyl vinyl ether
Ter group, n-propyl vinyl ether group, n-butyl
Nyl ether group, isobutyl vinyl ether group, 2-E
Tylhexyl vinyl ether group, cyclohexyl vinyl
Vinyl ether groups such as ether groups and their corresponding
Vinylthioether group; 2,3-dihydrofuranyl group,
3,4-dihydro-2H-pyranyl group, 3,4-dihydric
B-2-methoxy-2H-pyranyl group, 3,4-dihydrido
B-2-ethoxy-2H-pyranyl group, 2,3-dihydrido
Lobenzopyranyl group, 2,3-dihydrobenzofuranyl
Cyclic vinyl ether group bonded at the 2-position such as a group
And the corresponding cyclic vinyl thioether groups
Can be. In the general formula (1), R^1-3Each
And a hydrogen atom or an alkyl group having 1 to 18 carbon atoms is preferable.
K, R^FourOr R^FiveIs a hydrogen atom or carbon number, respectively
1-18 alkyl or alkylene groups are preferred
No. (R¹Or R^TwoAnd R^FourOr R^FiveAre joined to each other
To form a heterocyclic ring containing X,^FourOr
R^FiveRepresents a ring containing no X together with the carbon to which they are attached.
It may be formed. ) In particular, R^1-3Are preferably each a hydrogen atom
K, R^FourOr R^FiveOne of them is a hydrogen atom, the other is
Hydrogen atom or methyl group, ethyl group or its bond
That forms a cyclohexane ring with a growing carbon
It is preferably part of a sun ring. Improved reactivity,
This is because it is easy to obtain the fee. When two or more of the above functional groups are present in one molecule
If it is, the crosslink density is high and the physical properties of the cured product are excellent. See below
High molecular vinyl ether compounds, etc. (including prepolymers)
If used, it depends on the application and required properties of the cured product.
Thus, the number of functional groups can be arbitrarily set. Compound (b) having two or more of the above functional groups
Is not particularly limited and is a low molecular weight (monomer) compound
And high-molecular compounds (including prepolymers)
Can be. Specific examples include the compounds shown below.
You. 1) Ethylene glycol divinyl ether, diethylene
Glycol divinyl ether, triethylene glycol
Divinyl ether, tetraethylene glycol divinyl
Ether, propylene glycol divinyl ether,
Tandiol divinyl ether, butanediol diiso
Propenyl 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-
Bis [p- (2-vinyloxyethoxy) phenyl] pro
Bread, cyclohexanediol divinyl ether, shik
Rohexane dimethanol divinyl ether, acrolei
Low molecular weight polyvalent vinyl such as dimer thicitiencoester
And the oxygen atom of these vinyl ether groups
Vinylthioe in which part or all of
-Tel. 2) The polyvalent vinyl ether described in 1) above
Or vinyl thioether and polyols
Vinyl ether obtained by reacting with an excess such as a ter group
And / or vinyl thioether compounds.
You. Here, polyols are specifically ethanediol
, Propanediol, butanediol, pentanedio
Octanediol or homologues thereof,
Oligomer ethers; glycerin, trimethylol
Tan, trimethylolpropane, hexanetriol,
Pentaerythritol, dipentaerythritol, sol
Bitol, polyvinyl alcohol, bisphenol A,
Resorcinol, hydroquinone or derivatives thereof;
Shydroxyethyl isocyanurate; hydroxyl group
-Containing epoxide; hydroxyl-containing polyether;
Droxyl group-containing polyester; hydroxyl group-containing polyester
And polyols such as acryl. 3) Hydroxyl group-containing monovinyl ether
And / or monovinyl thioether and polyvalent isocyanate
Adducts with anate compounds, such as ethylene glycol
Monovinyl ether, propylene glycol monovinyl
Ether, 1,4-butylene glycol monovinyl A
Ter, methanol dihydropyran, hydroxyethylbi
Nyl ether, hydroxybutyl vinyl ether, 9-
Hydroxynonyl vinyl ether, 4-hydroxycyclyl
Rohexyl vinyl ether, cyclohexane dimethano
Monovinyl ether, triethylene glycol monobi
Nyl ethers and their corresponding vinylthioates
Ter compound, tetramethylene diisocyanate,
Samethylene diisocyanate, 2,2,4-trimethyl
Hexamethylene diisocyanate, 1,12-dodecane
Diisocyanate, cyclohexane-1,3- or
1,4-diisocyanate, isophorone diisocyanate
G, perhydro-2,4'- or -4,4'-dife
Nylmethane 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'-methyldiffee
Nylmethane, naphthalene-1,5-diisocyanate,
Xylylene diisocyanate, tetramethyl xylylene
Diisocyanate, norbornane diisocyanate,
Riphenylmethane-4,4 ', 4 "-triisocyane
Of low molecular weight polyvalent isocyanates
Cyanurate type, buret type, polyol addition type
Lisocyanate, high polyvalent isocyanate compound
(Including prepolymers). here
In the high polyvalent isocyanate compound (prepolymer
Including tolylene diisocyanate, hexamethyl
Range isocyanate, diphenylmethane diisocyanate
, Xylylene diisocyanate, tetramethyloxy
Reylene diisocyanate and polypropylene glycol
, Polytetramethylene ether glycol, polyes
Urethane prepolymer synthesized from terpolyol
And the like. Among these compounds (b),
Low molecular weight polyvalent vinyl ethers and corresponding low
Is polyvalent vinyl thioether of molecular weight a viewpoint of cost reduction?
And hydroxyl group-containing monovinyl ethers and
And / or monovinyl thioether and polyvalent isocyanate
The adduct with the compound is easy to adjust the physical properties,
It is used well. As the vinyl ether compound and the like,
Molecular weight of main chain when using vinyl ether compound
Is not particularly limited, and may be determined according to the performance and use of the composition.
Any desired molecular weight can be used. Also, these vinyls
The ether compound or vinyl thioether compound is
Used alone or in combination of two or more
it can. The mixing ratio in this case depends on what is required for the cured product.
The ratio can be set arbitrarily according to the nature, use and the like. The compound (B) is a vinyl compound of the compound (b).
All or part of the
Compounds. The carboxylic acid used in the present invention is not particularly limited.
No, aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic
Any of rubonic acid, saturated carboxylic acid and unsaturated carboxylic acid
May also be used, and may have a substituent.
In addition, polycarboxylic acids can be used. An example
For example, acetic acid, propionic acid,
Tearic acid, etc .; cyclopentane as alicyclic carboxylic acid
Carboxylic acid, cyclohexanecarboxylic acid, furancarbo
Acid, etc .; benzoic acid and toluyl as aromatic carboxylic acids
Acid, nicotinic acid, etc .; acrylic as unsaturated carboxylic acid
Acid, maleic acid, crotonic acid, etc .; as polycarboxylic acid
Malonic acid, adipic acid, 1,3,5-naphthylene trica
Rubonic acid, phthalic acid, terephthalic acid, trimellitic acid, etc.
Is mentioned. Aromatic carboxylic acids, specifically benzoic
Acid, toluic acid, nitrobenzoic acid, pt-butyl benzoate
Perfic acid, phthalic acid, terephthalic acid, trimellitic acid
Good for lowering the thermal dissociation temperature of cetal esters, etc.
Good. Benzoic acid is inexpensive, and phthalic acid is easy to handle.
Easy and trimellitic acids are particularly preferred because of their good physical properties.
New Vinyl ether compound of compound (B)
The combination of and carboxylic acid is not particularly limited.
They can be combined. Preferred vinyl ether compounds
Combinations of substances and carboxylic acids as described below
Combinations can be mentioned. 1) All low molecular weight polyvalent vinyl ethers and
And low molecular weight polyvalent vinyl thioethers corresponding thereto
At least one selected from the group consisting of benzoic acid, toluic acid,
Nitrobenzoic acid, pt-butylbenzoic acid, phthalic acid,
At least one selected from terephthalic acid and trimellitic acid
Combination with. A particularly preferred combination
And ethylene glycol divinyl ether and benzoic acid,
Phthalic or trimellitic acid, butanediol divinyl
Luether and benzoic acid, phthalic acid or trimellit
Acid, triethylene glycol and benzoic acid, phthalic acid or
Is trimellitic acid, hexanediol divinyl ether
And benzoic acid, phthalic acid or trimellitic acid,
Xandiol divinyl ether and benzoic acid, phthalic acid
Or trimellitic acid, cyclohexane dimethanol dim
Vinyl ether and benzoic acid, phthalic acid or trimellitic
Tonic acid, trimethylolpropane trivinyl ether and ammonium
With benzoic acid, pentaerythritol tetravinyl ether
Combinations of benzoic acid. 2) All of the hydroxyl groups described above
Monovinyl ether and / or monovinylthioe
Selected from adducts of ter and polyvalent isocyanate compounds
Benzoic acid, toluic acid, nitrobenzoic acid
Acid, pt-butylbenzoic acid, phthalic acid, terephthalic acid
Combination with at least one selected from acid and trimellitic acid
And so on. Particularly preferred combinations include hydro
Xylethyl vinyl ether and polyvalent isocyanate described below
An adduct consisting of a compound and benzoic acid, phthalic acid or
Limellitic acid, hydroxybutyl vinyl ether and later
Adducts consisting of polyisocyanate compounds of benzoic acid and benzoic acid
Acid, phthalic acid or trimellitic acid, 9-hydroxyno
Nyl vinyl ether and polyvalent isocyanate compound described below
An adduct consisting of benzoic acid, phthalic acid or trimellit
Acid, 4-hydroxycyclohexyl vinyl ether
And an adduct comprising a polyvalent isocyanate compound described below and
Benzoic acid, phthalic acid or trimellitic acid, cyclohexyl
Sandimetal monovinyl ether and polyvalent isocyanate described later
An adduct consisting of an anate compound and benzoic acid, phthalic acid
Or trimellitic acid, triethylene glycol monobi
Nyl ether and polyvalent isocyanate compound described below
Adduct and benzoic, phthalic or trimellitic acid
Combinations. Where the polyvalent isocyanate
The compound is tolylene diisocyanate, hexamethylene
Diisocyanate, diphenylmethane diisocyanate
G, xylylene diisocyanate, tetramethyl xyl
Range isocyanates or these isocyanates
And polypropylene glycol, polytetramethylene a
From terglycol or polyester polyol
Urethane prepolymers to be synthesized are mentioned. Compounds such as vinyl ether group of compound (b)
The amount blocked by boric acid is 10
0 mol% to 1 to 100 mol%
You. Preferably, 5 to 80 mol%, particularly preferably,
10 to 50 mol%. Within this range, one-pack type
The curable composition is excellent in curability and storage stability. Also sealed
The chain amount depends on the physical properties and use of the cured product, especially the hardness of the composition.
To an arbitrary value according to the balance between chemical stability and storage stability
be able to. Compounds such as vinyl ether groups of compound (b)
The method (conditions) for blocking with boric acid is not particularly limited.
It suffices if the carboxylic acid reacts with a carbonyl ether or the like. Ingredient
Physically, it is easy to mix both at room temperature to about 150 ° C.
Method. The composition of the present invention comprises a compound (A) and a compound
(B). Compound (A) and
The combination of compound (B) is not particularly limited, and any combination
They can be combined. Specifically, glycerin,
Limethylolpropane, polyester polyol, poly
Vinyl alcohol, polyoxyalkylene polyol,
And these polyols and polyisocyanate compounds
Are mixed in a molar ratio such that the NCO / OH is less than 1.
One or more compounds (A) selected from the solubilized polyols
And the above-mentioned vinyl ether compound or the like and a carboxylic acid
Selected from compounds obtained by preferred combinations
One or more compounds (B) can be used in combination.
Wear. Preferred combination of compound (A) and compound (B)
A first aspect of the combination is glycerin and ethylene glycol
Divinyl ether / benzoic acid, phthalic acid or trimelli
Acid reactants, glycerin and butanediol divinyl ether
-Tell / benzoic acid, phthalic acid or trimellitic acid reaction
Substance, glycerin and cyclohexane dimethanol divinyl
Ether / benzoic acid, phthalic acid or trimellitic acid
Preparation, trimethylolpropane and ethylene glycol di
Vinyl ether / benzoic acid, phthalic acid or trimellitic
Tonic reactant, trimethylolpropane and butanediol
Divinyl ether / benzoic acid, phthalic acid or trimelli
Acid reactants, trimethylolpropane and cyclohexa
Dimethanol divinyl ether / benzoic acid, phthalic acid
Or trimellitic acid reactant, polypropylene glycol
And ethylene glycol divinyl ether / benzoic acid,
Phthalic acid or trimellitic acid reactant, polypropylene
Glycol and butanediol divinyl ether / benzoic
Acid, phthalic acid or trimellitic acid reactant, polypropylene
Len glycol and cyclohexane dimethanol divinyl
Ether / benzoic acid, phthalic acid or trimellitic acid
Reaction product, polytetramethylene ether glycol and ethyl
Glycol divinyl ether / benzoic acid, phthalic acid
Or trimellitic acid reactant, polytetramethylene ether
Glycol and butanediol divinyl ether / repose
Perfume, phthalate or trimellitic acid reactant, polyteto
Ramethylene ether glycol and cyclohexanedimeta
Nor divinyl ether / benzoic acid, phthalic acid or
Limellitic acid reactant, polyester polyol and ethyl
Glycol divinyl ether / benzoic acid, phthalic acid
Or trimellitic acid reactant, polyester polyol
Butanediol divinyl ether / benzoic acid, phthalic acid
Or trimellitic acid reactant, polyester polyol
And cyclohexane dimethanol divinyl ether / repose
Perfume, phthalic or trimellitic acid reactants
You. The compound (A) and the compound (B) are preferably
A second aspect of the novel combination is that compound (A)
Serine, trimethylolpropane, polypropylene
Coal, polytetramethylene ether glycol and
One selected from the group consisting of polyester polyols
And benzoic acid, phthalic acid, or
Limellitic acid and the hydroxyl-containing moieties described below
Novinyl ether and / or monovinyl thioate
Reaction product of the compound with the adduct of the polyvalent isocyanate compound
I can do it. Hydroxyl group-containing monovinyl ether and
And / or monovinyl thioether and polyvalent isocyanate
Examples of adducts of ethylene glycol monobi
Nyl ether, propylene glycol monovinyl ether
, Hydroxyethyl vinyl ether, 4-hydroxy
Cyclohexyl vinyl ether, cyclohexanedimeta
Nol monovinyl ether, triethylene glycol
Novinyl ethers and their corresponding vinylthioers
And a tetramethylene diisocyanate;
Xamethylene diisocyanate, cyclohexane diiso
Cyanate, tolylene diisocyanate, diphenylmeth
Of tandiisocyanate and xylylenediisocyanate
Low molecular polyvalent isocyanate compound or tolylene diiso
Cyanate, hexamethylene diisocyanate, xylyl
Diisocyanate, tetramethylxylylenediiso
Cyanate, polypropylene glycol, polytetra
Methylene ether glycol, polyester polyol
Polymer polyisocyanate compound synthesized from
Adducts (including repolymers). Compound (A) in the composition of the present invention
The ratio of the compound (B) to the hydroxyl group of the compound (A) and the compound
(B) all vinyl ether groups, etc.
Ratio (including vinyl ether groups etc.) (OH / vinyl)
Is 0.5 to 2.0. Preferably,
0.8 to 1.5, more preferably 0.9 to 1.2,
Is preferably 1.0. Within this range, curing
Good later physical properties and less residual tack. In addition, the curable resin composition of the present invention
If necessary, other polymers may be used without deteriorating the purpose of the description.
ー, reinforcing agents, antioxidants, antioxidants, pigments (dyes),
Plasticizer, thixotropic agent, ultraviolet absorber, flame retardant, solvent,
Surfactants (including leveling agents), dispersants, dehydrating agents,
Add rust inhibitor, adhesion promoter, antistatic agent, filler, etc.
Can be Other polymers include, for example, thermoplastics
Examples include polymers having an elastomer as a main chain. Heatable
The main chain of plastic elastomers is generally vulcanized (
Bridges, curing) natural polymers known as rubber elastic materials
Is a synthetic polymer. Such an elastomeric polymer
Specific examples of natural rubber, isoprengo
Rubber, butadiene rubber, 1,2-butadiene rubber, styrene
-Butadiene rubber, nitrile rubber, chloroprengo
Rubber, butyl rubber, ethylene-propylene diene rubber (E
Diene rubbers such as PDM), ethylene-propylene rubber
(EPM), ethylene-butyne rubber (EBM), chloro
Sulfonated polyethylene, acrylic rubber, fluoro rubber, etc.
Olefin rubber, epichlorohydrin rubber, polysulfide
Rubber, silicone rubber, urethane rubber and the like.
In addition, thermoplastic elastomer containing resin component (TPE)
And may be, for example, polystyrene, which may be hydrogenated.
Ren-based elastomeric polymer (SBS, SIS, SE
BS), polyolefin-based elastomeric polymer,
Polyvinyl chloride elastomeric polymer, polyurethane
Elastomeric polymer, polyester elastomer
Polymer or polyamide-based elastomeric polymer
-Etc. As the reinforcing agent (filler), for example,
Carbon black, fumed silica, calcined silica, sedimentation
Silica, ground silica, fused silica, diatomaceous earth, oxidation
Iron, zinc oxide, titanium oxide, barium oxide, magne oxide
Cium, calcium carbonate, magnesium carbonate, subcarbonate
Lead, pyroxene clay, kaolin clay, calcined clay and
These surface-treated products are exemplified. As an anti-aging agent
Are, for example, hindered phenols; aliphatic and aromatic
Examples include aromatic hindered amine compounds. acid
As the antioxidant, for example, butylhydroxytoluene
(BHT), butylhydroxyanisole (BHA), etc.
Is mentioned. As the pigment, titanium dioxide, zinc oxide,
Ultramarine, bengara, lithopone, lead, cadmium, iron, koba
Inorganic pigments such as sodium, aluminum, hydrochloride and sulfate;
Azo pigment, phthalocyanine pigment, quinacridone pigment, quina
Cridone quinone pigment, dioxazine pigment, anthrapiri
Midine pigment, ensemthlon pigment, indanthrone face
Pigment, flavanthrone pigment, perylene pigment, perinone face
Pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment,
Anthraquinone pigment, thioindigo pigment, benzimida
Zolone pigment, isoindoline pigment, carbon black, etc.
Organic pigments and the like. Benzo, as a plasticizer
Acid, phthalic acid, trimellitic acid, pyromellitic acid,
Pinic acid, sebacic acid, fumaric acid, maleic acid, itacone
Derivatives such as acid and citric acid, polyester, poly
Ether, epoxy and the like can be mentioned. Examples of the thixotropic agent include Benton and anhydrous ketone.
Examples thereof include an acid, a silicic acid derivative, and a urea derivative. ultraviolet
As the line absorber, 2-hydroxybenzophenone type,
Benzotriazole type, salicylic acid ester type, etc.
It is. Phosphorus such as TCP, chlorinated para
Halogen such as fin and perchlorpentacyclodecane
System, antimony system such as antimony oxide, aluminum hydroxide
And the like. Examples of the solvent include charcoal such as hexane and toluene.
Hydrocarbons; halogenated hydrocarbons such as tetrachloromethane
System; ketone system such as acetone and methyl ethyl ketone;
Ethers such as tyl ether and tetrahydrofuran; vinegar
Esters such as ethyl acid are exemplified. Surfactant
(Leveling agent) as polybutyl acrylate,
Polydimethylsiloxane, modified silicone compound, fluorine
Elementary surfactants and the like. As a dehydrating agent, vinyl
Lusilane or the like can be used. As rust inhibitors,
Phosphate, tannic acid derivative, phosphate ester
, Basic sulfonic acid salts, various rust preventive pigments, etc.
You. As an adhesion promoter, a known silane coupling
Agent, silane compound having alkoxysilyl group, titanium
Coupling agents, zirconium coupling agents, etc.
Can be For example, trimethoxyvinylsilane,
Vinyl triethoxysilane, vinyl tris (2-methoxy
Siethoxy) silane, γ-methacryloxypropyltri
Methoxysilane, 3-glycidoxypropyl trimethoxy
Sisilane and the like. Commonly used as antistatic agent
In addition, quaternary ammonium salts, or polyglycols
Hydrophilic compounds such as ethylene oxide derivatives
You. The content of the reinforcing agent (filler) depends on the compound
(A) and 100 parts by mass of compound (B)
And preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass.
Parts by weight are preferred. If less than 10 parts by mass, depending on the additive
No effect can be expected, and if it exceeds 300 parts by mass, the cured product is hard
Because it becomes too much. The content of other additives depends on the compound
(A) and 100 parts by mass of compound (B)
And preferably 0.1 to 100 parts by mass, more preferably 1 to 100 parts by mass.
It is preferably from 70 to 70 parts by mass. Less than 0.1 parts by mass
Can not expect the effect of the additive,
Is because the physical properties of the cured product decrease. The production method of the composition of the present invention is not particularly limited.
For example, rolls, kneaders, extruders, universal stirrers, etc.
Can be mixed and produced. Specifically, first
Compound (b) and carboxylic acid are mixed at room temperature to about 100 ° C.
The reaction is completed completely and unreacted carboxylic acid disappears
After that, the polyol compound is mixed at about room temperature. In the composition of the present invention, the vinyl ether compound
Products such as acetal esters, vinyl ether groups, etc.
Is blocked, so that during storage,
Reaction with the riol compound is prevented. Therefore, the group
The product has excellent storage stability. On the other hand, under heating,
Tar ester is a vinyl ether compound etc. and carboxylic acid
To cause thermal dissociation to regenerate vinyl ether groups. Again
Vinyl ether group etc. of the generated vinyl ether compound
Is the condition for thermal dissociation of acetal ester,
Immediately reacts and cures. Also, this regenerated carvone
Acid reacts with alcohol and vinyl ether compound
Functions as a suitable catalyst, and the curing reaction proceeds more quickly
You. The use of the composition of the present invention is not particularly limited.
However, for example, as a thermosetting resin, with a hot melt adhesive
Or by including it in a hot melt adhesive
It can be suitably used for adhesives for automobiles, building materials, etc.
You. Further, as a rubber modifier, for example, as a flow inhibitor
Resin or rubber that causes cold flow at room temperature
To prevent extrusion flow and cold flow.
Can be. Excellent storage stability and thermosetting properties
Excellent in weather resistance and chemical stability,
In particular, it can be suitably used for automobiles. That
Depending on the application, organic solvent solution type, organic solvent dispersion type,
Solvent-free liquid type, solvent-free solid type, or powder type
It can be used in any form such as (powder).
Wear. The curable resin composition of the present invention is
And can be used as a
Composition, in particular, an enamel composition
Can be used as [0047] EXAMPLES The present invention will be described specifically with reference to examples.
However, the present invention is not limited to this. <Synthesis of Vinyl Ether Compound A>
100 g of hexyl dimethanol divinyl ether (0.
51 mol, Nippon Carbide Co., Ltd., CHDVE)
41.5 g of benzoic acid (0.34 mol, vinyl ether group
/ Carboxyl group = 3/1), and mixed at 100 ° C.
Allowed to react for hours. <Synthesis of Vinyl Ether Compound B> Cyclohexyldim
Trimethylol instead of tanol divinyl ether
Using propane trivinyl ether, vinyl ether
Synthesized in the same manner as Compound A (vinyl ether group / carbo
Xyl group = 3/1). <Synthesis of vinyl ether compound C> Vinyl ether group /
Vinyl etherification with carboxyl group = 1 / 1.2.
It was synthesized in the same manner as Compound A. Synthesis of ester type triol is commercially available
(Placcel 305: manufactured by Daicel Chemical Industries)
did. The diol compound (PTMG) is commercially available (po
ly-THF650: BASF) was used. <Example 1> 100 mass of triol compound
Part and vinyl ether compound A83 parts by mass (hydroxyl group / vinyl
And mixed with a flask and stirred.
I got something. <Example 2> 100 parts by mass of a triol compound, vinyl alcohol
Compound A 69 parts by mass and cyclohexyldimeta
10 parts by mass of nordivinyl ether (hydroxyl group / vinyl ether
And the composition was stirred and mixed with a flask.
Obtained. <Example 3> 100 parts by mass of a diol compound and vinyl acetate
42 parts by mass of a tellurium compound B (hydroxyl group / vinyl ether group)
1.0) was mixed and stirred in a flask to obtain a composition. Comparative Example 1 100 mass of triol compound
Part and cyclohexyl ditanol divinyl ether 58
Amount (hydroxyl group / vinyl ether group ≒ 1.0) in flask
And mixed to obtain a composition. <Comparative Example 2> 100 parts by mass of a triol compound, cyclohexane
58 parts by mass of xyl dimethanol divinyl ether (hydroxyl
Group / vinyl ether group {1.0) and benzoic acid 25
Parts (vinyl ether group / carboxyl group ≒ 3/1)
The mixture was mixed and stirred in a flask to obtain a composition. <Comparative Example 3> 100 parts by mass of a triol compound and vinyl alcohol
146 parts by mass of a hydroxyl compound / vinyl ether
The base # 1.0) was mixed and stirred in a flask to obtain a composition. <Thermosetting Test> The obtained composition was treated with 14
Heated at 5 ° C. for 15 minutes. Hardened and tack on surface and inside
If there is no, mark "○"
And The results are shown in Table 1. <Storage stability test> Each of the obtained compositions was
After sealing and leaving at 40 ° C for 5 days, keep liquid
The case was indicated by “○”, and the solidified one was indicated by “×”. Table of results
1 is shown. [0054] [Table 1][0055] The latent thermosetting agent of the present invention is easy to synthesize.
Thus, the manufacturing cost can be reduced. Also, two or more in one molecule
The compound having a hydroxyl group is temporarily converted to a urethane prepolymer
Urethane tree used as a one-part curable composition
Compared to fat compositions, etc., the main component of the one-part composition as it is
The composition of the present invention, which can be used as
The manufacturing cost can be reduced. further,
The composition of the present invention comprises a vinyl ether compound and the like.
Chemical and physical properties of cured products composed of
Retains quality and is storage-stable as a prepolymer
One-part curable resin composition having excellent heat resistance and thermosetting properties
It is. That is, according to the present invention, a compound having a hydroxyl group
Compounds and vinyl ether compounds (derivatives)
Thermosetting composition with excellent storage stability and thermosetting properties
A one-part curable resin composition can be provided. Ma
In addition, one liquid that can reduce the number of manufacturing processes and reduce manufacturing costs
A mold-curable resin composition can be provided.

Claims (1)

[Claims] 1. A compound having two or more hydroxyl groups in one molecule.
A functional group represented by the following general formula (1) in one molecule:
All or some of the functional groups of the compound having two or more
A compound blocked with a carboxylic acid;
The curable resin composition characterized by the above. Embedded image (R^1-5Is a hydrogen atom or a group having 1 to 18 carbon atoms, respectively.
An organic group, R¹Or R ^TwoAnd R^FourOr R^FiveAre mutually
R may combine to form a heterocyclic ring containing X.^FourMa
Or R^FiveDoes not include X with the carbon to which they are attached
A ring may be formed. X is an oxygen or sulfur atom
is there. )