JP2609881B2 - Curable resin composition and curing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition and a method for curing the same.

Conventional technology and its problems Conventionally, when heating and curing a resin having an unsaturated group,
It is common practice to add a radical polymerization catalyst or polythiol to cause a radical addition polymerization reaction to crosslink a resin. However, this method has drawbacks that the curability of the curable resin composition is poor in storage stability and that oxygen in the air hinders curing of the resin surface. As an alternative to the above method, a method of reacting a compound having active hydrogen with a polymerizable unsaturated group by the Michael addition in the presence of a basic catalyst to cure the compound has been developed. The storage stability of the cured product is poor, and the basic catalyst remains in the cured product to lower the water resistance of the cured product.

Means for solving the problems The object of the present invention is a curable resin composition without the above-mentioned disadvantages,
That is, the present invention provides a curable resin composition which has excellent storage stability and good curability, and can impart excellent water resistance to a cured product, and a method for curing the resin composition. .

 According to the present invention, (a) a resin having a polymerizable unsaturated group in the molecule, and (b) the following formula (I) in the molecule:(R in the formula₁Is a hydroxyl group, alkoxy group, ester group or
Is a carbon atom having 1 to 8 carbon atoms which may be substituted by a halogen atom.
A hydrogen atom group or a hydrogen atom is shown. -W IsIs shown. Here, Z is a nitrogen atom or a phosphorus atom, and Y is sulfur
Indicates an atom. R₂, R_ThreeAnd R_FourAre the same or different, and
The organic groups of the numbers 1 to 14 are shown. Also these R₂And R_ThreeOr R₂,
R_ThreeAnd R_FourTogether form the nitrogen source to which they are attached.
Form a heterocyclic group with a hydrogen atom, a phosphorus atom or a sulfur atom
You may. ] A tree having an aprotic onium salt-containing group represented by
Curable resin composition containing fat, and the resin composition
A tree characterized by heating an object to 80 ° C or higher to cure it
A method of curing a fat composition is provided.

The curable resin composition of the present invention comprises a resin having a polymerizable unsaturated group in the molecule (hereinafter sometimes referred to as “resin (a)”) and a resin having the above-mentioned specific aprotic onium salt-containing group ( The following (sometimes referred to as "resin (b)") is included.

Here, as the resin having a polymerizable unsaturated group, as long as the resin contains at least one polymerizable unsaturated group in a molecule and does not contain the above-mentioned onium salt-containing group, an acrylic resin, a polyester resin, or a urethane resin may be used. Any known resin such as a resin, a polybutadiene, an alkyd, an epoxy, and a phenol resin may be used, and is not particularly limited. In the present invention, a resin having a primary hydroxyl group is preferable from the viewpoint of curability. The molecular weight of the resin is also not particularly limited, but the peak molecular weight by gel permeation chromatography (GPC) is 250 to 100,000.
Those of about 500 to 20,000 are more preferable. If the molecular weight of the resin exceeds the above range, coating workability tends to decrease, which is not preferable.

Examples of the polymerizable unsaturated group include, for example, acryloyl, methacryloyl, itaconate, maleate, fumarate, crotonate, acrylamide, methacrylamide, cinnamic acid, vinyl, allyl, and drying oil fatty acid. Examples thereof include saturated groups and unsaturated groups in polybutadiene.

At least one polymerizable unsaturated group is required per molecule, and from the viewpoint of curability, 0.1 to 10 per 1 kg of resin solid content.
It is preferably in the range of moles, more preferably in the range of 0.5 to 5 moles. If the amount is less than 0.1 mol, curing of the resin will be insufficient, while if it is more than 10 mol, the mechanical properties of the cured product will tend to be deteriorated.

Introduction of the polymerizable unsaturated group into the resin can be carried out by adopting conventionally known means. For example, (i) addition reaction of carboxyl group with epoxy group, (ii) addition reaction of hydroxyl group with epoxy group, (iii) esterification reaction of hydroxyl group with carboxyl group, (iv) addition reaction of isocyanate group with hydroxyl group (V) a half-esterification reaction between a hydroxyl group and an acid anhydride, (vi) a transesterification reaction between a hydroxyl group and an ester group, and the like. It can be carried out by using those having a group.

As the resin having the onium salt-containing group, as long as it is a resin containing at least one onium salt-containing group in a molecule, an acrylic, polyester, urethane, polybutadiene, alkyd, epoxy, phenol, or phenol Any known resin such as a resin may be used, and is not particularly limited. However, a resin having good compatibility with the resin (a) is preferable. In the present invention, a resin having a primary hydroxyl group is preferable from the viewpoint of curability. The molecular weight of the resin is also not particularly limited, but the peak molecular weight by GPC is preferably about 150 to 100,000, and 200 to
Those having about 20000 are more preferable. If the molecular weight of the resin exceeds the above range, coating workability tends to decrease, which is not preferable.

The aprotic onium salt-containing group is represented by the formula (I)
It is necessary that the carbon atom at the β-position from the nitrogen atom, phosphorus atom or sulfur atom of the onium salt has a secondary hydroxyl group. Such an aprotic onium salt is any of a quaternary ammonium salt, a quaternary phosphonium salt and a tertiary sulfonium salt. Specific examples of the cation in the aprotic onium salt-containing group are shown below.

[In the above formulas, R ₂ , R ₃ and R ₄ are the same or different and each represents an organic group having 1 to 14 carbon atoms. In addition, these R ₂ and R ₃
Alternatively, R ₂ , R ₃ and R ₄ may together form a heterocyclic group with the nitrogen atom, phosphorus atom or sulfur atom to which they are attached. As the organic group having 1 to 14 carbon atoms represented by R ₂ , R ₃ and R ₄ , it is not particularly limited as long as it does not substantially interfere with ionization of ammonium base, phosphonium base or sulfonium base, For example, a hydrocarbon group having 1 to 14 carbon atoms which may contain a hetero atom such as an oxygen atom in the form of a hydroxyl group or an alkoxy group is generally used.

Examples of such a hydrocarbon group include aliphatic, alicyclic or aromatic hydrocarbon groups such as an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group and an aralkyl group. The alkyl group may be linear or branched, and preferably has a carbon number of 8 or less, preferably a lower one. For example, methyl, ethyl, n- or iso-propyl, n- , Iso-, sec- or tert-
Butyl, pentyl, heptyl, octyl groups and the like can be mentioned. The cycloalkyl group or cycloalkylalkyl group preferably has 5 to 8 carbon atoms, and examples thereof include cyclopentyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl. The aryl group includes phenyl, toluyl, xylyl group and the like. A benzyl group is preferred as the aralkyl group.

Preferred examples of the hydrocarbon group containing a heteroatom such as an oxygen atom include a hydroxyalkyl group (especially a hydroxy lower alkyl group), specifically, hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl , Hydroxyoctyl group and the like, alkoxyalkyl group (particularly lower alkoxy lower alkyl group), specifically methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, iso-propoxymethyl, n-butoxymethyl, iso.
Examples thereof include -butoxyethyl and tert-butoxyethyl groups.

 R₂And R_ThreeOr R₂, R_ThreeAnd R_FourTogether, these are
Co-exists with bound nitrogen, phosphorus or sulfur atoms
-W when the heterocyclic group is formed As below
The following can be exemplified.

Further, the hydroxyl group, alkoxy group, ester group or hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a halogen atom represented by R ₁ in the above formula (I) includes an alkyl group, an alkenyl group and a cycloalkyl group. And aliphatic, alicyclic or aromatic hydrocarbon groups such as a group, a cycloalkylalkyl group, an aryl group and an aralkyl group. Among these, an alkyl group and an alkenyl group are preferable, and these groups may be any of a linear group and a branched group, and particularly preferably a lower group such as methyl, ethyl, n- or iso-propyl. , N-, iso-, sec- or ter
t-butyl, pentyl, heptyl, octyl, vinyl,
2-methyl vinyl group etc. are mentioned. Preferred examples of the hydroxyl group-substituted hydrocarbon group include a hydroxyalkyl group (particularly a hydroxy lower alkyl group), specifically, a hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl, hydroxyoctyl group and the like. Preferable examples of the alkoxy group-substituted hydrocarbon group are alkoxyalkyl groups (particularly lower alkoxy lower alkyl groups), specifically methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, iso-propoxymethyl, n-butoxy. Methyl, iso-butoxyethyl, tert-butoxyethyl groups and the like can be mentioned. Preferred examples of the ester group-substituted hydrocarbon group include a lower alkoxycarbonylalkyl group, a lower alkoxycarbonylalkenyl group and the like, specifically, methoxycarbonylmethyl, propoxycarbonylethyl,
Ethoxycarbonylpropyl, methoxycarbonylbutyl, methoxycarbonylethylenyl, ethoxycarbonylethylenyl and the like. Preferable examples of the halogen atom-substituted hydrocarbon group specifically include chloromethyl, bromomethyl, iodomethyl, dichloromethyl, trichloromethyl, chloroethyl, chlorobutyl groups and the like.

The aprotic onium salt-containing group is preferably in the range of 0.01 to 5 mol per kg of resin solids,
More preferably, it is in the range of 2 to 2 mol. If it is less than 0.01 mol, curing tends to be insufficient, which is not preferable. On the other hand, if the amount is more than 5 mol, the water resistance of the cured product obtained by curing may decrease, which is not preferable.

The onium salt can be introduced into the resin according to the method shown in (A) or (B) below.

(A) 2-halogeno-in a water-miscible inert organic solvent
A tertiary amine on a resin having a 1-hydroxyethyl group,
After reacting with phosphine or thioether, the halogen atom is replaced with a hydroxyl group by anion exchange, and then this is reacted with an organic acid.

Taking a case where a tertiary amine is used as a compound to be reacted with the above resin as an example, the reaction formula is as follows.

[In the formula, the base portion of the resin is shown, and X is a halogen atom. R ₂ , R ₃ and R ₄ are the same as above. ] When phosphine is used instead of the tertiary amine,
In the above reaction formula, N may be replaced with P. When a thioether is used instead of the tertiary amine, N may be replaced with S and -R ₄ may be deleted in the above reaction formula.

The reaction between the above resin and tertiary amine, etc. is about 100-150 ° C.
The reaction is completed in about 1 to 20 hours.

In order to replace the halogen atom with a hydroxyl group, a resin to be treated may be passed through an ordinary anion exchange resin such as a bead type anion exchange resin.

Further, the reaction of the resin thus obtained, in which the hydroxyl group is substituted, and the organic acid easily proceed by mixing both at room temperature.

(B) A method in which a tertiary amine, phosphine or thioether and an organic acid are simultaneously reacted with a resin having a 1,2-epoxy group in a water-miscible inert organic solvent.

Taking a case where a tertiary amine is used as a compound to be reacted with the above resin as an example, the reaction formula is as follows.

[Wherein R ₁ , R ₂ , R ₃ , R ₄ and are the same as defined above. When phosphine is used instead of the tertiary amine and thioether is used instead of the tertiary amine, N is replaced with P in the above reaction formula or N is replaced as in the case of the above (A). and replaced with S may be deleted the -R _4.

The reaction of the above resin, tertiary amine, etc. and organic acid is about 40
It is carried out under heating at -80 ° C, and the reaction is completed in about 1 to 20 hours.

Examples of the water-miscible inert organic solvent used in (A) and (B) above include ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethanol, propanol, butanol, etc. It is possible to increase the alcohol solvent and the like.

The organic acid is an organic carboxylic acid that produces an anion in which R ₁ in the above formula (I) is a hydroxyl group, an alkoxy group, an ester group or a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a halogen atom. As long as it is, conventionally known ones can be widely used, specifically, acetic acid, formic acid, trimethylacetic acid,
Examples thereof include acrylic acid, methacrylic acid, lactic acid, hydroxyacetic acid, crotonic acid, chloroacetic acid, maleic acid monomethyl ester, fumaric acid monoethyl ester, and itaconic acid monomethyl ester. Among them, those having a dissociation constant (pKa value) of 1 × 10 ⁻⁵ or more are particularly preferable.

When the resin is an acrylic resin, the onium salt can be introduced into the resin according to the above methods (A) and (B). [In the formula, R ₅ represents a hydrogen atom or a methyl group. R ₁ and W are the same as above. ] It is also possible to polymerize the (meth) acrylic acid ester monomer represented by the above by a conventional method alone or with a comonomer copolymerizable therewith.

Further, the resin (b) in the present invention may have a polymerizable unsaturated group in the molecule, and the amount of the polymerizable unsaturated group may be the solid of the resin (b) from the viewpoint of physical properties of the cured product to be obtained. It is preferably 10 mol or less per 1 kg of the component. The introduction of the polymerizable unsaturated group into the resin (b) can be performed in the same manner as the introduction of the polymerizable unsaturated group into the resin (a).

The blending ratio of the resin (a) and the resin (b) in the present invention is preferably 99.99% by weight or less, and more preferably 99.9% by weight or less, in terms of solid content weight ratio. Further, when the resin (b) has less than 0.1 mol of polymerizable unsaturated group per 1 kg of solid content or does not have polymerizable unsaturated group, the resin (a) has a weight ratio of 99.99 to 50 in terms of solid content.
% By weight, more preferably from 99.9 to 70% by weight, and the resin (b) is preferably from 0.01 to 50% by weight, more preferably from 0.1 to 30% by weight.

To the resin composition of the present invention containing the resin (a) and the resin (b), various kinds of additives such as coloring pigments, extender pigments, rust preventive pigments, dyes, other leveling agents, defoaming agents, anti-sagging agents, etc. You may mix | blend an agent.

The resin composition of the present invention is used in a form of being dissolved or dispersed in an organic solvent, or using a water-miscible solvent as a solvent at the time of preparing the resin, and adding water to the obtained resin liquid, Alternatively, it is used in the form of an aqueous solution or an aqueous dispersion by being mixed in water.

When curing the resin composition of the present invention, for example, a solution or dispersion of the resin composition, spray coating, brush coating, roll coating, dip coating and the like are applied to the object to be coated, and this is applied. 80 ° C or higher, preferably 100 ° C
As described above, the heat treatment may be performed at a temperature of about 120 to 200 ° C., preferably for about 5 minutes or more, and more preferably for about 10 to 30 minutes. Although the curing reaction mechanism in this case is not clear,
Since the disappearance of the unsaturated group is observed in the change of the infrared absorption spectrum, it is considered to be due to the polymerization of the polymerizable unsaturated group or the addition reaction of active hydrogen such as a hydroxyl group to the polymerizable unsaturated group. In addition to the curing reaction, Hoffman decomposition of the onium salt in the resin occurs in addition to the curing reaction, and as a result, excellent water resistance can be imparted to the cured product.

In the present invention, in the present invention, a specific aprotic onium salt contained in the resin acts as a catalyst at the time of crosslinking and curing of the resin, and Hoffman decomposition easily occurs during or after the crosslinking and curing of the resin, The onium salt is no longer contained in the cured product, and as a result, an excellent effect of preventing a decrease in water resistance of the cured product is exhibited. Therefore, the resin composition of the present invention has excellent storage stability and curability. Further, according to the method of the present invention, a cured product having excellent water resistance can be obtained.

The resin composition of the present invention can be suitably used, for example, as a low-temperature curing type paint.

Examples The present invention will be further clarified with reference to the following examples. The terms “parts” and “%” simply mean “parts by weight” and “% by weight”, respectively.

Production example of resin (a) having polymerizable unsaturated group Production example 1 Epicoat # 154 (manufactured by Ciel Chemical Co., Ltd.) 627 parts, ethylene glycol monobutyl ether 883 parts, acrylic acid 252
Part, hydroquinone 1 part and tetraethylammonium bromide 3 parts were charged in a four-necked flask,
The reaction was carried out at 120 ° C. for 6 hours, and the point where the acid value became 3 or less was regarded as the end point. The obtained resin liquid (hereinafter, this resin liquid is referred to as "resin liquid (1-A)") has a nonvolatile content of 49.5%,
The Gardner viscosity (25 ° C.) was K. GPC of this resin
The peak molecular weight was about 900.

Production Example 2 116 parts of 2-hydroxyethyl acrylate, 284 parts of glycidyl methacrylate, 600 parts of n-butyl methacrylate
Parts and a mixture of 30 parts of azobisisobutyronitrile, 13 parts
Polymerization was carried out by adding the mixture into a four-necked flask containing 1000 parts of n-butyl alcohol kept at 0 ° C. for 3 hours. Then cooled to 110 ℃, further 172 parts of methacrylic acid,
1 part of hydroquinone and 2 parts of tetraethylammonium chloride were added and reacted until the acid value became 3 or less. The obtained resin solution (hereinafter, this resin solution is referred to as "resin solution (2
-A) ") had a nonvolatile content of 54.0% and a Gardner viscosity (25 ° C) of Q. The peak molecular weight by GPC of this resin was about 10,000.

Production Example 3 A mixture of 650 parts of itaconic acid and 248 parts of ethylene glycol was dehydrated and condensed at 220 ° C. to synthesize a polyester having a carboxyl group at the terminal, and 754 parts of toluene was further added. The obtained resin solution (hereinafter referred to as “resin solution (3
-A) ") had a nonvolatile content of 50.0% and a Gardner viscosity (25 ° C) of Y. The peak molecular weight by GPC of this resin was about 700.

Production Example of Resin (b) Having Onium Salt-Containing Group Production Example 4 Epicoat # 154 (manufactured by Ciel Chemical) 627 parts, ethylene glycol monobutyl ether 1306 parts, acrylic acid 252
And a mixture of 427 parts of thiodiglycol were charged into a four-necked flask and reacted at 80 ° C. for 3 hours. The obtained resin liquid (hereinafter, this resin liquid is referred to as “resin liquid (1-B)”)
Had a nonvolatile content of 47.8% and a Gardner viscosity (25 ° C.) of P. The peak molecular weight of this resin by GPC is about 100.
It was 0.

Production Example 5 A mixture of 900 parts of Epicoat # 1001 (manufactured by Ciel Chemical Co., Ltd.), 204 parts of pivalic acid, 180 parts of pyridine and 1284 parts of n-butanol was placed in a four-neck flask and reacted at 50 ° C. for 10 hours. The obtained resin liquid (hereinafter, this resin liquid is referred to as “resin liquid (2-B)”) had a nonvolatile content of 48.2% and a Gardner viscosity of 25 ° C. (H). The peak molecular weight by GPC of this resin was about 1200.

Production Example 6 93 parts of epichlorohydrin, dimethylaminoethanol
A mixture of 89 parts and 88% formic acid 50 parts was charged into a four-necked flask and reacted at 70 ° C for 40 minutes. The obtained resin liquid (hereinafter, this resin liquid is referred to as “resin liquid (3-B)”) has a non-volatile content.
It was 95% and the Gardner viscosity (25 ° C) was T. The peak molecular weight of this resin by GPC was about 200.

Example 1 98 parts of resin liquid (1-A) obtained in the above Production Example 1 and Production Example 4
The mixture with 2 parts of the resin liquid (1-B) obtained in step 1 was applied to a mild steel plate and a glass plate so that the wet film thickness was 100 μm, and heated at 120 ° C. for 30 minutes to cure.

Example 2 50 parts of the resin liquid (1-A) obtained in the above Production Example 1 and Production Example 4
A mixture with 50 parts of the resin liquid (1-B) obtained in the above was applied to a mild steel mild steel plate and a glass plate so as to have a wet film thickness of 100 μm, and was heated at 120 ° C. for 30 minutes to be cured.

Example 3 30 parts of the resin liquid (1-A) obtained in Production Example 1 and Production Example 4
The mixture with 70 parts of the resin liquid (1-B) obtained in the above was applied to a mild steel mild steel plate and a glass plate so as to have a wet film thickness of 100 μm, and heated at 120 ° C. for 30 minutes to be cured.

Example 4 98 parts of the resin liquid (2-A) obtained in Production Example 2 and Production Example 5
The mixture with 2 parts of the resin solution (2-B) obtained in the above was applied to a mild steel mild steel plate and a glass plate so as to have a wet film thickness of 100 μm, and was heated at 100 ° C. for 10 minutes to be cured.

Example 5 95 parts of the resin liquid (2-A) obtained in Production Example 2 and Production Example 5
The mixture with 5 parts of the resin solution (2-B) obtained in the above was applied to a mild steel mild steel plate and a glass plate so as to have a wet film thickness of 100 μm, and was heated at 100 ° C. for 10 minutes to be cured.

Example 6 70 parts of the resin liquid (2-A) obtained in Production Example 2 and Production Example 5
The mixture with 30 parts of the resin solution (2-B) obtained in 1. was applied to a mild steel plate and a glass plate so that the wet film thickness was 100 μm, and heated at 100 ° C. for 10 minutes to cure.

Example 7 A mixture of 99.5 parts of the resin solution (3-A) obtained in Production Example 3 and 0.5 part of the resin solution (3-B) obtained in Production Example 6 was applied to a mild steel plate and a glass plate to give a wet film thickness of 100 μm. And heated at 160 ° C. for 2 hours to cure.

Example 8 95 parts of resin liquid (3-A) obtained in Production Example 3 and Production Example 6
The mixture with 5 parts of the resin solution (3-B) obtained in step 3 was applied to a mild steel plate and a glass plate so that the wet film thickness would be 100 μm, and heated at 160 ° C. for 2 hours to cure.

Example 9 90 parts of the resin liquid (3-A) obtained in Production Example 3 and Production Example 6
The mixture with 10 parts of the resin solution (3-B) obtained in 1. was applied to a mild steel plate and a glass plate so that the wet film thickness was 100 μm, and heated at 160 ° C. for 2 hours to cure.

Comparative Example 1 100 parts of the resin solution (1-A) obtained in Production Example 1 was applied to a mild steel plate and a glass plate so that the wet film thickness was 100 µ, and heated at 150 ° C for 30 minutes to cure.

Comparative Example 2 A mixture of 98 parts of the resin solution (1-A) obtained in Production Example 1 and 2 parts of benzoyl peroxide was applied to a mild steel plate and a glass plate so as to have a wet film thickness of 100 μm, and heated at 150 ° C.
It was heated at 30 minutes for curing.

Comparative Example 3 A mixture of 98 parts of the resin solution (2-A) obtained in Production Example 2 and 2 parts of sodium ethylate was applied to a mild steel plate and a glass plate so as to have a wet film thickness of 100 μm.
Heated for a minute to cure.

Comparative Example 4 A mixture of 95 parts of the resin solution (3-A) obtained in Production Example 3 and 5 parts of tetramethylammonium chloride was applied to a mild steel plate and a glass plate so as to have a wet film thickness of 100 µ, and the mixture was heated at 160 ° C. The following tests were performed on the coated plates obtained in Examples 1 to 9 and Comparative Examples 1 to 4 which were heated and cured for 2 hours. That is, an acetone extraction test was performed using a material coated on a glass plate, and a water resistance test was performed using a material coated on a mild steel plate. A storage stability test was conducted on each of the resin solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 above. The results are shown in Table 1 below.

Claims (2)

(57) [Claims] (1) A tree having a polymerizable unsaturated group in a molecule thereof.
The following formula (I) in the fat and (b) molecule:(R in the formula₁Is a hydroxyl group, alkoxy group, ester group or
Is a carbon atom having 1 to 8 carbon atoms which may be substituted by a halogen atom.
A hydrogen atom group or a hydrogen atom is shown. -W IsIs shown. Here, Z is a nitrogen atom or a phosphorus atom, and Y is sulfur
Indicates an atom. R₂, R_ThreeAnd R_FourAre the same or different, and
The organic groups of the numbers 1 to 14 are shown. Also these R₂And R_ThreeOr R₂,
R_ThreeAnd R_FourTogether form the nitrogen source to which they are attached.
Form a heterocyclic group with a hydrogen atom, a phosphorus atom or a sulfur atom
You may. ] A tree having an aprotic onium salt-containing group represented by
A curable resin composition containing a fat. 2. A tree having a polymerizable unsaturated group in its molecule.
The following formula (I) in the fat and (b) molecule:(R in the formula₁Is a hydroxyl group, alkoxy group, ester group or
Is a carbon atom having 1 to 8 carbon atoms which may be substituted by a halogen atom.
A hydrogen atom group or a hydrogen atom is shown. -W IsIs shown. Here, Z is a nitrogen atom or a phosphorus atom, and Y is sulfur
Indicates an atom. R₂, R_ThreeAnd R_FourAre the same or different, and
The organic groups of the numbers 1 to 14 are shown. Also these R₂And R_ThreeOr R₂,
R_ThreeAnd R_FourTogether form the nitrogen source to which they are attached.
Form a heterocyclic group with a hydrogen atom, a phosphorus atom or a sulfur atom
You may. ] A tree having an aprotic onium salt-containing group represented by
Curable resin composition containing fat is heated to 80 ℃ or higher
Of curing a resin composition characterized by curing by curing
Law.