JPH01139606A - Curable resin and composition thereof - Google Patents

Abstract

PURPOSE:To obtain a curable resin having excellent low-temperature curability, thick coating properties, weather and water resistance and adhesive properties, etc., by polymerizing an acidic resin having a specific amount of carboxyl groups with a specific monomer in the presence of a polymerization initiator. CONSTITUTION:A curable resin obtained by polymerizing (A) an acidic resin having 0.05-1mol carboxyl groups as functional groups in 1kg resin with monomers consisting essentially of (B) an alkoxysiloxane group-containing vinyl monomer and/or (C) a polysiloxane based macromonomer and (D) an oxirane group-containing vinyl monomer in the presence of a polymerization initiator (e.g., azo based or diazo compound). A chelate compound is blended with the above-mentioned resin to provide a low-temperature curable composition. Curing reaction simultaneously proceeds on the surface and in the interior even at a temperature as low as <=120 deg.C in cooperation of silanol groups derived from the monomers (B) and (C) with the oxirane groups derived from the monomer (D) and the chelate compound.

Description

[Detailed description of the invention] The present invention relates to a novel curable resin and a composition thereof.

BACKGROUND OF THE INVENTION Conventional techniques and their problems In order to reduce energy costs, there is a strong desire to develop resin compositions that harden at low temperatures.

Conventionally, two-component resin compositions such as polyol/isocyanate-based and epoxy/polyamine-based resin compositions have been mainly used as low-temperature curable resin compositions. It is necessary to mix the same components immediately beforehand, making the operation complicated. Furthermore, when isocyanates are used, they have the disadvantage of being highly toxic. Furthermore, one-component polymerizable unsaturated resin compositions of active energy curing type using ultraviolet rays, electron beams, etc. are also known, but these have the disadvantage that an irradiation device is indispensable.

On the other hand, as a one-component, non-toxic, low-temperature curing composition that does not require an irradiation device, for example,
Japanese Patent No. 67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxyglopyltrimethoxysilane.

However, in the conventional compositions described above, only the silanol groups produced by hydrolysis of the alkoxysilane are crosslinking functional groups, and a large amount of water is required for curing, and a large amount of by-products such as alcohol are produced during this hydrolysis. Please note that the physical properties of the cured product may not be sufficient, and that when curing only with moisture in the air, it hardens from the surface, making it difficult to harden the inside and causing stiffness in the cured product. Due to the by-products and the hardening between the surface and the inside,
For example, there are drawbacks such as poor adhesion to base materials such as plastics, metals, and ceramics.

In order to improve the above-mentioned drawbacks, instead of the vinyl copolymer, polyester or epoxy resins, which themselves have excellent adhesive properties to substrates, are used, which cure at low temperatures and also have excellent adhesive properties. It is difficult to obtain a composition that forms a film with ft=.

Means for Solving the Problems The present inventors have conducted extensive research in order to solve the above-mentioned drawbacks of the prior art. As a result, an acidic resin (A) having a specific amount of carboxyl groups and an alkoxysiloxane group-containing vinyl monomer (a) (hereinafter referred to as "monomer (ω)")
) and/or polysiloxane macromonomer (b) (hereinafter, this may be abbreviated as "monomer (b)") and oxirane group-containing vinyl monomer (hereinafter, this may be abbreviated as "monomer (b)") When a film is formed with a composition obtained by blending a chelate compound into a curable resin obtained by polymerizing monomer (C) (sometimes abbreviated as "monomer (C)") in the presence of a polymerization initiator, monomer (a) The silanol groups generated by hydrolysis of the silanol groups and alkoxyl groups derived from the monomer (υ) and the oxirane groups and chelate compounds derived from the monomer (C) combine to form Also, the curing reaction proceeds simultaneously on the surface and inside, and there is little difference in the degree of curing between the surface and inside of the cured product, making it difficult to cause stiffness.Also, the adhesion of the copolymer to the base material due to the monomer component In order to improve the properties, the present inventors discovered that by chemically bonding a copolymer with a resin having different properties, it was possible to impart different properties to the film than in conventional coatings, thereby completing the present invention.

Acidic resin (A) used in the curable resin of the present invention 0.05 to 1 mole of carboxyl group as a functional group per resin, preferably 0.1 to 0.5 mole, more preferably 0.1 to 0
．． It is a resin having 3 moles. As such resin,
Conventionally known materials can be used. In the present invention, polyester, urethane-modified polyester, epoxy-modified polyester, silicone-modified polyester, caprolactone-modified polyester, alkyd resin, epoxy-modified alkyd resin, phenol-modified alkyd resin, silicone-modified alkyd resin, urethane-modified alkyd resin, epoxy ester, etc. Can be mentioned.

The carboxyl group content of the acidic resin (A) is 0.05
If the amount is less than mol, the storage stability of the curable resin solution will deteriorate, and the formed film will become cloudy, resulting in poor finish and durability. On the other hand, if the carboxyl group content is more than 1 mole, it is not preferable because there is a risk of thickening or gelation during the radical polymerization reaction.

The curable resin of the present invention combines the above resin (A), an alkoxysiloxane group-containing vinyl monomer (a) and/or a polysiloxane macromonomer (b), and an oxirane group-containing vinyl monomer (c) in the presence of a polymerization initiator. It can be obtained by polymerization and filtration.

The alkoxysiloxane group-containing vinyl monomer (a) has the following general formula (R1 represents a hydrogen atom or a methyl group, R2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R3 and R4 are the same or different and each represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and R5 represents an alkyl group having 1 to 6 carbon atoms. n is an alkyl group having 1 to 6 carbon atoms. Indicates an integer.] This is a vinyl monomer containing an alkoxine group, which is a compound represented by the following.

In the general formula (RI, R2 represents 1 to 1 carbon atoms)
Examples of the divalent aliphatic saturated hydrocarbon group of 6 include linear or branched alkylene groups, such as methylene, ethylene, propylene, nathodimethylene, ethylethylene, pentamethylene, and hexamethylene groups. R3,
Examples of the alkyl group having 1 to 6 carbon atoms represented by R4 and R5 include straight chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5se-7'thyl, tert -butyl, n-pentyl, inpentyl, neopentyl, n-hexyl, isohexyl groups, and the like. The alkoxy group having 1 to 6 carbon atoms represented by R3 and R4 includes straight chain or branched alkoxy groups such as methoxy, ethoxy,
Examples include n-propoxy, isobutoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexyloxy, and isohexyloxy groups. Further, in the general formula (2), when n is 2 or more, R3 and R4 may be the same or different.

Among the compounds of general formula (1) used as monomers in the present invention, examples of those in which A is 10-0- include r-(meth)acryloxyglobyltrimethoxysilane, r-(meth) ) Acryloxyglobyltriethoxysilane, r-(meth)acryloxypropyltriglopoxysilane, r-(meth)acryloxypropylmethyldimethoxysilane, r-(meth)acryloxypropylmethyldimethoxysilane, r-(meth)acryloxypropylmethyldimethoxysilane, r-(meth)acryloxypropylmethyldimethoxysilane, ) Acryloxypropylmethyldimethoxysilane, r-(meth)acryloxybutylphenyldimethoxysilane, r-(meth)acryloxybutylphenyldimethoxysilane, r-(meth)acryloxybutylphenyldimethoxysilane, r
-(meth)acryloxypropyldimethylmethoxysilane, r-(meth)acryloxypropyldimethylethoxysilane, r-(meth)acryloxypropylphenylmethylmethoxysilane, '-(meth)acryloxypropylphenylmethylethoxysilane, CH2 =C-C
Examples of -0-CH2CH2CH2-51-OCH3 include H3 0C2H50C2H5 0CH3.

The above-mentioned siloxane-based macromonomer has a main skeleton composed of siloxane bonds, and an aliphatic hydrocarbon group, phenyl group, hydroxyl group, alkoxyl group, polymerizable unsaturated bond, etc. are bonded directly or indirectly to St of this main skeleton. % (1) (wherein, R6 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R7, R9, and R9 are % to 4 carbon atoms).
represents an aliphatic hydrocarbon group or a water atom. ) Compound (b) represented by 70 to 99.999 mol % and general formula % formula % (wherein, R1 is a hydrogen atom or a methyl group, RIOI
R11 and R12 represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. However, this excludes the case where all of RIOT R11 and R12 are aliphatic hydrocarbon groups having 1 to 8 carbon atoms. m represents an integer of 1 to 6. ) Compound (b2) 30 to 0.001 mol%
and has an average of one polymerizable unsaturated bond per molecule and at least two hydroxyl groups and/or alkoxyl groups in the portion corresponding to the terminal, and has a number average molecular weight of 400 to 400. In the siloxane macromonomer compound (b) having a molecular weight of 100,000, examples of the alkoxyl group having 1 to 4 carbon atoms include linear or branched ones such as methoxy, ethoxy, propoxy, and butoxy groups. Also, examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include linear or branched ones such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. can be mentioned.

In the above compound (i), R6 is particularly preferably a methyl group or a phenyl group. R7+ Rg and R9 are particularly preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a hydroxyl group. Preferred specific examples of the compound (bl) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltriptoxysilane, phenyltrisilanol, and methyltrisilanol.

Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used. Compound (bl) can be used alone or in combination.

In the above compound (b2), R1 represents a hydrogen atom or a methyl group, RIOI R11 and R12 are a hydroxyl group,
It represents an alkoxyl group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. m represents an integer of 1 to 6. RIO
I R11 and R12 may be all the same or partially or entirely different, but they must not all be aliphatic hydrocarbon groups having 1 to 8 carbon atoms.

As the aliphatic hydrocarbon group having 1 to 8 carbon atoms and the alkoxyl group having 1 to 4 carbon atoms in compound (b2), the same ones as in compound (bl) can be mentioned. RIOI R11 and R12 are particularly preferably a methoxy group, an ethoxy group, or a hydroxyl group, and m is particularly preferably in the range of 2 to 4. Preferred specific examples of compound (b2) include r-methacryloxyglopyltrimethoxysilane, r-methacryloxypropyltriethoxysilane, and r-methacryloxyglopyltrimethoxysilane.
-acryloxyglobyltrimethoxysilane, r-methacryloxybutyltriethoxysilane, r-acryloxypropyltrisilanol, and the like. Among these, r-methacryloxypropyltriethoxysilane,
r-methacryloxypropyltriethoxysilane, r-
Acryloxypropyltrisilanol and the like are particularly preferred. Compound (b2) can be used alone or in appropriate combinations.

In the present invention, the polysiloxane macromonomer is
It is obtained by mixing the above compound (bl) and compound (b2) and reacting them. The mixing ratio of solid compounds is
Based on the total tK of the solidified compound, the compound (bl) is 7
0 to 99.999 mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99 mol%, compound (b2
) is 30 to 0.001 mol%, preferably 10 to 0.1
mol%, more preferably within the range of 5 to 1 mol%.

If the compound (bl) is less than 70 mol%, gelation will easily occur in the copolymerization reaction, while if it is more than 99.999 mol%, the amount of polysiloxane that will not be copolymerized will increase, which is preferable since the resin liquid will become cloudy. do not have.

This reaction is carried out by dehydration condensation of the hydroxyl group of the solid compound or the hydroxyl group produced by hydrolysis of the alkoxyl group.Depending on the reaction conditions, dehydration and condensation may occur. Not only this, but also some dealcoholization condensation occurs.

Although this reaction can be carried out without a solvent, it is preferably carried out using an organic solvent capable of dissolving compound (bl) and compound (b2), or water as a solvent. Such organic solvents are preferably hydrocarbon solvents such as heptane, toluene, xylene, octane, mineral spirit, ethyl acetate, n-butyl acetate, inbutyl acetate,
Ester solvents such as methyl seron lupacetate and butylcarpitol acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone, alcohols such as ethanol, impropatol, n-butanol, (6)-butanol, and imbutanol. Ether solvents such as i-solvent, n-butyl ether, dioxane, ethylene glycol monomethyl ether, and ethylene glycol monoether ether can be used. These solvents can be used alone or in appropriate combinations.

Compound (b2) when used in a solution state (b2)
It is appropriate that the concentration of the total amount is about 5% by weight or more.

In the reaction between compound (bl) and compound (b2) in the present invention, the reaction temperature is usually about 20 to 180°C, preferably about 50 to 120°C. Also,
It is appropriate that the reaction time is usually about 1 to 40 hours.

Moreover, in this reaction, a polymerization inhibitor may be added as necessary. The polymerization inhibitor is effective for preventing the unsaturated bonds contained in the compound (b2) from polymerizing during the reaction with the compound (bl), and specifically, for example,
Hydroquinone, hydroquinone monomethyl ether, etc. can be used.

In addition, in the production of this polysiloxane macromonomer, 5C6 of the above compound (bl) and compound (b2)
There is no problem in adding tetraalkoxysilane, dialkyldialkoxysilane, etc. to the system, and they can be added in an amount of about 20 mol % or less of the solid compound.

In the reaction between compound (b'') and compound (b2), R
7°R8, Re*Rloe When R11 and R12 are all hydroxyl groups, it is preferable to carry out dehydration condensation in an organic solvent under heating and stirring.

In addition, when compound (bl) and/or compound (b2) have an alkoxyl group that binds with st K, 1
It is preferable to carry out hydrolysis prior to bonding, and the hydrolysis reaction and condensation reaction can be carried out continuously by heating and stirring usually in the presence of water and a catalyst. The amount of water used in this case is not particularly limited, but it is preferably about 0.0, t mol or more per 1 mol of alkoxyl group. If the amount decreases by about 0.1 mole, the reaction of the solid compound may decrease.

Most preferred is a method in which water is used as a solvent for large excess III. Further, in this reaction, if water and an organic solvent are used together, the reaction system can be made homogeneous when algol, which is sparingly soluble in water, is produced by condensation. As the organic solvent, those of the alcohol type, ester type, ether type, ketone type, etc. mentioned above can be preferably used. As a catalyst for this hydrolysis reaction, an acid catalyst or an alkali catalyst can be used. Specifically, as an acid catalyst, hydrochloric acid, sulfuric acid,
Phosphoric acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, etc. can be used, and as an alkali catalyst, sodium hydroxide, triethylamine, ammonia, etc. can be used. The amount of catalyst added is determined by the amount of the above compound (bl) and compound (b).
With respect to the total of 2), a range of about 0.0001 to 5%, preferably about 0.01 to 0.13[rj1%] is suitable.

In the present invention, the polysiloxane macromonomer used has a number average molecular weight of about 400 to 100,000, preferably about 1,000 to 20,000. If the number average molecular weight is less than about 400, gelation tends to occur during copolymerization, and if it exceeds about 100,000, compatibility tends to decrease, which is not preferred. 2 In the present invention, the main skeleton of the polysiloxane macromonomer obtained by the reaction of compound (bl) and compound (b2) is constituted by siloxane bonds, and the structure of the main skeleton is long chain (1i near) as species. From the viewpoint of water resistance, heat resistance, light resistance, etc., it is preferable to use a material having a shape, a ladder shape, or a mixture thereof, or a mixture thereof, which has a large number of ladder-like parts. These structures are compound (bl) and compound (b2
), mixing ratio of water and acid catalyst, etc.
Therefore, it can be selected arbitrarily.

Then, the polysiloxane-based macromonomer connects R6+R7 to Si of the general formula (n) to this siloxane bond.
Which of R9 is CH2=C-COO(CH2)frl+ Rto -R
It is a structure in which any of 12 °R1 etc. are bonded, and free functional groups such as hydroxyl group and/or alkoxyl group having 1 to 4 carbon atoms (i.e., silanol group and (primary (2) alkoxysilane groups) per molecule.

Further, the polysiloxane macromonomer preferably has an average of 0.2 to 1.9 polymerizable unsaturated bonds per molecule, more preferably 0.6 to 1.4, It is most preferable to have 0.9 to 1.2 pieces. If there are too few polymerizable unsaturated bonds, the copolymerization reaction product of the macromonomer and vinyl monomer tends to become cloudy,
On the other hand, if there are too many polymerizable unsaturated bonds, there is a risk of gelation in the typical polymerization core, which is not preferable.

The oxirane group-containing vinyl monomer (C), which is the other essential monomer component, preferably has the following general formula [in each general formula, s R1 represents a hydrogen atom or a methyl group]. R13 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R14 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. T represents an integer of 0 to 10. ] etc. can be mentioned.

In the above, the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R13 is a linear or branched full chain group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene,
Examples include hexamethylene group. Also, R1
Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by 4 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, -()-1-
CH2+ CH2- groups and the like can be mentioned.

In particular, it is preferable to use a vinyl monomer containing an alicyclic epoxy group from the viewpoint of curability and the like. That is, when an alicyclic epoxy group-containing vinyl monomer is used, the reactivity of the ring-opening polymerization reaction of the epoxy group is high, so that the effects of rapid curing and further improvement of the physical properties of the cured coating film can be obtained. .

The α,β-ethylenically unsaturated monomer that can be used as an arbitrary monomer component in the above copolymer can be selected from a wide range depending on the desired performance.

Representative examples of certain unsaturated monomers are as follows.

(esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic acid) Ethyl, propyl methacrylate, inglovir methacrylate,
C1-18 alkyl esters of acrylic acid or methacrylic acid such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, diacrylic methacrylate;
Acrylic acid or methacrylic acid with 2 carbon atoms, such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate.
~18 alkoxyalkyl ester; allyl acrylic V
Alkenyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as -, allyl methacrylate; 2 to 8 carbon atoms of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, etc. Hydroxyalkyl ester of acrylic acid or methacrylic acid having 3 to 18 carbon atoms, such as allyloxyethyl acrylate and allyloxymethacrylate.

(m) Vinyl aromatic compounds: for example, styrene, σ
-Methylstyrene, vinyltoluene, p-chlorostyrene.

(Creation Polyolefin compounds: For example, butadiene,
Isoprene, Risoprene.

(IT) Others: Acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate heoba monomer (Shell Chemicals), vinyl gropionate, vinyl bivalate, etc.

The blending ratio of the above monomers (a) and/or (b) and (c) components is determined based on the total amount of monomers from the viewpoint of curability, finishing properties, etc. /or (b)
0.1 to 75% by weight, monomer (c) 1.0 to 75% by weight
and other vehicle weight ranges from 0 to 98.9 itf%.

The blending ratio of monomer (a) and/or (0 is 0.1% by weight)
If the amount is less than 75% by weight, the hardness and adhesion of the coating will decrease, and if the proportion of the monomer is more than 75% by weight, the mechanical properties of the coating will decrease and the stiffness ε will decrease. This results in poor finish.

If the proportion of monomer (c) is less than 1.01% by weight, the curability of the coating will decrease, while if the proportion of monomer (c) is more than 75% by weight, the adhesion and water resistance will be reduced. This results in an inferior coating.

Furthermore, in the presence of the resin (A), the monomers (a) to (c)
Furthermore, examples of the polymerization initiator used when radically polymerizing other monomers include azo compounds, barcarbonate compounds, peroxide compounds, diazo compounds, nitrone compounds, redobux compounds, and ionizing radiation. Any initiator that can be used for radical polymerization can be used.

The method for preparing the zero-spark curable resin is not particularly limited, but for example, monomer (a) is added to resin (A) or its solvent solution.
(d) After blending other monomers (hereinafter, these monomers may be abbreviated as "monomer mixture") and a polymerization initiator as necessary, heating is performed to polymerize. Resin (A)
Alternatively, a part of the monomer mixture and a part of the polymerization initiator are mixed in the solvent solution, and then heated polymerization is carried out (usually for 30 minutes to 3 hours), and then the remaining monomer mixture and polymerization initiation are carried out. The polymerization can be carried out by dropping the resin (A) or its solvent solution, a monomer mixture, and a polymerization initiator into a heated solvent. The temperature of the above heating is usually 70 to 150°C, preferably 90 to 13°C.
Performed at 0°C. In addition, in the curable resin of the present invention, the resin (A) and the monomer (a) and/or the monomer (b), and if necessary, other monomers are polymerized in the presence of a polymerization initiator. The resin obtained by mixing the resin (A) with the monomer (c), or other monomers as necessary in the presence of a polymerization initiator, is also 1 ml. 1
It can be used in various ways. The resin (A) solvent bath solution is an organic solvent that dissolves or fractionates the resin (A) and is inactive in the reaction system.

In addition, if these solvents remain in the dry coating, they may deteriorate the hardness and adversely affect the durability, so preferably aromatic, aliphatic hydrocarbon, or
It is preferable to use an organic solvent such as a ketone type, alcohol type, or ester type.

Further, these organic solvents can be contained in an amount of about 10 to 150 parts by weight per 100 parts by weight of the curable resin.

The blending ratio of the resin (A) and the monomer is 95 to 20% by weight, preferably 80 to 30% by weight in terms of solid content.
Weight%, monomer 5-20% by weight, preferably 20-70%
It is in the range of 5%. If the resin (A) is more than 95% by weight (monomer is less than 5% by weight), the curability decreases, while if the resin (A) is less than 20% by weight (monomer is less than 80% by weight) adhesion to various materials is poor.

Reihattan's curable composition uses at least one of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound as a crosslinking reaction curing agent. Further, among these chelate compounds, a chelate compound containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring is preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diaheptone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β-
Suitable results are obtained using diketones.

The aluminum chelate compound has, for example, the general formula % formula % (
() [In the formula, R1 represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] Preferably prepared by mixing a compound capable of forming the above-mentioned cutoenol tautomer at a molar ratio of usually about 3 moles or less to 1 mole of the aluminum alcoholade represented by the formula, and heating as necessary. Can be done.

Examples of alkyl groups having 1 to 20 carbon atoms include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl groups, etc., in addition to the above alkyl groups having 1 to 6 carbon atoms, and examples of alkenyl groups include: Examples include vinyl and allyl groups.

The aluminum alcoholades represented by the general formula (XX) include aluminum trimethoxide 1, aluminum trimethoxide, aluminum tri-n-propoxide, aluminum triisobutoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum Examples include tri-tert-butoxide, aluminum tri-tert-butoxide, and it is particularly preferable to use aluminum triisopropoxide, aluminum tri-butoxide, aluminum tri-tert-butoxide, and the like.

For example, the titanium chelate compound has the general formula [wherein T
lt, an integer of 0 to 10; R1 represents an alkyl group or alkenyl group having 1 to 20 carbon atoms; ] For 1 mole of Ti in titanates represented by
It can be suitably prepared by mixing compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. Carbon number 1
The alkyl group and alkenyl group of ~20 are the same as above.

Titanates represented by general formula (XXI) include:
When T is 1, tetramethyl titanate, tetraethel titanate, tetra-n-probyl titanate, tetraisoglobyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-n-pentyl titanate, keto 2- n-hexyl titanate,
Examples include tetraisooctyl titanate, tetra-n-lauryl titanate, and the like. Particularly preferable results are obtained when using tetraisobutyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, and the like. In addition, for those where T is 1 or more, tetraisoglobil titanate, tetra-n-
1 liter from 2-ji form of butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate
fi body (general formula (Xll) Kt?ff T = 1 to 10)
gives suitable results.

For example, the zirconium chelate compound has the general formula [wherein,
T is an integer of θ to 10, and R17 represents an alkyl group or alkenyl group having 1 to 20 carbon atoms. ] A compound capable of forming the above-mentioned ke)-enol tautomer is mixed with 1 mol of Zr in the zirconates represented by the formula at a molar ratio of usually about 4 mol or less, and is preferably heated if necessary. It can be prepared as follows. The alkyl group and alkenyl group having 1 to 20 carbon atoms are the same as described above.

Examples of the zirconates represented by the general formula (xXI) include tetraethylzirconate, tetra-n-propylzirconate, tetraisopropylzirconate, tetra-n-butylzirconate, tetra-butylzirconate, and tert-9-tert. -butylzirconate, tetra-n-pentylzirconate, tetra-tert-pentylzirconate, tetra-tert-hexylzirconate, keto 2-n-hebutylzirconate, tetra-n-octylzirconate, tetra- n-stearyl zirconate, in particular, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-butyl zirconate, tetra-n-butyl zirconate, tetra-dai-butyl zirconate, tetra-ter
Suitable results are obtained using t-butyl zirconate and the like. In addition, for those where T is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-butyl zirconate, tetra-tert-butyl Zirconate 2 from the body 11
mer (T=1 to 10 in the general formula (top) IC) gives preferable results. Further, these zirconates may be associated with each other to contain the following structural unit.

Particularly preferred chelate compounds in the present invention include aluminum diisopropylate ethyl acetoacetate, tris(ethyl acetoacetate) aluminum, tris(n-propylacetoacetate) aluminum, tris(isopropylacetoacetate) aluminum, tris( n-butylacetoacetate) aluminum, impropoxybisetheracetoacetate aluminum, diimpropoxyetheracetoacetate aluminum, tris(acetylacetonato)aluminum, tris(ethylacetonato)aluminum, diisoglobilate ethylacetonatoaluminum, monoacetyl Acetonate bis(ethylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(impropylate)aluminum, tris((6)-butyrate)aluminum, diisopropylate mono-butoxyaluminum , aluminum chelate compounds such as tris(acetylacetone)aluminum; diisopropoxy bis(ethelacetoacetate) titanate,
Titanium chelate compounds such as diisopropoxy bis(acetylacetate) titanate and diisopropoxy bis(acetylacetone) titanate; tetrakis(
acetylacetone) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (
Examples include zirconium chelate compounds such as zirconium (acetylacetonate) and zirconium tetrakis(etheracetoacetate).

In the present invention, any one of an aluminum chelate compound, a zirconium chelate compound, and a titanium chelate compound may be used as the crosslinking reaction curing agent, or two or more thereof may be used in combination as appropriate. It is appropriate that the amount of the crosslinking reaction curing agent is about 0.01 to 30 parts by weight based on 100 parts by weight of the total solid content of the curable resin. If it is less than this range, the crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 10 parts by weight.
5 parts by weight.

A tonic, a coloring pigment, a dye, etc. may be added to the composition of the present invention, if necessary. In addition, if necessary, other materials such as -functional or polyfunctional epoxy compounds, low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, and silicone resins having general alkoxysilane groups may be used. Resins can also be added.

The composition of the present invention can be suitably used, for example, in paints, adhesives, inks, and the like.

The method of coating the composition of the present invention is not particularly limited, and for example, it can be coated by general coating methods such as spray coating, roll coating, and brush coating.

The composition of the present invention can be easily crosslinked and cured at a low temperature of 120°C or lower. For example, when cured at room temperature without any heating, it can be sufficiently cured in about 8 hours to 7 days. Furthermore, when heated to about 40 to 120°C, it can be sufficiently cured in about 5 minutes to 3 hours.

It is believed that the curing reaction of the composition proceeds in a chain manner due to volatilization of the chelating agent from the crosslinking curing agent. It is presumed that the progress of the curing reaction by the crosslinking curing agent follows the mechanism shown below. That is, for example, when an organoaluminum chelate compound is used as a crosslinking curing agent, the first reaction is that after the chelating agent has volatilized, the aluminum compound undergoes hydrolysis of the alkoxyl group in the alkoxysiloxane group-containing vinyl monomer. reacts with the silanol groups generated by the reaction or with the silanol groups in the polysiloxane macromonomer, the silanol groups coordinate to the bonds, and the silanol groups become polarized. This polarized silanol group reacts with the epoxy group to form occhinium salt and O!・It becomes. Next, ionic polymerization of the epoxy group and addition reaction to the hydroxyl group occur.

It is presumed that the curing reaction in the composition of the present invention proceeds by various reactions such as a condensation reaction between silanol groups, in addition to the crosslinking reaction caused by the catalytic action of the crosslinking curing agent described above. It is thought that the following various curing reactions occur.

(A) Condensation of silanol groups (B) Condensation of silanol groups with nonacid groups generated from oxirane groups (C) Addition of silanol groups to oxirane groups (D) Addition of hydroxyl groups to oxirane groups (E) Oxirane Ionic polymerization between groups In the composition of the present invention, when the polysiloxane macromonomer contains an alkoxyl group as a functional group (that is, when it contains an alkoxysilane group), K is hydrolyzed to produce a silanol group. However, this hydrolysis reaction proceeds sufficiently in the presence of a small amount of moisture, such as that in the air.

In the composition of the present invention, the vinyl copolymer used contains functional silanol groups such as silanol groups generated by hydrolysis of the alkoxysiloxane group-containing vinyl monomer as a monomer component or silanol groups derived from a polysiloxane macromonomer. and oxirane groups derived from vinyl septamers containing oxirane groups. Therefore, various curing reactions as shown in (A) to (E) above occur concurrently. As a result, curing progresses simultaneously on the surface and inside of the cured product,
The degree of hardening is low on the surface and inside of the cured product, and sagging is less likely to occur.

Furthermore, in the composition of the present invention, a curable resin having excellent compatibility with the copolymer and the resin (A) obtained by combining monomer components in the presence of the resin (A) having a carboxyl group is used. Because it uses , it has excellent storage stability and finishing properties, making it easy to use. Furthermore, even if the resin (A) is a resin that has poor compatibility with conventional copolymers,
It is not particularly limited and can be selected from a wide range of materials depending on the required performance (especially visibility).

The cured product obtained from the composition of the present invention has excellent weather resistance and water resistance, and is suitable for applications such as painting and repair of automobiles and containers, painting of outdoor building materials, and PCM (precoated metal). used.

Effects of the Invention The composition of the present invention has the following excellent characteristics.

(2) It has excellent low temperature curability and can be easily crosslinked and cured at a low temperature of 120'C or less. For example, by curing at 80° C. for 30 minutes, a cured product having a gel fraction of 95% or more can be obtained.

(2) Moisture is not necessary for the curing reaction, or the curing reaction proceeds in the presence of a very small amount of moisture, comparable to the humidity in the air.

(2) Since curing begins with solvent volatilization, storage stability is good even when used as a one-component composition.

■ Do not use highly toxic curing agents such as incyanate.

■ Since various crosslinking reactions such as the bonding reaction of silanol groups and the ionic polymerization reaction of epoxy groups occur simultaneously, there is little difference in hardenability between the surface and the inside, so there is no sagging and excellent thick coating properties. .

(2) Since there are few by-products during curing, a cured product with excellent physical properties can be obtained. In particular, the cured product has excellent weather resistance and water resistance.

(2) Almost no uncured material exists on the surface layer of the cured product, resulting in a hardened product with excellent overcoatability, recoatability, adhesion, etc.

■ Since the resin (A) and the copolymer are chemically bonded together, a curable resin containing two components with different properties is used, so it can be used on substrates for which the copolymer alone does not have sufficient adhesion. It can also exhibit excellent adhesion.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples. In the examples, "part" and "%" each represent a weight basis.

Production Example of Resin (A-1) The following mixture of 125.8 parts of phthalic anhydride, 26.8 parts of trimethylolpropane, and 83.2 parts of neopentyl glycol was charged into a reaction vessel and subjected to a dehydration condensation reaction at 220°C for 8 hours to form an acid. Value 12.0 polyester resin (carboxyl group 0.21 mol/61)
I got it.

Production Example of Resin (A-2) The following mixture H3: 440 parts of Plaxel 205 (Daicel Chemical Industries, trade name) was dissolved in 665.6 parts of butyl acetate. 6 parts were added dropwise over 2 hours, held for an additional 1 hour, then the temperature was raised to 80°C and held for 4 hours, and it was confirmed by infrared spectrum analysis that incyanate groups disappeared.

Next, 7.4 parts of phthalic anhydride was added to the reaction mixture and reacted at 140°C for 1.5 hours to obtain a urethane-modified polyester resin (carboxyl MO, 074 mol/Kf) with an acid value of 4.2.

Production example of resin (A-3) The following mixture Epon 1001 860 parts (Shell Chemical Petroleum, trade name) Adipic acid 195 parts Tetraethylammonium bromide 2 parts were placed in a reaction vessel and dehydrated at 130°C for 8 hours. Acid value 35.5
Epoxy polyester resin (carboxyl group 0.63 mol/auxiliary) was obtained.

Production example of resin (A-4') The following mixture: 155.2 parts of dimethyl terephthalate, 26.8 parts of trimethylolpropane, 83.2 parts of neopentyl glycol, 1 part of dibutyltin oxide was charged into a reaction vessel.
A methanol condensation reaction was carried out at 220° C. for 5 hours to obtain a polyester resin having an acid value of 0.1 or less.

Example 1 100 parts of the resin (A-1) A resin solution containing 100 parts of 2-butoxyshetanol was heated to 110°C, and to this was added 30 parts of the following n-butyl methacrylate and 20 parts of r-acryloxyglobylphenylmethoxysilane. A mixture of 5 parts of azobisisobutyronitrile was added dropwise over 3 hours, and then maintained at the same temperature for 5 hours to achieve a solid content of 6.
A clear resin solution (1) of 7% Gardner foam viscosity (25°C) U was then obtained. The solution (1) remained stable with no increase in viscosity, separation, or cloudiness even after being stored in a hermetically sealed container at 30° C. for 3 months. Using the resin solution, a chelate compound was added in the formulation shown in Table IK to obtain the composition of Example 1.

Example 2 40 parts of the resin (A-2) 40 parts of xylene 40 parts of 2-ethoxyethyl acetate was added to 12 parts of the resin solution.
Heat to 0℃ and add the following styrene to this material.
60 parts CH2=CH-C-0-CH2°
H・-003・1°" A mixture of 3 parts of CH3 tert-butyl perbenzoate was added dropwise over 3 hours, and kept for 1 hour, y!,
2 parts of Ktert-butyl perbenzoate was added and kept at the same temperature for 3 hours until the solid content was 55% and the Gardner foam viscosity (
25° C.) A clear resin solution (2) of W was obtained. The solution (2
) was stable with no thickening, separation, or cloudiness observed even after 3 months of sealed storage at 30°C. Using the resin solution, a chelate compound was added in the formulation shown in Table IK to obtain the composition of Example 2.

Example 3 100 parts of the resin (A-3) 100 parts of butyl acetate was added to 1 part of the resin solution.
Heating to 10°C, this was reacted with 30 parts of n-butyl acrylate shown below, 7 parts of r-methacryloxyglobytrimethoxysila, 15 parts of azobisisovaleronitrile, and 6 parts.
Further, the reaction mixture was added with a mixture of felled wood for 2.5 hours at the same temperature, and kept for 3 hours to form a transparent resin solution (with a solid content of 60% and a Gardner foam viscosity (25°C) Y). 3) was obtained. The solution was stable, with no thickening, separation, or cloudiness observed during closed storage at 30° C. for 3 months. Using the resin solution, a chelate compound was added in the formulation shown in Table 1 to obtain the composition of Example 3.

Example 4 Using the resin solution (J), a chelate compound was added in the formulation shown in Table 1 to obtain the composition of Example 4.

Example 5 Using the resin solution (υ), a chelate compound was added in the formulation shown in Table 1 to obtain the composition of Example 5.

Comparative Example 1 Resin (A-4) was used instead of resin (A-1) in Example 1.
) was prepared using the same formulation and manufacturing method as in Example 1, except that 2 parts of
5° C.) A Tatli solution (4) was obtained.

The solution was slightly cloudy, and the solution separated into two layers and was unstable when stored tightly at 30° C. for 7 days. Using this solution, a chelate compound was added in the formulation shown in Table 1 to obtain a composition of Comparative Example 1.

Comparative Example 2 100 parts of 2-butoxyshetanol was heated to 110°C,
To this product, a mixture of the same substance and initiator as used in Example 1 was prepared in the same manner as in Example 1, and the solid content was 50.
%, Gardner foam viscosity (25°C) L resin solution (5) was obtained. Next, 500 parts of the resin solution (5) and the resin (A-1')
100 parts of the resin was mixed to obtain a resin solution (6) with a solid content of 67%. The solution was self-turbid and separated into two layers during closed storage at 30° C. for 3 days, making it unstable. Using this solution, a chelate compound was added in the formulation shown in Table 1 to obtain a composition of Comparative Example 2.

Same formulation as Example 1 except that styrene was used instead of ! ! Is it prepared using the same method as a resin solution with a solid content of 67%? &(7) was obtained. Using this solution, a chelate compound was added in the formulation shown in Table 1 to obtain a composition of Comparative Example 3.

Comparison Pot 4 Example I except that n-butyl methacrylate was used in place of r-acryloxypropylphenylmethoxysilane.Example 1 and Example 1 were prepared according to the blending and manufacturing method, and the solid content was 67%. 4i'l+fat solution (8)
I got it. Using this solution, a chelate compound was added in the formulation shown in Table 1 to obtain a composition of Comparative Example 4.

Comparative Example 5 Comparative Example 5 was prepared by adding no chelate compound to Example 1.

Comparative Example 6 A composition of Comparative Example 6 was obtained by adding a chelate compound to the resin solution (5) in the formulation shown in Table 1.

Properties of the compositions of Examples and Comparative Examples flF! The test results are shown in Table-2.

Film Performance Test Each of the compositions of Examples and Comparative Examples was coated to a dry film thickness of 100 μm, dried under the drying conditions shown in Table 2, and subjected to testing.

Appearance: Observe the appearance and check for gloss, smoothness, distortion, cracks,
Next, evaluate the presence or absence of stains, etc.

Gel fraction: The dried film was peeled off from the glass plate and extracted with acetate/methane at reflux temperature using a Soxhlet extractor for 6 hours, and the residual content of the film was expressed in %.

Placement property: A test plate was prepared by immersing the plate coated on each material and drying it in hot water of 90° C. or higher for 1 hour, and then immediately cooling it with cold water. 100 percentage squares were made on the coating using a cutter, and the squares were peeled off using cellophane tape, and the number of squares cut without peeling was shown.

Patent Applicant (140) Kansai Paint Co., Ltd. Procedural Amendment (Autopsy January 22, 1988)

Claims (1)

[Claims] 1. 0.0 carboxyl group as a functional group in 1 kg of resin
Acidic resin (A) having 5 to 1 mol, an alkoxysiloxane group-containing vinyl monomer (a) and/or a polysiloxane macromonomer (b), and an oxirane group-containing vinyl monomer (c) as essential components. A curable resin obtained by polymerizing a polymer in the presence of a polymerization initiator. 2. 0.0 carboxyl group as a functional group in 1 kg of resin
Acidic resin (A) having 5 to 2 moles, an alkoxysiloxane group-containing vinyl monomer (a) and/or a polysiloxane macromonomer (b), and an oxirane group-containing vinyl monomer (c) as essential components. A low-temperature curable composition prepared by blending a chelate compound into a curable resin obtained by polymerizing a chelate compound in the presence of a polymerization initiator.