JPH10140019A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in curability, wide in a selection range of a copolymerization monomer, excellent in adhesion to a metal member, by using a resin containing two primary hydroxyl groups per monomer unit. SOLUTION: This composition comprises a resin containing two or more dihydroxy functional groups of the formula (R1 is H, a 1-6C alkyl, a fluorine atom, a 1-6C fluoroalkyl, allyl, an aryl, an aralkyl, etc.; R2 is a 1-6C organic group) on the average in one molecule as an essential component and preferably an amino resin or a blocked polyisocyanate compound as a curing agent. Preferably, the resin in the composition has about 300-200,000 numer-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel curable resin composition.

[0002]

2. Description of the Related Art At present, hydroxyl groups are widely used as cross-linking functional groups of many cross-linking curable resins. In the case of producing a hydroxyl group-containing acrylic resin, as the hydroxyl group-containing monomer, for example, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxyethyl (meth) acrylate, etc. are used. Since only one hydroxyl group is contained in the monomer unit, it is necessary to copolymerize these monomers in a large amount in order to improve the crosslinking reactivity and adhesion of the resin. There were problems that the film performance was lowered and the selection range of other copolymerized monomers was narrowed.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to develop a curable resin composition which is excellent in curability, has a wide selection range of copolymerizable monomers, and has good adhesion to metal members. Things.

[0004] The present inventors have conducted intensive research to solve the above-mentioned disadvantages of the prior art. As a result, they have found that, by using a resin containing two primary hydroxyl groups per monomer unit as the curable resin composition, the above-mentioned drawbacks of the prior art are solved and the object is achieved. The present invention has been completed based on such new knowledge.

According to the present invention, the following general formula (I)

[0006]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
Represents an alkyl group, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group, and R ₂ represents an organic group having 1 to 6 carbon atoms). A curable resin composition characterized by containing an acrylic resin containing two or more dihydroxy functional groups on average in one molecule as an essential component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention is a composition containing a resin having a dihydroxy functional group represented by the general formula (I).

In the general formula (I), the "alkyl group having 1 to 6 carbon atoms" as R ₁ may be linear or branched, for example, methyl, ethyl, n-propyl Group, isopropyl group, n-butyl group, isobutyl group,
Examples thereof include a sec-butyl group, a tert-butyl group, and an n-hexyl group. The “fluoroalkyl group having 1 to 6 carbon atoms” is a group in which at least one hydrogen atom of the above alkyl group is substituted with a fluorine atom, and examples thereof include a fluoropropyl group, a fluorobutyl group, and a trifluoropropyl group. . Examples of the “aryl group” include a phenyl group, a toluyl group, a xylyl group, and the like. Examples of the “aralkyl group” include a benzyl group, a phenethyl group and the like. Among R ₁ , a lower alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group is particularly preferable.

In the general formula (I), the “organic group having 1 to 6 carbon atoms” as R ₂ may be linear or branched.

The dihydroxy functional group has an ether linkage,
It is preferable to use one bonded to the side chain or main chain of the resin via a bond containing oxygen such as an ester bond or a urethane bond or a hydrocarbon group containing at least one of these bonds.

The dihydroxy function in the resin of the present invention is:
On average about 2 or more, preferably about 2 to 10 per molecule
The amount that falls within the range is preferred. If the number of the dihydroxy functional groups is less than about 2 on average per molecule, the thermosetting property is undesirably reduced.

The resin of the present invention has a number average molecular weight of about 3
00 to 200,000, preferably about 500 to 100,
000 is preferable. Number average molecular weight is about 300
If the number average molecular weight exceeds about 200,000, there is a disadvantage that coating workability is deteriorated, which is not preferable.

The resin of the present invention can be used without any particular limitation as long as it satisfies the above conditions.
Specifically, for example, an acrylic resin, a polyester resin, a fluororesin, an alkyd resin, a polyether resin, and modified resins thereof are included.

Specific examples of the acrylic resin as a typical example of the above resin include, for example, the following general formula (II):

[0016]

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(Wherein, R ₂ represents an organic group having 1 to 6 carbon atoms), and (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (Meth) acrylate, 2-carboxypropyl (meth) acrylate,
A carboxyl group-containing unsaturated monomer such as 5-carboxypentyl (meth) acrylate was reacted at a reaction temperature in the range of 80 ° C. to 120 ° C., where one end of the molecule was a radically polymerizable unsaturated group and the other end. The following general formula (I)

[0018]

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(Wherein, R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
Represents an alkyl group, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group, and R ₂ represents an organic group having 1 to 6 carbon atoms). An unsaturated monomer having a dihydroxy functional group as an essential monomer component, a product obtained by radical polymerization of the dihydroxy functional group-containing unsaturated monomer, or a radical polymerization of the dihydroxy functional group-containing unsaturated monomer and another radical polymerizable unsaturated monomer. Copolymerized ones are included.

The synthesis of the above dihydroxy functional group-containing unsaturated monomers is carried out in bulk or in an organic solvent, using an acid-epoxy reaction catalyst if necessary, and about 5% if necessary.
It can be carried out in the presence of a radical polymerization inhibitor in the range of from 00 to 1,000 ppm.

The other radically polymerizable unsaturated monomers used in the above-mentioned radical (co) polymerization are not particularly restricted but include, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (n-, i- or t-) butyl (meth) acrylate, (meth)
Hexyl acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. (Meth) acrylic acid alkyl or cycloalkyl ester having 1 to 24 carbon atoms; (meth)
C2-C18 alkoxyalkyl esters of (meth) acrylic acid such as methoxybutyl acrylate, methoxyethyl (meth) acrylate, and ethoxybutyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate tri (meth) acrylate, neopentylperichol diacrylate, 1,6-hexanediol di (meth) acrylate Glycerol allyloxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,
Polyhydric alcohols such as 1,1-tris (hydroxymethyl) ethanetri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, and divinylbenzene ( (Meth) acrylic acid ester compounds and the like, and these can be used alone or in combination of two or more.

As a specific example of the polyester resin, the following general formula (II):

[0023]

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(Wherein, R ₂ represents an organic group having 1 to 6 carbon atoms) by subjecting a hydroxyoxetane compound represented by the following formula to a polyester compound having a methoxy group or a methyl ester group at its terminal by an ether exchange reaction or an ester exchange reaction. A terminal dihydroxy polyester in which the terminal is an oxetane group and the oxetane group is finally opened with water is used. As the polyester compound, linear,
Any of branched chains may be used.

The terminal dihydroxy polyester can also be produced by adding the hydroxyoxetane compound represented by the general formula (II) to a polyester compound having a terminal acid group such as a carboxyl group.

When the resin having an average of two or more dihydroxy functional groups in one molecule of the present invention contains a self-crosslinkable functional group (for example, alkoxysilyl group, glycidyl group, N-methylol group, etc.) The three-dimensional crosslinked resin can be obtained by heating the resin as it is or by adding a curing catalyst and optionally heating.

When the resin of the present invention contains a crosslinkable functional group (for example, a hydroxyl group, a carboxyl group, a glycidyl group, an alkoxysilyl group, an N-methylol group), it reacts with the crosslinkable functional group. A three-dimensional crosslinked resin can be obtained by using a curing agent having a susceptible group in combination.

As the curing agent, for example, amino resin,
Examples thereof include a polyisocyanate compound and a blocked polyisocyanate compound, and these can be used alone or in combination of two or more.

Examples of the amino resin include a methylolated amino resin obtained by reacting an aldehyde with an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steloguanamine, spiroguanamine and dicyandiazide. Aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. In addition, those obtained by etherifying the methylolated amino resin with an appropriate alcohol can also be used. Examples of the alcohol used for the etherification include methyl alcohol, ethyl alcohol, and n.
-Propyl alcohol, i-propyl alcohol, n-
Butyl alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.
Aliphatic diisocyanate compounds such as dimer acid diisocyanate and lysine diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-
Alicyclic diisocyanate compounds such as (or -2,6-) diisocyanate and 1,3- (or -1,4-) di (isocyanatomethyl) cyclohexane; xylylene diisocyanate, meta-xylylene diisocyanate, tetramethyl xylylene diisocyanate Isocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 1,4
-Naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate,
Aromatic diisocyanate compounds such as 3,3'-dimethyl-4,4'-biphenylenediisocyanate, bis (4-isocyanatophenyl) sulfone, and isopropylidenebis (4-phenylisocyanate); triphenylmethane 4,4 ', 4 " Triisocyanates, 1,3
Polyisocyanate compounds having three or more isocyanate groups such as 5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-dimethyldiphenylmethane 2,2 ', 5,5'-tetraisocyanate; ethylene Adducts obtained by reacting a polyisocyanate compound in an amount such that an isocyanate group is in excess with respect to a hydroxyl group of a polyol such as glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, trimethylolpropane, or hexanetriol; Hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate,
Burette type adducts such as xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate), and isocyanurate ring type adducts.

The blocked polyisocyanate compound can be an addition reaction product of a stoichiometric amount of each of the above-mentioned polyisocyanate compounds and an isocyanate blocking agent. The isocyanate blocking agent is one that blocks by adding to the polyisocyanate compound, and the blocked polyisocyanate compound formed by the addition is stable at normal temperature and is released by dissociation of the blocking agent when heated to about 100 to 200 ° C. It is desirable that the isocyanate group of the above can be regenerated. Examples of the blocking agent satisfying such requirements include lactam compounds such as ε-caprolactam and γ-butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol. Compound; n
Aliphatic alcohols such as butanol and 2-ethylhexanol; aromatic alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and ether alcohol compounds such as ethylene glycol monobutyl ether.

The curable resin composition of the present invention is preferably used after being dissolved or dispersed in an organic solvent. As the organic solvent, those that do not substantially react with the curable resin composition are used. Specifically, aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; alcohol solvents such as butanol and ethylene glycol monobutyl ether. These can be used alone or in combination of two or more.

The compounding ratio of the organic solvent is not particularly limited, and may be used as needed. Usually, the solid content of the curable resin composition is about 1 to 95% by weight, preferably about 10 to 90% by weight.
A range of weight percent is preferred.

In the present invention, in addition to the above-mentioned components of the curable resin composition, a coloring agent, a filler, an ultraviolet absorber, a fluidity modifier and other additives can be further compounded, if necessary. .

The use of the curable resin composition of the present invention is not particularly limited, and it may be selected from a wide range, for example,
It can be applied to fields such as printing and coloring agents.

[0036]

The curable resin composition of the present invention exhibits excellent effects such as excellent curability, a wide selection range of copolymerizable monomers, and good adhesion to metal members.

[0037]

The present invention will be described more specifically below with reference to examples. “Parts” and “%” are based on weight, respectively.

Production Example 1 3-Ethyl-3-hydroxymethyloxetane 1 was placed in a 500 mL three-necked flask equipped with a stirrer and a condenser.
16 parts, acrylic acid 72 parts and tetraethylammonium bromide 0.2 part were added, and the mixture was stirred at 80 ° C. for about 5 hours to be reacted. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 150
Parts of 1-acryloxy-2,2- (dihydroxymethyl) butane were obtained.

Production Example 2 In a 500 mL three-necked flask equipped with a stirrer and a condenser, 200 parts of 3-octyl-3-hydroxymethyloxetane, 72 parts of acrylic acid and 0.4 part of tetraethylammonium bromide were added. The mixture was stirred for about 5 hours to react. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 250
Part of 1-acryloxy-2,2- (dihydroxymethyl) decane was obtained.

Production Example 3 3-Ethyl-3-hydroxymethyloxetane 1 was placed in a 500 mL three-necked flask equipped with a stirrer and a condenser.
16 parts, 86 parts of methacrylic acid and 0.2 parts of tetraethylammonium bromide were added, and the mixture was stirred and reacted at 80 ° C. for about 5 hours. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 160
Parts of 1-methacryloxy-2,2- (dihydroxymethyl) butane were obtained.

Production Example 4 In a 500 mL three-necked flask equipped with a stirrer and a condenser, 200 parts of 3-octyl-3-hydroxymethyloxetane, 86 parts of methacrylic acid and 0.4 part of tetraethylammonium bromide were added. The mixture was stirred for about 5 hours to react. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 260
Of 1-methacryloxy-2,2- (dihydroxymethyl) decane.

Production Example 5 (for comparison) Hydroxyethyl acrylate 348 parts n-butyl methacrylate 642 parts Acrylic acid 10 parts Azobisdimethylvaleronitrile 40 parts Xylene 700 in a 3 L four-necked flask equipped with a stirrer, a condenser and a dropping funnel. And 100 parts of n-butanol, and the mixture was heated to 100 ° C., and the above mixture was added dropwise from a dropping funnel over 3 hours. After dropping, aging was performed for 1 hour, followed by azobisdimethyl valeronitrile 1
A solution in which 0 parts was dissolved in 200 parts of xylene was added dropwise over 1 hour. After completion of the dropping, aging was performed for 30 minutes to obtain a hydroxyl group-containing acrylic resin solution (a) having a resin solid content of 50%. The number average molecular weight of the obtained resin measured by GPC was 10,000.

Production Example 6 1-acryloxy-2,2- (dihydroxymethyl) butane obtained in Production Example 1 282 parts N-butyl methacrylate 708 parts Acrylic acid 10 parts Azobisdimethylvaleronitrile 40 parts Stirrer, cooler and 700 parts of xylene and 100 parts of n-butanol were added to a 3 L four-necked flask equipped with a dropping funnel, heated to 100 ° C., and the above mixture was dropped from the dropping funnel over 3 hours. After dropping, aging was performed for 1 hour, followed by azobisdimethyl valeronitrile 1
A solution in which 0 parts was dissolved in 200 parts of xylene was added dropwise over 1 hour. After completion of the dropping, aging was performed for 30 minutes to obtain a hydroxyl group-containing acrylic resin solution (b) having a resin solid content of 50%. The number average molecular weight of the obtained resin measured by GPC was 10,000.

Production Example 7 1-acryloxy-2,2- (dihydroxymethyl) decane 408 parts obtained in Production Example 2 n-butyl methacrylate 582 parts Acrylic acid 10 parts Azobisdimethylvaleronitrile 40 parts Stirrer, cooler and 700 parts of xylene and 100 parts of n-butanol were added to a 3 L four-necked flask equipped with a dropping funnel, heated to 100 ° C., and the above mixture was dropped from the dropping funnel over 3 hours. After dropping, aging was performed for 1 hour, followed by azobisdimethyl valeronitrile 1
A solution in which 0 parts was dissolved in 200 parts of xylene was added dropwise over 1 hour. After completion of the dropping, aging was performed for 30 minutes to obtain a hydroxyl group-containing acrylic resin solution (C) having a resin solid content of 50%. The number average molecular weight of the obtained resin measured by GPC was 10,000.

Production Example 8 1-methacryloxy-2,2- (dihydroxymethyl) butane obtained in Production Example 3 306 parts n-butyl methacrylate 684 parts Acrylic acid 10 parts Azobisdimethylvaleronitrile 40 parts Stirrer, cooler and 700 parts of xylene and 100 parts of n-butanol were added to a 3 L four-necked flask equipped with a dropping funnel, heated to 100 ° C., and the above mixture was dropped from the dropping funnel over 3 hours. After dropping, aging was performed for 1 hour, followed by azobisdimethyl valeronitrile 1
A solution in which 0 parts was dissolved in 200 parts of xylene was added dropwise over 1 hour. After completion of the dropping, aging was performed for 30 minutes to obtain a hydroxyl group-containing acrylic resin solution (d) having a resin solid content of 50%. The number average molecular weight of the obtained resin measured by GPC was 10,000.

Production Example 9 1-methacryloxy-2,2- (dihydroxymethyl) decane obtained in Production Example 429 parts n-butyl methacrylate 561 parts acrylic acid 10 parts azobisdimethylvaleronitrile 40 parts stirrer, cooler and 700 parts of xylene and 100 parts of n-butanol were added to a 3 L four-necked flask equipped with a dropping funnel, heated to 100 ° C., and the above mixture was dropped from the dropping funnel over 3 hours. After dropping, aging was performed for 1 hour, followed by azobisdimethyl valeronitrile 1
A solution in which 0 parts was dissolved in 200 parts of xylene was added dropwise over 1 hour. After dropping, aging was performed for 30 minutes to obtain a hydroxyl group-containing acrylic resin solution (e) having a resin solid content of 50%. The number average molecular weight of the obtained resin measured by GPC was 10,000.

Production Example 10 (for comparison) 0.84 mol of neopentyl glycol, 0.16 mol of trimethylolpropane, 0.47 mol of adipic acid and 0.47 mol of tetrahydrophthalic anhydride were placed in a reaction vessel.
The reaction was performed at 200 to 230 ° C for 5 hours. Then 100
C. and the toluene was added.
% Of a hydroxyl group-containing polyester resin solution (F). The number average molecular weight of the obtained resin measured by GPC was about 2.8.
00.

Production Example 11 0.93 mol of neopentyl glycol, 0.07 mol of trimethylolpropane, 0.64 mol of adipic acid and 0.3 mol of tetrahydrophthalic anhydride were placed in a reaction vessel.
After reacting at 00 to 230 ° C for 5 hours, 0.18 mol of tetrahydrophthalic anhydride is added, and the mixture is further reacted at 140 ° C for 2 hours.
Allowed to react for hours. Then, after adding 0.175 mol of 3-hydroxymethyloxetane and reacting at 160 ° C. for 3 hours, the temperature is lowered to 100 ° C., and toluene is added, and a hydroxyl group-containing polyester resin solution having a resin solid content of 70% (g) I got The number average molecular weight of the obtained resin measured by GPC was about 2,800.

Examples 1 to 10 and Comparative Examples 1 to 4 Hydroxyl-containing resins (a) to (g) obtained in Production Examples 5 to 11,
As a curing agent, “Cymel 370” (trade name, manufactured by Mitsui Cytec Co., Ltd., melamine resin, solid content: 88%, abbreviated as “C-370” in Table 1) or “Duranate T”
PA-100 "(manufactured by Asahi Kasei Corporation, trade name, polyisocyanate compound, solid content 100%, in Table 1," TPA10
0 ". ) And, if necessary, a curing catalyst, dibutyltin dilaurate (abbreviated as “DBTDL” in Table 1), in a formulation (solid content) shown in Table 1 and thoroughly diluted to an appropriate spray viscosity. Paint on tin, tin and stainless steel respectively, 140
20 ° C. for 20 minutes (abbreviated as A in Table 1) or 80 ° C.
For 20 minutes (abbreviated as B in Table 1).

The obtained coated plate was subjected to an adhesion test. The results are shown in Table 1.

Adhesion test: JIS K5400
According to 5.2 (1990), 100 pieces of 1 mm x 1 mm Gobang eyes are made on the coating film, an adhesive cellophane tape is adhered to the surface, and the Gobang eyes coating film remaining on the coated surface after being rapidly removed. The number was recorded.

[0052]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Osamu Isozaki 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Kansai Paint Co., Ltd.

Claims (3)

[Claims] 1. A compound represented by the following general formula (I) (Wherein, R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms,
An allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group, and R ₂ represents an organic group having 1 to 6 carbon atoms)
A curable resin composition comprising, as an essential component, a resin containing on average two or more dihydroxy functional groups represented by the following formula: 2. The curable resin composition according to claim 1, further comprising an amino resin as a curing agent. 3. The curable resin composition according to claim 1, further comprising a blocked polyisocyanate compound as a curing agent.