JPH0940743A - Polyester-modified epoxy polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester-modified epoxy polymer having good weatherability, processibility, adhesivity, hardness, and solvent resistance and esp. excellent resistances to staining and chemicals. SOLUTION: This polymer comprises a structural part comprising a carboxylated polyester resin and having a number - average mol.wt. of 1,500-50,000 and an acid value of 2-30mgK0H/g and a structural part comprising a polymer of an epoxidized vinyl monomer, subject to the condition that the former and the latter structural part are bonded to each other in such a way that carboxyl groups of the former structural part and a part of epoxy groups of the latter structural part are reacted with each other in an equivalent ratio of 0.1 or lower to give the modified epoxy polymer with an poxy equivalent of 200-2,000g/mol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel epoxy group-containing polyester modified polymer and a method for producing the same. More specifically, the present invention is a polymer of a vinyl monomer modified with a polyester resin, and is characterized by containing a large number of epoxy groups in the polymer. The epoxy group-containing polyester modified polymer of the present invention is suitably used, for example, in paints, inks, adhesives, molded articles and the like.

[0002]

2. Description of the Related Art Polymers of vinyl monomers are generally excellent in hardness, chemical resistance, stain resistance, and are transparent, as represented by methacrylic acid ester polymers and styrene polymers. It is widely used in paints, inks, adhesives and molded products as a resin with excellent gloss. However, although it has high hardness, it has the drawback of being brittle and poor in workability. On the other hand, polyester resin is generally flexible,
It is widely used in paints, inks, adhesives and molded products as a resin with excellent processability and transparency. However, this product is excellent in workability, but has a drawback that it is inferior in hardness, chemical resistance such as alkali resistance and acid resistance, and stain resistance against various pollutants. As a means for overcoming the drawbacks of both and making the best use of the characteristics of both, a method of blending a polymer of a vinyl monomer and a polyester resin can be considered. However, because the high molecular weight vinyl monomer polymer and the polyester resin have poor compatibility with each other, phase separation occurs, and the desired hardness, chemical resistance and processability cannot be obtained, and at the same time transparency is also not achieved. It has the drawback of being damaged. On the other hand, a high molecular weight linear polyester resin synthesized from a dicarboxylic acid and a diol has excellent mechanical properties such as processability of the resin itself, but the amount of functional groups in the molecule is extremely poor (usually, Since it has a hydroxyl group or a carboxyl group at both ends of the molecule), it has a drawback that it is difficult to participate in the curing reaction when it is used as a thermosetting composition for paints, inks, adhesives, molded products, etc. . In addition, it is difficult to introduce an epoxy group and other functional groups into such a high molecular weight linear polyester resin because the original resin itself has few reaction sites.

[0003]

The object of the present invention is to obtain a composite polymer composed of two different polymer moieties, a polymer of vinyl monomers and a polyester resin.
The object is to solve various problems caused by the poor compatibility. That is, the object of the present invention, the excellent hardness of the polymer of vinyl monomers, chemical resistance, properties in stain resistance,
Another object of the present invention is to provide an epoxy group-containing polyester modified polymer which has good processability of a polyester resin and maintains transparency. According to the present invention, a large amount of epoxy groups can be introduced even in a high molecular weight linear polyester having few functional groups. Therefore, the epoxy group-containing polyester modified polymer of the present invention can be widely applied to paints, inks, adhesives, molded products and the like.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop a polymer having the above-mentioned vinyl monomer polymer and a polymer having desirable properties of polyester resin. The carboxyl group of the carboxyl group-containing polyester resin having a molecular weight and a resin acid value, and a part of the epoxy group of a vinyl monomer having an epoxy group or a polymer of this and another vinyl monomer is an epoxy group. It was found that the epoxy group-containing polyester-modified polymer bonded by reacting at a specific ratio with a large excess amount with respect to the above-mentioned carboxyl group achieves the above object, and completed the present invention. Further, as a method for producing the epoxy group-containing polyester modified polymer, in the presence of a carboxyl group-containing polyester resin having a constant number average molecular weight and a resin acid value and an organic solvent, a large excess with respect to the carboxyl group. The present invention has been completed by finding that a method of polymerizing a vinyl monomer having an epoxy group or another vinyl monomer with a radical polymerization initiator is suitable.

That is, according to the present invention, (a) the number average molecular weight is 1,500 to 50,000 and the resin acid value is 2.
To 30 mgKOH / g of a carboxyl group-containing polyester resin and (b) a vinyl monomer polymer having an epoxy group, and the carboxyl group and a part of the epoxy group And (b) the epoxy group of the polymer of the component is reacted and bonded at a ratio of 0.1 or less of the carboxyl group of the component (a), and the epoxy equivalent is 200 to 2,000 g / mol. An epoxy group-containing polyester-modified polymer characterized by the above is provided. In the present invention, (a) a carboxyl group-containing polyester resin having a number average molecular weight of 1,500 to 50,000 and a resin acid value of 2 to 30 mgKOH / g and an organic solvent, (b) A vinyl-based monomer having an epoxy group is characterized in that the equivalent ratio of the carboxyl group of the component (a) to the epoxy group of the component (b) is 0.1 or less, and is polymerized by a radical polymerization initiator. Epoxy equivalent is 200-2,000
The present invention provides a method for producing a 0 g / mol epoxy group-containing polyester modified polymer. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy group-containing polyester modified polymer of the present invention essentially has (a) a number average molecular weight of 1,
500 to 50,000 and a resin acid value of 2 to 30
It has a constituent part consisting of mgKOH / g of a carboxyl group-containing polyester resin and (b) a constituent part consisting of a polymer of a vinyl monomer having an epoxy group. The carboxyl group-containing polyester resin as the component (a) is characterized by containing a carboxylic acid ester bond in the main chain of the molecule, and is a component that imparts flexibility to the epoxy group-containing polyester modified polymer of the present invention. The number average molecular weight of the carboxyl group-containing polyester resin as the component (a) is 1,
500 to 50,000, preferably 1,500 to
25,000, more preferably 1,500 to 2
It is 0000. When the number average molecular weight is less than 1,500, the mechanical properties of the resulting polymer are poor. When the number average molecular weight exceeds 50,000, the solubility in organic solvents becomes poor.

The resin acid value of the carboxyl group-containing polyester resin as the component (a) is 2 to 30 mgKOH / g.
And preferably 3 to 20 mgKOH / g, more preferably 4 to 15 mgKOH / g. Resin acid value is 2
When the amount is less than mgKOH / g, the amount of the chemical bond between the carboxyl group of the component (a) and the polymer of the vinyl-based monomer of the component (b) becomes poor, phase separation easily occurs, and a stable epoxy group-containing polyester It becomes difficult to obtain a modified polymer. Further, when the resin acid value is 30 mgKOH / g or more, the amount of chemical bonds between the component (a) and the polymer of the component (b) vinyl monomer is extremely large, so that the entire reaction system is It is not preferable because it causes gelation. As the method for producing the component (a), a production method based on a heretofore known technique can be applied. For example, a compound having a carboxyl group, or an ester thereof with an alcohol, a compound having a hydroxyl group, an acid anhydride, a compound having an epoxy group, a compound having a plurality of kinds of the above functional groups in one molecule, etc. It can be obtained by a polycondensation reaction or an addition polymerization reaction using a suitable combination selected from the group as a raw material. The combination of the types of these compounds can be freely selected as long as it is a combination which results in a carboxyl group-containing polyester resin satisfying the conditions of the component (a) as a result of the polycondensation reaction and the addition polymerization reaction.

As the compound having a carboxyl group or an ester thereof with an alcohol, the number of carboxyl groups or carboxylic acid ester groups in one molecule is preferably 1 to 4, and the number of dicarboxylic acid is 2. Acids are more preferred. Examples of the compound having a carboxyl group, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, succinic acid, adipine Acids, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and other aliphatic carboxylic acids having 2 to 22 carbon atoms and esters with these alcohols; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. Aromatic carboxylic acids and ester forms thereof with these alcohols; and alicyclic carboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid and ester forms with these alcohols. here,
The alcohol used is preferably a monohydric alcohol having 1 to 12 carbon atoms, and specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, hexanol, heptanol. ,
Octanol, isooctanol, nonanol, decanol, 2-ethylhexanol, cyclohexanol,
Methyl cyclohexanol, cyclooctanol, etc. are mentioned. The compound having a carboxyl group or an ester thereof with an alcohol may be used alone or in combination of two or more.

The number of hydroxyl groups in one molecule of the compound having a hydroxyl group is preferably 1 to 4, and more preferably 2 diols. Examples of the compound having a hydroxyl group include, for example, n
-Propyl alcohol, n-butyl alcohol, n-octyl alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,
n-octadecyl alcohol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutane Diol, hydrogenated bisphenol A, glycerin, sorbitol, neopentyl glycol, 1,8
-Octanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 1,
2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol,
Polyhydric alcohols such as trishydroxyethyl isocyanurate and dipentaerythritol; Ring-opening adducts of these polyhydric alcohols and lactone compounds such as γ-butyrolactone and ε-caprolactone; The polyhydric alcohols and tolylene diisocyanate , Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and other isocyanate compounds in the presence of an excess of alcohol. The compound having a hydroxyl group may be used alone, or 2
You may combine more than seeds.

The number of epoxy groups in one molecule of the above epoxy compound is preferably 1 to 4, more preferably 1
˜2, and more preferably 1. Specific examples of the epoxy compound include ethylene oxide,
Aliphatic monoepoxide compounds derived from alkenes such as propylene oxide and butylene oxide; Celoxide 2,000, Celoxide 3000 (all are trade names, manufactured by Daicel Chemical Industries, Ltd.), Licarezin E-8
(Trade name, manufactured by Shin Nippon Rika Co., Ltd.) and the like, alicyclic monoepoxide compounds derived from cycloalkene; aromatic monoepoxide compounds having an aromatic ring such as styrene oxide and stilbene oxide; methyl glycidyl ether,
Glycidyl ethers such as ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether, (meth) allyl glycidyl ether, polyalkylene oxide monoglycidyl ether; glycidyl isobutyrate, cardura E-10 (commodity) Name, manufactured by Shell Chemical Co., Ltd.) and the like.
The epoxy compounds may be used alone or in combination of two or more.

Examples of the acid anhydride include succinic acid,
Glutaric acid, adipic acid, azelaic acid, sebacic acid,
Examples thereof include acid anhydrides of polycarboxylic acids such as decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid. The acid anhydride may be used alone or in combination of two or more. The above lactones include β
-Propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone and the like.

Further, the monomer for producing the component (a) may be a compound having a plurality of kinds of functional groups such as a hydroxyl group and a carboxyl group in one molecule. Representative examples of the compound having a plurality of types of functional groups include carboxylic acids such as lactic acid, citric acid, malic acid, hydroxypivalic acid, and 12-hydroxystearic acid.

Further, as a method for obtaining the component (a),
A high molecular weight polyester resin outside the scope of the present invention or a polyester resin having an acid value less than the lower limit of the present invention as a starting material is subjected to modification such as acidolysis, alcoholysis, addition of acid anhydride, etc. It is also possible to use a polyester resin within the range of the component a). Among the above polyesters, the polyester that is preferably used for the epoxy group-containing polyester modified polymer of the present invention is a linear polyester resin containing dicarboxylic acid and diol as constituent unit raw materials. Preferred as the dicarboxylic acid are succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid and other aliphatic dicarboxylic acids having 2 to 22 carbon atoms, phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids. Acid; tetrahydrophthalic acid,
Examples thereof include alicyclic dicarboxylic acids such as hexahydrophthalic acid and methylhexahydrophthalic acid. Further, among the diols, preferred are ethylene glycol,
Carbon such as 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol and pentanediol Examples thereof include aliphatic diols having a number of 2 to 22.

The linear polyester is trifunctional in a slight amount as long as it does not impair the properties of the linear polyester for the purpose of deteriorating the crystallinity and introducing a carboxyl group necessary for the present invention. It does not matter if it contains the constituents derived from the above-mentioned compounds having a carboxyl group, compounds having a hydroxyl group, and the like. Examples of such cases include, for example, linear polyester having a carboxyl group by addition reaction of a linear hydroxyl group-terminated polyester with trimellitic acid, or trimellitic acid or trimethylol in the molecular skeleton in order to reduce crystallinity. 3 such as propane
An example is one in which a compound having a functional structure is slightly introduced.

The epoxy group-containing vinyl polymer, which is another component of the epoxy group-containing polyester modified polymer of the present invention, is a polymer of vinyl monomer (b) having an epoxy group. The number of epoxy groups in one molecule of the (b) component vinyl monomer having an epoxy group is preferably 1 to 4, and more preferably 1 to 2.
The number is one, and more preferably one. Specific examples of the component (b) include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth).
Acrylate, glycidyl (meth) allyl ether,
Examples thereof include vinyl monomers having an epoxy group such as 3,4-epoxycyclohexylmethyl (meth) allyl ether. Of these, glycidyl (meth) acrylate, which is a (meth) acrylic acid ester compound, having higher radical polymerization and higher reactivity between epoxy groups / carboxyl groups, 3,
4-Epoxycyclohexylmethyl (meth) acrylate is mentioned as a more preferable component (b).

The above-mentioned vinyl polymer having an epoxy group includes (b) a vinyl monomer having an epoxy group and (c)
A copolymer with another vinyl-based monomer is preferable. The other vinyl-based monomer of the component (c) to be copolymerized with the component (b) is, for example, a (meth) acrylic acid ester, preferably a general formula

[0017]

Embedded image

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated hydrocarbon group of 1 to 20 or an organic group containing a reactive functional group such as a hydroxyl group) Is. Specific examples of the (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate.
Examples thereof include 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Among the other vinyl-based monomers, preferable ones include, for example, itaconic acid, maleic acid, esters of fumaric acid, styrene,
Examples include nuclear-substituted styrenes such as vinyltoluene, dimethylstyrene and ethylstyrene, acrylonitrile, vinyl acetate and vinyl chloride. These may be used alone or in combination. On the other hand, examples of unfavorable vinyl-based monomers to be copolymerized include: (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. Examples thereof include a monomer having a functional group that may react with. The vinyl polymer having an epoxy group is obtained by polymerizing the vinyl monomer of the component (b) or the vinyl monomer of the component (b) and another vinyl monomer of the component (c). Obtainable. The vinyl-based polymer may contain other constituent components as long as the effects of the present invention are not impaired.

In the epoxy group-containing polyester modified polymer of the present invention, the carboxyl group of the component (a) and a part of the epoxy groups of the vinyl polymer having an epoxy group react with each other and are bonded. This can significantly improve the compatibility of the two different polymers. (A)
The ratio of the epoxy groups in the polymer of the vinyl monomer having the carboxyl group of the component and the epoxy group of the component (b) is determined by the polymer of the vinyl monomer having the epoxy group of the component (b). The equivalent ratio of the carboxyl group of the component (a) to the epoxy group is 0.1 or less, preferably 0.08 or less, and more preferably 0.06 or less.

Further, the epoxy equivalent of the resin of the modified polyester containing an epoxy group of the present invention is 200 to 2,
000 g / mol, preferably 250-1,50
0 g / mol, more preferably 275 to 1,0
It is 00 g / mol. Epoxy equivalent is 2,000 g /
When it exceeds mol, when the epoxy group-containing polyester modified polymer of the present invention is used as a thermosetting composition for paints, inks, adhesives, molded articles, etc., the curability is insufficient, and conversely, epoxy is used. When the equivalent weight is less than 200 g / mol, the crosslink density becomes too high and flexibility and the like are impaired.

In the epoxy group-containing polyester modified polymer of the present invention, the component of the component (a), the polymer of the component (b) or the component of the polymer of the component (b) and the component (c). To the weight ratio is 1/99 to 8
The range of 0/20 is preferable, and more preferably 1/99 to
The range is 70/30, and more preferably 1/99 to
It is in the range of 50/50. When the amount of the component comprising the polymer comprising the component (b) or the polymer comprising the components (b) and (c) is larger than 1/99, the epoxy group-containing polyester modified polymer of the present invention May have insufficient flexibility. On the other hand, when the ratio of the constituent part consisting of the polymer consisting of the component (b) or the polymer consisting of the component (b) and the component (c) is smaller than 80/20, the epoxy group-containing polyester modification of the present invention is carried out. The hardness, chemical resistance and stain resistance of the polymer may decrease. (B)
In the case of a polymer in which the component and the component (c) are copolymerized,
The weight ratio of the component (b) to the component (c) depends on the epoxy equivalent of the component (b), but is preferably in the range of 7/93 to 80/20, more preferably 10/90 to 70/30. It is a range, More preferably, it is a range of 15 / 85-60 / 40. Weight ratio of component (b) and component (c) is 7/9
When the amount of component (b) is less than 3, the curability may be insufficient when the epoxy group-containing polyester modified polymer of the present invention is used in a thermosetting composition.
On the other hand, when the amount of the component (b) is more than 80/20, the flexibility of the epoxy group-containing polyester modified polymer of the present invention may be impaired. The epoxy group-containing polyester modified polymer of the present invention may contain other constituent components in addition to the above constituent components, as long as the effects of the present invention are not impaired. The epoxy group-containing polyester modified polymer of the present invention is a solution of an organic solvent having a nonvolatile content of 50 ± 1% at 20 ° C.
The appropriate viscosity is usually 1 to 2,000 poise.

Next, a method for producing the epoxy group-containing polyester modified polymer of the present invention will be described. The epoxy group-containing polyester modified polymer of the present invention has (a) a carboxyl group-containing polyester resin having a number average molecular weight of 1,500 to 50,000 and a resin acid value of 2 to 30 mgKOH / g and an organic solvent. It can be produced by a method in which (b) a vinyl-based monomer having an epoxy group is polymerized with a radical polymerization initiator. In this production method, it is preferable to polymerize (c) another vinyl-based monomer together with (b) a vinyl-based monomer having an epoxy group. The same carboxyl group-containing polyester resin as the component (a) can be used. Also,
As the vinyl monomer having an epoxy group as the component (b) and the other vinyl monomer as the component (c), the same ones as described above can be used. The vinyl-based monomer having an epoxy group as the component (b) is polymerized with another vinyl-based monomer having an epoxy group as the component (b), or another vinyl-based monomer as the component (c). By copolymerizing with (a) and forming a chemical bond with the carboxyl group in the component (a), a polymer of vinyl monomer having an epoxy group of the component (b) and (a)
It acts to form a chemical bond between the constituent polyesters, which can result in a marked improvement in the compatibility of the two different polymers. Further, among the epoxy groups of the component (b), a large amount of epoxy groups are introduced into the epoxy group-containing polyester modified polymer of the present invention by the epoxy groups remaining without reacting with the carboxyl group in the component (a). You can

The amount of the component (b) used is selected so that the equivalent ratio of the carboxyl group of the component (a) to the epoxy group of the component (b) is 0.1 or less, preferably 0.08 or less. And more preferably 0.06 or less. By using a large excess of the component (b) with respect to the carboxyl group of the component (a), the chemical reaction between the vinyl monomer polymer and the component (a) can be efficiently performed simultaneously with the progress of the polymerization reaction. A bond can be created. On the contrary, when the equivalent ratio of the carboxyl group of the component (a) to the epoxy group of the component (b) exceeds 0.1, the chemical bond between the vinyl monomer of the component (b) and the component (a) is It is not preferable because there is a tendency of not being sufficiently obtained and causing phase separation.

The weight ratio of the component (a) to the component (b) or the total weight ratio of the vinyl monomers of the components (b) and (c) is preferably in the range of 1/99 to 80/20. , More preferably 1/99 to 70/30, still more preferably 1/99 to 50/50. When the weight of the vinyl-based monomer of the component (b) or the total weight of the vinyl-based monomers of the components (b) and (c) is larger than 1/99, the epoxy group-containing polyester of the present invention The modified polymer may have insufficient flexibility. On the other hand, when the ratio of the weight of the vinyl-based monomer of the component (b) or the total weight of the vinyl-based monomers of the components (b) and (c) is less than 80/20, the The hardness, chemical resistance, and stain resistance of the epoxy group-containing polyester modified polymer may decrease. The weight ratio of the component (b) and the component (c) is the same as that described above.

The radical polymerization initiator used in the method for producing the epoxy group-containing polyester modified polymer of the present invention includes, for example, 2,2'-azobisisobutyronitrile,
2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, 1-azobis-1-cyclohexanecarbonitrile, dimethyl-
Azo compounds such as 2,2′-azobisisobutyrate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5,5-trimethylhexanone peroxide, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, t-butylhydroperoxide, diisopropylbenzene hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, isobutyl peroxide, lauroyl peroxide, benzoyl peroxide , Diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate and the like. The above may be used in a single type or in a plurality of types. In the present invention, since it is necessary to simultaneously proceed with the polymerization reaction of the vinyl-based monomer mixture containing the component (b) and the reaction between the carboxyl group of the component (a) and the epoxy group of the component (b), It is preferable to select from the radical polymerization initiators mentioned above, an azo compound having a 10-hour half-life temperature of 50 ° C. or higher, or an organic peroxide. Examples of such azo compounds or organic peroxides include:
2,2'-azobisisobutyronitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5,5-trimethylhexanone peroxide,
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, t-butylhydroperoxide, diisopropylbenzene hydroperoxide, dicumyl peroxide, t-butylcumyl Peroxide,
Lauroyl peroxide, benzoyl peroxide, t
-Butylperoxy-2-ethylhexanoate, t-
Butyl peroxy neodecanate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, etc. are mentioned. In these radical polymerization initiator systems, reduction of dimethylaniline, ferrous salts such as ferrous sulfate, ferrous chloride, and ferrous acetate, sodium acid sulfite, sodium thiosulfate, Rongalit, etc. may be carried out as necessary. The agents may be combined, but care must be taken to ensure that the polymerization temperature does not drop too low.

The organic solvent used in the present invention preferably has no functional group that reacts with the carboxyl group of the component (a) or the epoxy group of the component (b). Examples of suitable substances as the organic solvent used in the present invention include alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and aromatic naphtha, acetone and methyl ethyl ketone. , Methyl isobutyl ketone, cyclohexanone,
Ketone solvents such as isophorone, ethyl acetate, n-butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, ester solvents such as bis (2-ethylhexyl) adipate, dibutyl ether, tetrahydrofuran, 1,4-
Examples thereof include ether solvents such as dioxane and 1,3,5-trioxane, and nitrogen-containing solvents such as acetonitrile, valeronitrile, N, N-dimethylformamide and N, N-diethylformamide. The above may be used alone or as a mixed solvent of plural kinds. At this time, the concentration of the non-volatile component of the epoxy group-containing polyester-modified polymer can be arbitrarily selected within a range that does not impair the dispersion stability of the polymer, but usually the non-volatile component concentration is 1
0 to 70%. If necessary, a known reaction catalyst such as a Lewis acid, a tertiary amine, an ammonium salt or a phosphonium salt may also be used for the purpose of promoting the reaction between the carboxyl group of the component (a) and the epoxy group of the component (b). Can be used.

In the production of the epoxy group-containing polyester modified polymer of the present invention, the method of mixing the vinyl monomers containing the components (a) and (b), the method of adding the organic solvent and the radical polymerization initiator are arbitrary. However, for the purpose of controlling the heat of polymerization and the heat of reaction, a component (a) or an organic solvent solution thereof is charged into a reaction tank and stirred, while a vinyl monomer containing the component (b) or an organic solvent solution thereof is added from a dropping tank. Is preferred, or both of the component (a) or the organic solvent solution thereof and the vinyl monomer containing the component (b) or the organic solvent solution thereof are dropped from the dropping tank. The vinyl-based monomer containing the component (b) is
Only the vinyl monomer having an epoxy group as the component (b) may be used, or a mixture of the vinyl monomer having an epoxy group as the component (b) and another vinyl monomer as the component (c) may be used. Good.

The polymerization temperature during the above-mentioned polymerization depends on the type of radical polymerization initiator, the presence / absence of a reducing agent used in combination, and the presence / absence of a reaction catalyst of a carboxyl group and an epoxy group.
It is preferably carried out under the condition of 00 ° C, and 80 ° C to 160 ° C.
It is more preferable to carry out under the conditions of Polymerization temperature is 50 ℃
In the following cases, the carboxyl group of component (a) and (b)
In some cases, the reaction of the epoxy group of the component does not proceed sufficiently, and the vinyl monomer and the polyester resin are likely to undergo phase separation. On the other hand, when the temperature exceeds 200 ° C, unexpected side reactions such as depolymerization may occur. These epoxy group-containing polyester modified polymers produced under the conditions of the present invention have a resin acid value and a molecular weight of the component (a) at the time of polymerization, and a molecular weight of the vinyl monomer polymer containing the component (b). Depending on the content of the vinyl-based monomer including the component (b) and the type of solvent, the solution may be a transparent solution or a milky white dispersion. Of these, the milky white dispersion is considered to be because the polyester portion of the epoxy group-containing polyester modified polymer to be produced and the polymer portion of the vinyl-based monomer are microphase-separated. In the epoxy group-containing polyester modified polymer within the range, the stability of the dispersion is excellent, and there is no problem in the stability during storage and the transparency during film formation.

The epoxy group-containing polyester modified polymer of the present invention thus obtained can be used also as a thermoplastic resin composition, but is thermoset in combination with a curing agent such as an amine, an acid anhydride or a carboxylic acid compound. It can also be used as a sexual composition. Further, the epoxy group-containing polyester modified polymer of the present invention is preferably used in the fields of paints, inks, adhesives, plastic molded products and the like. In the field, if necessary, acrylic resin, polyester resin, alkyd resin, epoxy resin, epoxy ester resin, silicone resin, fluorine resin, polyurethane resin, melamine resin, urea resin, benzoguanamine resin, phenol resin, xylene resin, toluene. Resins, vinyl chloride resins, phenoxy resins, etc. can be arbitrarily selected and mixed in consideration of compatibility, and further, color pigments, fillers, solvents, UV absorbers, antioxidants, flow control agents, etc. are blended. be able to.

[0030]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited to these examples. Production Example 1 Synthesis of polyester resin (solution) Four equipped with a thermometer, Dean Stark (distiller for removing water in condensation reaction during polyester synthesis), reflux condenser, nitrogen introducing pipe, stirrer A neck flask was charged with 367 parts by weight of dimethylphthalic acid, 179 parts by weight of 1,6-hexanediol, 141 parts by weight of ethylene glycol, 314 parts by weight of isophthalic acid, 5 parts by weight of dibutyltin dilaurate, and 50 parts by weight of xylene, and from 170 ° C. 24
While heating to 0 ° C., the mixture was stirred to carry out a condensation polymerization reaction. Then, 757 parts by weight of xylene was added, and as a result, the nonvolatile content was 5
A polyester resin solution having 0%, a resin acid value of 5.3 and a number average molecular weight of 6,600 was obtained. The nonvolatile content measurement conditions are
It is 3 hours at 50 ° C. and 0.1 mmHg.

Production Example 2 Synthesis of polyester resin (solution) Thermometer, Dean Stark, reflux condenser, nitrogen introducing pipe,
Isophthalic acid 463 was added to a four-necked flask equipped with a stirrer.
Parts by weight, 590 parts by weight of 1,5-pentanediol were charged, and the mixture was heated and stirred from 170 ° C. to 240 ° C. with stirring to carry out a condensation polymerization reaction so that the acid value became 5 or less.
Next, 447 parts by weight of phthalic anhydride was charged, and the temperature was raised and stirred while reducing the pressure from 140 ° C. to 240 ° C. to carry out an addition reaction and a condensation polymerization reaction. Then, 350 parts by weight of xylene was added, and as a result, a solution of a polyester resin having a nonvolatile content of 80%, a resin acid value of 12.6 and a number average molecular weight of 5,600 was obtained. The nonvolatile content measurement conditions are 50 ° C., 0.1 mmHg and 3
Time.

Production Example 3 Synthesis of polyester resin (solution) Thermometer, Dean Stark, reflux condenser, nitrogen inlet pipe,
A four-necked flask equipped with a stirrer was charged with 24 parts by weight of isophthalic acid, 14 parts by weight of adipic acid, 33 parts by weight of neopentyl glycol, and 7 parts by weight of xylene, and stirred while heating from 170 ° C to 240 ° C, A condensation polymerization reaction was performed. The acid value of the mixture was measured, and when the acid value became 8 or less, 37 parts by weight of xylene was added.
%, A resin acid value of 12.9 and a number average molecular weight of 2100 were obtained as a polyester resin solution. The nonvolatile content measurement conditions are
It is 3 hours at 50 ° C. and 0.1 mmHg.

Production Example 4 Synthesis of polyester resin (solution) Thermometer, Dean Stark, reflux condenser, nitrogen introducing tube,
A four-necked flask equipped with a stirrer was charged with 24 parts by weight of isophthalic acid, 14 parts by weight of adipic acid, 23 parts by weight of neopentyl glycol, 7 parts by weight of trimethylolpropane, and 5 parts by weight of xylene, and heated from 170 ° C to 240 ° C. Stirring was performed while raising the temperature to carry out a condensation polymerization reaction. The acid value of the mixture was measured, and when the acid value became 8 or less, 37 parts by weight of xylene was added. As a result, the nonvolatile content was 61%, the resin acid value was 12.5,
A solution of a polyester resin having a number average molecular weight of 2300 was obtained. The nonvolatile content measurement conditions are 50 ° C and 0.1 mmH.
3 hours in g.

Production Comparative Example 1 Synthesis of Low Molecular Weight Polyester Resin (Solution) Thermometer, Dean Stark, reflux condenser, nitrogen introducing pipe,
A four-necked flask equipped with a stirrer was charged with 189 parts by weight of 1,6-hexanediol, 149 parts by weight of ethylene glycol, and 663 parts by weight of isophthalic acid, and the mixture was stirred while heating until the resin acid value became 45, and condensed. A polymerization reaction was carried out. Then, 870 parts by weight of cyclohexanone was added, and as a result, the nonvolatile content was 50%, the resin acid value was 45, and the number average molecular weight was 12
A solution of 50 polyester resins was obtained. The nonvolatile content measurement conditions are 50 ° C. and 0.1 mmHg for 3 hours.

Production Comparative Example 2 Synthesis of Low Acid Value Polyester Resin (Solution) 100 parts by weight of the polyester resin (solution) of Production Example 1 was made of KURURA E-10 (trade name of versatic acid glycidyl ester, manufactured by Shell Chemical Co., Ltd.). ) 1.77 parts by weight and 0.1 parts by weight of triethylbenzylammonium chloride were added, and the mixture was stirred at 80 ° C. until the acid value became 0.3 to synthesize a solution of a low acid value polyester resin.

Production Comparative Examples 3 and 4 Synthesis of Epoxy Group-Containing Acrylic Resin (Solution) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 94 parts by weight of an initially charged solvent (cyclohexanone) was prepared. Is charged and heated under stirring to 100 ° C.
Kept. Next, at a temperature of 100 ° C., a mixture of the monomer having the composition shown in Table 1 and the polymerization initiator (dropping component) was added dropwise at a constant rate from a dropping funnel over 2 hours. 100 ° C after dropping
The temperature was maintained for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 1 was added, and the reaction was terminated when the temperature of 100 ° C. was further maintained for 2 hours. A resin solution was obtained.

[0037]

[Table 1]

Note 1) The abbreviations in the table are as follows. GMA: Glycidyl Methacrylate HEMA: 2-Hydroxyethyl Methacrylate BMA: n-Butyl Methacrylate MMA: Methyl Methacrylate EHA: 2-Ethylhexyl Acrylate AIBN: 2,2′-Azobisisobutyronitrile 2) Nonvolatile Content: 50 ° C., 0. Dry for 3 hours at 1 mmHg 3) Epoxy equivalent: After the ring-opening reaction of the epoxy group was carried out with an excess of 0.2N hydrochloric acid dioxane solution, unreacted hydrochloric acid was back-titrated with 0.1N KOH ethanol solution to give a resin per resin. The epoxy equivalent of was calculated. 4) Viscosity: JIS K-5400 (1
990) 4.5.3 Measured by a rotational viscometer method.

Examples 1 to 9 Synthesis of Epoxy Group-Containing Polyester Modified Polymer In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, the initial charge solvent shown in Tables 2 and 3, respectively, Charge polyester resin (or its solution),
The solution was heated under stirring and kept at 120 ° C. Then 12
At a temperature of 0 ° C., a mixture of the monomers having the compositions shown in Tables 2 and 3 (a dropping component) was added dropwise at a constant rate from a dropping funnel over 2 hours. After the dropping, the temperature of 120 ° C. is maintained for 1 hour, then the temperature is lowered to 100 ° C., the polymerization initiator solution (additional catalyst) having the composition shown in Table 2 and Table 3 is added, and the temperature of 100 ° C. is further maintained for 2 hours. When the reaction was terminated while it was kept, epoxy modified polyester-containing polymers having the properties shown in Tables 2 and 3 were obtained. As shown in Tables 2 and 3, it was found that the epoxy group-containing polyester modified polymer of the present invention became a transparent solution or a stable dispersion liquid, and existed stably even when left at 50 ° C. for 1 month. . The cast film obtained by casting these epoxy group-containing polyester modified polymers on a transparent glass plate had good transparency.

[0040]

[Table 2]

[0041]

[Table 3]

Note 1) The abbreviations in the table are as follows. GMA: glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate BMA: n-butyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate BPL: t-butyl peroxylaurate AIBN: 2,2'-azobisisobutyronitrile GK- 150: Toyobo Co., Ltd. polyester resin: resin acid value 6.0, number average molecular weight 12,000, solid at room temperature 2) Property: The appearance of the epoxy group-containing polyester modified polymer is visually observed. 3) Nonvolatile matter: dried at 50 ° C., 0.1 mmHg for 3 hours 4) Epoxy equivalent: After the ring-opening reaction of the epoxy group was carried out with an excess of 0.2N hydrochloric acid dioxane solution, unreacted hydrochloric acid was removed with 0.1N KOH ethanol. -Titrate with epoxy solution to calculate epoxy equivalent per resin. 5) Viscosity: at 20 ° C., JIS K-5400 (1
990) 4.5.3 Measured by a rotational viscometer method. As the viscosity after storage, the viscosity of the sample subjected to the storage stability test was measured. 6) Transparency of cast film: Epoxy group-containing polyester modified polymer is cast on a transparent glass plate and coated at 140 ° C 3
The appearance after the solvent was evaporated under the condition of 0 minutes was visually confirmed. 7) Storage stability: A solution or dispersion of the epoxy group-containing polyester modified polymer was placed in a constant temperature bath at 50 ° C. for 1 month and examined for abnormalities such as resin separation and gelation.

Comparative Examples 1 to 3 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with the initially charged solvent and polyester resin (or a solution thereof) shown in Table 4, respectively, with stirring. The mixture was heated to homogenize and kept at 120 ° C. Next, at a temperature of 120 ° C., a mixture of the monomer having the composition shown in Table 4 and a polymerization initiator (dropping component) was added dropwise at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the temperature of 120 ° C. was maintained for 1 hour, then the temperature was lowered to 100 ° C., the polymerization initiator solution (additional catalyst) having the composition shown in Table 4 was added, and the temperature of 100 ° C. was further maintained for 2 hours. By the way, when the reaction was terminated, in Comparative Example 1 using a polyester having a molecular weight and a resin acid value outside the range of the present invention, gelation of the system occurred during the polymerization.
Further, in Comparative Example 2 in which a polyester having a resin acid value smaller than the range of the present invention is used, or in Comparative Example 3 in which the proportion of the component (b) is smaller than the range of the present invention, an oil droplet resin dispersion liquid is obtained. Separated into two phases at 50 ° C within a short time. The cast film obtained by casting these resin dispersions on a transparent glass plate was completely opaque.

[0044]

[Table 4]

Note 1) The abbreviations in the table are as follows. GMA: glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate BMA: n-butyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate BPL: t-butyl peroxylaurate AIBN: 2,2'-azobisisobutyronitrile GK- 150: Toyobo Co., Ltd. polyester resin: resin acid value 6.0, number average molecular weight 12,000, solid at room temperature 2) Property: The appearance of the epoxy group-containing polyester modified polymer is visually observed. 3) Nonvolatile matter: dried at 50 ° C., 0.1 mmHg for 3 hours 4) Epoxy equivalent: After the ring-opening reaction of the epoxy group was carried out with an excess of 0.2N hydrochloric acid dioxane solution, unreacted hydrochloric acid was removed with 0.1N KOH ethanol. -Titrate with epoxy solution to calculate epoxy equivalent per resin. 5) Viscosity: at 20 ° C., JIS K-5400 (1
990) 4.5.3 Measured by a rotational viscometer method. 6) Transparency of cast film: Epoxy group-containing polyester modified polymer is cast on a transparent glass plate and coated at 140 ° C 3
The appearance after the solvent was evaporated under the condition of 0 minutes was visually confirmed. 7) Storage stability: A solution or dispersion of the epoxy group-containing polyester modified polymer was placed in a constant temperature bath at 50 ° C. for 1 month and examined for abnormalities such as resin separation and gelation.

Comparative Examples 4 to 9 Byron GK150 (manufactured by Toyobo Co., Ltd .: polyester resin: resin acid value 6.0) was placed in a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer. , Number average molecular weight 12,000, solid at room temperature) 25 parts by weight, and initially charged solvent 25 parts by weight, and heated under stirring to dissolve. Next, after lowering the temperature to room temperature, the solutions of the acrylic resins synthesized in Production Comparative Examples 3 and 4 were added and stirred at the mixing temperature shown in Table 5. As a result, in Comparative Examples 4, 5, and 8 in which the mixing temperature was room temperature, the resin dispersion liquid was in the form of oil drops and separated into two phases at room temperature in a short time. The cast film obtained by casting these resin dispersions on a transparent glass plate was completely opaque. On the other hand, the mixing temperature was set to 1 as in Comparative Examples 6, 7, and 9.
At 20 ° C., the mixture gradually thickened, and finally gelled.

[0047]

[Table 5]

Note 1) GK-150: polyester resin manufactured by Toyobo Co., Ltd .:
Resin acid value 6.0, number average molecular weight 12,000, solid at room temperature 2) Property: The appearance of the epoxy group-containing polyester modified polymer is visually observed. 3) Nonvolatile matter: dried at 50 ° C., 0.1 mmHg for 3 hours 4) Epoxy equivalent: After the ring-opening reaction of the epoxy group was carried out with an excess of 0.2N hydrochloric acid dioxane solution, unreacted hydrochloric acid was removed with 0.1N KOH ethanol. -Titrate with epoxy solution to calculate epoxy equivalent per resin. 5) Viscosity: at 20 ° C., JIS K-5400 (1
990) 4.5.3 Measured by a rotational viscometer method. 6) Transparency of cast film: Epoxy group-containing polyester modified polymer is cast on a transparent glass plate and coated at 140 ° C 3
The appearance after the solvent was evaporated under the condition of 0 minutes was visually confirmed. 7) Storage stability: A solution or dispersion of the epoxy group-containing polyester modified polymer was placed in a constant temperature bath at 50 ° C. for 1 month and examined for abnormalities such as resin separation and gelation.

Comparative Examples 10 to 15 A three-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with the polyester solution and the initially charged solvent shown in Table 6, respectively, and heated under stirring to dissolve. Next, after lowering the temperature to room temperature, the solution of the acrylic resin of Production Comparative Example 3 was added, and the mixture was stirred at the mixing temperature shown in Table 6. as a result,
In Comparative Examples 10 to 12 in which the mixing temperature was room temperature, oil-droplet-shaped resin dispersions were formed and separated into two phases within a short time at room temperature. The cast film obtained by casting the resin dispersion liquid onto a transparent glass plate was completely opaque. On the other hand, Comparative Example 1
When the mixing temperature of 3 to 15 was 120 ° C., the mixture gradually thickened and finally gelled.

[0050]

[Table 6]

[0051]

INDUSTRIAL APPLICABILITY The epoxy group-containing polyester modified polymer of the present invention has very good compatibility between the polyester portion and the vinyl monomer polymer portion. Furthermore, the storage stability of the solution or dispersion is also excellent. Further, since it has a large amount of an epoxy group as a reactive functional group, and if necessary, it is possible to introduce a reactive functional group such as a hydroxyl group into the epoxy group-containing polyester modified polymer, the melamine It is possible to obtain a thermosetting composition by combining it with a resin, an isocyanate, a carboxylic acid compound, an acid anhydride or other crosslinking agent. Therefore, the epoxy group-containing polyester modified polymer of the present invention can have excellent hardness, chemical resistance, stain resistance, and good processability of the polyester, which are possessed by the vinyl monomer polymer, and can be used as a coating material. It can be widely applied to the fields of ink, ink, adhesives and molded products. Further, according to the method for producing an epoxy group-containing polyester modified polymer of the present invention, it is possible to efficiently produce a composite of the above polyester having excellent properties and a polymer of a vinyl monomer.

Claims (8)

[Claims] 1. A number-average molecular weight of 1,500 to 50,
000 and the resin acid value is 2 to 30 mgKOH / g
Of the carboxyl group-containing polyester resin of (b) and (b) the epoxy group-containing vinyl monomer polymer, and the carboxyl group and a part of the epoxy group are (b) The epoxy group of the component (a) is reacted and bonded at a ratio of 0.1 or less with respect to the epoxy group of the component polymer and has an epoxy equivalent of 20.
Epoxy group-containing polyester modified polymer, which is 0 to 2,000 g / mol. 2. The epoxy group-containing polyester modified polymer according to claim 1, wherein the component (a) is a linear polyester resin containing a dicarboxylic acid and a diol as constituent unit raw materials. 3. A copolymer of a vinyl-based monomer having an epoxy group according to claim 1, wherein (b) a vinyl-based monomer having an epoxy group and (c) another vinyl-based monomer. The epoxy group-containing polyester modified polymer according to claim 1, which is a united body. 4. The weight ratio of the constituent part comprising the component (a) to the constituent part comprising the polymer of the component (b) or the copolymer of the component (b) and the component (c) is 1/99 to 80/20. The epoxy group-containing polyester modified polymer according to claim 1 or 3, wherein (A) Number average molecular weight of 1,500 to 50,
000 and the resin acid value is 2 to 30 mgKOH / g
In the presence of the carboxyl group-containing polyester resin and the organic solvent, the vinyl group-containing monomer (b) has an equivalent ratio of the carboxyl group of the component (a) to the epoxy group of the component (b) of 0.1. A method for producing a polyester modified polymer containing an epoxy group having an epoxy equivalent of 200 to 2,000 g / mol, which comprises polymerizing with a radical polymerization initiator in the following proportions. 6. The method for producing an epoxy group-containing modified polyester polymer according to claim 5, wherein the component (a) is a linear polyester resin containing a dicarboxylic acid and a diol as constituent unit raw materials. 7. The process for producing an epoxy group-containing polyester modified polymer according to claim 5, wherein (b) a vinyl-based monomer having an epoxy group is polymerized with (c) another vinyl-based monomer. 8. The weight ratio of the component (a) to the component (b) or the total weight of the components (b) and (c) is 1/99 to 80.
The method for producing an epoxy group-containing polyester modified polymer according to claim 5 or 7, which is / 20.