JPH06157736A - Terminal-modified copolyester and its production - Google Patents

Abstract

PURPOSE:To obtain a copolyester raised in active hydrogen equivalent owing to branched structure at the new molecular chain end(s). CONSTITUTION:This copolyester can be obtained by reaction between (A) an active hydrogen-terminated copolyester and (B) a polycarboxylic anhydride and/or (C) a heterocyclic compound having ring opening addition reactivity with carboxyl group. This copolyester is raised in active hydrogen equivalent 1.5 times or more that of the component A owing to branched structure of the molecular end(s).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel copolyester having an active hydrogen equivalent increased by a branched structure at the terminal of a molecular chain and a process for producing the same. More specifically, it relates to a copolyester having excellent adhesiveness, crosslinkability, mechanical properties after crosslinking, and durability, and a method for producing the same, which enables stable production without gelation. And the terminal-modified copolymer polyester of the present invention is a coating material, an adhesive, an ink,
It can be widely used for various coating agents.

[0002]

2. Description of the Related Art Copolyesters have hitherto been used in a wide variety of fields such as adhesives, can coating agents, coil coatings for building materials and home appliances, and inks. In particular, a relatively high molecular weight saturated linear copolyester has excellent flexibility, high cohesive strength, and excellent adhesive properties, and further has relatively good heat resistance. In recent years, it has received more attention because of its presence.

Even when using these copolyesters, when higher durability and heat resistance are required,
Similar to other resins, melamine resin, epoxy resin,
Cross-linking reaction is carried out by adding a cross-linking agent such as an isocyanate compound.

Generally, in the copolyester, the hydroxyl groups and carboxyl groups existing at the terminal of the molecular chain are involved in the above-mentioned crosslinking reaction, but in the linear copolyester, the higher the molecular weight, the lower the concentration of the terminal group. It is destined to do. For this reason, for example, when a polyisocyanate compound is added to a high molecular weight linear copolyester as a crosslinking agent, the concentration of the crosslinking reactive group in the copolyester is too low, the reaction rate becomes slow, and the time required for curing May become longer, or the curing may not proceed sufficiently, and desired durability and heat resistance may not be obtained. If curing takes a long time, even if the performance appears, it cannot be used considering the actual productivity.

Therefore, conventionally, a branched structure is introduced into the molecular chain by lowering the molecular weight of the copolyester or by adding a trifunctional or higher functional polycarboxylic acid or polyol at the time of polymerization to form an end group, that is, a crosslinkable group. Ways to increase have been taken. The former method improves the reaction rate but sacrifices the characteristics of the original high molecular weight linear copolyester, and the latter method causes gelation when trying to obtain a high molecular weight polyester. There is also a limit to the amount of crosslinkable groups that can be formed. In either method, the molecular weight between cross-linking points must be reduced, and the resulting performance was limited.

[0006]

Cross-linking is a very effective means for improving the durability of the coating film. Crosslinking means forming a new covalent bond between polymer chains, which increases cohesive force between polymer chains, but conversely, it restricts the free movement of polymer chains. Means to do. Further, it is apparent that simply increasing the number of cross-linking reactive groups in the resin by the conventional method will increase the curing shrinkage and adversely affect the adhesive performance. Thus, there is a strong demand for the appearance of a copolyester capable of imparting excellent durability to a crosslinking reaction while maintaining the excellent properties of a saturated linear copolyester having a relatively high molecular weight.

On the other hand, as described above, in the method of adding a trifunctional or higher functional polyester-forming component from the initial stage of polymerization,
There is a limit to the amount of crosslinking reactive groups that can be introduced into the resin,
Attempts to go beyond the limits pose the risk of gelation. Therefore, if there is a method for stably producing a resin in which the concentration of such a cross-linking reactive group is increased to a level that has never existed before, there is a possibility that a new function can be exhibited.

[0008]

Means for Solving the Problems While maintaining the excellent properties of such a linear copolyester, the present inventors have
The present invention has been achieved as a result of intensive research on a copolyester capable of increasing the amount of cross-linking reactive groups and imparting excellent durability.

That is, the copolyester of the present invention is
(A) a copolyester having active hydrogen at the terminal,
(B) a polycarboxylic anhydride and / or (C) a carboxyl group and a heterocyclic compound having a ring-opening addition reactivity are reacted to give an active hydrogen equivalent of (A) due to a branched structure at a molecular chain end. It is a terminal-modified copolyester characterized by being increased to 1.5 times or more of the active hydrogen equivalent.

The present invention also provides a method for producing such a terminal-modified copolymerized polyester, wherein (B) a polycarboxylic acid anhydride is reacted with (A) a copolymerized polyester having an active hydrogen at the terminal ( 1 step), then (C) a carboxyl group and a heterocyclic compound having a ring-opening addition reactivity are reacted (2nd step), and these steps are sequentially repeated to obtain a desired active hydrogen equivalent, or , (A) the copolymerized polyester (C) is reacted with a carboxyl group and a heterocyclic compound having a ring-opening addition reactivity to convert it to a hydroxyl group terminal, and if necessary, the above-mentioned first step and the second step are treated with desired active hydrogen. It is characterized in that it is sequentially repeated so as to be equivalent.

The carboxylic acid component of the copolymerized polyester having active hydrogen at the terminal (A) of the present invention includes terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like. Aromatic dicarboxylic acids, p-oxybenzoic acid, aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids,
There are unsaturated aliphatic and alicyclic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid and tetrahydrophthalic acid. If necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid may be contained.

Examples of the glycol component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct and propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene group Call, p- xylene glycol, m- xylene glycol, and the like tricyclodecane dimethylol. Trimethylolethane, if necessary,
It may contain a small amount of triols such as trimethylolpropane, glycerin, and pentaerythritol, and tetraols.

In addition, in some cases, improvement in freshness to water,
The polar group-containing compound shown below may be used in order to improve the pigment dispersibility and the adhesive performance.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

(Wherein M ₁ represents a hydrogen atom, an alkali metal, tetraalkylammonium or tetraalkylphosphonium, M ₂ represents a hydrogen atom, an alkali metal atom, a monovalent hydrocarbon group or an amino group, and R ₁ to R ₃ represents a hydrogen atom, alkyl having 1 to 8 carbons, aryl or aralkyl.)

In the production of the (A) copolyester having active hydrogen at the terminal, all the amounts of the carboxylic acid component and the alcohol component may be mixed at once, or may be dividedly added as the reaction progresses. I don't care. The polycondensation reaction may be carried out by a usual transesterification method or an esterification method, or a combination of both methods, and the polymerization degree can be increased by pressurizing or depressurizing the system at an arbitrary stage.

Other copolyesters of (A) include ε
Examples thereof include lactone-based polyesters obtained by ring-opening polymerization of lactones such as caprolactone and δ-valerolactone.

The thus-obtained (A) copolymerized polyester having active hydrogen at the terminal has a molecular weight of 500 to 50.
000, preferably 700 to 40,000, and more preferably 1000 to 30,000. Molecular weight is 50
When it is less than 0, the flexibility of the finally obtained coating film becomes poor, and when it exceeds 50,000, the concentration of active hydrogen becomes too low and the subsequent reaction does not proceed sufficiently, and the effect of the present invention is obtained. It will be difficult to be affected.

The (A) copolymerized polyester having active hydrogen at the terminal may be a hydroxyl group-terminated polyester urethane obtained by reacting a hydroxyl group-terminated one with an isocyanate compound.

The (B) polycarboxylic acid anhydride of the present invention is a cyclic or linear acid anhydride of a divalent or trivalent or more acid such as aliphatic, alicyclic or aromatic.

Examples of the aliphatic polycarboxylic acid anhydrides include acid anhydrides such as succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid and dodecanedioic acid.

Examples of the alicyclic polycarboxylic acid anhydride include acids such as hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hymic acid, head acid, and 1,4-cyclohexanedicarboxylic acid. An anhydride may be mentioned.

Examples of the aromatic polycarboxylic acid anhydrides include terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, ethylene glycol bis trimellitate, glycerol tris trimellitate and biphenyl tetracarboxylic acid. Examples thereof include acids and acid anhydrides such as diphenisulfone tetracarboxylic acid.

It has a function of esterifying one hydroxyl group of a divalent acid anhydride to give one carboxyl group,
An anhydride of a trivalent or higher acid has a function of esterifying one hydroxyl group and imparting two or more carboxyl groups by branching at the molecular end. These (B) polycarboxylic acid anhydrides can be used alone or in combination.

The heterocyclic compound (C) having a ring-opening addition reactivity with a carboxyl group of the present invention is a ring-opening addition reaction with a carboxyl group of a copolyester, and after the addition, at least one hydroxyl group is added. Heterocyclic compound. The first such compound is a cyclic ether. As the cyclic ether, a monoepoxy compound is first mentioned. The monoepoxy compound is a compound having one epoxy group in the molecule, and as specific examples, ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide, cyclohexene oxide, α-pinene oxide, 1- Oxides such as phenylpropylene oxide, methyl glycidyl ether, butyl glycidyl ether, 2-
Glycidyl ethers of monoalcohols such as ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidyl ethers of phenols such as p-butylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl butyrate, etc. Esters, further, monoglycidyl ethers of polyols such as ethylene glycol monoglycidyl ether, propylene glycol, and monoglycidyl ether,
Glycidol, 2-methylglycidol, 3-propyloxiranemethanol, 3-phenylglycidol, 2
Examples thereof include epoxy compounds having a hydroxyl group such as methyl-3-phenylglycidol.

Also, for example, X-22-173B manufactured by Shin-Etsu Chemical Co., Ltd. (trade name) or manufactured by Chisso Co., Ltd. (3), which is introduced under an epoxy group at one end of polysiloxane for the purpose of modification at the same time. -Glycidoxypropyl) bis (trimethylsiloxy) methylsilane, 3-glycidoxypropylpentamesyldisiloxane and PS404 (trade name)
Silicone-containing monoepoxy and the like may be used. Other cyclic ethers include oxetanes such as 3,3-dimethyloxetane and 3-methyl-3-oxetanemethanol.

Other heterocyclic compounds include lactones having a hydroxyl group such as β-hydroxy-β-methyl-δ-valerolactone, azirines such as 1-aziridineethanol, and 1,5,7, 11-tetraoxaspiro [5,5] undecane, 1,4,6-trioxaspiro [4,4] nonane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo [2,2]
2,2] octane and other spiro orthocarbonates, spiro orthoesters, bicyclo orthoesters, and bicyclic amide acetals having a structure represented by the following general formula.

[0035]

[Chemical 9]

(Wherein R ₁ , R ₂ , R ₅ , R ₆ and R ₇ are each hydrogen or an alkyl group having 1 to 20 carbon atoms, R ₃ is hydrogen, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
~ 12 aryl group, or an ether group having 1 to 20 carbon atoms, and R ₄ represents an alkyl group having 1 to 20 carbon atoms or an alkaryl group having 7 to 22 carbon atoms. )

These heterocyclic compounds can be used alone or in combination.

However, as the heterocyclic compound (C) having a ring-opening addition reactivity with the carboxyl group, a monoepoxy compound is desirable from the viewpoint of maintaining the polyester structure and maintaining the properties. Use of a polyepoxy compound is not suitable because chain extension and eventually gelation occur in the reaction step. For the purpose of increasing active hydrogen by the branched structure at the terminal of the molecular chain of the present invention, it is preferable to use a monoepoxy compound having a hydroxyl group capable of introducing a large amount of active hydrogen in one reaction. The monoepoxy compound having a hydroxyl group originally has a hydroxyl group in the molecule in addition to the addition reaction in which the epoxy group is opened by the carboxyl group at the terminal of the copolyester to generate one hydroxyl group. It is possible to give two or more hydroxyl groups to one carboxyl group at the end of the copolyester by one reaction.

The terminal-modified copolyester of the present invention is
(A) a copolyester having active hydrogen at the end and (B)
It is obtained by reacting a polycarboxylic acid anhydride and / or (C) a carboxyl group with a heterocyclic compound having a ring-opening addition reactivity.

Although the method for obtaining the desired terminal-modified copolymerized polyester of the present invention includes many cases, it is not particularly limited to this in order to explain the concept of the present invention in an easy-to-understand manner. A typical manufacturing method will be described with reference to the schematic diagrams shown in FIGS. FIG. 1 illustrates the case where the active hydrogen of the copolyester having active hydrogen at the (A) end is a hydroxyl group, and FIG. 2 illustrates the case where the active hydrogen is a carboxyl group. In each case, (B) polycarboxylic acid anhydride was selected from trivalent carboxylic acid anhydrides, and (C) a monoepoxy compound having a hydroxyl group was selected as a heterocyclic compound having a ring-opening addition reactivity with a carboxyl group. The case is illustrated.

When the active hydrogen of the copolyester having the active hydrogen of the active polyester at the terminal (A) of FIG. 1 is a hydroxyl group, the first step is
Addition reaction between the hydroxyl group of (A) and the acid anhydride group of (B) polycarboxylic acid anhydride is carried out. Such a reaction is under melting 180
It can be carried out at ˜240 ° C. for 0.5 hours to 2.0 hours, or in an inert solvent with an acid anhydride group at 50 to 180 ° C. for several hours. It is carried out without a catalyst or in the presence of a catalyst. In the reaction in a solvent, it is preferable to use a catalyst such as pyridine or 4-dimethylaminopyridine. With respect to the hydroxyl group of (A), the polycarboxylic acid anhydride is contained in an amount of 0.1 to 1.0 equivalent of the acid anhydride group per 1 equivalent of the hydroxyl group, preferably 0.4 to
React at a ratio of 1.0 equivalent. When the equivalent ratio of the acid anhydride group of the polycarboxylic acid anhydride to the hydroxyl group of (A) exceeds 1.0, free polycarboxylic acid anhydride remains, and the molecular weight of the obtained polyester is lowered, resulting in good flexibility. Is difficult to obtain. If it is less than 0.1, the effect of the present invention is difficult to obtain. When the free polycarboxylic acid anhydride remains, an unfavorable reaction as shown by the following reaction formula deviated from the object of the present invention may occur in the second step.

[0042]

[Chemical 10]

The acid-terminated polyester thus obtained can be used as it is, but when an anhydride of a divalent carboxylic acid is used, for example, one terminal hydroxyl group is converted into one carboxyl group. However, a branched structure at the terminal of the molecular chain is not taken, and addition of a trivalent carboxylic acid anhydride is difficult to obtain a sufficiently satisfactory performance.

The resulting acid terminated polyester is then (C)
It is subjected to a second step of carrying out an addition reaction of a carboxyl group and a heterocyclic compound having a ring-opening addition reactivity. The (C) carboxyl group-reactive heterocyclic compound undergoes a ring-opening addition reaction with the terminal carboxyl group of the obtained acid-terminated polyester to newly generate an active hydrogen group such as a hydroxyl group. Figure 1
When a monoepoxy compound having a hydroxyl group is selected as described above, since there is a hydroxyl group originally present in addition to one hydroxyl group formed by ring-opening addition of an epoxy group, for example, a divalent carboxylic acid in the first step. Even when the anhydride of 1 is used, one carboxyl group is converted to two hydroxyl groups in the second step, and thus it has a branched structure in the present invention. This reaction can also be carried out in the presence or absence of a solvent.

In this reaction, it is desirable to use an appropriate catalyst in order to smoothly proceed the reaction. As a catalyst, triethylamine, N, N-dimethylbenzylamine, 4
-Tertiary amines such as dimethylaminopyridine, metal halides such as aluminum trichloride, lithium chloride, potassium chloride and sodium chloride, ammonium salts such as tetra-n-butylammonium iodide, 1,8-diazabicyclo [5,5] 4,0] undecene-7, 2-ethyl-4-methylimidazole and the like can be mentioned.

The reaction temperature is suitably in the range of 80 to 150 ° C. As shown in FIG. 1, if it is desired to convert almost all the carboxyl groups of the acid-terminated polyester into hydroxyl groups in this second step, the carboxyl groups of the acid-terminated polyester 1
The epoxy group may be added and reacted at a ratio of about 1 equivalent per equivalent. Of course, it is also possible to react the epoxy group in a proportion less than that to obtain a terminal-modified copolyester having both a carboxyl group and a hydroxyl group.

The terminal-modified copolymerized polyester of the present invention can be obtained in the second step. Of course, if the first step and the second step are sequentially repeated as appropriate to further advance the branched structure, an active hydrogen group can be obtained. Obviously, the amount can be increased.

As shown in FIG. 2, when the active hydrogen of the copolymerized polyester (A) having active hydrogen at the terminal is a carboxyl group, first, the second step is carried out to carry out the carboxyl group of (A). Is converted to a hydroxyl group. At this stage, when a monoepoxy compound having a hydroxyl group is selected as shown in FIG. 2, the terminal-modified copolymerized polyester of the present invention is obtained in this step. However, as in the case shown in FIG. 1, it is also possible to repeat the first step and the second step as appropriate in sequence, so that the desired active hydrogen equivalent is obtained. You can

Although not shown in the figure, (A) when the active hydrogen of the copolyester having active hydrogen at the end has both a hydroxyl group and a carboxyl group, the production method shown in FIG. 1 or FIG. It is apparent that the terminal-modified copolyester of the present invention can be obtained by appropriately selecting and carrying out.

What is important in these manufacturing methods is (B)
A polycarboxylic acid anhydride containing an anhydride of a carboxylic acid having a valence of 3 or more is used at any stage and / or (C) a heterocyclic compound having a ring-opening addition reactivity with a carboxyl group, for example, as described above. It is necessary to use a compound capable of giving two or more active hydrogens by reacting with one carboxyl group such as a monoepoxy compound having a hydroxyl group at any stage. It is clear that the active hydrogen equivalent cannot be increased due to the branched structure at the chain end. Of course, the first (A) copolymerized polyester having an active hydrogen group at the terminal may be one type, or two or more types may be mixed, but (B) polycarboxylic acid It is necessary to avoid charging and reacting the anhydride and the (C) carboxyl group and the heterocyclic compound having the ring-opening addition reactivity at the same time. Usually above
When (A), (B), and (C) are charged at the same time, the side reaction as shown in the above reaction formula occurs preferentially over the reaction of (A) with active hydrogen. This is because the terminal modified copolymerized polyester of the invention cannot be obtained.

The active hydrogen equivalent of the terminal-modified copolymerized polyester of the present invention thus obtained is at least 1.5 times the active hydrogen equivalent of the copolymerized polyester having active hydrogen at the terminal (A) used as a raw material. It needs to be elevated. If it is less than 1.5 times, it is difficult to obtain the effect of sufficient modification.

The terminal-modified copolyester of the present invention can be used as it is, but it should be used by blending one or more compounds selected from the group of isocyanate compounds, epoxy compounds and amino resins, which are crosslinking agents. You can

As the isocyanate compound, there are aromatic, aliphatic, and araliphatic diisocyanates, and trivalent or higher polyisocyanates, which may be low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate,
An isocyanate compound such as isophorone diisocyanate or a trimer of isophorone diisocyanate, or an excess amount of these isocyanate compounds and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine And the like, and a terminal isocyanate group-containing compound obtained by reacting with a low molecular weight active hydrogen compound such as, or a high molecular weight active compound such as various polyether polyols, polyester polyols, polyamides, and the like.

The isocyanate may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenol, thiophenol, methylthiophenol, ethylphenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol and other phenols, acetoxime, methylethylketoxime, cyclohexanone oxime and other oximes, methanol, Alcohols such as ethanol, propanol, butanol, ethylene chlorohydrin, 1,3
-Halogen-substituted alcohols such as dichloro-2-propanol, tertiary alcohols such as t-butanol, t-pentanol, and t-butanethiol, ε-caprolactam, δ-valerolactam, τ-putyrolactam, β-propyl Examples include lactams such as lactams, and other active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetic acid esters, malonic acid ethyl esters, mercaptans, imines, ureas, diaryl compounds, and bisulfite. Examples include soda. The blocked isocyanate is obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

Bisphenol A as an epoxy compound
Diglycidyl ether and its oligomer, hydrogenated bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid glycidyl ester ether, tetrahydrophthal Acid diglycidyl ester,
Hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester,
Triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl dimethylhydantoin, diglycidyl ethylene urea, diglycidyl propylene urea, glycerol polyglycidyl ether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Examples thereof include polyglycidyl ether and polyglycidyl ether of glycerol alkylene oxide adduct.

Examples of the amino resin include formamide adducts such as urea, melamine and benzoguanamine, and alkylated products of alcohols having 1 to 6 carbon atoms.

It is desirable to add a curing catalyst or an accelerator to these crosslinking agents. Pigments, solvents, additives, resins and the like can be added to the terminal-modified copolyester of the present invention depending on the purpose and application.

As the pigment, various inorganic pigments and organic pigments used in the coloring material industry are usually used. Examples of the pigment include barite powder, precipitated barium sulfate, ground calcium carbonate, precipitated calcium carbonate, talc, clay, alumina white, white carbon glass and other extender pigments, lead white, zinc white, zinc sulfide, lithopone, titanium dioxide, etc. White pigments, blue pigments such as ultramarine blue, navy blue, cobalt blue, green pigments such as chromium oxide, viridian, chrome green,
Yellow lead, molybdate orange, cadmium pigments, titanium yellow, yellow iron oxide, yellow-orange-red pigments such as red iron oxide, black pigments such as iron black and carbon black, metal powder pigments such as aluminum powder and bronze powder, red lead , Lead suboxide powder, cyanamide lead, MIO, zinc chromate, strontium chromate, zinc-free, cuprous oxide aluminum tripolyphosphate, and other antirust pigments, antifouling pigments and the like. Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, vat pigments, dyed lake pigments, γ-Fe ₂ O ₃ , γ-Fe.
Mixed crystal of ₂ O ₃ and Fe ₃ O ₄ , CrO ₂ , cobalt ferrite, cobalt-coated iron oxide, barium ferrite, Fe
Examples thereof include magnetic powders such as —Co and Fe—Co—Ni, and fillers such as glass fibers, carbon fibers and metal fibers.

As the solvent, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and hesophorone, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane and ethylene glycol monoethyl ether, benzene, toluene, There are aromatic hydrocarbons such as xylene, Solvesso # 100 and Solvesso # 150, aliphatic hydrocarbons such as hexane and heptane, alcohols such as methanol, ethanol and isopropyl alcohol, or a mixture thereof. The reaction solvent used during the synthesis of the terminal-modified copolyester of the present invention can be used as it is.

It is also possible to prepare an aqueous resin composition by using an aqueous medium. As a method of dissolving, dispersing, and emulsifying the terminal-modified copolymerized polyester of the present invention in an aqueous medium, for example, in the case of the terminal-modified copolymerized polyester obtained by reacting in the absence of a solvent, a water-soluble organic compound and A method of premixing at 50 to 150 ° C. and adding water to this mixture and stirring to disperse it, or conversely, adding the mixture to water and stirring to disperse it, or a terminal-modified copolymerized polyester and water, if necessary. There is a method of coexisting with a water-soluble organic compound and stirring at 40 to 120 ° C. In the case of a terminal-modified copolyester obtained by reacting in a solvent, for example, water and, if necessary, a water-soluble organic compound are added to the solution, the system is depressurized, and the solvent is removed from the system by azeotropic distillation. leave. In the method for obtaining the aqueous resin composition of these polyesters, if necessary, an alkali or acid neutralizing agent, a surfactant, etc. may be used, and as described above, various polar groups may be added to the terminal-modified copolymerized polyester. May be introduced.

The above water-soluble organic compound is an organic compound having a solubility of 20 g or more in 1 liter of water at 20 ° C., and is specifically an aliphatic or alicyclic alcohol, ether, ester or ketone compound, such as methanol. , Ethanol, isopropanol, n-butanol and other monohydric alcohols, ethylene glycol, propylene glycol and other glycols, methyl cellosolve, n-
Glycol derivative such as butyl cellosolve, dioxane,
These include ethers such as tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds may be used alone or in combination of two or more. Among the above compounds, ethanol, isopropanol, methyl cellosolve, butyl cellosolve and ethyl cellosolve are preferable in view of dispersibility in water and coatability.

The additives include plasticizers, ultraviolet absorbers,
Antioxidant, Stabilizer, Drying agent, (Dryer), Antistatic agent, Hardening agent, Lubricant, Dispersing agent, Emulsifier, Anti-precipitation agent, Wetting agent, Thickening agent, Anti-drip agent, Anti-freezing agent, Color component Anti-reflective agent, anti-skin agent, anti-foaming agent, leveling agent, tackifier, rust inhibitor, anti-blocking agent, antiseptic agent, anti-mold agent, anti-algal agent, etc. are selected appropriately according to the application. Used.

The terminal-modified copolyester of the present invention is
Unlike the conventionally known linear and / or intramolecular branched copolyester, it has a plurality of reactive groups at the molecular chain end due to the branched structure at the molecular chain end. As a result, it is possible to introduce a sufficient amount of the cross-linking reactive group (active hydrogen group) into the resin while keeping the molecular weight between cross-linking points large.
A coating film that has excellent adhesiveness of conventional linear copolyester, excellent crosslinking reactivity while maintaining flexibility, and excellent properties such as solvent resistance, water resistance, and heat resistance after crosslinking. Can be obtained. In addition, it is possible to provide new performance that is not available in the past. Therefore, the terminal-modified copolymerized polyester of the present invention can be used in a wide variety of fields such as adhesives, paints, inks, coating agents, and treating agents for textiles and paper.

[0064]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight".

Production Example of Hydroxyl Terminated Copolyester Polyester 291 parts dimethyl terephthalate, 291 parts dimethyl isophthalate, 443 parts ethylene glycol, 400 parts neopentyl glycol, 0.4 parts zinc acetate and 0.4 parts antimony trioxide are placed in a reaction vessel. Prepared in 140-22
Transesterification was carried out at 0 ° C. for 3 hours. Then, 292 parts of adipic acid was added, and the esterification reaction was performed at 220 to 230 ° C. for another 30 minutes, and then 240 to 2
Polycondensation reaction is carried out at 60 ° C. under reduced pressure (10 to 0.2 mmHg) for 2 hours to give a molecular weight of 7100 and a hydroxyl value of 280.
eq. / 10 ⁶ g, acid value 2 eq. / 10 ⁶ g of hydroxyl-terminated copolymerized polyester A-1 was obtained. The hydroxyl-terminated copolymerized polyester obtained by the same method is shown in Table 1. The resin composition was analyzed by ¹ H NMR.

[0066]

Example 1 400 parts of the above hydroxyl-terminated copolyester A-1 was charged into a kneader and melted under a nitrogen atmosphere, then 21.5 parts of trimellitic anhydride was added and the mixture was heated to about 3 ° C. at about 3 ° C.
The addition reaction was carried out for 0 minutes. The acid-terminated polyester thus obtained has a molecular weight of 7,100 and an acid value of 530e.
q. It was / 10 ⁶ g. Next, 421.5 parts of the acid-terminated polyester and 150 parts of isophorone were charged into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and after dissolution, 17.4 parts of glycidol and 4-dimethylaminopyridine 1 were added. 0.5 part was added and reacted at 80 to 110 ° C. for about 3 hours to give a molecular weight of 7200 and a hydroxyl value of 1070 eq. / 10
⁶ g, acid value 2 eq. / 10 ⁶ g of terminal modified copolymerized polyester (T-1) was obtained. After the reaction, Solvesso # 1
00 162.4 parts was added to dilute, solid content concentration 50w
It was a t% solution. Terminal-modified copolymerized polyesters T-2 and T-3 were obtained from hydroxyl group-terminated copolymerized polyesters A-2 and A-3 by the same method.

Example 2 In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, the hydroxyl-terminated copolymerized polyester A-1 400 shown in Table 1 was used.
Parts, and 150 parts of toluene were charged and dissolved by heating, 11.2 parts of succinic anhydride and 1 part of 4-dimethylaminopyridine were added, and the mixture was reacted at about 100 ° C. for 3 hours to obtain an acid-terminated polyester. At this stage, absorption of acid anhydride groups (1865 cm ^-1 and 1782 cm ^-1 ) was not detected by IR measurement, and unreacted succinic anhydride did not remain. The acid-terminated polyester thus obtained has a molecular weight of 7,000 and an acid value of 27.
5 eq. It was / 10 ⁶ g. Then, 8.7 parts of glycidol was added to the system and the reaction was continued at 90 to 110 ° C. for another 3 hours. The acid value decreased steadily, and at this stage, 1 eq. /
It was 10 ⁶ g. The terminal modified copolymerized polyester (T-1 ') thus obtained had a molecular weight of 7,100 and a hydroxyl value of 475.
eq. It was / 10 ⁶ g. After completion of the reaction, it was diluted with methyl ethyl ketone to obtain a solution having a solid content concentration of 50 wt%.

Example 3 A hydroxyl-terminated copolymerized polyester A-4 400 shown in Table 1 was placed in a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser.
Parts, and 200 parts of isophorone were charged and dissolved by heating, 34.6 parts of trimellitic anhydride and 3 parts of 4-dimethylaminopyridine were added, and the mixture was reacted at 100 to 150 ° C. for 6 hours.
At this stage, absorption of acid anhydride groups (1860 cm ^-1 and 1782 cm ^-1 ) by IR was not observed, and the acid-terminated polyester obtained had a molecular weight of 4400 and an acid value of 830 eq.
It was / 10 ⁶ g. Then, after cooling the system, 28 parts of glycidol was added and the reaction was continued at 90 to 110 ° C. for 3 hours. The acid value is steadily decreased, and the acid value of the obtained terminal-modified copolyester T-4 is 3 eq. / 10 ⁶ g, the molecular weight is 4500, and the hydroxyl value is 1650 eq. / 10 ⁶ g
Met. Then, it was diluted with Solvesso # 100 to obtain a solution having a solid content concentration of 50 wt%. Table 2 shows the compositions and characteristic values of the terminal-modified copolymerized polyesters obtained in Examples 1 to 3.

[0070]

Comparative Example 1 The following production was attempted to obtain a copolyester having the same composition as in Example 3. Dimethyl terephthalate 44
2 parts, dimethyl isophthalate 442 parts, ethylene glycol 403 parts, neopentyl glycol 364 parts, glycerin 77 parts and tetra n-butyl titanate 0.5.
Parts were placed in a reaction vessel, and transesterification reaction was carried out at 140 to 220 ° C. for 3 hours. Then, 85 parts of trimellitic anhydride was added, the esterification reaction was performed at 220 to 230 ° C., and then the system was gelated during the polycondensation reaction under reduced pressure at 240 to 260 ° C.

Example 4, Comparative Example 2 Terminal-modified copolymerized polyesters T-1 to T shown in Table 2
-4 was blended with Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd. in such a manner that the isocyanate group was 1 in an equivalent ratio to the hydroxyl group in the polyester, and 0.1 part of di-n-butyltin dilaurate was further added, Immediately, it was applied on a polyethylene terephthalate sheet using an applicator so that the thickness after curing was 10 μm, and dried by heating at 80 ° C. for 20 minutes to prepare a cured film. A cured film was produced on an aluminum plate, a galvanized steel plate, a polycarbonate sheet, and a vinyl chloride sheet by the same method. The cured film was evaluated by the following methods. The evaluation results are shown in Table 3. or,
As a comparison, the results of carrying out the same evaluation using the hydroxyl-terminated copolymerized polyesters A-1 to A-4 which are the raw materials of T-1 to T-4 are also listed.

The evaluation was carried out by the following method. -Gel Fraction The cured film was put on a cylindrical filter paper and extracted with methyl ethyl ketone for 24 hours using a Soxhlet extractor.
The residue in the cylindrical filter paper was dried and then weighed, and the weight fraction of the insoluble matter was calculated from the weight before extraction to obtain the gel fraction. -Adhesiveness A 1 mm x 100 cross-cut was cut into the film with a cutter, cellophane tape was attached, and peeled off to test the adhesiveness.・ Solvent resistance The surface of the cured film is 50% by adding ethanol to gauze.
The surface condition after rubbing was observed. ○: There is no abnormality. Δ: There are scratches. X: The coating film peels off. -Water resistance to boiling After immersing the cured film in boiling water, it was boiled for 2 hours, and the surface condition of the film was visually judged. ○: There is no abnormality. Δ: Slightly cloudy or slightly peeled off. X: Severely clouded or peeled.

[0074]

[Table 1]

Example 5 The terminal-modified copolymerized polyester T-1 shown in Table 2 was used and dispersed by a paint shaker to prepare a white coating composition having the following composition. Terminal modified copolymerized polyester varnish 200 parts (solid content concentration NV = 50 wt%, isophorone / Solvesso # 100 solution) Methylated melamine resin (Sumimal M-4OS) 31.3 parts Paratoluenesulfonic acid (10% butanol solution) 2. 5 parts Titanium dioxide 125 parts Anon 100 parts Next, it is applied on a zinc-plated steel plate with a thickness of 0.5 mm, and is heat-cured for 1 minute at a maximum attainable plate thickness of 230 ° C. in a hot air oven to give a white film of 20 μm in thickness. A cured coating film was prepared. The performance of the coated steel sheet thus produced was evaluated by the following method.

[0076] tested using hardness Mitsubishi Pencil Uni, expressed in hardness one rank lower hardness scratching. It was tested by a bending test with a workability vise, and evaluated by the number of plates sandwiched between the minimum cracks. The surface state of the xylene scrub cured film was observed after rubbing 50 times with gauze containing xylene. ○: No abnormality. Δ: There is a tight feeling. X: The coating film peels off. The evaluation results are hardness 2H (* Note), workability OT (20 ° C),
OT (10 ° C.), xylene rub: ◯, boiling water resistance: ◯, which were very excellent. (* Note) Immediately after the hardness evaluation, it is F, and when it is H or more, the indentation with the pencil is seen. However, after 1 hour, the dents returned and no change was observed in the coating film appearance even at 2H.

Example 6 With respect to the white paint of Example 5 and the clear paint containing no titanium dioxide, a cured coating film was prepared on a tin plate in the same manner as in Example 5, and peeled by an amalgam method to obtain a white film and a clear film. I got a film. Using this coating film, the residual strain rate was measured by Tensilon. Conditions: Test length (distance between chucks): 5 cm, sample width:
0.5 cm Crosshead speed: 100 cm Measurement temperature: 20 ° C. Measurement was performed by extending the coating film by 50% (distance between chucks: 7.5 cm) under the above conditions, immediately returning it to its original position, and changing the sample length after leaving it for 10 minutes. Was measured. The residual strain rate was defined as what percentage of the given strain remained. That is, If the test length is not recovered, the residual strain rate is 100%. The white coating film had a residual strain rate of 22.0%, and the clear coating film had a residual strain rate of 15%, which can be said to be an elastic paint.

Example 7, Comparative Example 3 Isophthalic acid // diethyl glycol = 100 // 100
(Molar ratio), molecular weight 7,000, hydroxyl value 280e
q. / 10 ⁶ g of copolyester (A-5) was used, and in the same manner as in Example 1, the molecular weight of the following composition was 7,500,
Hydroxyl value 1060 eq. / 10 ⁶ g of terminal modified copolymerized polyester (T-5) was obtained. Composition: Polyester A-5 / trimellitic anhydride / glycidol = 100 / 5.3 / 4.3 (parts) Solvent removed terminal modified copolyester (T-5)
After charging 150 parts and 250 parts of n-butyl cellosolve into a container and stirring at 150 to 170 ° C. for about 3 hours to obtain a uniform and viscous melt, 600 parts of water was gradually added with vigorous stirring. After about 1 hour, a uniform light blue water dispersion (W-5) was obtained. The particle diameter of the obtained aqueous dispersion was 1 μm or less. When this aqueous dispersion was allowed to stand at 10 ° C. for 20 days, no change in appearance was observed, and on the other hand, there was no change in viscosity and excellent storage stability was exhibited. For comparison, an aqueous dispersion was tried to be obtained in the same manner as above except that the terminal modified copolyester (T-5) was changed to the copolyester (A-5), but it was separated without being dispersed at all.

Example 8 To 200 parts of a resin solution of the terminal-modified copolymerized polyester T-1 of Example 1 (solid content concentration 50 wt%), 16 parts of Karenz MOI (2-methacryloyloxyethyl isocyanate) manufactured by Showa Denko KK , Hydroquinone 0.01
And 0.03 part of di-n-butyltin dilaurate were added and reacted at about 80 ° C. for 5 hours, no NCO peak was observed by IR, and polyester urethane acrylate was obtained without any problem in the reaction. This solution was applied onto a polyester film so that the thickness after curing would be 10 μm.
It was applied using an applicator and dried at 80 ° C. for 20 minutes. Then, electron beam irradiation with an accelerating voltage of 165 KV, a current of 2.5 mA and an absorbed dose of 5 Mrad was performed to form a cured film. When the characteristics of this cured film were carried out in the same manner as in Example 4, the results were as follows: adhesion 100/100, gel fraction 95.
%, Solvent resistance ○ (no abnormality), boiling water resistance ○ (no abnormality)
And was excellent.

Example 9, Comparative Example 4 The following copolymerized polyester (A-6) was obtained in the same manner as in the production example of hydroxyl group-terminated copolymerized polyester. Composition: terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // ethylene glycol / neopentyl glycol = 50 / 48.5 / 1.5 // 55/45 (molar ratio), molecular weight 14000, hydroxyl value 140 eq. / 1
0 ⁶ g. Then, the following terminal-modified copolymerized polyester (T-6) was obtained in the same manner as in Example 1 except that the solvent was changed to a solvent containing only methyl ethyl ketone. Composition: Polyester A-6 / trimellitic anhydride / glycidol = 100 / 2.6 / 2.0 (parts), molecular weight 15
000, hydroxyl value 510 eq. / 10 ⁶ g. After the methyl ethyl ketone was dried and removed from this resin solution, the solid content of the terminal modified copolyester (T-6) was 3
0 part, n-butyl cellosolve 10 parts, and water 60 parts were charged into a container and stirred at 80 ° C. for about 5 hours to obtain a uniform pale bluish white aqueous dispersion (W-6). Furthermore, 450 parts of water and 450 parts of ethyl alcohol were added to dilute to obtain a solid content concentration of 3%.
A coating liquid was obtained. This coating solution was applied to a polyester film by an air knife method and dried with hot air at 120 ° C. to obtain a coated polyester film having a coating amount of 0.3 g / cm ² . An uncoated polyester film was provided as a comparative example. For these, the adhesiveness of the magnetic agent was evaluated.

Γ-F was used to evaluate the adhesiveness of the magnetic agent.
e ₂ O ₃ differential powder particles 250 parts, dioctyl sulfonate 2 parts, copolyester (45 mol% terephthalic acid,
Isophthalic acid 20 mol%, sebacic acid 32.5 mol%,
5 Sodium sulfoisophthalic acid 2.5 mol%, ethylene glycol 50 mol%, neopentyl glycol 50
48 parts by mole and 600 parts of cellosolve acetate were mixed in a ball mill for about 24 hours. This mixture 4
Copolymerized polyester resin 100 parts to 00 parts, nitrocellulose 30 parts, vinyl chloride-vinyl acetate copolymer 70
Part, 30 parts of polyisocyanate, 400 parts of methyl ethyl ketone, and 400 parts of cyclohexane were added and mixed again using a ball mill for about 70 hours.
To the above film. Furthermore, 100
An adhesive tape was attached to the surface of the magnetic layer that was cross-cut into individual pieces, and the whole surface was adhered uniformly, and then the state of instantaneous peeling was observed. The numerical value shows the remaining number. In Example 9, the magnetic layer had an adhesion of 100, whereas the comparative uncoated polyester film had an adhesion of 50.

Example 10 Trimellitic anhydride 2 was added to 400 parts (solid content 200 parts) of a resin solution of the terminal-modified copolyester T-1 of Example 1.
1 part was added and reacted at 100 to 150 ° C. for 5 hours.
The characteristics of the obtained terminal modified copolymerized polyester (T-7) have a molecular weight of 7400 and an acid value of 990 eq. / 10 ⁶ g, hydroxyl value 530 eq. It was / 10 ⁶ g. After the solvent was dried off from this resin solution, 30 parts of solid content and 10 parts of n-butyl cellosolve were added and melted, and then 1% ammonia water 6
When 0 part was gradually added with vigorous stirring, a uniform light blue water dispersion (W-7) having a particle size of 1 μm or less was obtained. When this dispersion was left to stand at 10 ° C. for 20 days, no change in appearance was observed, and there was no change in viscosity, and it had excellent storage stability.

[0083]

As is apparent from the above examples, the terminal-modified copolyester of the present invention not only has excellent adhesiveness and flexibility, but also exhibits excellent crosslinking reactivity by the addition of a crosslinking agent. Excellent durability such as solvent resistance and water resistance. Furthermore, it has excellent mechanical properties. In addition, since the concentration of active hydrogen groups can be increased to a level that has never existed before, new functions such as water dispersibility can be imparted. Further, it is clear that a copolyester having a high branch, which has not been heretofore, in which branches are concentrated at the end of the molecular chain can be stably produced.

[Brief description of drawings]

FIG. 1 is a schematic view showing a typical method for producing a terminal-modified copolymerized polyester.

FIG. 2 is a schematic view showing another typical method for producing a terminal-modified copolymerized polyester.

Claims (2)

[Claims] 1. A reaction of (A) a copolyester having an active hydrogen at the terminal with (B) a polycarboxylic acid anhydride and / or (C) a carboxyl group and a heterocyclic compound having a ring-opening addition reactivity. An end-modified copolymerized polyester characterized in that the active hydrogen equivalent is increased to 1.5 times the equivalent of the active hydrogen equivalent of (A) or more by the branched structure at the end of the obtained molecular chain. 2. A copolymerized polyester having (A) an end having active hydrogen is reacted with (B) a polycarboxylic acid anhydride (first step), and then (C) a carboxyl group and ring-opening addition reactivity. By reacting the heterocyclic compound with (the second step) and sequentially repeating these steps so as to obtain a desired active hydrogen equivalent, or (C) a carboxyl group and a ring-opening addition reaction to the copolyester of (A) Of a heterocyclic compound having properties to convert it to a hydroxyl group terminal, and if necessary, the above first step, second step
The method for producing a terminal-modified copolymerized polyester according to claim 1, wherein the steps are sequentially repeated until a desired active hydrogen equivalent is obtained.