JPS6025050B2 - Manufacturing method of modified polyester resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel modified polyester resin that exhibits various performances, and is useful in coating materials such as various adhesives, coping agents, binders for printing, vehicles for paints, and varnishes for inks. The purpose of the present invention is to provide a polyester resin with a novel structure that is useful as such.

Accordingly, so-called thermoplastic elastomers, which exhibit plasticity that allows easy molding above a certain temperature and have excellent elasticity after being shaped, are known and are widely used industrially.

Among the thermoplastic elastomers mentioned above, the present inventors aimed to further expand the use of thermoplastic polyester resins.As a result of intensive research, the present inventors discovered that polyester polymer chains with high crystallinity or cohesiveness and unsaturated double bonds The present invention was completed after discovering that a modified polyester resin in which a compound containing a mercapto group is added to a block copolymer with a polyester polymer chain contained therein is excellent as a variety of coating materials, adhesives, etc. did. That is, the present invention provides a modified polyester system characterized by adding a mercabuto group-containing compound to an unsaturated double bond in a block copolymer consisting of a saturated polyester chain and a polyester chain having an unsaturated double bond. This is a method for producing resin.

To explain the present invention in detail, the raw material block copolymer used in the present invention is a block copolymer consisting of a highly crystalline or highly cohesive polymer chain, that is, a hard segment, and a polymer chain containing an unsaturated double bond group. As is known from Industrial Materials No. 2, No. 12 (1976), Special Feature on Thermoplastic Elastomers, Journal of the Japan Petroleum Institute, Vol. 19, p. As expressed by the name Tele-block copolymer type or multi-block copolymer type, a polymer chain containing an unsaturated double bond group is It is a polymer having a structure sandwiched between hard segments.
A copolymer may be mixed therein.

Examples of the block copolymers used in the above-mentioned invention include the following.

The hard segment is a saturated polyester chain, for example, a polyester chain of polycarboxylic acids such as phthalic anhydride, terephthalic acid, isophthalic acid, succinic acid, adipic acid, and sebacic acid and lower diols that do not have addition reactivity. , the unsaturated segment is a polyester chain having an unsaturated double bond; for example, unsaturated group-containing polycarboxylic acids (or their anhydrides) such as maleic anhydride and itaconic anhydride, and polyethylene glycol, polypropylene glycol, and polybutylene. It is a terefloc type or multi-block type block copolymer of polyester chains obtained by reacting polyols such as glycol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, and dipropylene glycol.

These can be obtained by continuously performing a condensation polymerization reaction to form both polymer chains, or by subjecting both polymers to a bonding reaction. In the above,
Advantageously, the polyester portion with unsaturated double bonds in the copolymer accounts for about 10 to 8% by weight.

The present invention has succeeded in obtaining a very useful new polymer by subjecting the block copolymer described above to an addition reaction with a mercapto group-containing compound.

The mercapto group-containing compound used in the present invention is not limited to any type as long as it has a mercapto group, but examples include carboxyl group, sulfonic acid group, hydroxyl group,
By using a compound that simultaneously has a hydrophilic group such as a primary to quaternary amino group, it is possible to introduce a polar group, a reactive group, etc. into the resulting polymer, and it is also possible to introduce a polar group, a reactive group, etc. into the resulting polymer. By using a compound having at the same time a lipophilic group such as a long-chain alkoxy group, the solubility in a solvent and the flexibility of the resin can be improved as a lipophilic polymer.

Examples of such mercapto group-containing compounds include methyl mercaptan, ethyl mercaptan, n- or isopropyl mercaptan, n-, sec-, ten- or inbutyl mercaptan, n-, SeC-, te
n- or in-amyl mercaptan, active amyl mercaptan, n- or sec-hexyl mercaptan, n
1 or Sec-heptyl mercaptan, n- or S
eC octyl mercaptan, n- or sec nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-cetyl mercaptan, monothioethylene glycol, monothiopropylene glycol, Q-monothioglycerin, monothioethylene chlorohydrin, 3-chloropropylmercabutane, thioglycolic acid, thiohydroacrylic acid, thiolactic acid, thiomalic acid, mercaptopropanesulfonic acid, thioethanolamine,
B-dituthylaminoethyl mercaptan, y-dituthylaminopropyl mercaptan, 8-nitroethyl mercaptan, various dihydric mercaptans, thiophenol, thiocresol, thiosalicylic acid, alkyl esters and alkylamides of the above-mentioned thioalkyl acids. etc. The method of adding such a mercapto group-containing compound to an unsaturated group of a segment containing a Q.B-ethylene unsaturated double bond of the block copolymer is a generally known method of adding to an unsaturated double bond. It is carried out according to the reaction.

In such a method, the mercapto group-containing compound for the copolymer varies depending on the nature and type of the copolymer, and the properties required for the product, but generally it is 0.02 to 2 molar equivalents, preferably 0.2 to
It is 1 molar equivalent.

This introduction into the unsaturated double bond group can be carried out without a catalyst if the unsaturated group has a high degree of activity, but if necessary, a free radical generating compound may be used as a catalyst. Catalysts such as azobisisoputilonitrile, azobiscyanovaleric acid, benzoyl peroxide, lauroyl peroxide, kyumene hydro/gu oxide, methyl ethyl ketone peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. carried out in the presence of The base of the catalyst used at this time also varies depending on the nature, type, and amount of the mercapto group-containing compound used, but in general, the mercapto group-containing compound 10
It is 0.1 to 5 parts by weight per part by weight. The solvent used in the addition reaction of the mercapto group-containing compound varies depending on the block copolymer and cannot be specified in general, but preferred solvents include, for example, cyclohexane, toluene, xylene, nitrobenzene, turbene, bentane,
Hydrocarbon solvents such as naphthene, chlorine solvents such as tricrene, perchlorene, chloroform, and carbon tetrachloride, ether solvents such as methyl cellosolve, ethyl cellosolve, diethyl cellosolve, dioxane, and tetrahydrofuran, N
- Amide solvents such as N-dimethylformamide and N.N-dimethylacetamide, hydrophilic solvents such as methanol, ethanol, isopropanol, butanol, dimethyl sulfoxide, water, or mixtures thereof.

The reaction concentration is 2.5 to 50% by weight, preferably 5 to 2% by weight. The reaction temperature is 0~
12,000, but usually about 40 to 90
It is carried out within the range of It is preferable to carry out the reaction in the absence of air, that is, in an inert gas stream or at a boiling point. The reaction time is 30 minutes to one feeding time, but the reaction is usually carried out for 3 to 5 hours.

After the reaction is complete, the solution can be used as a binder for textile printing, paints, inks, etc., vehicles, varnishes, etc., coating agents, adhesives, etc.; however, it is generally necessary to remove the solvent,
A solid target product is obtained through a purification process, a drying process, etc.

The modified polyester resin of the present invention obtained as described above exhibits many properties depending on the type of mercabuto group-containing compound used, but especially hydrophilic properties such as carboxyl groups, sulfonic acid groups, hydroxyl groups, and amino groups. When a group is introduced, by introducing a polar group or a reactive group depending on the group into the resin made of the copolymer, the dispersion or solution of the wood,
Adhesive strength to cloth, glass, metal, etc. is dramatically improved,
When a reactive group is introduced, it is useful as an adhesive, a coating agent, a binder for textile printing, a vehicle for paint, a varnish for ink, etc., due to its effects.

Furthermore, the excellent properties of the polymer of the present invention are such that the block copolymer used as a raw material has polymer chains with high crystallinity or cohesiveness as hard segments, and polymer chains with low crystallinity as soft segments. When a mercapto-containing compound is added to the unsaturated double bond in this soft segment by the method of the present invention,
The hard segment, which does not have double bonds, is not affected in any way, and after all, it retains sufficient high crystallinity or high cohesiveness even after the reaction, and it is obtained from a normal random copolymer as a raw material. It is thought that it exhibits superior physical properties when compared to other mercapto group-containing compounds, and that it has the various properties described above due to the mercapto group-containing compound.

Therefore, by utilizing these properties, it is useful for various industrially useful applications such as adhesives, coating agents, binders for textile printing, vehicles for paints, coating materials for printing ink varnishes, and the like. Next, the present invention will be specifically explained with reference to Examples.

In the text, parts or percentages are important criteria. Example 1 Obtained by co-condensation of polyethylene terephthalate and polyethylene maleate (polyethylene terephthalate)
A block polymer of polyethylene maleate ÷ polyethylene terephthalate (polyethylene terephthalate: polyethylene maleate = 60:40), 45 parts of nitrobenzene, and 450 parts of xylene were placed in a reaction vessel, dissolved by overflowing, and nitrogen was added at 9,000 ℃. Gas flows in.

Add 0.5 parts of asobisisobutyronitrile, and after 5 minutes add 26 parts of thioglycolic acid dropwise over 1 minute.
000 for 4 hours.

When 100 parts of water is added to the reaction vessel and steam distillation is performed while stirring, a polymer is precipitated. This precipitate was filtered, washed with water, and dried at 8,000 ℃ to obtain 115 parts of a polymer. A 15% solution of this resin in cresol and brazed at 200 oo for 30 minutes had adhesion properties that passed tests such as bending, cross-cutting, and impact. Example 2 A resin solution obtained in the same manner as in Example 1 except that 22 parts of thioglycolic acid was used in place of thioglycolic acid in Example 1 had excellent adhesion to wood and metal. Ta.

Example 3 A resin solution obtained in the same manner as in Example 1 except that the thioglycolic acid of Example 1 was added to 21 parts of thioethanolamine was useful as a varnish for gravure ink.

Claims (1)

[Claims] 1. A method for producing a modified polyester resin, which comprises adding a mercapto group-containing compound to an unsaturated double bond in a block copolymer consisting of a saturated polyester chain and a polyester chain having an unsaturated double bond.