JPH0558027B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition with excellent stability. Conventionally, water-soluble polymer compounds include, for example, polyvinyl alcohol (hereinafter referred to as PVA), methyl cellulose, polyethylene oxide,
Starch-based, acrylic acid-based, and hydroxypropylcellulose-based are known, but today PVA is particularly popular in water-soluble films or sheets.
is mainly used. A water-soluble PVA film or sheet is colorless and transparent, has excellent physical properties such as tear strength, has a suitable amount of moisture absorption, is oil resistant, and does not dissolve in most organic solvents. In view of this situation, the present inventors have developed a water-soluble film or sheet that has physical properties similar to or better than that of PVA water-soluble film or sheet, is water-soluble, and is soluble in a specific organic solvent. As a result of various studies on the new high molecular weight compounds to be provided, we have discovered a specific high molecular weight compound that provides a water soluble film or sheet that has excellent physical properties, is water soluble, and dissolves in a specific organic solvent. A patent application for this is already pending. However, when certain high molecular weight compounds are heated alone in the air for long periods of time or exposed to sunlight for long periods of time, they deteriorate severely, and as a result of the decrease in molecular weight, they may lose their own film-forming ability. Also, cracks may occur in the film state. In order to improve these shortcomings,
As a result of further various studies, we have arrived at the present invention. That is, (A) prepared by reacting a polyoxyalkylene glycol with an average molecular weight of 8000 or more and an ethylene oxide chain content of 70% by weight or more and a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester. (B) A compound in which 2 moles of N,N-dimethylhydrazine and 1 mole of a diisocyanate compound are bonded with urea (hereinafter referred to as compound B) is added to a high molecular weight compound with an average molecular weight of 50,000 or more. It is an excellent composition (hereinafter referred to as composition). The polyoxyalkylene glycol with an average molecular weight of 8,000 or more and an ethylene oxide chain content of 70% by weight or more (hereinafter referred to as specific polyoxyalkylene glycol) used in the present invention is an organic compound having two active hydrogen groups. Examples include polyoxyalkylene glycols with an average molecular weight of 8,000 or more and an ethylene oxide chain content of 70% by weight or more, which are prepared by addition polymerizing alkylene oxides containing ethylene oxide. The active hydrogen group includes an alcoholic hydroxyl group, an amino group, a phenolic hydroxyl group, and the like. Specific examples of the organic compound having two active hydrogen groups (hereinafter referred to as starting material) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neo Examples include pentyl glycol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, butylamine, octylamine, laurylamine, and cyclohexylamine. The alkylene oxide used in addition polymerization contains ethylene oxide as an essential component, and examples of alkylene oxides other than ethylene oxide include propylene oxide, butylene oxide, and styrene oxide. Such addition polymerization is preferably carried out using a caustic alkali such as sodium hydroxide or potassium hydroxide as a catalyst at a temperature of about 90 to 200°C for about 2 to 30 hours. Next, a specific polyoxyalkylene glycol is reacted with a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester to form a high molecular weight compound having an average molecular weight of 50,000 or more. Specific examples of the polyhydric carboxylic acid, its anhydride, or its lower alkyl ester include (a) malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, Terephthalic acid, itaconic acid, trimellitic acid, pyromellitic acid or dimer acid, (b) acid anhydride of (a), or (c) monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester of (a),
Monopropyl ester, dipropyl ester,
Examples include monobutyl ester and dibutyl ester. Such a reaction involves adding a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester to a specific polyoxyalkylene glycol and then raising the temperature to 80°C.
Dehydration or dealcoholization is carried out by heating at ~250°C and reducing the pressure from 0.001 to 20 mmHg. The required reaction time is usually preferably 30 minutes to 10 hours. In high molecular weight compounds, if the average molecular weight is less than 50,000, there is no ability to form a film or sheet;
Or the strength becomes small. Next, the compound B used in the present invention includes a compound in which 2 moles of N,N-dimethylhydrazine and 1 mole of a diisocyanate compound are bonded with urea. Examples of diisocyanate compounds include tolylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
Examples include dodecamethylene diisocyanate, methylene bisdiphenyl diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate dimer, isophorone diisocyanate, naphthalene diisocyanate, chlorobenzene diisocyanate, xylylene diisocyanate, and lysine diisocyanate. Such a reaction is carried out by a known method, for example, by reacting the two at a temperature below the boiling point of N,N-dimethylhydrazine, if necessary in the presence of a solvent. The composition according to the present invention includes a composition in which the above-mentioned compound B is added to the above-mentioned high molecular weight compound. When compound B is added to a high molecular weight compound, the amount of compound B added is 0.01 to 0.01 to the high molecular weight compound.
It is 10% by weight. In addition, as for the addition method, 60~
Examples include a method of kneading a predetermined amount of both at 100°C, or adding and mixing compound B to a high molecular weight compound immediately after reaction and preparation. The composition obtained according to the invention is water-soluble and
Since it is soluble in specific solvents and has excellent light resistance and heat resistance, it is thought that its use will expand not only to the field of films and sheets but also to other fields. Next, the present invention will be explained with reference to Examples. In the examples, "%" and "part" are based on weight. Production example Diethylene glycol 106 in autoclave
and 20 parts of flaked caustic potash were heated at 130°C to produce ethylene oxide at a concentration of 2 kg/cm ² G or less.
The reaction was carried out while gradually adding 12,000 parts. The weight average molecular weight of the product (intermediate) was calculated by measuring the hydroxyl value and alkali value, and was found to be approximately 10,000.
It was hot. Next, 100 parts of this product were taken, 1.94 parts of dimethyl terephthalate was added thereto, the temperature was raised to 120°C, and methanol was removed under reduced pressure of 1 mmHg to obtain a high molecular weight compound.
The weight average molecular weight of this high molecular weight compound was measured by gel permeation chromatography and was found to be approximately 200,000. In addition, 5 parts of it was taken and its solubility in 95 parts of water or solvent was examined. Various high molecular weight compounds were obtained in the same manner. They are shown in Table 1.

【table】

[Table] Examples The light resistance of various compositions obtained by adding Compound B shown in Table 2 to various high molecular weight compounds was evaluated.
The results are shown in Tables 3 and 4. In Table 3, films were formed using a hot roll at about 75°C, exposed to sunlight, and the change in molecular weight over time was measured by gel permeation chromatography. Table 4 shows that films were formed using hot rolls at about 75°C, placed in a hot air dryer at 80°C, and the change in molecular weight over time was measured by gel permeation chromatography.

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) A polyoxyalkylene glycol having an average molecular weight of 8,000 or more and an ethylene oxide chain content of 70% by weight or more, and a polyhydric carboxylic acid or anhydride thereof, or a lower alkyl ester thereof. (B) One or more compounds in which 2 moles of N,N-dimethylhydrazine and 1 mole of a diisocyanate compound are bonded with urea are added to a high molecular weight compound with an average molecular weight of 50,000 or more prepared by reacting, at a concentration of 0.01 to the high molecular weight compound. A highly safe composition made by adding ~10% by weight.