JPH09132709A - Resin composition and product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition comprising a specific biodegradable copolymer and a solvent, excellent in processability, safety and stability, having good biodegradability, thereby excellent in environmental pollution prevention, and useful for processed paper for printing and wrapping, printing inks, etc. SOLUTION: This resin composition comprises (A) a biodegradable copolymer having ester groups and amide groups (e.g. a copolymer resin having 5-80wt.% of polyamide units and produced from a 3-12C lactone compound and a polyamide-forming compound comprising the nylon salt of a 4-12C dicarboxylic acid and a 4-12C diamine or a 4-12C aminocarboxylic acid, and having a melting point of >=60 deg.C), (B) an alcoholic solvent such as methanol, ethanol, propanol or butanol, and, if necessary, further water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an alcohol-soluble polyesteramide composition. More specifically, a soluble polyesteramide-based composition and an alcohol,
The present invention relates to a resin composition which is biodegradable and is excellent in paintability, adhesiveness and flexibility and is environmentally friendly, and a product using the same.

[0002]

2. Description of the Related Art Generally, a resin called polyamide (nylon) is currently widely used for fiber materials, engineering plastics, powder coatings and adhesives. Some of them are soluble polyamides that are soluble in solvents such as alcohol and water, and are used as solution type adhesives, synthetic leather and fiber treating agents. Recently, photosensitive resins, photoresist base materials, ceramic binders, paints,
It is also used as a vehicle for ink. The general production method of this soluble polyamide is polyamide 6,6
6, 610, 12 and the like by means of multi-component copolymerization, and those by alkoxy-modification, etc. In addition, a production method by means of multi-component copolymerization of aliphatic rings and heterocycles is disclosed in JP-B-49-2752
No. 2,27523. As the alcohol-soluble polyamide, Japanese Patent Publication No. 35-14719, 4
0-10068, 45-7330, 49-43565
JP-A-48-42049, 50-7605, 4
It is disclosed in Japanese Patent Publication No. 9-76602 and the like. But,
These polyamides, like other plastics, contribute to pollution when washed away in the natural environment.

Therefore, a biodegradable polylactone amide is used as a biodegradable resin composition which is decomposed by microorganisms when the product is washed out in a natural environment or when waste water is treated by copolymerizing with polylactone diol or the like. Resin
JP-A-5-156008, 15609, 156010
It is disclosed in Japanese Patent Publication No.

[0004]

However, the conventional biodegradable polylactone amide resin is a fluid resin composition containing a solvent, which is uniform and has a sufficiently high resin concentration because a suitable solvent cannot be found. Alternatively, it was difficult to obtain a solution. Therefore, the processing method is limited to a processing method such as melt spinning in which a resin simple substance is heated to its melting point temperature, and the manufacturing method and application of the product are limited. Further, even if a resin composition containing a stable solvent was obtained by using a special solvent, it was not practical because of the toxicity, corrosiveness, and odor of the solvent.

The present invention aims to solve such problems.

[0006]

The present invention basically has the following configuration in order to achieve the above object.

"A resin composition comprising a biodegradable copolymer having an ester and an amide group and a solvent containing an alcohol solvent." That is, the above-mentioned problem is to solve a specific polyamide-forming compound and a specific lactone compound. By reacting, to obtain a copolymer in which the polyamide unit and the polylactone unit are in a specific ratio,
Further, it is achieved by a resin composition in which the present copolymer is dissolved in a solvent mainly containing alcohol.

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, aminocarboxylic acids having 4 to 12 carbon atoms and dicarboxylic acids having 4 to 12 carbon atoms and 4 to 12 carbon atoms.
80 to 5% by weight of polyamide unit obtained by reacting one or more polyamide-forming compounds selected from nylon salts consisting of 12 diamines with a lactone compound having 3 to 12 carbon atoms
It has been found that the copolymer resin which is the above can be applied as a plastic molding material which is completely decomposed by microorganisms and is also dissolved in alcohol. Especially preferred as the lactone compound used in the present invention is ε-caprolactone, and its polymer polycaprolactone (hereinafter abbreviated as PCL) has biodegradability, but its use is limited as a plastic molding material because of its low melting point. It was being done. On the other hand, a polyamide resin has a high melting point and is used as a plastic molding material in a wide range of fields such as fibers, films and molded products, but a high molecular weight resin does not have microbial degradability. In the present invention, by co-polymerizing both, a practical microbial degradable plastic molding material is obtained while maintaining the microbial degradability of PCL.

Considering the resin strength and the like, PCL having a number average molecular weight of 530 to 120,000, preferably 1,000 to 50,000 is used.

The polyamide component is formed from a polyamide-forming compound. A polyamide-forming compound means a compound capable of forming an amide oligomer or amide polymer by an amide bond, and is a chain compound having a carboxyl group at one end of the molecule and an amino group at the other end, or a ring-openable compound in the ring. And a cyclic compound having an amide bond.

In the present invention, a nylon compound composed of an aminocarboxylic acid having 4 to 12 carbon atoms and a lactam having 4 to 12 carbon atoms is preferably used as such a compound. Particularly preferably, ω-aminocaproic acid,
From the economical aspect, ε-caprolactam is used.

In the present invention, it is also preferable to use a dicarboxylic acid in order to adjust the copolymerization reaction and the molecular characteristics of the produced resin, particularly preferably a dicarboxylic acid having 4 to 12 carbon atoms, and more preferably adipic acid. Can be mentioned.

The proportion of PCL and polyamide component is 90 to 5% by weight, preferably 80 to 10% by weight of PCL component in the copolymer.
The proportion is 20% by weight, particularly preferably 70 to 20% by weight. This copolymer can be obtained by heating and reacting PCL and a polyamide component monomer in the presence of a catalyst. This reaction is a transesterification reaction between PCL and an amide, and a conventional transesterification reaction catalyst such as anhydrous zinc acetate, zinc stearate, antimony trioxide is used as a catalyst. The amount of catalyst used is 100
The amount is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight. The melting point of the copolymer thus obtained is usually in the range of 70 to 170 ° C. When the ratio is the same, the melting point can be lowered by raising the reaction temperature or prolonging the reaction time. The copolymer of the present invention includes a heat-resistant agent, an antioxidant, a light-proofing agent, a colorant such as a dye / pigment, an antistatic agent, a conductive agent, a flame retardant, a reinforcing agent, a filler, and a plasticizer, if necessary. Additives can be optionally added.

An example of the synthesis method is shown below.

60 parts of ε-caprolactum, 5 parts of aminocaproic acid, 2.4 parts of adipic acid, polycaprolactone diol (Placcel 220 manufactured by Daicel Corp., molecular weight 2)
000) 33.2 parts and 0.1 part of antimony trioxide as a ring-opening reaction catalyst are charged in a reaction vessel and sufficiently replaced with nitrogen. The temperature was raised to 240 ° C with stirring and about 1 in a nitrogen stream.
Pre-react for a period of time. Then, 0.1 part of tetrabutoxy titanate was added as a dehydration condensation reaction catalyst, the temperature was raised to 260 ° C., and the polycondensation reaction was performed for about 1.5 hours under reduced pressure of 1 mmHg or less over about 1 hour. To get

The copolymer of the present invention is soluble in C _{1 to} C ₄ lower alcohols, and its resin solution is used for surface treatment and surface modification of fibers, films, leather, paper and various parts. It can be used as a substance, an adhesive or the like.

Regarding the solubility of the polymer, the solubility and solution stability are higher when water is used in combination than when alcohol is used alone as a solvent. The proportion of water used in combination is 2 to 30% by weight, preferably 5 to 25% by weight, and the dissolution rate can be swiftly and easily carried out by heating to the boiling point while stirring. The dissolution method is not particularly limited, but a large amount of dissolution can be easily performed by the following method. 50% or higher, preferably 60 ° C or higher, by adding about ⅓ amount of the polymer that dissolves in a solvent at room temperature with stirring,
Particularly preferably, the temperature is raised to the boiling point to dissolve. After completely dissolving, the temperature is cooled to 50 ° C. or lower, the remaining polymer is added, and then the temperature is raised to the boiling point again to dissolve. The storage stability of the solution varies depending on the solvent composition, the resin concentration, and the storage temperature, and generally, the lower the resin concentration and the higher the storage temperature, the higher the stability. Even if turbidity or gelation occurs during storage, it can be returned to a uniform and transparent solution by reheating.
For preventing gelation, phenol, benzyl alcohol, chloroform, carbon tetrachloride, etc. are effective. The amount of addition
It is effective at 5 to 15% by weight in the solvent. In addition, as a solvent component of the copolymer resin composition of the present invention, a composition having excellent solution stability can be obtained even if hexafluoroisopropanol or orthochlorophenol is used, but the solvent is expensive. It also has a peculiar odor and is not practical. Although the concentration of the resin solution of the present invention varies depending on the composition and molecular weight of the resin used, the coating method, the shape of the article to be coated, the solvent composition, etc., it is usually used at a concentration of 1 to 60% by weight. The copolymer resin of the present invention has microbial degradability and enzyme degradability in addition to the properties of conventional soluble polyamide resins, and is used as an adhesive or treating agent for natural products having biodegradability. Does not impair their properties. In particular, when used for processing paper products and the like, it is not necessary to remove the resin at the time of recycling and can be treated in the same manner as conventional natural adhesives and treatment agents such as starch. As a paper product, a liquid container, particularly a mill carton or the like is suitable. When the copolymer resin solution of the present invention is used for processing a paper product or the like, a coating machine that is suitable for all purposes, such as a commonly used coating machine, can be used. For example, blade coater, air knife coater, roll coater, metering bar coater, gravure coater, curtain coater.
Data, spray coater, beat coater, brushing coater
And the like.

The polyesteramide resin of the present invention is
It also has a strong adhesion to metals without primer coating. Conventional polyamide-based adhesives have been widely used as hot-melt adhesives for metals, but in recent years in the field of producing metal containers such as food cans and petroleum cans, chrome-plated steel or surface instead of tin-plated steel is used as the can body material. Treated TFS (tin-free steel sheet) such as a chromic acid-treated steel sheet having an oxide film on its surface has been widely used. Since this TFS cannot be soldered, nylon-11
Adhesion of the side seam portion has been carried out by using a 12-type polyamide hot melt adhesive, but it has drawbacks such as an essential primer and low water resistance. The degree of polymerization of the polyesteramide resin of the present invention is not particularly limited, but generally speaking, in orthochlorophenol, the relative viscosity at a concentration of 0.5% at 25 ° C. is 1.00 to 3.
Anything in the range of 0 can be set arbitrarily, especially 1.2 ~
Those in the range of 2.0 can be preferably used.

[0019]

Next, the present invention will be described in more detail by way of examples. All parts in the examples are shown by weight.

-Synthesis method Synthesis example: 57.96 parts of aminocaproic acid, 47.4 parts of polycaprolactone diol (Placcel 220 manufactured by Daicel Corp., molecular weight 2000, abbreviated as PCL), adipic acid 3.4.
Charge 6 parts and 0.1 part antimony trioxide into the reaction vessel,
After sufficiently substituting with nitrogen, the temperature was raised to 240 ° C. with stirring, and a preliminary reaction was performed in a nitrogen stream for 1 hour. Then, 0.05 part of tetrabutyl titanate was added, and then 260
The temperature was raised to 0 ° C. and the pressure was reduced to 1 mmHg or less to carry out a polycondensation reaction for 1.5 hours to obtain a transparent polyesteramide resin (A-3). Nylon 6 determined by elemental analysis
The proportion of polyamide units consisting of was 50% by weight.
Similarly, the proportion of polyamide units is 80
%, 60% by weight, 25% by weight, 5% by weight of polyesteramide resin (A-1, 2, 4, 5) were produced.

Solubility 1 Examples 1 and 2, Comparative Examples 1 to 18 10 parts of the resin (A-3) prepared in the Synthesis Example was added to 100 ml of an organic solvent with stirring, and the mixture was heated to 70 ° C. for 5 minutes. The state of the resin composition at room temperature after dissolution over time and standing overnight was evaluated. The results are shown in Table 1.

[0022]

[Table 1] Good transparency / fluidity: ○ Partially dissolved or turbid: △ Not dissolved: × As shown in Table 1, Examples 1 and 2 are transparent.・ Fluidity was good, and solvent characteristics were satisfactory.

Solubility 2 Examples 3 to 7 and Comparative Example 19 Ten parts of each of Resins A-1 to A-5 were placed in 100 ml of a mixed solvent having an ethanol / water ratio of 80:20 (volume ratio). A resin composition was prepared by heating to 0 ° C., and dissolution stability and solubility were tested. The results showed good solubility as shown in Table 2.

[0024]

[Table 2] Completely dissolved ... ・ ○ Not dissolved ・ ・ ・ × ・ Adhesiveness Examples 8 and 9, Comparative Examples 19 and 20 15 parts of the polyesteramide resin of the present invention Was dissolved in 85 parts of ethanol to prepare a resin composition. 35 this solution
A micron electrolytically treated copper foil and a 50 micron aluminum foil were coated with an applicator to a dry film thickness of about 10 microns. Two coated surfaces were stuck together and pressure-bonded at 170 ° C. for 10 seconds to prepare a 1 cm wide sample. For comparison, commercially available Goodyear "Vitel" 207 (copolymerized polyester) and Toyobo "Byron" 30p (copolymerized polyester) were similarly evaluated. Adhesive strength is JIS
According to K-6854, T-peel peel strength was measured by using Tensilon manufactured by Toyo Seiki. The peeling speed was measured at 20 cm / min. The results are shown in Table 3.

[0025]

[Table 3] Adhesiveness ・ ・ ・ ○ No adhesiveness ・ ・ ・ × ・ Low temperature stability Examples 10, 11 and Comparative Examples 21, 22 The low temperature stability of the polyesteramide resin solution is ethanol / ethyl acetate = 9 / 35% in 1 (weight ratio) mixed solvent
This was done by dissolving the resin to the concentration. As comparative resins 1 and 2, alcohol-soluble polyamides corresponding to JP-B-40-10068 were used. That is, reference resin 1 (hereinafter, reference resin 2 in parentheses) is 0.777 parts by weight (0.777 parts by weight) of a polymerizable fatty acid obtained from tall oil fatty acid, 0.223 parts by weight of acetic acid (0.223 parts by weight). ), 0.90 parts by weight (0.80 parts by weight) of ethylenediamine, and 0.10 parts by weight (0.20 parts by weight) of diethylenetriamine are non-biodegradable resins which are products obtained by heating. Table 4 shows the results
It was shown to.

[0026]

[Table 4] Good fluidity: ○ Semi-gel: △: No fluidity: × ・ Ink characteristics: Examples 12, 13 and Comparative Examples 23, 24: Polyesteramide resin obtained in Example Each was dissolved in ethanol to prepare a solution (a) having a resin concentration of 35%. On the other hand, to prevent blocking and improve heat resistance, use digested cotton RS1 / 2 with isopropanol / ethyl acetate = 1
Solution of 25% resin concentration (b) dissolved in a mixed solvent of 1/1
Was adjusted. 76 parts of resin solution (a), resin solution (b)
And 15 parts of Watch Young Red Calcium as a pigment were charged in a ball mill and dispersed for 16 hours. The resulting red ink was printed on EC-treated stretched polypropylene and soft aluminum with a wire coater # 13 and dried at room temperature for 16 hours. The printed matter was evaluated for adhesiveness, water resistance, blocking resistance, and heat resistance. Reference resins 1 and 2 are the same as those in Table 4. Table 5 shows the results.

[0027]

[Table 5] The evaluation method and criteria are as follows.

(1) Adhesiveness: Peeling test using Nichiban cellophane tape What the printing surface cannot be taken on the side of the cellophane tape ... ○ What part of the printing surface is taken on the side of the cellophane tape ... △ Most of the printing surface Is taken on the side of the cellophane tape. × (2) Blocking resistance: Using an IC block tester, stuck at 60 ° C for 24 hours, the printing surface is perfect and there is no peeling resistance. If there is a star-like point on the part △ △ The printing surface is fused and it is difficult to peel off × (3) Water resistance: The printed matter is immersed in tap water for 4 hours, then underwater Printed surface is perfect after 10 times ..... ○ Cracked but no surface loss ..・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ × (4) Heat resistance: Thermal tilt tester (Toyo Seiki Seisakusho) using 1 kg / cm ^2, and 1 second thermocompression bonding, printing the heat resistance of the printing surface in the evaluation 100 ° C. But ··············· ○ 100 ° C. printed surface perfection A part of the surface is taken by the heat seal bar ... △ Most of the printed surface is taken by the heat seal bar at 100 ° C. × Photosensitive resin Example 14 Polyethylene glycol having a number average molecular weight of 1000 Acrylonitrile was added to both terminals, and an equimolar salt of α, ω-dicarboxypolyoxyethylene and hexamethylenediamine obtained by hydrolysis of this: 20 parts, aminocaproic acid: 40 parts, polycaprolactonediol (Placcel 220 / (Daicel): 40 parts were polymerized by the method of the present invention to obtain a polyesteramide resin having an amount of polyoxyethylene in the main chain: 16%. 60 parts of the polyesteramide resin obtained here, 28 parts of a reaction product of metaxylylenediamine and glycidyl methacrylate, chloro-2-methacrylate
Oxypropyl 5 parts, methylenebisacrylamide 3
Parts, benzophenone 3 parts, triphenylphosphine 1
And 0.02 parts of phenothiazine were dissolved in a mixed solvent of ethanol / water = 80/20 (weight ratio) so that the concentration became 65%, the solution was cast into a sheet and dried at 60 ° C. A resin sheet was obtained. Next, a 0.3 mm thick iron plate with an adhesive layer, the above-mentioned photosensitive resin sheet, and a thickness of 0.1 mm
The polyester cover film of 1 was laminated and hot press molded to obtain a photosensitive original plate having a total thickness of 0.9 mm. After that, the cover film of the photosensitive original plate was peeled off, the negative film was adhered thereto, and exposed at a distance of 65 cm by a 2 KW ultra-high pressure mercury lamp for 2 minutes. This was ethanol / water at a temperature of 30 ° C. and a pressure of 3 kg / cm ² = 90 / When the unexposed area was removed by spraying at 10 (weight ratio) for 3 minutes, the image lines of the negative film were faithfully reproduced and a sharp printing plate with a sharp relief head was obtained. In addition, the transparency and printing durability of the printing plate had practically sufficient values.

Further, only the resin portion of the exposed printing plate was peeled off, and the resin was freeze-pulverized to 150 to 70 microns using liquid nitrogen. As a result of biodegradability using this crushed resin by an activated sludge method (coulometer) according to JIS K-6950 (1994), it was found that the resin had an easy degradability comparable to PCL.

Evaluation of cohesiveness Example 15 A 0.5% kaolin suspension was added with 1/100 volume of 0.2% resin emulsion or 1% of 2% resin emulsion.
After adding 1000 volumes and stirring vigorously, the mixture was allowed to stand. In the case of the polyester amide (A-3) of the present invention, the polyester amide rapidly aggregated and settled after standing, but no change was observed in PCL.

[0031]

The polyesteramide resin composition of the present invention is excellent in processability, safety and stability, has good biodegradability, and has an effect of preventing environmental pollution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03F 7/037 D21H 1/34 J

Claims (9)

[Claims] 1. A resin composition comprising a biodegradable copolymer having ester and amide groups and a solvent containing an alcohol solvent. 2. The resin composition according to claim 1, wherein the ratio of the ester to the amide in the copolymer is 20:80 to 95: 5. 3. The resin composition according to claim 1, wherein the copolymer has a melting point of 60 ° C. or higher. 4. The alcohol solvent is methanol, ethanol, n-propanol, isopropanol, (n
2. The resin composition according to claim 1, comprising one or more selected from-, t-, sec-) butanol. 5. The resin composition according to claim 1, wherein the alcohol solvent of claim 4 contains water. 6. A resin processed product, which can be produced using the resin composition according to claim 1. 7. A resin-processed product, wherein the product according to claim 6 is a printing, a processed paper for packaging, a liquid container or a milk carton. 8. A resin processed product, wherein the product according to claim 6 is a printing ink. 9. A resin processed product, wherein the product according to claim 6 is a photosensitive resin plate for printing or a photoresist base material.