JPS6021618B2 - plasticized resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cellulose resin, vinyl acetate resin, and ethylene copolymer resin composition plasticized with mixed carboxylic acid esters of polyhydric alcohols.

Specifically, it relates to cellulose resins, vinyl acetate resins, and ethylene copolymer resin compositions plasticized with 3- to 60-valent polyhydric alcohol compounds esterified with lower aliphatic carboxylic acids and aromatic carboxylic acid mixtures. It is something.

Cellulose-based resins are generally more durable than other synthetic resins, and have excellent transparency, gloss, and optical selectivity, and also have a smooth surface and a good feel to the touch.

Therefore, the resins have a wide variety of uses, such as sheets, films, wire coatings, toys, medical equipment, and food packaging materials. However, this resin does not have thermoplasticity and must be melted at high temperatures during processing and molding, but at the same time it undergoes thermal decomposition and becomes colored. In order to reduce this, it is necessary to mix an appropriate plasticizer to lower the softening point. For such purposes, from the following, for example, triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl Glycolate, butylphthalylbutyl glycolate, op-toluenesulfonamide, triacetin or pentaerythritol tetraacetate, etc. have been used. However, the above plasticity has
Compatibility with cellulose resin, plasticization efficiency, non-volatility,
Currently, there is no one that satisfies a wide range of properties such as stability against heat and light, non-migration, non-extractability, and water resistance, and this is currently an obstacle to further expanding the use of the resin composition. be.

In addition, plasticizers are often used for vinyl acetate resins and the like to improve brittleness and lower the film forming temperature.

However, there is no plasticizer developed specifically for polyvinyl acetate, and dibutyl phthalate, a general-purpose plasticizer for PVC, is being used. In addition, dialkyl glycol esters and the like are also used, but resin compositions obtained using these plasticizers still have the drawback of not exhibiting sufficient processability or low-temperature properties.

Furthermore, ethylene-vinyl acetate copolymer alone is insufficient in terms of flexibility and texture, and further flexibility is desired, but a suitable plasticizer for such a copolymer has not yet been found. Not yet.

In view of the above-mentioned current situation, as a result of many years of research and consideration, the present invention has non-volatility, non-migration, non-extractability, water resistance, good processability, low surface tackiness, and good low-temperature properties. We have successfully developed plasticizers for cellulose resins, vinyl acetate resins, and ethylene copolymer resins.

That is, the present invention relates to a plasticized cellulose resin, a vinyl acetate resin, and an ethylene copolymer resin containing at least one mixed carboxylic acid ester of a polyhydric alcohol represented by the following general formula [1]. The present invention relates to a composition.

(In the formula, ■ indicates a trivalent to hexavalent polyhydric alcohol residue,
R represents a methyl or ethyl group, R2 represents an ethyl, propyl or isopropyl group, and R3 represents a phenyl, alkylphenyl, arylalkyl or aryloxyalkyl group.

However, when R is an ethyl group, R2 represents a propyl or isopropyl group. 1, m and n each represent a number from 1 to 4, and the total of 1, m and n represents a number from 3 to 6.

In addition, when the same symbol exists in the same molecule, it may be the same or different. ). Specifically, the polyhydric alcohol residue indicated by ■ is a trivalent to hexavalent polyhydric alcohol residue, and specifically, glycerin, diglycerin, triglycerin, tetraglycerin, 2-methyl-2-methylol-1, 3-propanediol, 2,4-dihydroxy-3-methylolbentane, 1,2,6-hexanetriol, erythritol, bentaerythritol, diventaerythritol, ditrimethylolpropane, ditrimethylolethane, trimethylolpropane, 2,2
-dimethylol-3-hydroxybutane, 1,2,3-
Butanetriol, 1,2,3-benthanetriol,
Examples include residues such as 2-methyl-1,2,3-propanetriol, xylitol, sorbitol, mannitol, glucose, maltose, lactose, and tris(2-hydroxyethyl)isocyanurate.

? As the aromatic ring-containing carboxylic acid represented by R3COH,
Benzoic acid, o-, m-, p-tolylic acid, ethylbenzoic acid, n-butylbenzoic acid, t-butylbenzoic acid, octylbenzoic acid, phenylacetic acid, phenylpropionic acid, phenoxyacetic acid, 2-phenoxybutyric acid, etc. .

The plasticizer represented by the above general formula [1] is used in an amount of 5 to 20 parts by weight based on 10 parts by weight of the cellulose resin, vinyl acetate resin, and ethylene copolymer resin, depending on the purpose. However, it is particularly preferred to use 20 to 10 parts by weight. Examples of the resins used in the present invention include cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose butyrate, cellulose nitrate, polyvinyl acetate, ethylene vinyl acetate copolymer, and ethylene-acrylic acid copolymer. However, the plasticizer of the present invention is particularly useful for di- or triacetyl cellulose.

Furthermore, the performance of the composition of the present invention may be improved by using other known plasticizers depending on the purpose.

Next, the present invention and the remarkable effects obtained by the present invention will be explained using examples.

These Examples show only one example of the present invention, and the present invention is not limited in any way by these Examples. Example 1 Acetyl cellulose (degree of acetylation 61.5%, degree of polymerization 260
) in a mixed solvent consisting of 9 parts by weight of methylene chloride and 1 part by weight of methyl alcohol,
A solution having a concentration of 15% by weight was prepared.

To this, the plasticizer of the first notation was mixed in an amount of 1% by weight based on acetyl cellulose, and the solution was cast onto a metal support to approx.
．． A film was formed to a thickness of one rib. Next, various performance tests were conducted using the obtained film. The results are shown in Table 1 below. However, in Table 1 *1: ASTM D-638-67r *2: 10 indicates bleeding *3: 170 "○, weight loss after 3 special intervals *4: Polyhydric alcohol constituting the residue Candle Example 2 Acetylcellulose (acetyl cellulose 55.0%, polymerization degree 160
) 10 parts by weight, 4 parts by weight of the plasticizer shown in Table 2 and a usual stabilizer are blended, extruded and pelletized,
Test pieces were made using a screw-type injection molding machine.

Next, various performance tests were conducted using the obtained test pieces. The results are shown in Table 2. However, in Table 2 *I ASTM ○ 638 *2 ASTM D 648 *3 ASTM D 1499 Weathering test The surface of the test piece after 60 feeding hours was visually judged (x indicates severe deterioration).

) *4 Test piece used in ASTM D 648 at 55℃
, The state after being left in the field for 2 hours under 100% RH conditions was visually judged (x indicates a severe dimensional change).

) Brain Ship Example 3 Acetyl cellulose (degree of acetylation 53.4%, average degree of polymerization 2
60) Mix 10 parts by weight of Plasticizer 3 having the composition in Table 3, heat for 10 minutes at 195:00, and then heat at 195:00 for 10 minutes.
Pressing was performed under the conditions of 00 x 300 kg/f for 10 minutes to produce a sheet.

The gelation condition, bleedability, coloring property, and fire resistance were observed. The results are shown in Table 3. However, *1 in Table 3 is the proportion (%) of plasticizer eluted into water.

From the results in Funanaka Table 3, it can be seen that the plasticizer according to the present invention has excellent coloring resistance, compatibility, and especially water resistance, does not bleed, and has good gelation.

Example 4 Ethylene-acrylic acid copolymer (acrylic acid 13% by weight)
) and 1 part by weight of a plasticizer were thoroughly kneaded on a 120 minute roll mill.

The plasticized copolymer composition was then removed from the mill and its physical properties were measured. The results are shown in Table 4. Measurement method Tensile strength: ASTM D 638-67R Elongation: ASTM D 638-6 Stiffness: ASTM D 882-61T Ship Example 5 Ethylene-vinyl acetate copolymer (ethylene: 75% by weight)
10 parts by weight of the plasticizer and 3 parts by weight of the plasticizer were processed using a mixing roll to form a film having a thickness of 1.

Mechanical properties etc. were measured using this film. The results are shown in Table 5. Measurement method Tensile modulus: ASTMD 747-63 Tensile strength: ASTM D 638-6 Water resistance: ASTM D-1043-61T Transparency: JISK 6714 Ship length ○× Ri 33 ○○ Banless Isoko QQ Shaga Vine 99 Total Thin Cloud Q ■ 3. * From the results in Table 5, it can be seen that the plasticizer according to the present invention improves transparency and is particularly excellent in compatibility, extensibility, and low-temperature flexibility.

Example 6 An emulsion was prepared by adding 30 parts by weight of vinyl acetate monomer, 3 parts by weight of a plasticizer, 2 parts by weight of a nonionic surfactant, an appropriate amount of a catalyst (hydrogen peroxide redox), and water to make a total of 10 parts by weight. The mixture was poured onto a plate and placed in a warmer at around 30 qo to form a film with a thickness of 0.4 ribs.

Next, after drying this film in a vacuum desiccator,
300% or 500% modulus (
Trial length 25 arcs, width 0.5 skins, thickness 0.04 skins, tensile speed 1
00 skin/min) and the weight loss of the film was measured when heated at 100 degrees Celsius for 1Q hour. The results are shown in Table 6.

From the results in Table 6, it is clear that the plasticizer according to the present invention has excellent flexibility, properties, and extensibility, and is low in volatility.

Claims (1)

[Scope of Claims] 1. A plasticized cellulose resin, vinyl acetate resin, and ethylene copolymer resin composition containing an ester compound represented by the following general formula [I]. (In the formula, (A) represents a trivalent to hexavalent polyhydric alcohol residue, R_1 represents a methyl or ethyl group, R_2 represents an ethyl, propyl or isopropyl group, and R_3 represents a phenyl, alkylphenyl, aryl group. It represents an alkyl or aryloxyalkyl group. However, when R_1 is an ethyl group, R_2 represents a propyl or isopropyl group. l, m and n each represent a number from 1 to 4, and the total of l, m and n is from 3 to Indicates the number 6.If the same symbol is in the same molecule, it may be the same or different.)