JPS60235852A - Cellulose ester film - Google Patents

Abstract

PURPOSE:To obtain a cellulose ester film free of degeneration, coloration or inclusion of insoluble matter, by incorporating a specified compound into a cellulose ester film. CONSTITUTION:A compound of formula I (wherein R is H, alkyl, an aryl or allyl) (e.g. a compound of formula II or III) is incorporated into a film of the cellulose ester of a lower fatty acid (e.g. cellulose acetate or cellulose propionate). In formula I, the alkyl is preferably of 1-18C; the alkyl and aryl may be substituted by a halogen atom, an alkyl of 1-3C, an alkoxy, phenyl, phenoxy, etc.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to cellulose ester films.

In particular, the present invention relates to a cellulose ester film characterized in that a lower fatty acid ester solution (referred to as "dope") during its production is stabilized.

(Prior Art) Cellulose ester is formed into a film by a solution casting method and is used in films that require a high level of transparency, such as photographic supports, moving picture films, packaging films, and the like. Cellulose ester solution film production generally uses a low boiling point, evaporative solvent and a plasticizer.

The solution is dissolved with other optional additives to form a highly viscous but fluid solution, which, after filtration, is poured onto a Hopper Giesser, polished band or drum. It is then partially dried, stripped from the band or drum, and further dried to evaporate any remaining solvent and form a film.

When preparing cellulose ester dope.

Although it dissolves in a solvent, the dope must be heated during its dissolution, or heated to defoam air bubbles during dissolution or filtration, or the dope must be left for a long time after it has been prepared before it is cast. It's very strong.

(Problem to be solved by the invention) When dope is heated or left for a long time, it absorbs a small amount of moisture contained in the organic solvent or moisture in the air, and the cellulose ester in the dope is hydrolyzed and denatured. It may cause In particular, if a container containing iron is used, the iron plays a catalytic role and promotes hydrolysis, and the lower fatty acids produced during this hydrolysis further promote hydrolysis.

When cellulose ester is hydrolyzed and denatured, it produces a yellowish-brown color and a gel that is insoluble in solvents, which may cause failures in film production or significantly reduce the quality of the film produced. Therefore, it is desirable to suppress the modification of cellulose ester as much as possible.

U.S. Patent No. J, J, 4 discloses that IC/, λ propylene oxide is added to the dope as a substance to scavenge the acid generated by the slow hydrolysis to prevent the modification of cellulose ester.
It is disclosed in issue 7/.

However, 2-propylene oxide is easily decomposed and unstable, making it difficult to handle safely.

(Objective of the Invention) The first object of the present invention is to provide a cellulose ester film that does not undergo denaturation, become colored, or contain insoluble matter.

1.2 It is an object of the present invention to provide a method for producing a cellulose ester film using a cellulose ester dope with improved K stability.

The third object is to provide a method for improving the stability of cellulose ester dope using a non-toxic and safe method.

(Means for Solving the Problems) These objects of the present invention were achieved by incorporating a compound represented by the following general formula (I) into a cellulose ester dope.

(I) However, R represents a hydrogen atom, an alkyl group, an aryl group, or an allyl group.

The alkyl group of R in general formula (I) has carbon atoms i, it
Preferably, each of the alkyl group and the aryl group may be substituted.

Examples of the substituent include a halogen atom, an alkyl group having 7 to 3 carbon atoms, an alkoxy group, a phenyl group, a phenoxy group, and the like.

Specific examples of the compound represented by general formula (I) include the following.

(I) (■) (III) (IV) (V) (Vl) (■) (■) (IX) (XI) (■) The cellulose ester used in the present invention is a lower fatty acid ester of cellulose, Examples include cellulose triacetate, cellulose acetate such as cellulose diacetate, cellulose propionate), cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, and the like. As the solvent for these cellulose ester dopes, for example, a mixed solvent system consisting mainly of chlorine-containing solvents such as methylene dichloride and ethylene dichloride with a boiling point of about 100' C. or less and mixed with other solvents, or acetone.

Ketones such as methyl ethyl ketone, esters such as ethyl vinegar, methanol, ethanol, propatool,
Alcohols such as tsutanol, ethers such as dioxane and tetrahydrofuran, etc. can be used, but are not limited to these.

Plasticizers added to the dope vary depending on the type of cellulose ester, but examples include phthalate esters such as dibutyl phthalate and dioctyl phthalate, and triphenyl phosphate.

Phosphates such as tricresyl phosphate, adipate esters such as dibutyl adipate, dicoethylhexyl adipate, etc., esters of sodium glycol such as ethylene glycol cyphthylate, ethylene chloride dipropionate.

Examples include diacetin, triacetin, and glycerin derivatives.

If necessary, the dope also contains fine particles such as silicon oxide as a matting agent, and a coloring agent for N color.

There is no problem even if an antistatic agent is added.

The concentration of cellulose ester in the dope varies depending on the casting method for film formation, the molecular weight of cellulose ester, etc., but it ranges from about IO% (weight) to ≠ θ (weight)
The amount of plasticizer is generally 7% of cellulose ester (
(weight) or G), approximately 20% (weight) is added.

The amount of bulking of the compound represented by the general formula (I) of the present invention varies depending on the concentration of the dope and the type of cellulose ester, but it is 0.00% by weight with respect to the cellulose ester dope.
TL is desirable from 2nd.

Preferably it is 0.001% to 3%.

Cellulose ester film H of the present invention Cellulose ester dope having the composition as described above is filtered, polished with a potspar Giesser, cast on a metal band or drum, and partially dried (e.g., 7 to 15 minutes at 10 to 1000C After a few minutes), the band or drum is stripped and dried (e.g. IO).

~/30 In DC! −μθ min) to evaporate the remaining solvent.

There are no particular limitations on the method for producing the cellulose ester film in the present invention, and methods commonly used in the art can be suitably used.

Regarding the W method for cellulose ester films, for example, U.S. Patent No. 2≠riλ27g, U.S. Patent No.
Same No.273ri01, Same No.-≠riλ277, Same No.2
No. 337,310, No. Jj474OJ, No. 2≠2
Utah No. 7g, λt077044, British Patent No. 1u
No. 073/, No. 73319.2, Special Public Sho μj-ta 0
7≠ publication, same lter≠, 5'jμ publication, 4th reference z
It is possible to refer to the descriptions in the tiII publication and the like.

Examples are shown below.

Examples The following dope formulation was prepared.

Cellulose triacetate (acetyl group ≠ 3. 3 parts by weight) iro parts by weight methylene dichloride 7 parts by weight methanol / parts by weight tsutanol t♂ parts by weight triphenyl phosphate 12 parts by weight 200 g each of this dope Add orthophenylphenol glycidyl ether (exemplary compound V) to one side and
Dope A was added with g added, and B was the dope without g added. A small piece of steel (SUS, 30 pieces) (g0
5&Xλo')6×i%) in an autoclave.7
00CVC heating! I left it for days. No change was observed in Dope A, but in Dope B, a brown gel-like substance was observed to adhere to the surface of the steel.

Example 2 The following dope formulation was prepared.

Cellulose estate (3 parts of acetyl group, 300 parts of polymerization, λ10): methylene dichloride, 300 parts by weight, methanol, 60 parts by weight, ethylhexyl phthalate, 1 part by weight. Divide this dope into 3 parts of 1,200 parts by weight and add Dope C.

D,E,! :did. Orthoethylphenol glycidyl ether (exemplified compound (■)) 3y was added to Dope C, but Dopes D and EK were not added.

Small pieces of doped C and DK steel (uo'lxλOXX
/X) was added, and the mixture was placed in an autoclave and left at OoC for 7 days. E did not add steel or heat.

Dopes C, D, and E are combined with a furnace material made of three sheets of gold cloth/flannel/F paper, and the area of 3 mm in diameter is μkl? /α2 pressure. Dope C and E could be filtered, but dope D
could not be filtered.

Example head The following dope formulation was prepared.

cellulose tocetate frame (acetyl group λ,! H, butyryl group/79M, heavy Next time 3oo) ISO weight part Methylene chloride 〇〇 parts by weight Ethylene chloride 200 parts by weight Ethanol to parts by weight Triphenyl phosphate 71 parts by weight All of this dope is divided into λ parts F and G.

It was set as H. Dope FIC uses exemplified compound (III), and dope G uses exemplified compound (V)? Add 3g of each and add dope HKFi without adding it. Put a small piece of steel ($O%XJ17XX/X) into each dope.

Leave it in an autoclave at 20°C for j days.

A brown gel-like substance adhered to the surface of the steel of Dope H, and was not dissolved by the adhered substance methylene dichloride/methanol CY2/r).

On the other hand, no change was observed in doped F and GVi.

The above cellulose ester dopes A, C, F, and G were cast onto a stainless steel band using a Hopper Giesser, dried at 10°C for io minutes, peeled off from the band, and dried at <ioo 0c, sf 7 min 1 s [drying]. Then, a cellulose ester film was formed.

These films have good transparency and no discoloration.

In addition, there was no insoluble matter mixed in, and O contained desirable properties as a photographic film.

Claims (1)

[Claims] A cellulose ester film containing a compound represented by the following general formula (1). (I) However, R is a hydrogen atom, an alkyl group, an aryl group, or a1)
represents a group.