JPS591544A - Production of photographic thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To produce the titled compsn. contg. less microgrit, by using TiO2 pigment obtd. by milling it under impact and then pulverizing it with a fluid energy pulverizer. CONSTITUTION:TiO2 having a surface treated with 0.2-1.2wt% (in terms of Al2O3) hydrated aluminum oxide and a weight reduction of 0.25-0.60% when heated at 300 deg.C for 30min, is milled under impact, e.g., hammer-milled and then pulverized by a fluid energy pulverizer such as steam mill or air mill to obtain TiO2 pigment. 5-40wt% TiO2 pigment and, if necessary, 0.01-5wt% lubricant such as fatty acid soap, fatty alcohol soap or metallic soap are blended with a thermoplastic resin such as PS.

Description

[Detailed Description of the Invention] The present invention relates to a photographic thermoplastic resin composition)
More specifically, the present invention relates to a photographic thermoplastic resin composition having extremely low microgrit.

Microgrit here refers to the process of producing photographic resin-coated paper by melt extrusion coating a photographic thermoplastic resin composition onto at least one side of a paper or synthetic paper substrate using a melt extruder, for example. Refers to minute foreign matter or minute particles that appear on the surface of the resin coated on the surface.

There are various main causes of microgrit, for example: 1) The thermoplastic resin used itself tends to generate a lot of gel.

2) When the molten resin is extruded from the melt extruder through the die into a film, there is a screen to maintain the temperature at an appropriate temperature, and if the flow is uneven, 3) A screen attached to the breaker plate in the melt extruder. 4) If there is a crack in the barrel liner inside the melt extruder 5) If there is a shortage in the barrel liner inside the melt extruder It is often resolved.

However, the most difficult microgrit countermeasures are:
Thermoplastic resin and titanium dioxide pigment (hereinafter abbreviated as T101)
For example, when preparing a mackerel masterbatch by melting and kneading with a pressurized knead such as a Banbury mixer, or creating a desired compound in which the pigment is contained in the resin at the desired composition ratio from the beginning. When used as a thermoplastic resin, relatively coarse Tie particles are dispersed in a thermoplastic resin and extruded into a film using a melt extruder.
This is a case where relatively coarse particles in the Tie protrude to the resin surface. If such a masterbatch that causes log grit is used and applied to resin-coated paper as a photographic support, it will cause serious problems! i wake up That is, when photographing a person using photographic resin-coated paper with black grit, if black grit appears in areas such as the face, the photograph has no commercial value.

Pigments used in masterbatches for resin-coated papers used as photographic supports are usually Tie because of their excellent whiteness, hiding power, resolution, etc.

is used.

In general, the average particle size of commercially available 110 filtration is 0.
．． It is 2 to 0.4 seconds. However, it almost never exists in the state of a single particle, and usually coexists with a state in which several particles, or even tens of particles, are condensed together. Of course, the numerical value of 0.2 to 0.4μ is an average particle size, so it is natural that it includes particles in which the size of a single particle itself is 1.0p or more.

In the pigment industry, a single particle is called a primary particle, and a particle that is agglomerated with several particles or more is called a secondary particle. As mentioned above, it is the secondary particles that pose a problem with the black grid. Among the secondary particles, the reversibly coagulated particles with a relatively low coagulation strength are destroyed by being given dispersion energy in the thermoplastic resin (for example, by a Banbury mixer, etc.), and the -secondary particles Sometimes it comes close to.

However, the coagulated particles, which have a high coagulation strength among secondary particles, are not destroyed in the thermoplastic resin, which has a relatively small dispersion energy, and are mixed as they are and exist as secondary particles in the masterbatch. When it is pressed in film form onto a paper or synthetic paper substrate through a machine, it appears as microgrit on the resin surface. Therefore, the reality is that the pigment industry is constantly concerned with how to eliminate these secondary particles. be.

For example, if we take the production of Tie Yu as an example, in a series of manufacturing processes, there is a sintering process using a rotary kiln, a compression dehydration process using a filter press, a drying process using a continuous dryer, etc., which are sufficient to develop secondary particles with high coagulation strength. Currently, they are manufactured through a process that meets certain conditions.

In the final stage of heating, impact pulverization is performed using a hammer mill, etc. to get as close to the next particle as possible.
Although it has undergone a pulverization process, it is not possible to sufficiently convert the secondary particles into secondary particles by this process alone.

Therefore, if the normally commercially available Tie is applied as it is to a photographic thermoplastic resin composition, only a photographic resin-coated paper containing a large number of microgrits will inevitably be obtained.

As a result of intensive research, the present inventors discovered a method for preparing T1 with almost no secondary particles, and by applying this 'L'10m as a component in a photographic thermoplastic resin composition, micro- This was a successful production of a photographic thermoplastic resin composition with almost no grit.

The TiO□ according to the present invention is produced in a conventional Ti1111m production process, after impact pulverization by a pulverizer used in the final version, such as a hammer mill, etc., by a fluid energy mill such as a steam mill. By passing it through, the crushing strength is further increased and the presence of secondary particles is reduced. More preferably, after passing through a fluid energy mill such as the steam mill, the material is further passed through a fluid energy mill such as an air mill to further increase the crushing strength and significantly reduce the presence of secondary particles. Most preferably, the T108 is heated at 300° C. for 30 minutes before passing through the above three types of crushers, that is, before passing through the impact pulverization Ia (e.g., a mill), which is the first of the three types to be subjected to the crushing process. When the weight loss is 0.25 to 0.60-,
Similarly, T108, which has almost no secondary particles, is obtained by successively passing through an impact pulverizer, a fluid energy mill such as a steam mill, and a fluid energy chamber such as an air mill. According to this pulverization method, after passing through a steam mill and fc, titanium dioxide reaches a relatively high temperature, so its moisture content decreases, and when it is further passed through an air mill, it approaches an equilibrium moisture value.

T10 according to the invention. Among them, the most preferable T10° is T10° before passing through the first pulverizer. However, at 300℃
The reason why the weight loss when heated for 1 minute is 0.25 to 0.60% is as follows.

That is, if the heating loss of Ti1l is less than 0.25%,
Since the T101 particles are strongly aggregated with each other, it is extremely difficult to pulverize the strongly bonded secondary particles into primary particles even if the particles are subsequently passed through several pulverizers. or,
If the heating loss of Tie exceeds 0.60 inch, this Ti
When melt-extruding a thermoplastic resin composition containing es into a film from a slit die of a melt extruder, needle-like or icicle-like deposits or stains (hereinafter simply referred to as die lip stains) may form on the tip of the die lip. There is a tendency for this to occur,
Unfortunately, this die lip stain tends to grow larger and larger as the melt extrusion time passes.

When this die lip stain occurs during melt extrusion coating, streaks appear in the vertical direction on the surface of the directly manufactured photographic support, and streak-like unevenness occurs due to uneven coating amount. At times, dirt adheres to the film and is coated, causing foreign matter to appear. As a result, the surface quality of thermoplastic resin-coated paper manufactured as a photographic support, for example, is significantly impaired, making it cold, unsuitable, and without commercial value as a photographic support that requires excellent surface quality. In addition, the only way to completely remove die lip stains once generated is to stop production and clean the die lip, which requires a great deal of effort and time and causes a significant drop in productivity. It turns out.

Furthermore, T10 before passing through the first crusher. If the heating loss of
8 became sticky and the grinding efficiency decreased significantly. Therefore, T10 according to the present invention. o before passing through the first crusher
! The heating loss of 1'10m is extremely important and 300℃
The weight loss when heated for 30 minutes is 0.25 to 0.601
must be strictly managed. However, even if the T10. Assuming that the heating loss (after 30 minutes at 300°C) is adjusted to 0.25 to 0.60%, 4,
For example, it is not possible to sufficiently crush solidified secondary particles into secondary particles using only an impact crusher such as a hammer mill.
10. It is difficult to pulverize strongly consolidated secondary particles into primary particles even if they are passed through a By using a different type of pulverizer, for example, a fluid energy pulverizer such as a steam mill, or a fluid energy pulverizer such as an air mill, it has been possible to improve the pulverization efficiency significantly. In other words, as for the effect on microgrit due to the combination of crushers, even when a fluid energy crusher such as a steam mill is used next to an impact crusher such as a hammer mill, a significant reduction in microgrit is observed, but in addition, an air mill The microgrit can be further reduced by passing it through a fluid energy grinder such as .

The photographic thermoplastic resin composition referred to in the present invention is produced by using the above-mentioned T108 according to the present invention as a polyolefin resin, for example.
It refers to a composition that is kneaded into a so-called thermoplastic resin such as a polystyrene resin or a polyester resin and is used as a part of a photographic material.

Other pigments in the photographic thermoplastic resin composition according to the present invention,
For example, coloring pigments such as Gunyo, Prussian blue, and Red Garla, and white pigments such as fine linearized zinc, barium sulfate, and antimony oxide may be added.Also, as necessary, for example, fatty acid-based, fatty alcohol-based, fatty acid amide-based pigments may be added. A lubricant such as ester, metal soap or the like may be added. The amount added is Tie
The range of o and oi to 5% by weight is preferable with respect to the resin composition containing s. Further, if necessary, an antioxidant, a fluorescent brightener, etc. may be added.

These materials may be mixed using a mixing machine such as a pressure motor, a two-diameter roll, a three-diameter roll, or the like.

T10. used in the practice of the present invention. As for the closing method, those having a rutile structure, those having an anatase structure, those made by the chlorine method, and those made by the sulfurization method can be used. Further, although both those without surface treatment and those with surface treatment can be used, those treated with an inorganic surface treatment agent, especially hydrous aluminum oxide <= cum, are suitable.

The surface treatment amount is preferably 0.2 to 1.2 perpendicular to TiOs (calculated in terms of An). When the amount of surface treatment is less than 0.2 weight tIb, deterioration due to light and heat is large and it is not practical. Moreover, if the weight exceeds 1.2, the occurrence of black grids tends to increase, which is not preferable.

As a surface treatment method for TiO, for example,
The method described in No. 17620 may be used.

Thermoplastic resins used in the practice of the present invention include polyolefins, polystyrene, polyvinyl chloride, polyacrylic esters, linear polyesters such as polyethylene terephthalate, polycarbonates, polyamides, homopolymers such as nylon, cellulose esters, polyacrylonitrile, etc. Copolymers, such as ethylene-vinyl acetate copolymers and mixtures thereof, can be coated with a resin film on the base paper. Any surface resin may be used, but thermoplastics such as polyolefin, polystyrene, polyethylene terephthalate, and polyvinyl chloride are particularly suitable. Among them, polyolefin resins are particularly advantageous in terms of extrusion coating properties, good adhesion to base paper, and cost. The polyolefin resins used in the present invention include low-temperature polyethylene, high-density polyethylene, polypropylene, homopolymers such as polybutene and polybentene, or copolymers consisting of two or more O-V fins such as ethylene-propylene copolymers, and mixtures thereof], with various densities and melt viscosity indices (melt index; (abbreviated as M) can be used alone or in combination.

When producing photographic resin-coated paper using the photographic thermoplastic resin composition of the present invention, the content of T1 to be included in the resin layer is 5 weight or less relative to the resin; A) It has insufficient hiding power as a photographic support.
On the other hand, 40 layers! : If it is more than
It is within the range of

In order to produce a photographic resin-coated paper using the photographic thermoplastic resin composition of the present invention, a T.
When the resin produced by melt extrusion coating a resin composition containing ies into a film from a slit die is a polyolefin resin, the melt extrusion temperature is preferably 200°C to 350°C. Furthermore, before applying the resin composition to the base paper, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment. There are no particular limitations on the thickness of the resin layer of the resin-coated paper, but it is generally advantageous to extrude coat it to a thickness of about 5 microns to 50 microns. In addition, in ordinary resin-coated paper in which both sides of the base paper are coated with resin, the resin surface containing Ti1l has a glossy surface, a matte surface, a silky surface, etc. depending on the application, and the surface of the resin on the opposite side The back side is usually a matte surface, and if necessary, the front side or both the front and back sides can be subjected to activation treatment such as corona discharge treatment or flame treatment.

The base paper used in the practice of the present invention is ordinary natural pulp paper,
Synthetic fibers or so-called synthetic paper made from synthetic resin film may be used, but softwood pulp, wide
#Natural pulp paper whose main component is wood pulp such as tree pulp or softwood/hardwood mixed pulp is advantageously used. There is no particular restriction on the thickness of the base paper, but a base paper with good surface smoothness is preferred, and its basis weight is 5017w1~250w.
11/wl is preferred.

The base paper mainly composed of natural pulp, which is advantageously used in carrying out the present invention, can contain various polymeric compounds and additives. For example, as a dry paper strength enhancer, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinylallurol, gelatin, etc.; as a sizing agent, fatty acid salt,
As pigments, such as rosin fusion, dialkyl ketene dimer emulsion, petroleum resin margin, styrene-maleic anhydride copolymer alkyl ester ammonium salt, etc.
Clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc. as wet paper strength enhancers, melane resin,
As urea resin, epoxidized polyamide resin, fixing agent,
Polyvalent metal salts such as aluminum sulfate and aluminum chloride, cation-modified polymers such as cationized starch, etc.
R regulators such as caustic soda, soda carbonate, and hydrochloric acid may be used, and inorganic electrolytes such as common salt, nitric acid, dyes thereof, fluorescent brighteners, latex, and the like may be contained in appropriate combinations.

The photographic resin-coated paper produced using the photographic thermoplastic resin composition of the present invention can be provided with various silver halide photographic emulsion layers. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide emulsion layers can be provided.

Furthermore, a multilayer silver halide photographic constituent layer can be provided by incorporating a color coupler in the silver halide photographic emulsion layer. As the binder for these silver halide emulsion layers, in addition to ordinary gelatin, hydrophilic polymeric substances such as polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide sulfate ester compounds can be used. Further, the above-mentioned silver halide emulsion layer can contain various additives. For example, as a sensitizing dye, cyanine dye,
Chemical sensitizers such as merocyanine dyes, water droplet gold compounds, sulfur compounds, antifoggants or stabilizers such as hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, hardeners such as formalin, vinyl sulfone, etc. compounds, aziridine compounds, etc.
As coating aids, benzene sulfonate and sulfosuccinate salts, as anti-staining agents, dialkyl ha(tri:I=?non compounds, etc.), as development accelerators, as hydroquinone, phenidone, etc., as ultraviolet II! absorbers, In addition to benzotriazole compounds, fluorescent whitening agents, sharpness-enhancing dyes, antistatic agents, PHi [moderating agents, and water-soluble iridium compounds, water-soluble pdium compounds, etc. may be appropriately combined during dispersion during the production of silver halide. Further, on the back side of the photographic resin-coated paper produced using the photographic thermoplastic resin composition of the present invention, a photographic constituent layer, often a silver halide photographic constituent layer, is provided. On the surface of the support opposite to the surface to be coated, a coating layer consisting of a hydrophilic rhoid layer called a back coat layer may be provided for the purpose of preventing curling, antistatic, adhesion, and prevention of slippage. The back coat layer contains binders or protective colloids, curing agents, antistatic agents, surfactants,
It can contain a matting agent, latex, etc.

Next, examples will be described to further specifically explain the present invention.

[Example 1] Anatase type dioxide protein tank linker produced by the sulfuric acid method was dry-pulverized in a centrifugal μm ram mill, and the pulverized product was suspended in water in the presence of sodium hydroxide. .0 titanium dioxide slurry, wet milling in a wet ball mill, and wet classification using a continuous testing horizontal centrifuge to produce a slurry of approximately 25% by weight that is substantially free of coarse titanium dioxide. About 9.
2, and after heating the slurry to about 70°C, add a 50% by weight aqueous sodium aluminate solution in an amount of 0.75% AItos based on the dry basis of teta/dioxide. was added and held for 30 minutes. The H of the slurry P1 was then reduced to 0 by adding 20 sulfuric acid, and the slurry was further aged for 2 hours.

After aging, the first mother liquor of the titanium dioxide slurry whose surface had been treated with hydrous alkaline oxide was treated with a fibreter press to obtain a wet cake of titanium dioxide.Then, this titanium dioxide cake was heated in an atmosphere of 140°C. The powder was continuously dried in a vacuum cleaner, and then impact-pulverized in a hammer mill equipped with a quantitative feeder.

(Sample 1). This sample 1 was further passed through a steam mill to obtain finely pulverized CX material 2) 0 This sample 2 was further passed through an air mill to be further pulverized (hereinafter referred to as sample 3).

For comparison, sample 1 was further subjected to impact pulverization using a hammer mill with a quantitative feeder (repeat for a second time), and a sample was prepared by performing hammer mill pulverization a total of three times. (Same as sample 4) 0 Thus, low density polyethylene (MI-71!).

70 parts by weight of titanium dioxide pigment, 30 parts by weight of titanium dioxide pigment and 1.5 parts by weight of zinc stearate were thoroughly kneaded at 150'C using a Banbury mixer, and a master batch of the above four types of titanium dioxide pigments was prepared. were obtained respectively.

On the other hand, a mixed paper stock of 50 parts by weight of bleached hardwood kraft pulp and 50 parts by weight of softwood bleached sulfide pulp was beaten to Canadian Standard 7 consistency 310wLl, and 3 parts by weight of cationized starch was added to 100 parts by weight of the pulp.
parts by weight, 0.2 parts by weight of anionized polyacrylamide,
0.4 parts by weight of an alkene dimer emulsion (as a ketene dimer content) and 0.4 parts by weight of a polyaminopolyamide shrimp chlorohydrin resin were added to form paper with a basis weight of 1601/d. The resulting 1 Jti paper was dried at 110'C, followed by 3 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of fluorescent bleach, 0.002 parts by weight of blue dye, 0.2 parts by weight of citric acid and 97 parts by weight of water. After impregnating 25,117 d of impregnating liquid consisting of 25,117 d with hot air at 110°C and further supercalendering at a linear pressure of 90 kI/am, both sides of the impregnating liquid were subjected to corona discharge treatment to form a base paper for photographic resin-covered paper. Manufactured.

Next, apply high-density polyethylene (density 0.96
JF/Jo, M knee 5) and low density polyethylene (density 0
．． 92~-1M knee 5) l:l mixture at resin temperature 330
It was coated to a thickness of 30μ using a melt extrusion coater at °C. Next, 30 parts by weight of the masterbatch of the titanium dioxide pigment described above and high-density polyethylene (
Density 0.96N/l.

M knee 5) 20 parts by weight and low density polyethylene (density 0
．． 92JF/cj, Mnee 5) Polyethylene resin-coated paper containing titanium dioxide pigments with different liquid conductivities, coated with a resin composition containing 50 parts by weight at a resin temperature of 330°C to a thickness of 30 degrees. were manufactured respectively. At that time, the surface of the polyethylene containing titanium dioxide pigment was processed into a completely flat glossy surface, and the surface quality of the back polyethylene was processed into a paper-like matte surface.

Tie of polyethylene resin coated paper obtained in this way
The number of microgrits generated on the polyethylene resin surface containing , was visually counted.

The results obtained are shown in Table 1.

Table 1 (Note 1) 1) HM... Hammer mill 2) HM-
8M --- Hammer Mill Steam Engine 3) HM
-8M-AM...T10 with only hammer mill, steam mill, and air mill pulverization! Resin-coated paper containing material No. 1) contains a large number of microgrits and is completely unsuitable as a photographic support.
It can be seen that the resin-coated paper containing S (Sample No. 2) is well-prevented from generating black grit and is preferable as a photographic support. Furthermore, it can be seen that the resin-coated paper containing Ti0m (sample number 3), which was subjected to steam milling after being hammered and then air milled, is particularly preferable because it further prevents build-up black grid.

On the other hand, T
In the resin-coated paper containing IES (Sample No. 4), there were many occurrences of reduced black grid, and the effect was hardly improved.

[Example 2] In place of T10,0 used in Example 1, the surface treatment amount of Ties with hydrous oxidized aliecum was calculated in the form of A-nocrystals with respect to dry standard titanium dioxide, and Olo,1
5.0.25.0.5.0.75.1.0.1.25 and 2.0% by weight, and the grinding history of titanium dioxide is 0.25.0.5.0.75.1.0.1.25 and 2.0% by weight, and the grinding history of titanium dioxide is no. Furthermore, T10! was added to the resin layer in the same manner as in Example 1 except that TIO which had been subjected to air mill pulverization and T103 which had only been subjected to hammer mill pulverization were used. A polyethylene resin-coated paper containing the following was produced.

The results obtained are shown in Table 2.

In addition, the light resistance (Note 2) of the polyethylene resin-coated paper described in the table was tested as follows.

Tie of resin coated paper, and the resin surface including Tie test machine made 7z
1 with tometer (Il'AL-251-HOI, model)
The sample was irradiated for 20 hours, and then the negative density (hereinafter abbreviated as Y density) of the irradiated surface of the sample was measured and verified using a Macbeth density needle (TD-504). The larger the value, the higher the Y concentration, and the higher the Y concentration, the worse the light resistance of the sample. On the other hand, the lower the Y concentration, the better the light resistance of the sample.

Table 2 (note 1) shows a sample obtained from the same second group as described in Example 1, and a polyethylene resin layer containing hammered A/pulverized paper 7' (resin-coated paper containing TiOs other than the present invention). In comparison, the resin-coated paper of the present invention, which contains fcTiO, which has been subjected to hammer mill followed by steam sill crushing and further air φ mill crushing in the resin layer, is preferable because the generation of microgrit is well prevented.However, the present invention Even on resin-coated paper in i, the amount of surface treatment of hydrous aluminum oxide "ffi 'I'10a is 0.2 weight - calculated in the form of mu J, 0. with respect to titanium dioxide on a dry basis. Those using TiOx below have poor light resistance, while those using T106 above 1.2, weight - are insufficient in preventing microgrit.The amount of surface treatment is between 0.2 and It can be seen that in the case of using 1.2% by weight of T10., the generation of microgrit is significantly prevented, the light resistance is good, and it is more preferable as a photographic support.

[Example 3] In place of Ti0g0 used in Example 1, the surface treatment amount of Tie with hydrous aluminum oxide was calculated as 0.5 in 0.0 form with respect to titanium dioxide on a dry basis. 3% by weight and at 300°C before hammer mill grinding.
Weight loss when heated for 0 minutes is 0.20.0.25.0.4
5.0.60.0.80 and 0.90 titanium dioxide is crushed with a hammer mill stone and steam mill,
Furthermore, when air milling was performed, the weight loss was 102, and the weight loss when heated at 300°C for 30 minutes before hammer milling was 0.
A polyethylene resin-coated paper containing Tiet in the resin layer was produced in the same manner as in Example 1, except that 45% titanium dioxide was used in each case.

The results obtained are shown in Table 3.

In the table, (Note 3) indicates the number of die lip stains in the layer 2 hours after the start of extrusion of the door section in each sample.

Table 3 (note 1) is the same as that described in Example 1. From Table 3, resin-coated paper containing TiOx with a heating loss of 0.25 to 0.9% before hammer mill crushing in the polyethylene resin layer has the following properties: It can be seen that the generation of microgrit is extremely well prevented. However, those with a heating loss of 0.8% or more cause die lip staining and are therefore unsuitable as photographic supports. Father, if the heating loss before hammer mill grinding is 0.2%, it is not preferable because the generation of microgrit will increase.On the other hand, if the heating loss before hammer mill grinding is 0.45%, even if the hammer mill grinding is 3%. It can be seen that even if the process is repeated several times, only a photographic support with a large number of microgrits can be obtained.

Claims (1)

[Claims] 1. A photographic thermoplastic resin composition characterized in that, in producing the photographic thermoplastic resin composition, an impact crushing layer and a titanium dioxide pigment crushed by a fluid energy crusher are used. Manufacturing method. 2. The method for producing a photographic thermoplastic resin composition according to claim 1, wherein the fluid energy crusher is a steam building. 3. The method for producing a photographic thermoplastic resin composition according to claim 1, wherein the fluid energy crusher is an air mill and is used in combination with a steam mill. 4.30 of the titanium dioxide pigment before entering the impact crusher
The weight loss when heated at 0°C for 30 minutes is 0.25 to 0.
Special B7 which is 60 inches! f. A method for producing a photographic thermoplastic resin composition according to claim 1. 5. Titanium dioxide pigment is 0% with hydrous aluminum oxide
．． 2. The method for producing a photographic thermoplastic resin composition according to claim 1, wherein the photographic thermoplastic resin composition is surface-treated in an amount of 2 to 1.2% by weight (calculated on a 0.0 form). 6. The method for producing a photographic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin resin. 7. Special feature where the polyolefin resin is polysaccharide resin
! Method for producing a photographic thermoplastic resin composition according to item 6 of the scope of FM requirements 0