JP2000239528A - Molding material, molded product and vessel for photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material for photosensitive material that includes, as main components, a mixture of vegetable fiber and thermoplastic resin, dissolves the thermal deterioration on molding, provides molded product of good appearance, resists to cracking on falling, particularly causes no adverse effect on the photographic performance, when it is used as vessels for photosensitive materials. SOLUTION: Vegetable fiber and halogen-free thermoplastic resin in a lower content than the vegetable fiber are mixed and the mixture is used as the main component to prepare the objective molding material that satisfies the following conditions. One gram of the conditioning specimen is accurately weighed and its moisture is adjusted under the conditions of 23 deg.C temperature and 55% RH atmosphere for 24 hours. Then, the specimen is placed in a vial of 300 cc capacity, tightly sealed with an aluminum seal and is heated in an oil bath kept at 120 deg.C for 30 minutes, resulting in that the amount of furfural occurring in the vial is <=10 μ g/1 g of the specimen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material and a molded product mainly composed of a vegetable fiber and a thermoplastic resin, and more particularly to a container for a photographic material.

[0002]

2. Description of the Related Art Molded articles of various shapes have been used by molding methods such as injection molding, compression molding, injection compression molding, and extrusion molding using a thermoplastic resin composition containing plant fibers as a main component. For example, it is used as a material suitable for skirting boards and peripheral edges in houses, floor materials, handrails, members around kitchens and bathrooms, materials for furniture, board core materials for automotive interior materials, and the like by extrusion molding. Wood powder-filled vinyl chloride resin has already been used for similar applications. However, when this resin is used, there is a problem in that toxic gas is generated during incineration during disposal or fire.

[0003] Recently, there has been a demand for dechlorinating vinyl chloride due to pollution problems at the time of combustion, etc., and as a substitute material has been strongly demanded, polyethylene is the most harmless and has attracted the most attention in terms of processability and cost. And polyolefin resins such as polypropylene.

[0004] However, it is technically difficult to mix a non-polar polyolefin resin with a highly polar plant fiber to exhibit the characteristics and new functions of each. For example, a plant such as wood flour contains a large amount of polysaccharides, lignin, tannins, and other components that are easily thermally and chemically decomposed or deteriorated, in addition to water. Further, even if these are removed, there is a problem that the cellulose and the polyolefin resin have no affinity. The mixing of such a substance requires a considerably large amount of energy, so that the plant fiber and the resin are deteriorated after the completion of the mixing.

[0005] In the prior art, the following techniques are mainly based on a mixture of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber. JP-A-54-7224
No. 7 is a process in which wood flour is previously heat-treated at 160 ° C. to 260 ° C., and a processing aid of a thermoplastic resin is added thereto to be melt-impregnated, and the temperature and time are reduced to reduce the water content of the plant fiber. Are described. However, this method has a problem that the wood flour component is altered and the strength is deteriorated. Further, as a resin processing aid, the melting point is from 40 ° C to 2 ° C.
Organics at 50 ° C. are mentioned. Some of the organic processing aids are not preferable because they have poor compatibility with the polyethylene resin and the bleed-out phenomenon and the degree of deterioration in physical properties are large. Japanese Patent Application Laid-Open No. 63-12639 discloses a composition in which a polyolefin resin is blended with a mineral oil or a synthetic oil, and a wax, an inorganic filler, and an organic filler including wood flour. The appearance of the synthetic oil mixture as a molded article was problematic. JP-A-55-127451 discloses a composition comprising a polyolefin powder and wood flour, calcium carbonate or talc. The use of polyolefin powder is a preferred method of improving hopper bridges and improving dispersibility. JP-A-58-217552 discloses a composition in which wood flour and a lubricant are mixed with polypropylene. Lubricants include esters of higher alcohols and acids and esters of glycerin and fatty acids, whose role is to improve the wetting of wood flour and polypropylene, and to improve physical properties and extrudability. Next, Tokiko Sho 58-
No. 56534 discloses a composition comprising rosin or a rosin derivative or a petroleum resin, a plasticizer and a vegetable fiber powder in a polyolefin resin. JP-A-7-225453
The light-shielding containers for photosensitive materials obtained by mixing and molding the resin described in the above item and the cellulosic fibers have been proposed, but any of these may damage the fibers when mixed with plant fibers and have insufficient strength and toughness. Met.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the problem that, in a resin component to be combined with plant fiber, there is no incineration during disposal or generation of toxic gas at the time of fire, and the plant fiber is degraded. Another object of the present invention is to provide a molded article which is hard to be broken even when dropped, and has a good appearance, and particularly provides a molding material which does not affect photographic performance even when used as a container for photographic photosensitive materials.

[0007]

The above object has been attained by the following constitution of the present invention.

(1) A molding material comprising a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom as a main component, and satisfying the following conditions: .

Conditions 1 g of a sample is precisely weighed and placed at 23 ° C. in a 55% RH atmosphere for 24 hours.
After humidity control for a period of time, the mixture was placed in a vial having a capacity of 30 cc sealed with an aluminum seal, and further heated in an oil bath kept at 120 ° C. for 30 minutes, after which the amount of furfural generated in the vial was 10 μg / ( 1 g sample) or less.

(2) A molding material comprising a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom as a main component, and satisfying the following conditions: .

Conditions A 0.3 g sample was burned at a combustion temperature of 850 ° C. at an air flow rate of 300 ml / min in a tubular electric furnace in accordance with JIS K 2541, and the combustion heat detected by a calorimeter of JIS M 8814 was 5,000 to 5,000. It is 8000 cal / g.

(3) A molding material comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions: .

Conditions A test piece obtained by cutting a flat plate having a length of 114 mm × a width of 33 mm × a thickness of 10 mm into a compact tension shape described in the ASTM-D5045 standard (having two holes each having a diameter of 5 mm. AST
According to the M-D5045 standard, a jig is inserted between the two holes using an Instron type testing machine, and the jig is pulled so as to open a wedge-shaped notch, and the obtained fracture toughness value is 0.5.
５０50 kg / mm ^3/2 .

(4) A mixture of plant fibers and a thermoplastic resin having a lower content than the plant fibers and containing no halogen atom as a main component, and having a linear expansion coefficient of 1
A molding material having a temperature of 2 × 10 ⁻⁵ / ° C. or less.

(5) The molding material according to (4), wherein the coefficient of linear expansion is 7 × 10 ⁻⁵ / ° C. or less.

(6) A flexural stress of 18.6 kgf / cm based on ASTM-D648, containing as a main component a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom. Heat deformation temperature at ² is 50
A molding material having a temperature of at least ℃.

(7) The molding material according to (6), wherein the heat deformation temperature is 70 ° C. or higher.

(8) A mixture mainly composed of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom, and having a volume resistance of at least 10 ⁹ Ωcm as measured according to JIS K 6911. A molding material, characterized in that:

(9) The molding material according to the above (8), wherein the material has a volume resistance of 10 ¹⁶ Ωcm or more.

(10) A molded article characterized by comprising a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom as a main component, and satisfying the following conditions.

Conditions 1 g of a sample was precisely weighed and placed at 23 ° C. in a 55% RH atmosphere for 24 hours.
After humidity control for a period of time, the mixture was placed in a vial having a capacity of 30 cc sealed with an aluminum seal, and further heated in an oil bath kept at 120 ° C. for 30 minutes, after which the amount of furfural generated in the vial was 10 μg / ( 1 g sample) or less.

(11) A molded article comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions.

Conditions A 0.3 g sample was burned at a combustion temperature of 850 ° C. at an air flow rate of 300 ml / min in a tubular electric furnace conforming to JIS K2541 and the combustion heat detected by a calorimeter of JIS M 8814 was 5,000 to 5,000. It is 8000 cal / g.

(12) A mixture mainly composed of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom, and a mixture of the vegetable fiber and the thermoplastic resin is prepared under the following conditions. A molded product characterized by satisfying.

Conditions A test piece obtained by cutting a flat plate having a length of 114 mm × a width of 33 mm × a thickness of 10 mm into a compact tension shape described in the ASTM-D5045 standard (having two holes each having a diameter of 5 mm. AST
According to the M-D5045 standard, a jig is inserted between the two holes using an Instron type testing machine, and the jig is pulled so as to open a wedge-shaped notch, and the obtained fracture toughness value is 0.5.
５０50 kg / mm ^3/2 .

(13) A mixture of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom as a main component, and having a linear expansion coefficient of 12 × 10 ^−5.
/ ° C or lower.

(14) The molded article according to the above (13), wherein the coefficient of linear expansion is 7 × 10 ⁻⁵ / ° C. or less.

(15) ASTM-D648 comprising a mixture of vegetable fibers and a thermoplastic resin having a lower content than the vegetable fibers and containing no halogen atom as a main component, and a mixture of vegetable fibers and a thermoplastic resin. Stress 18.6 based on
A molded article having a heat distortion temperature of 50 ° C. or more at kgf / cm ² .

(16) The molded article according to the above (15), wherein the heat deformation temperature is 70 ° C. or more.

(17) A mixture mainly composed of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom, and having a volume resistance of at least 10 ⁹ Ωcm measured according to JIS K 6911. A molded article characterized by being:

(18) The molded article according to the above (17), wherein the molded article has a volume resistance of 10 ¹⁶ Ωcm or more.

(19) A container for a photographic light-sensitive material, formed by using the molding material according to any one of the above (1) to (9).

(20) A container for a photographic material having the features described in any one of the above (10) to (18).

Hereinafter, the present invention will be described in detail.

In the present invention, the main component is a mixture of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom. It has been found that the thermoplastic resin does not contain a halogen atom, and that the molding material or the molded product satisfies the above-mentioned various properties, so that an excellent molding material or a molded product can be obtained. Further, when this molding material or molded article is used as a container for photographic light-sensitive materials, there is no adverse effect on photographic characteristics, and a packaging material that can be easily incinerated at the time of disposal can be obtained.

The plant fiber of the present invention is a fiber possessed by a plant, and is a product obtained by directly drying a plant or a product generally sold as pulp. Pulp production methods include chemical pulping methods such as kraft pulping, sulfite pulping, and alkali pulping, and are bleached by a multi-stage bleaching method. Further, pulp or pulp obtained by chemically treating such pulp by a known crosslinking reaction or mercerization reaction may be used. Raw materials used in the pulp production method include pine, cedar, cypress and other softwood materials,
Hardwoods such as beech, syrup, eucalyptus and the like, and non-wood fibers such as flax, mulberry, mitsumata, bamboo, bacas, and the like are included, but are not particularly limited. In addition, paper resources are being actively reused due to proposals on global environmental issues related to forest resources, etc.Newspapers, weekly magazines, magazines, advertising flyers, etc. collected at home, companies and stations, bookbinding and printing Recycled waste paper pulp may be used from various processes such as defibration, rough screening, aging, deinking, fine screening, and bleaching from cuts and waste paper generated in factories.

Various additives, for example, an inorganic pigment such as carbon black, an organic pigment, a light-shielding substance such as a light-shielding cellulose fiber, a lubricant and the like are optionally added to the mixture of the plant fiber and the thermoplastic resin in the present invention. be able to.

The thermoplastic resin used in the present invention is a resin which does not contain a halogen atom and which can be obtained by applying heat to obtain fluidity. Specifically, natural rubber, acrylate rubber, butyl rubber, nitrile rubber, butadiene Rubber, isoprene rubber, styrene-butadiene rubber, urethane rubber, silicone rubber, acrylic rubber, neoprene rubber,
Epichlorohydrin, EPDM (ethylene / propylene / diene rubber), elastomers such as urethane elastomers, polyethylene, polypropylene, polybutadiene,
Polybutene, impact-resistant ABS resin, polyurethane, AB
S resin, cellulose acetate, amide resin, nitrocellulose, polystyrene, epoxy resin, phenol-
Examples include formaldehyde resin, polyester, impact-resistant acrylic resin, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene copolymer, and polyvinyl acetate. As the thermoplastic resin, a polyethylene resin, a polyethylene-vinyl acetate copolymer resin, or the like, which has a low possibility of generating a toxic gas other than carbon dioxide and water during incineration, is preferable. Among polyethylenes, an ethylene-α-olefin copolymer is preferable, having a density of 0.86 to 0.94 g / cm ³ , a melt index of 0.01 to 40 g / 10 min, and D
The value of the main peak of the melting point of SC is in the range of 50 to 115 ° C, particularly preferably an ethylene-α-olefin copolymer using a metallocene catalyst as a polymerization catalyst. More preferably, the density is 0.89 to 0.92 g / cm ³ , the melt index is 5 to 25 g / 10 min, and the metallocene catalyst is obtained as a polymerization catalyst. The α-olefin is 4-methylpentene, 1-hexene, or 1 -It is a copolymer of octene 1 and ethylene, the copolymerization ratio of which is preferably 9 to 30% by weight of ethylene and the remainder α-olefin. The mixing ratio of vegetable fiber and thermoplastic resin is
From the viewpoint of injection moldability, strength, and hardness, the mixing ratio of the plant fiber is preferably 50 to 90% by weight, and particularly preferably 55 to 75% by weight. The method for producing the mixed molded product composed of the vegetable fiber and the thermoplastic resin is not particularly limited, and a known method can be used. For example, pulp, waste paper, or the like ground with a shearing machine and a thermoplastic resin are sufficiently mixed at a temperature equal to or higher than the melting point of the thermoplastic resin plus 10 ° C. to form a desired molded product.

In particular, in the case of injection molding, it is necessary to adjust the temperature conditions so that the material is sufficiently injected to the corners of the mold. The mixed molded product composed of vegetable fiber and thermoplastic resin has a significantly lower shrinkage ratio after injection molding than plastic, so that the efficiency during molding processing can be improved (cooling time can be shortened) and the dimensional stability is good. Less deformation, significantly reduces assembly failure, light-shielding failure due to distortion and poor pull-out of photosensitive material.Furthermore, since it contains fibrous material, it is better entangled with wood-based adhesives and has better adhesion than plastic. However, joining with another member such as a paper body is facilitated, and the strength of the joining portion can be increased. In the present invention, the mixed molded product composed of the vegetable fiber and the thermoplastic resin may be used for some or all of the members constituting the molding material.

When the molding material of the present invention is used in a container for a photographic light-sensitive material, particularly a body of a film unit with a lens, the objects and effects of the present invention can be sufficiently exhibited.

[0041]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Commercially available North American office waste paper pulp (Nippon Paper Pulp Trading)
Was cut into a size of 5 mm square.

Cut pulp 60 parts by weight Ethylene vinyl acetate copolymer (EV40W.Y manufactured by Mitsui DuPont) 35 parts by weight Butyl stearate (Kao Corporation) 1 part by weight Hydrogenated rosin (Arakawa Chemical Co., Ltd. ester gum) 4 parts by weight Using a Banbury mixer (Plasticorder PL-2000 manufactured by Brabender), the rotation speed, the temperature of the thermostat,
By changing kneading conditions such as kneading time, 1-A,
Six types of samples 1-B, 1-C, 1-D, 1-E and 1-F were obtained. 1 g of each sample was precisely weighed and conditioned for 24 hours in an atmosphere of 23 ° C. and 55% RH, then placed in a 30 cc capacity vial sealed with an aluminum seal, and further placed in an oil bath kept at 120 ° C. for 30 minutes. Heat.

The gas in the vial was measured by GC-MASS in which a calibration curve was prepared with reference furfural in advance, and the amount of furfural generated was quantified and converted to 1 g of the sample. Further, evaluation was made by the following method. Table 1 shows the results
Shown in

<Evaluation of photographic performance> Using a negative film having an ISO sensitivity of 400 (manufactured by Konica Corporation: JX400), evaluation was made by the following method.

A photosensitive material 100 cm ² left for 24 hours in an atmosphere of 23 ° C. and 55% RH was subjected to an inner diameter of 79 mm and a height of 5 cm.
Stored in a 0 mm cylindrical aluminum container, then 65 ° C
At room temperature for 72 hours, allowed to cool for 12 hours in an atmosphere of 23 ° C. and 55% RH, and then taken out of the photosensitive material taken out of the aluminum container. ² and 4 g of a molding material left for 24 hours in an atmosphere of 23 ° C. and 55% RH for an inner diameter of 79
mm, 50mm height in a cylindrical aluminum container,
Then, after standing at 65 ° C. for 72 hours, 23 ° C., 55% R
When the photosensitive material taken out of the aluminum container after cooling in an H atmosphere for 12 hours was used as Sample B, Sample A and Sample B were subjected to white exposure through a sensitometric step wedge, and subjected to the following development processing. The evaluation was performed based on the difference in fog density of the green-sensitive layer (fog density of sample B-fog density of sample A). If the difference in fog density is 0.2 or less, it is within an allowable range.

Processing conditions Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 45 seconds 38 ° C. Fixing 1 minute 30 seconds 38 ° C. Stable 1 minute 38 ° C. Drying 1 minute 55 ° C. Color developing water 800 cc potassium carbonate 30 g Carbon dioxide Sodium hydrogen 2.5 g potassium sulfite 3.0 g sodium bromide 1.3 g potassium iodide 1.2 mg hydroxylamine sulfate 2.5 g sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N- (β (Hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 L, and adjust to pH 10.06 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 cc Ammonium iron (III) 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 L, and use ammonia water or glacial acetic acid. Adjust to pH 4.4.

Fixing solution Water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 L.

Stabilizer Water 900 cc Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (manufactured by UCC) L-77) 0.1 g ammonia water 0.5 cc Add water to make 1 L, and adjust the pH to 8.5 using ammonia water or 50% sulfuric acid.

<Evaluation of Odor> Evaluation was carried out by 10 observers according to the following evaluation criteria, and the results were expressed as average values.

Smell intensity Smell sensation intensity 5 No odor 4 Smell felt barely 3 (Detection threshold) 3 Smell easily felt 2 Smell felt clearly 1 Strong smell 0 Smell felt unbearably strong Smell level is 4 If it is above, there is no practical problem.

[0053]

[Table 1]

As described above, furfural was 10%.
Samples of less than μg / (1 g sample) had practically no problem in photographic performance and odor.

Example 2 The sample 1-A obtained in Example 1 was injection-molded as follows.

Molding machine: J75SA (manufactured by Nippon Steel Co., Ltd.) Gate: 0.5 mm pin at the center Die: Die for front cover and rear cover of Konica clearly Injection molding, melting temperature, injection pressure By changing the injection molding conditions such as the injection amount, the mold temperature, etc., six types of Konica outer container samples (1-A
-1, 1-A-2, 1-A-3, 1-A-4, 1-A-
5, 1-A-6). Each was evaluated as follows, and the results are shown in Table 2.

<Evaluation of photographic performance> Dark room at 23 ° C., 55%
Photosensitive material 100 adjusted to RH atmosphere and left for 24 hours
cm ² was housed in a cylindrical aluminum container having an inner diameter of 79 mm and a height of 50 mm, and was then left at 65 ° C. for 72 hours, then allowed to cool at 23 ° C. and a 55% RH atmosphere for 12 hours, and then cooled from the aluminum container. Sample C, 23
Photosensitive material 1 left for 24 hours in a 55 ° C., 55% RH atmosphere
00 cm ² and a molded product formed into a desired shape at 23 ° C.
After standing for 24 hours in a 55% RH atmosphere, 4 g of a crushed molded product crushed to a size of about 5 mm
It was stored in a cylindrical aluminum container having a height of 9 mm and a height of 50 mm, and was then left at 65 ° C. for 72 hours.
When the photosensitive material taken out of the aluminum container after being allowed to cool for 12 hours in an atmosphere of% RH was used as Sample D, Sample C and Sample D were exposed to white light through a step wedge for sensitometry. The difference in fog density of the green-sensitive layer after the same development processing as in Example 1 was measured in the same manner as in Example 1.

<Evaluation of Appearance> Ten observers evaluated according to the following evaluation criteria, and the results were expressed as average values.

Rank of appearance Level of sensation 5 There is gloss 4 There is little gloss 3 There is fine undulation on the surface 2 Lumps of plant fiber material are visible on the surface 1 Surface is rough 0 Plant fibers appear on the surface If the appearance level is 4 or more, there is no practical problem.

[0060]

[Table 2]

As described above, furfural was 10%.
Samples of less than μg / (1 g sample) had practically no problem in photographic performance and odor.

Example 3 Using the same material as in Example 1, the ratio between the vegetable fiber and the resin was changed such that the content of the vegetable fiber was higher than that of the resin, and the Banbury mixer (Plastic made by Brabender) was used. Using kneader PL-2000), the number of revolutions, the temperature of the thermostat, and the kneading time were also changed in accordance with the kneading conditions, and 2-A, 2-B, 2-C, 2-D, 2-E, 2- F
Were obtained. This was evaluated in the same manner as in Example 1.

[0063]

[Table 3]

As described above, the heat of combustion was 5,000.
Samples of ~ 8000 cal / g have photographic performance,
There was no practical problem with the smell.

Example 4 The sample of Example 3 was injection molded as follows.

Molding machine: J75SA (manufactured by Nippon Steel Co., Ltd.) Gate: 0.5 mm pin at the center Die: Die for front and rear covers of Konica clearly Injection molding requires melting temperature and injection pressure By changing the injection conditions such as injection amount, mold temperature, etc., six types of Konica samples (2-A-2, 2-B-2, 2-C-
2, 2-D-2, 2-E-2, 2-F-2).
Each was evaluated in the same manner as in Example 2. The results are shown in Table 4.

[0067]

[Table 4]

As described above, the heat of combustion was 5,000.
The sample of 〜8000 cal / g had no practical problem.

Example 5 A Banbury mixer was prepared by changing the ratio of recycled kraft paper to polypropylene / modified polyphenylene ether composite resin (Remaloy PX620: Mitsubishi Engineering Plastics Co., Ltd.) so that the proportion of recycled kraft paper was 50% or more of the whole. Brabender Plasticorder P
L-2000) to change the number of revolutions, the temperature of the thermostat, the kneading time, etc., to obtain 3-A, 3-B, 3-C, 3-D,
Six types of samples, 3-E and 3-F, were obtained. This is ASTM
-Injection molded in a mold conforming to D5045 standard.

Further, a shot material was injected into the mold of the cover of Konica to produce a molding material, the photographic performance of Example 2 was measured, and a commercially available Konica component was incorporated. 23 ° C,
It was dropped from a height of 1 m under the condition of 55% RH and evaluated according to the following criteria.

Evaluation Level Standard 5 No cracking or disengagement of nails when dropped 10 times 4 Cracking or disengagement of engaging claws occurs when falling 8 to 10 times 3 Cracking or disengagement of engaging claws after falling 5 to 7 times 2 Cracks and disengagement of nails occur when dropped 2 to 4 times 1 Cracks and disengagement of engagement claws occur when dropped once.

[0072]

[Table 5]

As described above, when the fracture toughness value is 0.
The sample of 5 kg / mm ^3/2 had no practical problems in photographic performance and drop characteristics.

Example 6 After cutting cultivated kenaf (one-year grass of the Aoi family), the kenaf pulp was delignified by heating in distilled water and washing with water at 1.5 atm in a pressure cooker, and metallocene. Polyethylene (15200 manufactured by Ube Industries, Ltd.), butyl stearate (manufactured by Kao Corporation), and hydrogenated rosin (ester gum manufactured by Arakawa Chemical Co., Ltd.) were changed so that the amount of kenaf pulp with respect to the entire composition was 50% or more. According to the Banbury mixer (Plasticorder PL manufactured by Brabender)
-2000) to change the kneading conditions such as the number of revolutions, the temperature of the thermostatic layer, and the kneading time, to obtain 4-A, 4-B,
Six types of samples of -C, 4-D, 4-E and 4-F were obtained.
Further, a molding material was prepared by injecting the image into the mold of the cover of Konica clearly, the photographic performance was evaluated in the same manner as in Example 2, and a commercially available Konica component was incorporated.
Drop from a height of 1 m under the conditions of 3 ° C. and 55% RH,
The evaluation was performed in the same manner as in Example 5.

[0075]

[Table 6]

As described above, the coefficient of linear expansion is 12 ×
Samples having a temperature of 10 ⁻⁵ / ° C. or lower had no practical problems in photographic performance and drop characteristics, and samples having a temperature of 7 × 10 ⁻⁵ / ° C. or lower were more excellent.

Example 7 After cultivating kenaf (one-year grass of the Aoi family), kenaf pulp pulp delignified by heating in distilled water at 1.5 atm in a pressure cooker and ethylene vinyl acetate resin (Mitsui DuPont), butyl stearate (Kao), hydrogenated rosin (Arakawa Chemical Co., Ltd. ester gum), so that the type of ethylene vinyl acetate and the amount of kenaf pulp to the entire composition are 50% or more. The kneading conditions such as the number of revolutions of the Banbury mixer (Plasticorder PL-2000 manufactured by Brabender Co., Ltd.), the temperature of the thermostat, and the kneading time were changed accordingly.
Six samples of -B, 5-C, 5-D, 5-E, and 5-F were obtained.

Further, a shot material was injected into the mold of the cover of Konica clearly to prepare a molding material, the photographic performance was evaluated in the same manner as in Example 2, and a commercially available Konica component was incorporated at 50 ° C. After being left in a 55% RH atmosphere for 48 hours, it was dropped from a height of 1 m and evaluated according to the same criteria as in Example 5.

[0079]

[Table 7]

As described above, the heat distortion temperature was 50 ° C.
The above samples had no practical problems in photographic performance and drop characteristics. Further, those having a heat distortion temperature of 70 ° C. or more had an evaluation level of 4 or more even under test conditions in which the temperature of the evaluation conditions was 60 ° C., and were excellent.

Example 8 After cultivating kenaf (one-year grass of the Aoi family), the kenaf pulp which had been delignified by heating in distilled water at 1.5 atm in a pressure cooker, and metallocene polyethylene ( Ube Industries, Ltd. 15200), butyl stearate (Kao Corporation), hydrogenated rosin (Arakawa Chemical Co., Inc. ester gum) is added so that the kenaf pulp becomes 50% or more, and the amount of gold powder is adjusted therein, Accordingly, use a Banbury mixer (Plasticorder PL manufactured by Brabender)
-2000), the kneading conditions such as the number of revolutions, the temperature of the thermostatic layer, and the kneading time are changed to obtain 6-A, 6-B, 6-A.
Six samples of -C, 6-D, 6-E, and 6-F were obtained.

Further, a molding material was prepared by injecting into the mold of the Konica Mini Flash, and the photographic performance was evaluated in the same manner as in Example 2, and the parts of the commercially available Konica Mini Flash were incorporated. Evaluation was performed by lighting the strobe or changing the humidity from 20% RH to 80% RH at 40 ° C.

Evaluation level Criteria 5 Lights under any condition 4 Does not light below 70-80% RH 3 Does not light below 55-70% RH 2 Does not light below 20-55% RH 1 Conditions under 20% RH However, it does not light up.

[0084]

[Table 8]

As described above, the volume resistivity is 10%.
Samples with ^-9 Ωcm or less had no practical problems with photographic performance and strobe lighting, and those with 10 ^-16 Ωcm or less were even better.

[0086]

According to the present invention, an excellent molding material can be obtained by using a mixture of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber as a main component and having the physical properties of the present invention. Further, the containers for photographic light-sensitive materials using these molding materials did not affect photographic characteristics.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiroshi Kibayashi 1st Konica Stock Company, Sakura-cho, Hino-shi, Tokyo In-house (72) Inventor Yuichi Shin 1st Konica Stock Exchange, 1st Sakura-cho, Hino-shi, Tokyo F-term (reference) 4J002 AA012 AB011 AB021 AC011 AC031 AC061 AC071 AC081 AC091 BB031 BB061 BB121 BB151 BB171 BB181 BC031 BF021 BG041 BL011 BN151 CC031 CD001 CF001 CH041 CK021 CL001 CP031 GG01

Claims (20)

[Claims] 1. A molding material comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions. Conditions 1 g of a sample is precisely weighed and placed under an atmosphere of 23 ° C and 55% RH for 24 hours.
After humidity control for a period of time, the mixture was placed in a vial having a capacity of 30 cc sealed with an aluminum seal, and further heated in an oil bath kept at 120 ° C. for 30 minutes, after which the amount of furfural generated in the vial was 10 μg / ( 1 g sample) or less. 2. A molding material comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions. Conditions A 0.3 g sample is burned at a combustion temperature of 850 ° C. at an air flow rate of 300 ml / min in a tubular electric furnace in accordance with JIS K 2541, and the combustion heat detected by a calorimeter of JIS M8814 is 5,000 to 8000 cal / g. It is. 3. A molding material comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions. Conditions A test piece obtained by cutting a flat plate having a length of 114 mm, a width of 33 mm and a thickness of 10 mm into a compact tension shape described in the ASTM-D5045 standard (having two holes of 5 mm diameter, and the center distance between the holes is 11 mm. ) AST
According to the M-D5045 standard, a jig is inserted between the two holes using an Instron type testing machine, and the jig is pulled so as to open a wedge-shaped notch, and the obtained fracture toughness value is 0.5.
５０50 kg / mm ^3/2 . 4. A mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom as a main component, and having a linear expansion coefficient of 12 × of a molding material.
A molding material having a temperature of 10 ⁻⁵ / ° C. or less. 5. The molding material according to claim 4, wherein a coefficient of linear expansion is 7 × 10 ⁻⁵ / ° C. or less. 6. A bending stress of 18.6 kgf / cm ² based on ASTM-D648, comprising a mixture of vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom. A molding material having a heat distortion temperature of 50 ° C. or more at 50 ° C. 7. The molding material according to claim 6, wherein the heat distortion temperature is 70 ° C. or higher. 8. A mixture mainly composed of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and having a volume resistance of at least 10 ⁹ Ωcm measured according to JIS K 6911. A molding material, characterized in that: 9. The molding material according to claim 8, wherein the volume resistance is 10 ¹⁶ Ωcm or more. 10. A molded article comprising a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom as a main component, and satisfying the following conditions. Conditions 1 g of a sample is precisely weighed and placed under an atmosphere of 23 ° C and 55% RH for
After humidity control for a period of time, the mixture was placed in a vial having a capacity of 30 cc sealed with an aluminum seal, and further heated in an oil bath kept at 120 ° C. for 30 minutes, after which the amount of furfural generated in the vial was 10 μg / ( 1 g sample) or less. 11. A molded article comprising, as a main component, a mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and satisfying the following conditions. Conditions A 0.3 g sample is burned at a combustion temperature of 850 ° C. at an air flow rate of 300 ml / min in a tubular electric furnace in accordance with JIS K 2541, and the combustion heat detected by a calorimeter of JIS M8814 is 5,000 to 8000 cal / g. It is. 12. A mixture mainly comprising a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and a mixture of the vegetable fiber and the thermoplastic resin satisfying the following conditions: A molded article characterized by: Conditions A test piece obtained by cutting a flat plate having a length of 114 mm × a width of 33 mm × a thickness of 10 mm into a compact tension shape described in the ASTM-D5045 standard (having two holes of 5 mm diameter, and the center distance between the holes is 11 mm. ) AST
According to the M-D5045 standard, a jig is inserted between the two holes using an Instron type testing machine, and the jig is pulled so as to open a wedge-shaped notch, and the obtained fracture toughness value is 0.5.
５０50 kg / mm ^3/2 . 13. A mixture mainly comprising a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and having a linear expansion coefficient of 12 × 10 ⁻⁵ / ° C.
A molded article characterized by the following. 14. The molded article according to claim 13, wherein the linear expansion coefficient is 7 × 10 ⁻⁵ / ° C. or less. 15. An ASTM-D648 mixture of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and containing no halogen atom as a main component, and a mixture of the vegetable fiber and the thermoplastic resin. Bending stress based on 18.6kg
A molded product having a heat deformation temperature at f / cm ² of 50 ° C. or more. 16. The molded article according to claim 15, wherein the heat deformation temperature is 70 ° C. or higher. 17. A mixture mainly composed of a vegetable fiber and a thermoplastic resin having a lower content than the vegetable fiber and not containing a halogen atom, and having a volume resistance of at least 10 ⁹ Ωcm measured according to JIS K 6911. A molded article characterized by being present. 18. The molded product according to claim 17, wherein the molded product has a volume resistance of 10 ¹⁶ Ωcm or more. 19. A container for a photographic light-sensitive material formed by using the molding material according to claim 1. Description: 20. A container for a photographic light-sensitive material having the features according to claim 10. Description: