JPS587630A - Manufacture of support for photography - Google Patents

Abstract

PURPOSE:To manufacture the titled support with high sharpness by coating one side or both sides of paper or a synthetic substrate with a polyolefin resin composition contg. TiO2 surface-treated with organopolysiloxane. CONSTITUTION:TiO2 surface-treated with 0.2-1.2wt% Al2O3 hydrate is further surface-treated with 0.04-4wt% organopolysiloxane such as dimethylsiloxane and heat-treated at 50-250 deg.C for several min - several 10hr to obtain surface- treated TiO2. A polyolefin resin composition prepared by blending polyolefin resin such as polyethylene with 10-40wt% said surface-treated TiO2 is melted and extruded from a slit die in the form of a film to coat one side or both sides of paper or a synthetic substrate with the composition by 50-250g/m<2> basis weight. Thus, the contamination of the die lip can be inhibited, and polyolefin resin coated paper for photography can be manufactured almost continuously.

Description

[Detailed Description of the Invention] Overlapping is a paper groove on at least one image of a synthetic paper substrate,
Polyolefin resin relatives containing titanium dioxide are melt-extruded coated into a film and placed in a pot (4h) regarding photographic polyolefin resin-coated paper 0III fibers, specifically, the paper is placed between at least one of the synthetic paper substrates, The present invention relates to a method for preventing poor image quality due to stains on grips that occur on photographic polyolefin/tree-coated paper TM 111 by melt-extrusion coating a polyolefin resin composition containing titanium dioxide in the form of a Vt film.

[KFor details, see photographic support 0III with improved hiding power.
It is about law.

The essential structure of photographic polyolefin resin-coated paper is already known, for example,
, s O1,111! tcM show le c i! ! Sea urchin,
The paper substrate is coated with MT polyethylene resin, and the polyethylene layer on both sides of the emulsion coating is coated with titanium dioxide, and in fact, it is a method that contains T-containing materials such as Group II and fluorescent brighteners.

However, polyolefin containing titanium dioxide - Zeng composition! When melt-extruding the polyethylene am composition snout to fI# from a slit die in the form of WC1L, a needle-like or icicle-like O# kimono 4L is formed at the end of the grip in a short period of extrusion.
There is a tendency for stains (hereinafter referred to as gripp stains) to occur, and to make matters worse, these gripp stains tend to grow larger and larger as the extrusion time passes.

When chain extrusion coating is applied, if stains occur on the paper, streaks will appear on the vertical lines on the polyolefin tree-coated paper. This is because streak-like unevenness due to non-uniformity occurs, and dirt adheres to the film and the material is finished. As a result, the image quality of the manufactured polio V-fin tree cover is seriously impaired, and because of its excellent image quality, it is unsuitable as a photographic support and has no commercial value. .

1 In addition, in order to remove the dirt once it occurs, there is no other way than to stop production and clean the dirt, and cleaning requires a lot of effort and time, resulting in significant productivity. This would lead to a decline in P1, and an immediate decision was needed.

Akira Shigeki et al. have conducted various studies on this OG lip stain OIi, and found that there are major problems with titanium dioxide contained in polyolefin tree layer substances.9.Titanium dioxide When the O content is 0 and the O content of titanium dioxide in the polyolefin tree is low, the occurrence of gripp stains is small, but the hiding power is small and it cannot be used as a photographic support. It was found that when the content is high, the hiding power is sufficient, but the occurrence of greasy stains is significant.

It was also discovered that there was a very serious problem not only with the amount of titanium dioxide added, but also with the titanium dioxide itself used. ! In this case, the photographic device deteriorates and becomes useless as a photographic support.

That is, titanium dioxide, which is normally used in the photographic industry, is prepared by precipitating hydrous aluminum oxide and hydrous silicon dioxide on the surface of titanium dioxide particles as described in, for example, JP-A-4B2-3511211). Modified titanium 92 saponified titanium, etc. Enzan, which is widely used in the photographic industry and uses titanium dioxide that has been surface-treated in this way, has a light weight [( If the amount of surface release agent (oJ6s) for titanium dioxide is less than O, S weight

2) The dispersibility of titanium dioxide becomes black.

S) The Ill■ layer, emulsion layer, and 011 adhesion deteriorate.

4) If the white background of the photo changes over time, black it out.

5) The whitening effect is inferior to that of fluorescent brighteners.

Photographic polyolefin coated paper 0 @ M layer Kl 1 side Asahi l
It can be said that there is no possibility of using titanium dioxide which has not been subjected to the SUI treatment except in equipment. However, in order to meet the demands of the photo industry, this Oa
t high lI! The more surface treatment is applied to the surface, the more likely it is that greasy stains will occur.

Overview of Akio et al. points out that there are contradictions between the two, namely, quality problems such as the background discoloration over time of Gun Shinshiro (hereinafter referred to as photodeterioration), and texture problems due to the occurrence of severe grip stains. It is a shame that we are far from achieving the invention of the present invention after intensive research to simultaneously solve the four problems of Tojo (resulting in poor quality).

The present invention provides that at least one OIi of the paper or synthetic paper substrate,
IIK manufactures a polyolefin tree parent composition containing a titanium dioxide alloy, a polyolefin tree coated paper for nine-thickness coating, and a polyolefin composition comprising a polyolefin tree Ii) and an organopolysilone medium. For titanium dioxide (LO4~4 weight 4v table mm passed through 92 saponified titanium, etc.) t41IIIl [Also ofbb regarding the manufacturing method of photographic support O.

A polyolefin tree containing 0.04 to 4% of titanium dioxide by weight based on titanium dioxide by adding organoborisiloxane to the polyolefin tree layer.
In the case of brass energy using a II-containing extruder, the occurrence of die lip stains is significantly suppressed, and thick polyolefin coated paper sheets can be produced with almost no machine downtime.

In addition, in the case of photographic polyolefin made using this method, titanium dioxide whose surface has been made J6111 by aluminum oxide ζ oxide flow volume etc. is used because it is not commonly used. A 4-hour diet that is resistant to photodegradation provides superior quality that is comparable. Moreover, compared to surface gold, it uses two-year-old titanium that is made of titanium dioxide and has no surface treatment.
It is possible to obtain a photographic support with high Kameyaba force.

In addition, titanium dioxide is organoposisilokina 7 Table 11J6
Prior to 11, the amount of aluminum (Nium) to titanium dioxide is 0.8 to 1 bulk weight Titanium oxide containing titanium oxide having α04 to 4 weight x*mam relative to titanium and blended in a polyurethane resin film can greatly improve the shielding power of a photographic support.

From the details of previous research by the present inventors, it has been found that when high-grade polyethylene is contained in a polyolefin tree fiber composition, or when the content of titanium dioxide is increased in a polyolefin tree composition, greasy stains occur. It has been found that the disease occurs more frequently and becomes a bird.

However, the photographic support usually has a titanium dioxide-containing resin layer 1
Since the iK1 true emulsion layer tube is provided, the structure of the front and back surfaces of the photographic support is significantly different, resulting in curling. To correct this, it is common practice in the industry to incorporate high-density polyethylene resin into the tin dioxide-containing resin layer and the back resin layer to create a curl balance.

Although it is known that the inclusion of high-II polyethylene resin M in a polyolefin tree fiber composition promotes the occurrence of grip stains, its use is unavoidable from a quality standpoint. is the reality. In addition, increasing the content of titanium dioxide in the resin layer of a photographic support improves sharpness, so it is appropriate to increase the amount of titanium dioxide in photographic supports that require high quality. However, as the content of titanium dioxide increases, the occurrence of smearing and gripping stains increases significantly, and it becomes impossible to produce a 4-hour product. Therefore, in @autumn, the amount of titanium dioxide society is at a minimum @l! A photographic support with a high titanium dioxide content of 90% is produced without having to be manufactured in a suppressed form and of high quality.

As a result of research to meet the demands of the industry, the polyolefin tree fiber composition of the present invention can increase the titanium dioxide content in the resin layer of a photographic support. As a result, a support with extremely high sharpness is obtained.

Device 11! As the organanane used in the process, dimethylsiloxane, dimethylzenylsiloxane, methylhydrodiene siloxane, etc. can all be used, but methylhydrodienesiloxane is particularly preferred in terms of the apparatus. In addition, the amount of 1lIWi treated by these organoborisilokinanes with respect to titanium dioxide is (LO4
~4 weight S is preferred. Table i1 If the amount of hot water is less than (LO4 weight), the effect will not appear; if it exceeds 4 weight The polymerization ratio of organoborisilokinane O in the invention is, for example, 3 to 1 in the case of dimethyl sodP! OOO
The weight is preferably 5 to 100G.

Titanium dioxide in these organopolysilonan
After heating at 80-1I0℃ for several minutes to 10 hours, a good Table III & field condition was obtained, and 41IK
Most effective in the case of methylhydrogene.

The titanium dioxide used in Li#4 can be either rutile or anatomical. Also, surface II&l
For 11, titanium dioxide can also be used, preferably hydrated aluminum in a ratio of &2 to 1.1 to titanium dioxide.
1 weight x (calculated in the form of K2O2) surface-coated titanium dioxide. In addition, there is no restriction on the particle number of titanium dioxide used in superimposition to 41, but commercially available 0 and 1
-1jll[01E valence may be used, but preferably O, 1I
-1 out of 7 seeds where CLB s@ML seed value is used
Hydrous saponification to obtain titanium dioxide used in? =Table i by Um
The method described in No. 171120-tK may be used.

Organopolysilokinane h*II*yia is produced by a method normally used in the powder industry, for example, by dissolving organopolysilokinane in 111 kilograms of a powerful organic solution and then adding titanium dioxide to the surface with a liquid solution. This is done by the table J & m12F method, etc., which is based on the m interpretation of the organic relation.

If the content of titanium dioxide in the polyolefin resin is less than S weight for the polyolein tree specimen, then 1
Toll has insufficient hiding power as a practical support, while 40
In terms of weight, fluidity, etc. decreases, which is undesirable, and q#
The preferred weight is NPJ'li weight x011m and 6! .

Polyolefins in superposition@ include low-density polyethylene, high-density polyethylene, and polyethylene. (Fil Peng @l111a
*One stone is made by using O ingredients alone or by mixing them together.

In the present invention, due to the excellent effects of titanium dioxide as referred to in the present invention, there is no need to add a substance such as a party deterioration casting agent or a die lip stain prevention aid to the polyolefin layer composition. If necessary, lIl fat llO metal salts and the like may be added.

Examples of the fat metal salts that can be used for overlaying include stearic lead, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium pallinate, calcium palladium, sodium thurate, etc. can give. The amount added can be used in the range of Q, 01-8 weight to a polyolefin tree composition containing titanium dioxide, and is usually Q, O! ~Snow weight X.

In addition to titanium dioxide, the polyolefin resin layer composition in the superposition also contains amplified lead, tal! , white pigments such as calcium carbonate, stearic acid a(donato layer 1slIl!a(do, tetrakis [methylene-3 (LIS-di t@rt-phthyl-4-hydroxy-phenyl) propylene There are 4 types of oxidizing casting agents such as onate comethane, ml-di-t@rt-butyl-4-methylphenol, coloring pigments such as ultramarine and red iron, and fluorescent steel.

Polyolefin resin-coated paper is usually made by extruding a polyolefin resin composition into a film through a slit on a conductive paper or synthetic paper substrate (hereinafter simply referred to as base paper). Manufactured. At that time, it is preferable that the extrusion temperature is 100C to 110C.The slit die is preferably Tl die, L die, fish till die, and the slit die is Q, l to l■. There is something wrong with mtt. Yixu, applying the tree layer composition to the base paper #, applying a corona discharge treatment site to the base paper, Tu IILJ6
11 etc., it is preferable to apply it in the case of 011111110 thickness, but the thickness is not 41KIllll, but generally it is extrusion coated on S<Kronnoben so Kronm degree OMi animal. 0 is advantageous. In polyolefin resin-coated paper with 1 ft. of base paper and 9 layers of wood coated with a layer of wood, 1111 m (L
The surface coated with M has a glossy surface, a matte surface, a silk pattern, etc. depending on the structure, and the back surface is usually a matte surface. Also corona subsidy processing,
It is difficult to use 0fti sex salts such as Flame II&ll in the vagina.

The base paper used in the practice of the present invention may generally be any of O natural pulp, paper, synthetic fiber paper, or synthetic paper made from synthetic am film TA paper. A natural pulp paper whose main component is a wood valve pipe of a mixed pulp of Guangsu tree is advantageously used. In addition, there is no restriction on the thickness of the base paper for llI#, but a base paper with good surface smoothness is preferred, and its basis weight is sO1/d-
1Is Of/d'l1g is good.

The base paper, which is mainly composed of natural pulp and is advantageously used for overlapping @O, contains various polymer compounds and additives to increase dry paper strength. Agents include cationized starch, cationized polyacrylic acid, anionized polyacrylide, carboxylic acid alcohol, gelatin, etc.; as wetting agents, fatty acid salt, rosin trout conductor, ketene dimer emulsion in sial. Pigments include clay, kaolin, calcium carbonate, palicum sulfate,
Titanium dioxide, etc., can be used as a warm paper strength enhancer, melaken one layer, urea tree layer, epoxidized boriyad tree, etc. As a fixing agent, alium sulfate, aluminum chloride, etc.
#metal salts, cationic sapon 11 quasi-which cationic poly!
- etc. as PHIIil agent, W soda, soda carbonate, salt at, etc. as inorganic electrolyte, salt, mirabilite, etc.
It is possible to contain the ot*-ipm family, a fluorescent whitening agent, and a latex compound in combination.

For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, It is difficult to provide a solid iodobromide chain emulsion layer. Alternatively, a color coupler may be contained in the silver halide photographic emulsion layer to provide a multilayer silver halide photographic constituent layer. As a binder for these silver halide emulsion layers, a water-filling polymeric substance such as polyhinylpyrrolidone, polyvinyl alcohol, polysaccharide 11IO nitrate ster compound, etc., can be used in addition to ordinary gelatin. t7t, upper v3t) The silver halide emulsion layer can be enhanced by containing various additives. Koji uses sensitizing dyes such as cyanine dyes and merocyanine dyes, chemical sensitizers such as water #I-based all-gold compounds, sulfur compounds, etc., and anti-capri agents or stabilizers such as hydroxy-triazolobiridine compounds and mercapto-heterocycles. Compounds, such as hardening agents, formalin, vinyl sulfone compounds, aziridinated metals 11E, 111m agents, benzene sulfonates, sulfur 7-ocuccinic acid ester salts, anti-fouling agents, dialkylhydroquinonated metals, etc.
As ultraviolet absorbers, benzotriazole metals, etc.
In addition, fluorescent whitening agents, sharpness improving dyes, antistatic agents, P
During the generation and dispersion of silver halide in H119g agent (water S
This can be achieved by appropriately combining and containing chemical iridium, rhodium compounds, etc.

Next, this threat was made to K11-S1's friends in order to block the JII Confucian meeting.

Example 1 Low setting l poly z vy (MI -t, 111 [(L 5i
n) Record 70 parts by weight, 30 parts by weight of titanium dioxide, and 1.11 parts by weight of stearin 1M brass in 1111 (basket 1)*O
The mixture was thoroughly kneaded at 110C using a Banbury kinater to obtain a masterbatch (containing titanium dioxide). P master patch containing titanium dioxide obtained in this way 3
4 wt- and low equipment polyethylene (MI-
! l,l[asx m
IIVK dry-warmed and coated onto a polyester film with a basis weight of 1 m fed using a melt extruder.
/5w1m, temperature [coating amount ao t74 at 110℃
In addition, we have a close relationship with IIIK Kishin and we are friends with melt extrusion coating. This chain extruder has 0 cages/vessels for extrusion and 7s
It has a T-die with an o width. Also, the surface of the cast cooling roll is smooth and has hard chrome metal I? I am a friend of what Asahiba is doing.

Table 10 (Notes indicate the number of grip stains in each sample 8 hours after the bath-melt extrusion-pongee process.

Also, (note) shows the results of the opacity Jyilt, 9 (using G filter) using Hunter White WL for the round can sample obtained by the fusion process in Table 1.

The numbers are great, and the concealment power is high. Obtained nine experimental details tl
It is shown in ll.

111101111 Kara, Kuramoto Aluminum Oxide 2N
It can be seen that surface-treated titanium dioxide is not suitable for practical use because of the generation of grip stains. On the other hand, titanium dioxide, dimethylsiloxane, and dimethylphenylsilokinane without surface treatment did not cause grip stains.
It was good. In addition, the opaque device shows low opacity tstt for titanium dioxide without a table m and water-containing aluminium(2 *It can be seen that all of them show high opacity @WL except for mm wear weight o, on weight
It was found that almost no discoloration or fading was observed in the case of titanium dioxide without surface treatment.

Example 2 Used the same method as Example 1 and used 1 meter of edible spindle tree, and stated the true intention. Compatible with melt extrusion and coating in one set. Your test method is the same as in Example 1. Table 2 shows the obtained nine oats.

From the experimental result column in Table 2, it can be seen that the opacity of titanium dioxide treated with methylhydrogen silane (LSI weight) is higher than that of the methylhydrogen silica (LSI weight), as shown in the details of @l. 3. The saponified aluminum obtained in step 3 and methyl I.
In the case of titanium dioxide obtained in combination with hydrogen chloride treatment, it is possible to show a much more opaque @* than in the case of titanium dioxide obtained in Table 1. Recognize.

Example 3 Low gI! i1 polyz chivun (MIm9, @(Q, 5ts
70 parts by weight of titanium dioxide, 30 parts by weight of titanium dioxide, and stearin 11Ni I added 4 p master patches. 9 master patches containing titanium dioxide obtained in this way SO@ and 1
20 parts by weight of low book polyethylene V-n (MI 9.1!Jaku α918) and high straight polyethylene y (MI-
y, density i [Q, 1162) 80 weight SS dry-dry mixed.

A photographic support was obtained in the same manner as in Example 1, and the results are shown in Table 3.

Based on the experimental results of Table Lu, in the case of titanium dioxide without surface treatment and titanium dioxide using water-containing aluminum oxide treatment and methylhyde a-die/silokinane, the content of titanium dioxide in the polyethylene tree composition Despite the high content of 11 parts by weight, no Guri lip stains occurred even after the extrusion time had elapsed.
In the case of bisodium chloride, after only 3 minutes of filtration,
The key/rear needle had stains of 1004 or more and was removed.

Misfortune-Jakuha #&33~Nll5・Hazu31 and Arashi s3
I'm glad to see that it has improved considerably compared to before. Implementation of Kame 31 to Kame 36 O single-layer polyethylene compositions listed in Table S 91
Basis weight 1 @ Ot/d using OII Ugly extruder described in 11
Coating amount 1 [t00m/Ugly 1, Tao Uguri [3] on O photographic base paper
Melt extrusion coating was carried out at 0°C to a coating weight of 10 f/-.

A 1111-13.O photographic support obtained by this process was provided with a chalk I.silver rognide photographic emulsion layer to improve resolution #.
As a result of cm force tube test by Ill Sadao, -11 and 1
It was found that compared to SIK, Seed 33~Nll1@ provides a much better image power.

Claims (1)

[Claims] 1. A photographic polyolefin 1111HII covering paper is prepared by extruding a polyolein resin relative containing titanium dioxide into a film on at least one side of a paper or synthetic paper substrate. -Then, polyolein resin relatives are milled with 0.04 to 4 weight x*m of titanium dioxide in the polyolefin tree layer and organoboric acid to form titanium 92 oxide and mold. support for photo
t. Meaning titanium dioxide is organopoly VH XA7 Table 11M
IIK Previously, hydrated, aluminum oxide and cum were added to titanium dioxide to a weight of 0.2 to 1.1 (calculated in the form of Aj20).
f# Method a of the photographic support described in claim 111111111. 3. The OS method for a support for zero spindle according to claim 1 or 2, wherein the polyolefin tree layer is a polyethylene tree layer. 4. The polyolefin tree layer must contain at least one type of high-density polyolefin tree. O photographic support OJIll method. 8 The titanium dioxide content in the polyolefin composition is 1
Patent claim 0@II characterized by being upwind
O photographic support Om method described in Section 1, Section 1, Special Section, or Section 4.