JPS5994756A - Photographic support - Google Patents

Abstract

PURPOSE:To obtain a photographic support having a firmly adhered hydrophilic colloidal layer such as a photosensitive emulsion layer or a backing layer by coating a polyester support with an aqueous composition contg. a specified copolymer to form an underlayer. CONSTITUTION:At least one side of a polyester support is coated with an aqueous coating composition contg. a copolymer consisting of 10-70wt% diolefin (A) such as butadiene, 31-59wt% vinyl monomer (B) having an epoxy group such as glycidyl (meth)acrylate and 3-60wt% styrene (C) to form an underlayer. A flat photographic support having high adhesive strength between the polyester film and a photographic hydrophilic colloidal layer is obtd. Since an org. solvent is not required to be used as a swelling agent or a dissolving agent, the harmful org. solvent is not released into exhaust gas or waste water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic support having a subbing layer. More specifically, in order to firmly adhere a hydrophilic colloid layer such as a photosensitive emulsion layer or a backing layer onto a polyester support, a specific aqueous copolymer composition is coated and subjected to subbing treatment. The present invention relates to a photographic support provided with the following.

Polyester films have excellent physical properties as supports for silver halide photographic materials and the like, so their demand has increased in recent years and they have been widely used. However, polyester films are extremely hydrophobic, and it is often difficult to provide strong adhesion between such supports and photographic hydrophilic colloid layers using substances such as gelatin as a binder. Conventionally, in photographic materials using polyester films, many subbing methods have been known to bond the support and the hydrophilic colloid layer. In order to achieve strong adhesion, it is often necessary to use a swelling or dissolving agent for the polyester film in either method.

However, when a subbing composition containing these swelling agents or dissolving agents is applied to a polyester film, the flatness of the support is impaired during the subbing process, and most of these swelling agents or dissolving agents are Because it uses harmful organic solvents, it has many drawbacks, such as impairing work safety and health.

For this reason, it has been proposed to undercoat polyester films without using swelling agents or solubilizing agents. One technique is to create a polyester film whose surface has been chemically or physically treated, such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, etc. Supports subjected to surface activation treatments such as laser treatment, mixed acid treatment, and ozone oxidation treatment have been proposed. This technology is disclosed in U.S. Patent No. 2.943°937, U.S. Pat.
゜557, British Patent No. 1,215,234, U.S. Patent No. 3,590,107, JP-A-53-13
This method has been proposed in No. 672, No. 55-18469, and the like. However, these surface-treated polyester films have some copolar groups on the originally hydrophobic film surface, and the thin layer that is a negative factor for surface adhesion has been removed. Although the adhesive force with the photographic hydrophilic colloid layer increased, sufficient adhesive strength could not be obtained.

Furthermore, in order to increase the adhesion to the photographic hydrophilic colloid layer, polyester films have been proposed in which a water-based coating composition layer is provided after surface treatment. This aqueous coating composition layer, so-called subbing layer, must have sufficient adhesion to both the polyester film and the photographic hydrophilic colloid layer. In particular, in order to ensure sufficient adhesion between the subbing layer and the photographic hydrophilic colloid layer, the resin of the subbing layer (
Hereinafter, it will be referred to as the resin cited below. ) A hydrophilic group or a reactive group is included in the component.

Examples of the hydrophilic or reactive group include acids (e.g. acrylic acid, itaconic acid, semi-alkyl esters of itaconic acid, etc.), epoxy groups (e.g. glycidyl acrylate,
glycidyl methacrylate, etc.), N-alkanol group [
Examples include N-methylolacrylamide, hydroxymethylated N-(1,1-dimethyl-3-oxobutyl)acrylamide, etc.), hydroxyl groups (eg, hydroxyethyl methacrylate, hydroxyethyl acrylate, etc.).

Among the above, examples of undercoat resins containing acid components include Japanese Patent Publications No. 48-3564, JP-A No. 1123-1983, JP-A No. 50-1718, European Patent No. 1484, Kaisho 54-61518, Kaisho 55-69138
Publication, U.S. Patent No. 3,545,972, etc.
Further, examples in which an undercoating resin containing an N-alkanol group component is included in the undercoat layer include French Patent No. 140,408, Japanese Patent Application Laid-open No. 131516/1983, British Patent No. 1,178,
597 specification, Japanese Patent Publication No. 57-3054, etc., examples of the undercoating resin containing a hydroxyl group component included in the undercoat layer include JP-A Nos. 49-113868 and 51-12313.
No. 9, No. 51-135526, No. 52-19786, No. 55-69138, etc., the aqueous composition liquid containing a copolymer is applied to a hydrophobic film.
In order to provide excellent adhesion by subbing, it is difficult to select the type of aqueous composition liquid and processing conditions, and it has been difficult to ensure sufficiently satisfactory adhesion.

On the other hand, examples in which the undercoat layer contains an undercoating resin containing an epoxy group component are disclosed in Japanese Patent Publication No. 34-9629 and Japanese Patent Application Laid-open No. 51-5846.
No. 9, No. 52-104913, No. 51-27918, No. 52-19786, No. 55-121437, No. 51-123139, British Patent No. 1,168,1
It is disclosed in the specification of No. 71, Japanese Patent Application Laid-Open No. 55-69138, etc.

Epoxy groups have self-crosslinking properties and react with carboxyl groups and amino groups, so they exhibit excellent adhesion to polyester supports and photographic hydrophilic colloid layers. It was difficult to obtain adhesive strength and it was difficult to select synthesis and processing conditions.

As described above, photographic polyester films containing an undercoat resin containing a hydrophilic group or a reactive group in the undercoat layer have not always been satisfactory in ease of manufacturing process control and undercoat performance.

On the other hand, as an example of a subbing resin that does not necessarily contain the above-mentioned hydrophilic group or reactive group,
Publication No. 70 discloses an undercoat in which a undercoat resin containing styrene as a main component is coated on a polyester film and then subjected to a corona discharge treatment. However, with this undercoat, the film-forming properties of the undercoat resin are insufficient, and the transparency of the undercoat layer polyester film tends to deteriorate due to fluctuations in the drying conditions of the undercoat. It was difficult to get it consistently.

SUMMARY OF THE INVENTION In view of the above problems, the first object of the present invention is to provide a photographic support having strong adhesive strength between a polyester film and a photographic hydrophilic colloid layer.

The second object of the present invention is that it does not necessarily require the use of organic solvents as swelling agents or solubilizers for polyester, and there is no need to release harmful organic solvents into exhaust or wastewater, thereby reducing the risk of pollution. The objective is to provide a photographic support that is not available.

A third object of the present invention is to provide a photographic support with good flatness.

A fourth object of the present invention is that it does not require the use of polyester swelling or dissolving agents, and therefore there is no deterioration in the flatness and transparency of the polyester film caused by this, and the coating of the underlying resin layer does not require the use of polyester swelling or dissolving agents. To provide a photographic support without deterioration of transparency.

A fifth object of the present invention is to provide a photographic support having a subbing layer made of a subbing resin that can be stably and easily produced.

A sixth object of the present invention is to provide a photographic support that can be stably produced and does not cause fluctuations in subbing performance due to variations in coating and drying conditions during the subbing process.

A seventh object of the present invention is to provide a photographic support that does not adversely affect various photographic hydrophilic colloid layers, especially photographic emulsion layers.

The present inventors focused on undercoat resins containing hydrophilic or reactive groups, and as a result of intensive research into undercoat layers that are easy to manufacture and can provide excellent undercoat performance. discovered that the above-mentioned drawbacks could be overcome and satisfactory results could be obtained only when the hydrophilic group-containing monomer and hydrophobic monomer in the resin cited below had a very limited combination. , the present invention has been completed, and the above-mentioned object of the present invention is to provide (
a)) Offin 10-70% by weight, (b) 31-59% by weight of a vinyl monomer having an epoxy group, and (
c) This is achieved by a photographic support characterized in that it has a subbing layer obtained by coating an aqueous coating composition containing a copolymer consisting essentially of 3 to 60% by weight of styrene.

As a specific monomer of the diolefin (a) in the copolymer according to the present invention, for example, butadiene 9 isoprene! Chloroprene, 1,4-pentadiene.

Examples include 1.4-hexadiene, 1.5-hexadiene, 3-mef-1,5-hexadiene, and the like. If the amount of component (a) in the copolymer is small, the adhesion will be poor, whereas if it is too large, production will be difficult. The proportion of component (a) is 10 to 70% by weight, preferably 2LJ to 5% by weight based on the copolymer.
It is 0% by weight.

Specific examples of the vinyl monomer (b) having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

If the amount of component (b) is small, the hydrolysis rate of epoxy groups will increase in emulsion polymerization, resulting in poor dry film adhesion to the hydrophilic colloid layer, especially the backing layer. vice versa,
If the amount is too large, it generally becomes difficult to polymerize and the processing film adhesion of the photographic light-sensitive material becomes poor.

The proportion of component (b) is 31 to 59% by weight, preferably 35 to 45% by weight, based on the copolymer.

Styrene (e) is an essential component to improve production stability in the emulsion polymerization of diolefins and vinyl monomers having epoxy groups, but when styrene is little or not present, production stability is poor and polymerization does not occur. Agglomeration is likely to occur in the
On the other hand, if the amount is too large, the lower limit temperature for film formation will rise, and the film forming properties of the undercoat layer will deteriorate. The proportion of styrene is preferably 3 to 60% by weight based on the copolymer, and monomers that can be combined may also be added within a range that does not impair the object of the present invention.

The average particle size of the suspended particles in the aqueous coating composition (hereinafter referred to as latex) containing the resin cited below is desirably 1 μm or less, particularly preferably 0.1 μm or less. Fine particles improve the mechanical stability and adhesive strength of the latex. K for synthesizing the above-mentioned latex having an average particle size of 1 μm or less, particularly 0.1 μm or less, can be easily synthesized at a synthesis temperature of 60° C. or higher, particularly preferably 70° C. or higher.

A method for obtaining adhesive strength between the polyester film and the photographic emulsion layer by coating a vinyl monomer-styrene copolymer having a butadiene-epoxy group on a polyester film is as follows:
For example, JP-A-49-11118, JP-A-51-121
It is disclosed in the No. 323 specification.

Eight of these publications state that the ratio of the vinyl monomer having an epoxy group to the copolymer is 30% by weight or less, and when the present inventors conducted follow-up experiments, the weighted f!
The transparency of the subbing layer support is good when the content is less than 2 Cl to 30% by weight, but the dry film adhesion of the hydrophilic colloid layer, especially the backing layer, is poor. It got worse. However, by deviating from the conventional technique and increasing the amount to more than 30% by weight, the dry film adhesion of the backing layer was improved, and the transparency of the undercoat layer support was also improved.

However, if the proportion of the vinyl monomer is too high, different disadvantages occur. That is, in JP-A-55-121437, the epoxy group '&! The latex cited below is disclosed in which the ratio of vinyl monomers having an epoxy group to the copolymer is 60 to 90% by weight. If it exceeds 1%, the viscosity will increase significantly, the synthesis stability will deteriorate, and the dry film formation will deteriorate.

Particularly preferred monomer combinations in the copolymer in the present invention include butadiene-glycidyl acrylate-styrene, butadiene-glycidyl methacrylate-styrene, butadiene-allyl glycidyl ether styrene,
Examples include isoprene-glycidyl acrylate-styrene, isoprene-glycidyl methacrylate-styrene, isoprene-allyl glycidyl ether-styrene, and the like, but this description is not intended to limit the scope.

The copolymer used in the present invention can be synthesized by a known emulsion polymerization method. For example, Chemistry of Polymer Latex (Kobunshi Publishing Association, So-M Muroi), Volume 18 and Emulsion Latex Handbook (Taiseisha Publishing) Volume 1.
Polymerization methods, polymerization initiators, emulsifiers, etc. as described in Volumes 1 to 3 can be used. Furthermore, as an emulsifier, see the list of surfactants published by the Japan Surfactant Industry Association (
1981! - version) can also be used. The polymerization temperature is such that the average particle size is 1 μm or less,
In order to obtain a latex with a particularly preferably O6 of 1 μm or less, the temperature is preferably 60° C. or higher, particularly preferably 70° C. or higher.

In the present invention, the copolymer is used as a subbing liquid in the form of an aqueous coating composition in which the copolymer is dispersed as fine particles in an aqueous dispersion medium. Note that, depending on the purpose, part of the water may be replaced with an organic solvent that is miscible with water (for example, methanol or acetone). The copolymer of the present invention obtained by the emulsion polymerization method is obtained as an aqueous dispersion of a fine-grain emulsion polymer, so-called latex.

Aqueous coating composition (subbing liquid) containing the copolymer according to the present invention
varies depending on the purpose of use and coating method, but it is preferable to use a copolymer prepared as an aqueous dispersion as required.

The subbing liquid containing the copolymer according to the present invention (Shimoto Kiki Koshu) contains 0.1 to 40 wt% of the above-mentioned copolymer component, and optionally contains a surfactant, a hydrophilic organic colloid, It may contain additives such as matting agents, lubricants, antistatic agents, and crosslinking agents. Examples of crosslinking agents include so-called hardening agents for photographic gelatin, such as formaldehyde, aldehyde compounds such as glyoxal, mucochloric acid, and tetramethylene-1.
, 4-bis(ethyleneurea), hexamethylene-1,
Compounds having an ethyleneimine group such as 6-bis(ethyleneurea), methanesulfonic acid esters such as trimethylene-1,3-bismethanesulfonic acid ester, active vinyl compounds such as bisacryloyl urea, metaxylene vinyl sulfonic acid, etc. - Compounds having active halogens such as methoxy-4,6-dichlorotriazine and 2-sodiumoxy-4,6-dichlorotriazine, compounds having epoxy groups such as bisphenol glycidyl ether,
Incyanate etc. can be used. Among these, compounds having an ethyleneimine group, methanesulfonic acid esters, and compounds having an active halogen are particularly preferred.

The subbing liquid is applied onto the polyester film.

Here, polyester refers to a linear structure obtained by polycondensation of dicarboxylic acid and glycol, transesterification of dicarboxylic acid ester and glycol or diol diacetate and dicarboxylic acid, and condensation reaction of dicarboxylic acid chloride and diol. Of these, polyethylene terephthalate is the most convenient in terms of availability.

There is no particular limit to the thickness of polyester, but it is approximately 12μ.
Thicknesses having a diameter of m to 500 μm, preferably 40 μTL to 200 μm are advantageous in terms of ease of handling and versatility.

In particular, biaxially stretched crystallized materials are advantageous in terms of stability, strength, and the like. It is preferable that the surface of the polyester film be subjected to various surface activation treatments to make it hydrophilic before applying the subbing liquid onto the Beaujester film. As a surface activation treatment, for example, U.S. Pat. No. 2,943,9
Oxidizing agent solution treatment as described in US Pat. No. 37, etc., ultraviolet absorption treatment as described in US Pat. No. 3,475,193, etc., and US Pat. No. 3,615,557, etc. electric discharge treatment of corona discharge such as 5, active gas exposure treatment as described in British Patent No. 1,215.234, etc., and US Pat. No. 3,590,107, etc. It's a monkey who can't get rid of the flames like that.

The above-mentioned subbing liquid is applied onto the polyester film by a known method. For example, curtain weight, reverse roll application,
It can be applied onto polyester film by fountain air doctor coating, slide hopper coating, extrusion coating, dip coating, etc. The coating amount of the copolymer is preferably 0.01 to 5 V, particularly preferably 0.03 to 2 g/m''. Drying after application of the subbing liquid can be carried out by a known method. For example, hot air drying, infrared heating drying, heater roll drying, microwave drying, etc. can be used.
.

In the present invention, preferably, one additional layer is coated on top of this subbing layer. The upper layer may contain known natural hydrophilic organic colloids such as gelatin and casein, synthetic hydrophilic organic colloids, and antistatic agents, such as Japanese Patent Publication No. 46-24159.
It is possible to apply an aqueous solution of a hydrophilic polymer as described in Japanese Patent Publication No. 1U11, 1982-93165, and Japanese Patent Publication No. 49-23828. This upper layer liquid may contain a matting agent, a hardening agent, a surfactant, etc. As with the processing of the lower layer, any known method can be used for coating and drying the upper layer liquid. Before applying or after drying these subbing liquids and the dotan coating liquid provided as necessary, flame radiation treatment, plasma treatment, corona discharge treatment, Guse discharge treatment, and ultraviolet irradiation are performed as necessary. A known surface treatment process such as treatment may be performed.

The photographic support of the present invention, which is provided with a subbing layer on at least one side in this manner, can have a photographic hydrophilic colloid layer coated on at least one side by a commonly used method. Specifically, various photographic photosensitive layered compositions,
For example, a silver halide photographic emulsion, a diazo photosensitive composition, a gelatin composition containing a haleysilon inhibitor, or a gelatin backing composition for adjusting the curl balance of the support film can be coated, and the obtained product can be coated with a gelatin backing composition for adjusting the curl balance of the support film. The photographic material has excellent adhesive properties, and even when subjected to photographic processing such as development, the photographic material layer does not peel off from the support, and the photographic performance is not adversely affected.

Next, typical production examples of the copolymer used in the present invention will be shown. All of the following concrete measurable numerical relations represent the heavy L1 part.

Synthesis Example (1) The anti-corrosive formulation was placed in a simple autoclave with a capacity of 500 ml, and the tube was completely sealed, and the stirring speed was adjusted to 600 revolutions per minute. At this time, the internal temperature is 5°C and the internal pressure is 1. It was Oatm. Next, the internal temperature was gradually raised and maintained at 80°C. At this time, the internal pressure is 4. When the reaction was continued for 2 hours at 080°C, which was Oatm, the internal pressure reached 10.3 atm and the polymerization was completed. A latex with a dry solid content of 30% by weight and a pH of 4.1 was obtained.

For combination examples (2) to (8) and comparative combination examples (■) to (5), which are also listed in the examples below, the compositions described in each example were prepared in the same manner as in combination example (1) above. A copolymer latex (resin cited below) was synthesized.

The effects of the present invention will be demonstrated below using Examples.

Of course, the present invention is not limited to the following examples.

Next, the evaluation method performed in the examples will be explained.

1) Adhesion test and dry film test> On the surface of the hydrophilic colloid layer for sample photography, make shallow scratches in the shape of the substrate with a razor, then press cellophane adhesive tape on top of it, and then press the cellophane adhesive tape on top of it. , the residual rate of the emulsion film relative to the adhesive area of the cellophane tape was expressed as a percentage.

Processed film attachment test> During processing, the surface of the photographic hydrophilic colloid layer of the sample was scratched in the shape of the substrate with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage. .

In practice, there is no problem if this percentage is 80% or more.

2) Transparency test Turbidity meter MODEL T-2600D manufactured by Tokyo Electric Co., Ltd.
The film support was measured using E and expressed as a percentage.

In practice, if it is 1% or less, there is no problem.

3) Mechanical stability test JISK6381 using a high-speed stirring tester manufactured by Uejima Manufacturing Co., Ltd.
14.00% solids latex liquid in a container according to
Stir with a spindle rotating at high speed with Or, p, m,
The time required for the formation of aggregates is given in minutes. Practical 30
There is no problem if it is more than a minute.

Example (1) A 100 μm polyethylene terephthalate film K after biaxial stretching and heat setting was subjected to corona discharge treatment at 30 W/Id min. Next, the first subtraction of the composition shown below.
The layer was applied to a film thickness of 20 μm and dried at 100° C. for 1 minute to form the layer.

Next, a second undercoat layer having the composition shown below was further applied onto the first undercoat layer to a film thickness of 20 μm, and was dried at 100° C. for 1 minute to form a layer.

A packing layer for printing sensitive materials was applied to the subbed polyester film obtained by the above operations. Further, as a comparative example, as shown in Table M1 below, only the copolymer of the undercoat liquid was changed, and otherwise the undercoating process and backing layer coating were performed in exactly the same procedure. Evaluation of each sample (IB results were as shown in Table 1.

As is clear from Table 1, the sample according to the present invention [Inventive Example (1)] is clearly excellent in all four evaluated items. Further, in Comparative Example (1), the dry film adhesion of the backing layer was poor, and in Comparative Example (2), the dry film adhesion of the backing layer was slightly better than that of Comparative Example (2), but the transparency was poor.

Example (2) An undercoat layer polyester film was prepared in the same manner as in Example (1) except that the copolymer latex (resin cited below) shown in Table 2 was used, and on this undercoat layer a polyester film was prepared. A photosensitive layer for a photosensitive material for printing photosensitive materials was coated.

In addition, comparison was made with a sample made from a comparative compound in the same manner as in Example q).

The evaluation results were as shown in Table 2.

As is clear from Table 2, it is clear that Sample C according to the present invention, Invention Examples (2) and (3) :), is excellent in all four evaluated items. Comparative Example (3) had poor dry film adhesion and was poorly evaluated for photographic performance. In contrast, Examples (2) and (3) of the present invention had no adverse effect on photographic performance.

Example (3) 2 was rolled (a 175 μm polyethylene terephthalate film after El setting was treated with a 300 W high-pressure mercury layer for 5 minutes. Then, the subbing of the composition shown below was added to 1 M'% μm)
It was coated to a film thickness of 100° C. and dried for 1 minute at 100° C. to form a layer, and then a second undercoat layer was applied in the same manner as in Example (1).

Next, an X-ray photographic photosensitive layer was coated on the polyester support having the obtained subbing layer. For comparison, butyl acrylate-styrene copolymer latex was applied;
After drying and forming a layer, 30W/m in
A photographic photosensitive layer for X-rays was directly coated on a polyethylene terephthalate film that had been subjected to a corona discharge treatment.

The evaluation results are shown in Table 3.

-,...l Table 3 Neither Inventive Example (4) nor Comparative Example (4) had any adverse effect on photographic performance. It is clear from Table 3 that 1.
It can be seen that the example of the present invention is excellent in all four evaluated items.

Example (4) A subbing layer polyester film was prepared in the same manner as in Example 1 except that the copolymer latex (resin cited below) shown in Table 4 was used, and a color cut film was placed on the subbing layer.・
A backing layer for the film was applied.

However, the resins cited below were stored at 6℃ for 2 days and 21 days after synthesis. The results of each evaluation are shown in Table 4.

Table 4 As is clear from Table 4, the example of the present invention shows no change over time in all four evaluated items and is excellent.

Example (5) Same as Example (1) except that the surface of the polyethylene terephthalate support before applying the second undercoat layer and after applying the first undercoat layer was subjected to corona discharge treatment at a treatment intensity of 30 W/m"min. It can be seen that the undercoat layer and the backing layer of bad printing materials were coated using the same method as in Example (2), and then the printing was performed in the same manner as in Example (2). It can be seen that the corona discharge treatment effect is advantageously added, and the treated film adhesion and dry film adhesion are further improved compared to Invention Example (9) and (3).
) and +゛(IQ) had no negative effect on photographic performance.

Procedural amendment 1. '11i'1 Noshiko Showa 5th Fii 1. ↑II' Fl 1st 205888
-2 Name of the invention Photographic support: 3 Nagisa 411 I'1 to Sodeyama Which relationship Cow - Applicant Ijsu Tokyo 'A'l? f'i-ku Nishi-Shinjuku I
J' [12612, +3 name (127) Roku Konishi Photography - V Gyo Co., Ltd.? 1. Representative Director Nobuhiko Kawamoto 4. Sponsored by the agent 6. Column 7 of “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment (1) Specification, page 5, additional line “What is polyester? ," should be corrected to "Polyester means, for example."

(2) 3rd line from the bottom of the same page r # (2) replaces ``outside the scope of the present invention'' with ``Comparative synthesis example (2) is within the invention of JP-A-51-121323''
I am corrected.

Claims (1)

[Claims] On at least one side of the polyester support, (a) 10 to 70% by weight of a diolefin, (b) 31 to 59% by weight of a vinyl monomer having an epoxy group, and (c) styrene 3
A photographic support comprising a subbing layer obtained by coating an aqueous coating composition containing a copolymer consisting essentially of ~60% by weight.