JPH0361534A - Waterproof recording material - Google Patents

Abstract

PURPOSE:To obtain a waterproof recording material having excellent tear strength and recording properties by successively laminating an adhesive layer, a rigid synthetic-resin film layer and a waterproof-recording synthetic-resin film layer onto a base material. CONSTITUTION:An adhesive layer 2, a rigid synthetic-resin film layer 3, an undercoating layer 4 and a waterproof-recording synthetic-resin film layer 5 are laminated successively onto a base material 1. Pulp paper, coated paper, these laminate, etc., are cited as the base material 1. A polyester resin, a polyamide resin, etc., and substances prepared by blending fillers of organic or inorganic particles, fibers, etc., and a compatibilizing agents, etc., with these resins are quoted as the rigid synthetic-resin film layer 3. The adhesive layer 2 is formed by a poly-sandwich laminating method, a dry laminating method, etc., besides various adhesives. A resin composition in which fillers are compounded with various thermoplastic synthetic resins is proper as the waterproof-recording synthetic-resin film layer 5. A polyolefin resin and the polyester resin are particularly suitable as the thermoplastic synthetic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a waterproof recording material, and more particularly to a waterproof recording material with excellent tear strength.

[Conventional technology and problems]

Conventionally, paper used for slips, tags, labels, computer paper, etc. is made by laminating an OPP (biaxially oriented polypropylene) film on a paper base material (high-quality paper) with an adhesive, and then laminating the OPP film on top of the OPP film. A material with an inorganic coating layer on its surface has been put into practical use.

However, although it has a tear strength that is satisfactory for practical use in an undamaged state, if it has a -degree scratch (cut),
The tear strength from these scratches becomes extremely weak. Thus, once some kind of damage occurs due to contact with other packages during delivery, it is easily damaged and there is a risk that the original purpose of the slip etc. cannot be fulfilled.

[Means for solving problems]

In view of the above circumstances, the present inventors have completed the present invention as a result of intensive research to solve the above problems.

That is, the first aspect of the present invention is to provide a waterproof recording material in which an adhesive layer, a tough synthetic resin film layer, and a waterproof/recordable synthetic resin laminate layer are sequentially laminated on a base material. No. 2 is a waterproof recording material formed by sequentially laminating an adhesive layer, a tough synthetic resin film layer, and an inorganic coating layer on a base material.

The present invention will be explained based on drawings showing embodiments. In FIG. 1, the waterproof recording material of the present invention has a base material (1).
On top, there is an adhesive layer (2 layers) and a tough synthetic resin film layer (3 layers).
), an anchor coat layer (4), and a waterproof/recordable synthetic resin film layer (5) are sequentially laminated.

Examples of the base material (1) used in the present invention include valve paper, coated paper, size press paper, supercalendered paper, synthetic paper, nonwoven fabric, laminated paper, etc., as well as synthetic resin film, metal foil, and metallized film. and a laminate thereof. The selection of the base material is determined by the purpose and use of the base material.

The thickness of the base material layer is preferably in the range of 30 to 80 μm.

The tough synthetic resin film layer (3) used in the present invention may include stretched or unstretched polyester resins, polyamide resins, polyarylate resins, and polymer alloys (e.g. polyamide resins), which are tougher than the conventionally used OPP. -polyolefin alloys), modified polyolefin resins, etc., and those blended with organic or inorganic particle-based or fiber-based fillers and compatibilizers, etc., and the thickness thereof is in the range of 15 to 30 pm. is suitable.

The base material (1) and the tough synthetic resin film (3) are laminated via an adhesive layer (2).
In addition to various adhesives, it can be formed by a polysandwich lamination method, a dry lamination method, or the like. In particular,
A polysandwich lamination method is preferred.

The anchor coat layer (4) used in the present invention may be a known one, such as rAC-5050J (manufactured by Dainippon Ink), and the coating amount is 0.5 to 2 g.
A range of /rrr is preferred. The anchor coat layer is omitted when the same type of synthetic resin is used for the tough synthetic resin film layer and the waterproof/recording synthetic resin film layer, or when resins with good compatibility and adhesiveness are used even if they are different types. Is possible.

The waterproof/recordable synthetic resin film layer used in the present invention (
For 5), resin compositions in which fillers are blended with various thermoplastic synthetic resins are suitable. Particularly suitable thermoplastic synthetic resins are polyolefin resins and polyester resins. Furthermore, in order to further improve the recording properties of these resins and to improve the dispersibility of fillers, it is desirable to use copolymerized functional groups or mixtures thereof. Polyolefin resins include polyethylene, polypropylene, poly4-methylpentene-1, copolymers thereof, copolymers of these with other monomers having functional groups such as maleic anhydride, acrylic acid, and itaconic acid, Examples include mixtures of the following. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, monomers of these with different acid components and/or glycol components, copolymers and mixtures thereof.

The above-mentioned filler includes not only inorganic substances but also organic substances, but any shape such as particulate or fibrous is suitable.

The first purpose of blending the inorganic filler is to gasify water adhering to the inorganic filler and crystallization water by using the heat during film forming or ξnate processing, and to reduce the heat of the inorganic filler itself. The purpose is to use decomposed gas to form voids. The voids are preferably fine open-celled or closed-celled, and improve writing performance and printing ink fixability.

The second purpose is to impart hydrophilicity, improve the wettability of the surface of the film layer, and further improve printability and coating properties.

The third purpose is to reduce chargeability by imparting hydrophilicity,
Improve handling workability.

The fourth purpose is to make the film layer white and opaque, to provide concealing properties and a texture similar to natural paper, and to increase the contrast between the recorded image and the ground color.

In particular, the purpose of blending organic fillers is to form voids as described above, but here we will use phase separation with the thermoplastic synthetic resin or decomposition gas of the organic filler to create voids. However, when an organic filler is added, the specific gravity of the resin mixture is reduced, which is advantageous in terms of weight reduction.

Preferred inorganic fillers include calcium carbonate, silica, mica, talc, clay, zeolite, alumina, magnesia, titanium oxide, tin oxide, glass powder, barium sulfate, bentonite, diatomaceous earth, gypsum, sodium hydrogen carbonate, etc. On the other hand, examples of the organic filler include urea resin, phenol resin, thermosetting polyester resin, silicone resin, polystyrene resin, and methyl methacrylate resin. These may be used alone or in combination of two or more depending on the purpose of use.

The blending amount of the filler is preferably in the range of 0.5 to 60% by weight; if it is less than 0.5% by weight, the effect of promoting void formation will be small, and if it exceeds 60% by weight, lamination processability will deteriorate. The amount to be blended is appropriately determined depending on the lamination processing temperature, amount of gas generated, etc.

Also, the use of a compatibilizer is a preferred embodiment. The compatibilizer acts between the thermoplastic synthetic resin, the filler, and the gas that forms the voids, thereby making the formed voids uniform and finer. Desirable compatibilizers are common surfactants such as silicone-based and fluorine-based surfactants, as well as molecular-based propylene oxide, sodium polystyrene sulfonate, functional group-containing olefin resins, etc. High molecular compounds such as ethylene-vinyl alcohol copolymer and α-olefin adduct of polymethylhydrogensiloxane can be used.

The selection and blending amount of the compatibilizer are determined by the blending ratio and HLB value of each component constituting the resin composition. Depending on the type of compatibilizer, it may have an antistatic effect or void-forming performance due to thermal decomposition. The blending ratio is usually preferably in the range of 0.1 to 15% by weight.

If it is less than 0.1% by weight, the effect is not sufficient, and if it is less than 15% by weight.
Exceeding this will adversely affect extrusion processability.

Furthermore, if a water-absorbing resin is blended into the resin composition, the hydrophilicity of the film layer will further improve, and the formation of voids will increase due to thermal decomposition, which will improve the wettability of the film layer surface and reduce the charging property. It is effective in improving sexual performance. Water-absorbing resins include commercially available starch-based and acrylic acid-based resins, and are determined by their compatibility with the constituent components in the resin composition.

Furthermore, commonly used additives such as antistatic agents and antioxidants may be added to the resin mixture.

The thickness of the synthetic resin layer is preferably in the range of 15 to 30 μm.

FIG. 2 shows another embodiment of the material of the present invention, which comprises a base material (1), an adhesive layer (2), a tough synthetic resin film layer (3), and an adhesive synthetic resin film layer. (6) and a waterproof/recordable synthetic resin film layer (5) are sequentially laminated.

As the adhesive synthetic resin film layer (6), for example, ethylene-vinyl acetate copolymer, ethylene=(meth)
Suitable examples include acrylic ester copolymers, ethylene-(meth)acrylic acid copolymers, and mixtures thereof with additives. The thickness of the adhesive synthetic resin film layer (6) is preferably in the range of 5 to 25 μm. The adhesive force can be adjusted by changing the type of resin or adding an adhesive force regulator.

The above-mentioned adhesive synthetic resin film layer (6) and waterproof/recordable synthetic resin film N (5) may be laminated by pre-manufactured films via an adhesive layer, but they may be laminated by extrusion lamination. Desirably, the extrusion lamination method may be a tandem method or a co-extrusion method.Also, if the waterproof/recordable synthetic resin film layer (5) is laminated using a pine roll, it will be easy to write with a ballpoint pen or pencil. can be increased. Further, by subjecting the surface of the film layer (5) to corona discharge treatment, the wettability of the film surface is further improved, and the fixing properties of printing ink and the coating properties of chemical liquids are improved.

FIG. 3 shows still another embodiment of the material of the present invention, in which an adhesive layer (2) and a tough synthetic resin film layer (3) are provided on the base material (1). Film layer (3)
An inorganic coating layer (7) is provided on the surface.

The above-mentioned inorganic coating layer (7) may be a conventionally known one, such as one in which an inorganic substance such as clay or calcium carbonate is mixed and dispersed in a latex such as a styrene-butadiene-rubber copolymer or an acrylic polymer. The coating amount is preferably 1 to 15 g/po.

In the present invention, it is a preferred embodiment to provide an anti-curl synthetic resin film layer on the back surface of the substrate (1). Suitable examples of such synthetic resins include polyolefin resins such as polyethylene and polypropylene, and resin compositions made by blending these with additives.Although a pre-manufactured film may be used, it is also possible to use extrusion lamination. It is preferable to provide one. This film layer not only prevents curling, but also has the effect of further increasing waterproofness. The thickness is 15
A range of ˜30 μm is suitable. Furthermore, by mixing an antistatic agent into this anti-curl synthetic resin film layer, the antistatic performance can be further improved.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto.

Example 1 Using high-quality paper (basis weight 50.Og/nf) as a base material,
This is fed out from the first feeding machine and subjected to corona discharge treatment (30W
/rrt/+win) was applied. On the other hand, surface-treated biaxially stretched nylon film rONM15”
(Fj size 15 μm, made by Unitika) is fed out from the second feeder, and the treated surface is placed between the facing press roll and cooling roll at a lower temperature than the T-die extruder (screw diameter 40 mm, T-die temperature 335°C). Density polyethylene resin "Kauson M-16SPJ (manufactured by Mitsui Petrochemical Industries) with a thickness of 18
It was extruded in μm and laminated with a so-called polysandwich laminate.

Next, an anchor coating agent rAc-5050J (manufactured by Dainippon Inc.) was applied to the surface of the two-wheel stretched nylon film of the bonded laminate at a rate of 5 g/rrr, and on this coating layer, polypropylene rLA-221J (Mitsui Petrochemical Co., Ltd.) 55% by weight of calcium carbonate "Whiten SB (red)" (manufactured by Shiraishi Calcium), 10% by weight of titanium dioxide rJR-600AJ (manufactured by Teika) and modified polyolefin resin "Atomer QEO50J (Mitsui Petrochemical Co., Ltd.)" The compound (industrial) from 5% by weight is extruded through T-die R (screw diameter 40m, T-die temperature 300°C).
Extrusion laminate (thickness 201 Im) L using
in) to obtain a laminate.

The surface wettability index of this laminate was 52 dynes/cm, the surface specific electrical resistance was 2.0 x 10''Ω, and the writability and printability were good.The Elmendorf tear strength (JI
S P 8116) is 95g in the vertical direction and 103g in the horizontal direction.
g, and had sufficient tear resistance against handling during shipping and the like.

Example 2 In Example 1, 50 parts by weight of clay as a pigment was added to the surface of a biaxially stretched nylon film of a bonded laminate consisting of a base material-low density polyethylene-biaxially stretched nylon film obtained by polysandwich lamination. 50 parts by weight of calcium carbonate, styrene-butadiene copolymer (SBR) latex and starch (15:
5) Coating and drying the aqueous slurry by a conventional method,
Provide an inorganic coating layer (coating amount 6.0g/bo),
A laminate was obtained.

This laminate has good offset printability, and its Elmendorf tear strength is 84 g in the vertical direction and 96 g in the horizontal direction.
The tear resistance was sufficient.

Comparative Example A biaxially oriented polypropylene film (thickness 20 μm) was bonded to high-quality paper (basis weight 73 g/box) using an adhesive (W-thickness 8 μm) as a base material, and silica,
Coating layer consisting of titanium dioxide and binder (
5g/rr? ) The Elmendorf tear strength of the commercially available laminate was 51 g in the vertical direction and 45 g in the horizontal direction.
This commercially available product had extremely low tear strength when cut.

[Action/Effect]

As described above, according to the present invention, it is possible to provide a waterproof recording material that has excellent tear strength and good recording properties (printing and writing properties).

[Brief explanation of drawings]

1 to 3 are schematic cross-sectional views showing embodiments of the present invention, respectively. Base adhesive layer Tough synthetic resin film layer Anchor coat layer Waterproof/recordable synthetic resin film layer Adhesive synthetic resin film layer Inorganic coating layer

Claims (1)

[Claims] 1. A waterproof recording material comprising an adhesive layer, a tough synthetic resin film layer, and a waterproof/recording synthetic resin film layer successively laminated on a base material. 2. Claim 1, wherein an anchor coat layer is provided between the tough synthetic resin film layer and the waterproof/recordable synthetic resin film layer.
Materials listed. 3. The material according to claim 1, wherein an adhesive synthetic resin film layer is provided between the tough synthetic resin film layer and the waterproof/recordable synthetic resin film layer. 4. A waterproof recording material formed by sequentially laminating an adhesive layer, a tough synthetic resin film layer, and an inorganic coating layer on a base material. 5. The material according to claim 1 or 4, wherein an anti-curling synthetic resin film layer is provided on the back side of the base material. 6. The material according to claim 5, wherein the anti-curl synthetic resin film layer contains an antistatic agent. 7. The material according to any one of claims 1 to 3, wherein the waterproof/recordable synthetic resin film layer is provided by an extrusion lamination method. 8. The material according to claim 5 or 6, wherein the anti-curl synthetic resin film layer is provided by an extrusion lamination method.