JPH0345341A - Waterproof recording material - Google Patents

Abstract

PURPOSE:To obtain waterproof recording material, which is excellent in tear and has satisfactory recordability (printability and writing quality), by a structure wherein tough synthetic resin laminate ply and waterproof and recorable synthetic resin laminate ply are laminated in the order named to base material. CONSTITUTION:Tough synthetic resin laminate ply 2, anchor coat ply 3 and waterproof and recordable synthetic resin laminate ply 4 are laminated in the order named to base material 1. As the base material 1, pulp paper, coat paper, synthetic paper, non-woven fabric, laminated paper or the like, synthetic resin film, metal foil, metallized film, their laminate or the like is exampled. As the tough synthetic resin laminate ply 2, resin, the tear of which is excellent and which is extrudable, is used. As the anchor coat ply 3, publicly known anchor coat is allowed and the preferable spread lies in the range of 0.5 - 2g/m<2>. As the recordable synthetic resin laminate ply 4, resin composition, which is prepared by blending filler with various thermoplastic synthetic resin, is preferable.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a waterproof recording material, and more particularly to a waterproof recording material that has excellent tear strength and can be manufactured by a simplified process. It is.

[Prior art and problems]

Traditionally, paper used for slips, tags, labels, computer paper, etc. has a laminate layer of inorganic-containing polypropylene on a paper base material (high-quality paper), or a laminate layer of polypropylene containing inorganic substances on a paper base material (high-quality paper). In practical use, OPP (biaxially oriented polypropylene) films are laminated via a ○PP film, and an inorganic coating layer is further provided on the surface of the ○PP film.

However, in the former case, since the laminate layer contains inorganic substances, there is a drawback that the laminate layer has low tear strength, and therefore there is a high risk of damage during shipping. On the other hand, the latter requires two coating processes: applying an adhesive to bond the OPP film and the paper base material together, and applying an inorganic coating agent onto the OPP film, which slows down the manufacturing process. This increases the complexity and therefore the resulting product must be very expensive. In addition, although it has tear strength that is satisfactory for practical use in a state without scratches, if a scratch (cut) is formed, the tear strength from the scratch 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 a waterproof recording material formed by sequentially laminating a tough synthetic resin laminate layer and a waterproof/recordable synthetic resin laminate layer on a base material, and the second aspect of the present invention is a base material. Each content is a waterproof recording material formed by sequentially laminating a tough synthetic resin laminate layer and an inorganic coating layer thereon.

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, a tough synthetic resin laminate layer (2), an anchor coat layer (3), and a waterproof/recordable synthetic resin laminate layer (1).
4) are successively laminated.

The substrate (1) used in the present invention includes pulp paper, paper, size press processed paper, super calendered paper, synthetic paper, nonwoven fabric, laminated paper, etc., as well as synthetic resin film, metal foil, metal Examples include sputum-adhering films and laminates 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.

Tough synthetic resin laminate layer (2) used in the present invention
As the resin, a resin having excellent tear strength and extrusion moldability is used, such as polyester resin, boria resin, modified polyolefin resin, etc., and the thickness thereof is preferably in the range of 15 to 30 μm. be.

The anchor coat layer (3) used in the present invention may be a known one, such as rAC-5050 (manufactured by Dainippon Ink), and the coating amount is 0.5 to 2ge.
A range of m is preferred. The anchor coat layer is made of a tough synthetic resin laminate layer and a waterproof/recording synthetic resin laminate.
1. Layer - This layer can be omitted if a ζζ extraction synthetic resin is used or resins with good compatibility and adhesiveness are used even if they are different types.

As the waterproof and recordable synthetic resin ester layer (4) used in the present invention, resin silk or a material prepared by blending a filler with various thermoplastic synthetic resins is suitable.

Particularly suitable thermoplastic synthetic resins are polyolefin resins and polyester resins.

In addition, in order to further improve the recording properties of these resins and to improve the dispersibility of fillers, it is of course possible to use copolymerized functional groups or mixtures of I9 and the like. Preferably -. Examples of poly-11-fin-based materials include polyethylene, -1 millicarbonyl pyrene, poly-4-methylbenylbenyl-5-2, and this: +0)
) j(, polymers, copolymers of these with other monomers having functional groups such as maleic anhydride, acrylic acid, itaconic acid, etc., mixtures thereof, etc. are exemplified. , polycothilene terephthalate, polybutylene terephthalate, polybutylene terephthalate, monomers of these with different acid components and/or glycol fractions, copolymers and mixtures thereof, and the like.

The above-mentioned filling +4 refers to inorganic substances. 4 Of course, it also includes organic substances, but any shape such as particulate or fibrous is suitable.

The first purpose of blending the inorganic filler is to gasify the water adhering to the inorganic filler and crystallization water by using the heat during film forming or during addition. Inorganic filling +4
' The purpose is to form voids using the pyrolysis gas of the FJ body. These voids are preferably open or closed cells and are fine, which improves writability and print ink fixability.

The second objective is to impart hydrophilic properties, improve the stiffness of the surface of the film layer, and further improve printing and coating properties.

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

The fourth objective is to make the fill 1 layer self-opaque, imparting concealing properties and a texture similar to natural paper, and increasing the contrast l- between the recorded image and the ground color.

In particular, the purpose of blending the organic filler is to form the void described above, but here this is done by phase separation with the thermoplastic synthetic resin or by utilizing decomposed gas from the organic filler. Furthermore, there is an advantage in weight reduction that the specific gravity of the resin mixture is smaller when the mixture is mixed with the right machine charge @+J rather than the electric machine charge +4.

Preferred inorganic filling shrines include calcium carbonate, warp, mica, talc, clay, zeolite, alumina, magnesia, titanium oxide, tin oxide, glass powder, barium sulfate, hennite, diatomaceous earth, gypsum, and hydrogen carbonate.
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 filler composition fJ l:l' 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 is small, and if it exceeds 60% by weight, the lamination processability is poor. Become. 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 include common surfactants such as brass, silicone-based and fluorine-based surfactants, as well as polymer-based propylene oxide,
Polymer compounds such as sodium polystyrene sulfonate, functional group-containing olefin resins, ethylene-vinyl alcohol copolymers, and α-olefin adducts of polymethylhydrogen 1:I 4-san can be used.

The selection and blending amount of the compatibilizer are determined by the blending ratio of each bone material constituting the resin composition, the HLB value, etc.

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 0.1 to 15
A range of % Shigesato is suitable.

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 oxidized fat I agents may be added to the resin mixture. The thickness of the synthetic resin layer is preferably in the range of 15 to 30 m.

FIG. 2 shows another embodiment of the material of the present invention, in which the base material (), J= is made of a tough synthetic resin.
Layer (2), adhesive synthetic resin laminate (5), and waterproof recording synthetic resin laminate (4) are laminated in this order.

The first layer (5) of double-adhesive synthetic resin may be, for example, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid ester copolymer, or ethylene-(meth)acrylic acid copolymer. Combinations and combinations of these with additives are preferred. Adhesive 1st grade resin laminate layer (5
) 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 tough synthetic resin laminate layer (2), the adhesive synthetic resin laminate layer 2-1 layer (5), and the waterproof/recordable synthetic resin laminate layer (4) may each be formed in tandem. Alternatively, a coextrusion method may be used. Furthermore, if the waterproof/recordable synthetic resin ξ layer 1 layer (4) is laminated using pine roll, writing performance with a ballpoint pen or pencil can be improved. Furthermore, by subjecting the surface of the laminated film JW (4) to a corona discharge treatment, the film surface's slip resistance 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 a tough synthetic resin laminate layer (2) is placed on the base material (1).
) is provided, and an inorganic coating layer (6) is further provided on the surface of the Kinutate layer (2).

The above-mentioned inorganic coating layer (6) 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/bo.

In the present invention, it is a preferred embodiment to provide an anti-curl synthetic resin laminate layer on the back side of the base material ( ). Suitable examples of such synthetic resins include polyolefin resins such as polyethylene and polypropylene. This Udanate layer not only prevents curling, but also has the effect of further increasing waterproofness. Thickness is 15-30 // m
A range of is suitable. Furthermore, by mixing an antistatic agent into this anti-curl synthetic resin laminate layer, the antistatic performance can be further improved.

(Examples) Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited by these in any way.

Example 1 Dual-quality paper (basis weight 50.0 g/paper) J as base material (1)
Second, corona treatment (30 W/bo/m1n) was performed. On this corona-treated surface, polyester resin "Duranesox 600FP" (manufactured by Polyplastics) was applied using a T-die extruder (screw diameter 401w1, T-die temperature 300°C).
Using extrusion laminate I/L (thickness: 20 μm), a tough synthetic resin laminate layer (2) was formed. Next, an anchor coating agent rA is applied to the surface of this laminate layer (2).
C-5050” (manufactured by Dainippon Ink) at 2.0 g/+d
An anchor coat layer (3) was provided. Next, on this anchor coat layer (3), 55% by weight of polypropylene 2 rLA-221J (manufactured by Mitsui Petrochemical Industries), 30% by weight of calcium carbonate "Whiten SB (red)" (manufactured by Shiraishi Calcium), and 30% by weight of calcium carbonate "Whiten SB (red)" (manufactured by Shiraishi Calcium) were added. Titanium rJR-600
AJ (manufactured by Teika) 10 heavy weight and modified polyolefin resin "Atomer QE-050" (manufactured by Mitsui Petrochemical Industries) were tri-blended with 5% by weight, and a twin-screw kneader rPC was used.
The compound was melt-kneaded with M-30 (manufactured by Jikai Tekko) and extruded and laminated using an F die extruder (screw diameter 40 mm, T die temperature 300°C) to form a waterproof/recordable synthetic resin laminate layer (4 ), and the surface of this laminate layer (4) was subjected to after-corona treatment (30 W/n (7
m1n) to obtain a laminate as shown in FIG.

The surface wettability index of this laminate was 52 dynes/mark, the surface specific electrical resistance was 2.3×10'3 Ω, and printability was good. In addition, Elmendorf tear strength (JIS P 8
11.6) had a tear strength of 132 g in the vertical direction and 145 g in the horizontal direction, which was sufficient for practical use.

Example 2 Base material (1) High quality paper (tsubo IJt45.Og/M)
After corona treatment (30 W/n (/min)) using polyester resin "DURANEX 600FP"
, is extruded using a T-die extruder with a thickness of 1- (thickness 2
271m) L, a tough synthetic resin laminate layer (2) is formed, and then the adhesive synthetic resin laminate layer (5) and the compound of Example 1 are applied by a tandem method and a coextrusion lamination method. Waterproof/recordable synthetic resin used
One layer (4) of Ho was laminated.

That is, the first extruder on the polyester resin side (screw diameter 32 mm, T Gui temperature 300
°C) is adhesive synthetic resin “Atomer AT-499J”.
(manufactured by Mitsui Petrochemical Industries) (thickness 10 μm),
Extruder (screw diameter 40mm, T die temperature 300°C
), the compound of Example 1 (thickness: 15 μm) was used. In addition, waterproof/record P [synthetic resin veneer (4)
The surface of the sample was subjected to the same corona treatment as in Example 1 to obtain a laminate as shown in FIG.

The surface wettability index of this laminate was 52 dynes/Cm, the surface specific electrical resistance was 4.5×]013Ω, and the printing test I results were also good. In addition, Elmendorf tear strength (JIS
P 8116) is 142g in the vertical direction and 15g in the horizontal direction.
6g, and the tear resistance was sufficient.

Example 3 In the same manner as in Example 1, “two-quality paper” (
Tsubo fJ: 50.0 g/n () After U2 Nico treatment,
Polyester resin "Duranenx 600FP1" was extruded to form a tough synthetic resin laminate layer (2).

An aqueous slurry containing 50 parts by weight of clay and 50 parts by weight of calcium carbonate as pigments, and styrene-butadiene copolymer (SBR) latex and starch (15.5) as a binder is applied to the surface of the laminate layer (2) of this laminate. , coated and dried by a conventional method to form an inorganic coating layer (6
) (A coating weight of 6°Q (X/nr) was provided, and a laminate as shown in FIG. 3 was prepared (:F).

5 This laminate has good off-sera I printability, and Elmendorf tear strength is 109 g in the vertical direction and 1 in the horizontal direction.
Tear resistance was sufficient at 22 g.

(Function/Effect) As mentioned 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 writability). It can be manufactured using the coating method, and even when providing an anchor film layer or an inorganic coating layer, two coating processes (O
The process that required the application of an adhesive between the PP film and the base material and the application of an inorganic coating layer to the surface of the OPP film is one process of coating the anchor film 1 layer or coating the inorganic coating layer. It is possible to save a lot of labor.

[Brief explanation of drawings]

1 to 3 are schematic cross-sectional views showing embodiments of the present invention, respectively. 1... Base material 2... Tough synthetic resin film layer 6 - Anchor coat layer - Waterproof/recording synthetic resin laminate layer - Adhesive synthetic resin Uchofu-I layer Inorganic coating layer

Claims (1)

[Claims] 1. On the base material, a tough synthetic resin laminate layer and a waterproof/
A waterproof recording material made by sequentially laminating recording synthetic resin laminate layers. 2. The material according to claim 1, wherein an anchor coat layer is provided between the tough synthetic resin laminate layer and the waterproof/recordable synthetic resin laminate layer. 3. The material according to claim 1, wherein an adhesive synthetic resin laminate layer is provided between the tough synthetic resin laminate layer and the waterproof/recordable synthetic resin laminate layer. 4. A waterproof recording material formed by sequentially laminating a tough synthetic resin laminate layer and an inorganic coating layer on a base material. 5. The material according to claim 1 or 3, wherein an anti-curl synthetic resin laminate layer is provided on the back side of the base material. 6. The material according to claim 5, wherein the anti-curling synthetic resin laminate layer contains an antistatic agent.