JPH02103137A - Waterproof recording paper - Google Patents

Abstract

PURPOSE:To provide excellent recording characteristics, handling workability and tear strength by laminating a film layer composed of a resin composition wherein an inorg. substance is mixed with a thermoplastic synthetic resin to a paper base material. CONSTITUTION:A film layer composed of a resin composition wherein an inorg. substance is mixed with a thermoplastic resin is laminated to the single surface or both surfaces of a paper base material. As the thermoplastic resin, a resin possible to be subjected to laminating processing is designated, and a polyolefinic resin or a polyester resin is pref. By compounding the inorg. substance, the adhesion water or crystal water of the inorg. substance can be gasified using the heat at the time of laminating processing and voids can be formed by the use of the pyrolysis gas of the inorg. substance itself. Further, hydrophilicity can be imparted and printability of coating properties can be enhanced and, furthermore, chargeability is lowered and handling workability can be enhanced.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to waterproof recording paper, and more particularly, to waterproof recording paper that has excellent recording properties and handling workability, and has excellent tear strength. It is something.

(Prior art and problems) Synthetic paper has traditionally been used as waterproof recording paper. For example, ■Synthetic resin film coated with inorganic material on the surface; ■Synthetic resin film made of a mixture of polypropylene resin and inorganic material and stretched; Synthetic resin film layer provided on paper and roughened; For example, paper is used that is extrusion laminated with polypropylene resin using Mantrol.

However, in addition to the resin being expensive, method (2) requires a large number of steps, and methods (2), (2), and (2) also require a large number of steps and are all expensive. In addition, although the material (■) is easy to process, it does not fully satisfy the characteristics required as a recording paper, and it also has the drawback of poor workability because it is easily charged.

Recording paper can be used for direct writing or printing, or can be used with the desired agent depending on the recording method (for example, for electrostatic recording, heat-sensitive paper, pressure-sensitive paper,
There are cases where a coating process is applied (such as for sublimation transfer), but in both cases, surface smoothness and surface wettability are important and greatly affect recording performance.

[Means to solve the problem]

The present invention solves the problem of soft soil by laminating a film layer made of a resin composition containing a thermoplastic synthetic resin and an inorganic substance on a paper base material, thereby making it inexpensive and easy to use for recording paper. The purpose is to provide a material with excellent properties as a base material for use.

That is, the present invention provides a waterproof recording paper in which a film layer made of a resin composition in which an inorganic substance is mixed with a thermoplastic synthetic resin is laminated on a paper base material.

The thermoplastic resin in the present invention refers to a resin that can be laminated, and particularly preferred are polyolefin resins and polyester resins.

Examples of the polyolefin resin include polyethylene, polypropylene, poly4-methylpentene=1, copolymers thereof, copolymers of these with other hexamers, and mixtures thereof. 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.

Next, the first purpose of blending the pA organic material is to use the heat during lamination processing to gasify the water adhering to the inorganic material and crystallization water, and to use the thermal decomposition gas of the inorganic material itself to eliminate voids. Let it form. This void formation improves the coating properties and fixing properties of the chemical layer to be post-processed, and is particularly suitable as a base material for heat-sensitive recording paper since it imparts heat insulating properties and cushioning properties. The second objective is to impart hydrophilicity to improve the wettability of the surface of the film layer, further improving printability and coating properties. The third objective is to reduce the charging property by imparting hydrophilicity and improve the suction workability. The fourth purpose is to make the film layer white and opaque, giving it a natural paper texture, and increasing the contrast between the recorded image and the background color.

Inorganic substances used in the present invention include calcium carbonate,
Silica, mica, talc, clay, zeolite, alumina, titanium oxide, tin oxide, glass powder, barium sulfate,
Bentonite, diatom, gypsum, sodium hydrogen carbonate, etc. are exemplified, and these may be used alone or in combination of two or more depending on the purpose of use. The blending amount of the inorganic material is desirably 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.

In the present invention, the use of a compatibilizer is a preferred embodiment. The compatibilizer used in the present invention acts between the thermoplastic resin, the inorganic substance, and the gas forming the voids that constitute the resin composition, and This aims to make the voids formed uniform and finer. Desirable compatibilizers include ordinary surfactants, silicone-based and fluorine-based surfactants, as well as polymer-based propylene oxide, functional group-containing olefin resins, and ethylene-vinyl alcohol copolymers. , a polymer compound such as an 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 0.1-15%
A range of is suitable. If O is less than 1% by weight, the effect will not be sufficient, and if it exceeds 15% by weight, it will adversely affect the coloring performance.

Next, in the present invention, 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, improving the wettability of the film layer surface and It is effective in improving workability by reducing chargeability.

The water-absorbing resin used in the present invention includes commonly commercially available starch-based and acrylic acid-based resins, and is determined depending on the compatibility with the constituent components in the resin composition.

The paper base material in the present invention includes not only pulp paper but also processed paper, and particularly for patents characterized by high smoothness, coated paper, size press processed paper, super calendered paper, etc. are suitably used.

The present invention is carried out by an extrusion lamination method or a true melt lamination method, and the extrusion lamination method is particularly suitable. According to the extrusion lamination method, the film surface smoothness can be controlled by changing the surface condition of the cooling roll. In addition, if high smoothness is required,
By laminating two or more film layers, the influence of unevenness on the paper surface is reduced and a highly smooth film surface can be obtained.

Next, if the present invention is laminated using MANODROL, it is possible to provide writing properties with a ballpoint pen or pencil. Further, by subjecting the film surface of the waterproof recording paper according to the present invention to corona discharge treatment, the wettability of the film surface is further improved, and the fixing property of printing ink and the coating property of chemical liquid are improved. Further, since the waterproof recording paper according to the present invention has a film layer on the paper, it has better tear strength than synthetic paper made of 100% synthetic resin film.

〔Example〕

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

Example 1 Polypropylene resin rLA-221J (manufactured by Nil Petrochemical Industries) 56% by weight, calcium carbonate [Boyton S
40% by weight of "B (red)" (manufactured by Shiraishi Calcium), and modified polypropylene resin "Atomer QE-0" as a compatibilizer.
50J (manufactured by Nil Petrochemical Industries) was triblended, and melt-kneaded (dice exit temperature: 220°C) using a twin-screw kneader rPCM-30J (manufactured by Ikegai Iron Works) to pelletize.

The pelletized resin composition was supplied to a T-die extruder (diameter: 40°, T-die temperature: 300°C), and high-quality paper (scale: 166°C) was fed.
3 g/rrr) was extrusion laminated (using a cooling mirror roll with a thickness of 30 μm). The surface wettability index, charging voltage, and printability of the laminated surface of the laminated paper prepared as described above were tested, and the results are shown in Table 1.

Example 2 Polypropylene resin rLA-221J was mixed with 49 heavy molds, calcium carbonate "Wheaton S [3 (red)]" 40% by weight,
10% by weight of water-absorbing resin [Purawet G14°HJ (manufactured by Nil Petrochemical Co., Ltd.) and as a surfactant with antistatic function [Electro Stripper TS-6J (manufactured by Kao Corporation) 1]
The same operation as in Example 1 was performed except that a resin composition consisting of % by weight was used, and the results are shown in Table 1.

Example 3 Polypropylene resin rLA-221J at 6011%,
The same operations as in Example 1 were carried out, except that a resin composition consisting of 40% by weight of calcium carbonate "Whitton SB (red)" was used, and the results are shown in Table 1.

Example 4 Copolyester resin “Kodabond PF, TG5116”
Tri-blend 40% by weight of calcium carbonate "Whitton SB (red)" in a 60-heavy cylinder (manufactured by Eastman Chemical), melt-knead it in a twin-screw kneader rPCM-30 (dice outlet temperature 210°C), and pelletize it. did. The pelletized resin composition was transferred to a T-die extruder (T-die temperature: 280
℃), and the same operation as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 1 Polypropylene resin rLA-221J was processed using a T-die extruder (
The same operation as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 2 Copolyester resin "Kodabond PETG5116" was supplied to a T-die extruder (T-die temperature: 280'C), and the same operation as in Example 1 was carried out, and the results are shown in Table 1.

[Action/Effect]

As expected from soft soil, according to the present invention, a waterproof film layer with fine voids on the surface and antistatic and hydrophilic properties is laminated on paper using an inexpensive manufacturing method, and has excellent tear strength. , it is possible to provide a material suitable for recording paper.

Patent Applicant: Goyo Giko Co., Ltd. Procedural Netit Official Book (spontaneous) 1. Indication of the case Patent Application No. 257898 of 1988 2. Name of the invention Waterproof recording paper 3. Person making the amendment Relationship with the case: Patent applicant address: 4-13-18 Anritsu, Suminoe-ku, Osaka Name: Goyo Shiko Co., Ltd. Representative: Kojibe Hirose 4, agent address: 3-2-4-5 Nishitenma, Kita-ku, Osaka Increased due to amendment Number of rust claims 6, Specification to be amended 7, Full text of amendment 10 Name of invention Waterproof recording paper 2, Scope of claims! , a waterproof recording paper in which a film layer made of a resin composition in which an inorganic substance is mixed with a thermoplastic synthetic resin is laminated on a paper base material.

2. The waterproof recording paper according to claim 1, wherein the thermoplastic synthetic resin is a polyolefin resin.

3. The waterproof recording paper according to claim 1, wherein the thermoplastic synthetic resin is a polyester resin.

4. The waterproof recording paper according to claim 1, wherein the resin composition further contains a compatibilizer and/or a water-absorbing resin.

3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to waterproof recording paper, and more specifically, to waterproof recording paper that has excellent recording properties and handling workability, and has excellent tear strength. It is.

[Prior art and problems]

Conventionally, synthetic paper has been used as waterproof recording paper, but conventional synthetic paper °ζ is, for example, ■ PET film surface roughened (sandblast), ■ synthetic resin film surface (1) A mixture of polypropylene resin and an inorganic substance is formed into a film and stretched, (0) a synthetic resin film layer is provided on paper and the surface is roughened, and (2) polypropylene resin is coated on paper. Extrusion lamination using pine rolls, etc. are used.

However, in addition to the resin being expensive, method (2) requires a large number of steps, and methods (2), (2), and (2) also require a large number of steps and are all expensive. In addition, although the material (■) is easy to process, it does not fully satisfy the necessary properties as a recording paper, and it has the drawback of poor workability because it is easily charged.

Recording paper can be used for direct writing or printing, or can be used with the desired agent depending on the recording method (for example, for electrostatic recording, heat-sensitive paper, pressure-sensitive paper,
There are cases where a coating process is applied (such as for sublimation transfer), but in both cases, surface smoothness and surface wettability are important and greatly affect recording performance.

[Means for solving the problem] The present invention solves the problem of ridges by laminating a film layer made of a resin composition in which an inorganic substance is mixed with a thermoplastic synthetic resin on a paper base material. The object of the present invention is to provide a material that is inexpensive and has excellent properties as a base material for recording paper.

That is, the present invention is a waterproof recording paper in which a film layer made of a resin composition in which an inorganic substance is mixed with a thermoplastic synthetic resin is laminated on one or both sides of a paper base material.

The thermoplastic resin in the present invention refers to a resin that can be laminated, and any resin can be selected depending on the required physical properties. In addition, the front and back sides may be made of different resins, and particularly preferred are polyolefin resins and polyester resins. Polyolefin resins include polyethylene,
Examples include polypropylene, poly4-methylpentene-1, copolymers thereof, copolymers of these with other monomers, and mixtures thereof. 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.

Next, the first purpose of blending inorganic substances is to use the heat during lamination processing to gasify the water adhering to the inorganic substance and crystallization water, and to form voids by using the thermal decomposition gas of the inorganic substance itself. . This void formation improves the coating properties and fixing properties of the chemical layer to be post-processed, and is particularly suitable as a base material for heat-sensitive recording paper since it imparts heat insulating properties and silane properties. The second objective is to impart hydrophilicity to improve the wettability of the surface of the film layer, further improving printability and coating properties. The third objective is to reduce charging property by imparting hydrophilicity and improve handling workability. The fourth purpose is to make the film layer white and opaque, giving it a natural paper texture, and increasing the contrast between the recorded image and the background color.

Inorganic substances used in the present invention include calcium carbonate,
Silica, mica, talc, clay, zeolite, alumina, titanium oxide, tin oxide, glass powder, barium sulfate,
Bentonite, diatomaceous earth, gypsum, sodium hydrogen carbonate, etc. are exemplified, and these may be used alone or in combination of two or more types depending on the purpose of use. The amount of the inorganic added is desirably 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 laminating temperature, gas cover, etc.

In the present invention, the use of a compatibilizer is a preferred embodiment. The compatibilizer used in the present invention acts between the thermoplastic resin, the inorganic substance, and the gas forming the voids that constitute the resin composition, and This aims to make the voids formed uniform and finer. Desirable compatibilizers include ordinary surfactants, silicone-based and fluorine-based surfactants, as well as polymer-based propylene oxide and functional group-containing olefin resins (maleic anhydride copolymers, Polymer compounds such as acrylic acid copolymers, itaconic acid copolymers, etc.), ethylene vinyl alcohol copolymers, and α-olefin adducts 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 compatible agent, it may have an antistatic effect or the ability to form voids due to thermal decomposition. The blending ratio is usually 0, 1-1
A range of 5% by weight is preferred. If it is less than 0.1% by weight, the effect will not be sufficient, and if it exceeds 15% by weight, it will adversely affect the coloring performance.

Next, in the present invention, 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, improving the wettability of the film layer surface and It is effective in improving workability by reducing chargeability.

The water-absorbing resin used in the present invention includes commonly commercially available starch-based and acrylic acid-based resins, and is determined depending on the compatibility with the constituent components in the resin composition.

The paper base material in the present invention includes not only pulp paper but also processed paper, and when particularly high smoothness is required, coated paper, size press processed paper, super calendered paper, etc. are preferably used.

In addition to the extrusion lamination method, hot melt lamination method, dry lamination method, and wet lamination method, the present invention
This may be carried out by a known lamination method such as bonding with an adhesive or an adhesive, but an extrusion lamination method is particularly suitable. It goes without saying that one or both sides of the base material may be laminated depending on the application. According to the extrusion lamination method, the film surface smoothness can be controlled by changing the surface condition of the cooling roll.

Furthermore, when high smoothness is required, by laminating two or more film layers, the influence of unevenness on the paper surface is reduced and a film surface with high smoothness can be obtained.

Of course, known methods such as fire treatment, corona treatment, ozone treatment, and methods that use these methods in combination can be used to improve the adhesion to the paper base material.

Next, if the present invention is laminated using pine roll, it can also be written with a ballpoint pen or pencil. Further, by subjecting the film surface of the waterproof recording paper according to the present invention to corona discharge treatment, the wettability of the film surface is further improved, and the fixing property of printing ink and the coating property of chemical liquid are improved. Further, since the waterproof recording paper according to the present invention has a film layer on the paper, it has better tear strength than synthetic paper made of 100% synthetic resin film.

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

Example 1 Polypropylene resin rL, A-221J (manufactured by Nil Petrochemical Industries) 55% by weight, calcium carbonate [Whiten SB
(Red)" (Shiraishi Calcium) 40% by weight, and modified polypropylene resin "Atomer QE-05" as a compatibilizer.
0J (manufactured by Mitsui Petrochemical Industries, Ltd.) in an amount of 5% by weight was triblended, and the mixture was melt-kneaded (dice outlet temperature: 220'C) using a twin-screw kneader rPCM-30J (manufactured by Ikegai Iron Works) and pelletized.

The pelletized resin composition was extruded through die A (diameter 4).
0 ■, T-die temperature 300℃), high-quality paper (basis weight 6
6.3 g/nf) onto extrusion laminate (thickness 30 μm,
(using a cooling mirror roll). The surface wettability index of the laminated surface of the laminated paper prepared as above, the electrostatic voltage,
and printability tests were conducted and the results are shown in Table 1.

Example 2 Polypropylene resin r1. 49% by weight of A-221J,
Calcium carbonate "Whiten SB (red)" 40wt%,
Water-absorbing resin "Plough-C; 140HJ (manufactured by Mitsubishi Yuka) 10% by weight and as a surfactant with antistatic function [Electrostripper-TS-3J (manufactured by Kao) 1 type tank %" The same operations as in Example 1 were performed except that the resin composition was used, and the results are shown in Table 1.

Example 3 60% by weight of polypropylene resin rLA-221J, 40% by weight of calcium carbonate "Whiten SB (h) J"
The same operations as in Example 1 were performed except that a resin composition consisting of was used, and the results are shown in Table 1.

Example 4 Copolyester resin r Kodabond PETG5116”
Tri-blend 60% by weight (manufactured by Eastman Chemical) and 40% by weight of calcium carbonate "Whiten SB (red)" and melt-knead with a twin-screw kneader rPCM-30 (dice exit temperature 210°C). and pelletized. The pelletized resin composition is transferred to a T-die extruder (T-die temperature: 28
0'C), and the same operations as in Example 1 were performed, and the results are shown in Table 1.

Example 5 The resin composition kneaded in Example 1 was heated using a T-die extruder (diameter 4
0, T-die temperature 300°C), high quality paper (1 tsubo 1 tsubo)
Sequential extrusion lamination was performed on both sides of the t66.3g/rrf) to a thickness of 25 μm on each side. The results are shown in Table 1.

Example 6 The resin composition kneaded in Example 4 was heated using a T-die extruder (diameter 4
Qm, T-die temperature: 280°C), high-quality paper (basis weight: 6
6.3g/rrf) on each side. .

Sequential extrusion lamination was performed with a thickness of m. The results are shown in Table 1.

Comparative Example 1 Polypropylene resin rLA-221J was processed using a T-die extruder (
The same operation as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 2 T-die extrusion of copolyester resin [Kodabond PETG5116]! 11 (T die temperature 280°C),
The same operations as in Example 1 were performed, and the results are shown in Table 1.

Comparative Example 3 Using polypropylene resin rLA-221J, Example 5
Under the same conditions as above, sequential extrusion lamination was performed on both sides of the high-quality paper to a thickness of 25 μm on each side, and the results are shown in Table 1.

Comparative Example 4 Copolyester resin [Kodabond PETG5116J was used, and 30% of each was applied to both sides of high-quality paper under the same conditions as in Example 6.
Sequential extrusion lamination was performed to a thickness of μm, and the results are shown in Table 1.

[Action/Effect]

As mentioned above, according to the present invention, a waterproof film layer with fine voids on the surface and having antistatic and hydrophilic properties is laminated onto paper using an inexpensive manufacturing method, resulting in excellent tear resistance. A material that is strong and suitable for recording paper can be used.

Patent applicant: Goyo Giko Co., Ltd.

Claims (1)

[Claims] 1. A waterproof recording paper in which a film layer made of a resin composition in which an inorganic substance is mixed with a thermoplastic synthetic resin is laminated on a paper base material. 2. The waterproof recording paper according to claim 1, wherein the thermoplastic synthetic resin is a polyolefin resin. 3. The waterproof recording paper according to claim 1, wherein the thermoplastic synthetic resin is a polyester resin. 4. The waterproof recording paper according to claim 1, wherein the resin composition further contains a compatibilizer and/or a water-absorbing resin.