JP3289613B2 - Moisture proof paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a moisture-proof paper. More specifically, the present invention relates to a moisture-proof paper having a moisture-proof layer of a specific composition formed on a paper support and capable of recovering and recycling used paper. The moisture-proof paper of the present invention is useful for applications such as moisture-proof wrapping paper, waterproof paper, and moisture-proof heavy bags.

[0002]

2. Description of the Related Art Moisture proof paper which forms a film layer of a hydrophobic, film-forming resin such as polyethylene, polypropylene or polyvinylidene chloride on at least one surface of a paper support to prevent the transmission of water vapor and moisture is known. Widely known.
Such conventional moisture-proof paper has the advantage that the moisture-proof coating layer is strong and has excellent moisture-proof properties.However, when this moisture-proof paper is recovered and recycled as used paper, the pulp fibers become floc. There is a problem that the film is not sufficiently disaggregated and dispersed after being formed, or the moisture-proof film itself remains in a sheet form. For this reason, the conventional moisture-proof paper has a drawback that the used paper cannot be collected and recycled. In addition, the waste paper of such conventional moisture-proof paper must be incinerated, which is contrary to demands for environmental protection and reuse of natural resources. Furthermore, if such conventional moisture-proof waste paper is mixed with ordinary waste paper, it is difficult to separate the waste paper, which causes a remarkable reduction in the recovery / reuse rate of waste paper.

[0003] Various attempts have been made to solve the above problems. For example, Japanese Patent Application Laid-Open No. 50-367
No. 11 describes a method of applying an emulsion containing a paraffin wax having a specific composition to kraft paper and drying it under heating to produce a moisture-proof paper that can be recovered and reused. I have. Also, JP-A-56-148
No. 997 discloses a synthetic hydrocarbon resin and wax,
A styrene-maleic acid-based copolymer and a surfactant obtained by dispersing in water using a surfactant and a thermoplastic acrylic resin emulsion are disclosed. The moisture-proof paper obtained by forming a moisture-proof layer with the composition is one that can recover and reuse used paper. Furthermore, "Packaging technology", September 1982
Monthly, pp. 42-46, recoverable and reusable based on coating a paper support with a coating solution containing a specific synthetic rubber latex and a specific wax-based emulsion. It describes a method for producing a moisture-proof paper.

[0004] The above-mentioned wax-containing moisture-proof paper can be re-disintegrated and regenerated, but when it is wound into a roll, the wax contained in the moisture-proof layer contacts the moisture-proof layer from the surface thereof. Transfer to the back of the moisture-proof paper, and as a result, the back of the moisture-proof paper becomes extremely slippery,
It becomes difficult to hold in a predetermined shape or position.
For example, when packaging an article or object using such a wax-containing moisture-proof paper, when the back surfaces of the moisture-proof paper contact each other, at this contact surface, the moisture-proof papers slide on each other,
It becomes difficult to maintain a predetermined shape or stay in a predetermined position. For this reason, the packaging state of the package is poor, irregular, or slips easily. In particular, if a heavy article is wrapped with the wrapping paper as described above, the packages may be displaced from each other during transportation or the like, and the package may be broken or the article may fall. In order to prevent such a problem, an attempt has been made to provide an anti-slip layer on the back surface of the wax-containing moisture-proof paper, but no satisfactory solution has yet been obtained.

Further, in the wax-containing moisture-proof paper, the bleed of the wax (the wax located inside the moisture-proof layer is
(This refers to the phenomenon of migration to the surface of the moisture-proof layer over time.)
Inevitably, the adhesion of the moisture-proof layer surface where the wax bleeds is remarkably low, and even if an attempt is made to attach a label or the like to the moisture-proof layer, the adhesion or adhesion does not sufficiently occur, and the wax tends to peel off. There is. When using a hot-melt adhesive for wrapping, only a specific type of hot-melt adhesive that is effective at room temperature is effective. Limited.

Further, when packaging using wax-containing moisture-proof paper, it is possible to use a pressure-sensitive adhesive tape having a re-disintegration property. There is a problem that the workability is significantly reduced as compared with the case where an adhesive or a pressure-sensitive adhesive is used.

Furthermore, conventional moisture-proof papers using a synthetic resin latex, for example, SBR latex, as a resin for forming a moisture-proof layer are wound up in a roll shape, and a number of rolls are stacked in multiple stages to form a long length. Under severe conditions, such as when stored for a long period of time or when articles packed with this moisture-proof paper (for example, printing paper reams) are stored in multiple stages and stored for a long period of time, the moisture-proof inside the roll The front and back surfaces of the paper that are in contact with each other are sticky, or the surface of the wrapping paper and the surface (or back surface) of the article (printing paper) that is in contact with it are blocked (by heat and / or pressure) to block the contact surface. (A phenomenon that the contact surfaces adhere to each other), which makes it difficult to release the blocking.

In order to prevent the above-mentioned blocking, it is known to use a resin having a relatively high glass transition temperature (Tg, for example, 40 ° C. or more) as a synthetic resin used as a latex. T
It is known that when a synthetic resin latex having a high g) is used, the obtained moisture-proof layer becomes hard, and when it is bent, the moisture-proof property of the bent portion is reduced. Therefore, there has been a strong demand for moisture-proof paper having high blocking resistance and satisfactory moisture-proof properties.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a method for recovering used paper.
An object of the present invention is to provide a moisture-proof paper which can be reused, does not cause slippage on its surface, and does not cause blocking. Another object of the present invention is to provide a moisture-proof paper which is easy to adhere to a label or the like and has practically sufficient adhesiveness.

[0010]

The moisture-proof paper of the present invention comprises a paper support and a moisture-proof layer formed on at least one surface of the paper support, wherein the moisture-proof layer comprises (a) a moisture-proof material. A film-forming synthetic resin, (b) flat phyllosilicate compound particles having an average particle diameter of 5 to 50 μm and an aspect ratio of 5 or more, and (c) a moisture-proofing agent. Is what you do. In the moisture-proof paper of the present invention,
The moisture-proof and film-forming synthetic resin (a) is (a-1)
Conjugated diene compound having 4 to 6 carbon atoms, acrylate ester having 4 to 11 carbon atoms, 5 to 5 carbon atoms
12 methacrylates, ethylenically unsaturated nitrile compounds having 3 to 4 carbon atoms, 6 to 6 carbon atoms
Polymers and copolymers of at least one monomer selected from seven ethylenically unsaturated carboxylic acid glycidyl esters and an aromatic vinyl compound having 8 to 11 carbon atoms, and (a-2) a carbon atom A conjugated diene compound having 4 to 6 carbon atoms, an acrylic acid ester having 4 to 11 carbon atoms, a methacrylic acid ester having 5 to 12 carbon atoms, an ethylenically unsaturated compound having 3 to 4 carbon atoms Nitrile compounds, ethylenically unsaturated carboxylic acid glycidyl esters having 6 to 7 carbon atoms, and 8 to 11 carbon atoms
At least one hydrophobic comonomer selected from aromatic vinyl compounds, an ethylenically unsaturated carboxylic acid having 3 to 7 carbon atoms, and an ethylenically unsaturated carboxylic acid having 3 to 9 carbon atoms It is preferable to include at least one selected from copolymers with one or more hydrophilic comonomers selected from acid amides. In the moisture-proof paper of the present invention, the moisture-proof property improving agent (c) is a urea-formaldehyde condensation reaction product, a melamine-formaldehyde condensation reaction product, an aldehyde compound having 1 to 8 carbon atoms, and one or more aldehyde compounds. Epoxy compound having epoxy group, crosslinking reactive polyvalent metal compound, organoalkoxysilane compound, organoalkoxy metal compound, organic amine compound, polyamide compound, polyamide polyurea compound, polyamine polyurea compound, polyamide amine polyurea compound, polyamide amine Compound, polyamidoamine-epihalohydrin or formaldehyde condensation reaction product, polyamine-epihalohydrin or formaldehyde condensation reaction product, polyamidepolyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine polyamine Urea - epihalohydrin or formaldehyde condensation reaction products, and polyamide amine polyurea - preferably comprises at least one selected from epihalohydrin or formaldehyde condensation reaction products. In the moisture-proof paper of the present invention, the moisture-proof improving agent (c) contains a cross-linking reactive compound (c-1) by a covalent bond, and the compound (c-1) is the moisture-proof and film-forming synthetic resin. It may be made hydrophobic by reacting with (a). In the moisture-proof paper of the present invention, the moisture-proof improving agent (c) contains an ionic crosslinking reactive compound (c-2), and the compound (c-2) reacts with the moisture-proof and film-forming synthetic resin. This may be made hydrophobic. In the moisture-proof paper of the present invention, the moisture-proof improver (c) contains a cross-linking coordination reactive compound (c-3),
This compound (c-3) may react with the moisture-proof / film-forming synthetic resin to make it hydrophobic. In the moisture-proof paper of the present invention, at least one selected from the organoalkoxysilane compounds and the organoalkoxy metal compounds is preferably supported on the surface of the phyllosilicate compound particles. In the moisture-proof paper of the present invention, the weight ratio (a) :( b) of the moisture-proof and film-forming synthetic resin (a) to the phyllosilicate compound particles (b) is 30 to 70:70. -30, and the compounding weight of the moisture-proofing agent (c) is 0.05-
It is preferably 10 parts by weight.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The moisture-proof paper of the present invention has a paper support and a moisture-proof property formed on at least one surface of the paper support. And (b) a flat phyllosilicate compound particle having an average particle diameter of 5 to 50 μm and an aspect ratio of 5 or more, and (b) a moisture-proofing agent.

In the moisture-proof paper of the present invention, the moisture-proof and film-forming synthetic resin (a) is not particularly limited, but at least one selected from the following groups (a-1) and (a-2): Preferably, it contains a polymer or copolymer of some kind. (A-1): a conjugated diene compound having 4 to 6 carbon atoms, an acrylic acid ester having 4 to 11 carbon atoms, a methacrylic acid ester having 5 to 12 carbon atoms, and having 3 carbon atoms At least one selected from ethylenically unsaturated nitrile compounds having 4 to 4 carbon atoms, glycidyl esters of ethylenically unsaturated carboxylic acids having 6 to 7 carbon atoms, and aromatic vinyl compounds having 8 to 11 carbon atoms. Polymers and copolymers of monomers. And (a-2): a conjugated diene compound having 4 to 6 carbon atoms, an acrylic acid ester having 4 to 11 carbon atoms, a methacrylic acid ester having 5 to 12 carbon atoms, and a carbon atom having 5 to 12 carbon atoms At least one selected from 3 to 4 ethylenically unsaturated nitrile compounds, 6 to 7 carbon atoms of ethylenically unsaturated carboxylic acid glycidyl ester and 8 to 11 carbon atoms of an aromatic vinyl compound And at least one hydrophilic comonomer selected from an ethylenically unsaturated carboxylic acid having 3 to 7 carbon atoms and an ethylenically unsaturated carboxylic acid amide having 3 to 9 carbon atoms With a copolymer.

In the moisture-proof paper of the present invention, carbon used as a monomer or comonomer of the polymer and copolymer (a-1) and (a-2) contained in the moisture-proof and film-forming synthetic resin (a) The conjugated diene compound having 4 to 6 atoms is preferably selected from butadiene (1,3-butadiene), isoprene, and 2,3-dimethyl-1,3-butadiene, more preferably 1,3-butadiene. Butadiene and isoprene.

The acrylates having 4 to 11 carbon atoms include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,
Sec-butyl acrylate, n-pentyl acrylate (amyl), isoamyl acrylate (pentyl), n-hexyl acrylate, 2-ethylhexyl acrylate,
It can be selected from n-heptyl acrylate, n-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, n-nonyl acrylate and the like, and is preferably methyl acrylate and ethyl acrylate.

The number of carbon atoms used in the present invention is 5-12.
The methacrylates are, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, sec-methacrylic acid.
Butyl, n-pentyl methacrylate (amyl), isoamyl methacrylate (pentyl), n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-hydroxyethyl methacrylate, methacryl Hydroxypropyl, n-nonyl methacrylate and the like, and preferably methyl methacrylate and ethyl methacrylate.

The ethylenically unsaturated nitrile compound having 3 to 4 carbon atoms used in the present invention is preferably selected from acrylonitrile and methacrylonitrile, and is preferably acrylonitrile.

The ethylenically unsaturated carboxylic acid glycidyl ester having 6 to 7 carbon atoms used in the present invention is:
Preferred are glycidyl acrylate and glycidyl methacrylate, with glycidyl acrylate being preferred.

The number of carbon atoms used in the present invention is 8-11.
Aromatic vinyl compounds are preferably styrene, α-
It is selected from methylstyrene, α-ethylstyrene, vinyltoluene, p-tert-butylchlorostyrene and the like, and is more preferably styrene.

The ethylenically unsaturated alcohol glycidyl ether having 5 to 6 carbon atoms used in the present invention is:
It is selected from acrylic glycidyl ether and methacryl glycidyl ether, and is preferably acrylic glycidyl ether.

In the moisture-proof paper of the present invention, the ethylenic resin having 3 to 7 carbon atoms used as a hydrophilic comonomer of the copolymer (a-2) contained in the moisture-proof and film-forming synthetic resin (a). Unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, pentenoic acid (such as angelic acid and tiglic acid), hexenoic acid (such as 2-hexenoic acid and 3-hexenoic acid) and heptenoic acid ( 2-butenoic acid), butenedioic acid (fumaric acid, maleic acid), itaconic acid, and the like, and are preferably selected from acrylic acid and methacrylic acid.

A polymer or copolymer obtained by using such a carboxylic acid group-containing monomer, for example, a carboxylic acid-modified styrene-butadiene copolymer is prepared by using an aqueous alkali solution,
That is, it is soluble or partially swollen in an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and is a basic compound having a hydrophobic group such as an organic amine. Hydrophobicity and water-insolubility can be achieved by a salt-forming reaction with the compound.

The ethylenically unsaturated carboxylic acid amide having 3 to 9 carbon atoms used in the present invention includes acrylamide, methacrylamide, vinylacetamide, pentenamide, butenedioic acid monoamide and diamide, Mono- and diamides of itaconic acid, N-methylol acrylamide, N-methylol methacrylamide, N
-Dimethylol acrylamide, N-dimethylol methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide and the like, and are preferably selected from acrylamide and methacrylamide.

In the copolymer (a-2) used for the moisture-proof waterproof paper of the present invention, there is no particular limitation on the copolymerization molar ratio of the hydrophobic comonomer and the hydrophilic comonomer. 60: 5 to 40, preferably
The ratio is more preferably 90 to 70:10 to 30. When the copolymerization molar ratio of the hydrophobic comonomer and the hydrophilic comonomer is less than 60:40, the content of the hydrophilic comonomer becomes excessively large, and the moisture resistance and water resistance of the obtained copolymer may be insufficient. When it is more than 95: 5, the content of the hydrophilic comonomer becomes too small, and the contribution of the hydrophilic comonomer to the physical properties of the obtained copolymer, particularly the effect of the moisture-proofing agent, becomes insufficient. is there.

The moisture-proof / film-forming synthetic resin (a) used in the present invention mainly functions as a moisture-proof layer-forming binder and prevents water vapor transmission.
Used as an aqueous solution, aqueous dispersion, or aqueous emulsion. When the synthetic resin (a) is water-insoluble, it is preferable to use a dispersant and / or an emulsifier as little as possible and / or to use a reactive surfactant,
In the polymerization, it is preferable to use as little emulsifier or dispersant as possible and to reduce the particle diameter as much as possible (preferably 150 nm or less). Further, the synthetic resin (a) preferably has a glass transition temperature (Tg) of 5 to 30.

In the moisture-proof paper of the present invention, the flat phyllosilicate compound particles (b) contained in the moisture-proof layer are 5 to 5%.
0 μm, preferably an average particle diameter of 10 to 40 μm,
It has an aspect ratio of 5 or more, preferably 10 or more. Since the phyllosilicate compound particles used in the present invention have a plate-like shape, when a coating liquid containing the plate-like particles is applied on the surface of a paper support, the plate-like particles have the plate-like surface thereof. It is arranged almost parallel to each other and almost parallel to the surface of the support, and since this arrangement is laminated, the gap between the plate-like particles becomes narrower. It has to be detoured along the surface, so that the permeation distance of the water vapor is lengthened, and the permeation amount of the water vapor per unit time is thought to be reduced. In addition, the moisture-proof layer of the present invention has a small moisture permeation flow rate as described above. A thickness of several tens of μm is sufficient for the layer.

In the moisture-proof paper of the present invention, when the average particle diameter of the phyllosilicate compound particles is less than 5 μm, the phyllosilicate compound particles are coated with each other and parallel to the surface of the support. Orientation becomes difficult, and therefore, a sufficient effect of improving moisture-proof property cannot be obtained. It is 50
If the particle size is larger than μm, the plate-like particles are easily broken down during preparation of the coating liquid, and some of the plate-like particles may protrude from the coating surface. The number of laminar disc-shaped particles decreases, and a sufficient effect of improving the moisture-proof property cannot be obtained.

In the moisture-proof paper of the present invention, if the aspect ratio of the flat phyllosilicate compound particles is less than 5,
It becomes difficult to arrange the plate-like particles mutually and almost parallel to the surface of the paper support, which makes the moisture-proof layer obtained insufficiently moisture-proof. As for the aspect ratio, the larger the aspect ratio, the larger the number of stacked flat particles in the coating layer, and accordingly, the better the moisture resistance. The thickness of the plate-like particles varies depending on the type of the phyllosilicate compound, the pulverization method, the average particle diameter, and the like. Generally, in the case of flat disk-shaped particles having an average particle diameter of 20 μm, the particle diameter is distributed in the range of 2 to 60 μm, and the thickness of the particles is also distributed in the range of 0.1 to several μm.

When the flat phyllosilicate compound particles are contained in the moisture-proof layer of the present invention, if the particle diameter is excessively small with respect to the thickness of the coating layer, the flat phyllosilicate compound particles contained in the coating liquid may be used. Of the particles, the proportion of particles oriented almost parallel to the surface of the paper support decreases, and the thickness of the moisture-proof layer required to obtain desired moisture-proof performance increases. For this reason, in order to obtain as high a moisture-proof performance as possible with the smallest possible moisture-proof layer thickness, the average particle diameter of the plate-like phyllosilicate compound particles is determined by the thickness of the coating liquid layer. Is preferably 20% or more. Further, the maximum major axis of the flat phyllosilicate compound particles is smaller than the thickness of the obtained moisture-proof layer, and is 1% of the thickness of the moisture-proof layer.
It is preferably at most 00%. If the maximum major axis of the flat disk-shaped particles is excessively large, some of the particles may protrude from the surface of the moisture-proof layer obtained, or when the moisture-proof paper is bent, voids may be formed in the moisture-proof layer. It is preferable that the amount of such flat disk-shaped particles used is small because it may occur.

The phyllosilicate compound particles used in the present invention have a plate-like or flaky shape and show a clear cleavage. Planar phyllosilicate compounds include, for example, mica, pyrophyllite, talc, chlorite, septe chlorite, serpentine, and stilp-nomelane, among which, during production, the particles at the time of production are large, It is preferable to use minerals with high yield, such as mica and talc. Mica family minerals are muscovite (muscovite), sericite (sericite), biotite (flokopite), biotite (biotite), fluorophlogopite (artificial mica), red mica, soda mica, vanadin mica, illite, Chin mica, paragolite, brittle mica and the like. Delamikaolin, a kind of kaolin, is also included in the flat phyllosilicate compound of the present invention.

Of the above-mentioned flat phyllosilicate compounds, muscovite, sericite, and talc are preferably used in the present invention in consideration of the particle size, aspect ratio, and cost. The chemical composition of muscovite is represented by the general formula: K ₂ O
· 3Al ₂ O ₃ · 6SiO ₂ · 2H ₂ O In order to prepare the muscovite particles, the raw muscovite is pulverized and classified by a dry pulverizer such as a hammer mill, and a portion having a desired particle size distribution is collected. Wet pulverization is performed by a wet pulverizer such as a sand mill to obtain mica having a desired particle size distribution. At this time, in order to maintain the aspect ratio within a predetermined value range, pulverization is performed without applying an excessive force, or wet pulverization while applying ultrasonic waves (US Pat.
No. 0203), mica powder having a high aspect ratio can be prepared. Usually, the aspect ratio of muscovite powder obtained by these methods is 20 to 30 according to observation with an electron microscope. Although particles having an aspect ratio of about 100 can be obtained, such high aspect ratio particles are difficult to industrially produce and increase the cost, so that practical use is difficult.

The chemical composition of sericite, referred to as sericite, is similar to that of muscovite, but SiO ₂ / Al ₂
The O ₃ ratio is slightly higher and the K ₂ O content is lower. However, sericite has a finer ore compared to muscovite, so that sericite generally has an average particle diameter of about 0.5 to 2 μm obtained by pulverization and classification. Things are mostly. For this reason, in order to use in the present invention, it is necessary to select a sericite having a specific large particle size distribution. Classify further from inside and use those having the required average particle size and aspect ratio. By such a method, sericite having almost the same aspect ratio as muscovite can be obtained, and the aspect ratio is generally 10 to 30.

Talc is also called fluorite, and is a hydrate of magnesium silicate, and is generally in the form of a strip of foil.
However, commercially available talc has a particle size of 0.1.
Since it is about 3 μm, the talc used in the present invention is selected from coarse particles for the ceramic industry, not for general papermaking, or has a particle diameter of about 10 μm by performing the same pulverization and classification operation as sericite. Is prepared. The aspect ratio of talc is smaller than that of muscovite and sericite, and is about 5 to 10.

As described above, the size of muscovite is very large compared to sericite and talc, and the particle size distribution can be freely selected by pulverizing and classifying. On the other hand, sericite is preferable because the ore is small but has a large cleaving property, and the pulverized material exhibits a plate-like shape like muscovite. Although talc is not so large in particle diameter and aspect ratio, it can be used in a large amount because it is advantageous in cost.

The mixing ratio of the flat disk-shaped phyllosilicate compound particles (b) and the synthetic resin (a) is preferably 30/70 to 70/30 in terms of solids weight ratio. When the weight ratio of the component (b) to the total weight of the components (a) and (b) is less than 30%, the number of laminations of the plate-like particles decreases, and the moisture-proof layer obtained because the separation distance between the particles is too large. May be insufficient in moisture resistance, which requires an increase in the amount of coating, which is uneconomical and tends to cause blocking. On the other hand, if it exceeds 70%, a large number of voids are generated between the flat particles in the coating layer and the synthetic resin matrix, which may lower the moisture resistance.

In the moisture-proof paper of the present invention, the moisture-proof layer comprises a moisture-proof and film-forming synthetic resin (a) and a flat phyllosilicate compound particle (b), and a moisture-proof improver (c). included. The moisture-proofing agent (c) reacts with the moisture-proof and film-forming synthetic resin (a) to modify it to be hydrophobic, or to crosslink it to make it hydrophobic, or Coating the acid salt compound particles (c) to increase its adhesion to the synthetic resin (a) or to make it hydrophobic,
Alternatively, the lamination orientation parallel to each other is promoted, or the adhesion between the particles of the synthetic resin (a) and / or the plate-like phyllosilicate compound particles (b) is enhanced, or the gap between them is reduced. It is intended to improve the moisture-proof performance of the moisture-proof layer by filling.

The moisture-proofing agent used in the present invention includes, for example, a urea-formaldehyde condensation reaction product, a melamine-formaldehyde condensation reaction product, an aldehyde compound having 1 to 8 carbon atoms, and one or more epoxy compounds. Epoxy compound having a group, crosslinking reactive polyvalent metal compound, organoalkoxysilane compound, organoalkoxy metal compound, organic amine compound, polyamide compound, polyamide polyurea compound, polyamine polyurea compound, polyamide amine polyurea compound, polyamide amine compound Polyamide amine-epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine polyurea-epihalohydrin or formaldehyde condensation reaction product And polyamidoamine polyurea -
It preferably contains at least one selected from epihalohydrin or formaldehyde condensation reaction product.

Among the compounds used for the moisture-proofing agent, the urea-formaldehyde condensation reaction product and the melamine-formaldehyde condensation reaction product have a methylol group derived from formaldehyde, which is a synthetic resin component (a). It reacts with the polymer or copolymer in it, and in particular dehydrates with a hydrophilic functional group such as its carboxyl group, amide group, and hydroxyl group to crosslink the polymer or copolymer molecule, Can be made hydrophobic and water-insoluble (three-dimensional network structure). Further, the condensation product stably binds the synthetic resin component (a) and the flat phyllosilicate compound particle component (b) without chemically reacting with the synthetic resin component (a). Thus, the moisture-proof performance of the moisture-proof layer can be enhanced.

The aldehyde compound having 1 to 8 carbon atoms used in the moisture-proofing agent is formaldehyde,
Acetaldehyde, glyoxal, propylaldehyde, propanedial, hexanedial, etc., which are added at their aldehyde groups with the hydrophilic functional groups of the polymer or copolymer contained in the synthetic resin component (a). It can react to render it hydrophobic and water-insoluble.

The epoxy compound having one or more epoxy groups used in the moisture-proofing agent includes, for example, a polyglycidyl ether compound, a polyamide-epoxy resin and the like, which are included in the synthetic resin component (a). A ring-opening addition reaction with the hydrophilic functional group of the contained polymer or copolymer can be made hydrophobic and water-insoluble. In addition, the epoxy compound firmly binds the synthetic resin component (a) and the particle component (b) during the heating and drying of the moisture-proof layer, fills the gap therebetween, and improves the moisture-proof effect of the moisture-proof layer. Can be done.

In the present invention, the crosslinking reactive polyvalent metal compound used as a moisture-proofing agent includes, for example, ammonium zirconium carbonate, zirconium alkoxide, titanium alkoxide and aluminum alkoxide. The metal is coordinated or covalently bonded to the polymer or copolymer in the synthetic resin component, particularly to the hydrophilic functional group, to make these polymers or copolymers hydrophobic and water-insoluble. Can be

In the present invention, the organoalkoxysilane compound and the organoalkoxy metal compound used as the moisture-proofing agent are generally referred to as a coupling agent, and are used in the inorganic-organic composite material system. The component and the organic component are chemically cross-linked or chemically or physically bonded to at least one of the two to enhance the affinity between the two, thereby increasing the heat resistance of the inorganic-organic composite material. , Water resistance, mechanical strength and the like. In the present invention, the organoalkoxysilane compound and the organoalkoxy metal compound improve the affinity and adhesion between the synthetic resin component (a) and the plate-like phyllosilicate compound particles (b) so that the two adhere to each other. In addition, it is possible to prevent the formation of gaps, thereby improving the moisture-proof performance of the moisture-proof layer.

The organoalkoxysilane compound used in the present invention contains a Si atom in its hydrophilic portion, and is, for example, vinyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N-β- (aminoethyl)
-Γ-aminopropyltrimethoxysilane and the like.

The organoalkoxy metal compound used in the present invention contains a polyvalent metal atom (for example, Ti, Al, etc.) in the hydrophilic portion thereof. Iltitanol, isopropyl isostearyl diacryl titanate, isopropyl tricumyl phenyl titanate, and isopropyl tri (N-
Titanate compounds such as (amidoethyl / aminoethyl) titanate, and aluminum compounds such as acetoalkoxyaluminum diisopropylate are included.

The organoalkoxysilane compound and the organoalkoxy metal compound (hereinafter referred to as a coupling agent) have a molecular structure of Si, Ti, or Al.
It has a hydrophilic portion containing atoms and having high reactivity or affinity for inorganic substances, and a hydrophobic portion having high reactivity or affinity for organic compounds. The hydrophilic portion is formed by hydrolyzing an alkoxy group bonded to a Ti, Al, or Si atom.

It is said that the reaction between the hydrophilic group of the coupling agent and the inorganic compound proceeds in the following order. That is, (1) formation of a hydrophilic group formed by hydrolysis of an alkoxy group in the coupling agent, (2) oligomerization of the hydrophilic group of the coupling agent by dehydration condensation, and (3) hydrophilic group or adsorbed water on the inorganic surface. And (4) formation of a covalent bond between the hydrophilic group of the coupling agent and the hydrophilic group on the inorganic surface by the thermal dehydration reaction. As the alkoxy group to be hydrolyzed, a methoxy group, an ethoxy group, an isopropoxy group, an octyloxy group and the like are used. The reactivity of the hydrophilic compound and the inorganic compound of the coupling agent is high when the inorganic compound has a hydroxyl group on the surface such as glass, silica, alumina, talc, clay, and mica, but in the case of the titanate coupling agent, Even if the inorganic compound is calcium carbonate, barium sulfate or calcium sulfate, it shows high reactivity.

On the other hand, regarding the hydrophobic group portion of the coupling agent, when the hydrophobic group portion is an organic oligomer, a high molecular weight organic film is formed on the surface of the inorganic compound and the surface is completely hydrophobized to form a synthetic resin matrix. Enhance the adhesion of Further, when the hydrophobic group has a reactive organic functional group such as an epoxy group, a vinyl group, or an amino group, the functional group and the reactive functional group of the synthetic resin matrix are cross-linked, and the adhesiveness to the synthetic resin matrix is reduced. Increase. Therefore, the composition of the hydrophobic group portion of the coupling agent can be selected according to the composition of the synthetic resin component.

The moisture-proof layer containing the coupling agent used as the moisture-proofing agent in the present invention is obtained by mixing the synthetic resin component (a) and the flat phyllosilicate compound particles (b) with the coupling agent. The coated coating solution may be applied to the surface of a paper support and dried to form the surface. Alternatively, the surface of the flat phyllosilicate compound particles is treated with a coupling agent in advance, and It may be fixed to. That is, as a method of using the coupling agent, an integral blend method and a pretreatment method are known. The integral blending method is a method of directly adding a coupling agent to a coating solution containing phyllosilicate compound particles (b) and a synthetic resin (a). The pretreatment method is a method in which the surface of the phyllosilicate compound particles is treated in advance with a coupling agent, and includes a dry method and a wet method. In the dry method, powdery phyllosilicate compound particles are put into a mixer,
This is a method of adding a coupling agent after preheating and stirring at high speed under heating.In the wet method, a coupling agent and a phyllosilicate compound particle are added to water, a solvent or a mixture thereof, and the mixture is rapidly stirred. And then drying to obtain a powder. Although the use of the coupling agent is slightly inferior to the pretreatment method in the integral blend method, the workability is excellent because there is no step of pretreatment of the phyllosilicate compound particles.

When the phyllosilicate compound particles are treated in an aqueous treatment system by the integral blend method or the wet pretreatment method, in order to increase the water solubility of the coupling agent,
It is preferable to use a relatively weakly hydrophobic methoxy group, an ethoxy group, and an isopropoxy group as the alkoxy group,
It is preferable that the hydrophobic group portion of the coupling agent contains a hydrophilic epoxy group, amino group, or hydroxyl group. When the coupling agent is hardly soluble in water, a very small amount of a surfactant may be used in combination.

The amount of the coupling agent added is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the phyllosilicate compound particles. If the amount of the coupling agent is less than 0.1 part by weight, the effect of the coupling agent on the surface of the ferrosilicate compound particles may be insufficient because the coating of the surface of the ferrosilicate compound particles is insufficient. If the amount exceeds the limit, the effect of the coupling agent may be saturated, which may be uneconomical.

The hydrophobicity of the surface of the phyllosilicate compound particles treated with the coupling agent becomes excessively high, which results in an increase in the viscosity of the aqueous dispersion to make it impossible to apply the coating or poor dispersion. Aggregates may occur. In this case, the dispersion can be carried out using a surfactant, a polyacrylic acid-based dispersant, or a wetting agent such as isopropyl alcohol or sodium dialkyl sulfosuccinate.

In the present invention, the organic amine compound and the polyamide compound used as a moisture-proofing agent are:
When it has a cationic property and is in contact with the flat phyllosilicate compound particles (b) exhibiting anionic property, it promotes the soft aggregation and the lamination orientation parallel to each other, and can improve the moisture-proof performance of the moisture-proof layer. it can. Since the organic amine compound and the polyamide compound do not crosslink the synthetic resin (a) or are crosslinked by an ionic bond, the moisture-proof layer obtained by using them can be combined with water in the recovery and regeneration step. Upon contact, it is easily disintegrated from the paper support, which can facilitate pulping of the paper support.

In the present invention, the synthetic resin component (a)
When the copolymer contained in the above has a carboxylic acid group, this can react with an organic monoamine, an organic polyamine, or an organic quaternary ammonium salt to increase its hydrophobicity or water insolubility.

In the present invention, the organic amine compound used as the moisture-proofing agent may be any of a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound. Alternatively, any of an organic monoamine and an organic polyamine may be used. Further, the organic amine compound includes those having a different functional group other than an amino group, for example, an epoxy group, a hydroxyl group, a carboxylic acid group, a nitrile group and the like. Examples of such a modified organic amine compound include an adduct of a compound having an epoxy group such as a monoepoxy compound or a diepoxy compound and an amine compound, an adduct of a compound having a hydroxyl group such as ethylene oxide or propylene oxide and an amine compound, and acrylic. Examples include a Michael adduct of a nitrile and an amine compound, and an adduct obtained by a Mannich reaction of a phenol compound, an aldehyde compound, and an amine compound.

The above modifications include 1) reducing the toxicity of the amine compound, such as irritating odor and skin irritation, 2) reducing the viscosity of the amine compound, and 3) increasing the molecular weight and weighing. There are effects such as reducing the error. The degree of modification of the amine compound is not particularly limited.

Examples of the organic amine compound used in the present invention are as follows. 1) Aliphatic polyamines (polyalkylene polyamines)
Or monoamine ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobis-propylamine, bis (hexamethylene) triamine, dimethylaminopropylamine, diethylaminopropylamine, aminoethylethanolamine, methyl Iminobispropylamine, menthanediamine-3, N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, triethylenediamine, polyvinylamine, stearylamine, laurylamine and the like. 2) aromatic polyamine or monoamine m-phenylenediamine, 4,4'-methylenedianiline, benzidine, diaminodiphenyl ether, 4,
4'-thiodianiline, dianisidine, 2,4-toluenediamine, diaminodiphenylsulfone, 4,4'-
(O-toluidine), o-phenylenediamine, methylenebis (o-chloroaniline), m-aminobenzylamine, aniline and the like. 3) Aliphatic polyamine or monoa having an aromatic ring group
Min m-xylylenediamine, tetrachloro-xylene diamine, trimethyl aminomethyl phenol, benzyldimethylamine, etc. α- methylbenzyl dimethylamine. 4) Secondary amine N-methylpiperazine, piperidine, hydroxyethylpiperazine, pyrrolidine, morpholine and the like. 5) tertiary amine tetramethylguanidine, triethanolamine, N,
N'-dimethylpiperazine, N-methylmorpholine, hexamethylenetetramine, triethylenediamine, 1-
Hydroxyethyl-2-heptadecylglyoxalidine, pyridine, pyrazine, quinoline and the like. 6) Quaternary ammonium salts diallyldimethylammonium chloride, hexyltrimethylammonium chloride, cyclohexyltrimethylammonium chloride, octyltrimethylammonium bromide, 2-ethylhexyltrimethylammonium bromide, 1,3-bis (trimethylammoniomethyl) cyclohexanedichloride, lauryldimethyl Benzylammonium chloride, stearyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride and the like. 7) Betaine compounds, glycine compounds, amino acid compounds coconut oil alkyl betaine, lauryl dimethylamino acetate betaine, amidopropyl betaine laurate, polyoctyl polyaminoethyl glycine, sodium lauryl aminopropionate and the like. Among the above organic amine compounds, it is preferable to use an aliphatic polyamine, an aliphatic polyamine having an aromatic ring group, and a modified polyamine.

The polyamide compound (also referred to as a polyamidoamine compound) used in the present invention is obtained by a dehydration condensation reaction between the above amine compound and a compound having a carboxylic acid group. For example, a reaction product of tall oil with diethyltriamine, a reaction product of a dimer of linolenic acid with tetraethylpentamine, a reaction product of triethylenetetramine with a saturated dibasic acid (adipic acid, sebacic acid, isophthalic acid, terephthalic acid) Products, reaction products of a polymerized fatty acid and diethyltriamine, and the like. The molecular weight of these polyamide compounds is preferably about 1,000 to 5,000.

The organic amine compound or polyamide compound used in the present invention is preferably water-soluble.
Even if it is insoluble in water, it can be used after emulsification or dispersion treatment. The above amine compound or polyamide compound is
A mixture of more than one species may be used. The amine value of the organic amine compound or polyamide compound is generally 100-1.
It is preferably 000, but there is no particular limitation.

In the present invention, the epoxy compound used as the moisture-proofing agent may be a monoepoxy compound. The monoepoxy compound includes an aliphatic monoepoxy compound and an aromatic monoepoxy compound. It can be selected from glycidyl ether, lauryl alcohol polyethylene glycol glycidyl ether and the like.

The monoepoxy compound used in the present invention is preferably a water-soluble monoepoxy compound. Can be used.

The monoepoxy compound is used in an amount of 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts of the synthetic resin component (a). If the amount of the monoepoxy compound is less than 0.05 part by weight, the effect of improving the moisture resistance may be insufficient, and if it exceeds 10 parts by weight, the effect of the moisture resistance is saturated,
It can be economically disadvantageous.

When a moisture-proofing agent containing the above-mentioned monoepoxy compound is used, a synthetic resin (a) used therewith is a hydrophilic functional group capable of reacting with an epoxy ring such as acrylic acid, acrylamide, etc. Group, amide group, and hydroxyl group, etc.).

In the present invention, the polyamide polyurea compound, the polyamine polyurea compound, the polyamidoamine polyurea compound and the polyamidoamine compound used as the moisture proofing agent include: i) polyalkylene polyamine or alkylene polyamine; ii) ureas; ) Dibasic carboxylic acids, and if necessary iv) aldehydes, epihalohydrins and α, γ-
It can be obtained by reacting a compound selected from dihalo-β-hydrins (Japanese Patent Publication No. 59-32597, Japanese Patent Application Laid-Open No.
097). In the above synthesis, if a dibasic carboxylic acid (iii) is used, a polyamide polyurea compound or a polyamidoamine polyurea compound is obtained, and if not used, a polyamine polyurea compound is obtained. When aldehydes and epihalohydrins are used, it is preferable that the amount used is very small or that self-crosslinking occurs during the synthesis process so that almost no free methylol group or epoxy group remains. In the above reaction, the urea number (i
When polyalkylene polyamine or alkylene polyamine (i) is reacted with dibasic carboxylic acid without using i), a polyamidoamine compound is obtained. Ingredient (iv)
The reaction amount of aldehydes, epihalohydrins, and α, γ-dihalo-β-hydrins is 100 parts of component (i).
It is preferable that the amount is in the range of 5 to 300 mol with respect to the molar amount.

The polyalkylene polyamine or alkylene polyamine used as component (i) includes, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, 4,7
-Diazadecane-1,10-diamine, ethylenediamine, propyldiamine, 1,3-propanediamine, hexamethylenediamine and the like. Among them, it is preferable to use diethylenetriamine and / or triethylenetetramine. These compounds (i) are used alone or as a mixture of two or more.
In addition, one or more of an alicyclic amine such as cyclohexylamine and an alicyclic epoxy compound may be used in combination with the compound (i).

The ureas used as component (ii) include urea, thiourea, guanylurea, methylurea, dimethylurea and the like. Among these, it is preferable to use urea. These urea compounds may be used alone or as a mixture of two or more. The dibasic carboxylic acid used as the component (iii) has a carboxyl group or two groups derived therefrom in the molecule and may be a free acid, or may be an ester or an acid. It may be an anhydride or the like.
The dibasic carboxylic acid may be any of aliphatic, aromatic and alicyclic dibasic carboxylic acids. Specific examples thereof include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Further, polyesters which are a reaction product of a dibasic carboxylic acid and a glycol and have a free carboxylic acid group at a terminal may be used.
These dibasic carboxylic acids may be used alone or as a mixture of two or more. Aldehydes used as component (iv) include formaldehyde,
Examples of alkyl aldehydes such as propyl aldehyde, glyoxal, propane dial, butane dial, and epihalohydrins include epichlorohydrin, epibromohydrin, and the like. Further, examples of the α, γ-dihalo-β-hydrin used as the component (iv) include 1,3-dichloro-2-propanol.

These aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins may be used alone or as a mixture of two or more.

Further, as a monomer component, an alicyclic epoxy compound, an alkylating agent (general formula RX; R = lower alkyl group, alkenyl group, benzyl group, phenoxyethyl group, etc., X = halogen atom), R'-C (= Y) -N
A compound represented by H ₂ [R ′ is an alkyl group or —NR ′ ₂ group, and Y is an oxygen atom or a sulfur atom] may be reacted.

The above components can be reacted in an arbitrary order, and the following method can be used as an example of the synthesis method. That is, an alkylenediamine or a polyalkylene polyamine is subjected to a deammonification reaction with a urea, and then the reaction product is dehydrated and condensed with a dibasic carboxylic acid. A compound is obtained.
When the polyamide polyurea compound is reacted with a compound selected from aldehydes, epihalohydrins and α, γ-dihalo-β-hydrins, a polyamide polyurea-aldehyde (epihalohydrin) resin is obtained.

Aldehydes, epihalohydrins, α,
The γ-dihalo-β-hydrins are used for the purpose of adjusting the molecular weight and the water solubility, but it is preferable that the methylol group and the epoxy ring are self-crosslinked and hardly remain.

In the present invention, the above-mentioned polyamide polyurea compound, polyamine polyurea compound, polyamidoamine polyurea compound and polyamidoamine compound used as a moisture-proofing agent show a slight cationic property in an aqueous coating solution. It is considered that the flat phyllosilicate compound particles having a property are softly agglomerated in the process of forming a film, and at this time, these flat particles are stacked and oriented parallel to each other. Such improvement in the lamination orientation of the flat particles improves the moisture-proof performance of the moisture-proof layer. In addition, among the above compounds, those having an epoxy ring and / or a methylol group in the molecule are included, and the content of these functional groups is very small. And / or the majority of the methylol group-forming compounds are self-crosslinking, so that the effect of these functional groups is negligible. Therefore, the moisture-proof layer containing the above compound as a moisture-proof property improving agent easily disintegrates from the paper support when collecting and regenerating moisture-proof paper, and hardly inhibits the disintegration of the recycled pulp.

In the present invention, polyamidoamine-epihalohydrin or formaldehyde condensation reaction product, polyamine-epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine polyurea- Epihalohydrin or formaldehyde condensation reaction products and polyamidoamine polyurea-epihalohydrin or formaldehyde condensation reaction products can be used.

The above condensation reaction product contains an amino group in its molecular skeleton and has an epoxy ring or a methylol group in its side chain, and generally has the following components: (i) polyalkylene polyamine (ii) ureas (Iii) Dibasic carboxylic acids (iv) It can be synthesized by reacting epihalohydrins or formaldehyde (JP-B-52-22).
No. 982, JP-B-60-31948, JP-B-61-3
9435, JP-A-55-127423).

By reacting the above components (i) to (iv), a polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product or a polyamideamine polyurea-epihalohydrin or formaldehyde condensation reaction product is obtained, and the component (i) , (Ii) and (iv) give a polyamine polyurea-epihalohydrin or formaldehyde condensation reaction product, and reacting components (i), (iii) and (iv) gives polyamidoamine- An epihalohydrin or formaldehyde condensation reaction product is obtained, and when the components (i) and (iv) are reacted, a polyamine-epihalohydrin or formaldehyde condensation reaction product is obtained.

The polyalkylenepolyamine used as component (i) includes diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and 3-azahexane-1,6-
Diamine, 4,7-diazadecane-1,10-diamine, ethylenediamine, propyldiamine, 1,3-propanediamine, hexamethylenediamine, bis (3-
Examples thereof include polymers of diallylamines such as aminopropyl) methylamine, bishexamethylenetriamine, poly (N-methyldiallylamine hydrochloride), and polyvinylbenzylamine dimethylamine hydrochloride, and dicyandiamide. Of these, polymers of diethylenetriamine, triethylenetetramine, and diallylamine are preferred. These may be used alone or as a mixture of two or more.

The ureas used as component (ii) include urea, thiourea, guanylurea, methylurea, dimethylurea and the like. Among these, it is preferable to use urea. These urea compounds may be used alone or as a mixture of two or more.
The dibasic carboxylic acid used as the component (iii) has a carboxyl group or two groups derived therefrom in the molecule and may be a free acid, or may be an ester or an acid. It may be an anhydride or the like.
The dibasic carboxylic acid may be any of aliphatic, aromatic and alicyclic dibasic carboxylic acids. Specific examples thereof include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Further, polyesters which are a reaction product of a dibasic carboxylic acid and a glycol and have a free carboxylic acid group at a terminal may be used.
These dibasic carboxylic acids may be used alone or as a mixture of two or more.

The epihalohydrins used as component (iv) include epichlorohydrin, epibromohydrin, and α, γ-dihalo-β-hydrins such as 1,3-dichloro-2-propanol. . Epihalohydrins may be used alone, or
You may mix and use more than one type.

The reaction amount of the component (iv) is 5 to 300 per 100 parts by mole of the polyalkylene polyamine component (i).
It is preferably a molar part.

As an example of a method of synthesizing the above condensation reaction product, an example of a method of synthesizing a polyamide epihalohydrin compound is described below. Diethylene triamine 0.9 in the reaction vessel
7 mol are added, 1 mol of adipic acid is gradually added to the reactor with stirring, and the mixture is heated at 170 ° C. for 1.5 hours. After cooling the obtained viscous liquid to 140 ° C., water is added so that the solid content becomes 50% by weight to prepare a polyamide solution. Water is added to the polyamide solution so that the solid content concentration becomes 13.5% by weight, and the solution is heated to 40 ° C., and epichlorohydrin is added to the solution at a concentration of 1.32 mol per mol of the secondary amine in the polyamide. Add slowly by volume. Further, at a temperature of 60 ° C., the Gardner viscosity becomes E
Heat until ~ F. Next, water is added so that the solid content concentration becomes 12.5% by weight, and the mixture is cooled to 25 ° C. to obtain a polyamide epihalohydrin compound. Other condensation reaction products can be synthesized by a synthesis method similar to the above method.

In the present invention, the polyamidoamine-epihalohydrin or formaldehyde condensation reaction product, polyamine-epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine polyamine The urea-epihalohydrin or formaldehyde condensation reaction product and the polyamidoamine polyurea-epihalohydrin or formaldehyde condensation reaction product show good solubility in an aqueous coating solution, but the moisture-proof performance of the moisture-proof layer formed from this coating solution Can be improved. However, the moisture-proof layer of the obtained moisture-proof paper exhibits good disintegration properties in the regeneration step, separates from the paper support, and does not hinder the disintegration of the pulp of the paper support. Therefore, it is recognized that the condensation reaction product hardly causes a crosslinking reaction with the synthetic resin component (a) in the moisture-proof layer. All of the above condensation reaction products show microcationicity in the aqueous solution thereof, and thus soft-aggregate flat anionic phyllosilicate compound particles (b) in the process of forming the film of the moisture-proof layer, The flat particles are stacked and arranged in parallel with each other,
Thereby, the moisture proof performance is improved.

In the present invention, the moisture-proofing agent is preferably used in a proportion of 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the synthetic resin component (a). More preferably, there is. When this blending amount is 0.1
If the amount is less than 10 parts by weight, the effect of improving the moisture resistance may be insufficient. If the amount exceeds 10 parts by weight, the effect of improving the moisture resistance may be saturated, which may be economically disadvantageous.
Further, a moisture-proofing agent composed of two or more compounds may be used.

When the moisture-proofing agent used in the present invention is strongly cationic and coagulates with the synthetic resin component (a), the pH of the synthetic resin-containing solution is adjusted to an alkaline side (for example, 8 or more). After that, an aqueous solution of a cationic moisture-proofing agent may be added to this and used.

In the moisture-proofing agent (c) used in the moisture-proofing paper of the present invention, a crosslinking agent and a coupling agent may be used in combination. In this case, the crosslinking agent is a urea-formaldehyde condensation reaction product, a melamine-formaldehyde condensation reaction product, an aldehyde compound having 1 to 8 carbon atoms, an epoxy compound having at least one epoxy group, a crosslinking reactive compound. It may include one or more selected from a valence metal compound, an organic amine compound, a polyamide compound, and the like, and the coupling agent may include one or more selected from the aforementioned organoalkoxysilane compounds and organoalkoxy metal compounds. Can be included. Further, the polymer or copolymer contained in the synthetic resin component (a) preferably has a hydrophilic functional group such as a carboxyl group, an amide group, a hydroxyl group, a nitrile group, and a carbonyl group. More preferably, the modification rate is 5 mol% or more.

In the moisture-proofing agent (c) of the above embodiment,
The crosslinking agent is used in an amount of 0.0 to 100% by weight of the synthetic resin (a).
It is preferably used in an amount of 5 to 10 parts by weight, and the coupling agent is a flat phyllosilicate compound particle (b) 10
It is preferable to use 0.1 to 5 parts by weight based on 0 part by weight.

The paper support used in the present invention is mainly composed of pulp which is easily dispersed in water by mechanical disaggregation, and examples of such pulp include hardwood kraft pulp and softwood kraft pulp. There are various chemical pulps and mechanical pulps. The paper support may be any of high quality paper, medium quality paper, matte kraft paper, double-ended kraft paper, kraft stretch paper, and the like. Although the basis weight of the paper support is not particularly limited, it is generally in the range of 30 to 300 g / m ² , and base paper of an appropriate type and basis weight can be used as the paper support according to the purpose.

To produce the moisture-proof paper of the present invention, an aqueous coating solution containing desired components is prepared, and this coating solution is applied to one or both sides of a paper support. May be dried to form a moisture-proof layer. There are no particular restrictions on the coating method and apparatus, and for example, an appropriate apparatus such as an air knife coater, a bar coater, a roll coater, a blade coater, or a gate roll coater may be used. There is no particular limitation on the drying method and apparatus. For example, a hot air dryer, a contact heating plate, a contact heating roll, an infrared dryer, a high-frequency heating dryer, or the like can be used. The drying temperature is 70 to 17 depending on the type and amount of the components of the moisture-proof layer.
The temperature is preferably 0 ° C, more preferably 100 to 1 ° C.
50 ° C.

[0085]

The present invention is further described by the following examples. However, the following examples do not limit the scope of the present invention. In the examples, "parts by weight" all mean parts by weight of solid content.

The moisture-proof paper prepared in the following examples was subjected to the following tests. (1) Moisture permeability JIS Z020 with the moisture-proof layer surface of the moisture-proof paper facing outward
8. The moisture permeability was measured by the cup method and the B method. Generally, paper having a moisture permeability of 50 g / m ² · 24 hr or less can be practically used as a moisture-proof paper.
g / m ² · 24 hr or less is more preferable.

(2) Moisture Permeability of Synthetic Resin Component (a) On one side of unbleached kraft paper having a basis weight of 70 g / m ^2, a test synthetic resin paint was applied at a dry coating amount of 20 g / m ² . And dried at 110 ° C. for 2 minutes to produce a synthetic resin coated paper. This synthetic resin-coated paper was subjected to moisture permeability measurement according to JIS Z0208, the cup method, and the B method, with the surface of the coating layer facing outside.

(3) Coefficient of friction Two sheets of moisture-proof paper are superposed so that the surface of one moisture-proof layer and the back of another sheet are in contact with each other, and a super calendar is applied under a linear pressure of 12 kg / cm. After one pass, the coefficient of kinetic friction between the back surfaces was measured by the method of JIS P8147. However, the measurement speed was 150 mm / min. The coefficient of friction measured by the above test corresponds to the coefficient of friction between the back surfaces when the moisture-proof paper is rolled up.

(4) Blocking Resistance The moisture-proof paper was cut into a size of 20 cm × 20 cm, and A2 coated paper was superimposed on the moisture-proof layer of the moisture-proof paper. 30 kg under the condition of 12 kg / cm ²
Crimped for minutes. Next, observe the state of adhesion of this laminate,
The evaluation was as follows. ○ Both papers were easily peeled off △ Both papers could be peeled off, but burrs and peeling noise occurred × Both papers could not be peeled without breaking

(5) Disintegration test method-1 A test paper was cut into a size of 1 cm × 1 cm, and 8 g thereof was mixed with 500 ml of water in a household mixer (concentration: 1.6).
%) And stirred for 2 minutes to prepare a regenerated pulp. The contents were taken out, and a paper sheet was prepared from the pulp slurry using a laboratory hand-making machine. The obtained sheet was dried in a hot air circulating oven at a temperature of 120 ° C. for 20 minutes. The dried sheet was visually inspected for the presence of undisintegrated materials (film pieces, fiber lumps, undisintegrated paper pieces, etc.). Does not include undisintegrated material,
Those that formed a uniform sheet were judged to be good. Test method-2 The moisture-proof paper sample was left at 40 ° C for 1 week (2
~ 3 months), then 450g for 15kg of water
A sample (concentration: 3%) (cut to A4 size) was prepared, and this sample was put together with the above water using a Cowles type stirrer, stirred at 1500 rpm for 20 minutes, and the contents were taken out. A sheet was prepared. The obtained sheet was dried with a ferro-type dryer at a temperature of 120 ° C., and the presence or absence of undisintegrated materials (film pieces, paper pieces, etc.) was visually inspected to evaluate disintegration. Those which did not contain undisintegrated material and formed a uniform sheet were judged to be good.

(6) Average particle size The particle size of the pigment dispersed in water was measured using a Shimadzu laser diffraction type particle size distribution analyzer SALD-1100 V2.0 (manufactured by Co., Ltd.).
(Manufactured by Shimadzu Corporation) by the following method. In addition,
The average particle diameter is a particle diameter at which the cumulative volume ratio is 50%. Measurement range: 1 to 150 μm or 0.1 to 45 μm Refractive index: 1.6 Calculation method: Direct calculation method Number of measurements: 4 Measurement intervals: 2 seconds

Example 1 Muscovite pigment (flat phyllosilicate compound particles (b),
Trademark: Mica A21, manufactured by Mika Yamaguchi, average particle size:
20 μm, aspect ratio: 20-30) 50 parts by weight,
48 parts by weight of a carboxylic acid-modified SBR latex (synthetic resin (a), trade name: LX407S1X1, manufactured by Zeon Corporation, acid modification ratio: about 20%, Tg: 18 ° C., solid content concentration: 48%), and sorbitol polyglycidyl ether ( 2 parts by weight of a moisture-proofing agent (c), trade name: Denacol EX614B, manufactured by Nagase Kasei Co., Ltd .; solid content concentration: 98% or more) to prepare a moisture-proof coating solution. This coating liquid was applied to a basis weight of 70 g / m
^On one side of the unbleached kraft paper of No. ² , using a Meyer bar, apply a dry coating amount of 30 g / m ² and heat-dry at 110 ° C. for 2 minutes using a hot air circulation dryer. To form a moisture-proof layer, thereby producing a moisture-proof paper. The obtained moisture-proof paper was subjected to the test. Table 1 shows the test results.

Examples 2 to 5 Moistureproof papers were prepared in the same manner as in Example 1. However, in Example 2, muscovite pigment (trade name: mica A11, manufactured by Mica Yamaguchi Mfg. Co., Ltd., average particle size: 5 μm, aspect ratio: flat phyllosilicate compound particles (b))
20 to 30), and in Example 3, a muscovite pigment (trade name: Mica A61, manufactured by Yamaguchi Mica Industries, average particle diameter 50 μm, aspect ratio: 20 to 30) was used. In Example 4, talc was used. Pigment (trade name: Shuen, manufactured by Chuo Kaolin, average particle size: 15 μm, aspect ratio: 5 to 5)
10), and in Example 5, sericite pigment (trademark:
Sericite ST, manufactured by Horie Kako, average particle diameter 14 μm, aspect ratio: 20 to 30) was used. Table 1 shows test results
Shown in

Examples 6 to 9 Moistureproof papers were produced in the same manner as in Example 1. However, in Example 6, as the moisture proofing agent (c),
Melamine-formaldehyde condensation reaction product (trade name: Euramine P-6300, manufactured by Mitsui Toatsu, solid content: 80
%), In Example 7, polyamide polyurea-formaldehyde condensation reaction product (trademark: Sumireze Resin 302, manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 60%), and in Example 8, zirconium ammonium carbonate (trademark:
Zircosol AC-7, first rare element, solid concentration: 1
In Example 9, glyoxal (manufactured by Wako Pure Chemical Industries, solid content concentration: 40%) was used. Table 1 shows the test results.

Examples 10 to 13 In the same manner as in Example 1, moisture-proof paper was produced. However, instead of the carboxylic acid-modified SBR latex (LX407S1X1), in Example 10, a carboxylic acid-modified SBR latex (trademark: PT1120, manufactured by Zeon Corporation, acid modification ratio: about 15%, Tg: 2 ° C., solid content concentration) In Example 11, carboxylic acid-modified SBR latex (trade name: OX1060, manufactured by Zeon Corporation, acid modification rate: about 3%, Tg: 8 ° C., solid content concentration: 50%), 40 parts by weight And a mixture of 8 parts by weight of the carboxylic acid-modified SBR latex (LX407S1X1) described in Example 1,
In Example 12, 43 parts by weight of the same carboxylic acid-modified SBR latex (OX1060) as in Example 11,
Example 1 Using a mixture of 5 parts by weight of the same carboxylic acid-modified SBR latex (PT1120) as in Example 10,
In Example 3, the same carboxylic acid-modified SB as in Example 11 was used.
43 parts by weight of R latex (OX1060), acrylic polymer latex (trade name: Aron A104, manufactured by Toagosei Co., Ltd., Tg: 40 ° C., acid modification rate: about 10%, solid content concentration:
40%) of 5 parts by weight. Table 1 shows the test results.

Comparative Example 1 A polyethylene-laminated paper having 15 μm of polyethylene laminated on one side of kraft paper was subjected to a test.
Table 1 shows the test results.

Comparative Example 2 Carboxylic acid-modified SBR latex (LX407S1X)
1) 65 parts by weight and wax emulsion OKW-40
(Arakawa Chemical Co., Ltd., paraffin wax, polybutene, mixed emulsion of rosin resin, solid content: 45%) 35 parts by weight of a moisture-proof paint was mixed with unbleached kraft paper having a basis weight of 70 g / m ^2. 20g / m as solids with Meyer bar
After coating so as to be ² , drying was performed at 110 ° C. for 1 minute to produce a moisture-proof paper. Table 1 shows the test results.

Comparative Examples 3 and 4 In Comparative Example 3, talc (trademark: PC
Talc, average particle diameter 2 μm, aspect ratio 2-4, manufactured by DIO Engineering Co., Ltd., and in Comparative Example 4, muscovite pigment (trade name: mica B72 (average particle diameter 82 μm, aspect ratio 20-30, Yamaguchi) A moisture-proof paper was manufactured in the same manner as in Example 1 except that Mica Industrial Co., Ltd. was used, and the test results are shown in Table 1.

Comparative Example 5 Carboxylic acid-modified SBR latex (LX407S1X)
Except that the solid content ratio of 1) and muscovite pigment (mica A-21) was 50/50, and no moisture-proofing agent (crosslinking agent) was added, the other steps were the same as in Example 1. A moisture-proof paper was manufactured. Table 1 shows the test results.

Comparative Example 6 The mixing ratio of the solid content of the carboxylic acid-modified SBR latex (PT1120) and the muscovite pigment (mica A-21) was 50 /
The moisture-proof paper was manufactured in the same manner as in Example 10 except that the moisture-proof paper (crosslinking agent) was not added. Table 1 shows the test results.

Comparative Example 7 The solid content of the carboxylic acid-modified SBR latex (OX1060) and the muscovite pigment (mica A-21) was 50/50.
The moisture-proof paper was manufactured in the same manner as in Example 1 except that the moisture-proof paper was set to 50 and no moisture-proofing improver (crosslinking agent) was added. Table 1 shows the test results.

[0102]

[Table 1]

Table 1 shows that the moisture-proof papers of Examples 1 to 13 according to the present invention are superior in the disintegration property to the polyethylene laminated paper (Comparative Example 1), and are superior to the wax-containing coated paper (Comparative Example 2). This shows that the anti-slip property is superior.

When the pigment did not satisfy the average particle diameter and aspect ratio of the present invention (Comparative Examples 3 and 4), the moisture-proof paper obtained had insufficient moisture-proof properties. Furthermore, when the moisture proofing agent according to the present invention is not used (Comparative Examples 5, 6,
In 7), the resulting moisture-proof paper had insufficient blocking resistance.

Example 14 Glycidoxysilane coupling agent (trade name: KBM40)
3, a 10% by weight toluene solution of Shin-Etsu Chemical Co., Ltd.) was prepared, and 10 parts by weight of this solution was dried at 120 ° C. for 1 hour to obtain a muscovite pigment (trade name: mica A21, average particle diameter 20 μm, aspect ratio: (20-30, manufactured by Mika Yamaguchi) was stirred in a mixer at 1,000 rpm for 10 minutes and dried at 80 ° C. for 2 hours. As a result, a surface-treated muscovite pigment (a) having a coupling agent was obtained. In 100 parts by weight of water, 100 parts by weight of the surface treated muscovite pigment (a) of the coupling agent and 0.2 parts by weight of a polyacrylic acid-based dispersant (trade name: Cariblon L4)
00, manufactured by Toa Gosei Co., Ltd.) and subjected to a dispersion treatment at 2,000 rpm for 30 minutes using a Cowles disperser. The dispersion and a carboxylic acid-modified SBR latex (trade name: LX407S1X1, manufactured by Zeon Corporation, solid content concentration: 48%, moisture permeability of synthetic resin: 120 g / m ² · 24 h)
and r) were mixed so that the weight ratio of the solid content of the phyllosilicate compound and the synthetic resin was 50/50 to prepare a coating solution. This coating solution was applied to one side of unbleached kraft paper having a basis weight of 70 g / m ² using a Meyer bar so that the dry coating amount was 30 g / m ^2. Layers
After drying at a temperature of 110 ° C. for 2 minutes to form a moisture-proof layer, a moisture-proof paper was produced. Table 2 shows the test results.

Example 15 Methacryloxysilane coupling agent (trade name: KBM5)
03, manufactured by Shin-Etsu Chemical Co., Ltd.) in a 10% by weight toluene solution, and 10 parts by weight of this solution was dried at 120 ° C. for 1 hour to obtain a muscovite pigment (trade name: mica A21, average particle diameter: 20 μm, aspect ratio: (20-30, manufactured by Mica Yamaguchi) was stirred in a mixer at 1,000 rpm for 10 minutes and dried at 80 ° C. for 2 hours. Coupling agent surface treated muscovite pigment (b)
was gotten. In a mixture of 95 parts by weight of water and 5 parts by weight of isopropyl alcohol, 100 parts by weight of the coupling agent surface-treated muscovite pigment (b), and 0.2 parts by weight of a polyacrylic acid-based dispersant (trademark: Carribbon L400,
Toa Gosei) and 0.4 parts by weight of a surfactant (trademark:
(Dapro U99, manufactured by Sannobuco) and dispersed using a Cowles disperser at 2000 rpm for 30 minutes. And the dispersion, the carboxylic acid-modified SBR latex (trademark: LX407S1X1, Nippon Zeon Ltd., solid content concentration: 48%, synthetic resin moisture permeability: 120g / m ² · ²
4 hr) was mixed with the phyllosilicate compound and the synthetic resin so that the solid content weight ratio became 50/50 to prepare a coating liquid. This coating liquid was applied to one side of unbleached kraft paper having a basis weight of 70 g / m ² using a Meyer bar so that the dry coating amount was 30 g / m ^2. Drying the layer at 110 ° C. for 2 minutes to form a moisture barrier layer;
A moisture-proof paper was produced. Table 2 shows the test results.

Example 16 In the same manner as in Example 14, a surface-treated muscovite pigment (c) having a coupling agent was prepared. However, an aminosilane coupling agent (trademark: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the glycidoxysilane coupling agent (KBM403). In a mixture of 80 parts by weight of water and 20 parts by weight of 5% by weight ammonia water, 100 parts by weight of the surface treated muscovite pigment (c) of coupling agent and 0.2 parts by weight of a polyacrylic acid-based dispersant (Carribbon L400) was mixed and dispersed using a Cowles disperser at 2000 rpm for 30 minutes. The dispersion and a carboxylic acid-modified SBR latex (trademark: LX407S1X1,
Made by Zeon Corporation, solid content: 48%, moisture permeability of synthetic resin:
120 g / m ² · 24 hr) to prepare a coating liquid by mixing the phyllosilicate compound and the synthetic resin such that the weight ratio of the solid content becomes 50/50. This coating liquid is applied to a basis weight of 70
g / m ² of unbleached kraft paper is coated using a Meyer bar so that the dry coating amount is 30 g / m ² , and the coating liquid layer is heated at a temperature of 110 ° C. After drying for 2 minutes, a moisture-proof layer was formed to produce a moisture-proof paper. Table 2 shows the test results.

[0108] was prepared moisture-proof paper in the same manner as in Example 15 in each of Examples 17 and 18 Examples 17 and 18. However, in the preparation of the surface treated muscovite pigment of the coupling agent, a stearoyl titanate coupling agent (trade name: KRET, manufactured by Ajinomoto) was used in Example 17 instead of the methacryloxysilane coupling agent. A surface-treated muscovite pigment (d) was prepared, and in Example 18, a coupling agent surface-treated muscovite pigment (e) was prepared using an isopropyl aluminum coupling agent (trade name: AL-M, manufactured by Ajinomoto). did. Table 2 shows the test results.

[0109] was prepared moisture-proof paper in the same manner as in Example 14 in each of Examples 19 and 20 Examples 19 and 20. However, in preparing the surface-treated muscovite pigment of the coupling agent, the muscovite pigment (KBM40
Instead of 3), in Example 19, sericite (trademark:
Sericite KF1325, average particle size: 13 μm, aspect ratio: 20-30, manufactured by Central Kaolin) was used to prepare a sericite mica pigment (f) having a surface treated with a coupling agent.
In No. 0, talc pigment (g) was prepared using talc (trademark: Schwen, average particle diameter: 18 μm, aspect ratio 5-10, manufactured by Central Kaolin). Table 2 shows the test results.

Example 21 100 parts by weight of muscovite pigment (mica A21), 0.2 part by weight of a dispersant (Carribbon L400), and 100 parts by weight of water were mixed, and the mixture was rotated at a rotational speed using a Cowles disperser. The dispersion treatment was performed at 2000 rpm for 30 minutes. The above dispersion and a carboxylic acid-modified SBR latex (LX407
S1X1) and a glycidoxysilane coupling agent (K
BM403) was mixed with the muscovite pigment, the modified SBR, and the coupling agent so that the solid content weight ratio became 50/50 / 0.5 to prepare a coating solution. The above coating solution,
On one side of unbleached kraft paper having a basis weight of 70 g / m ² , it is applied using a Meyer bar to a dry coating amount of 30 g / m ^2, and dried at 110 ° C. for 2 minutes to form a moisture-proof layer. Then, a moisture-proof paper was produced. Table 2 shows the test results.

Example 22 100 parts by weight of muscovite pigment (mica A21), 1 part by weight of a glycidoxysilane coupling agent (KBM40)
3), 0.2 parts by weight of a dispersant (Carribbon L400) and 100 parts by weight of water were mixed, and this mixture was subjected to a dispersion treatment at 2000 rpm for 30 minutes using a Cowles disperser. This dispersion and the carboxylic acid-modified SBR
Latex (LX407S1X1) was mixed with the muscovite pigment and the modified SBR such that the solid content weight ratio was 50/50 to prepare a coating solution. The coating liquid was applied to one side of unbleached kraft paper having a basis weight of 70 g / m ² using a Meyer bar so that the dry coating amount was 30 g / m ^2, and dried at 110 ° C. for 2 minutes. Thus, a moisture-proof layer was formed to prepare a moisture-proof paper. Table 2 shows the test results.

[0112] In each of Examples 23 and 24 Examples 23 and 24 were prepared moisture-proof paper in the same manner as in Example 14. However, in the preparation of the coupling agent surface-treated pigment, muscovite pigment (mica A2
Instead of 1), in Example 23, a muscovite pigment (trade name: Mica A11, manufactured by Mica Yamaguchi, average particle size: 5)
μm, aspect ratio: 20 to 30) to prepare a surface-treated muscovite pigment (h) of a coupling agent, and prepare Example 24.
In the above, muscovite pigment (trade name: mica A61, manufactured by Yamaguchi Mica Industrial Co., Ltd., average particle diameter: 50 μm, aspect ratio: 2)
0-30) to prepare a coupling agent surface-treated muscovite pigment (i). Table 3 shows the test results.

[0113] In each of Examples 25-29 Example 25-29 were prepared moisture-proof paper in the same manner as in Example 14. However, the following synthetic resin was used as the synthetic resin component (a). Example 25: Carboxylic acid-modified SBR latex (trademark:
OX1060, manufactured by Zeon Corporation, solid content concentration: 50%, moisture permeability of synthetic resin: 160 g / m ² · 24 hr) plastic moisture permeability: 317g / m ² · 24hr) example 27: modified SBR latex (trademark: J056
9, manufactured by Japan Synthetic Rubber, solid content concentration: 48%, synthetic resin moisture permeability: 200 g / m ² · 24 hr) Example 28: Modified SBR latex (trademark: Polylac 760K-10R, manufactured by Mitsui Toatsu Chemicals, solid content concentration) : 48
%, Synthetic resin moisture permeability: 460 g / m ² · 24 hr) Example 29: Acrylic-styrene copolymer latex (trade name: ARON A104, manufactured by Toagosei Co., Ltd., solid content concentration: 4)
(0%, moisture permeability of synthetic resin: 450 g / m ² · 24 hr) The test results are shown in Table 3.

[0114] In each of Comparative Examples 8-12 Comparative Examples 8-12, except for the following matters, others were produced moisture-proof paper in the same manner as in Example 14. Comparative Example 8: A surface-untreated muscovite pigment (mica A21) was used in place of the coupling agent surface-treated muscovite pigment (a). Comparative Example 9: A surface-untreated sericite pigment (Serisite KF132) was used instead of the coupling agent surface-treated muscovite pigment (a).
5) was used. Comparative Example 10: Coupling agent surface treated muscovite pigment (a)
Instead, a surface-untreated talc pigment (Sween) was used. Comparative Example 11: A talc pigment (trade name: PC talc, manufactured by Dio Engineering, average particle diameter 2 μm, aspect ratio: 2 to 4) was used instead of the muscovite pigment (mica A21) in preparing the coupling agent surface-treated pigment. Using this, a talc pigment (j) having a surface treated with a coupling agent was prepared. Comparative Example 12: When preparing a surface-treated pigment for a coupling agent, a muscovite pigment (trade name: mica B72, manufactured by Yamaguchi Mica Kogyo Co., Ltd., average particle diameter: 82 μm, aspect ratio: 20 to 20 m) instead of muscovite pigment (mica A21) Using 30), a coupling agent surface-treated muscovite pigment (k) was prepared. The test results are shown in Table 2 or Table 3.

[0115]

[Table 2]

[0116]

[Table 3]

As is clear from Tables 2 and 3, the moisture-proof papers of Examples 14 to 29 according to the present invention show excellent moisture-proof performance by using the coupling agent (c) and are sufficiently disintegrated for practical use. Showed sex.

Example 30 100 parts by weight of muscovite pigment (trade name: mica AB32, manufactured by Mica Yamaguchi, average particle size: 22 μm, aspect ratio 20 to 30) were mixed with 100 parts by weight of water, and this mixture was mixed. Was subjected to a dispersion treatment for 2 hours at a rotation speed of 2000 rpm using a Cowles disperser. The dispersion and a methyl methacrylate-ethyl acrylate-methacrylic acid copolymer (polymerization molar ratio: 50/30/20, Tg: 55 ° C.) were mixed with a muscovite pigment and a copolymer at a solid weight ratio of 50: The mixture was mixed to 50, and dimethylamine in a molar equivalent to the methacrylic acid content of the copolymer was added to prepare a coating liquid. The above coating solution was applied to one surface of unbleached kraft paper (basis weight: 70 g / m ² ) using a Meyer bar.
The coating was performed so that the dry coating amount was 15 g / m ^2, and dried at 110 ° C. for 2 minutes with a hot air circulating drier to form a moisture-proof layer, thereby producing a moisture-proof paper. Table 4 shows the test results.

Comparative Example 13 A coating solution was prepared by adding 65 parts by weight of SBR latex (trade name: T2)
004F, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 35 parts by weight of a wax emulsion (trademark: OKW-40, a mixed emulsion of paraffin wax, polybutene and rosin resin, manufactured by Arakawa Chemical Industries). This coating solution was applied to one surface of unbleached Ryosara kraft paper (basis weight: 70 g / m ² ) using a Meyer bar so that the dry coating amount was 20 g / m ^2. It dried similarly to 30 and formed the moisture-proof layer, and the moisture-proof paper was produced. Table 4 shows the test results.

Comparative Example 14 In the same manner as in Example 30, a moisture-proof paper was produced. However,
Instead of the muscovite pigment (mica AB32), a talc pigment (trade name: PC talc, manufactured by Dio Engineering, average particle diameter: 2 μm, aspect ratio 2 to 4) was used. Table 4 shows the test results.

Comparative Example 15 A moisture-proof paper was produced in the same manner as in Example 30. However, in place of the muscovite pigment (mica AB32), a muscovite pigment (trademark: mica B72, manufactured by Mica Yamaguchi, average particle diameter: 8)
2 μm, aspect ratio: 20 to 30). Table 4 shows the test results.

[0122]

[Table 4]

The moisture-proof paper of Example 30 according to the present invention had practically good moisture-proof properties, defibration properties and friction coefficients, but the moisture-proof paper of Comparative Example 13 (flat disk-shaped particles (b) , Containing a moisture-proofing agent (c) but containing a wax) has a low coefficient of friction and is slippery, and the moisture-proofing papers of Comparative Examples 14 and 15 (where the pigment has an average particle diameter or aspect ratio,
Which did not satisfy the requirements of the present invention) had low moisture resistance.

Example 31 1 part by weight of xylene diamine (aliphatic polyamine containing an aromatic ring, manufactured by Wako Pure Chemical Industries, Ltd.) in 50 parts by weight of water and carboxylic acid-modified SBR latex (LX) as a synthetic resin
407S1X1, solid content 48%) 50 parts by weight (solid content)
Was added and stirred. Next, 50 parts by weight of sericite pigment (trade name: Sericite KF1325, manufactured by Chuo Kaolin Co., Ltd., average particle diameter: 13 μm, aspect ratio: 20 to 30) as a phyllosilicate pigment was added thereto, and the mixture was dispersed with a Cowles disperser.
The mixture was stirred at 2000 rpm for 0 minutes to prepare a coating solution. This coating solution was applied to one surface of unbleached kraft paper (basis weight: 70 g / m ² ) using a Meyer bar at a dry coating amount of 30 g / m 2.
After hand-painting so as to obtain ² , use a hot air circulation dryer
C. for 1 minute to form a moisture-proof layer to produce a moisture-proof paper. Table 5 shows the test results.

Examples 32 to 43 and Comparative Example 16 A moisture-proof paper was produced in the same manner as in Example 31 except that the following compound was used instead of xylenediamine. Example 32: Ethylenediamine (aliphatic polyamine, manufactured by Wako Pure Chemical Industries, Ltd.) Example 33: Triethylenetetramine (aliphatic polyamine, manufactured by Wako Pure Chemical Industries, Ltd.) Example 34: Epoxy-modified xylenediamine (modified) Amine, trademark: EH265, manufactured by Asahi Denka Kogyo Co., Ltd.) Example 35: acrylonitrile-modified xylenediamine (modified amine, trademark: X13A, Sanwa Chemical Industry Co., Ltd.) Example 36: octylamine (aliphatic monoamine, Example 37: m-phenylenediamine (aromatic amine,
Example 38: Pyrrolidine (secondary amine, manufactured by Wako Pure Chemical Industries, Ltd.) Example 39: Hexamethylenetetramine (tertiary amine, manufactured by Wako Pure Chemical Industries, Ltd.)
Example 40: Stearyldimethylbenzylammonium chloride (quaternary ammonium salt, trademark: Cation S,
Example 41: Betaine lauryl dimethylaminoacetate (betaine compound, trademark: Obazoline LB, manufactured by Toho Chemical Industry Co., Ltd.) Example 42: Polycondensation product of polymerized fatty acid and polyethylene polyamine (polyamide) Resin, trademark: 315H, manufactured by Sanwa Chemical Industry Co., Ltd. Example 43: Polycondensation product of linolein dimer and ethylenediamine (polyamide resin, trademark: Versamid, Gener)
al Mills) Comparative Example 16: No moisture-proofing agent was used. Table 5 shows the test results.

Examples 44 to 48 and Comparative Examples 17 to 19 The following phyllosilicate compound pigments were used in place of sericite pigments (sericite KF1325) having an average particle diameter of 13 μm as phyllosilicate compounds. Produced a moisture-proof paper in the same manner as in Example 31. Example 44: Muscovite having a mean particle diameter of 20 μm (mica A
21) Example 45: Talc (Sween) having an average particle size of 15 μm Comparative Example 17: Average particle size: 2 μm, aspect ratio: 5
10 kaolins (trade name: HydraPrint, manufactured by Nissei Kyoeki Co., Ltd.) Example 46: Muscovite having a mean particle diameter of 5 μm (mica A1
1) Example 47: average particle diameter: 33 µm, aspect ratio: 2
Example 48: Average mica diameter: 45 µm, aspect ratio: 2
0-30 muscovite (trademark: mica A51, manufactured by Yamaguchi Mica Co., Ltd.) Comparative Example 18: average particle diameter: 55 μm, aspect ratio: 2
0-30 muscovite (trademark: # 4-K, manufactured by KMG MINERALS) Comparative Example 19: Average particle size: 3.5 μm, aspect ratio:
About 1 to 2 calcium carbonate pigments (trademark: Softon BF-
Table 100 shows the test results.

Examples 49 to 52 A moisture-proof paper was produced in the same manner as in Example 31 except that the following synthetic resin was used in place of the carboxylic acid-modified SBR latex (LX407S1X1) as the synthetic resin (a). did. Example 49: Carboxylic acid-modified SBR latex (OX1
060) Example 50: Modified SBR Latex (686A3) Example 51: Acrylic-Styrene Copolymer Latex (Alon A104) Example 52: Modified NBR Latex (LX55)
0, manufactured by Zeon Corporation) The test results are shown in Table 7.

Example 53 1 part of xylene diamine in 50 parts by weight of water and an aminosilane coupling agent (N-β (aminoethyl) γ-aminopropyltrimethoxysilane, trademark: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0 0.5 parts by weight and 50 parts by weight (solid content) of a modified SBR latex (LX407S1X1) as a synthetic resin (a) were added and stirred. Next, 50 parts of sericite (sericite KF1325) having an average particle diameter of 13 μm was added as the phyllosilicate compound (b), and the mixture was stirred with a Cowles disperser at 2000 rpm for 30 minutes to prepare a coating liquid. Using a Mayer bar, the obtained coating liquid was applied to one side of unbleached kraft paper (basis weight: 70 g / m ² ) at a dry coating amount of 30 g / m ^2.
m ² and then 12 with a hot air circulation dryer.
After drying at 0 ° C. for 1 minute, a moisture-proof layer was formed to produce a moisture-proof paper. Table 8 shows the test results.

[0129] except using a coupling agent having the following in place of Example 54 to 58 aminosilane coupling agent, the other to produce a moisture-proof paper in the same manner as in Example 53. Example 54: Epoxysilane coupling agent (γ-glycidoxypropyltrimethoxysilane, trademark: KBM4)
03, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 55: Vinyl silane coupling agent (vinyl trimethoxysilane, trademark: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 56: Methacryloxy silane coupling agent (γ
-Methacryloxypropyltrimethoxysilane, trademark:
Example 57: Methylsilane coupling agent (methyltrimethoxysilane, trademark: KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 58: amino titanate coupling agent (isopropyl tri ( N-aminoethylaminoethyl) titanate, trademark: KR44, Ajinomoto Co., Ltd. The test results are shown in Table 8.

[0130]

[Table 5]

[0131]

[Table 6]

[0132]

[Table 7]

[0133]

[Table 8]

As is apparent from Tables 5 to 7, when an organic amine compound or a polyamide compound is used as the moisture-proofing agent (c) (Examples 30 to 52), the obtained moisture-proofing paper has good moisture-proofing properties. And disintegration properties. Table 8
As is evident from the above, when an organoalkoxysilane compound or an organoalkoxy metal compound is used in combination with the above-mentioned organic amine compound or polyamide compound, the moisture-proof paper obtained further improved in moisture-proof properties.

Example 59 In 50 parts by weight of water, phenol pentaethylene glycol glycidyl ether (trade name: Denacol Ex145, manufactured by Nagase Kasei Kogyo Co., Ltd.) was used as a moisture-proofing agent (c).
1 part by weight, modified SBR latex (trade name: LX407S1X1, styrene / butadiene /
50 parts by weight (solid content) of a carboxylic acid-containing comonomer = 34/47/19, manufactured by Nippon Zeon Co., Ltd., solid content concentration: 48%) were added and stirred. Next, sericite pigment (trade name: Sericite KF) having a mean particle diameter of 13 μm and an aspect ratio of 20 to 30 as a phyllosilicate pigment (b) was added to this mixture.
1325, manufactured by Chuo Kaolin Co., Ltd.), and the mixture was stirred with a Cowles disperser at 2000 rpm for 30 minutes to prepare a coating solution. The obtained coating liquid was hand-coated on unbleached kraft paper (basis weight: 70 g / m ² ) using a Meyer bar so that the dry weight was 30 g / m ² , and then dried with a hot-air circulation dryer. After drying at 120 ° C. for 1 minute to form a moisture-proof layer, a moisture-proof paper was produced. Table 9 shows the test results.

[0136] In each of Examples 60-63 Example 60-63 were prepared moisture-proof paper in the same manner as in Example 59. However, the following compounds were used as the moisture-proofing agent (c) instead of phenolpentaethylene glycol glycidyl ether. Example 60: Butylene oxide (Wako Pure Chemical Industries, Ltd.)
Example 61: Phenyl glycidyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) Example 62: allyl glycidyl ether (trademark: Denacol EX-111, manufactured by Nagase Kasei Kogyo Co., Ltd.) Example 63: lauryl alcohol polyethylene oxide Glycidyl ether, trademark: Denacol EX171,
Table 9 shows the test results.

[0137] In each of Examples 64-68 Example 64-68 were prepared moisture-proof paper in the same manner as in Example 59. However, the following phyllosilicate compound particles were used as the phyllosilicate compound particles (c) instead of sericite pigment (sericite KF1325) having an average particle diameter of 13 μm. Example 64: Average particle diameter: 20 μm, aspect ratio: 2
Example 65: Average particle size: 15 µm, aspect ratio: 5
Example 66: Average particle diameter 5 μm, aspect ratio: 20 to 10
30 muscovite (trademark: mica A11, Yamaguchi mica Co., Ltd.)
Example 67: Average particle diameter 33 μm, aspect ratio: 20
~ 30 muscovite (trademark: mica A31, Yamaguchi mica Co., Ltd.)
Example 68: average particle diameter 45 μm, aspect ratio: 20
~ 30 muscovite (trademark: mica A51, Yamaguchi mica Co., Ltd.)
Table 10 shows the test results.

[0138] In each of Examples 69 to 72 Example 69 to 72 were prepared moisture-proof paper in the same manner as in Example 59. However, the following synthetic resin was used in place of the synthetic resin used in Example 59. Example 69: Modified SBR (trademark: OX1060, styrene / butadiene / hydrophilic functional group-containing comonomer copolymer = 58/36/6, manufactured by Zeon Corporation) Example 70: Modified SBR (trademark: 686A3, styrene) / Butadiene / hydrophilic functional group-containing comonomer copolymer =
46/34/20, manufactured by Mitsui Toatsu Co., Ltd.) Example 71: Acrylic styrene copolymer (trade name: Alon A104, manufactured by Toagosei Co., Ltd.) Example 72: NBR (trade name: LX550, Nippon Zeon Co., Ltd.) Table 10 shows the test results.

Example 73 50 parts by weight of water and 1 part by weight of phenol pentaethylene glycol glycidyl ether (trade name: Denacol Ex145, manufactured by Nagase Kasei Kogyo Co., Ltd.)
N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trademark: K as an aminosilane coupling agent)
0.5 parts by weight of BM603, manufactured by Shin-Etsu Chemical Co., Ltd., modified SBR latex (LX407) as synthetic resin (a)
S1X1, solid content concentration: 48%) 50 parts by weight (solid content)
Was added and stirred. Next, sericite mica pigment (sericite KF132) having an average particle diameter of 13 μm and an aspect ratio of 20 to 30 was added to this mixture as phyllosilicate compound particles (b).
5) Add 50 parts by weight, and use a Cowles disperser for 20 minutes for 30 minutes.
The coating solution was prepared by stirring at 00 rpm. The obtained coating solution was unbleached using a Meyer bar to obtain unbleached kraft paper (basis weight:
70 g / m ² ) was hand-coated on one side so that the dry coating amount was 30 g / m ^2, and dried with a hot-air circulating drier at 120 ° C. for 1 minute to form a moisture-proof layer to produce a moisture-proof paper. Table 11 shows the test results.

[0140] In each of Examples 74 to 78 Example 74 to 78 were prepared moisture-proof paper in the same manner as in Example 73. However, the following coupling agent was used instead of the aminosilane coupling agent used in Example 73. Example 74: Epoxysilane (γ-glycidoxypropyltrimethoxysilane, trademark: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 75: Vinylsilane (vinyl trimethoxysilane, trademark: KBM1003, Shin-Etsu Chemical Co., Ltd.) Example 76: methacryloxysilane (γ-methacryloxypropyltrimethoxysilane, trademark: KBM503)
Example 77: Methylsilane (methyltrimethoxysilane, trademark: KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 78: aminotitanate (isopropyl tri (N
-Aminoethylaminoethyl) titanate, trademark: KR
44, Ajinomoto Co., Inc. Table 11 shows the test results.

Comparative Example 20 Example 5 except that no monofunctional epoxy compound was added.
A moisture-proof paper was produced in the same manner as in No. 9. Table 9 shows test results
Shown in

Comparative Example 21 A moisture-proof paper was produced in the same manner as in Example 59. However, calcium carbonate (trade name: Softon BF-100, Bihoku Powder Chemical Co., Ltd.) having an average particle size of 3.5 μm and an aspect ratio of about 1 to 2 was used instead of the flat particles used in Example 59. Using. Table 10 shows the test results.

[0143]

[Table 9]

[0144]

[Table 10]

[0145]

[Table 11]

Tables 9 to 11 show that, in the moisture-proof paper of the present invention, the epoxy compound added as a moisture-proof property enhances the moisture-proof properties of the moisture-proof paper. Table 11 further shows that the addition of the coupling agent
It is shown that it is effective for improving the moisture resistance. In addition, it was confirmed that the moisture-proof papers of Examples 59 to 78 according to the present invention exhibited good disintegration.

Example 79 In 50 parts by weight of water, 1 part by weight of a polyamine polyurea resin (trade name: Sumireze Resin 302, manufactured by Sumitomo Chemical Co., Ltd.) as a moisture-proofing agent (c), and as a synthetic resin (c) Modified SBR latex (LX407S1X1, solid content concentration:
48%) (50% by weight (solid content)) and stirred. Next, the phyllosilicate pigment (b) has an average particle diameter of 13 μm,
Aspect ratio: sericite pigment with a 20-30 (sericite K
F1325) Add 50 parts by weight, and add 30
The mixture was stirred at 2000 rpm for 1 minute to prepare a coating solution. Using a Mayer bar, the obtained coating liquid was dried on one side of unbleached kraft paper (basis weight: 70 g / m ² ) with a dry weight of 30 g / m 2.
After hand-painting so as to obtain ² , use a hot air circulation dryer
C. for 1 minute to form a moisture-proof layer to produce a moisture-proof paper. Table 12 shows the test results.

[0148] In each of Examples 80 to 83 Example 80 to 83 were prepared moisture-proof paper in the same manner as in Example 79. However, the following compounds were used in place of Sumireze resin 302 used as a moisture-proofing agent in Example 79. Example 80: Sumireze resin 633 (polyamide polyurea resin, manufactured by Sumitomo Chemical Co., Ltd.) Example 81: Sumireze resin 632 (polyamideamine polyurea resin, manufactured by Sumitomo Chemical Co., Ltd.) Example 82: PA -620 (polyamine polyurea resin,
Example 83: PA-622 (polyamideamine polyurea resin, manufactured by Japan PMC Co., Ltd.) Table 12 shows the test results.

Examples 84 to 88 In the same manner as in Example 79, moisture-proof paper was produced. However, the following phyllosilicate compound was used in place of sericite pigment (sericite KF1325) having an average particle diameter of 13 μm used in Example 79. Example 84: Average particle diameter: 20 μm, aspect ratio: 2
Example 85: Average particle size: 15 µm, aspect ratio: 5
Example 86: Average particle size: 5 µm, aspect ratio: 20
Example 87: Average particle size: 33 µm, aspect ratio: 2
Example 88: Average particle size: 45 µm, aspect ratio: 2
Table 12 shows the test results of muscovite mica (trade name: mica A51, manufactured by Mica Yamaguchi Co., Ltd.).

Examples 89 to 92 In each of Examples 89 to 92, a moisture-proof paper was produced in the same manner as in Example 79. However, the following synthetic resin was used in place of the synthetic resin used in Example 79. Example 89: Modified SBR (trademark: OX1060, styrene / butadiene / hydrophilic functional group-containing monomer = 58/3)
Example 90: Modified SBR (trademark: 686A3, styrene / butadiene / hydrophilic functional group-containing monomer = 46/34)
/ 91, manufactured by Mitsui Toatsu Co., Ltd.) Example 91: Acrylic styrene copolymer (trade name: Alon A104, manufactured by Toagosei Co., Ltd.) Example 92: NBR (trade name: LX550, manufactured by Zeon Corporation) Table 12 shows the test results.

Example 93 One part by weight of a polyamine polyurea resin (trade name: Sumireze Resin 302, manufactured by Sumitomo Chemical Co., Ltd.) as a moisture-proofing agent was added to 50 parts by weight of water, and an aminosilane coupling agent (N
-Β (aminoethyl) γ-aminopropyltrimethoxysilane, trademark: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.5 parts by weight, modified SBR latex (LX407S1X1, solid content concentration: 48%) as synthetic resin (a) 5
0 parts by weight (solid content) was added and stirred. Next, a phyllosilicate compound (c) was added to this mixture to obtain an average particle diameter of 13 μm.
m, and 50 parts by weight of sericite pigment (Serisite KF1325) having an aspect ratio of 20 to 30 were added, and the mixture was stirred with a Cowles disperser at 2000 rpm for 30 minutes to prepare a coating liquid. Using a Meyer bar, the obtained coating liquid was dried on one side of unbleached kraft paper (basis weight: 70 g / m ² ) to a dry coating amount of 30 g.
/ M ² after hand-coating, and 1
After drying at 20 ° C. for 1 minute, a moisture-proof layer was formed to produce a moisture-proof paper. Table 13 shows the test results.

[0152] In each of Examples 94 to 98 Example 94 to 98 were produced moisture-proof paper in the same manner as in Example 93. However, the following coupling agent was used in place of the aminosilane coupling agent used in Example 93. Example 94: Epoxysilane (γ-glycidoxypropyltrimethoxysilane, trademark: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 95: Vinylsilane (vinyl trimethoxysilane, trademark: KBM1003, Shin-Etsu Chemical Co., Ltd.) Example 96: methacryloxysilane (γ-methacryloxypropyltrimethoxysilane, trademark: KBM503)
Example 97: Methylsilane (methyltrimethoxysilane, trademark: KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 98: Amino titanate (isopropyl tri (N
-Aminoethylaminoethyl) titanate, trademark: KR
44, Ajinomoto Co., Inc. Table 13 shows the test results.

Comparative Example 22 A moisture-proof paper was produced in the same manner as in Example 79. However, instead of the phyllosilicate compound, the average particle diameter is 3.5 μm.
m, aspect ratio: about 1-2 calcium carbonate (trademark:
Softon BF-100, Bihoku Powder Chemical Co., Ltd.) was used. Table 12 shows the test results.

[0154]

[Table 12]

[0155]

[Table 13]

As shown in Tables 12 and 13, the moisture-proof papers of Examples 79 to 98 according to the present invention exhibited excellent moisture-proof properties due to the polyamine polyurea compound added as a moisture-proof improver. Table 13 shows that the moisture resistance is further improved by the combined use of the coupling agent. The moisture-proof papers of Examples 79 to 98 had practically sufficient disintegration properties.

Example 99 A resin obtained from 50 parts by weight of water, 0.1 part by weight of ammonia, diethylenetriamine, adipic acid and epichlorohydrin (trade name: WS535, Japan PMC Co., Ltd.)
0.5 parts by weight). Next, a modified SBR latex (LX407S) was used as a synthetic resin.
50 parts by weight (1 × 1, solid content concentration: 48%) (solid content) were added and stirred. Next, the mixture was added as a phyllosilicate pigment (c) with an average particle diameter of 13 μm and an aspect ratio of 2
0-30 sericite pigment (Serisite KF1325) 50
Add the parts by weight and use a Cowles disperser for 30 minutes at 2000 rpm
To prepare a coating solution. The obtained coating solution was unbleached using a Meyer bar to obtain unbleached kraft paper (basis weight: 70 g / m2).
After hand-coating one side of ² ) so that the dry coating amount was 30 g / m ² , it was dried with a hot air circulating drier at 120 ° C. for 1 minute to form a moisture-proof layer, thereby producing a moisture-proof paper. Table 14 shows the test results.

[0158] was prepared moisture-proof paper in the same manner as in Example 99 in each of the examples 100 to 102 Example 100-102. However, the following compounds were used in place of the diethylenetriamine-adipic acid-epichlorohydrin condensation reaction product (WS535) used in Example 99. Example 100: Resin obtained from a polymer of diallylamines and epichlorohydrin (trade name: WS564, Japan P
Example 101: Resin obtained from bishexamethylenetriamine and epichlorohydrin (trade name: WS500, manufactured by Nippon PMC Co., Ltd.) Example 102: Resin obtained from diethylenetriamine, dicyandiamide and epichlorohydrin (trademark:
(WS515, manufactured by Japan PMC Co., Ltd.) Table 14 shows the test results.

[0159] was prepared moisture-proof paper in the same manner as in Example 99 in each of Examples 103-107 and Comparative Example 23 Examples 103-107 and Comparative Example 23. However, the following phyllosilicate compound was used in place of the sericite pigment having an average particle diameter of 13 μm used in Example 99. Example 103: Average particle size: 20 μm, aspect ratio:
20 to 30 muscovite (mica A21) Example 104: Average particle diameter: 15 μm, aspect ratio:
5 to 10 talc (Schwen) Example 105: Average particle size: 5 µm, aspect ratio: 2
Example 106: Average particle diameter: 33 µm, aspect ratio: 0-30 muscovite (mica A11)
20 to 30 muscovite (mica A31) Example 107: Average particle size: 45 µm, aspect ratio:
20-30 muscovite (mica A51) Comparative Example 23: Average particle size: 3.5 μm, aspect ratio:
Approximately 1-2 calcium carbonate (Softon BF-100) The test results are shown in Table 14.

[0160] In each of Examples 108-111 Example 108 to 111 were prepared moisture-proof paper in the same manner as in Example 99. However, the following synthetic resin was used in place of the synthetic resin used in Example 99. Example 108: Modified SBR (trademark: OX1060, styrene / butadiene / hydrophilic functional group-containing monomer = 58 /
Example 109: Modified SBR (trademark: 686A3, styrene / butadiene / hydrophilic functional group-containing monomer = 46/3)
4/20, manufactured by Mitsui Toatsu Co., Ltd.) Example 110: Acrylic styrene copolymer (trade name: Alon A104, manufactured by Toagosei Co., Ltd.) Example 111: NBR (trade name: LX550, manufactured by Zeon Corporation) Table 14 shows the test results.

Example 112 50 parts by weight of water, 0.1 part by weight of ammonia, 0.5 part of the diethylenetriamine-adipic acid-epichlorohydrin condensation reaction product (WS535), and an aminosilane coupling agent (N-β (aminoethyl)) 0.5 part by weight of γ-aminopropyltrimethoxysilane (trademark: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added sequentially with stirring.
Furthermore, as a synthetic resin (a), a modified SBR latex (L
(X407S1X1, solid content concentration 48%) 50 parts by weight (solid content) was added and stirred. Next, sericite pigment (sericite KF132) having a mean particle diameter of 13 μm and an aspect ratio of 20 to 30 was added as a phyllosilicate compound (b) to the mixture.
5) Add 50 parts by weight, and use a Cowles disperser for 20 minutes for 30 minutes.
The mixture was stirred at 00 rpm to prepare a coating solution. The obtained coating solution is unbleached using a Meyer bar to obtain unbleached kraft paper (basis weight: 7
(0 g / m ² ) was manually applied on one side to a dry weight of 30 g / m ^2, and dried at 120 ° C. for 1 minute with a hot-air circulating drier to form a moisture-proof layer, thereby producing a moisture-proof paper. Table 15 shows the test results.

[0162] In each of Examples 113 to 117 Example 113 to 117 were prepared moisture-proof paper in the same manner as in Example 112. However, the following coupling agent was used in place of the aminosilane coupling agent used in Example 112. Example 113: Epoxysilane (γ-glycidoxypropyltrimethoxysilane, trademark: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 114: Vinyl silane (vinyl trimethoxysilane, trademark: KBM1003, Shin-Etsu Chemical Co., Ltd.) Example 115: Methacryloxysilane (γ-methacryloxypropyltrimethoxysilane, trademark: KBM50)
3. Shin-Etsu Chemical Co., Ltd.) Example 116: Methylsilane (methyltrimethoxysilane, trademark: KBM13, Shin-Etsu Chemical Co., Ltd.) Example 117: Amino titanate (isopropyl tri (N-aminoethylaminoethyl) Titanate, trademark:
KR44, Ajinomoto Co., Inc. The test results are shown in Table 15.

[0163]

[Table 14]

[0164]

[Table 15]

As shown in Tables 14 and 15, the moisture-proof papers of Examples 99 to 117 according to the present invention were prepared by using a condensation reaction product of a polyamine compound or a polyamide compound and epihalohydrin as a moisture-proof agent. And the moisture proofness could be improved. Further, as shown in Table 15, the moisture resistance can be further improved by using the condensation reaction product in combination with the coupling agent. Each of the moisture-proof papers of Examples 99 to 117 had practically sufficient disintegration properties.

Example 118 Glycidoxysilane coupling agent (trade name: KBM40)
3, a 10% by weight toluene solution of Shin-Etsu Chemical Co., Ltd.) was prepared, and 10 parts by weight of this solution was dried at 120 ° C. for 1 hour to obtain a muscovite pigment (trade name: mica A21, average particle diameter 20 μm, aspect ratio: (20-30, manufactured by Mika Yamaguchi) was stirred in a mixer at 1,000 rpm for 10 minutes and dried at 80 ° C. for 2 hours. As a result, a surface-treated muscovite pigment (a) having a coupling agent was obtained. In 100 parts by weight of water, 100 parts by weight of the surface treated muscovite pigment (a) of the coupling agent and 0.2 parts by weight of a polyacrylic acid-based dispersant (trade name: Cariblon L4)
00, manufactured by Toa Gosei Co., Ltd.) and subjected to a dispersion treatment at 2,000 rpm for 30 minutes using a Cowles disperser. The dispersion and the carboxylic acid-modified SBR latex (trade name: LX407S1X1) are mixed so that the solid content weight ratio of the phyllosilicate compound and the synthetic resin is 50/50, and further 1 part by weight (solid content) Melamine-formalin condensation reaction product (trademark: Euramine P63)
00, manufactured by Mitsui Toatsu Co., Ltd.) to prepare a coating solution. This coating solution was applied to one side of unbleached kraft paper having a basis weight of 70 g / m ² using a Meyer bar to obtain a dry coating amount of 2 g / m 2.
0 g / m ² , and this coating liquid layer was
It was dried at a temperature of 0 ° C. for 2 minutes to form a moisture-proof layer, thereby producing a moisture-proof paper. Table 16 shows the test results.

Example 119 A methacryloxysilane coupling agent (trade name: KBM5)
03, manufactured by Shin-Etsu Chemical Co., Ltd.) in a 10% by weight toluene solution, and 10 parts by weight of this solution was dried at 120 ° C. for 1 hour to obtain a muscovite pigment (trade name: mica A21, average particle diameter: 20 μm, aspect ratio: (20-30, manufactured by Mica Yamaguchi) was stirred in a mixer at 1,000 rpm for 10 minutes and dried at 80 ° C. for 2 hours. Coupling agent surface treated muscovite pigment (b)
was gotten. In a mixture of 95 parts by weight of water and 5 parts by weight of isopropyl alcohol, 100 parts by weight of the coupling agent surface-treated muscovite pigment (b) and 0.2 parts by weight of a polyacrylic acid-based dispersant (trademark: Carribbon L40
0, manufactured by Toa Gosei Co., Ltd.) and using a Cowles disperser,
The dispersion treatment was performed at a rotation speed of 2000 rpm for 30 minutes. The dispersion and the carboxylic acid-modified SBR latex (LX4
07S1X1) and a solid content ratio of the phyllosilicate compound and the synthetic resin is 50/50,
1 part by weight (solid content) of a polyamide resin (trademark:
Sumirezu Resin 5001, Sumitomo Chemical Co., Ltd.) was added to prepare a coating solution. This coating liquid was applied to a basis weight of 70 g / m
^The uncoated bleached kraft paper is coated on one side with a Mayer bar so that the dry coating amount is 20 g / m ² , and the coating liquid layer is dried at a temperature of 110 ° C. for 2 minutes. Thus, a moisture-proof layer was formed to produce a moisture-proof paper. Table 16 shows the test results.

Example 120 100 parts by weight of sericite pigment (trade name: Sericite KF1325, average particle size: 13 μm, aspect ratio: 20 to 30, manufactured by Chuo Kaolin Co., Ltd.) were dispersed in 100 parts by weight of water. 1 part by weight of a stearoyl titanate coupling agent (trade name: KRET, manufactured by Ajinomoto Co., Inc.) was added dropwise to the dispersion, and the dispersion was stirred at 2000 rpm with a colorless disperser.
Dispersed for minutes. 100 parts by weight of solid content of modified SBR latex (LX407S1X1) was added to this dispersion, and 2 parts by weight of solid content of glyoxal (Wako Pure Chemical Industries, Ltd.)
Was added to prepare a moisture-proof paint. Using this paint, a moisture-proof paper was produced in the same manner as in Example 118. Table 16 shows the test results.

Example 121 A moisture-proof paper was produced in the same manner as in Example 120. However,
Sorbitol polyglycidyl ether (trade name: Denacol EX614B, manufactured by Nagase Kasei Co., Ltd.) is used instead of glyoxal, and a modified SBR (LX407S1X) is used.
In place of 1), a styrene-butadiene-carboxylic acid group-containing comonomer copolymer (trade name: JO619, manufactured by Nippon Synthetic Rubber Co., Ltd., solid content: 48%, carboxylic acid modification ratio: 4)
%). Table 16 shows the test results.

[0170]

[Table 16]

As shown in Table 16, Example 11
The moisture-proof paper obtained according to Examples 8 to 121 has a good moisture-proof property and a good blocking resistance by using a moisture-proof property improving agent composed of a crosslinking compound and a coupling agent.
Moreover, it had a sufficient disintegration property for practical use.

[0172]

The moisture-proof paper according to the present invention has good moisture-proof and defibration properties, has a suitable friction coefficient and excellent blocking resistance, and can be recovered and reused. It has high practicality.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideyuki Mimon 1-10-6 Shinonome, Koto-ku, Tokyo Shin-Oji Paper Co., Ltd. Shinonome Research Center (72) Inventor Shinichi Koga 1-chome, Shinonome, Koto-ku, Tokyo No. 10 No. 6 Shin Oji Paper Co., Ltd. Shinonome Research Center (56) References JP-A-9-67795 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 11/00 -27/42

Claims (8)

(57) [Claims] 1. A paper support comprising: a paper support; and a moisture-proof layer formed on at least one surface of the paper support, wherein the moisture-proof layer comprises: (a) a moisture-proof and film-forming synthetic resin;
A moisture-proof paper comprising (b) flat phyllosilicate compound particles having an average particle diameter of 5 to 50 μm and an aspect ratio of 5 or more, and (c) a moisture-proof property improving agent. 2. The moisture-proof and film-forming synthetic resin (a)
(A-1) a conjugated diene compound having 4 to 6 carbon atoms,
Acrylate having 4 to 11 carbon atoms, methacrylate having 5 to 12 carbon atoms, ethylenically unsaturated nitrile compound having 3 to 4 carbon atoms, 6 to 7 carbon atoms A polymer or copolymer of at least one monomer selected from ethylenically unsaturated carboxylic acid glycidyl ester and an aromatic vinyl compound having 8 to 11 carbon atoms, and (a-2) having at least one carbon atom 4 ~
6 conjugated diene compounds, acrylic acid esters having 4 to 11 carbon atoms, methacrylic acid esters having 5 to 12 carbon atoms, ethylenically unsaturated nitrile compounds having 3 to 4 carbon atoms, carbon Ethylenically unsaturated carboxylic acid glycidyl ester having 6 to 7 atoms, having 5 carbon atoms
And at least one hydrophobic comonomer selected from -6 to 6 ethylenically unsaturated alcohol glycidyl ethers and an aromatic vinyl compound having 8 to 11 carbon atoms, and 3 to 7 ethylenically unsaturated alcohols having 3 to 7 carbon atoms. 2. A polymer containing at least one selected from saturated carboxylic acids and copolymers with one or more hydrophilic comonomers selected from ethylenically unsaturated carboxylic acid amides having 3 to 9 carbon atoms. The moisture-proof paper according to 1. 3. The moisture-proofing agent (c) comprises a urea-formaldehyde condensation reaction product, a melamine-formaldehyde condensation reaction product, an aldehyde compound having 1 to 8 carbon atoms, and one or more epoxy groups. Epoxy compounds, crosslinking reactive polyvalent metal compounds, organoalkoxysilane compounds, organoalkoxy metal compounds, organic amine compounds, ammonia, polyamide compounds, polyamide polyurea compounds, polyamine polyurea compounds, polyamide amine polyurea compounds, polyamide amine compounds Polyamide amine-epihalohydrin or formaldehyde condensation reaction product, polyamine-epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine poly The urea-epihalohydrin or formaldehyde condensation reaction product and at least one selected from polyamidoamine polyurea-epihalohydrin or formaldehyde condensation reaction product.
The moisture-proof paper according to 1. 4. The moisture-proofing agent (c) contains a covalently cross-linking reactive compound, which reacts with the moisture-proofing and film-forming synthetic resin (a) to make it hydrophobic. The moisture-proof paper according to claim 2. 5. The moisture-proofing agent (c) contains an ion-crosslinking reactive compound, which reacts with the moisture-proofing and film-forming synthetic resin (a) to make it hydrophobic. The moisture-proof paper according to claim 2. 6. The moisture-proofing agent (c) contains a crosslinking coordination-reactive compound, and this compound reacts with the moisture-proofing / film-forming synthetic resin (a) to make it hydrophobic. ,
The moisture-proof paper according to claim 2. 7. The moisture-proof paper according to claim 3, wherein at least one selected from the group consisting of an organoalkoxysilane compound and an organoalkoxy metal compound is supported on the surface of the phyllosilicate compound particles. 8. The moisture-proof and film-forming synthetic resin (a)
And the weight mixing ratio (a) :( b) of the phyllosilicate compound particles (b) is 30 to 70:70 to 30,
The moisture-proofing agent (c) is added in an amount of 0.05 to 100 parts by weight of the moisture-proof and film-forming synthetic resin (a).
The moisture-proof paper according to claim 1, wherein the amount is from 10 to 10 parts by weight.