JP2007283613A - Primer composition for inkjet recording material, and inkjet recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording material in which respective interlaminar adhesive properties between a substrate/a primer layer/an ink receiving layer are excellent, uniformity of the ink receiving layer can be obtained by suppressing cissing especially when the ink receiving layer is formed on a primer layer, and improvement of printing characteristics is attempted. <P>SOLUTION: A polyolefin resin (A) comprising 0.01-5 mass% unsaturated carboxylic acid unit (A1) and 99.9-85 mass% sum of ethylene unit (A2) and (meth)acrylate unit (A3) and in which the mass ratio (A2)/(A3) is 55/45-99/1, and/or another polyolefin resin (B) comprising 0.01-15 mass% unsaturated carboxylic acid unit (B1) and 50-98 mass% 3-6C unsaturated hydrocarbon unit (B2) are incorporated. In addition, 2-60 parts mass wax (C) are incorporated in 100 parts mass sum of (A) and (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a primer composition for an ink jet recording material and an ink jet recording material, and in particular, a primer composition for an ink jet recording material containing a specific proportion of a polyolefin resin and a wax in a specific ratio, and an ink jet recording material using the primer composition for a primer layer It is about.

  Various output printing systems such as computers and word processors have been developed, such as wire dot recording system, thermal color recording system, thermal melt transfer recording system, thermal sublimation transfer recording system, electrophotographic recording system, and ink jet recording system. . Among them, the ink jet recording system has features such as that plain paper can be used as a recording sheet, printing cost is low, the apparatus is compact and noise-free, and high-speed recording is possible. It also has the feature that it can be easily colored. For this reason, the use as a printer that outputs image information such as characters and figures produced by a computer quickly and accurately has been attracting attention.

  Usually, an ink jet printer ejects recording ink from a nozzle by the pressure of a fine piezoelectric element (piezo element) or the pressure of air generated by heating of a thermal head, and attaches the recording ink to a recording sheet. Do. For this reason, ink that is difficult to dry is used as a recording ink used in ink jet recording. This is to prevent ink ejection failure from the nozzles due to an increase in viscosity due to ink drying. This ink component is generally one in which a dye, a polymer, an additive and the like are dissolved in water and alcohol. Therefore, a recording material for recording with an ink jet printer is required to have the ability to absorb the liquid content of the attached ink and dry and solidify the ink. For this reason, a recording material is used in which an ink receiving layer is formed on a substrate to enhance ink absorbability.

  Furthermore, in recent years, water-based inkjet recording has come to be used for printing outdoor advertisement poster paper, standing signs, hanging advertisement paper, and the like. However, the paper using pulp paper as the base material is water-absorbing pulp paper used as a support, so the drying time after printing is long, and the printed recording paper is wrinkled and curled. Problems such as occurrence and easy breakage (particularly when exposed to rain outdoors) have occurred.

  In order to prevent this, Patent Documents 1 and 2 describe using a thermoplastic resin film as a base material. Patent Documents 3 and 4 propose using a synthetic paper made of a stretched resin film containing an inorganic fine powder as a base material. However, these materials have a problem that the substrate and the ink receiving layer are easily peeled off.

  In order to solve this problem, it has been proposed to provide a primer layer between the base material and the ink receiving layer (for example, Patent Documents 5 to 7). As the resin used for the primer, chlorinated propylene resin, acrylic resin, polyester resin, polyamide resin, and the like are known, and a primer layer is formed by applying an aqueous or non-aqueous solvent solution of such resin to a substrate. It has been known.

On the other hand, Patent Document 8 proposes an aqueous dispersion of polyolefin resin that does not use emulsifiers, but it has not been known to apply such an aqueous dispersion to the primer layer.
JP-A-7-76162 Japanese Patent Publication No.3-25352 JP 7-89218 A Japanese Patent Publication No. 6-62003 JP-A-9-99638 Japanese Patent Laid-Open No. 10-44587 JP-A-10-309863 International Publication No. 02/055598 Pamphlet

  In the resin used for the primer layer described in Patent Documents 5 to 7, when the ink receiving layer of various resins is further formed thereon by coating, the wettability of the coating liquid to the primer layer is not always excellent. However, it may not be applied evenly due to repelling. In addition, such a primer layer has a good adhesiveness to the base material when the base material is a synthetic paper formed of acrylic resin, but when the base material is polyethylene terephthalate. The adhesion to it was not sufficient. Furthermore, the current situation is that there is a strong demand for non-chlorine materials, such as chlorinated propylene resins, that generate harmful substances such as acidic gas during incineration from the viewpoint of environmental problems.

  In addition, when a primer layer is formed using an aqueous coating agent, the conventional coating agent contains a large amount of emulsifiers, so this component remains in the primer layer and the amount used is large. The water resistance of the primer layer and the adhesion to the substrate are impaired, and the bleed-out is not preferable from the environmental and hygiene viewpoints, and the performance may change over time. Also, some inks contain a large amount of solvent components (for example, ethylene glycol, propylene glycol, glycerin, or derivatives thereof, 1,2-hexanediol, 2-pyrrolidone, etc.). Depending on the type, when the glycol resistance of the coating film is not good, the adhesion after applying the ink may be lowered.

  As a result of intensive studies, the inventors have used a mixture of a polyolefin resin and a wax having a specific composition as a primer layer, in addition to good adhesion to the base material, the solvent resistance of the coating is improved, In addition, excellent coatability without repelling of the ink receiving layer is obtained, and if this primer layer is produced using an aqueous dispersion of a specific resin, the environment can be considered from the viewpoint of solvent removal. It has been found that by reducing the use of an emulsifier in the aqueous dispersion as much as possible, it is possible to improve the adhesion between the respective layers and to obtain an ink jet recording material that is hygienic and excellent in the present invention.

That is, the gist of the present invention is as follows.
(1) The following polyolefin resin (A) and / or polyolefin resin (B) and wax (C) are contained, and a total of 100 parts by mass of the polyolefin resin (A) and / or polyolefin resin (B) A primer composition for an ink jet recording material, comprising 2 to 60 parts by mass of a wax (C).

  Polyolefin resin (A): The unsaturated carboxylic acid unit (A1) is contained in an amount of 0.01 to 5% by mass, and the ethylene unit (A2) and the (meth) acrylic ester unit (A3) in total 99.9 to A polyolefin resin containing 85% by mass and having a mass ratio (A2) / (A3) of the ethylene unit (A2) to the (meth) acrylic acid ester unit (A3) of 55/45 to 99/1.

  Polyolefin resin (B): Polyolefin resin containing 0.01 to 15% by mass of unsaturated carboxylic acid units (B1) and 50 to 98% by mass of unsaturated hydrocarbon units (B2) having 3 to 6 carbon atoms .

  (2) The primer composition for an inkjet recording material according to (1), wherein the polyolefin resin (A) is an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer.

  (3) The primer composition for inkjet recording materials according to (1) or (2), wherein the unsaturated hydrocarbon having 3 to 6 carbon atoms constituting the polyolefin resin (B) is propylene and / or butene.

  (4) The wax (C) is at least one selected from polyolefin wax, carnauba wax, candelilla wax, and paraffin wax, for any one of the ink jet recording materials from (1) to (3) Primer composition.

  (5) 0.1 to 30 parts by mass of a crosslinking agent component is contained with respect to a total of 100 parts by mass of the polyolefin resin (A) and / or the polyolefin resin (B). 1) The primer composition for inkjet recording materials.

  (6) An inkjet recording material obtained by laminating a substrate, a primer layer, and an ink receiving layer in this order, wherein the primer layer is a primer composition for an inkjet recording material of any one of (1) to (5) An ink jet recording material characterized by being formed.

  (7) The inkjet recording material according to (6), wherein the substrate is formed of synthetic paper or a thermoplastic resin film.

  The ink jet recording material of the present invention uses the primer composition for an ink jet recording material of the present invention containing a specific polyolefin resin and a wax in a specific ratio, thereby allowing adhesion between the respective layers of the substrate / primer layer / ink receiving layer. Not only can a material with excellent properties be obtained, it also has excellent solvent resistance. This makes it possible to deal with a wide range of inks. In particular, by suppressing the repelling when the ink receiving layer is formed on the primer layer, the uniformity of the ink receiving layer can be obtained, which can contribute to the improvement of printing characteristics. Furthermore, it is possible to use a polyolefin resin aqueous dispersion for forming a primer layer on a base material, which does not contain an emulsifier, so that no emulsifier remains in the primer layer. It is possible to provide an ink jet recording material in which adhesion between layers is further improved and hygienically improved.

The present invention will be described in detail below.
The ink jet recording material of the present invention is formed by laminating a base material, a primer layer, and an ink receiving layer in this order, and the primer layer comprises an aqueous polyolefin resin (A) and / or an aqueous polyolefin resin (B), The wax (C) is contained in a specific ratio. The polyolefin resin (A) and the polyolefin resin (B) are preferably non-chlorine (having no chlorine atoms) resin from the viewpoint of the environment.

  Although the thickness of a primer layer is not specifically limited, It is preferable that it is 0.1-20 micrometers, It is more preferable that it is 0.3-15 micrometers, It is further more preferable that it is 0.3-10 micrometers, 0.5- A thickness of 8 μm is particularly preferable. When the thickness is less than 0.1 μm, the effect as a primer is small, and when it exceeds 20 μm, the drying time when applied to the substrate becomes long.

  The polyolefin resin (A) contains the unsaturated carboxylic acid unit (A1) in an amount of 0.01 to 5% by mass, and the ethylene unit (A2) and the (meth) acrylic acid ester unit (A3) in total 99.9. Contains ~ 85% by mass. The mass ratio of the ethylene unit (A2) to the (meth) acrylic acid ester unit (A3) is (A2) / (A3) = 55/45 to 99/1.

  The unsaturated carboxylic acid unit (A1) needs to be contained in the polyolefin resin (A) in an amount of 0.01 to 5% by mass, more preferably 0.1 to 5% by mass as described above. More preferably, it is 0.5-5 mass%, Most preferably, it is 1-4 mass%. When the content of the unsaturated carboxylic acid unit (A1) is less than 0.01% by mass, the adhesive property of the resulting primer layer with the ink receiving layer tends to decrease. On the other hand, when content of unsaturated carboxylic acid unit (A1) exceeds 5 mass%, the polarity of polyolefin resin (A) becomes high and adhesiveness with a material with low polarity falls.

  The unsaturated carboxylic acid unit (A1) is introduced by an unsaturated carboxylic acid or an anhydride thereof. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc., as well as unsaturated dicarboxylic acid half esters, half amides, etc. Can be mentioned. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable from the viewpoint of easy availability of the resin. The unsaturated carboxylic acid unit (A1) may be copolymerized in the polyolefin resin (A), and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization. When an acid anhydride is introduced, an acid anhydride structure is formed in which the adjacent carboxyl group is dehydrated and cyclized in the dry state of the resin, but in particular in a medium containing a basic compound, a part of the acid anhydride structure is formed. Or all ring-opened to take the structure of a carboxylic acid or a salt thereof.

  As described above, the mass ratio of the ethylene unit (A2) and the (meth) acrylic acid ester unit (A3) is (A2) / (A3) = 55 when the total amount of the two components is 100% by mass. It is necessary to be in the range of / 45 to 99/1. This range is more preferably 60/40 to 97/3, and 65/35 to 95/5 in order to provide good adhesion between the primer layer and various substrates and ink receiving layers. More preferably, it is particularly preferably 70/30 to 92/8, and most preferably 75/25 to 90/10. When the content ratio of the (meth) acrylic acid ester unit (A3) is less than 1% by mass, the adhesion between the primer layer and the ink receiving layer may be lowered. On the other hand, if the content ratio of the (meth) acrylic acid ester unit (A3) exceeds 45% by mass, the properties of the olefin-derived resin are lost, and the adhesion between the primer layer and the substrate may be reduced.

  Examples of the (meth) acrylic acid ester (A3) unit include esterified products of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms. Among these, an esterified product of (meth) acrylic acid and an alcohol having 1 to 20 carbon atoms is preferable from the viewpoint of availability. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Of these, methyl (meth) acrylate (ethyl) (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesion to the substrate and the ink receiving layer. Ethyl acid and butyl acrylate are more preferable, and ethyl acrylate is particularly preferable. In the present specification, “(meth) acrylic acid˜” means “acrylic acid˜ or methacrylic acid˜”.

  As the polyolefin resin (A), an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer is excellent in adhesion to the base material and has good compatibility with the wax (C) described later. And most preferred. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like, but those of a random copolymer and a graft copolymer are preferable from the viewpoint of easy availability.

  The (meth) acrylic acid ester (A3) unit may be converted into an acrylic acid unit by hydrolyzing a small part of the ester bond when the resin is made aqueous as described later. In such a case, the ratio of each constituent component taking these changes into account only needs to be within the specified range.

  The polyolefin resin (A) has a melt flow rate at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, usually from 0.01 to 10000 g / 10 minutes, preferably from 0.1 to 1000 g / 10 minutes, more preferably from 1 to 500 g. / 10 minutes, more preferably 2 to 300 g / 10 minutes, particularly preferably 2 to 200 g / 10 minutes. When the melt flow rate of the polyolefin resin (A) is less than 0.01 g / 10 minutes, the adhesion between the resulting primer layer and the ink receiving layer is lowered, or it becomes difficult to make the resin water-based. On the other hand, when the melt flow rate of the polyolefin resin (A) exceeds 10,000 g / 10 minutes, the coating film becomes hard and brittle, and the adhesion to the substrate and the ink receiving layer is lowered.

  The method for synthesizing the polyolefin resin (A) is not particularly limited, and can be generally synthesized by high-pressure radical copolymerization of the monomers constituting the polyolefin resin in the presence of a radical generator. Moreover, the unsaturated carboxylic acid unit (A1) may be graft-copolymerized (graft-modified).

  You may contain other components other than the said component about 10 mass% or less of the whole polyolefin resin (A). Other components mentioned here include maleic esters such as alkenes and dienes having 3 to 20 carbon atoms such as propylene, butenes, 1-octene and norbornenes, dimethyl maleate, diethyl maleate and dibutyl maleate. Bases such as (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl esters Examples include vinyl alcohol obtained by saponification with a functional compound, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like. Mixtures of these can also be used.

  The polyolefin resin (B) contains 0.01 to 15% by mass of the unsaturated carboxylic acid unit (B1) and 50 to 98% by mass of the unsaturated hydrocarbon unit (B2) having 3 to 6 carbon atoms. Resin.

  The unsaturated carboxylic acid unit (B1) needs to be contained in the polyolefin resin (B) in an amount of 0.01 to 15% by mass as described above, more preferably 0.1 to 10% by mass. More preferably, it is 0.5-7 mass%, Most preferably, it is 1-5 mass%. When the content of the unsaturated carboxylic acid unit (B1) is less than 0.01% by mass, the adhesion between the resulting primer layer and the ink receiving layer may be lowered. On the other hand, when content of unsaturated carboxylic acid unit (B1) exceeds 15 mass%, the polarity of polyolefin resin (B) will become high and adhesiveness with a material with low polarity will fall.

  The unsaturated carboxylic acid unit (B1) is introduced by an unsaturated carboxylic acid or an anhydride thereof. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc., as well as unsaturated dicarboxylic acid half esters, half amides, etc. It is done. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable from the viewpoint of easy availability of the resin. The unsaturated carboxylic acid unit (B1) may be copolymerized in the polyolefin resin (B). The form is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization. When an acid anhydride is introduced, an acid anhydride structure is formed in which the adjacent carboxyl group is dehydrated and cyclized in the dry state of the resin, but in particular in a medium containing a basic compound, a part of the acid anhydride structure is formed. Or all ring-opened to take the structure of a carboxylic acid or a salt thereof.

  The method for introducing the unsaturated carboxylic acid unit (B1) into the polyolefin resin (B) is not particularly limited. For example, in the presence of a radical generator, the polyolefin resin (B) and the unsaturated carboxylic acid are mixed with the polyolefin resin ( A method of reacting by heating and melting to a temperature equal to or higher than the melting point of B) or a method of dissolving and reacting the polyolefin resin (B) in an organic solvent followed by heating and stirring in the presence of a radical generator. The method of graft-copolymerizing an unsaturated carboxylic acid unit is mentioned. The former method is preferable because the operation is simple. Examples of the radical generator used for graft copolymerization include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, Examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, ethyl ethyl ketone peroxide, and di-tert-butyl diperphthalate, and azonitriles such as azobisisobutyronitrile. These may be appropriately selected depending on the reaction temperature.

  In the polyolefin resin (B), the content of the unsaturated hydrocarbon unit (B2) having 3 to 6 carbon atoms needs to be 50 to 98 mass%, preferably 60 to 98 mass%, more preferably. It is 70-98 mass%, More preferably, it is 75-98 mass%. When the content of the unsaturated hydrocarbon unit (B2) having 3 to 6 carbon atoms is less than 50% by mass, the adhesion to polyolefin materials such as polypropylene is lowered, and conversely exceeds 98% by mass. Since the content of the unsaturated carboxylic acid unit (B1) is relatively reduced, the adhesion to the ink receiving layer may be reduced when the primer layer is used. Examples of unsaturated hydrocarbons having 3 to 6 carbon atoms include alkenes such as propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, and butadiene And dienes such as isoprene. Among these, from the viewpoint of easy production of the resin, adhesion to various materials, and the like, a propylene component and / or a butene component (1-butene, isobutene, etc.) are preferable, and both can be used in combination. As polyolefin resin (B), it is preferable to contain 2-50 mass% of ethylene components other than the above-mentioned unsaturated hydrocarbon of 3-6 carbon atoms. By containing the ethylene component, the adhesion to various materials is improved.

  A particularly preferable configuration of the unsaturated hydrocarbon unit (B2) having 3 to 6 carbon atoms is one containing three components, a propylene component, a butene component, and an ethylene component. The composition ratio is 8 to 90 parts by mass of the propylene component, 8 to 90 parts by mass of the butene component, and 2 to 50 parts by mass of the ethylene component when the total of the three components is 100 parts by mass.

  The copolymerization form of the unsaturated hydrocarbon unit (B2) having 3 to 6 carbon atoms is not limited, and examples thereof include random copolymerization and block copolymerization. Among these, random copolymerization is preferable from the viewpoint of easy polymerization. Moreover, you may mix 2 or more types of polyolefin resin so that it may become the structural component ratio of this invention.

  The polyolefin resin (B) may contain other components in addition to the above components in an amount of about 10% by mass or less of the entire polyolefin resin (B). Other components for this purpose include maleic acids such as 1-octene, norbornene and other alkenes and dienes having 6 or more carbon atoms, (meth) acrylic acid esters, dimethyl maleate, diethyl maleate, dibutyl maleate and the like. Esters, (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl esters Vinyl alcohol obtained by saponification with a basic compound, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, vinyl halides, vinylidene halides, carbon monoxide, two Sulfur, and the like. Mixtures of these can also be used. Among them, (meth) acrylic acid esters are contained in an amount of 0.1 to 10% by mass of the entire polyolefin resin (B) from the viewpoint of adhesion to a substrate and an ink receiving layer and ease of water-based resin. It is more preferable that it is contained, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 10% by mass. Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

  Since the polyolefin resin (B) is easily dissolved in an organic solvent such as tetrahydrofuran and toluene, the weight average molecular weight of the resin (B) can be obtained using a polystyrene resin as a standard using gel permeation chromatography. The weight average molecular weight of the polyolefin resin (B) is preferably 5,000 to 150,000, more preferably 20,000 to 120,000, and further preferably 30,000 to 100,000. It is preferably 35,000 to 90,000, particularly preferably 40,000 to 80,000. When the weight average molecular weight is less than 5,000, there is a tendency that the adhesion to the substrate is lowered, or the resulting coating film is hard and brittle. When the weight average molecular weight exceeds 150,000, the adhesiveness with the ink receiving layer is lowered, or it becomes difficult to make the resin water-based.

  The polyolefin resin (A) and the polyolefin resin (B) may be used alone, or may be used by mixing at an arbitrary mass ratio of (A) / (B) = 0 to 100 / 100-0. Good.

  The primer composition of the present invention contains a wax (C). The types of wax (C) are roughly classified into natural wax and synthetic wax. Natural waxes include plant waxes such as candelilla wax, carnauba wax, rice wax, and wax, animal waxes such as shellac wax and lanolin wax, mineral waxes such as montan wax and ozokerite, petroleum oils such as paraffin wax and microcrystalline wax. A wax etc. can be illustrated. Synthetic waxes include Fischer-Tropsch wax, polyolefin waxes such as polyethylene wax and polypropylene wax, and derivatives thereof (modified products such as acid modification), caster wax, opal wax, armor wax, glyceryl stearate, cetyl alcohols, Examples include stearic acids. Among these, polyolefin wax, candelilla wax, carnauba wax, and paraffin wax are preferable because they exhibit excellent solvent resistance, and candelilla wax and paraffin wax are particularly preferable.

  The content of the wax (C) in the primer composition is 2 to 60 parts by mass with respect to 100 parts by mass in total of the polyolefin resins (A) and (B) from the viewpoint of achieving both adhesiveness and solvent resistance. 3 to 50 parts by mass, more preferably 5 to 45 parts by mass, further preferably 7 to 40 parts by mass, and particularly preferably 10 to 40 parts by mass. . When the content of the wax (C) is less than 2 parts by mass, the effect of improving the solvent resistance is small. When the content of the wax (C) exceeds 60 parts by mass, the obtained primer layer has an adhesive property with the substrate or the receiving layer. May fall.

  In the primer composition of the present invention, depending on the type of base material and the type of ink receiving layer, polyurethane, polyester, ethylene-vinyl acetate polymer, rubber resin, polyamide, You may add polymers, such as an acrylic resin, 1-50 mass parts with respect to a total of 100 mass parts of polyolefin resin (A) and polyolefin resin (B), Preferably about 3-30 mass parts.

  In the primer composition of the present invention, in order to further improve performance such as adhesion to a substrate or an ink receiving layer, water resistance, solvent resistance, etc., the crosslinking agent is added in an amount of 0.000 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable to add 1 to 30 parts by mass. More preferably, it is 0.5-20 mass parts. When the addition amount of the crosslinking agent is less than 0.1 parts by mass, the degree of improvement in various performances is small, and when it exceeds 30 parts by mass, the performance such as workability is deteriorated. As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal having a multivalent coordination site, and the like can be used. As such a crosslinking agent, for example, an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline group-containing compound, a zirconium salt compound, a silane coupling agent, and the like are preferable. Moreover, you may use combining these crosslinking agents.

  Examples of the substrate constituting the ink jet recording material of the present invention include paper, synthetic paper, and a thermoplastic resin film. Among them, it is preferable to use a synthetic paper or a thermoplastic resin film in order to further develop the primer performance of the present invention.

  As the synthetic paper, it is preferable to use polyolefin synthetic paper. Here, the term “polyolefin-based” means, for example, mainly composed of polyethylene resins such as high-density polyethylene and medium-density polyethylene, and polyolefin resins such as polypropylene. These resins may be used alone or in combination of two or more. Among these, it is most preferable to use polypropylene from the viewpoint of chemical resistance, heat resistance, cost, and the like. The steric structure of polypropylene is not particularly limited. For example, propylene homopolymer having isotactic or syndiotactic and various degrees of stereoregularity, propylene as a main component, ethylene, 1-butene, Mention may be made of copolymers with α-olefins such as 2-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene. These copolymers may be binary or higher multi-component copolymers, and may be random copolymers or block copolymers.

  The synthetic paper preferably contains a filler in order to improve whiteness and to improve printing characteristics and printability. In general, the content is preferably 75% by mass or less. Examples of the filler used for the synthetic paper include inorganic carbonates such as calcium carbonate, clay, silica, diatomaceous earth, talc, titanium oxide, barium titanate, barium sulfate, and alumina. It is preferable that the average particle diameter of a filler is 0.01-15 micrometers. In the organic system, polymers such as polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, nylon 46, nylon 12, cyclic polyolefin, etc., having a melting point higher than the melting point of the polyolefin resin or glass transition temperature are used. be able to. However, inorganic fillers are preferred because they are inexpensive and can improve whiteness.

  The structure of the synthetic paper is not particularly limited. Therefore, it may be a single layer structure or a multilayer structure. As a multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces of the base material layer, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Each layer may or may not contain an inorganic or organic filler.

  As the polyolefin-based synthetic paper, microporous synthetic paper having many fine voids can be used. Among them, the one having a porosity of 5 to 60%, preferably 8 to 40% is preferable because printability and printability are improved. The thickness of the polyolefin synthetic paper is not particularly limited. In general, the thickness of such synthetic paper is usually about 20 to 400 μm.

  Polypropylene synthetic paper can be used as the polyolefin synthetic paper. Examples of the polypropylene synthetic paper include YUPO FPG, YUPO FGS, YUPO GFG, and YUPO KPK manufactured by Oji Oil Chemical Co., Ltd.

  As described above, the base material can be composed of a thermoplastic resin film. Examples of such a thermoplastic resin film include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate, polyethylene naphthalate, and poly Polyester resins such as trimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate and polybutylene naphthalate, aliphatic polyester resins such as polyethylene succinate, polyglycolic acid and polylactic acid, polyolefin resins such as polypropylene and polyethylene, polyimide resins , A film made of a polycarbonate resin, a polyarylate resin, or a mixture thereof, or a laminate of these films. Of these, polyethylene terephthalate is preferable from the viewpoints of cost and performance such as heat resistance. The thermoplastic resin film may be an unstretched film or a stretched film, and the production method is not limited. Although the thickness of the thermoplastic film is not particularly limited, it may be usually 5 to 500 μm.

  The thermoplastic resin film may contain a filler. In the same manner as described above, the filler is preferably an inorganic one because it is inexpensive and can improve whiteness. Specifically, calcium carbonate, clay, silica, diatomaceous earth, talc, titanium oxide, Examples thereof include barium titanate, barium sulfate, and alumina.

  The ink receiving layer constituting the ink jet recording material of the present invention is not particularly limited, and a known one can be used. Examples of the resin used in the ink receiving layer include derivatives modified with polyvinyl alcohol and silanol groups, proteins such as polyvinylpyrrolidone and casein, starch and derivatives thereof, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer. Conjugated diene polymer latex such as polymer, acrylic polymer latex such as polymer or copolymer of acrylic acid ester and methacrylic acid ester, vinyl polymer latex such as ethylene-vinyl acetate copolymer, or the like Carboxylated modified products of various polymers, functional group-containing modified polymer latexes such as cationic groups, melamine resins, synthetic resin-based aqueous adhesives such as thermosetting resins such as urea resins, maleic anhydride copolymer resin systems, Polyacrylamide, polymethyl methacrylate Polymer, polyurethane resin, unsaturated polyester resin, saturated polyester resin, polyvinyl butyral, alkyd resin, and other polymers such as synthetic resin adhesives have good adhesion to the plumer layer and water-based ink Can be preferably used because of its good affinity and improved liquid absorption.

  The ink receiving layer is a layer that contributes to absorption of ink, fixation of pigments and dyes in the ink, and coloring of pigments and dyes. For this reason, it is preferable that the pigment used in the ink receiving layer contains a pigment that is porous, has high ink absorbability, and enables clear color development. As such pigments, fine particle synthetic silica, zeolite, calcium carbonate, calcium silicate, aluminum hydroxide, calcined clay, kaolin clay, talc, white carbon, organic pigment (plastic pigment), etc. are generally used for paper coating. The pigment which can be illustrated can be illustrated. In particular, it is preferable to use fine particle synthetic silica. The use ratio of such a pigment is not limited, but may be 10 to 90% by mass of the total solid content of the receiving layer. If it is less than 10% by mass, the ink absorbability is insufficient, and if it exceeds 90% by mass, the strength of the ink receiving layer may be lowered.

In the inkjet recording material of the present invention, as a method of forming a primer layer containing a polyolefin resin (A) and / or a polyolefin resin (B) and a wax (C),
(A) Method of melting and laminating resin and wax,
(A) A method of applying and drying a resin or wax dissolved or dispersed in an organic solvent,
(C) A method of applying and drying a resin or wax in an aqueous dispersion,
Is mentioned.

  Among these, the method (a) is applied when a thermoplastic resin film having a relatively high heat resistance (for example, a film made of a resin having a melting point of 150 ° C. or higher such as polyethylene terephthalate or nylon 6) is used as the substrate. It is preferable to do. On the other hand, when synthetic paper or the like made of polyolefin resin is used as the base material, if the method (a) is used, the base material may be shrunk or damaged by the heat of the molten resin. Since the thickness of the base material layer and the primer layer may not be thin, in such a case, the methods (a) and (c) may be used.

  In the method (a), examples of the organic solvent include toluene, xylene, ethylcyclohexane, n-heptane, butyl acetate, and the like, and a mixture thereof can also be used. Since the polyolefin resin (B) is relatively easily dissolved in a solvent, this method can be used favorably. However, as mentioned above, since the use of organic solvents tends to be restricted depending on the situation such as environmental protection, resource saving, dangerous goods regulations by the Fire Service Act, workplace environment improvement, etc., use the method (c) Is particularly preferred.

  Hereinafter, the method of (c), in which the polyolefin resin (A) and / or the polyolefin resin (B) and the wax (C) are separately used as an aqueous dispersion, will be described in detail. To do. Here, the aqueous dispersion means a resin fine particle dispersed or dissolved in an aqueous medium. The aqueous medium is a medium containing water as a main component, and may contain a water-soluble organic solvent (alcohols, amines) described later.

  A method for producing an aqueous dispersion of polyolefin resin, that is, a method for producing an aqueous dispersion of polyolefin resin (A) and / or polyolefin resin (B) is not particularly limited. Accordingly, a method of heating and stirring other components in a hermetically sealable container can be employed.

  The container may be any container as long as it has a tank into which a liquid can be charged and can appropriately stir the mixture of the aqueous medium and the resin charged into the tank. As such an apparatus, an apparatus widely known to those skilled in the art as a solid / liquid stirring apparatus or an emulsifier can be used, and an apparatus capable of pressurization of 0.1 MPa or more is preferably used. The stirring method and the rotation speed of stirring are not particularly limited.

  After putting each raw material into the tank of such an apparatus, it is preferably stirred and mixed at a temperature of 40 ° C. or lower. Next, while maintaining the temperature in the tank at 50 to 200 ° C., preferably 60 to 200 ° C., the stirring is preferably continued for 5 to 120 minutes to make the resin sufficiently aqueous, and then preferably 40 with stirring. An aqueous dispersion can be obtained by cooling to below ℃. When the temperature in the tank when stirring is continued is less than 50 ° C., it becomes difficult to make the resin water-based. On the contrary, when the temperature in the tank at that time exceeds 200 ° C., the molecular weight of the polyolefin resin may be lowered.

  It is preferable to add a basic compound during the stirring and mixing. The carboxyl group or acid anhydride group of the polyolefin resin can be anionized with the basic compound, and aggregation between the resin fine particles can be prevented by the electrostatic repulsion of the anion, and the aqueous dispersion can be stabilized. The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent to the carboxyl group in the polyolefin resin (1 mol of acid anhydride group is regarded as 2 mol of carboxyl group), 0.8 It is more preferable that it is -2.5 times equivalent, and it is especially preferable that it is 1.0-2.0 times equivalent. When the amount is less than 0.5 times equivalent, the addition effect of the basic compound is not recognized. On the other hand, when the amount exceeds 3.0 times equivalent, the drying time for forming the primer layer becomes longer or the aqueous dispersion is colored. There is.

  As the basic compound to be added, in addition to metal hydroxides such as LiOH, KOH, and NaOH, compounds that volatilize at the time of layer formation are preferable from the viewpoint of water resistance of the primer layer, and ammonia or various organic amine compounds are preferable. . The boiling point of the organic amine compound is preferably 250 ° C. or lower. When it exceeds 250 ° C., it becomes difficult to scatter the organic amine compound from the resin coating film by drying, and thus the water resistance of the coating film may be deteriorated. Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N- Examples thereof include ethyl morpholine.

  Moreover, in order to improve the dispersibility in making the polyolefin resin aqueous, it is preferable to add an organic solvent. The organic solvent for this purpose is preferably one having a solubility in water at 20 ° C. of 20 g / liter or more, more preferably 100 g / liter or more, from the viewpoint of obtaining a good aqueous dispersion. The addition amount of the organic solvent is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of the aqueous dispersion of polyolefin resin. Is particularly preferred. In addition, by heating the aqueous dispersion with stirring under normal pressure or reduced pressure, a part of the organic solvent can be removed (stripping) out of the system, and finally the organic solvent is removed from the aqueous polyolefin resin. It can also be 1 mass part or less with respect to 100 mass parts of dispersions. Specific examples of the organic solvent used include methanol, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Can be mentioned. Among these, ethanol, isopropanol, and n-propanol are particularly preferable from the viewpoint of low temperature drying property.

  The number average particle diameter (hereinafter referred to as “mn”) of the resin particles in the aqueous dispersion is preferably 1 μm or less from the viewpoint of improving the storage stability of the aqueous dispersion, and the smoothness of the primer layer From the viewpoint of low-temperature film-forming properties, it is more preferably 0.5 μm or less, further preferably 0.3 μm or less, and most preferably 0.1 μm or less. Furthermore, the weight average particle diameter (hereinafter referred to as “mw”) is preferably 1 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.2 μm or less. By reducing the particle diameter, the smoothness and low-temperature film-forming property of the primer layer are improved. The degree of particle dispersion (mw / mn) is preferably from 1 to 5, more preferably from 1 to 2, from the viewpoints of storage stability of the aqueous dispersion and smoothness of the primer layer. It is particularly preferred that Although there is no particular lower limit of the particle diameter, it is usually preferable that both mn and mw are about 0.01 μm.

  The resin content of the aqueous dispersion can be appropriately selected depending on the film forming conditions, the desired thickness of the resin layer, its performance, etc., and is not particularly limited. However, it is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, from the viewpoint of keeping the viscosity of the aqueous dispersion moderate and exhibiting good primer layer forming ability. More preferably, it is 45 mass%, and it is especially preferable that it is 5-40 mass%.

  The aqueous dispersion of polyolefin resin (A) and / or polyolefin resin (B) has an emulsifier content based on 100 parts by mass of resin solids for reasons of water resistance, adhesion to a substrate, and hygiene. It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, particularly preferably 0.1 parts by mass or less, and the emulsifier is substantially reduced. Most preferably it does not contain. When the emulsifier exceeds 10 parts by mass per 100 parts by mass of the resin solid content, the emulsifier component remaining in the primer layer plasticizes the primer layer to deteriorate the performance or to easily elute from the primer layer.

  Examples of the emulsifier herein include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

  The aqueous dispersion of wax (C) may be prepared by making the wax (C) aqueous by the same operation as that of the polyolefin resin described above, or a commercially available aqueous wax dispersion may be used. Examples of commercially available paraffin wax aqueous dispersions manufactured by Nippon Seiki Co., Ltd. EMUSTAR-1015, 1115, 0135, 0136, 1055, 1155, 1070, 1170, etc. EMUSTAR-1045, 1145, 0001, 042X, etc., Carnauba wax aqueous dispersion EMUSTAR-0413 manufactured by Nippon Seiki Co., Ltd., Carnauba wax aqueous dispersion Cellosol 524, K-375, Trasol CN, K-927, etc. manufactured by Chukyo Yushi Co., Ltd. Polyethylene wax aqueous dispersion EMUSTAR-0443 manufactured by Nippon Seiki Co., Ltd. and Mitsui Chemicals polyethylene wax aqueous dispersion Chemipearl W100, W200, W300, W400, W401, W4005, W410, W500, WF640, W700 W800, W900, W950, mention may be made of polypropylene wax aqueous dispersion Chemipearl WP100 like.

  The primer composition for an ink jet recording material of the present invention comprises the polyolefin resin (A) and / or the aqueous dispersion of the polyolefin resin (B) and the aqueous dispersion of the wax (C) obtained as described above. It is obtained by mixing in the proportions.

  As a method for producing an ink jet recording material having a substrate, a primer layer, and an ink receiving layer according to the present invention, for example, a polyolefin having a number average particle diameter of 1 μm or less prepared by the above-described method on at least one surface of the substrate. A method of providing a primer layer by applying and drying an aqueous dispersion containing the resin (A) and / or the polyolefin resin (B) and the wax (C) is preferable.

  When the primer layer is provided on the substrate, the above aqueous dispersion is excellent in film forming ability, so that a known film forming method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating is used. , Curtain flow coating, spray coating, dip coating, brush coating method, etc., can be uniformly coated on the surface of various substrates, set as near room temperature as necessary, and then heat for drying or drying and baking By using the treatment, a uniform resin film can be formed by adhering to the surfaces of the various substrates. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. Further, the heating temperature and the heating time are appropriately selected depending on the characteristics of the substrate that is the object to be coated. In addition, when a crosslinking agent is added, in order to sufficiently advance the reaction between the carboxyl group in the polyolefin and the crosslinking agent, it is desirable to appropriately select the heating temperature and time depending on the type of the crosslinking agent. Further, an aging treatment may be performed to advance the crosslinking reaction.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited by these.
Various characteristics were measured or evaluated by the following methods.

1. Characteristics of resin (1) Composition of polyolefin resins (A) and (B)
^It calculated | required from the < ¹ > H-NMR analyzer (the product made by Varian, 300MHz). The polyolefin resin was measured at 120 ° C. using orthodichlorobenzene (d ₄ ) as a solvent. The content of the unsaturated carboxylic acid in the polyolefin resin was determined by measuring the acid value of the resin according to JIS K5407.

(2) Residual ratio of ester group after making aqueous polyolefin resin (A) The aqueous dispersion of polyolefin resin was dried at 150 ° C., and then ¹ H-NMR in orthodichlorobenzene (d ₄ ) at 120 ° C. The analysis was performed using an analyzer (manufactured by Varian, 300 MHz), and the residual amount (%) of the ester group was determined with the amount of the ester group of the (meth) acrylic acid ester before being made water-based as 100%.

(3) Polyolefin resin (A) melt flow rate (MFR)
JIS It was measured by the method described in 6730 (190 ° C., load 2160 g).

(4) Weight average molecular weight of polyolefin resin (B) Using a GPC analyzer (HLC-8020 manufactured by Tosoh Corporation, column is TSK-GEL), the sample was dissolved in tetrahydrofuran and measured at 40 ° C. The weight average molecular weight was determined from the prepared calibration curve.

2. Characteristics of Aqueous Dispersion and Primer Composition (1) Aqueousization yield The aqueous dispersion after water hydration was pressure filtered (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mM, plain weave). At that time, the mass of the resin remaining on the filter was measured, and the yield was calculated from the mass of the charged resin.

(2) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to obtain the solid content concentration.

(3) Average particle diameter of aqueous dispersion The number average particle diameter and the weight average particle diameter were determined using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) manufactured by Nikkiso Co., Ltd. Here, the refractive index of the resin used for calculating the particle diameter was set to 1.50.

(4) Pot Life of Aqueous Dispersion and Primer Composition The appearance after leaving the aqueous dispersion and primer composition at room temperature for 30 days was evaluated in the following three stages.

○: No change in appearance △: Thickening is observed ×: Solidification, aggregation and generation of precipitates are observed

3. Material characteristics In the following evaluation, YUPO paper (FGS-95 manufactured by Oji Oil Chemical Co., Ltd., hereinafter referred to as “synthetic paper”) which is a polypropylene synthetic paper as a synthetic paper, and biaxially stretched polyethylene as a thermoplastic resin film Terephthalate film (Unitika, Emblet PET12, thickness 12 μm, hereinafter referred to as “PET film”), biaxially stretched nylon 6 film (Unitika, emblem, thickness 15 μm; hereinafter referred to as “Ny film”), A stretched polypropylene film (manufactured by Tosero Co., Ltd., thickness 20 μm, hereinafter referred to as “PP film”) was used.

(1) Primer water resistance evaluation The primer composition was coated on the untreated surface of the PET film using a Meyer bar so that the thickness of the dried primer layer was 2 μm, and then dried at 100 ° C. for 2 minutes. I let you. The obtained coated film was allowed to stand at room temperature for 1 day, and then the coating film was rubbed 10 times with a cloth wetted with water, and the state of the coating film at that time was visually evaluated in the following three stages.

○: No change △: The coating film is cloudy ×: The coating film is completely dissolved

(2) Solvent resistance evaluation of primer After the primer composition was coated on the untreated surface of the PET film using a Mayer bar so that the thickness of the primer layer after drying was 2 μm, it was at 100 ° C. for 2 minutes, Dried. The obtained coated film was left to stand at room temperature for 1 day, and then the cloth was wet with ethylene glycol (hereinafter referred to as “EG”) or with glycerin (hereinafter referred to as “Gly”). After rubbing 10 times, the state of the coating film at that time was visually evaluated in the following three stages.

○: No change △: The coating film is cloudy ×: The coating film is completely dissolved

(3) Adhesive evaluation of substrate / primer layer (Adhesive I)
The primer composition was coated on the untreated surfaces of various substrates using a Meyer bar so that the thickness of the primer layer after drying was 2 μm, and then dried at 100 ° C. for 2 minutes. The obtained laminate was allowed to stand at room temperature for 1 day, and a cellophane tape (manufactured by Nichiban Co., Ltd., TF-12) was attached to the surface of the primer layer, and the degree of peeling when the tape was peeled off at a stroke was visually determined as follows. Evaluation was made in three stages.

○: No peeling at all △: Some peeling off ×: All peeling off

(4) Coatability of ink-receiving layer A coating agent for forming various ink-receiving layers on the surface of the primer layer of the laminate produced by the method (3) above has a coating thickness after drying of 20 μm. This was coated using a Mayer bar, and then dried at 100 ° C. for 10 minutes. Then, the suitability of the ink receiving layer was visually evaluated as follows.

○: No repelling, uneven coat ×: With repelling, uneven coat

(5) Adhesive evaluation of substrate / primer layer / receptive layer (Adhesion II)
Using a Mayer bar with a coating agent for forming various ink receiving layers on the surface of the primer layer of the laminate prepared by the method (3) above, so that the coating thickness after drying becomes 20 μm. After coating, it was dried at 100 ° C. for 10 minutes. The obtained laminate (ink jet recording material) was left at room temperature for 1 day. Then, a cellophane tape (manufactured by Nichiban Co., Ltd., TF-12) was attached to the surface of the ink receiving layer, and the degree of peeling when the tape was peeled at once was visually evaluated in the following three stages.

○: No peeling at all △: Some peeling off ×: All peeling off

(6) Evaluation of adhesiveness of printed part (ink) (Adhesiveness III)
When the ink-receiving layer surface of the laminate produced by the above method (5) was printed with an inkjet printer (PM-770C, manufactured by Seiko Epson Corporation, ink was yellow, magenta, cyan, black) (when using a film) Was printed on paper.) Cellophane tape (TF-12, manufactured by Nichiban Co., Ltd.) was attached to the printing surface, and the degree of peeling when the tape was peeled at once was visually evaluated in the following three stages.

○: No peeling at all △: Some peeling off ×: All peeling off

(7) Printability Printing was performed on the ink receiving layer surface of the laminate produced by the method of (5) above using an ink jet printer (PM-770C manufactured by Seiko Epson Corporation, the inks being yellow, magenta, cyan, and black). And the state of the printing part was observed with a 10-fold magnifier and evaluated in the following three stages.

○: No unevenness in the print area with all inks Δ: Unevenness in the print area with some inks ×: Unevenness in the print area with all inks

(Production of polyolefin resin P-1)
100 g of propylene-butene-ethylene terpolymer (manufactured by Huls Japan, Bestplast 708, propylene / butene / ethylene = 65/24/11% by mass), 500 g of toluene, stirrer, cooling tube, Into a four-necked flask equipped with a dropping funnel, the mixture was heated and melted in a nitrogen atmosphere. Next, with stirring while maintaining the system temperature at 110 ° C., a solution of 1.0 g of dicumyl peroxide as a radical generator in 20 g of heptane was added over 1 hour, and then maleic anhydride 7 as an unsaturated carboxylic acid. 0.0 g, 9.0 g of lauryl acrylate as a modifier, and a solution of 0.5 g of dicumyl peroxide as a radical generator in 10 g of heptane were added dropwise over 1 hour, and then reacted for 30 minutes. . After completion of the reaction, the reaction mixture was cooled to room temperature, and then the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted substances, and then dried under reduced pressure in a vacuum dryer to obtain polyolefin resin P-1. The weight average molecular weight of P-1 was 50,000, the acid value was 46 mgKOH / g, and the content of lauryl acrylate in the resin was 6% by mass.

  As other polyolefin resins, Bondin HX8290 (manufactured by Sumitomo Chemical Co., Ltd.), Bondine HX8210 (manufactured by Sumitomo Chemical Co., Ltd.), and Primacol 5980I (manufactured by Dow Chemical Co., Ltd.) are used. did.

  These polyolefin resins were used in the production of an aqueous dispersion as described below, and their compositions are shown in Table 1. As is clear from Table 1, Bondine HX8290 corresponds to the polyolefin resin (A) in the present invention, P-1 corresponds to the polyolefin resin (B) in the present invention, and Primacol 5980I is ( A) It was not applicable to any of (B).

(Production of aqueous polyolefin resin dispersion E-1)
Using a stirrer equipped with a 1 liter glass container having a pressure-resistant structure that can be sealed with a heater, 60.0 g of Bondine HX8290 and 60.0 g of isopropanol as an organic solvent as a dispersant (manufactured by Wako Pure Chemical Industries, Ltd.) Then, 2.2 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), which is a basic compound as a stabilizer, and 177.8 g of distilled water are charged into the glass container, and the rotation speed of the stirring blade is 300 rpm. Stir.

  As a result, no sedimentation of resin particles was observed at the bottom of the container, confirming that it was in a floating state. Therefore, while maintaining this state, the heater was turned on after 10 minutes to start heating. Then, the system temperature was kept at 120 ° C. and further stirred for 20 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. And it filtered by pressure (air pressure 0.2MPa) with the 300 mesh stainless steel filter (wire diameter 0.035mm, plain weave), and obtained milky white uniform polyolefin resin aqueous dispersion E-1. Various properties of this aqueous dispersion E-1 are shown in Table 2.

(Production of aqueous polyolefin resin dispersion E-2)
Bondine HX8210 (manufactured by Sumitomo Chemical Co., Ltd.) was used as the polyolefin resin. Otherwise, an aqueous polyolefin resin dispersion E-2 was obtained in the same manner as in the production of E-1. Various properties of the obtained aqueous dispersion E-2 are shown in Table 2.

(Production of aqueous polyolefin resin dispersion E-3)
Using a stirrer equipped with a 1 liter glass container having a pressure-resistant structure that can be sealed with a heater, 60.0 g of polyolefin resin (P-1) and 90.0 g of n-propanol which is an organic solvent as a dispersant (Manufactured by Wako Pure Chemical Industries, Ltd.), 3.9 g of N, N-dimethylethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) which is a basic compound as a stabilizer, and 146.1 g of distilled water are mixed with the above glass. The mixture was placed in a container and stirred at a rotation speed of the stirring blade of 300 rpm.

  As a result, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was floating. Therefore, while maintaining this state, the heater was turned on after 10 minutes to start heating. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. And it filtered under pressure (air pressure 0.2MPa) with the 300 mesh stainless steel filter (wire diameter 0.035mm, plain weave), and obtained the milky-white uniform polyolefin resin aqueous dispersion E-3. Various properties of this aqueous dispersion E-3 are shown in Table 2.

(Production of aqueous polyolefin resin dispersion E-4)
At the time of making the resin aqueous, 7 parts by mass of a nonionic surfactant (Asahi Denka Kogyo Co., Ltd., Adeka Pluronic F-108, average molecular weight 15500) as an emulsifier with respect to 100 parts by mass of the solid content of the polyolefin resin It added so that it might become. Other than that, a polyolefin resin aqueous dispersion E-4 was obtained in the same manner as in the production of E-1. Various properties of this aqueous dispersion E-4 are shown in Table 2.

(Production of aqueous polyolefin resin dispersion S-1)
As the polyolefin resin, Primacol 5980I (ethylene-acrylic acid copolymer resin, acrylic acid 20% by mass copolymer) was used. That is, using a stirrer equipped with a 1-liter glass container having a pressure-resistant structure that can be sealed with a heater, 45.0 g of Primacol 5980I and 11.4 g of triethylamine as a basic compound as a stabilizer, 243.6 g of distilled water was charged into a glass container, and the stirring blade was stirred at a rotational speed of 300 rpm. As a result, no sedimentation of resin particles was observed at the bottom of the container, confirming that it was in a floating state. Therefore, while maintaining this state, the heater was turned on after 10 minutes to start heating. Then, the system temperature was kept at 120 ° C. and further stirred for 40 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. And it filtered by pressure (air pressure 0.2MPa) with the 300 mesh stainless steel filter (wire diameter 0.035mm, plain weave), and obtained the slightly cloudy aqueous dispersion S-1. Various properties of this aqueous dispersion S-1 are shown in Table 2.

(Preparation of candelilla wax dispersion W-1)
40.0 g of candelilla wax (manufactured by Toa Kasei Co., Ltd., acid value: 15.8, saponification value: 55.4) using a stirrer equipped with a 1 liter glass container with a pressure-resistant structure that can be sealed with a heater 8.8 g (2.0 times equivalent of the amount necessary for complete neutralization and complete saponification of the wax) morpholine (manufactured by Nacalai Tesque) as a basic compound as a stabilizer, 151.2 g Distilled water was charged into a glass container, and the stirring blade was stirred at a rotational speed of 400 rpm. As a result, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was floating. Therefore, while maintaining this state, the heater was turned on after 10 minutes to start heating. Then, the system temperature was kept at 100 ° C. and further stirred for 10 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 600 rpm. As a result, a pale yellow uniform wax aqueous dispersion W-1 was obtained. In this aqueous wax dispersion W-1, the solid content concentration was 20.0% by mass and the number average particle size was 0.27 μm.

(Ink receiving layer A)
20 parts by mass of fine powder silica (manufactured by Tokuyama, Fine Seal) was added to 100 parts by mass of a solid content of a polyurethane binder (manufactured by Mitsui Takeda, Takelac W-6010) and dispersed therein.

(Ink receiving layer B)
A polyurethane-based binder (Dainippon Ink Industries, Pateracol IJ-30) and an aqueous solution of polyvinyl alcohol (UF100 manufactured by Unitika Chemical Co., saponification degree 99.4%, average polymerization degree 1000) have a solid content mass ratio. The liquid mixed so that it might become 50/50 was used.

Example 1
Aqueous polyolefin resin dispersion E-1 and aqueous candelilla wax dispersion W-1 were blended so as to be 100/30 (solid content mass ratio) to obtain primer composition J-1 for inkjet recording material. . Table 3 shows the results of various performance evaluations using this composition J-1.

Examples 2 and 3
The compounding ratio (solid content mass ratio) of the polyolefin resin aqueous dispersion E-1 and the candelilla wax aqueous dispersion W-1 was 100/5 (Example 2) and 100/55 (Example 3). And other than that was carried out similarly to Example 1, and obtained primer composition J-2, J-3 (Example 2, 3) for inkjet recording materials. Table 3 shows the results of various performance evaluations using these compositions J-2 and J-3.

Examples 4-6
An aqueous dispersion E-2 (Example 4) and E-4 (Example 5) of a polyolefin resin (A) and an aqueous dispersion E-3 (Example 6) of a polyolefin resin (B) were used. And other than that was carried out similarly to Example 1, and obtained primer composition J-4-J-6 (Examples 4-6) for inkjet recording materials. Table 3 shows the results of various performance evaluations using these compositions J-4 to J-6.

Example 7
The aqueous dispersion E-1 of the polyolefin resin (A) and the aqueous dispersion E-3 of the polyolefin resin (B) are mixed so that the solid content mass ratio of the resin is 50/50. E-5 was obtained. A primer composition J-7 for ink jet recording material was obtained in the same manner as in Example 1 except that this aqueous dispersion E-5 was used. Table 3 shows the results of various performance evaluations using this composition J-7.

Examples 8-10
Changed the type of wax. That is, an aqueous dispersion E-1 of a polyolefin resin (A), an aqueous paraffin wax dispersion (manufactured by Nippon Seiki Co., Ltd., EMUSTAR-0135) (Example 8), an aqueous dispersion of polyethylene wax (manufactured by Nippon Seiki Co., Ltd., EMUSTAR-0443) (Example 9) and carnauba wax aqueous dispersion (Nippon Seiki Co., Ltd., EMUSTAR-0413) (Example 10) were blended so as to be 100/30 (solid content mass ratio), respectively. Inkjet recording material primer compositions J-8 to J-10 (Examples 8 to 10) were obtained. Table 4 shows the results of various performance evaluations using these compositions J-8 to J-10.

Example 11
A polyfunctional isocyanate compound (BASF Corporation, Vasonate HW-100, isocyanate content of about 17%) as a crosslinking agent was diluted with water so that the content was 10% by mass. The primer composition J-2 for ink jet recording material obtained in Example 2 and the above isocyanate compound diluent are used in an amount of 5 mass of isocyanate compound with respect to 100 mass parts of the polyolefin resin in the composition J-2. The resulting mixture was mixed and stirred at room temperature for 5 minutes to obtain a primer composition J-11 for inkjet recording materials. Table 4 shows the results of various performance evaluations using this composition J-11.

Comparative Example 1
A primer composition H-1 was obtained in the same manner as in Example 1 except that the aqueous polyolefin resin dispersion S-1 (Table 2) was used. Table 4 shows the results of various performance evaluations using this composition H-1.

Comparative Example 2
The compounding ratio (solid content mass ratio) between the aqueous polyolefin resin dispersion E-1 and the aqueous candelilla wax dispersion W-1 was 100/65. And other than that was carried out similarly to Example 1, and obtained primer composition H-2. Table 4 shows the results of various performance evaluations using this composition H-2.

Comparative Example 3
Various performance evaluations were performed using only the aqueous polyolefin resin dispersion E-1 without adding a wax. The results are shown in Table 4.

  Examples 1 to 11 have a primer layer containing a specific polyolefin resin having a composition based on the present invention and a wax in a specific ratio, thereby providing water resistance, solvent resistance, various base materials and The properties such as the adhesion of the ink, the coatability of the ink receiving layer, the adhesiveness with the receiving layer, the adhesiveness of the printed part, and the printability were good. Especially in Example 11, the cross-linking agent was added, so that the solvent resistance with respect to EG was significantly improved as compared with other examples.

  On the other hand, Comparative Example 1 uses a polyolefin resin having a composition not corresponding to the present invention for the primer layer, so that various adhesive properties are inferior, and is not suitable as an ink jet recording material. In Comparative Example 2, the content of wax was too much outside the range of the present invention, so various adhesive properties were inferior, and were not suitable as an ink jet recording material. Comparative Example 3 had poor solvent resistance because no wax was added.

Claims (7)

The following polyolefin resin (A) and / or polyolefin resin (B) and wax (C) are contained, and wax (C) with respect to a total of 100 parts by mass of the polyolefin resin (A) and / or polyolefin resin (B). 2) to 60 parts by mass of a primer composition for an ink jet recording material.
Polyolefin resin (A): The unsaturated carboxylic acid unit (A1) is contained in an amount of 0.01 to 5% by mass, and the ethylene unit (A2) and the (meth) acrylic ester unit (A3) in total 99.9 to A polyolefin resin containing 85% by mass and having a mass ratio (A2) / (A3) of the ethylene unit (A2) to the (meth) acrylic acid ester unit (A3) of 55/45 to 99/1.
Polyolefin resin (B): Polyolefin resin containing 0.01 to 15% by mass of unsaturated carboxylic acid units (B1) and 50 to 98% by mass of unsaturated hydrocarbon units (B2) having 3 to 6 carbon atoms .   The primer composition for an ink jet recording material according to claim 1, wherein the polyolefin resin (A) is an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer.   The primer composition for an ink jet recording material according to claim 1 or 2, wherein the unsaturated hydrocarbon having 3 to 6 carbon atoms constituting the polyolefin resin (B) is propylene and / or butene.   The primer composition for an ink jet recording material according to any one of claims 1 to 3, wherein the wax (C) is at least one selected from polyolefin wax, carnauba wax, candelilla wax, and paraffin wax. object.   The crosslinker component is contained in an amount of 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of the polyolefin resin (A) and / or the polyolefin resin (B). The primer composition for inkjet recording materials according to 1.   An ink jet recording material comprising a base material, a primer layer, and an ink receiving layer laminated in this order, wherein the primer layer is formed of the primer composition for an ink jet recording material according to any one of claims 1 to 5. An ink jet recording material characterized by being made.   7. The ink jet recording material according to claim 6, wherein the base material is formed of a synthetic paper or a thermoplastic resin film.