JP2020147745A - Gravure printing ink composition for styrene film for heat lamination - Google Patents

Abstract

To provide a gravure printing ink composition for a styrene film for heat lamination that has good dispersibility of a pigment in an ink composition, has good transferability and blocking resistance of the ink composition, and has good thermal laminate strength and molding stability of a film on which the ink composition is printed.SOLUTION: A gravure printing ink composition for a styrene film for heat lamination contains an acrylic resin, a fibrous resin, a pigment and a solvent, in which a ratio A/B of a solid content weight (A) of the acrylic resin to a solid content weight (B) of the fibrous resin is 100/1 to 100/200, and the acrylic resin is obtained by synthesizing an acrylic monomer containing (meth)acrylate having 0.01-2 mass% of a phosphate group in 100% of the resin.SELECTED DRAWING: None

Description

The present invention relates to a gravure printing ink composition for a styrene film for thermal lamination.

Conventionally, food trays such as prepared food containers and lunch containers are made by printing a design pattern on a polystyrene film and laminating a polystyrene sheet in which the printed film is foamed or a polystyrene sheet having excellent impact resistance by thermal pressure bonding. It is made by (hereinafter referred to as thermal lamination). As the printing ink composition at this time, those containing an acrylic resin or a styrene-acrylic copolymer resin as a main component are known.

Patent Document 1 describes a styrene film for thermal lamination containing an acrylic resin, a binder resin containing a cellulose acetate butyrate (CAB) resin and / or a cellulose acetate propionate (CAP) resin, a pigment, and a solvent. A printing ink composition for use, wherein the acrylic resin is synthesized from an acrylic monomer containing methyl methacrylate and butyl methacrylate, is dissolved or dispersed in an alcohol-based or ester-based organic solvent, and the CAB resin is formed. A printing ink composition for a styrene film for thermal lamination, which has a number average molecular weight of 60,000 or less and a CAP resin having a number average molecular weight of 60,000 or less, has been proposed, and while maintaining the storage stability of the ink, it has resistance. It provides an ink having good blocking property.

However, in Patent Document 1, in the evaluation of the ink storage stability, good results were obtained when the acrylic resin was included in both Examples and Comparative Examples. Therefore, the acrylic resin used affects the ink storage stability. No consideration has been given to giving. In addition, since those skilled in the art can understand that the ink storage stability correlates with the dispersibility of pigments and the like with respect to resins and solvents, the evaluations are the same. Therefore, the dispersibility of the acrylic resin and pigments used Needless to say, it has not been considered.

The only evaluation that the ink has poor storage stability is the combined use of acrylic resin and nitrocellulose resin (Comparative Example 6), but the nitrocellulose resin is obtained by nitrating the hydroxyl groups of cellulose with nitric acid. Be done. The average degree of polymerization is about 35 to 480, and the degree of biomass changes depending on the degree of substitution with a nitro group, but about 50% by mass is a biomass-derived resin.

Since the cellulosic resin is effective as a biomass material, it can be said to be an environmentally superior resin, and it can be said that increasing the amount used is more environmentally advantageous. As described above, Patent Document 1 clearly shows that the ink storage stability is inferior when the acrylic resin and the nitrocellulose resin used are used in combination, and the use of the resin in combination has not been studied.

Japanese Patent No. 558332

Therefore, the present invention has good dispersibility of pigments and the like in the ink composition, good transferability and blocking resistance of the ink composition, and good thermal laminating strength and molding suitability of the film on which the ink composition is printed. It is an object of the present invention to provide a gravure printing ink composition for a styrene film for thermal laminating, which has a small environmental load.

The present inventors are gravure printing ink compositions for styrene films for thermal laminating containing an acrylic resin, a fiber-based resin, a pigment, and a solvent.
The ratio of the solid content weight (A) of the acrylic resin to the solid content weight (B) of the fiber-based resin is A / B = 100/1 to 100/200.
A gravure printing ink for a styrene film for thermal lamination, wherein the acrylic resin is synthesized from an acrylic monomer containing a (meth) acrylic acid ester having a phosphoric acid group of 0.01 to 2% by mass in 100% of the resin. It has been found that the above object can be achieved by using the composition, and the present invention has been completed.

That is, the present invention
(1) A gravure printing ink composition for a styrene film for thermal laminating containing an acrylic resin, a fiber-based resin, a pigment, and a solvent.
The ratio of the solid content weight (A) of the acrylic resin to the solid content weight (B) of the fiber-based resin is A / B = 100/1 to 100/200.
A styrene for thermal lamination, which is obtained by synthesizing the acrylic resin from an acrylic monomer containing a (meth) acrylic acid ester having a phosphoric acid group of 0.01 to 2% by mass in 100% of the resin. Gravure printing ink composition for film,
(2) The styrene for thermal lamination according to (1), wherein the fiber-based resin is at least one selected from cellulose acetate butyrate, cellulose acetate propionate, and nitrocellulose resin. Gravure printing ink composition for film,
(3) The gravure printing ink composition for a styrene film for thermal lamination according to (1) or (2), wherein the pigment is an inorganic pigment (excluding carbon black).
(4) The pigment is an organic pigment or carbon black.
The gravure printing ink for a styrene film for thermal lamination according to (1) or (2), wherein the acrylic resin is synthesized from an acrylic monomer containing a (meth) acrylic acid ester having an amino group. Composition,
It is about.

According to the present invention, the dispersibility of pigments and the like in the ink composition is good, the transferability and blocking resistance of the ink composition are good, and the thermal lamination strength and molding suitability of the film on which the ink composition is printed are good. It is possible to provide a gravure printing ink composition for a styrene film for thermal laminating.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is only one embodiment for carrying out the present invention, and the present invention is not limited to the present embodiment, and various modifications and embodiments are made without departing from the gist of the present invention. Is possible.

In the following description, (meth) acrylic or (meth) acrylate means acrylic and methacrylic, acrylate and methacrylate, respectively.

The gravure printing ink composition for a styrene film for thermal lamination of the present invention (hereinafter, also simply referred to as "ink composition" or "ink") contains an acrylic resin, a fiber-based resin, a pigment, and a solvent. A gravure printing ink composition for a styrene film for thermal lamination, wherein the ratio of the solid content weight (A) of the acrylic resin to the solid content weight (B) of the fiber-based resin is A / B = 100/1 to 1. It is 100/200, and it is preferable that the acrylic resin is synthesized from an acrylic monomer containing a (meth) acrylic acid ester having a phosphoric acid group.

The acrylic resin used in the gravure printing ink composition for a styrene film for thermal lamination of the present invention is obtained by synthesizing a (meth) acrylic acid ester having a phosphoric acid group as an acrylic monomer component by a conventional method. Is preferable. Two or more of these monomers may be used. By using an acrylic resin as an acrylic monomer component containing a (meth) acrylic acid ester having a phosphoric acid group, good dispersibility, good transferability of the ink composition, blocking resistance, and ink composition were printed. Good thermal lamination strength and moldability of the film are good.

Examples of the (meth) acrylic acid ester having a phosphoric acid group include compounds represented by the following general formulas (1) to (3).
CH ₂ = CRCOO (R ₁ O) _n P = O (OR ₂ ) ₂ (1)
(In the formula, R represents a hydrogen atom or a methyl group, R ₁ represents an alkylene group having 1 to 4 carbon atoms, R ₂ represents an alkylene group having 1 to 8 carbon atoms, n represents 1 to 8 carbon atoms. Represents an integer)
[CH ₂ = CRCOO (R ₁ O) _n ] _m P = O (OR ₃ ) _3-m (2)
(In the formula, R and R ₁ are the same as in the formula 1, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 or 2, and m represents an integer of 2 or 3. Represent)
CH ₂ = CRCOO (R ₁ O) _n P = O (O-Ph) _m (OH) _2-m (3)
(In the formula, R and R ₁ represent the benzene ring, n represents an integer of 1 or 2, and m represents an integer of 1 or 2 as in the formula 1.)

The amount of the (meth) acrylic acid ester having a phosphoric acid group in 100% of the acrylic resin is preferably 0.01 to 2% by mass, more preferably 0.02 to 1% by mass, and 0. It is more preferably 03 to 0.5% by mass. If it is less than 0.01% by mass, it may be difficult to disperse the pigment, and it is easy to settle. If it is more than 2% by mass, the pigment can be dispersed, but aggregation is likely to occur, and the ink viscosity is high. May change (thickening) (ink stability is inferior) or color development may change (color development is inferior).

The acrylic resin contains a (meth) acrylic acid ester having a hydrocarbon chain, a (meth) acrylic acid ester having a hydroxyl group, a (meth) acrylic acid ester having an epoxy group, and a (meth) acrylic acid ester having an amino group. You may.

Examples of the (meth) acrylic acid ester having a hydrocarbon chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl. Examples thereof include (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate, myristyl (meth) acrylate, lauryl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. .. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate are more preferable.

Examples of the (meth) acrylic acid ester having an amino group include dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. , Dimethylaminopropyl (meth) acrylate, dipropylaminomethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dipropylaminopropyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) Acrylate, diisobutylaminoethyl (meth) acrylate, dit-butylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, methylpropylaminopropyl (meth) acrylate, 1- (t-butylamino) ethyl (meth) ) Acrylic, 1- (t-butylamino) propyl (meth) acrylate, 2- (t-butylamino) ethyl (meth) acrylate, etc. Among them, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate. ) Acrylic, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate are more preferable.

The amount of the (meth) acrylic acid ester having an amino group in 100% of the acrylic resin is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.5. It is more preferably ~ 2% by mass. If it is less than 0.1% by mass, it may be difficult to disperse the pigment, and if it exceeds 5% by mass, the pigment can be dispersed, but aggregation is likely to occur and the ink viscosity changes (ink). There is a risk of (poor stability) or a change in color development (poor color development).

The weight average molecular weight of the acrylic resin is preferably 20,000 to 130,000, more preferably 30,000 to 110,000. When the weight average molecular weight of the acrylic resin is less than 20,000, the cohesive force with the polystyrene film tends to decrease during thermal laminating, and blister is likely to occur during molding, which is not preferable. On the other hand, the weight average molecular weight is high. If it exceeds 130,000, the resin viscosity becomes high, the transfer of ink is hindered during printing, and the printed matter has poor design. The weight average molecular weight can be evaluated as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).

The fiber-based resin used in the gravure printing ink composition for a styrene film for thermal lamination of the present invention includes cellulose acetate butyrate (hereinafter, also referred to as CAB), cellulose acetate propionate (hereinafter, also referred to as CAP), and It is preferably at least one selected from the nitrocellulose resins.

The cellulose acetate butyrate and cellulose acetate propionate are obtained by reacting cellulose with a suitable organic acid and / or acid anhydride. The CAB is obtained by triesterifying cellulose with acetic acid and butyric acid and then hydrolyzing it. Generally, acetylation is 2 to 29.5% by mass, butyrylation is 17 to 53% by mass, hydroxyl groups are 0.8 to 4.8% by mass, and the degree of biomass is about 50% by mass. The CAP is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing it. Generally, acetylation is 0.6 to 2.5% by mass, propionylation is 42.5 to 46% by mass, hydroxyl groups are 1.8 to 5% by mass, and the degree of biomass is about 50% by mass.
The nitrocellulose resin is obtained by nitrating the hydroxyl groups of cellulose with nitric acid. The average degree of polymerization is about 35 to 480, and the degree of biomass changes depending on the degree of substitution with a nitro group, but about 50% by mass is derived from biomass.

The ratio of the solid content weight (A) of the acrylic resin to the solid content weight (B) of the fiber-based resin is preferably A / B = 100/1 to 100/200, preferably 100/5 to 100/200. It is more preferably 150, and even more preferably 100/10 to 100/100. When the ratio of the solid content weight (B) of the fiber-based resin is less than 1, the blocking resistance is inferior, and when the ratio of the solid content weight (B) of the fiber-based resin is more than 200, the lamination strength is inferior. The number average molecular weight of CAB and CAP is preferably 60,000 or less, and more preferably 10,000 to 30,000. The lower the number average molecular weight, the lower the resin viscosity, but the desired blocking resistance does not decrease. When the number average molecular weight exceeds 60,000, the resin viscosity becomes high, the transfer of ink is hindered during printing, and the printed matter has poor design. In particular, by containing a nitrocellulose resin in the fiber-based resin, dispersibility and blocking resistance can be improved.

In addition to the acrylic resin and the fiber-based resin, other resins may be appropriately used in combination with the gravure printing ink composition for a styrene film for thermal lamination of the present invention, if necessary. Other resins include polyurethane urea resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyamide resin, acrylic resin, ethylene-vinyl acetate copolymer resin, chlorinated olefin resin, alkyd resin, vinyl acetate resin, etc. Rosin-based resin (rosin, cured rosin, polymerized rosin, rosin ester, rosin-modified maleic acid resin, etc.), ketone resin, polybutyral resin, cyclized rubber resin, chloride rubber resin, petroleum resin, olefin resin, polyester resin , Polylactic acid resin and the like.

The total resin content of the acrylic resin, the fiber-based resin, and the other resin is preferably 3 to 50% by mass, preferably 5 to 30% by mass, in the ink composition in terms of solid content. More preferably, it is more preferably 10 to 20% by mass. If the content of the resin is less than 3% by mass, the film-forming property of the ink composition is inferior, and if it is more than 50% by mass, the fluidity of the ink composition is poor and the production suitability of the ink composition is poor. When other resins are used in combination, it is preferably 30% by mass or less of the total resin solid content in the ink composition. In particular, when a nitrocellulose resin is used in combination, it is preferably 10% by mass or less of the total resin solid content in the ink composition. If it is larger than 10% by mass, the adhesiveness to the styrene film and the lamination strength are lowered.

The pigment used in the gravure printing ink composition for a styrene film for thermal lamination of the present invention is preferably an inorganic pigment and / or an organic pigment.
Examples of the inorganic pigment include titanium dioxide, iron oxide, barium sulfate, zinc oxide, calcium carbonate, silica, aluminum paste, pearl pigment, carbon black, brass, mica and the like. Carbon black may be classified as an inorganic pigment, but it is excluded in the present invention. Among them, at least one selected from titanium dioxide, iron oxide, and aluminum paste is preferable.
Examples of the organic pigments include monoazo pigments, disazo pigments, condensed azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthracinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, and isoindolinone pigments. Examples thereof include thioindigo pigments, quinofuralone pigments, dioxazine pigments, pyrolopyrrole pigments, nitro pigments, nitroso pigments and aniline blacks. Carbon black is also preferable. Among them, it is preferable that the pigment is at least one selected from monoazo pigments, disazo pigments, phthalocyanine pigments, and carbon black. In particular, in the case of an organic pigment or carbon black, the acrylic resin used preferably further contains a (meth) acrylic acid ester having an amino group as an acrylic monomer component. The amount of these pigments to be added is appropriately determined according to the concentration, coloring power, and hiding power of the ink composition, but it is preferably 0.1 to 50% by mass in the ink composition.

As the solvent used in the gravure printing ink composition for styrene film for thermal lamination of the present invention, the solvent usually used for gravure ink can be used, and the acrylic resin is dissolved or dispersed in the solvent. Is preferable. Solvents used for gravure ink include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol, isopropanol, normal propanol and butanol. , Alcohol-based solvents such as isobutanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, Ester solvents such as tert-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Glycol-based solvents such as butyl ether and esterified products thereof are mentioned, and as the esterified products, acetates are mainly selected. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol are selected. Examples thereof include monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These can be used alone or in combination of two or more.
The solvent is preferably in the range of 30 to 95% by mass in the ink composition. If it is less than 30% by mass, the solid content increases and the fluidity is lost. If it is more than 95% by mass, the viscosity becomes low and the pigment tends to settle. In addition, ethanol or the like can be used as a solvent derived from biomass. In particular, in consideration of the printing work environment, it is preferable not to contain an aromatic hydrocarbon solvent.

The gravure printing ink composition for a styrene film for thermal lamination of the present invention contains, if necessary, an anti-friction enhancer, an antiblocking agent, a pigment dispersant, an antistatic agent, a lubricant, a cross-linking agent, an antifoaming agent, and a drying agent. Adjusters, plasticizers, tackifiers, adhesion improvers, leveling agents, antioxidants and the like can be added. Of these, biomass-derived additives are even more preferable.

The gravure printing ink composition for a styrene film for thermal lamination of the present invention is produced by a known method in which an acrylic resin, a fiber-based resin, a pigment, and various additives are uniformly mixed and dispersed in the presence of a solvent. it can. When it is dispersed, it can be produced by finely dividing the agglomerated pigment to an average particle size of about 0.01 to 1 μm to obtain a dispersion.

Various stirrers or dispersers can be used for the mixing and dispersion, and a dispenser, ball mill, sand mill, attritor, bead mill, roll mill, pebble mill, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, and wet type can be used. Examples include jet mills, kneaders, and homomixers. The manufacturing method when the bead mill is used is not particularly limited, but a pass method or a circulation method may be used, and the pass method may be a multiple pass method in which the dispersion is passed a plurality of times.
The average particle size of the pigment in the dispersion depends on the bead separation mechanism of the bead mill, bead type, bead particle size, bead filling rate, shape and number of stirring blades, rotation speed, viscosity of the dispersion, discharge amount, premix time, etc. It can be adjusted as appropriate.
Coarse particles and bubbles in the ink composition can be removed by a known filter, centrifuge or the like.

The viscosity of the ink composition is preferably in the range of 10 to 1,000 mPa · s / 25 ° C. If it is less than 10 mPa · s, the viscosity is too low and the pigment tends to settle, and if it is larger than 1,000 mPa · s, the fluidity is poor, which hinders ink production and makes it difficult to fill the container. It becomes. In this case, the measurement can be performed using a commercially available viscometer such as a Brookfield type viscometer or a cone plate type viscometer.
The solid content in the ink composition is preferably in the range of 2 to 80% by mass. If it is lower than 2% by mass, the coating amount at the time of printing is not sufficient, and if it exceeds 80% by mass, the fluidity is poor and it becomes difficult to make ink.
The ink composition is appropriately diluted with a diluting solvent to a viscosity and concentration suitable for printing conditions, and then subjected to printing.

The diluting solvent can adjust the viscosity and concentration of the ink composition, and an alcohol-based solvent is particularly preferable. Examples of commercially available products include AC301 solvent (containing toluene) and AC372 solvent (non-toluene) (all manufactured by Tokyo Ink Co., Ltd.).
Of these, a non-toluene-based diluent solvent is preferable in consideration of the printing work environment. Further, it is preferable to use an organic solvent derived from biomass.

The viscosity of the ink composition when it is used for printing is determined by Zahn Cup No. 3 (manufactured by Rigosha Co., Ltd.) is preferably in the range of 13 to 25 seconds at 25 ° C. If it is less than 13 seconds, it is easy to swim, and if it is longer than 25 seconds, the transferability at the time of printing becomes poor.

At the time of printing, a curing agent can be added to the ink composition if necessary. For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexyldiisocyanate, pentane-1,5. Examples thereof include aliphatic diisocyanates such as -diisocyanate (stavioPDI) and polyisocyanate-based curing agents such as modified products such as trimethylolpropane trimerics, isocyanurates, bullets and allophanates thereof. These can be used alone or in combination of two or more.
Among them, pentane-1,5-diisocyanate and modified products thereof are preferable as the biomass origin.

The gravure printing ink composition for a styrene film for thermal laminating of the present invention is preferably applied onto a styrene film to form a printing layer, and a laminate having a laminating layer on the printing layer is preferable.

The styrene film may be any one that can be applied to thermal lamination, and stretched polystyrene (OPS) film and unstretched polystyrene (CPS) film are more preferable. The thickness of the styrene film is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 100 μm, more preferably 10 to 50 μm. Untreated ones can also be selected, but in order to improve the adhesion of the print layer and the laminate layer on the printed surface, corona treatment, low temperature plasma treatment, frame treatment, solvent treatment, coating treatment, etc. are applied or applied in advance. You can also choose the one.

The printed layer is preferably formed by coating by a gravure printing method because of its high quality and productivity. In particular, it is more preferable to produce by a gravure printing method using a multicolor gravure printing machine. The printing layer is printed by a gravure printing machine using a corrosive plate called a laser plate or an engraving plate dug by a diamond needle. The printing speed is usually in the range of 30 to 350 m / min.

The laminate layer is preferably provided on the print layer. The laminate layer is, for example, a thermal laminate by thermocompression bonding (laminator) of a heating roll, a dry laminate via an adhesive (adhesive film) containing a resin, a non-solvent laminate, a wet laminate, or an extrusion laminate by melting a resin, or adhesion. The resin is applied on the print layer by laminating with an agent or the like. In particular, thermal lamination and extrusion lamination are more preferable. Further, two or more layers of resin may be laminated and extruded and laminated. In this case, the resin used may be the same type or another resin.

The resin used for the thermal lamination is preferably polystyrene, polypropylene, polyethylene or polyester resin, and from the viewpoint of versatility, general-purpose polystyrene (GPPS), impact-resistant polystyrene (HIPS), expanded styrene paper (PSP) and the like are preferable. .. As a specific example of laminating by thermal lamination, when laminating a HIPS sheet or PSP with the styrene film, the styrene film side is heated with a heating roll, and the HIPS sheet and the nip roll arranged on the PSP side are used for HIPS. The sheet, PSP and styrene film are pressed and heat-bonded to each other.

The resins used for the extrusion lamination are polystyrene resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylate copolymer resin, ethylene- (meth) methyl acrylate copolymer resin, and ethyl ethylene- (meth) acrylate copolymer. Copolymer resin, ethylene-vinyl alcohol copolymer resin, polyamide resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, polyether acrylate resin, diallyl phthalate resin, It is preferable to contain at least one of a nitrocellulose resin, a polyurethane resin, a polyester resin, an acrylic resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer, and a rosin-based resin. Further, the resin may be the same type as the base material, or may be a different type of resin. As a specific example of laminating by extrusion lamination, an anchor coating agent is applied to the printed layer surface of the styrene film as necessary, and a heat-melted resin film (polyethylene, polypropylene, etc.) is formed on the resin film and the styrene film. It is extruded into a thin film between the printing layer surfaces, crimped, and laminated.

The thickness of the laminate layer is preferably 100 μm to 5 mm, more preferably 200 μm or more, and more preferably 300 μm or more in order to form a rigid container or a container or tray formed by deep drawing. Is even more preferable. Further, from the viewpoint of light weight and heat insulating property, a foamed thermoplastic resin sheet having a thickness of about 5 mm is preferable, and foamed polypropylene (EPP), foamed polyethylene (EPE), and foamed polystyrene (EPS) are particularly preferable.

The prepared laminates are for packaging, food preservation, agriculture, civil engineering, fishing, automobile interior / exterior, ships, daily necessities, building material interior / exterior, housing equipment, medical / medical equipment, and pharmaceuticals. It can be used for home appliances, furniture, stationery / office supplies, sales promotion, commercial use, electrical and electronic industry, etc.

Forms created using the laminate of the present invention include rockets, triangular packs, gable tops, bricks, shibori, cups, trays, bottles, bricks, containers, boxes, cases, weights, covers, lids, caps. , Labels, in-mold cups and other well-known forms used for packaging.

As a sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example represents a mass part, and% represents a mass%.

<Example 1>
10 parts of phthalocyanine pigment (CI Pigment Blue 15: 4), 340 parts of acrylic resin solution, 12 parts of CAP varnish, 9.5 parts of ethyl acetate, 9.5 parts of n-propyl acetate, 19 parts of isopropyl alcohol. After mixing and stirring, the ink No. 1 was dispersed by a paint shaker. I got 100 copies of 1. Similarly, according to the formulations shown in Tables 1 to 20, the ink Nos. 2-366 were prepared.

The materials used were as follows.
The weight average molecular weight was evaluated as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).
Acrylic resin solution 1: A (meth) acrylic acid ester having a phosphoric acid group contained in an amount of 0.01% by mass, methyl methacrylate containing 35% by mass, and butyl methacrylate containing 64.99% by mass in 100% by mass of the resin are usually used. Resin synthesized by the method, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 2: It is composed of a (meth) acrylic acid ester having a phosphate group containing 2% by mass in 100% by mass of the resin, methyl methacrylate containing 35% by mass, and butyl methacrylate containing 63% by mass by a conventional method. Resin, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 3: A (meth) acrylic acid ester having a phosphoric acid group containing 0.04% by mass, dimethylaminoethyl methacrylate containing 1% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin 63. Resin made by conventional synthesis with butyl methacrylate containing 96% by mass, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 4: (meth) acrylic acid ester having a phosphoric acid group contained in an amount of 0.01% by mass, dimethylaminoethyl methacrylate containing 1% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin 63. Resin made by conventional synthesis with butyl methacrylate containing 99% by mass, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 5: Contains 62% by mass of (meth) acrylic acid ester having a phosphate group containing 2% by mass, dimethylaminoethyl methacrylate containing 1% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin. Resin made by conventional synthesis with butyl methacrylate, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 6: (meth) acrylic acid ester having a phosphoric acid group containing 0.04% by mass, dimethylaminoethyl methacrylate containing 0.01% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin. Resin made by conventional synthesis with butyl methacrylate containing 64.95% by mass, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 7: (meth) acrylic acid ester having a phosphoric acid group containing 0.04% by mass, dimethylaminoethyl methacrylate containing 5% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin 59. Resin made by conventional synthesis with butyl methacrylate containing 96% by mass, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 8: Resin obtained by conventional synthesis of methyl methacrylate containing 35% by mass and butyl methacrylate containing 65% by mass in 100% by mass of the resin, solid content 40%, weight average molecular weight 50,000.
Acrylic resin solution 9: A (meth) acrylic acid ester having a phosphate group contained in an amount of 2.5% by mass, methyl methacrylate containing 35% by mass, and butyl methacrylate containing 62.5% by mass in 100% by mass of the resin. Resin synthesized by the method, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 10: A resin prepared by a conventional method of dimethylaminoethyl methacrylate containing 1% by mass, methyl methacrylate containing 35% by mass, and butyl methacrylate containing 64% by mass in 100% by mass of the resin, isopropyl alcohol / acetic acid. Ethyl = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
Acrylic resin solution 11: (meth) acrylic acid ester having a phosphoric acid group contained in an amount of 2.5% by mass, dimethylaminoethyl methacrylate containing 1% by mass, and methyl methacrylate containing 35% by mass in 100% by mass of the resin 61. Resin made by conventional synthesis with butyl methacrylate containing 5% by mass, isopropyl alcohol / ethyl acetate = 1/1 mixed solvent, solid content 40%, weight average molecular weight 60,000
CAP varnish 1: Created with the following formulation CAP varnish 2: Created with the following formulation CAB varnish 1: Created with the following formulation CAB varnish 2: Created with the following formulation Nitrocellulose resin varnish: Created with the following formulation Created in phthalocyanine pigment: Pigment Blue 15: 4
Monoazo pigment: Pigment Red 48: 3
Disuazo pigment 1: Pigment Yellow 14
Disuazo pigment 2: Pigment Yellow 83
Titanium dioxide: Pigment White 7
Valve handle (iron oxide): Pigment Red 101
Aluminum paste: Pigment Metal 1 (solid content 50%)
Carbon Black: Pigment Black 7

CAP varnish 1
In a round bottom flask equipped with a stirrer, 42.5 parts of isopropyl alcohol, 21.25 parts of ethyl acetate, and 21.25 parts of n-propyl acetate are charged, and cellulose acetate propionate CAP-504-0.2 is stirred while stirring. (Number average molecular weight 15,000, propionyl content 40-45%, manufactured by Eastman Chemical Company) was added in 15 parts to prepare CAP varnish 1. The resin solid content of CAP varnish 1 was 15%, and the biomass degree was 54.4 to 59.4%.

CAP varnish 2
In a round bottom flask equipped with a stirrer, 42.5 parts of isopropyl alcohol, 21.25 parts of ethyl acetate, and 21.25 parts of n-propyl acetate are charged, and cellulose acetate propionate CAP-482-0.5 is stirred while stirring. (Number average molecular weight 25,000, propionyl content 43-47%, manufactured by Eastman Chemical Company) was added in 15 parts to prepare CAP varnish 2. The resin solid content of CAP varnish 2 was 15%, and the biomass degree was 50.5 to 54.5%.

CAB varnish 1
In a round bottom flask equipped with a stirrer, 42.5 parts of isopropyl alcohol, 21.25 parts of ethyl acetate, and 21.25 parts of n-propyl acetate are charged, and cellulose acetate butyrate CAB-381-0.5 (Cerose acetate butyrate CAB-381-0.5) is charged while stirring. CAB varnish 1 was prepared by adding 15 parts (with a number average molecular weight of 30,000, a butyryl content of 36 to 40%, manufactured by Eastman Chemical Company). The resin solid content of CAB varnish 1 was 15%, and the biomass degree was 46.5 to 50.5%.

CAB varnish 2
In a round bottom flask equipped with a stirrer, 42.5 parts of isopropyl alcohol, 21.25 parts of ethyl acetate, and 21.25 parts of n-propyl acetate are charged, and cellulose acetate butyrate CAB-553-0.4 ( CAB varnish 2 was prepared by adding 15 parts (with a number average molecular weight of 20,000, a butyryl content of 44 to 50%, manufactured by Eastman Chemical Company). The resin solid content of CAB varnish 2 was 15%, and the biomass degree was 48 to 54%.

Nitrocellulose resin varnish A round bottom flask equipped with a stirrer is charged with 36 parts of isopropyl alcohol, 21.3 parts of ethyl acetate and 21.3 parts of n-propyl acetate, and vitrified cotton RS1 / 16 (manufactured by TNC) while stirring. Was added in an amount of 21.4 parts to prepare a nitrocellulose resin varnish. The resin solid content of the nitrocellulose resin varnish was 15%, and the biomass degree was 47.7%.

Dispersibility, transferability, blocking resistance, thermal laminate strength, and molding suitability were evaluated for each ink, and are shown in Tables 21 to 24, respectively.

<Dispersibility>
The state of the ink one week after the ink production was visually observed and evaluated. It was judged that the dispersibility was good when the pigment component in the ink did not settle and the viscosity did not change. Regarding the precipitation of pigment components, ○: No change from immediately after production (no sedimentation, no thickening), ×: Even a slight precipitation of pigment components is observed or significant thickening is observed, XX: Cannot be inked. , Was evaluated on a three-point scale. In addition, those evaluated as XX: cannot be converted into ink were not evaluated as follows (indicated by "-" in the table).

[Making printed matter]
1 to 4 color printing unit of 4-color gravure printing machine (manufactured by Fuji Kikai Kogyo Co., Ltd.), ceramic doctor (manufactured by Tokyo Seisakusho Co., Ltd.), chrome hardness 1050Hv / stylus 130 degree engraving Helio plate (Co., Ltd.) Towa Process Co., Ltd.), attach the finisher roll, and dilute the ink with the diluting solvent AC372 (manufactured by Tokyo Ink Co., Ltd.). After adjusting the viscosity to 15 seconds in 3, the ink was poured into the ink pan of the first unit. In all units, a styrene (OPS) film (GM, manufactured by Asahi Kasei Corporation) with a doctor pressure of 2 kgf / cm ² , a drying temperature of 50 ° C., a printing pressure of 2 kg / cm ² , and a printing speed of 150 m / min and a thickness of 20 μm was used. Printing was performed to obtain 8,000 m of printed matter. Also, during printing, the viscosity controller (manufactured by Meisei Co., Ltd.) kept it constant. Then, the metastatic property and blocking resistance were evaluated.

<Metastatic>
The presence or absence of omission was observed and evaluated for the 10% to 100% gradation portion of the printed matter produced in the above [Preparation of printed matter]. Those with no omission were judged to have good metastasis. The omissions were evaluated on a two-point scale: ○: no omissions and ×: omissions.

<Blocking resistance>
Cut the printed matter into a size of 3 cm x 3 cm, superimpose the printed surface and the non-printed surface, apply a load of 500 g / cm ² at 50 ° C. for 24 hours, and then superimpose the printed surface and the non-printed surface. The ink peeling state at the time of peeling was observed, and the peeling resistance at that time was evaluated. It was judged that the one with no ink peeling and no peeling resistance had good blocking resistance. Regarding ink peeling and peeling resistance, ○: No ink peeling and no peeling resistance, Δ: Slight ink peeling and peeling resistance, ×: Ink peeling was observed throughout and there was considerable peeling resistance. It was evaluated on a three-point scale.

<Heat laminate strength>
The printed layer surface of the printed matter and the expanded polystyrene sheet (highly expanded PS sheet) are combined, a polyester film having a thickness of 12 μm is placed on the film surface of the printed matter, and a laminator is used at a temperature of 150 ° C. and a speed of 5 m / min. Lamination was performed by thermocompression bonding, and then the polyester film was removed to form a laminate. Adhesive tape is attached to the styrene film surface of the laminate, cut into 25 mm widths, and heat-laminated by a tensile tester (manufactured by Orientec Co., Ltd., RTE-1210) under conditions of a peeling speed of 300 mm / min and a peeling angle of 90 °. The intensity was measured. In the peel strength test, it was judged that the styrene film was cut off. The peel strength test was evaluated in two stages: ◯: the styrene film was cut, ×: other than that.

In the peel strength test, peeling is performed from the portion having the weakest adhesive strength, and in the case of peeling between the ink and the highly foamed PS sheet, it is a guideline that the thermal lamination strength of the ink with respect to the highly foamed PS sheet is weak. In addition, when both adhesion to the styrene film and thermal lamination strength are strong, the peeling interface does not peel off at the "layer", and the ink is pulled by both the styrene film and the highly foamed PS sheet, and is torn off, resulting in coagulation failure. A phenomenon called occurs. Further, the most preferable peeling is considered to be a state in which the ink is pulled to both sides as described above, but the styrene film is cut instead of cohesive failure.

Moldability was evaluated by the following test.

<Blister test>
A laminate was formed by the same method as the above <heat laminate strength>. The formed laminate before molding was placed in a thermostat and preheated at 90 ° C. for 60 minutes, and the state of blister generation was visually observed. Those without blisters were judged to be good. Evaluated on a two-point scale: ◯: blister does not occur, ×: occurs. The blister is a phenomenon in which the surface of the printed film is partially peeled off and becomes blisters.

<Ink cracking during container molding>
A laminate was formed by the same method as the above <heat laminate strength>. A square container having a width of 100 mm on a side was prepared using a vacuum forming machine (small vacuum forming machine forming series 300X type, manufactured by Seikou Sangyo Co., Ltd.). The appearance of the prepared container was visually observed. It was judged that the one without ink cracking was good. Evaluated on a two-point scale: ◯: no ink cracking occurred, and ×: ink cracking occurred. Ink cracking refers to a phenomenon in which the ink film of the printing layer becomes like a crack in a portion having a large elongation such as a corner of the bottom of the container or a curved surface of a bowl-shaped container when molding a container or the like.

<Lamination strength of molded container>
The container was formed by the same method as the above <ink cracking during container molding>. Adhesive tape is attached to the styrene film surface of the formed container, cut into 25 mm widths, and heated by a tensile tester (manufactured by Orientec Co., Ltd.) at a peeling speed of 300 mm / min and a peeling angle of 90 °. Laminate strength was measured. In the peel strength test, it was judged that the styrene film was cut off. The peel strength test was evaluated in two stages: ◯: the styrene film was cut, ×: other than that.

From the results of Tables 21 to 24, the gravure printing ink composition for the styrene film for thermal lamination of the present invention of Examples 1 to 299 has good dispersibility (ink stability) of the ink composition, and the ink composition The transferability and blocking resistance were good, and the thermal laminating strength and molding suitability of the film on which the ink composition was printed were good. An ink composition using an acrylic resin synthesized from an acrylic monomer having a phosphoric acid group and not containing a (meth) acrylic acid ester, or a content of an acrylic monomer containing a (meth) acrylic acid ester having a phosphoric acid group. However, in Comparative Examples 1 to 67 using an ink composition using an acrylic resin obtained by synthesizing using an amount exceeding 2% by mass in the acrylic resin, it is assumed that the ink cannot be converted into ink or can be converted into ink. However, there is precipitation of pigments and thickening. In addition, the thermal lamination strength and molding suitability of the film printed using these are inferior.

Claims (4)

A gravure printing ink composition for a styrene film for thermal lamination containing an acrylic resin, a fiber-based resin, a pigment, and a solvent.
The ratio of the solid content weight (A) of the acrylic resin to the solid content weight (B) of the fiber-based resin is A / B = 100/1 to 100/200.
A styrene for thermal lamination, which is obtained by synthesizing the acrylic resin from an acrylic monomer containing a (meth) acrylic acid ester having a phosphoric acid group of 0.01 to 2% by mass in 100% of the resin. Gravure printing ink composition for film. The gravure for a styrene film for thermal lamination according to claim 1, wherein the fiber-based resin is at least one selected from cellulose acetate butyrate, cellulose acetate propionate, and nitrocellulose resin. Printing ink composition. The gravure printing ink composition for a styrene film for thermal lamination according to claim 1 or 2, wherein the pigment is an inorganic pigment (excluding carbon black). The pigment is an organic pigment or carbon black,
The gravure printing ink composition for a styrene film for thermal lamination according to claim 1 or 2, wherein the acrylic resin is synthesized from an acrylic monomer containing a (meth) acrylic acid ester having an amino group. ..