KR20120008426A - Dry lamination method and laminate obtained by using the same - Google Patents

Abstract

The dry-lamination method with the favorable appearance after lamination, and the laminated body obtained by this are provided. In the dry lamination method of coating the adhesive with a solid content of 35% by mass or more diluted with a solvent in a gravure method, and then volatilizing the solvent and bonding other films to obtain a laminate, the number of gravure lines is 135 to 270 lines / inch. Gravure plates with a cell volume of 10 to 30 cc / m2, gravure plates with stylus angles of 120 to 140 °, gravure plates with gravure lines of 120 to 270 lines / inch, or 135 to 350 lines of gravure lines on ceramic rolls Dry coating method of the said adhesive using a ceramic roll / inch, the cell volume of 10 ~ 30cc / ㎡.

Description

Dry lamination method and the laminated body obtained by the method {DRY LAMINATION METHOD AND LAMINATE OBTAINED BY USING THE SAME}

The present invention relates to a dry laminate method and a laminate obtained by the method.

As a method of bonding various plastic films, the method of bonding the plastic film and the plastic film which deposited the metal, or the method of bonding the plastic film and the metal foil, it has conventionally been performed by the dry lamination method. The dry lamination method is a method of laminating a solvent with a substrate such as an organic solvent or water, and then vaporizing the solvent with a dryer, and bonding the other substrate with heat and pressure.

As an adhesive agent used for a dry lamination method, the two-component hardening type organic solvent type adhesive agent is used a lot. For example, as a 1st liquid, the solution which melt | dissolved resin containing hydroxyl groups, such as a polyester resin and a polyurethane resin, in the organic solvent, and a polyisocyanate compound is contained as a 2nd liquid.

The organic solvent type adhesive contains a large amount of organic solvent. Therefore, the dry lamination method using this has many problems, such as environmental pollution by the exhaust, the danger of a fire explosion, and the sanitation of the work environment. Since a conventional organic solvent type adhesive agent has 30 mass% or less of solid content, after coating an adhesive agent, a large amount of organic solvents are discharged | emitted outside when volatilizing an organic solvent. Thus, a high solid adhesive having a high solid content in which the content of the organic solvent is reduced has been proposed (see Patent Document 1).

However, when such a high solid adhesive is used in a dry lamination method using a conventional gravure method, streaks are formed on the surface of the laminate after lamination with respect to the flow direction of coating. For this reason, there was a problem that a uniform appearance was not obtained and it was difficult to finish well. Moreover, the so-called tunneling phenomenon in which the laminated body after lamination peels in tunnel shape may generate | occur | produce.

In recent years, the demand for deorganization solvents for adhesives is increasing due to the improvement of the working environment, the strengthening of fire extinguishing methods and the regulation of VOC (Volatile Organic Compound) emission into the atmosphere. Thus, a dry lamination method using an aqueous adhesive obtained by emulsifying the adhesive has been proposed. The dry laminate method using an aqueous adhesive improves the working environment, problems with fire protection and VOC release into the atmosphere. However, there is a new inherent problem due to aqueous. That is, due to the poor wetting of the plastic substrate due to the height of the surface tension of the water, there was a problem in that the surface of the laminate after lamination had a stripe pattern and a good appearance was not obtained.

JP2005-298588 A

An object of the present invention is to provide a dry lamination method and a laminate obtained by the same, in which the appearance of the laminate after lamination is good and in which a tunneling phenomenon does not occur.

MEANS TO SOLVE THE PROBLEM As a result of various examinations in order to solve the said subject, when coating an adhesive of 35 mass% or more of solid content by the gravure method, the number of the gravure line and the cell volume of the gravure plate (hereinafter, gravure plate) chromium plated to the iron core Organic solvent by selecting the gravure angle and the number of gravure lines of the gravure plate engraved with an electronic engraving machine, or the gravure line number and the cell volume of the ceramic roll (hereinafter referred to as ceramic roll) coated on the iron core. Regardless of the type adhesive and the water-based adhesive, the appearance of the laminate after lamination was found to be good, and the present invention was completed.

In one embodiment of the present invention, after coating an adhesive of 35% by mass or more of a solid content diluted with a solvent to a film in a gravure method, the solvent is volatilized, and another film is bonded to obtain a laminate by

Gravure plate with gravure line number of 135 ~ 270 lines / inch, cell volume of 10 ~ 30cc / ㎡,

Gravure plates engraved with an electronic engraving machine with a stylus angle of 120 to 140 ° and a gravure line count of 120 to 270 lines / inch, or

Ceramic rolls with 135 ~ 350 lines / inch of gravure lines and 10 ~ 30cc / ㎡ of cell roll on ceramic rolls

It relates to a dry laminate method characterized by coating the adhesive using.

The adhesive is an organic solvent adhesive or an aqueous adhesive.

Moreover, one Embodiment of this invention relates to the laminated body obtained by the above-mentioned dry lamination method.

The subject matter of the present invention relates to Japanese Patent Application Nos. 2008-325327 (filed on December 22, 2008) and 2008-333277 (filed on December 26, 2008), which are incorporated herein by reference in their entirety. I do it.

According to one embodiment of the present invention, the laminate after lamination, the appearance of the dry laminate method without a stripe or orange peel (finished), a scratch-free uniform surface, and no tunneling phenomenon occurs And the laminated body obtained by this can be provided.

1 is a diagram illustrating a diamond blade (stylus).
2 is a diagram illustrating the concept of a cell shape carved by an electronic engraving machine.
3 is a diagram showing the cell shape of a ceramic roll carved by a laser.
4 is a conceptual diagram of the laminate of the present invention.

In the dry lamination method of this invention, after coating the adhesive film 35 mass% or more of solid content diluted with the solvent to a film by the gravure method, a solvent is made to volatilize, another film is bonded together, and the dry lamination method which obtains a laminated body is as follows. The said adhesive agent is coated using one of (i)-(iii).

(i) Gravure lines having a gravure line number of 135 to 270 lines / inch and a cell volume of 10 to 30 cc / m 2 (hereinafter referred to as gravure plates (I)).

(ii) Gravure plates carved with electronic engraving with a stylus angle of 120 to 140 ° and a gravure line number of 120 to 270 lines / inch (hereinafter referred to as gravure plate (II)).

(iii) A ceramic roll having a gravure line number of 135 to 350 lines / inch and a cell volume of 10 to 30 cc / m 2 on the ceramic roll.

(Gravure version (I))

First, a gravure plate having a gravure line number of 135 to 270 lines / inch and a cell volume of 10 to 30 cc / m 2 will be described.

The number of gravure lines of the gravure plate I is 135-270 lines / inch, Preferably it is 135-255 lines / inch.

When an adhesive of 35 mass% or more of solid content is coated using a gravure plate having a gravure line number of 135 lines / inch or more, streaks do not occur along the flow direction of the coating, and the laminate after lamination can obtain good appearance quality.

On the other hand, the gravure plate having the number of gravure lines of 270 lines / inch or less can have a cell volume of 10 cc / m 2 or more, thus ensuring a sufficient coating amount. Thereby, adhesive performance is favorable and favorable external appearance quality can be obtained.

The cell volume of the gravure plate (I) is 10-30 cc / m <2>, Preferably it is 10-27 cc / m <2>. If the said cell volume is 10 cc / m <2> or more, sufficient application amount of an adhesive agent can be ensured. As a result, the adhesive performance is good, and good appearance quality can be obtained. Moreover, when the said cell volume is 30 cc / m <2> or less, hardening time is short and it is excellent in workability, and a tunneling phenomenon does not arise in the laminated body after lamination.

 Although the core of the gravure plate I is not specifically limited, It is preferable that it is 25-100 micrometers, and it is more preferable that it is 27-85 micrometers. If the said plate core is 25 micrometers or more, a scratch does not generate | occur | produce on a coating surface, and if it is 100 micrometers or less, hardening time is short.

The shape of the gravure plate I is not specifically limited, For example, a pyramid board, a grid board, a diagonal board, etc. are mentioned.

The method for producing the gravure plate I is not particularly limited, but can be produced by a general plate making method. For example, by laser engraving, HELIO, OHIO, VALCUS, etc. A engraving plate, the conventional engraving by a corrosion method, etc. are mentioned.

(Gravure version (II))

Next, a gravure plate carved with an electronic engraving machine having a stylus angle of 120 to 140 ° and a gravure line number of 120 to 270 lines / inch will be described.

 Gravure plate (II) is a plate carved with an electronic engraving machine. Electronic engraving machines include HELIO made in Germany, OHIO made in USA and VALCUS made in Japan, but the most representative one is HELIO. The gravure plate engraved with an electronic engraving machine has a shape different from that of an engraved plate made of an em engraving or a corroded plate made by the corrosion method. The "bank" part has a narrow shape. Therefore, even when an adhesive with a high solid content is coated on a film, the adhesive is well leveled on the film.

The number of gravure lines of the gravure plate (II) is 120-270 lines / inch, Preferably it is 135-255 lines / inch. When the number of gravure lines is 120 lines / inch or more, streaks do not occur along the flow direction of the coating, and the laminate after lamination can obtain good appearance quality. If it is 270 lines / inch or less, since sufficient coating amount can be ensured, adhesive performance is favorable and favorable external appearance quality can be obtained.

In addition, the stylus angle of the gravure plate II is 120-140 degrees, Preferably it is 120-130 degrees. When the said stylus angle is 120 degrees or more, a stripe pattern does not generate | occur | produce along the flow direction of a coating, and the laminated body after lamination can obtain favorable external appearance quality. In addition, since the blade blade of a diamond blade (stylus) is excellent in durability and hardly deteriorates at the time of engraving, it is advantageous in terms of cost. If it is 140 degrees or less, since the depth of the cell of a gravure plate is sufficient and sufficient coating amount can be ensured, adhesive performance is favorable and favorable external appearance quality can be obtained.

The stylus angle refers to the angle of the blade of the electronic engraving machine. Since the angle of the tip of the cell (concave portion) of the gravure plate carved using this becomes the same angle as the blade, it is also called the stylus angle with respect to the angle of the cell tip. The cell is a diamond blade (stylus) of an electronic engraving machine, which is produced by engraving in a reverse pyramid shape on the surface of a metal gravure plate body. As shown in Fig. 1, the diamond blade 1 has a sharp tip shape, and the angle of the cell tip can be adjusted to a predetermined value by appropriately selecting the angle of the tip of the diamond blade.

 2, the conceptual diagram of a cell shape is shown. As the cell shape, there are five kinds of Compressed (10), Normal (11), Elongate (12), Coarse (13), and Fine (14), but usually Compressed (10), Elongate (12), Coarse (13), The kind of Fine 14 is mainly used. The cell is engraved in the cylinder as a recess of the square weight by an electromagnetic engraving machine. In Fig. 2, the "axial diagonal" means the diagonal of the cell in the axial direction of the cylinder, and the "diagonal diagonal" means the diagonal of the cell in the circumferential direction of the cylinder.

 The cell shape is strictly determined by the angle of the cell piece and the relative length of the cell diagonal. The angle of the cell piece refers to the angle at which the line passing through the intersection of the cell diagonal lines continuous in the cylinder axial direction and the line passing through the intersection of the cell diagonal lines continuous in the oblique direction with respect to the cylinder axis intersect.

The depth and volume of the cell are determined by the cell shape, the number of gravure lines, the stylus angle, and the length of the cell diagonal. Also, even in a cell having the same number of gravure lines and the stylus angle, the depth of the cell, the volume of the cell, and the length of the diagonal line of the cell differ depending on the shape. For example, Table 1 shows an example in the case where the number of gravure lines is 175 lines / inch and a stylus angle of 120 °, and Table 2 shows an example in the case where the number of gravure lines is 175 lines / inch and the stylus angle is 130 °.

175 lines / inch, stylus angle 120 ° Cell geometry Axial diagonal Circumferential diagonal depth volume (Μm) (Μm) (Μm) (㏄ / ㎡) Compressed 180 170 52 23 Elongate 140 205 40 17 Coarse 180 255 52 22 Fine 120 125 35 15

175 lines / inch, stylus angle 130 ° Cell geometry Axial diagonal Circumferential diagonal depth volume (Μm) (Μm) (Μm) (㏄ / ㎡) Compressed 180 170 42 18 Elongate 140 205 32 14 Coarse 180 255 42 18 Fine 120 125 28 12

Although the volume of the cell of gravure plate (II) is not specifically limited, Preferably it is 10-30 cc / m <2>, More preferably, it is 10-27 cc / m <2>. If the said cell volume is 10 cc / m <2> or more, since sufficient application amount of an adhesive agent can be ensured, adhesive performance will become favorable. Moreover, when the said cell volume is 30 cc / m <2> or less, hardening time is short and it is excellent in workability and a tunneling phenomenon does not arise in the laminated body after lamination. Moreover, although the depth of the cell of a gravure plate is not specifically limited, It is preferable that it is 20-100 micrometers, and it is more preferable that it is 25-85 micrometers. If the depth of the cell is 25 µm or more, no scratches occur on the surface of the coating, and if it is 100 µm or less, the curing time is short.

 (Ceramic Roll)

Next, the ceramic roll whose gravure line number is 135-350 line / inch and cell volume is 10-30 cc / m <2> is demonstrated.

The number of gravure lines of the ceramic roll is 180-350 lines / inch, Preferably it is 180-300 lines / inch.

When an adhesive having 35 mass% or more of solid content is coated using a ceramic roll having a gravure line number of 135 lines / inch or more, streaks do not occur along the flow direction of the coating, and the laminate after lamination can obtain good appearance quality.

On the other hand, a ceramic roll having a gravure line number of ceramic rolls of 350 lines / inch or less can have a cell volume of 10 cc / m 2 or more, thereby ensuring a sufficient coating amount. Thereby, adhesive performance is favorable and favorable external appearance quality can be obtained.

 The cell volume of the ceramic roll is 10-30 cc / m <2>, Preferably it is 10-27 cc / m <2>. If the said cell volume is 10 cc / m <2> or more, sufficient application amount of an adhesive agent can be ensured. As a result, the adhesive performance is good, and good appearance quality can be obtained. Moreover, when the said cell volume is 30 cc / m <2> or less, hardening time is short and it is excellent in workability and a tunneling phenomenon does not arise in the laminated body after lamination.

 Although the core of a ceramic roll is not specifically limited, It is preferable that it is 25-100 micrometers, and it is more preferable that it is 27-85 micrometers. If the said plate core is 25 micrometers or more, a scratched shape will not generate | occur | produce on a coating surface, and if it is 100 micrometers or less, hardening time will be short.

The shape of the ceramic roll is not specifically limited, For example, a honeycomb pattern, a diamond pattern, a helical pattern, etc. are mentioned. The honeycomb pattern (cell angle of 30 degrees) is shown to Fig.3 (a), the honeycomb pattern (cell angle of 60 degrees) is shown to (b), and the diamond pattern (cell angle of 45 degrees) is shown to (c).

 The method for producing the ceramic roll is not particularly limited, but can be produced by a general plate making method. For example, the core is undercoated to facilitate ceramic coating, and the ceramic layer is coated on the ceramic layer by a plasma spraying method of 0.3 to 0.5 mm. The surface is polished with diamond curb and carved by laser engraver according to the number of lines, volume and pattern.

(glue)

The adhesive agent used in the dry lamination method of this invention will not be specifically limited if solid content diluted with a solvent is 35 mass% or more, An organic solvent type adhesive agent and an aqueous adhesive agent can also be used. If the solid content is 35% by mass or more, the coating amount can be ensured, and the adhesion performance is excellent. 35-55 mass% is preferable, and, as for the said solid content, 35-50 mass% is more preferable.

 As an organic solvent type adhesive agent, what melt | dissolved resin which has an adhesive function by the organic solvent is mentioned. Examples of such resins include polyester resins, polyether resins, polyester ether resins, polyurethane resins, polyester urethane resins, polyether urethane resins, polyester ether resins, and polyester ether urethane resins. Can be mentioned. Although these adhesive agents may be used independently of resin, generally they are used as a two-component curable adhesive agent in combination with the hardening | curing agent containing a polyisocyanate compound.

As polyester resin, the polyester resin obtained by ring-opening-polymerizing dibasic acid or these dialkyl ester or its mixture, and the polyester resin or lactone obtained by making glycol or a mixture thereof react is mentioned. have. Examples of the dibasic acid include terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid. As glycols, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'- Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol is mentioned. Examples of the lactones include polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone).

As polyether resin, the polyether resin obtained by superposing | polymerizing an oxy compound using an initiator is mentioned. As an oxy compound, ethylene oxide, a propylene oxide, butylene oxide, tetrahydrofuran is mentioned, for example. As an initiator, low molecular weight polyols, such as water, ethylene glycol, propylene glycol, trimethylol propane, glycerin, are mentioned, for example.

As polyether ester resin, the polyether ester resin obtained by making a dibasic acid or these dialkyl ester or a mixture thereof, and the said polyether resin react is mentioned. Examples of the dibasic acid include terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid.

As a polyurethane-type resin, it is obtained by making the polyol which has a urethane bond in 1 molecule, and organic polyisocyanate react. Examples of the polyol include polyether polyols, polyester polyols and polyether ester polyols having a number average molecular weight of 200 to 20,000 (hereinafter referred to as organic polyol (1)). The ratio of NCO / OH at the time of reaction is less than 1, Preferably it is 0.9 or less. As said polyol, what has a carboxyl group (henceforth organic polyol (2)) in the molecule (inside a molecule or a molecule terminal) can be used. The organic polyol (2) is preferably obtained by reacting the organic polyol (1) described above with a polybasic acid or an anhydride thereof. As the organic polyol (1) used at this time, one containing two or more hydroxyl groups at the terminal of the molecule and having a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 15,000 is preferably used. At 1,000 or more, cohesion force is inadequate, and at 100,000 or less, since it is easy to react polybasic acid or its anhydride to the terminal synthetically, there is no fear of thickening or gelation. Examples of the polybasic acid or its anhydride include aromatic polybasic acids such as phthalic acid, trimellitic acid and pyromellitic acid, and anhydrides thereof, but phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride which are anhydrides thereof. The back is especially suitable. As an anhydride, ethylene glycol bis anhydro trimellitate derived from these anhydrides, glycerol tris anhydro trimellitate, ethylene glycol bis anhydro pyromellitate, glycerol tris anhydro pyromellitate, or abietin acid of the rosin component, Derivatives obtained by addition-reacting maleic anhydride to a C ₁₀ H ₁₆ diene compound or a mixture thereof. The synthesis of the organic polyol (2) may be carried out in two steps after the synthesis of the organic polyol (1) by adding polybasic acid or anhydride thereof, preferably polybasic acid anhydride under heating. Alternatively, in the synthesis of the organic polyol, the organic polyol (2) may be synthesized in one step from the polyhydric carboxylic acid and the polyhydric alcohol. The reaction with these polybasic acid anhydrides has a promoting effect in improving the adhesive performance of the adhesive composition, for example, hot water resistance, oil resistance, acid resistance and the like. In the reaction of the organic polyol and the polybasic acid anhydride, it is necessary to control the reaction temperature in the range of 200 ° C. or lower, preferably 150 to 180 ° C. so that the esterification reaction by the ring-opening reaction of the polybasic acid anhydride becomes the main reaction. The reaction ratio of both is such that the amount of the basic acid anhydride consumes 40% or more of the hydroxyl groups in the molecules of the organic polyol with respect to the organic polyol. "%" Is based on the number of hydroxyl groups in the molecule | numerator of an organic polyol here. If the said numerical value is 40% or more, the acid resistance of the composition obtained is excellent. Moreover, even if an aliphatic polyhydric carboxylic anhydride is used as a polybasic acid anhydride, a carboxyl group can be similarly introduced into a molecule | numerator, In this case, the improvement of acid resistance is not seen. Therefore, from the viewpoint of acid resistance, use of aliphatic polyhydric carboxylic anhydride is not preferable. In the case of using a polyester polyol or a polyether ester polyol as the organic polyol (1), if only aromatic polyhydric carboxylic acid is used as the carboxylic acid as their starting material, there is a problem in controlling the physical properties of the organic polyol (1). May occur. In particular, trivalent or tetravalent polycarboxylic acids give a branched organopolyol (1), which is liable to gel. Moreover, since aromatic polyhydric carboxylic acid is sublimable, these sublimates may adhere to a reaction kiln or dehydration apparatus at the time of synthesis | combination of the organic polyol (1), and may cause manufacturing difficulties. In this regard, when the organic polyol (organic polyol (2)) having a carboxyl group is used in the molecule, the above problems can be avoided. Examples of the organic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1, Aliphatic diisocyanates such as 3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, 1,4-cyclohexanediisocyanate, 1 , 3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2, Alicyclic diisocyanates, such as 6-cyclohexane diisocyanate, 1, 4-bis (isocyanate methyl) cyclohexane, and 1, 3-bis (isocyanate methyl) cyclohexane , M-phenylene diisocyanate, p-phenylenedi isocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2, Aromatic diisocyanates such as 6-trilene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 1,3- or 1,4-xylyl Aromatic aliphatic such as rendiisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof Organic triisocyanates such as diisocyanate, triphenylmethane-4,4 ', 4''-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene, 4,4'-di Organic tetra such as phenyldimethylmethane-2,2'-5,5'-tetraisocyanate Polyisocyanate having a polyisocyanate monomer such as isocyanate, a dimer, trimer, biuret, allophanate, carbon dioxide gas derived from the polyisocyanate monomer, and a 2,4,6-oxadiazinetrione ring obtained from the polyisocyanate monomer, eg For example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'- dimethylol propane, cyclohexane Adducts with low molecular weight polyols having a molecular weight of less than 200, such as dimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, and sorbitol, or polyester polyols and polyether esters having a molecular weight of 200 to 20,000 Polyol, polyesteramide polyol, polycaprolactone polyol, polyvalerolactone polyol, acrylic polyol, poly And adducts such as carbonate polyol, polyhydroxyalkane, castor oil and polyurethane polyol.

As said polyisocyanate compound used as a hardening | curing agent of an organic solvent type adhesive agent, the said organic polyisocyanate is illustrated.

Moreover, an aqueous polyurethane adhesive, an aqueous acrylic adhesive, an aqueous polyester adhesive, an aqueous polyether adhesive, etc. are mentioned as an aqueous adhesive agent.

The aqueous polyurethane adhesive may be a self-emulsifying water-dispersible or water-soluble aqueous urethane adhesive in which a polyurethane compound is dispersed or dissolved in water. Said polyurethane compound is a polyurethane compound which has the carboxyl group obtained by making the polyol compound which does not contain a carboxyl group in a molecule | numerator, and the polyol compound and polyisocyanate compound which contain a carboxyl group in a molecule | numerator. Moreover, the water-dispersible polyurethane adhesive in which the polyurethane compound was forcibly emulsified in water using surfactant can be sufficient. The polyurethane compound in this case is obtained by making the polyol compound and polyisocyanate compound which do not contain a carboxyl group in a molecule | numerator react. The polyol compound which does not contain a carboxyl group in the molecule | numerator used for aqueous urethane adhesive, For example, polyester polyol, polyether polyol, polyether polyester polyol, polyurethane polyol, polyesteramide polyol, acryl polyol, polycarbonate polyol And polyhydroxyalkane and castor oil. Dimethylol propionic acid, dimethylol butanoic acid, etc. are mentioned as a carboxyl group-containing polyol, Dimethylol butanoic acid is especially preferable. Examples of the polyisocyanate compound include triylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like. Triylene diisocyanate and 4,4'-diphenylmethane diisocyanate are particularly preferred.

An aqueous acrylic adhesive agent is an aqueous acrylic adhesive obtained by emulsion-polymerizing the acrylic monomer which does not contain a carboxyl group, and the acrylic acid monomer containing a carboxyl group.

(Dry lamination method)

In the dry lamination method of this invention, after apply | coating the said adhesive agent to a film by the gravure method, a solvent is volatilized and another film is bonded together and a laminated body is obtained. At the time of coating of an adhesive agent, said gravure plate (I) or (II) is used. A dryer may be used when the solvent is volatilized, and the drying conditions are not particularly limited, but the drying temperature is usually 50 to 90 ° C.

(film)

Although the film used for the dry lamination method of this invention is not specifically limited, For example, plastic films, such as polyester, a polyamide, polyethylene, and a polypropylene, metal deposition films, such as aluminum, a silicon oxide, aluminum oxide, and aluminum foil Metal foils, such as these, are mentioned. The combination is the plastic films, the plastic film and the metal deposition film, the plastic film and the metal foil. Although the thickness of a film is not specifically limited, either, Usually, it is 5-200 micrometers.

(Laminated body)

According to the dry lamination method of this invention, as shown in FIG. 4, the laminated body 20 in which the adhesive bond layer 22 is formed on the 1st film 21, and the 2nd film 23 is formed on it is Obtained.

In the dry lamination method of this invention, by using the adhesive with a high solid content, the dry application amount of an adhesive can be ensured in the range of 1-8 g / m <2>, and the laminated body excellent in adhesive performance is obtained. In addition, despite the use of a high solid adhesive, the appearance of the laminate is very excellent. Therefore, it can be suitably used especially for the food field use.

Example

Hereinafter, the present invention will be described in detail through examples. However, the following examples do not limit the present invention.

In addition, the gravure plate (I) from Example A-1 to Example A-4, the gravure plate (II) from Example B-1 to Example B-6, and Example C-1 to Example C- In 4, a ceramic roll was used.

 (Example A-1)

Based on a biaxially stretched polypropylene film (OPP; manufactured by TOYOBO CO., LTD., Having a thickness of 20 µm) and a styrene film OT P-2161, a gravure line number of 180 lines / inch and a cell volume of 19 cc / m2 produced by the emboss method Using a gravure plate using a dry laminator (FUJI KIKAI KOGYO Co., Ltd .: FL2 type), a high solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) After coating with 45 mass% of solid content, and making a solvent volatilize with a dryer (temperature 60 degreeC, 70 degreeC, 80 degreeC, 80 degreeC), the unstretched polypropylene film (CPP; TOHCELLO CO., LTD.) Of 25 micrometers in thickness is made. , GHC # 25) was laminated at 50 ° C with a nip roll to obtain a laminate.

After cut | disconnecting the obtained laminated body to the magnitude | size of 10 cm x 10 cm, the weight of A laminated body: A (g) was measured by precision balance. Then, the laminated body was peeled off and the adhesive agent affixed on both peeling surfaces was wiped off completely with ethyl acetate. The film after wiping off the adhesive was dried at 80 ° C. for 5 minutes, and then the weight: B (g) of both films peeled off with precision balance. It was 2.8 g / m <2> as a result of calculating the dry coating amount by the following formula.

 Dry coating amount (g / ㎡) = (A-B) /0.01

Moreover, when the external appearance of the obtained laminated body was observed visually, there was no tunneling phenomenon as a uniform and favorable surface.

(Example A-2)

A gravure plate was used as a laser using a gravure line of 200 lines / inch and a cell volume plate of 14 cc / m 2, and an aqueous acrylic adhesive (RBOND L-250 manufactured by Rohm and Haas Company) was used as a solid content of 45 mass%. Except that, the laminated body was obtained by the method similar to Example A-1. The dry coating amount of the adhesive was 2.1 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

(Example A-3)

As a gravure plate, a plate with a gravure line number of 250 lines / inch and a cell volume of 16 cc / m2 made of an electronic engraving plate (HELIO version) was used (stylus angle 145 degrees), and an aqueous acrylic adhesive (manufactured by Rohm and Haas Company, ROBOND) as an adhesive A laminated body was obtained by the same method as Example A-1 except using L-250) at 45 mass% of solid content. The dry coating amount of the adhesive was 2.4 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

(Example A-4)

As a gravure plate, a plate of 137 gravure lines made of an electronic engraving plate (HELIO version) and a plate having a cell volume of 26 cc / m2 (stylus angle of 145 degrees) was used, and a high-solid organic solvent type adhesive (Toyo-Morton) was used as an adhesive. , Ltd. product, polyester adhesive, TM-550), and the laminated body was obtained by the method similar to Example A-1 except using 45 mass% of solid content. The dry coating amount of the adhesive was 3.8 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

 (Comparative Example A-1)

A gravure plate was used as a gravure plate 120 lines / inch and a cell volume of 41 cc / m2, and an aqueous acrylic adhesive (ROBOND L-250 manufactured by Rohm and Haas Company) was used as a solid 45 mass% as an adhesive. Except that, the laminated body was obtained by the method similar to Example A-1. The dry coating amount of the adhesive was 6.0 g / m 2. As a result of visually observing the appearance of the obtained laminate, a tunneling phenomenon occurred.

(Comparative Example A-2)

The gravure plate is a gravure line of 300 lines / inch and a cell volume of 8 cc / m2 plate made by the embossing method, and a high solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., an ester adhesive, TM-) as an adhesive. A laminated body was obtained by the same method as Example A-1 except using 550) at 45 mass% of solid content. The dry coating amount of the adhesive was 1.2 g / m 2. As a result of visually observing the appearance of the obtained laminate, scratches occurred.

(Comparative Example A-3)

As gravure plate, a plate of 120 grams / inch of gravure lines made by the embossing method and a plate having a cell volume of 23 cc / m 2 was used.A high-solid-type organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., ester-based adhesive, TM-) A laminated body was obtained by the same method as Example A-1 except using 550) at 45 mass% of solid content. The dry coating amount of the adhesive was 3.4 g / m 2. As a result of visually observing the appearance of the obtained laminate, a stripe pattern was formed.

(Comparative Example A-4)

As a gravure plate, a plate having a gravure line number of 140 lines / inch and a cell volume of 34 cc / m2 was used as a gravure plate, and a high-solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., an ester adhesive, TM-) was used as an adhesive. A laminated body was obtained by the same method as Example 1 except using 550) by 45 mass% of solid content. The dry coating amount of the adhesive was 5.1 g / m 2. As a result of visually observing the appearance of the obtained laminate, a tunneling phenomenon occurred.

 (Comparative Example A-5)

As a gravure plate, a plate with a gravure line number of 200 lines / inch and a cell volume of 8 cc / m2 made of HELIO was used (stylus angle 145 degrees), and an aqueous acrylic adhesive (made by Rohm and Haas Company, ROBOND L) as an adhesive A laminated body was obtained by the same method as Example 1 except using -250) at 45 mass% of solid content. The dry coating amount of the adhesive was 1.2 g / m 2. As a result of visually observing the appearance of the obtained laminate, scratches occurred.

 (Comparative Example A-6)

As a gravure plate, a plate with a gravure line number of 300 lines / inch and a cell volume of 12 cc / m2 made of HELIO was used (stylus angle 145 degrees), and an aqueous acrylic adhesive (manufactured by Rohm and Haas Company, ROBOND L) as an adhesive. A laminated body was obtained by the same method as Example A-1 except using -250) at 45 mass% of solid content. The dry coating amount of the adhesive was 1.8 g / m 2. As a result of visually observing the appearance of the obtained laminate, scratches occurred.

The above result is shown in Table 3.

In addition, the "plate core" of Table 3 was calculated from the number of gravure lines and the cell volume.

Example Comparative example A-1 A-2 A-3 A-4 A-1 A-2 A-3 A-4 A-5 A-6 glue
type Organic solvent type Mercury Mercury Organic solvent type Mercury Organic solvent type Organic solvent type Organic solvent type Mercury Mercury Solid content of glue
(mass%) 45 45 45 45 45 45 45 45 45 45 The recipe for gravure Em laser Helio Helio Em Em Em Em Helio Helio Plate core (㎛) 45 299 35 54 85 20 75 75 30 24 Gravure Line Count
(Line / inch) 180 200 250 137 120 300 120 140 200 300 Cell volume
(㏄ / ㎡) 19 14 16 26 41 8 23 34 8 12 dry
Application amount
(g / ㎡) 2.8 2.1 2.4 3.8 6.0 1.2 3.4 5.1 1.2 1.8 Exterior Good Good Good Good Tunneling phenomenon Scratches Stripes Tunneling phenomenon Scratches Scratches

From Table 3, Example A-1-Example A-4 showed the external appearance of the laminated body after lamination as a uniform good surface, and there was no generation of a tunneling phenomenon. In contrast, the appearance of the laminate after lamination in Comparative Examples A-1 to A-6, in which the number of gravure lines and the cell volume were outside the scope of the present invention, did not provide a good surface due to the appearance of streaks or scratches. The tunneling phenomenon was also observed.

(Example B-1)

175 lines / inch of gravure lines made of a biaxially oriented polypropylene film (OPP; manufactured by TOYOBO CO., LTD., Pylen Film OT P-2161) having a thickness of 20 µm and made of an electronic engraving plate (HELIO plate), With dry laminator (FUJI KIKAI KOGYO Co., Ltd .: FL2 type) using a HELIO plate with a stylus angle of 120 °, Compressed, diagonal 180 μm in axial direction, 170 μm in circumferential direction, and 52 μm in cell depth, A high solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) is coated at a solid content of 45% by mass, and the solvent is dried (temperature 60 ° C, 70 ° C, 80 ° C, 80 ° C). After volatilization by a lamination), an unstretched polypropylene film (CPP; manufactured by TOHCELLO CO., LTD., GHC # 25) having a thickness of 25 μm was laminated at 50 ° C. with a nip roll to obtain a laminate.

After cut | disconnecting the obtained laminated body to the magnitude | size of 10 cm x 10 cm, the weight of A laminated body: A (g) was measured by precision balance. Then, the laminated body was peeled off and the adhesive agent affixed on both peeling surfaces was wiped off completely with ethyl acetate. The film after wiping off the adhesive was dried at 80 ° C. for 5 minutes, and then the weight: B (g) of both films peeled off with precision balance. It was 2.8 g / m <2> as a result of calculating the dry coating amount by the following formula.

Dry coating amount (g / ㎡) = (A-B) /0.01

Moreover, when the external appearance of the obtained laminated body was observed visually, it was a uniform and favorable surface.

(Example B-2)

As a HELIO plate, a number of gravure lines of 200 lines / inch, a stylus angle of 120 °, an elongate, an axial diagonal 125 μm, a circumferential diagonal 180 μm, and a cell depth of 36 μm are used. A laminate was obtained in the same manner as in Example B-1, except that Rohm and Haas Company, ROBOND L-250) was used at a solid content of 45 mass%. The dry coating amount of the adhesive was 2.2 g / m 2. As a result of visually observing the appearance of the obtained laminated body, it was a uniform and favorable surface.

(Example B-3)

As a HELIO plate, a number of gravure lines 250 lines / inch, a stylus angle 130 °, an elongate, an axial diagonal 98 μm, a circumferential diagonal 145 μm, and a cell depth of 22 μm are used. A laminate was obtained in the same manner as in Example B-1, except that Rohm and Haas Company, ROBOND L-250) was used at a solid content of 45 mass%. The dry coating amount of the adhesive was 1.5 g / m 2. As a result of visually observing the appearance of the obtained laminated body, it was a uniform and favorable surface.

(Example B-4)

HELIO plate is used as HELIO plate with 150 gravure lines / inch, stylus angle 130 °, coarse, axial diagonal 210 μm, circumferential diagonal 300 μm, and cell depth 49 μm. A laminate was obtained in the same manner as in Example B-1, except that a solvent adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) was used at a solid content of 45% by mass. The dry coating amount of the adhesive was 2.8 g / m 2. As a result of visually observing the appearance of the obtained laminated body, a uniform and favorable surface was seen.

(Comparative Example B-1)

As a HELIO plate, HELIO plate with 100 gravure lines / inch, stylus angle 130 °, Compressed, axial diagonal 310 μm, circumferential diagonal 305 μm, and cell depth 72 μm is used. A laminate was obtained in the same manner as in Example B-1, except that a solvent adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) was used at a solid content of 45% by mass. The dry coating amount of the adhesive was 5.2 g / m 2. As a result of visually observing the appearance of the obtained laminate, a stripe pattern was formed.

(Comparative Example B-2)

As HELIO plate, HELIO plate with 350 gravure lines / inch, stylus angle 130 °, Compressed, axial diagonal 85 μm, circumferential diagonal 80 μm, and cell depth 20 μm is used. A laminate was obtained in the same manner as in Example B-1, except that a solvent adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) was used at a solid content of 45% by mass. The dry coating amount of the adhesive was 1.2 g / m 2. As a result of visually observing the appearance of the obtained laminate, scratches occurred.

The above result is shown in Table 4.

Example Comparative example B-1 B-2 B-3 B-4 B-1 B-2 Adhesive type Organic solvent type Mercury Mercury Organic solvent type Organic solvent type Organic solvent type Adhesive solids
(mass%) 45 45 45 45 45 45 Recipe Helio Helio Helio Helio Helio Helio Gravure Line Count
(Line / inch) 175 200 250 150 100 350 Stylus angle 120 120 130 130 130 130 Cell depth (μm) 52 36 22 49 72 20 shape Compressed Elongate Elongate Coarse Compressed Compressed Axial diagonal
(Μm) 180 125 98 210 310 85 Circumferential diagonal
(Μm) 170 180 145 300 305 80 Coating amount (g / ㎡) 2.8 2.2 1.5 2.6 5.2 1.2 Exterior Good Good Good Good Stripes Scratches

From Table 4, Example B-1-Example B-4 were the surface where the laminated body after a lamination was uniform, and was favorable. On the other hand, in Comparative Examples B-1 to Comparative Example B-2 in which the number of gravure lines and the stylus angle were outside the scope of the present invention, the appearance of the laminate after lamination was streaked or scratched, so that a good surface could not be obtained.

(Example C-1)

Based on a biaxially stretched polypropylene film (OPP; manufactured by TOYOBO CO., LTD.) Having a thickness of 20 μm (Pylen Film OT P-2161), the number of gravure lines produced by laser engraving is 180 lines / inch and the cell volume is 21 cc / m2. Dry laminator (made by FUJI KIKAI KOGYO Co., Ltd .: FL2 type) using a phosphorus ceramic roll, and a high solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM-550) After coating with 45 mass% of solid content, and making a solvent volatilize with a dryer (temperature 60 degreeC, 70 degreeC, 80 degreeC, 80 degreeC), the unstretched polypropylene film (CPP; TOHCELLO CO., LTD.) Of 25 micrometers in thickness is made. , GHC # 25) was laminated at 50 ° C with a nip roll to obtain a laminate.

After cut | disconnecting the obtained laminated body to the magnitude | size of 10 cm x 10 cm, the weight of A laminated body: A (g) was measured by precision balance. Then, the laminated body was peeled off and the adhesive agent affixed on both peeling surfaces was wiped off completely with ethyl acetate. The film after wiping off the adhesive was dried at 80 ° C. for 5 minutes, and then the weight: B (g) of both films peeled off with precision balance. It was 3.0 g / m <2> as a result of calculating the dry coating amount by the following formula.

Dry coating amount (g / ㎡) = (A-B) /0.01

Moreover, when the external appearance of the obtained laminated body was observed visually, there was no tunneling phenomenon as a uniform and favorable surface.

(Example C-2)

As a ceramic roll, a plate with a gravure line number of 200 lines / inch and a cell volume of 23 cc / m 2 was prepared as a ceramic roll, and an aqueous acrylic adhesive (ROBOND L-250, manufactured by Rohm and Haas Company) was used as a 45 mass% solid as an adhesive. Except that, the laminated body was obtained by the method similar to Example C-1. The dry coating amount of the adhesive was 3.1 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

(Example C-3)

Gravure lines 250 lines / inch and cell volume 19cc / m2 plate made by laser method were used as ceramic rolls, and water-based acrylic adhesive (ROBOND L-250, manufactured by Rohm and Haas Company) was used as 45% by mass as an adhesive. Except that, the laminated body was obtained by the method similar to Example C-1. The dry coating amount of the adhesive was 2.5 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

 (Example C-4)

As a ceramic roll, a plate having a gravure line number of 300 lines / inch and a cell volume of 18 cc / m 2 produced by a laser method was used, and a high solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., polyester adhesive, TM) was used as the adhesive. A laminated body was obtained by the same method as Example C-1 except using -550) at 45 mass% of solid content. The dry coating amount of the adhesive was 2.1 g / m 2. As a result of visually observing the appearance of the obtained laminate, there was no tunneling phenomenon as a uniform and good surface.

(Comparative Example C-1)

As a ceramic roll, a plate of 120 grams / inch of gravure lines and a cell volume of 42 cc / m 2 produced by a laser method was used, and an aqueous acrylic adhesive (ROBOND L-250, manufactured by Rohm and Haas Company) was used as a solid 45 mass% as an adhesive. Except that, the laminated body was obtained by the method similar to Example C-1. The dry coating amount of the adhesive was 6.0 g / m 2. As a result of visually observing the appearance of the obtained laminate, a tunneling phenomenon occurred.

(Comparative Example C-2)

As a ceramic roll, a plate having a gravure line number of 400 lines / inch and a cell volume of 8 cc / m 2 produced by a laser method was used, and as the adhesive, a high-solid organic solvent type adhesive (manufactured by Toyo-Morton, Ltd., ester adhesive, TM- A laminated body was obtained by the same method as Example C-1 except using 550) at 45 mass% of solid content. The dry coating amount of the adhesive was 1.2 g / m 2. As a result of visually observing the appearance of the obtained laminate, scratches occurred.

The above results are shown in Table 5.

In addition, the "plate core" of Table 5 was calculated from the number of gravure lines and the cell volume.

Example Comparative example C-1 C-2 C-3 C-4 C-1 C-2 Type of glue Organic solvent type Mercury Mercury Organic solvent type Mercury Organic solvent type Adhesive
Solid content (% by weight) 45 45 45 45 45 45 Manufacturing method of ceramic roll plate laser laser laser laser laser laser Plate core (㎛) 55 55 43 35 85 20 Gravure line number
(Line / inch) 180 200 250 300 120 400 Cell volume
(㏄ / ㎡) 21 23 19 18 42 8 Dry coating amount
(g / ㎡) 3.0 3.1 2.5 2.1 6.0 1.2 Exterior Good Good Good Good Tunneling phenomenon flow

Claims (3)

In the dry lamination method of apply | coating the adhesive agent 35 mass% or more of solid content diluted with the solvent to a film by the gravure method, volatilizing a solvent, bonding another film, and obtaining a laminated body,
Gravure plate with gravure line number of 135 ~ 270 lines / inch, cell volume of 10 ~ 30cc / ㎡,
Gravure plates engraved with an electronic engraving machine with a stylus angle of 120 to 140 ° and a gravure line count of 120 to 270 lines / inch, or
Ceramic rolls with 135 ~ 350 lines / inch of gravure lines and 10 ~ 30cc / ㎡ of cell roll on ceramic rolls
Dry coating method of the adhesive using a. The method of claim 1,
Dry adhesive method characterized in that the adhesive is an organic solvent type adhesive or an aqueous adhesive. The laminated body obtained by the dry lamination method of Claim 1 or 2.

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