JP2017148988A - Decorative paper-impregnated body, and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative paper-impregnated body excellent in press workability, also printable by inkjet printing method and excellent in designability.SOLUTION: Provided is a decorative paper-impregnated body 10 comprising: a base paper 1 impregnated with an impregnated resin; and an ink receiving layer 2 capable of forming a printing image by printing using an aqueous pigment ink or an organic solvent based ink. This ink receiving layer 2 includes calcium carbonate. The application weight of the ink receiving layer to the base paper is 5 to 20 g/mor lower. The impregnation amount of the impregnated resin impregnated into the base paer 1 is 40 to 250 mass% to the basis weight of the base paper 1. Further, the outflow amount of the impregnated resin flowing out from the base paper 1 by the pressurization of the decorative paper-impregnated body 10 under the condition where pressure is 180 bar and temperature is 143±2°C exceeds 0.4 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative paper impregnated body and a decorative material.

  The decorative paper is used for manufacturing a decorative board used for furniture materials and interior / exterior materials for houses and the like. The decorative paper is configured to have an ink receiving layer on the base paper. By receiving and fixing the ink supplied by printing such as an ink jet printing method to the ink receiving layer, a printed image is formed on the surface of the decorative paper. It is formed (see, for example, Patent Document 1).

Special table 2011-508682 gazette

  It is an object of the present invention to provide a decorative paper impregnated body excellent in press workability, printable by an ink jet printing method, and excellent in design, and a cosmetic material produced using the decorative paper impregnated body. .

In order to solve the above problems, a decorative paper impregnated body according to one embodiment of the present invention is an ink capable of forming a printed image by printing using a base paper impregnated with an impregnating resin and an aqueous pigment ink or an organic solvent pigment ink. A receiving layer, the ink receiving layer contains calcium carbonate, the weight applied to the base paper of the ink receiving layer is 5 g / m ² or more and 20 g / m ² or less, and the impregnation amount of the impregnating resin impregnated in the base paper is The amount of impregnating resin flowing out of the base paper by pressure under the conditions of 40 to 250% by weight of the base paper, pressure 180 bar and temperature 143 ± 2 ° C. exceeds 0.4% by weight. It is a summary.
The gist of a decorative material according to another aspect of the present invention is that a printed image is provided on the surface of the decorative paper impregnated body according to the one aspect, and the decorative paper impregnated body is provided on the surface of the base material.

  According to the present invention, it is possible to provide a decorative paper impregnated body and a decorative material that are excellent in press workability, can be printed by an ink jet printing method, and have excellent design properties.

It is sectional drawing which shows the structure of the decorative material which concerns on one Embodiment of this invention.

  An embodiment of the present invention will be described below with reference to the drawings. The decorative paper impregnated body 10 of the present embodiment includes a base paper 1 impregnated with an impregnating resin, and an ink receiving layer 2 capable of forming a printed image. As shown in FIG. 1, an ink receiving layer 2 is laminated on one main surface of the base paper 1. The decorative paper impregnated body 10 may include other layers such as an adhesive layer. The ink receiving layer 2 contains calcium carbonate. Further, the impregnation amount of the impregnating resin impregnated in the base paper 1 is 40% by mass or more and 250% by mass or less of the basis weight of the base paper 1. Furthermore, the outflow amount of the impregnating resin flowing out from the base paper 1 by pressurization of the decorative paper impregnated body 10 under the conditions of a pressure of 180 bar and a temperature of 143 ± 2 ° C. is 0.4% by mass of the mass of the decorative paper impregnated body 10. Excess.

  The decorative material of the present embodiment is a plate-shaped decorative material (decorative plate) manufactured using the decorative paper impregnated body 10 of the present embodiment. As shown in FIG. A decorative paper impregnated body 10 provided with a printed image (not shown) in 2) is provided on the surface of the substrate 20. The material of the base material 20 is not specifically limited, A general material is applicable. Further, the method for attaching the decorative paper impregnated body 10 to the surface of the base material 20 is not particularly limited, and a general method such as adhesion with an adhesive can be applied.

  The decorative paper impregnated body 10 according to the present embodiment has excellent press workability because the impregnation amount and the outflow amount of the impregnating resin are appropriate, and the decorative paper impregnated body 10 is formed on the surface of the substrate 20. It is easy to produce a decorative material by providing The decorative paper impregnated body 10 of the present embodiment preferably has a water content of 3.5% by mass or more. When the amount of water contained is 3.5% by mass or more, the curing rate of the impregnating resin is reduced, and the impregnation property of the impregnating resin into the base paper is improved. Moreover, it is preferable that the impregnating resin in the decorative paper impregnated body 10 is still in a state having curing reactivity.

Moreover, since the ink receiving layer 2 contains calcium carbonate, the decorative paper impregnated body 10 and the decorative material of the present embodiment can be printed by the ink jet printing method and have excellent design properties.
Such a decorative paper-impregnated body 10 is suitable as a raw material of decorative paper used for cosmetic materials such as a high-pressure melamine decorative board, a low-pressure melamine decorative board, a polyester decorative board, and a dapp decorative board.

Hereinafter, the decorative paper impregnated body 10 and the decorative material of the present embodiment will be described in more detail.
(1) About the base paper 1 Although the kind of base paper 1 used for the decorative paper impregnation body 10 of this embodiment is not specifically limited, The thing which is not given inner surface sizing and surface sizing can be used. . That is, the base paper 1 is substantially composed of cellulose, a pigment, a filler, and an additive. Examples of the additive include a wet strength agent, a yield improver, and a fixing agent. The base paper 1 is different from normal paper in that the ratio of the filler content or the pigment content is very high and does not include the internal surface sizing agent or the surface sizing agent used in normal paper.

  The type of cellulose is not particularly limited, and examples thereof include softwood cellulose, hardwood cellulose, and a mixture of both types of cellulose. The hardwood cellulose is preferably 100%, but a mixture of softwood cellulose and hardwood cellulose can be used at a mass ratio of 5:95 to 50:50 (particularly 10:90 to 30:70).

  The base paper 1 can be produced by a long net paper machine or a Yankee paper machine by beating a cellulose mixture having a stock concentration of 2 to 5% by mass to a freeness of 10 to 45 ° SR. In mixed vats, fillers and / or pigments, colored pigments and / or dyes, and wet strength agents (eg, polyamide / polyamine-epichlorohydrin resins, cationic polyacrylates, modified melamine-formaldehyde resins, or cationized starches) Is added to the cellulose mixture and mixed well.

  The filler and / or pigment can be added in an amount of 55% by mass or less, particularly 10% by mass or more and 45% by mass or less, based on the mass of cellulose. The types of pigments and fillers are not particularly limited, and examples thereof include titanium dioxide, talc, zinc sulfide, kaolin, aluminum oxide, calcium carbonate, corundum, aluminum silicate, and magnesium silicate. These may be used individually by 1 type and may use 2 or more types together.

High concentrations of stock made in a mixing vat can be diluted to a stock concentration of about 1%. If necessary, additional auxiliaries (eg, retention aids, antifoam agents, dyes, and other such auxiliaries, or mixtures thereof) can be added. This low-concentration stock is introduced onto the wire section via the paper machine headbox. After forming the fibrous web, it is dewatered to obtain a base paper, which is then dried. The basis weight of the manufactured base paper 1 can be 30 g / m ² or more and 200 g / m ² or less.

Depending on the use and quality requirements of the decorative paper impregnated body 10 and the decorative material, the base paper 1 may have the following properties.
-The surface is smooth. That is, it has Beck smoothness exceeding 80 s.
-It has a Beck smoothness of less than 80 s and is not smoothed.
-Smoothed by Yankee cylinder or calendaring.
• Pre-impregnated with synthetic resin or not pre-impregnated.
・ Very air permeable (Gurley value less than 20 s / hml) or impervious (Gurley value greater than 20 s / hml) or over 200 s / hml in the case of pre-impregnated base paper It has a Gurley value and is extremely impermeable.

  The base paper 1 may be colored. Inorganic color pigments (eg, metal oxides, metal hydroxides, metal oxide hydrates, metal sulfides, metal sulfates, metal chromates, metal molybdates, or mixtures thereof), organic color pigments, dyes (For example, carbonyl colorants (for example, quinone, quinacridone), cyanine colorants, azo colorants, azomethine and methine, phthalocyanine, dioxazine) can be used for coloring the base paper 1. Particularly preferred are mixtures of inorganic and organic color pigments or dyes. The amount of the color pigment / pigment mixture or the dye / dye mixture can be 0.0001% by mass or more and 5% by mass or less based on the mass of the cellulose, depending on the type of material.

(2) Impregnating resin The impregnation amount of the impregnating resin impregnated in the base paper 1 is 40% by mass or more and 250% by mass or less, and preferably 80% by mass or more and 125% by mass or less of the basis weight of the base paper 1. If the impregnation amount of the impregnation resin is within the above numerical range, the impregnation amount of the impregnation resin is appropriate, and the press workability of the decorative paper impregnated body 10 is excellent.

  The type of impregnating resin is not particularly limited, and examples thereof include melamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, polyacrylate, and acrylate / styrene copolymer. These impregnating resins may be used alone or in combination of two or more. Particularly preferred among these impregnating resins are so-called “retarding” impregnating resins having a turbidity time of more than 4.5 minutes. The turbidity time is the time during which the resin exhibits initial turbidity (indicating the start of the polymerization reaction) at a temperature of 100 ° C.

(3) Ink Receiving Layer 2 The constitution of the ink receiving layer 2 is not particularly limited as long as it contains calcium carbonate, but contains a water-soluble polymer or water-dispersible polymer as a binder and calcium carbonate. A hydrophilic coating can be used. Such an ink receiving layer 2 can form a printed image by printing using a water-based pigment ink or an organic solvent-based pigment ink, and has a sufficient design property even when any ink is used.

  The type of calcium carbonate contained in the ink receiving layer 2 is not particularly limited, and those having an average particle size of 4.5 μm or less in the particle size distribution of the volume reference particle size can be used. If the average particle size exceeds 4.5 μm, the color of the printed image by ink jet printing may be reduced.

  Further, the content of calcium carbonate in the ink receiving layer 2 is not particularly limited, but may be 70% by mass or more and 90% by mass or less. If the content is less than 70% by mass, the impregnation property of the thermosetting resin is lowered, and therefore, when a decorative material is produced using the decorative paper impregnated body 10, there is a possibility that blisters (appearance defects such as blisters) may occur. is there.

  The type of the binder is not particularly limited, and may be a water-soluble polymer or a water-dispersible polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, starch, gelatin, carboxymethyl cellulose, ethylene / vinyl acetate copolymer, styrene. / Acrylic ester copolymer. These binders may be used individually by 1 type, and may use 2 or more types together. Polyvinyl alcohol having a saponification degree of 88% or more and 99% or less may be used.

  Further, the ink receiving layer 2 includes a filler, a pigment, a dye fixing agent (for example, a quaternary polyammonium salt), and other auxiliary agents (for example, a surfactant, a disinfectant, etc.) generally used for the ink receiving layer. (Foaming agent, thickener, waterproofing agent, etc.). A preferred quaternary polyammonium salt is polydiallyldimethylammonium chloride.

  The mass ratio of the pigment and the binder contained in the ink receiving layer 2 can be 10:90 to 90:10. The content of the pigment in the ink receiving layer 2 is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 60% by mass or less with respect to the dry mass of the ink receiving layer 2.

  Although the kind of pigment is not particularly limited, any pigment generally used in ink jet recording materials can be used. In particular, aluminum oxide, aluminum hydroxide, boehmite, and silica (eg, precipitated silica, exothermic silica) can be used.

  The ink receiving layer 2 may be colored. As the colorant, the same color pigments and / or dyes as those used for coloring the base paper 1 can be used. The amount (concentration) of the color pigment and / or dye in the ink receiving layer 2 is 45 of the amount of the color pigment and / or dye in the base paper 1 based on cellulose (absolute dry) with respect to the dried ink receiving layer 2. % To 75% is preferable, and 45% to 65% is more preferable.

Application weight for the base paper 1 for ink receiving layer 2, is preferably 2 g / ^{m 2} or more 25 g / ^{m 2} or less, 3 g / ^{m 2} or more 20 g / ^{m 2,} more preferably less, 5 g / ^{m 2} or more 20 g / ^{m 2} or less More preferably, it is 4 g / m ² or more and 15 g / m ² or less.
The ink receiving layer 2 can be applied to the base paper 1 by applying a coating liquid for the ink receiving layer to the surface of the base paper 1 by a general application method. For example, it can be applied by a roller application method, a slot die coating method, a gravure coating method, a nip coating method, a curtain coating method, an air knife coating method, or a coating method using a measuring bar. Moreover, it can provide also by various printing methods, such as a gravure printing method and an offset printing method.

(4) About the manufacturing method of the decorative paper impregnation body 10 The decorative paper impregnation body 10 of this embodiment can be manufactured, for example by the following processes.
(A) A base paper 1 having a basis weight of 30 g / m ^{2 to} 200 g / m ² is manufactured (base paper manufacturing process).
(B) Impregnating the base paper 1 with an impregnation resin (for example, thermosetting impregnation resin) so that the impregnation amount of the impregnation resin impregnated in the base paper 1 is 40% by mass or more and 250% by mass or less of the basis weight of the base paper 1 (Core impregnation) (impregnation step).

(C) The base paper 1 impregnated with the core is preliminarily dried (preliminary drying step). The temperature of the preliminary drying is such that the base paper 1 after drying has a water content of 9% by mass or more and 20% by mass or less, and the impregnated resin after drying is not cured yet has a curing reactivity. Adjust.
(D) At least one ink receiving layer 2 is applied on the surface of the pre-dried base paper 1 by coating (ink receiving layer applying step).

    (E) The base paper 1 provided with the ink receiving layer 2 is dried (main drying step) so that the residual moisture content is 3.5% by mass or more and 8.5% by mass or less. In this main drying step, the impregnated resin is crosslinked to a maximum degree of crosslinking of 30%. After the completion of this drying step, the impregnating resin is still in a state having curing reactivity. The decorative paper impregnated body 10 manufactured in this manner has an outflow amount of the impregnating resin that flows out from the base paper 1 due to pressurization under conditions of a pressure of 180 bar and a temperature of 143 ± 2 ° C. The mass should be over 0.4 mass%.

  The decorative paper impregnated body 10 produced as described above is excellent in press workability and can be printed by the ink jet printing method and is excellent in design. This effect is obtained after the base paper 1 is first core impregnated and pre-dried. This is achieved by applying one or more ink receiving layers 2 and carrying out main drying. In this case, after the pre-drying of the core-impregnated base paper 1 and after the finished decorative paper impregnated body 10 is dried, the impregnated resin is not cured and is still in a state of curing reactivity.

  Core impregnation can be performed off-line in a normal impregnation system or in-line in the paper machine using a conventional application unit. Further, the ink receiving layer 2 may be applied to the base paper 1 impregnated with the core without preliminary drying. Further, the ink receiving layer 2 may be applied to the base paper 1 impregnated with multiple impregnation resins. Furthermore, the decorative paper impregnated body 10 produced as described above has a curing reactivity of 2 minutes to 3 minutes at a pressure of 25 bar and a temperature of 140 ° C. Furthermore, the decorative paper impregnated body 10 manufactured in the above process may be wound in the system or divided into a plurality of sheets.

  The decorative paper impregnated body 10 of the present embodiment forms a printed image on the surface of the decorative paper impregnated body 10 by receiving and fixing the ink containing the glitter pigment supplied by printing in the ink receiving layer 2. Be able to. By forming a printed image on the ink receiving layer 2, it is possible to obtain decorative paper. The printing method is not particularly limited, and for example, an inkjet printing method, a gravure printing method, a micro gravure printing method, a finisher roll printing method, an offset printing method, and a silk screen printing method can be adopted. In particular, printing can also be performed by an ink jet printing method. Since it can be printed with high quality by the inkjet printing method, the decorative paper impregnated body 10 is excellent in design.

The type of pattern of the printed image formed by printing is not particularly limited, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a character, a symbol, or a combination thereof, as desired. It is optional and may be a solid color.
After printing, the decorative paper impregnated body 10 is hot-pressed on a wood-based paperboard or in a coating press to form a laminate. For this purpose, the resin-impregnated paper (underlay) or any other adhesive layer as a composite phase is not required for the decorative paper impregnated body 10. However, if necessary, the resin-impregnated underlay can be additionally applied to the decorative paper-impregnated body 10. The resin-impregnated overlay can be applied as a protective layer to the decorative paper impregnated body 10 before the hot pressing of the decorative paper impregnated body 10. However, the decorative paper impregnated body 10 (decorative paper) on which the printed image is formed can be first sealed with a varnish.

In addition, this embodiment shows an example of this invention and this invention is not limited to this embodiment. In addition, various changes or improvements can be added to the present embodiment, and forms to which such changes or improvements are added can also be included in the present invention.
For example, in the present embodiment, a plate-shaped decorative material (decorative plate) has been described as an example, but the shape of the decorative material of the present invention is not limited to a plate shape, and a decorative image on which a printed image is formed. Any shape may be used as long as the paper impregnated body 10 (decorative paper) is provided on the surface of the base material. For example, the shape of the decorative material (that is, the shape of the base material) may be a rectangular parallelepiped shape, a spherical shape, a cone shape, a column shape, or the like.

Further, in the present specification, when the impregnated resin is described as “not cured”, it means that the impregnated resin is crosslinked to a maximum degree of crosslinking of 65% (preferably a maximum of 30%). The method for determining the degree of crosslinking is as follows.
The decorative paper impregnated body is cut to obtain a test piece having an area of 100 cm ² , and its mass is measured, which is defined as “mass before extraction” (unit: “g”). Next, after immersing the test piece in 100 mL of N, N-dimethylformamide (DMF) at room temperature for 30 to 35 minutes, the test piece is taken out from the DMF. DMF is wiped off from the surface of the test piece and dried at 120 ° C. for 90 minutes. The mass of the test piece is measured after cooling, and this is defined as “mass after extraction” (unit: “g”).

The mass (initial mass) of the impregnating resin in the decorative paper-impregnated body before dipping is calculated by the following formula.
Initial mass (g) = mass before extraction (g) -basis weight of base paper (g / m ² ) × area of test piece (cm ² ) / 10000
Moreover, the mass (final mass) of the impregnation resin in the decorative paper impregnated body after immersion is calculated by the following formula.
Final mass (g) = mass after extraction (g) -basis weight of base paper (g / m ² ) × area of test piece (cm ² ) / 10000
Then, the degree of crosslinking is calculated by the following formula.
Crosslinking degree (%) = final mass (g) / initial mass (g) × 100

〔Example〕
The present invention will be described more specifically with reference to the following examples and comparative examples.
Example 1
An ink receiving layer was provided on the surface of the base paper impregnated with the impregnating resin to produce a decorative paper impregnated body for ink jet printing. As the base paper (titanium paper), a white base paper for printing (KW-1001P manufactured by KJ Special Paper Co., Ltd.) having a basis weight of 100 g / m ² was used. In addition, as the coating liquid for the ink receiving layer, one prepared as follows was used.

  That is, in 75 g of water, 35 g of calcium carbonate (Shiraishi Hana PZ made by Shiraishi Calcium Co., Ltd.) having an average particle size of 3.3 μm in the volume-based particle size distribution and a cationic emulsion (FK-820 made by Japan Coating Resin Co., Ltd.) 38.43 g was added, and this was stirred with a stirrer to obtain a coating solution.

This coating solution was applied onto the surface of the base paper using a gravure printing machine, and then dried by heating to 200 ° C. in an oven. As a result, a decorative paper impregnated body in which an ink receiving layer was coated on the surface of the base paper was obtained. The weight applied to the base paper of the ink receiving layer is 7.5 g / m ² . The content of calcium carbonate in the ink receiving layer is 70% by mass.

  The decorative paper impregnated body thus obtained was printed with an inkjet printer using a water-based pigment inkjet ink (LIOJET manufactured by Toyo Ink Co., Ltd.), and a printed image was formed on the ink receiving layer with a resolution of 1200 × 1200 dpi. The pattern of the printed image that was printed was solid printing of yellow, magenta, cyan, and black.

(Example 2)
A decorative paper impregnated body on which a printed image is formed in the same manner as in Example 1 except that the inkjet ink used for printing is changed to an organic solvent pigment ink (ECO-SOL MAX2 manufactured by Roland DG Co., Ltd.) Got.

(Comparative Example 1)
A decorative paper impregnated body on which a printed image was formed was obtained in the same manner as in Example 1 except that the inkjet ink used for printing was changed to an ultraviolet curable ink (FV03 manufactured by Toyo Ink Co., Ltd.).
(Comparative Example 2)
A decorative paper impregnated body on which a printed image was formed was obtained in the same manner as in Example 1 except that the weight applied to the base paper of the ink receiving layer was changed to 3.4 g / m ² .

(Comparative Example 3)
A decorative paper impregnated body on which a printed image was formed was obtained in the same manner as in Example 1 except that the weight applied to the base paper of the ink receiving layer was changed to 22.4 g / m ² .
Next, the performance of the decorative paper impregnated bodies of Examples 1 and 2 and Comparative Examples 1 to 3 was evaluated.

(Evaluation of impregnation of thermosetting resin)
Two sheets of core paper impregnated with phenol formaldehyde resin are stacked on the overlay paper impregnated with melamine formaldehyde resin, and the decorative paper impregnated body of Example or Comparative Example is laminated thereon, and further melamine formaldehyde is formed thereon. An overlay paper impregnated with resin was laminated. And the decorative board was obtained by heat-pressing with a heat press machine, and the external appearance of the surface of the decorative board was evaluated. The results are shown in Table 1.

  In Table 1, when there is no appearance defect such as blisters on the surface of the decorative plate, the performance is indicated as “◯” as good performance, and when appearance defects such as blisters occur, the performance is insufficient. As indicated by “×”.

(Evaluation of ink reflection density)
In the same manner as in the evaluation of the impregnation property of the thermosetting resin, a decorative board was produced using the decorative paper impregnated body. Then, the reflection density of the printed image was measured using a spectrocolorimeter (eXact manufactured by X-Rite). The results are shown in Table 1. If the reflection density is 1.0 or more, the performance is good, and if the reflection density is less than 1.0, the performance is insufficient.

DESCRIPTION OF SYMBOLS 1 Base paper 2 Ink receiving layer 10 Cosmetic paper impregnation body 20 Base material

Claims (5)

A base paper impregnated with an impregnating resin, and an ink receiving layer capable of forming a printed image by printing using a water-based pigment ink or an organic solvent-based pigment ink,
The ink receiving layer contains calcium carbonate, and the weight of the ink receiving layer applied to the base paper is 5 g / m ² or more and 20 g / m ² or less;
The impregnation amount of the impregnation resin impregnated in the base paper is 40% by mass or more and 250% by mass or less of the basis weight of the base paper,
A decorative paper impregnated body in which the amount of the impregnating resin flowing out from the base paper by pressurization under a pressure of 180 bar and a temperature of 143 ± 2 ° C. exceeds 0.4% by mass.   The decorative paper impregnated body according to claim 1, wherein the amount of water contained is 3.5% by mass or more.   The decorative paper impregnated body according to claim 1 or 2, wherein the impregnating resin is at least one of melamine formaldehyde resin, urea formaldehyde resin, and acrylate resin.   The decorative paper impregnated body according to any one of claims 1 to 3, wherein the impregnating resin has curing reactivity.   The decorative material which provided the printed image on the surface of the decorative paper impregnation body as described in any one of Claims 1-4, and provided this decorative paper impregnation body on the surface of the base material.

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