KR20120079061A

KR20120079061A - Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board

Info

Publication number: KR20120079061A
Application number: KR1020127005962A
Authority: KR
Inventors: 히로유키 도이; 코타로 코데라
Original assignee: 아이카고교 가부시키가이샤
Priority date: 2009-09-30
Filing date: 2010-09-30
Publication date: 2012-07-11
Also published as: MY165495A; CN102549035A; JP2011094132A; WO2011040533A1; KR20170029655A; CN106626854A; TWI481665B; TW201120139A

Abstract

The active energy ray-curable resin composition of the present invention includes (A) a urethane acrylate resin or acrylic resin containing two radical reactive groups, and (B) a urethane acrylate resin or acrylic resin containing six or more radical reactive groups, When the total amount of the component (A) and the component (B) is 100 parts by weight, the amount of the component (A) is 30 to 70 parts by weight.

Description

ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION, TRANSFER SHEET, DECORATIVE BOARD, AND METHOD FOR PRODUCING DECORATIVE BOARD}

This application claims the priority of Patent Application No. 2009-227539 for which it applied to Japan Patent Office on September 30, 2009, and all the content is integrated in this specification by reference.

The present invention relates to, for example, an active energy ray-curable resin composition, a transfer sheet, a decorative plate, and a manufacturing method thereof provided for use in a decorative plate.

Conventionally, as a means of improving the scratch resistance, chemical resistance, pollution resistance, and weather resistance of the surface of the decorative plate, a coating liquid containing active energy ray curable resin or thermosetting resin is used. After apply | coating to the surface of a decorative plate and hardening | curing, the coating liquid containing such resin is apply | coated to the base material with peelability, it hardens, and after making it a transfer sheet, the cured coating film of a transfer sheet is superimposed on a decorative plate, After heat-pressing or the like, the cured coating film is transferred to the surface of the decorative plate, the coating film provided on the substrate is made into a semi-cured state, and the transfer sheet is transferred to the surface of the decorative plate. The method of hardening again and providing the coating film which has the said tolerance on the surface of a decorative plate is known. In particular, since the coating film cured by the active energy ray has excellent coating film properties (scratch resistance, fouling resistance, etc.), various methods have been proposed for the method of installing the coating film on the surface of the decorative plate (Patent Documents 1 to 2). Reference).

Japanese Laid-Open Patent Publication No. 2003-137942 Japanese Laid-Open Patent Publication No. 2003-183339

In general, however, the coating film having the above resistance is formed by crosslinking a material having many reactive functional groups in a molecule, and often has a high crosslinking density. In many cases, adhesiveness to the surface of the decorative plate is significantly degraded due to the shrinkage, curing shrinkage, or the like. Moreover, when using a transfer sheet, it is a present state that a primer layer, an adhesive bond layer, etc. are provided in the coating film side or the makeup plate side of a transfer sheet, and adhesiveness is ensured.

The present invention does not necessarily use a primer or an adhesive, and an active energy ray-curable resin composition, a transfer sheet, a decorative plate, and a decorative plate, which can reliably adhere the cured product of the active energy ray-curable resin composition to a melamine resin layer or the like. An object of the present invention is to provide a method for producing the same.

The active energy ray-curable resin composition of the present invention comprises (A) a urethane acrylate resin or acrylic resin containing two radical reactive groups and (B) a urethane acrylic containing six or more radical reactive groups. It contains rate resin or acrylic resin, When the total amount of the said (A) component and the said (B) component is 100 weight part, the quantity of the said (A) component is 30-70 weight part, It is characterized by the above-mentioned.

By using the active-energy-ray-curable resin composition of this invention, even if it does not apply a primer process to the coating film side or the makeup plate side of a transfer sheet, it is a layer which consists of an active-energy-ray-curable resin composition, for example (cured product) ), A decorative plate having excellent adhesion, scratch resistance, and chemical resistance can be obtained.

It is preferable that the active-energy-ray-curable resin composition of this invention contains a conductive sol further.

The transfer sheet of this invention is equipped with a peelable base material and the layer which consists of the above-mentioned active-energy-ray-curable resin composition formed in the said peelable base material.

The decorative plate of this invention is equipped with the melamine resin layer and the layer which consists of hardened | cured material of the above-mentioned active energy ray hardening-type resin composition formed on the said melamine resin layer.

The manufacturing method of the toilet board of this invention is a resin material impregnated toilet paper formed by impregnating and drying the core material, the resin liquid which has a thermosetting resin as a main component on toilet paper, and the transfer mentioned above. The sheets are laminated, thermoformed, and the peelable substrate is removed after the thermoformed.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing when the material is laminated | stacked in order to obtain the chemical-resistant decorative plate of this invention.
2 is a cross-sectional view of the chemical-resistant decorative plate of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In the component (A) used in the present invention, the urethane acrylate resin containing two radical reactive groups is, for example, an isocyanate compound and hydroxyethyl obtained by reacting a polyol and a diisocyanate. It is a reaction product with the acrylate monomer which has hydroxyl groups, such as acrylate (hydroxyethyl acrylate), hydroxypropyl acrylate, and hydroxybutyl acrylate. As for the weight average molecular weight of (A) component, 500-1500 are preferable.

Moreover, as an acrylic resin containing two radical reactive groups among the (A) component used by this invention, it consists of polymers of acrylic acid, methacrylic acid, or derivatives thereof, for example. For example, methyl acrylate (ethyl acrylate), ethyl acrylate (butyl acrylate), such as acrylic ester (acrylic ester), methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), And polymers based on methacrylic esters such as butyl methacrylate.

Among the component (B) used in the present invention, the urethane acrylate resin containing six or more radical reactive groups is, for example, polyester polyol, polyether polyol, polycarbonate polyol. Isocyanate compounds obtained by reacting polyols such as diisocyanate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, and the like. It is a reaction product with the acrylate monomer which has a hydroxyl group. As for the weight average molecular weight of (B) component, 500-6000 are preferable.

Moreover, as an acrylic resin containing six or more radical reactive groups among the (B) components used by this invention, it consists of the polymer of acrylic acid, methacrylic acid, or these derivatives, for example, methyl acrylate, acrylic acid The polymer which has methacrylic acid ester, such as acrylate ester, such as ethyl and butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, is mentioned.

It is preferable to make the compounding ratio of (A) component and (B) component into 70: 30-30: 70 weight part (solid content ratio), and when (B) component does not reach a minimum, it consists of an active-energy-ray-curable resin composition. The adhesiveness of a layer and chemical-resistance are easy to deteriorate, and when it exceeds an upper limit, adhesiveness is easy to deteriorate.

As for the ratio (weight ratio) of the total amount of (A) component and (B) component with respect to the total solid of an active energy ray hardening-type resin composition, 90 to 100% of range is preferable.

It is preferable to mix | blend an electroconductive sol in addition to (A) component and (B) component to the active-energy-ray-curable resin composition of this invention. The conductive sol is effective in preventing the transfer sheet to which the active energy ray-curable resin composition is applied to the peelable substrate when the decorative plate is manufactured, and can prevent the adhesion of dust due to static electricity during the handling of the transfer sheet. have. In particular, an antimony-based conductive sol is preferable, and the amount of the conductive sol is preferably in the range of 8 to 15 parts by weight based on 100 parts by weight in total of the component (A) and the component (B). When it exceeds 15 weight part, coloring and chemical-resistant property are easy to deteriorate, and when less than 8 weight part, sufficient antistatic effect may not be acquired.

As an antimony-type electroconductive sol, the Cernax series (antimony acid zinc system) by Nissan Kagaku Kogyo Co., Ltd. is mentioned as a commercial item. CX-Z330H, CX-Z330H-F2 as water dispersing sol, CX-Z641M, CX-Z603M, CX-Z603M-F2, CX-Z610M-F2, CX-Z653M-F, CX- as methanol dispersing sol There are CX-Z210IP and CX-Z210IP-F2 (both trade names) as Z693M-F and isopropanol dispersing sol, and it can be appropriately selected and used according to the type and the mixing ratio of the component (A), the component (B).

Moreover, when irradiating an ultraviolet-ray, it is preferable to mix | blend a photoinitiator other than (A) component and (B) component with the active-energy-ray-curable resin composition of this invention. The photoinitiator is, for example, benzyl ketal, α-hydroxyacetophenone, α-aminoacetophenone, acyl phosphine oxide, titanocene-based Titanocene-based compounds, oxime esters and the like can be used. As a commercial item, IRGACURE 184, 369, 651, 819, DAROCUR 1173 (Ciba specialty chemicals make, brand name), etc. are mentioned. It is preferable that the usage-amount of a photoinitiator is 1-10 weight part with respect to a total of 100 weight part of (A) component and (B) component. When more than 10 weight part, a cured film will be easy to color, and when less than 1 weight part, sufficient hardening may not be obtained.

The peelable base material used for the transfer sheet of the present invention (for example, the active energy ray-curable resin composition is applied) is peeled off after the active energy ray-curable resin composition is transferred to the surface of the resin-impregnated toilet paper by thermo-pressure molding. As long as possible, polyester film, polyethylene film, polypropylene film, cellophane, diacetylcellulose film, triacetylcellulose film, Acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film film, polystyrene film, polycarbonate film, polymer Pentene film (polymethylpentene film), polysulfone film (polysulfone film), polyether ketone film (polyether ketone film), polyether sulfone film (polyether sulfone film), polyetherimide film, polyimide film ), Plastic films such as fluororesin film, nylon film and acrylic film, and metal foil such as aluminum foil, stainless steel foil and copper foil can be used.

When applying the active energy ray-curable resin composition to the surface of the peelable substrate, a known method, for example, spray coating method, gravure coating method, bar coating method, knife ( A knife coating method, a roll coating method, a blade coating method, a die coating method, a curtain coating method and the like can be used. It is preferable that the thickness of the coating film after drying is about 1-100 micrometers.

After apply | coating an active energy ray hardening type resin composition to the surface of a peelable base material, an electron beam and an ultraviolet-ray can be irradiated, for example. When irradiating ultraviolet rays, a wavelength of 100 to 400 nm, preferably 200 to 400 nm, using an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like. In the region, it is preferable to irradiate ultraviolet rays having an energy of 100 to 800 mJ / cm ² . If it is this condition, adhesive_contact | adherence with resin impregnated toilet paper will become strong at the time of thermocompression molding. Moreover, you may harden in nitrogen atmosphere as needed.

As the resin-impregnated toilet paper used in the decorative plate of the present invention, it is preferable to impregnate a known toilet paper for toilet paper with a thermosetting resin, in particular, a resin liquid containing a melamine formaldehyde resin as a main component and having excellent heat resistance and abrasion resistance. Is used.

The core material may be a resin-impregnated core paper obtained by impregnating a thermosetting resin with kraft paper, nonwoven fabric, cloth, or the like for plywood, plywood, medium-density fiberboard (MDF), or particle board. A wood-based base material such as) is used and is selected according to a suitable use and required quality.

Example One

(A) 70 parts by weight of UN-2301 (trade name Art-Resin, Negami Kogyo Co., Ltd., weight average molecular weight 740), which is a urethane acrylate resin containing two radical reactive groups, (B) radical reactivity 30 parts by weight of UN-904 (trade name Atresin, Negami Kogyo Co., Ltd., weight average molecular weight 4900) which is a urethane acrylate resin containing ten groups, and IRGACURE 184 (Shiba Specialty Chemicals Co., Ltd.) which is a photoinitiator 3 parts by weight of Kaisha, brand name) was diluted with 40 parts by weight of methyl ethyl ketone to obtain an ultraviolet curable resin composition (active energy ray curable resin composition).

Next, the UV curable resin composition is applied to an OPP (Oriented Polypropylene) film having a thickness of 80 μm so that the dry film thickness is 30 μm, and irradiated with ultraviolet rays such that the irradiation strength is 400 mJ / cm ² with a high-pressure mercury lamp. The transfer sheet was obtained, and the transfer sheet was cured for 1 week. As shown in FIG. 1, this transfer sheet 3 includes an OPP film 1 (peelable base material) and a layer 2 made of an ultraviolet curable resin composition formed on the OPP film 1. .

A resin solution containing a melamine-formaldehyde resin as a main component was impregnated into a printing paper having a basis weight of 100 g / m ² and dried to obtain a melamine resin impregnated toilet paper.

A resin solution containing phenol-formaldehyde resin as a main component was impregnated into kraft paper having a basis weight of 185 g / m ² , and dried to obtain a phenol resin-impregnated core paper.

As shown in FIG. 1, five phenol resin impregnated core papers 7, one melamine resin impregnated toilet paper 6 and one transfer sheet 3 are laminated | stacked in order from the bottom, and the temperature is 132 degreeC. The thermoforming was carried out under the conditions of a pressure of 70 kg / cm ² , and after molding, the OPP (Oriented Polypropylene) film was removed to obtain a chemical-resistant decorative plate 9 shown in FIG. 2. In the chemical-resistant decorative plate 9, 7a is a cured resin impregnated core paper, 6a is a cured resin impregnated toilet paper, and 2a is a cured product of an ultraviolet curable resin composition.

Example 2

(A) 70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyogisha Kagaku Co., Ltd., molecular weight 226) was used, and KAYARAD DPHA (Nihon Kayaku Co., Ltd.) was used as the component (B). A product, molecular weight 878) was carried out in the same manner as in Example 1 except that 30 parts by weight were used.

Here, light acrylate 1,6HX-A is an acrylic resin containing two radical reactive groups. KAYARAD DPHA is an acrylic resin containing six radical reactive groups.

Example 3

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 50 weight part, and the compounding quantity of (B) component was 50 weight part.

Example 4

As the component (A), 50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyogisha Kagaku Co., Ltd., molecular weight 226) was used, and KAYARAD DPHA (Nihon Kayaku Co., Ltd. product, molecular weight) was used as the component (B). 878) The same procedure as in Example 1 was carried out except that 50 parts by weight was used.

Example 5

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 30 weight part, and the compounding quantity of (B) component was 70 weight part.

Example 6

(A) 70 parts by weight of UN-2301 (trade name Atresin, Negami Kogyo Co., Ltd.) which is a urethane acrylate resin containing two radical reactive groups, and (B) a urethane acrylate resin containing ten radical reactive groups, 30 parts by weight of UN-904 (trade name Atresin, product of Negami Kogyo Co., Ltd.), 5 parts by weight of IRGACURE 184 (product of Shiba Specialty Chemicals, Inc., brand name) as a photoinitiator, IRGACURE 819 (Shiba 1 part by weight of Specialty Chemicals Co., Ltd., and isopropanol dispersion sol (Sernax CX-Z210IP-F2, ZnSb ₂ O ₆ : 20%, Nissan Kagaku Kogyo Co., Ltd.) Product, brand name) 12.5 parts by weight was diluted with 20 parts by weight of 4-methyl-2-pentanone (4-methyl-2-pentanone) to obtain an ultraviolet curable resin composition.

Next, the UV curable resin composition is applied to an OPP (Oriented Polypropylene) film having a thickness of 80 μm so that the dry film thickness is 30 μm, and irradiated with ultraviolet rays such that the irradiation strength is 400 mJ / cm ² with a high-pressure mercury lamp. To obtain a transfer sheet, and the transfer sheet was cured for one week.

A resin solution containing a melamine formaldehyde resin as a main component was impregnated into a printing paper having a basis weight of 100 g / m ² , and dried to obtain a melamine resin impregnated toilet paper.

A resin solution containing phenolformaldehyde resin as a main component was impregnated into kraft paper having a basis weight of 185 g / m ² , and dried to obtain a phenol resin impregnated core paper.

In order from the bottom, five phenolic resin impregnated core papers, one melamine resin impregnated toilet paper, and a transfer sheet were laminated, and thermo-pressure molding was carried out under conditions of a temperature of 132 ° C. and a pressure of 70 kg / cm ² . Oriented Polypropylene) film was removed to obtain a chemical-resistant decorative plate.

Example 7

As the component (A), 70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyogisha Kagaku Co., Ltd., molecular weight 226) was used, and KAYARAD DPHA (Nihon Kayaku Co., Ltd. product, molecular weight) was used as the component (B). 878) The same procedure as in Example 6 was repeated except that 30 parts by weight were used.

Example 8

It carried out similarly to the said Example 6 except that the compounding quantity of (A) component was 50 weight part, and the compounding quantity of (B) component was 50 weight part.

Example 9

As the component (A), 50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyogisha Kagaku Co., Ltd., molecular weight 226) was used, and KAYARAD DPHA (Nihon Kayaku Co., Ltd. product, molecular weight) was used as the component (B). 878) The same procedure as in Example 6 was carried out except that 50 parts by weight was used.

Example 10

It carried out similarly to the said Example 6 except that the compounding quantity of (A) component was 30 weight part, and the compounding quantity of (B) component was 70 weight part.

Example 11

It carried out similarly to Example 8 except having made the compounding quantity of CX-Z210IP-F2 into 10 weight part.

Example 12

It carried out similarly to Example 8 except having made the compounding quantity of CX-Z210IP-F2 into 15 weight part.

Comparative Example 1

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 0 weight part (not mix | blended), and the compounding quantity of (B) component was 100 weight part.

Comparative Example 2

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 10 weight part, and the compounding quantity of (B) component was 90 weight part.

Comparative Example 3

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 20 weight part, and the compounding quantity of (B) component was 80 weight part.

Comparative Example 4

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 80 weight part, and the compounding quantity of (B) component was 20 weight part.

Comparative Example 5

It carried out similarly to the said Example 1 except that the compounding quantity of (A) component was 90 weight part, and the compounding quantity of (B) component was 10 weight part.

Comparative Example 6

It carried out similarly to Example 1 except having made the compounding quantity of (A) component 100 weight part, and the compounding quantity of (B) component 0 weight part (not mix | blending).

The composition of each Example and a comparative example is shown in Tables 1-3.

[Table 1]

TABLE 2

[Table 3]

Next, the decorative plate of each Example and a comparative example was tested. The test method was as follows. The test of the following (a)-(c) is a test which evaluates the adhesiveness of the layer (transfer layer) which consists of an ultraviolet curable resin composition, all.

(a) Cross cut: A cross cut is put on the surface of a decorative plate by a cutter knife, and after peeling after sticking a cellophane tape once, the peeling state of a transfer layer is visually determined. (Conforms to JISK5400 Paint General Test Method and X Cut Tape Method). The evaluation criteria of the crosscut test were as follows.

(Circle): The transfer sheet is cured at room temperature for 1 week, and there is no peeling.

X: The transfer sheet was cured at room temperature for 1 week, and most of the X cut portions where the tape was stuck had peeling.

(b) Crosscut peeling: It evaluated by crosscut tape peeling (JISK5400 'crosscut test standard). The evaluation criteria of crosscut peeling were as follows.

(Circle): The transfer sheet is cured at room temperature for 1 week, and is tested and remains more than 95/100.

X: The transfer sheet was cured at room temperature for 1 week, and then tested to be 84/100 or less.

(c) Water-resistance adhesiveness: After boiling the makeup plate in boiling water for 2 hours, and drying it for 2 hours in an electric oven at 100 ° C, a crosscut is put on the surface by a cutter knife, and the cellophane tape is removed. After peeling off once and peeling off, the peeling state of the transfer layer is visually determined (according to JISK 5400 Paint General Test Method X Cut Tape Method). Evaluation criteria of water resistance were as follows.

(Circle): There is no peeling even if it tests after carrying out a transfer sheet | seat for 1 week at normal temperature.

X: After the transfer sheet was cured at room temperature for 1 week, the test sheet was peeled off in the majority of the X-cut portion to which the tape was attached.

(d) Chemical resistance: Based on the stain resistance of JIS K 6902: 1998, the resistance of various chemicals was visually observed. The contact time of contaminants is 16 to 24 hours. Evaluation criteria of chemical resistance were as follows.

(Circle): No change of appearance in a coating film.

(Triangle | delta): A trace remains to a coating film, or a coating film discolors.

X: Remarkable change is seen by a coating film.

(e) Surface resistance value: It measures using the digital ultrahigh resistance / microammeter R8340A (advan test) based on JISKK6911-5-13 (1995 edition).

The evaluation results of each test are shown in Tables 1 to 3 above. As is apparent from Tables 1 to 3, the decorative plate of each example was remarkably superior in terms of adhesiveness and chemical resistance of a layer (transfer layer) made of an ultraviolet curable resin composition to the decorative plate of the comparative example.

1: peelable base material
2: UV curable resin composition
2a: cured product of ultraviolet curable resin composition
3: transfer sheet
6: resin impregnated toilet paper
6a: cured resin impregnated toilet paper
7: resin impregnated core paper
7a: cured resin impregnated core paper
9: chemical resistance makeup plate

Claims

(A) a urethane acrylate resin or an acrylic resin containing two radical reactive groups,
(B) urethane acrylate resin or acrylic resin containing at least six radical reactive groups,
When the total amount of the said (A) component and the said (B) component is 100 weight part, the quantity of the said (A) component is 30-70 weight part, The active-energy-ray-curable resin composition characterized by the above-mentioned.

The method of claim 1,
An active energy ray curable resin composition, further comprising a conductive sol.

A peelable base material,
The transfer sheet provided with the layer which consists of the active-energy-ray-curable resin composition of Claim 1 or 2 formed in the said peelable base material.

With melamine resin layer,
The decorative plate provided with the layer which consists of hardened | cured material of the active-energy-ray-curable resin composition of Claim 1 or 2 formed on the said melamine resin layer.

The core material and the toilet paper are impregnated with a resin liquid containing a thermosetting resin as a main component, and the resin-impregnated toilet paper formed by drying the laminated sheet and the transfer sheet according to claim 3 are laminated, Vi) molding and removing said peelable base material after said hot-pressing molding.