JPH01269510A - Manufacture of heat curing resin decorative sheet - Google Patents

Abstract

PURPOSE:To control eluation of a polymerization inhibitor and obtain sharp emboss conforming with printing by using an aluminum group chelate as a curing retarder and curing type resin as an ink binder of an ink containing the curing retarder. CONSTITUTION:A regular printed layer 2 and a printing layer 3 containing a curing retarder successively on a decorative base 1. A composition used for providing the printed layer containing the curing retarder should preferably contain 5-50wt.% of vehicle resin, 20-70wt.% of solvent and 3-60wt.% of curing retarder for heat curing resin for immersing. The curing retarder to be used is an aluminum group chelate, for instance, N- nitrosophenylhydroxylamine aluminum salt. The curing retarder exercises curing control effect to heat curing resin for immersing, but hot for curing the curing type resin in the printed layer containing curing retarder. When a shaping plate 8 is released after the completion of pressing, the uncured heat curing resin 7 on the printed layer 3 containing curing retarder is adhered to the shaping plate 8 and removed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing thermosetting resin decorative laminates such as diallyl phthalate resin decorative laminates and dry polyester decorative laminates, and particularly relates to a method for manufacturing thermosetting resin decorative laminates such as diallylphthalate resin decorative laminates and dry-processed polyester decorative laminates. The present invention relates to a method for manufacturing decorative laminates.

(Prior art) Conventionally, as a method of imparting a three-dimensional effect to a thermosetting resin decorative board, an embossed pattern is applied by using roller embossing, template embossing, etc., and aligning the pattern pattern on the surface of the decorative board with the position of the embossing. There was a way. However, this method has the disadvantage that it is extremely difficult to perfectly match the pattern pattern on the surface of the decorative board with the position of the embossing, and that the embossing plate is expensive to manufacture.

Another method is the chemical embossing method, in which a pattern is formed on base paper for resin impregnation with ink containing a substance that has a repellent effect on resin, and then resin is applied or impregnated on top of the pattern. When printing, there is a method of repelling the resin above the ink area to form an embossed pattern. However, the repelling effect alone does not provide a sufficient embossing effect when a heat and pressure molding type resin is used.

Another chemical embossing method is to form a pattern on base paper for resin impregnation with ink containing hydroquinone as a resin polymerization inhibitor (hardening inhibitor), to create a difference in the curing speed of the impregnated resin, and to utilize this difference. There is a method of forming an embossed pattern on the surface of a decorative board. With this method, it takes time for the resin to harden, and the polymerization inhibitor itself is not sufficiently resistant to the solvent used in the impregnating liquid when impregnating with the thermosetting resin, resulting in problems with deterioration of physical properties. Since the polymerization inhibitor-containing ink is easily eluted by moisture or the like in areas other than the printed areas, it has the disadvantage that recesses are difficult to form.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of the conventional methods as described above, and provides a method for producing a thermosetting resin decorative board that can obtain a stable synchronization effect and form a sharp embossed pattern. In particular, the purpose is to obtain sharp embossing that is synchronized with printing by suppressing the elution of polymerization inhibitors (hardening inhibitors), which is a drawback in chemical embossing methods.

(Means for Solving the Problems) The present inventors used an aluminum-based chelating agent as a hardening inhibitor when forming embossing on a thermosetting resin decorative board by the chemical embossing method, and used an ink containing the hardening inhibitor. When using a curable resin as an ink binder,
The inventors have discovered that the above object can be achieved and have completed the present invention.

That is, the present invention provides a decorative sheet in which a normal printed layer with a desired pattern and a printed layer with a desired pattern containing a curing inhibitor for the thermosetting resin described below are sequentially formed on a decorative base paper, and a thermosetting resin is added to the decorative sheet. The impregnated decorative sheet is impregnated with the liquid and dried, and the resulting impregnated decorative sheet is laminated on the base material with the printed layer facing up.A molding plate is placed on top of this, and this is sandwiched between a pair of hot plates and heated. The laminate is integrated by pressure molding and curing of the thermosetting resin, and the thermosetting resin having an embossed pattern is formed by attaching the thermosetting resin on the printing layer containing the curing inhibitor to a molding plate and removing it. In the method of manufacturing a synthetic resin decorative board,
This is a method for producing a thermosetting resin decorative board, characterized in that an aluminum-based chelating agent is used as a curing inhibitor, and a curable resin is used as a binder in the printing layer containing the curing inhibitor.

Hereinafter, the present invention will be explained based on the drawings.

First, as shown in FIG. 1(A), a normal printing layer 2 and a hardening inhibitor-containing printing layer 3 are sequentially provided on a decorative base paper 1.

The decorative base paper that can be used in the present invention is ordinary paper such as titanium paper, thin paper, or kraft paper, and titanium paper is particularly preferably used.

To provide a printing layer on a decorative base paper, a known ink or paint composition can be used, for example, a coloring agent such as a dye or pigment is added to the ink or paint vehicle, and a plasticizer or stabilizer is added to the ink or paint vehicle. , wax, grease, desiccant, auxiliary desiccant, curing agent, thickener, dispersant, filler, and other known additives are optionally added thereto, and the ink or paint is sufficiently kneaded with a solvent, diluent, etc. Examples include compositions.

In the above ink or coating composition, the vehicle may be a known one, such as various oils and fats such as linseed oil, soybean oil, or synthetic drying oil, natural resins such as rosin copal dammar, hardened rosin, rosin ester, or polymerized rosin; Synthetic resins such as processed resins, rosin-modified phenolic resins, 100% phenolic resins, maleic acid resins, alkyd resins, petroleum resins, vinyl resins, acrylic resins, polyamide resins, epoxy resins, amino alkyd resins, Cellulose derivatives such as nitrocellulose and ethyl cellulose, rubber derivatives such as chlorinated rubber and cyclized rubber, etc., glue,
Casein, dextrin, zein, etc. can be used.

The composition used to provide the printed layer containing a curing inhibitor includes 5-50-t% vehicle resin and 20-70-1% solvent.
%, hardening inhibitor for thermosetting resin for impregnation described later 3 to 60
Preferably, it contains 50 wt%, and if necessary,
Up to wt% pigments or dyes and other additives such as those described above for conventional printing layer forming compositions can be added. As the vehicle resin, use a thermosetting resin different from the thermosetting resin for impregnation. When using a radical addition polymerization type as the thermosetting resin for impregnation, use melamine resin, urea resin, silicone resin, phenol resin, etc. When using an addition condensation thermosetting resin such as a thermosetting resin, and using the addition condensation thermosetting resin as the impregnation thermosetting resin,
Addition polymerizable thermosetting resins such as diallyl phthalate, unsaturated polyesters, urethane resins, amine-curable epoxy resins, and addition polymerizable silicone resins into which ethylenically unsaturated groups are introduced are used. Among these, urea-based
It is preferable to use melamine resin from the viewpoint of curing temperature and curing time. Along with these resins, these resins modified with cellulose, alcohol, alkyd, etc. may be partially included in the vehicle resin, for example, 5 to 30 wt%, or thermoplastics such as cellulose, acrylic resin, polyvinyl chloride, etc. By mixing 10 to 601 wt% of resin, it is possible to improve the printability of the ink and ease the solidification conditions of the vehicle resin after application of the ink, such as shortening the time and lowering the temperature, without reducing the performance of the ink film. Effects can be obtained.

As the solvent or dispersion medium in the ink, aromatic hydrocarbons such as toluene and xylene; aliphatic alcohols such as isopropyl alcohol, ethyl alcohol, and methyl alcohol; esters such as ethyl acetate and butyl acetate;
Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Ethers such as ethylene glycol monomethyl ether, dioxane, and tetrahydrofuran:
One or a mixture of two or more of lactones such as T-propiolactone and γ-butyrolactone and amides such as dimethylformamide and dimethylacetamide are used. Water can also be used as a dispersion medium. Incidentally, these solvents or dispersion media are also used for preparing the impregnating resin liquid.

The curing inhibitor used in the present invention is an aluminum chelate, such as N-nitrosophenylhydroxylamine aluminum salt. N-nitrosophenylhydroxylamine aluminum salt is suitable as a curing inhibitor in the present invention, and is also preferred as it is stable as a printing ink. The amount of curing inhibitor used in the ink is 1 to 20%, preferably 1 to 10%.

Although the curing inhibitor of the present invention has a curing suppressing effect on the thermosetting resin for impregnation, it does not affect the curing of the curable resin in the printing layer containing the curing inhibitor.

As a means for printing a pattern using the above-mentioned curing inhibitor-containing ink, commonly used direct printing or transfer methods can be used, and gravure printing is particularly suitable for this purpose.

The impregnating thermosetting resin 4 for impregnating the decorative sheet in which the normal printing layer 2 and the hardening inhibitor-containing printing layer 3 are sequentially formed on the decorative base paper 1 includes melamine resin, diallyl phthalate resin, guanamine resin, and polyester resin. , phenolic resins can be used, and examples of thermosetting resins for which the curing inhibitor of the present invention is particularly effective include diallyl phthalate resins and polyester resins. These resins are made into a resin liquid using the above-mentioned solvent or dispersion medium, and then impregnated into a decorative sheet using an ordinary impregnation machine, and then dried.

The impregnated decorative sheet thus obtained is laminated on the base material 5 with the printed side facing up. Examples of base materials that can be used include plywood, particle board, flexible board, calcium silicate board, pulp cement board, resin-impregnated laminated core board, and the like.

The forming plate 8 may be any material that is used in the production of ordinary thermosetting resin decorative boards, such as a duralumin plate or a stainless steel plate. Furthermore, a plastic film such as a polypropylene film or a release paper such as silicone-treated paper may also be used.

The heating and pressure molding may be performed using a normal press machine.

As shown in FIG. 1(c), when the forming plate 8 is released after pressing, the uncured thermosetting resin 7 on the hardening inhibitor-containing printed layer 3 adheres to the forming plate 8 and is removed. It will be destroyed.

〔Example〕

PM-6LP manufactured by Kojin ■ 80g/m” as a base paper for makeup
A wood grain pattern was printed on titanium paper using a conventional gravure ink having the following composition, and then a conduit portion was printed using a gravure printing machine using an ink containing a hardening inhibitor having the following composition.

Ordinary gravure ink Cellulose acetate 5-6% by weight coloring pigment
15-35% by weight dibutyl phthalate
2-3% by weight (desirable agent) Solvent 56-78% by weight
Ink aminoalkyd resin containing curing inhibitor, 30% by weight para-toluenesulfonic acid 8ffi 1% N-nitrosophenylhydroxylamine aluminum salt 3% by weight colored pigment
25% by weight solvent
The 42% by weight printed paper was heat-treated for 160°CCl2O seconds to harden the ink resin in the conduit portion, and impregnated with the following resin mixture using a conventional impregnation machine.

Resin mixture diallyl phthalate prepolymer 120 parts Unsaturated polyester 40 parts Benzoyl peroxide
12 parts lauric acid
After impregnating 0.6 parts with 150 parts of acetone, the paper was dried at 80°CIO for an impregnated paper. The amount of impregnation at this time was 12 g/square 2 dry.

Layer the cough-impregnated paper on a 12-value particle board with the ink side facing up, and place a polished duralumin board on top of it with the mirror surface facing down, at 140°C and at 110kg/cf.
Pressing was carried out for 10 minutes under fl conditions.

When the duralumin board was released from the mold after pressing, the uncured resin on the conduit ink part adhered to the duralumin board, resulting in a very stable decorative board with sharp embossing. When the obtained decorative board was subjected to a physical property test in accordance with Japanese Agricultural Standards (JAS) F-type, it was confirmed that it passed all items and was of good quality.

〔Effect of the invention〕

As detailed above, the method of the present invention can suppress the elution of a curing inhibitor in the chemical embossing method, which is one of the embossing methods, and can provide thermosetting resin makeup with sharp embossing that is synchronized with printing. It became possible to stably obtain plates.

[Brief explanation of the drawing]

FIG. 1 shows a process diagram for manufacturing a decorative board according to the method of the present invention. 1... Decorative base paper 2... Normal printing layer 3...Printed layer containing curing inhibitor 4... Impregnated resin (thermosetting resin) 5... Base material 6...Thermosetting resin 7...Thermosetting resin 8... Imprinting template

Claims (1)

[Claims] (1) A thermosetting resin liquid is applied to a decorative sheet formed by sequentially forming a normal printed layer with a desired pattern on a decorative base paper and a printed layer with a desired pattern containing a curing inhibitor for the thermosetting resin described below. After impregnating and drying, the obtained impregnated decorative sheet is laminated on the base material with the printed layer facing up, a forming plate is placed on top of this, and this is sandwiched between a pair of hot plates and molded under heat and pressure. Then, the laminate is integrated by curing the thermosetting resin, and the thermosetting resin having an embossed pattern is produced by attaching the thermosetting resin on the printing layer containing the curing inhibitor to a forming plate and removing it. A method for producing a decorative thermosetting resin board, which comprises using an aluminum-based chelating agent as a curing inhibitor and using a curable resin as a binder in the printing layer containing the curing inhibitor.