CN117888402A - Aldehyde-free printing decorative paper, preparation method thereof and facing artificial board - Google Patents

Abstract

The invention relates to the technical field of decorative paper, in particular to aldehyde-free printing decorative paper, a preparation method thereof and a facing artificial board. The formaldehyde-free printing decorative paper comprises printing base paper and a resin protective layer, wherein the resin protective layer is prepared from protective layer impregnating adhesive, and the protective layer impregnating adhesive comprises the following raw materials in parts by weight: 50-60 parts of acrylic emulsion, 12-18 parts of modified epoxy acrylate, 6-10 parts of organic silicon resin, 8-12 parts of filler, 6-10 parts of polyvinyl alcohol, 3-6 parts of polyethylene glycol, 3-6 parts of silane coupling agent, 2-4 parts of curing agent and 12-18 parts of deionized water. The formaldehyde-free printing decorative paper has excellent scratch resistance, pollution and corrosion resistance, water vapor resistance and other performances, and can greatly reduce formaldehyde release, and the method has the advantages of simple process, convenient operation, high production efficiency and low production cost; the manufactured facing artificial board has good decorative performance, is environment-friendly and has long service life.

Description

Formaldehyde-free printed decorative paper, preparation method thereof and veneer artificial board

Technical Field

The invention relates to the technical field of decorative paper, and in particular to formaldehyde-free printed decorative paper and a preparation method thereof, and a veneer artificial board.

Background technique

With the progress of society and the improvement of people's living standards, veneer panels have been widely used in interior decoration, furniture and other fields. Decorative paper is an important decorative panel veneer material, which can play a good role in protecting and decorating the wooden panel and improving the visual effect.

Decorative paper in the prior art is usually made by printing patterns or texts on base paper and then impregnating it with impregnating glue. However, the existing decorative paper impregnation process mostly adopts a two-stage impregnation process of urea-formaldehyde glue and melamine-formaldehyde glue to improve the durability and decorative effect of the decorative board. However, the obtained product releases free formaldehyde during production and use, which pollutes the environment and harms human health. Therefore, it is of great significance to improve the existing decorative paper and facing artificial board to achieve formaldehyde-free, reduce the release of formaldehyde, and make it have good decorativeness and durability.

Summary of the invention

In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide an environmentally friendly, formaldehyde-free printed decorative paper with excellent decorativeness and durability, and good environmental protection, which can greatly reduce the release of formaldehyde and reduce pollution to the environment.

Another object of the present invention is to provide a method for preparing formaldehyde-free printed decorative paper, which has simple process, convenient operation, high production efficiency, low production cost, and is conducive to industrial production.

Another object of the present invention is to provide a veneer artificial board, which is laminated with the above-mentioned printed decorative paper, has good decorative performance, is environmentally friendly, and has a long service life.

The purpose of the present invention is achieved through the following technical scheme: a formaldehyde-free printed decorative paper, comprising a printing base paper and a resin protective layer coated on the surface of the printing base paper, wherein the resin protective layer is made of a protective layer impregnated glue, and the protective layer impregnated glue comprises the following raw materials in parts by weight: 50-60 parts of acrylic emulsion, 12-18 parts of modified epoxy acrylate, 6-10 parts of silicone resin, 8-12 parts of filler, 6-10 parts of polyvinyl alcohol, 3-6 parts of polyethylene glycol, 3-6 parts of silane coupling agent, 2-4 parts of curing agent, and 12-18 parts of deionized water.

The present invention combines raw materials such as acrylic emulsion, modified epoxy acrylate, silicone resin, filler, polyvinyl alcohol, polyethylene glycol, etc., and the raw materials are evenly dispersed to obtain a protective layer impregnation glue. The resin protective layer formed after the protective layer impregnation glue is cured has good adhesion to the base paper, which can achieve good protection for the printing base paper and improve its scratch resistance and pollution corrosion resistance. Preferably, the printing base paper is digital printing base paper, which uses digital printing patterns and texts, has high efficiency and good flexibility, so that the patterns and texts have the advantages of high resolution and high color reproduction, and improve the decorative effect of the decorative paper.

Furthermore, the preparation method of the protective layer impregnation glue includes the following steps: adding acrylic emulsion, modified epoxy acrylate, and silicone resin in proportion, heating to 55-65°C, adding a curing agent and polyvinyl alcohol, and adding polyethylene glycol after heat preservation reaction for 20-30 minutes, continuing the reaction for 20-30 minutes, and then adding deionized water, silane coupling agent and filler, stirring for 15-20 minutes at a stirring speed of 900-1200r/min, and standing to obtain a protective layer impregnation glue.

Furthermore, the filler is at least one of nano calcium carbonate, nano silicon dioxide and nano zinc oxide.

Furthermore, the silane coupling agent is at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane and γ(vinyltri(β-methoxyethoxy)silane).

Furthermore, the curing agent is at least one of triethylenetetramine, triethylamine and N-hydroxymethyl acrylamide.

Furthermore, the preparation method of each modified epoxy acrylate comprises the following steps:

A1. By weight, 35-45 parts of propylene glycol methyl ether and 1-1.5 parts of oleic acid were mixed evenly, and then 6-9 parts of butyl titanate were added, and the mixture was heated to 72-78° C., kept warm for 2-3 hours, and then filtered. The obtained precipitate was washed with deionized water and dried, and 30-35 parts of deionized water and 10-14 parts of triester phosphate were added to obtain a mixture A.

A2. Heat the mixture A to 85-95°C under nitrogen protection, then add 30-34 parts of bisphenol A epoxy resin, 0.5-1.5 parts of catalyst, 0.2-0.4 parts of polymerization inhibitor, and dropwise add 6-9 parts of acrylic acid, 4-7 parts of methyl methacrylate and 4-7 parts of styrene, stir evenly, raise the temperature to 105-115°C, react at a constant temperature, and when the acid value drops below 3 mgKOH/g, cool to obtain modified epoxy acrylate.

The present invention adopts the above raw materials and preparation method, and controls the process parameters of each step to obtain epoxy acrylate, and the obtained epoxy acrylate is added to the protective layer impregnation glue, which can achieve good coordination with acrylic emulsion, silicone resin, polyvinyl alcohol, and polyglycol, which helps to improve the mechanical properties, water resistance and corrosion resistance of the resin protective layer and extend the service life of the decorative paper. The bisphenol A type epoxy resin adopts epoxy resin E-44.

Furthermore, in step A2, the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, triethylamine, N,N-dimethylbenzylamine, trimethylbenzylammonium chloride and triphenylphosphine.

Furthermore, in step A2, the polymerization inhibitor is at least one of p-methoxyphenol, hydroquinone, and 2,5-dimethylhydroquinone.

Another object of the present invention is achieved by the following technical solution: the preparation method of the above-mentioned formaldehyde-free printed decorative paper comprises the following steps: impregnating the printing base paper in a protective layer impregnation glue, forming a resin protective layer after drying, and preparing the formaldehyde-free printed decorative paper.

Furthermore, the drying temperature is 105-110° C., and the drying time is 1.5-3 min.

Another object of the present invention is achieved through the following technical solution: a veneer artificial board, comprising a board body and formaldehyde-free printed decorative paper, wherein the formaldehyde-free printed decorative paper is attached to the surface of the board body.

Furthermore, the preparation method of the above-mentioned veneered artificial board includes the following steps: hot pressing the formaldehyde-free printed decorative paper onto the surface of the board body to obtain the veneered artificial board.

Furthermore, the hot pressing temperature is 125-135° C., the pressure is 0.9-1.3 MPa, and the hot pressing time is 90-150 s.

The beneficial effects of the present invention are as follows: the formaldehyde-free printed decorative paper of the present invention can form a dense resin protective layer on the surface of the printed base paper after curing by impregnating the printed base paper in the protective layer impregnation glue, and has excellent scratch resistance, pollution corrosion resistance, water vapor resistance and other properties, and can greatly reduce the release of formaldehyde and reduce pollution to the environment. The preparation method of the formaldehyde-free printed decorative paper of the present invention is simple in process, easy to operate, high in production efficiency, low in production cost, and is conducive to industrial production. The veneer artificial board prepared by the present invention is bonded with the above-mentioned printed decorative paper, has good decorative properties, is environmentally friendly, and has a long service life.

Detailed ways

In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

Example 1

In this embodiment, a formaldehyde-free printed decorative paper includes a printed base paper and a resin protective layer coated on the surface of the printed base paper, wherein the resin protective layer is made of a protective layer impregnated adhesive, and the protective layer impregnated adhesive includes the following raw materials in parts by weight: 55 parts of acrylic emulsion, 16 parts of modified epoxy acrylate, 8 parts of silicone resin, 10 parts of filler, 8 parts of polyvinyl alcohol, 5 parts of polyethylene glycol, 4 parts of silane coupling agent, 3 parts of curing agent, and 16 parts of deionized water. The acrylic emulsion is BASF JONCRYLHRC 1661 acrylic emulsion, and the silicone resin is Kramar ZY1053 silicone resin.

Furthermore, the preparation method of the protective layer impregnation glue includes the following steps: adding acrylic emulsion, modified epoxy acrylate, and silicone resin in proportion, heating to 60°C, adding a curing agent and polyvinyl alcohol, and adding polyethylene glycol after heat preservation reaction for 25 minutes, continuing the reaction for 25 minutes, and then adding deionized water, silane coupling agent and filler, stirring for 20 minutes at a stirring speed of 1000r/min, and standing to obtain a protective layer impregnation glue.

Furthermore, the filler is composed of nano silicon dioxide and nano zinc oxide in a mass ratio of 1:1. The silane coupling agent is composed of γ-aminopropyl triethoxysilane and γ-glycidyloxypropyl trimethoxysilane in a mass ratio of 1:2. The curing agent is triethylamine.

Furthermore, the preparation method of each modified epoxy acrylate comprises the following steps:

A1. By weight, 40 parts of propylene glycol methyl ether and 1.2 parts of oleic acid were mixed evenly, and then 8 parts of butyl titanate were added, heated to 75° C., kept warm for 2.5 hours, and then filtered. The obtained precipitate was washed with deionized water and dried, and 32 parts of deionized water and 12 parts of triester phosphate were added to obtain a mixture A.

A2. Heat the mixture A to 90°C under nitrogen protection, then add 32 parts of bisphenol A epoxy resin, 1 part of catalyst, 0.3 parts of polymerization inhibitor, and dropwise add 7 parts of acrylic acid, 5 parts of methyl methacrylate and 6 parts of styrene, stir evenly, raise the temperature to 1010°C, carry out constant temperature reaction, and when the acid value drops below 3 mgKOH/g, cool to obtain modified epoxy acrylate.

Furthermore, the bisphenol A type epoxy resin is epoxy resin E-44.

Furthermore, in step A2, the catalyst is tetraethylammonium bromide and the polymerization inhibitor is hydroquinone.

In this embodiment, the preparation method of the above-mentioned formaldehyde-free printed decorative paper includes the following steps: impregnating the printing base paper in the protective layer impregnation glue, forming a resin protective layer after drying, and preparing the formaldehyde-free printed decorative paper, the drying temperature is 108° C., and the drying time is 2 minutes.

In the present embodiment, a veneer artificial board includes a board body and formaldehyde-free printed decorative paper, wherein the formaldehyde-free printed decorative paper is attached to the surface of the board body.

Furthermore, the preparation method of the above-mentioned veneered artificial board includes the following steps: hot pressing the formaldehyde-free printed decorative paper to the surface of the board, the hot pressing temperature is 130° C., the pressure is 1.1 MPa, and the hot pressing time is 120 seconds to obtain the veneered artificial board.

Example 2

In this embodiment, a formaldehyde-free printed decorative paper includes a printed base paper and a resin protective layer coated on the surface of the printed base paper, wherein the resin protective layer is made of a protective layer impregnated adhesive, and the protective layer impregnated adhesive includes the following raw materials in parts by weight: 55 parts of acrylic emulsion, 15 parts of modified epoxy acrylate, 9 parts of silicone resin, 11 parts of filler, 7 parts of polyvinyl alcohol, 4 parts of polyethylene glycol, 5 parts of silane coupling agent, 3 parts of curing agent, and 17 parts of deionized water. The rest of this embodiment is the same as that of Example 1.

Example 3

In the present embodiment, a formaldehyde-free printed decorative paper includes a printing base paper and a resin protective layer coated on the surface of the printing base paper, wherein the resin protective layer is made of a protective layer impregnated glue, and the protective layer impregnated glue includes the following raw materials in parts by weight: 50 parts of acrylic emulsion, 12 parts of modified epoxy acrylate, 6 parts of silicone resin, 8 parts of filler, 6 parts of polyvinyl alcohol, 3 parts of polyethylene glycol, 3 parts of silane coupling agent, 2 parts of curing agent, and 12 parts of deionized water.

Furthermore, the preparation method of the protective layer impregnation glue includes the following steps: adding acrylic emulsion, modified epoxy acrylate, and silicone resin in proportion, heating to 55°C, adding a curing agent and polyvinyl alcohol, and adding polyethylene glycol after heat preservation reaction for 30 minutes, continuing the reaction for 30 minutes, and then adding deionized water, silane coupling agent and filler, stirring for 15 minutes at a stirring speed of 1200r/min, and standing to obtain a protective layer impregnation glue.

Furthermore, the filler is composed of nano calcium carbonate and nano silicon dioxide in a mass ratio of 1:1. The silane coupling agent is γ-glycidyloxypropyl trimethoxysilane. The curing agent is triethylenetetramine.

Furthermore, the preparation method of each modified epoxy acrylate comprises the following steps:

A1. By weight, 35 parts of propylene glycol methyl ether and 1 part of oleic acid were mixed evenly, and then 6 parts of butyl titanate were added, heated to 72° C., kept warm for 3 hours and then filtered, the obtained precipitate was washed with deionized water and dried, and 30 parts of deionized water and 10 parts of triester phosphate were added to obtain a mixture A;

A2. Heat the mixture A to 85°C under nitrogen protection, then add 30 parts of bisphenol A epoxy resin, 0.5 parts of catalyst, 0.2 parts of polymerization inhibitor, and dropwise add 6-9 parts of acrylic acid, 4 parts of methyl methacrylate and 4 parts of styrene, stir evenly, raise the temperature to 105°C, react at a constant temperature, and when the acid value drops below 3 mgKOH/g, cool to obtain modified epoxy acrylate.

Furthermore, in step A2, the catalyst is tetrabutylammonium bromide and the inhibitor is p-methoxyphenol.

In this embodiment, the preparation method of the above-mentioned formaldehyde-free printed decorative paper includes the following steps: impregnating the printing base paper in the protective layer impregnation glue, forming a resin protective layer after drying, and preparing the formaldehyde-free printed decorative paper, the drying temperature is 105° C., and the drying time is 3 minutes.

In this embodiment, a veneer artificial board includes a board body and formaldehyde-free printed decorative paper, wherein the formaldehyde-free printed decorative paper is attached to the surface of the board body. The preparation method of the veneer artificial board includes the following steps: hot pressing the formaldehyde-free printed decorative paper to the surface of the board body, the hot pressing temperature is 125°C, the pressure is 1.3MPa, and the hot pressing time is 150s to obtain the veneer artificial board.

Example 4

In the present embodiment, a formaldehyde-free printed decorative paper includes a printing base paper and a resin protective layer coated on the surface of the printing base paper, wherein the resin protective layer is made of a protective layer impregnating glue, and the protective layer impregnating glue includes the following raw materials in parts by weight: 60 parts of acrylic emulsion, 18 parts of modified epoxy acrylate, 10 parts of silicone resin, 12 parts of filler, 10 parts of polyvinyl alcohol, 6 parts of polyethylene glycol, 6 parts of silane coupling agent, 4 parts of curing agent, and 18 parts of deionized water.

Furthermore, the preparation method of the protective layer impregnation glue includes the following steps: adding acrylic emulsion, modified epoxy acrylate, and silicone resin in proportion, heating to 65°C, adding a curing agent and polyvinyl alcohol, and adding polyethylene glycol after heat preservation reaction for 20 minutes, continuing the reaction for 30 minutes, and then adding deionized water, silane coupling agent and filler, stirring for 20 minutes at a stirring speed of 900 r/min, and standing to obtain a protective layer impregnation glue.

Furthermore, the filler is composed of nano calcium carbonate and nano zinc oxide in a mass ratio of 1:2. The silane coupling agent is γ (vinyl tri (β-methoxyethoxy) silane). The curing agent is N-hydroxymethyl acrylamide.

Furthermore, the preparation method of each modified epoxy acrylate comprises the following steps:

A1. By weight, 45 parts of propylene glycol methyl ether and 1.5 parts of oleic acid were mixed evenly, and then 9 parts of butyl titanate were added, heated to 78° C., kept warm for 2 hours and then filtered, the obtained precipitate was washed with deionized water and dried, and 35 parts of deionized water and 14 parts of triester phosphate were added to obtain a mixture A;

A2. Heat the mixture A to 95° C. under nitrogen protection, then add 34 parts of bisphenol A epoxy resin, 1.5 parts of catalyst, 0.4 parts of polymerization inhibitor, and dropwise add 9 parts of acrylic acid, 7 parts of methyl methacrylate and 7 parts of styrene, stir evenly, raise the temperature to 115° C., react at a constant temperature, and when the acid value drops below 3 mgKOH/g, cool to obtain modified epoxy acrylate.

Furthermore, in step A2, the catalyst is triphenylphosphine and the polymerization inhibitor is 2,5-dimethylhydroquinone.

In this embodiment, the preparation method of the above-mentioned formaldehyde-free printed decorative paper includes the following steps: impregnating the printed base paper in a protective layer impregnation glue, forming a resin protective layer after drying, and preparing the formaldehyde-free printed decorative paper, the drying temperature is 110° C., and the drying time is 1.5 minutes.

Another object of the present invention is achieved through the following technical solution: a veneer artificial board, comprising a board body and formaldehyde-free printed decorative paper, wherein the formaldehyde-free printed decorative paper is attached to the surface of the board body.

Furthermore, the preparation method of the above-mentioned veneered artificial board includes the following steps: hot pressing the formaldehyde-free printed decorative paper to the surface of the board, the hot pressing temperature is 135° C., the pressure is 1 MPa, and the hot pressing time is 90 seconds to obtain the veneered artificial board.

Comparative Example 1

The difference between this comparative example and Example 1 is that the protective layer impregnation glue does not contain modified epoxy acrylate, and an equal amount of acrylic emulsion is used instead.

Comparative Example 2

The difference between this comparative example and Example 1 is that the protective layer impregnation glue does not contain silicone resin, and an equal amount of acrylic emulsion is used instead.

Comparative Example 3

The difference between this comparative example and Example 1 is that the protective layer impregnation glue does not contain polyvinyl alcohol.

Take the printed decorative paper of Example 1 and Comparative Examples 1-3 and stick the printed decorative paper on one side to the artificial board body, the artificial board body is fiberboard, to obtain the veneered artificial board, the density of the veneered artificial board is 0.65-0.8g/cm ³ . The performance of the printed decorative paper and the veneered artificial board is measured respectively.

According to GB/T 28995-2012, the formaldehyde emission and the amount of glue on the printed decorative paper were tested and the appearance quality of the printed decorative paper was observed. It can be seen that there is no damage, stains, or gaps on the surface of the printed decorative paper in Example 1 and Comparative Examples 1-3, and the product appearance quality meets the standard of GB/T 28995-2012. The formaldehyde emission of the printed decorative paper is 0 mg/L, and the amount of glue on the paper in Example 1 and Comparative Examples 1-3 is 78%, 66%, 74% and 61%, respectively.

According to GB/T15102-2017, the surface bonding strength, surface scratch resistance (≥1.5N surface without more than 90% scratches), surface pollution corrosion resistance (the time of pollutants placed on the reagent surface at room temperature: 25% sodium hydroxide solution 10min, soap solution 24h, cola beverage 16h), surface light fastness and resistance to cold and hot cycles of the veneer wood-based panels were tested respectively. The test results are shown in the following table:

As can be seen from the above table, the present invention prepares a protective layer impregnation adhesive by combining raw materials such as acrylic emulsion, modified epoxy acrylate, silicone resin and polyvinyl alcohol, and the resin protective layer formed by curing can provide good protection for the printed base paper. Printed decorative paper is applied to veneer artificial boards and can be well combined with the board body, so that the veneer artificial boards have excellent scratch resistance, pollution corrosion resistance, water vapor resistance and other properties, have a long service life, and can greatly reduce the release of formaldehyde and reduce pollution to the environment.

The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, and the present invention is also intended to include these modifications and modifications.

Claims (10)

1. A formaldehyde-free printed decorative paper, characterized in that it comprises a printing base paper and a resin protective layer coated on the surface of the printing base paper, wherein the resin protective layer is made of a protective layer impregnated glue, and the protective layer impregnated glue comprises the following raw materials in parts by weight: 50-60 parts of acrylic emulsion, 12-18 parts of modified epoxy acrylate, 6-10 parts of silicone resin, 8-12 parts of filler, 6-10 parts of polyvinyl alcohol, 3-6 parts of polyethylene glycol, 3-6 parts of silane coupling agent, 2-4 parts of curing agent, and 12-18 parts of deionized water. 2 . The formaldehyde-free printed decorative paper according to claim 1 , wherein the filler is at least one of nano calcium carbonate, nano silicon dioxide and nano zinc oxide. 3. The weather-resistant decorative paper according to claim 2, characterized in that the silane coupling agent is at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane and γ (vinyltri(β-methoxyethoxy)silane). 4. The formaldehyde-free printed decorative paper according to claim 1, characterized in that: the preparation method of each portion of the modified epoxy acrylate comprises the following steps: A1. By weight, 35-45 parts of propylene glycol methyl ether and 1-1.5 parts of oleic acid were mixed evenly, and then 6-9 parts of butyl titanate were added, and the mixture was heated to 72-78° C., kept warm for 2-3 hours, and then filtered. The obtained precipitate was washed with deionized water and dried, and 30-35 parts of deionized water and 10-14 parts of triester phosphate were added to obtain a mixture A. A2. Heat the mixture A to 85-95°C under nitrogen protection, then add 30-34 parts of bisphenol A epoxy resin, 0.5-1.5 parts of catalyst, 0.2-0.4 parts of polymerization inhibitor, and dropwise add 6-9 parts of acrylic acid, 4-7 parts of methyl methacrylate and 4-7 parts of styrene, stir evenly, raise the temperature to 105-115°C, react at a constant temperature, and when the acid value drops below 3 mgKOH/g, cool to obtain modified epoxy acrylate. 5. The formaldehyde-free printed decorative paper according to claim 4, characterized in that: in the step A2, the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, triethylamine, N,N-dimethylbenzylamine, trimethylbenzylammonium chloride and triphenylphosphine. 6 . The formaldehyde-free printed decorative paper according to claim 4 , wherein in the step A2, the polymerization inhibitor is at least one of p-methoxyphenol, hydroquinone, and 2,5-dimethylhydroquinone. 7 . The formaldehyde-free printed decorative paper according to claim 1 , wherein the curing agent is at least one of triethylenetetramine, triethylamine and N-hydroxymethyl acrylamide. 8. A method for preparing formaldehyde-free printed decorative paper according to any one of claims 1 to 7, characterized in that it comprises the following steps: impregnating the printing base paper in a protective layer impregnation glue, forming a resin protective layer after drying, and preparing the formaldehyde-free printed decorative paper. 9. A veneered artificial board, characterized in that it comprises a board body and the formaldehyde-free printed decorative paper according to any one of claims 1 to 7, wherein the formaldehyde-free printed decorative paper is attached to the surface of the board body. 10. A method for preparing a veneered artificial board as claimed in claim 9, characterized in that the method for preparing a veneered artificial board comprises the following steps: hot pressing formaldehyde-free printed decorative paper onto the surface of a board to obtain the veneered artificial board.