KR100514717B1 - thermoset composition for dye sublimation and its manufacturing and dye sublimation printing method - Google Patents

Abstract

The present invention relates to a thermosetting resin composition for dye sublimation, and to a production and printing method thereof, comprising: a bisphenol-unsaturated polyester resin; Polymethyl methacrylate; Additives; Aluminum hydroxide; Calcium carbonate; Glass fiber; It is characterized by being mixed.

Wherein the additive is a dispersant; Sunscreens; Antioxidants; Silane coupling agents; Internal release agent; A polymerization inhibitor; A curing agent; In thickeners; It is preferable to comprise at least two or more.

Accordingly, there is an advantage that a heat-curable resin composition for dye-sublimation transfer having excellent color development and permeability due to uniform transfer properties of the transfer ink without a change in physical properties at high temperatures during transfer is produced.

Description

Thermoset composition for dye sublimation and its manufacturing and dye sublimation printing method

The present invention relates to a thermosetting resin composition for dye sublimation, and to a production and thermal transfer printing method, more specifically 10 to 15% by weight of a bisphenol-type unsaturated polyester resin; 8 to 15% by weight of polymethyl methacrylate; 3 to 5 weight percent of an additive; 30 to 45% by weight of aluminum hydroxide; 5-15% by weight of calcium carbonate; It relates to a resin composition in which 15 to 25% by weight of glass fibers are mixed, a method for producing the same, and a method for transferring the article made of the resin composition.

Currently, the printing method for general resin moldings has the disadvantage of printing by using screen printing, but the durability is low, there is a limit of expression, and the printing cost is high in a small amount of work.

On the other hand, dye sublimation printing is a printing method that is excellent in various expressiveness and durability, but the development of the dye sublimation due to the difference in the degree of printability and the limitation of the resin such as deformation occurs at high temperature during transfer.

Dye sublimation transfer is printed on a transfer-capable paper with a transfer ink, the printed paper is adhered to the surface of the object to be transferred and pressurized at a high temperature of 160 ~ 230 ℃ to print the printed surface printed on the paper It penetrates into and prints.

The transfer ink is vaporized without undergoing a liquid process at a high temperature, and at the same time, the tissue structure on the surface of the transfer object is relaxed and opened, and when the dye of gas is introduced into it, and the temperature drops, the tissue structure is restored to its original state and solidified. It is returned to the solid state again. As a result, the transfer ink becomes part of the transfer object and the printing operation is completed.

Materials such as 100% natural fibers or uncoated metal timber are difficult to transfer because they do not have a tissue that relaxes at high temperatures.

Generally, resin compositions used in building materials are made of thermoplastic resins or thermosetting resins. Here, the thermoplastic resin is melted when heat is applied and the tissue structure is relaxed and opened so that the transfer is possible. However, the thermoplastic resin is a change in physical properties by heat at a temperature of about 160 ~ 230 ℃ applied during the transfer. Therefore, the quality of the transfer printing is deteriorated due to the yellowing phenomenon or the decrease in strength and deformation caused by heat, where the color of the printed surface becomes yellow.

On the contrary, the thermosetting resin is more resistant to high temperature than the thermoplastic resin, but shrinkage or destruction of structure when heat is applied, so it is difficult to absorb the pigment at high temperature, which results in a poor transfer degree. Therefore, there is a problem that it is extremely difficult to print a pattern on the surface of the molded article made of thermoplastic resins or thermosetting resins.

Accordingly, the present invention has been made to solve the above problems, there is no thermal deformation at high temperatures, can withstand the pressure at the time of transfer, and the thermosetting resin composition for dye-sublimation transfer having excellent durability and flame retardancy than conventional printing quality It aims to provide.

It is also an object of the present invention to provide a method for producing a resin composition and a printing method for thermally transferring a surface of a molded article manufactured using the resin composition.

The present invention to achieve the above object, 10 to 15% by weight of bisphenol-type unsaturated polyester resin; 8 to 15% by weight of polymethyl methacrylate; 3 to 5 weight percent of an additive; 30 to 45% by weight of aluminum hydroxide; 5-15% by weight of calcium carbonate; 15-25% by weight of glass fibers; It is characterized by being mixed. Wherein the additive is a dispersant; Sunscreens; Antioxidants; Silane coupling agents; Internal release agent; A polymerization inhibitor; A curing agent; Thickeners; It is preferably configured to include at least two or more.

And a dispersant; Sunscreens; Antioxidants; Silane coupling agents; Internal release agent; A polymerization inhibitor; A curing agent; Thickeners; 3 to 5% by weight of an additive comprising at least two or more, 10 to 15% by weight of bisphenol-type unsaturated polyester resin, and 8 to 15% by weight of polymethyl methacrylate, are mixed at 20 to 40 ℃ 25 minutes to 35 minutes of stirring to form a primary mixture, the primary mixture, 30 to 45% by weight of aluminum hydroxide, and 5 to 15% by weight of calcium carbonate are mixed and mixed at 20 to 40 ° C for 25 minutes to After stirring for 35 minutes to form a secondary mixture, the secondary mixture and 15 to 25% by weight of glass fibers are mixed and stirred for 6 to 10 minutes at 20 to 40 ℃ to form a bulk tertiary mixture, the 3 Another feature is that the tea mixture is put into a mold and pressurized for a predetermined time according to the thickness of the product at a pressure of 50 to 160kg / cm ² at 130 to 150 ° C.

10 to 15% by weight of bisphenol-type unsaturated polyester resin, 8 to 15% by weight of polymethyl methacrylate, 30 to 45% by weight of aluminum hydroxide and 5 to 15% by weight of calcium carbonate, 3 to 5% by weight of the first additive, comprising at least one or more of a silane coupling agent and an internal mold release agent, is mixed and stirred at 20 to 40 ° C. for 25 to 35 minutes, and at least one of a curing agent and an antipolymerizing agent is added thereto. 0.3 to 0.4% by weight of the second additive and 0.2 to 0.3% by weight of the thickener are added at the same time and completely dispersed to prepare a final mixture, the glass fiber content of 15 to 25% by weight in a sheet machine It is manufactured to have a thickening (aging) process for 3 days at a temperature of 30 to 35 ℃ to obtain a mixture of thickened sheet state, the protective film is removed and put into a mold It is characterized in that it is molded by pressing for a predetermined time according to the product thickness at a pressure of 70 to 160kg / cm ² at 130 to 150 ℃.

 Then, the transfer ink is printed on a paper which can be transferred by screen printing, offset printing, gravure printing or inkjet printer, and the thermosetting resin composition of the dye sublimation transfer according to claim 1 or 2. Another method of printing a thermosetting resin composition for dye sublimation is characterized in that the transfer paper is attached to the surface and heated and pressurized to heat transfer printing.

The present invention can be seen that the main purpose is to provide a material excellent in color development and permeability with a uniform transfer property of the transfer ink without changing the physical properties at high temperatures during transfer. To this end, the bisphenol-type unsaturated polyester resin and polymethyl methacrylate is mixed. The reason for mixing the bisphenol-type unsaturated polyester resin and polymethyl methacrylate as described above is the shape stability by mixing the bisphenol-type unsaturated polyester resin having excellent reactivity with the transfer ink and polymethyl methacrylate which is a low shrinkage agent. This is to prevent shrinkage that occurs during molding by improving.

A predetermined additive is mixed in the mixture of the bisphenol-type unsaturated polyester resin and polymethyl acrylate. Here, the additive is preferably made by mixing a plurality of materials as follows.

1) 2- (2-hydroxy-5-t-octhylphenyl) -benzotriazole: A sunscreen that prevents discoloration or cracking of polymers by reducing or stopping photochemical reactions of polymers caused by ultraviolet rays.

2) pentaerylthritol tetrakis (3- (3,5-di-tert-buthyl-4-hydroxyphenyl) propionate: An antioxidant for improving weather resistance and minimizing discoloration or deformation under heat-treated processes.

3) gamma-methacryloxy propyl trimethoxy silane, which has two or more reactors in the molecule to chemically bond organic (resin) and inorganic (glass fiber, calcium carbonate, aluminum hydroxide) to increase the strength of the molded composition Silane coupling agent.

4) Polymer block copolymer: A dispersant that has a low shrinkage agent and an affinity group to increase the compatibility with the resin to prevent phase separation to have uniform physical properties.

5) Zinc Stearate (Zn (C ₁₇ H ₃₅ COO) ₂ ): Internal mold release agent that improves moldability by enabling work without separate release treatment in mold.

6) 2,6-di-tert-butyl-4-methyl-phenol: Anti-polymerization agent that suppresses the rapid reaction of resin.

7) t-butyl peroxy benzoate: A curing agent that starts the curing reaction of resin under heat and pressure.

8) Magnesium Oxide: A thickener that improves viscosity by reacting with resin.

In addition, it improves the elastic modulus of the composition, improves dimensional stability, and plays a role of flame retardant because it decomposes at high temperature to produce moisture with calcium carbonate (CaCO ₃ ) and chemical resistance, abrasion resistance, and hardness for the effect of preventing shrinkage and warpage. Aluminum hydroxide (Al (OH) ₃ ) is added.

In addition, the glass fibers are mixed together to improve the strength of the composition.

As described above, the glass fiber-reinforced thermosetting resin is manufactured and used in one of a bulk mold compound (BMC) form and a sheet mold compound (SMC) form.

The BMC-type resin and the reinforcing agent and additives are mixed to form a dough-like state and injected into the mold or positioned at the lower side of the mold during compression molding, and 50 to 160 kg / cm ² at a temperature of 130 to 150 ° C. Pressurized for a certain time according to the thickness of the thermosetting synthetic resin molded product of the desired shape.

After mixing the SMC-type resin and additives, thickeners and reinforcing agents, it is prepared by packaging with a protective film and aging for a certain time. The SMC form is a high viscosity by the added thickener to form a solid sheet form, after removing the protective film is cut into a suitable size and put into the mold. Pressing the SMC form into a mold at a temperature of 130 to 150 ° C. at a pressure of 70 to 160 kg / cm ² for a predetermined time to produce a thermosetting synthetic resin molded article having a desired shape. To do this, first, a pattern is printed on one of the screens that can be transferred by using screen printing, offset printing, gravure printing, or ink jet printer. When the printed transfer paper is attached to the surface of the dye sublimation transfer molded product and heat is applied at 160 to 230 ° C., the dye printed on the transfer paper is sublimed and bonded to the dye sublimation transfer substrate to form a pattern on the surface. do

Hereinafter will be described the preparation and printing method of the composition of the present invention through the examples. Example 1 is an example of preparing a composition of the BMC form, Example 2 is an example of a method of producing a composition of the SMC form.

Example 1

12% by weight of bisphenol-type unsaturated polyester resin, 10% by weight of polymethyl methacrylate, and 3% by weight of an additive were added to the stirrer, followed by stirring at 25 ° C. for 30 minutes to prepare a primary mixture. Wherein the additive is 2- (2-hydroxy-5-t-octhylphenyl) -benzotriazole and pentaerylthritol tetrakis (3- (3,5-di-tert-buthyl-4-hydroxyphenyl) propionate and gamma-methacryloxy propyl trimethoxy silane and polymer Block copolymer, Zinc Stearate (Zn (C ₁₇ H ₃₅ COO) ₂ ), 2,6-di-tert-butyl-4-methyl-phenol and t-butyl peroxy benzoate are prepared by mixing.

40% by weight of aluminum hydroxide and 15% by weight of calcium carbonate were mixed in the mixed primary mixture and stirred at 30 ° C. for 30 minutes to prepare a secondary mixture.

The secondary mixture and 20% by weight of glass fibers were mixed and stirred at 30 ° C. for 8 minutes to obtain a bulk composition.

The bulk composition is put into a mold having a desired shape and pressurized at 140 ° C. at 150 kg / cm ² for 8 minutes to produce a dye sublimation molded article.

A transfer paper printed with a pattern using an inkjet printer is attached to the surface of the dye-sublimation transfer molded article and pressurized at 200 ° C. for 2 minutes, and the dye printed on the transfer paper is sublimed and bonded to the dye-sublimation transfer substrate. A pattern is formed on it.

The bulk composition can be manufactured in various mold designs, such as ceiling, wall, floor, sink target plate, table top, door, advertisement, interior, etc.

It can be made into a transfer molded product to transfer various colors to make a high quality and durable product.

Example 2

2- (2-hydroxy-5-t-octhylphenyl) -benzotriazole and pentaerylthritol tetrakis (3- (3,5-di-tert-buthyl-4-hydroxyphenyl) propionate and gamma-methacryloxy propyl trimethoxy silane and polymer block copolymers Zinc Stearate (Zn (C ₁₇ H ₃₅ COO) ₂ ) is mixed in a certain ratio to prepare the first additive, and 2,6-di-tert-butyl-4-methyl-phenol and t-butyl peroxy benzoate are mixed. A second additive is prepared.

After adding 14.03% by weight of bisphenol-type unsaturated polyester resin, 11.69% by weight of polymethyl methacrylate, 35.06% by weight of aluminum hydroxide, 11.69% by weight of calcium carbonate and 3.51% by weight of the first additive, the mixture was stirred at 25 ° C for 30 minutes. .

0.39% by weight of the second additive and 0.27% by weight of magnesium oxide are added to the mixture to produce a final mixture. Here, the magnesium oxide should be added to the next process by mixing within 1 minute since the reaction starts immediately after the addition.

The final mixture is added to 23.38% by weight of glass fiber in the impregnator for producing SMC to prepare a SMC composition packaged in a protective film in the form of a roll or rack.

The SMC composition in the form of a roll or rack is aged at 35 ° C. for 3 days to become a thickened sheet.

After the protective film is removed, the sheet is cut into a predetermined size, put into a mold of a desired shape, pressurized at a pressure of 150 kg / cm ² at 140 ° C. for 10 minutes, and manufactured as a dye sublimation molded article.

A transfer paper printed with a pattern using an inkjet printer is attached to the surface of the dye sublimation transfer molded article, and pressurized at 200 ° C. for 2 minutes, the dye printed on the transfer paper is sublimed and bonded to the dye sublimation transfer substrate. A pattern is formed on it.

The bulk composition is made of various mold designs to make various types of transfer moldings such as ceiling, wall, floor, sink, plate, table, door, advertisement, interior, etc. You can make this good product.

As described above, according to the thermosetting resin composition for dye sublimation of the present invention, physical properties such as yellowing phenomenon, strength decrease, deformation due to high temperature during transfer are prevented, and excellent transfer depth and uniformity in all color areas. There is an advantage of being a warrior.

In addition, it is a flame retardant material, which is resistant to fire, is easy to process, and very resistant to scratches.

Therefore, when the molded product for dye sublimation is manufactured using the resin composition, there is an advantage that a small amount and a large amount of graphic transfer printing are possible, resulting in various designs and cost reduction due to productivity improvement. In addition, such a bulk composition is made of various mold designs and made into various forms of transfer moldings such as ceiling materials, wall cloths, floor materials, sink target plates, table tops, doors, advertisements, interiors, etc. It can be made of durable product.

Claims (5)

10 to 15% by weight of the bisphenol-type unsaturated polyester resin; 8 to 15% by weight of polymethyl methacrylate; 3 to 5 weight percent of an additive; 30 to 45% by weight of aluminum hydroxide; 5-15% by weight of calcium carbonate; 15-25% by weight of glass fibers; A thermosetting resin composition for dye sublimation which is mixed. The method of claim 1, wherein the additive Dispersants; Sunscreens; Antioxidants; Silane coupling agents; Internal release agent; A polymerization inhibitor; A curing agent; Thickeners; A thermosetting resin composition for dye sublimation, comprising at least two or more of them. Dispersants; Sunscreens; Antioxidants; Silane coupling agents; Internal release agent; A polymerization inhibitor; A curing agent; Thickeners; 3 to 5% by weight of an additive comprising at least two or more, 10 to 15% by weight of bisphenol-type unsaturated polyester resin, and 8 to 15% by weight of polymethyl methacrylate, are mixed at 20 to 40 ℃ Stirred for 25-35 minutes to form a primary mixture, The primary mixture, 30 to 45% by weight of aluminum hydroxide, and 5 to 15% by weight of calcium carbonate are mixed and stirred at 20 to 40 ° C. for 25 to 35 minutes to form a secondary mixture, The secondary mixture and 15 to 25% by weight of glass fibers are mixed and stirred at 20 to 40 ° C. for 6 to 10 minutes to form a tertiary mixture in a bulk state. The tertiary mixture is put into a mold and pressurized for a predetermined time depending on the thickness of the product at a pressure of 50 to 160kg / cm ² at 130 to 150 ℃ molded method for dye sublimation transfer thermosetting resin composition characterized in that the. Dispersant, sunscreen, antioxidant and silane in 10 to 15% by weight of bisphenol-type unsaturated polyester resin, 8 to 15% by weight of polymethyl methacrylate, 30 to 45% by weight of aluminum hydroxide and 5 to 15% by weight of calcium carbonate 3 to 5% by weight of the first additive, comprising at least one of a coupling agent and an internal mold release agent, is mixed and stirred at 20 to 40 ° C. for 25 to 35 minutes, A final mixture is prepared by simultaneously adding 0.3 to 0.4% by weight of the second additive and 0.2 to 0.3% by weight of the thickener including at least one of a curing agent and a polymerization inhibitor, and then dispersing it completely to prepare a final mixture. Prepared to have a glass fiber content of 15 to 25% by weight in a three-day thickening (aging) process at a temperature of 30 to 35 ℃ to obtain a thickened sheet mixture, After the protective film is removed is put into a mold and pressurized for a predetermined time depending on the product thickness at a pressure of 70 to 160kg / cm ² at 130 to 150 ℃, the method for producing a thermosetting resin composition for dye sublimation transfer. A transfer ink is printed on a paper that can be transferred by screen printing, offset printing, gravure printing, or ink jet printer, and the surface of the thermosetting resin composition for dye sublimation according to claim 1 or 2 A method of printing a heat-curable resin composition for dye sublimation, characterized in that for attaching the transfer paper to a heat transfer pressurized heat transfer printing.