KR100289099B1 - An unsaturated polyester resin composition having dyeing-supressed property and a method for preparation thereof, and a product manufactured by molding the same - Google Patents

Abstract

The present invention relates to a hard dyeing unsaturated polyester resin composition, a method for producing the same, and a molded article molded therefrom. The unsaturated polyester resin composition provided by the present invention has the property that the molded article molded therefrom is not dyed. These properties can be used to make selective or partially dyed button moldings.

Description

An unsaturated polyester resin composition having dyeing-supressed property and a method for preparation according to the present invention, and a product manufactured by molding the same

The present invention relates to a hard dyeing unsaturated polyester resin composition, a method for producing the same, and a molded article molded therefrom. The unsaturated polyester resin composition provided by the present invention has the property that the molded article molded therefrom is not dyed. These properties can be used to make selective or partially dyed button moldings.

In general, when the button is manufactured using an unsaturated polyester resin, the color of the button is given by a dyeing process, and before the resin is cured, each color pigment is first put into a sheet or rod shape (hereinafter, And "methods" and a method of forming a sheet or rod without dyeing and dyeing each color (hereinafter referred to as "dye dye"). Each method is called an ombre button and a posterior button.

The ombre buttons may produce buttons having a specific shape or color contrast, but have the disadvantage of having the same color buttons as the amount of pre-colored resin in one operation. On the other hand, the rear button can be adjusted to a desired color in small amounts to obtain as many buttons as necessary, but there is a disadvantage in that the dyeing to an undesired part due to the overall dyeing has a problem in that the product quality and added value of the product are lowered.

Accordingly, the present inventors have studied diligently in order to enable partial or selective dyeing in unsaturated polyester resin compositions for back dyeing buttons, and as a result, dyeing when a certain amount of isophthalic acid ( m -phthalic acid) is blended as a saturated acid It has been found that this is not the case and the present invention has been completed.

Accordingly, it is an object of the present invention to provide a non-stainable unsaturated polyester resin composition capable of producing a button capable of partial, selective dyeing.

Another object of the present invention is to provide a method for producing the above-mentioned non-stainable unsaturated polyester resin composition.

In addition, another object of the present invention is to provide a molded article molded using the above-mentioned non-stainable unsaturated polyester resin composition.

1 is a dyeing process of buttons (BS-485) molded using the composition of Example 1 and buttons (BS-210) molded using a conventional composition for ortho-based buttons (Comparative Example 2) for comparison. This is a photograph showing the degree of dyeing obtained by applying to.

Figure 2 (A) is a photograph showing the finished product of the after-dyed button molded and dyed by using the non-stainable unsaturated polyester resin composition of the present invention and the composition for general ortho-based buttons, Figure 2 (B) is for comparison It is a photograph which shows the color difference before and after dyeing of the button shape | molded using the composition for general ortho type buttons.

The non-stainable unsaturated polyester resin composition according to the present invention is characterized by containing 15 to 30 parts by weight of isophthalic acid as the saturated acid reacting with the polyhydric alcohol.

More specifically, the non-stainable unsaturated polyester resin composition according to the present invention is characterized by being composed of the following components (A) to (I) based on 100 parts by weight of the composition:

(A) 22 to 33 parts by weight of polyhydric alcohol;

(B) 15 to 30 parts by weight of isophthalic acid as saturated acid;

(C) 17.829-25 weight part unsaturated acid;

0.01 to 0.02 parts by weight of (D) polymerization inhibitor;

(E) 0.1 to 0.2 parts by weight of plasticizer;

(F) 0.001 to 0.02 parts by weight of copper salt;

(G) 0.05 to 0.1 parts by weight of paraffin wax;

(H) 0.01 to 0.02 parts by weight of ultraviolet absorbent; And

(I) 30-45 weight part of crosslinking agents.

The present invention relates to isophthalic acid in place of o -phthalic acid as a saturated acid in a conventional unsaturated polyester resin composition (hereinafter referred to as "ortho-based unsaturated polyester resin composition") containing o -phthalic acid as a saturated acid. Except for containing ( m -phthalic acid), it is the same structure as the conventional ortho-type resin composition.

o -Phthalic acid is more advantageous than isophthalic acid in terms of transparency and price of resin, and its use range is wide. However, when applied to the post-treatment process as described above, since the whole dyeing is made in itself, there is a limit to partial or selective dyeing itself.

On the other hand, it was confirmed by the present inventors that the isophthalic acid is used instead of o -phthalic acid as the saturated acid, and no dyeing is performed in the post dyeing process. In the case of using such hard dyeing properties of isophthalic acid, it can be partially or selectively dyed by appropriately blending with a general ortho-based resin composition and molding, thereby increasing the merchandise and added value of the product.

Hereinafter, the present invention will be described in more detail.

As described above, the non-stainable unsaturated polyester resin composition according to the present invention has the same structure as the conventional ortho-based resin composition, except that it contains isophthalic acid instead of conventional o -phthalic acid as saturated acid. have. That is, manufacture of an unsaturated polyester resin composition consists of the primary ester reaction of polyhydric alcohol and saturated acid, and the secondary ester reaction of polyhydric alcohol and unsaturated acid.

Specifically, it consists of the following steps:

(1) Primary Ester Reaction:

20 to 30 parts by weight of polyhydric alcohol and 15 to 30 parts by weight of saturated acid are injected under nitrogen supply, and then gradually heated up to about 215 ° C over about 14 hours, and the acid value is measured at 215 ° C every hour to reach an acid value of 2 or less. Cool down to 160 ° C.

(2) secondary ester reaction:

To (1), 1/10 of polyhydric alcohol is added to the amount of polyhydric alcohol added in (1) above, and 17.829 to 25 parts by weight of unsaturated acid at about 140 ° C., and then to about 225 ° C. for about 10 hours. The temperature is gradually raised over the temperature, and dilution is carried out every hour while maintaining at 225 ° C., to dilute the resin solid solution / toluene = 60/40 to start the cooling when the acid value 2 and the viscosity UV are reached.

(3) dilution:

0.01 to 0.02 parts by weight of a polymerization inhibitor and 0.1 to 0.2 parts by weight of a plasticizer are added to (2) at about 180 ° C, and the copper salt is 0.001 to 0.02 when it reaches about 60 ° C while diluting to 30 to 45 parts by weight of a crosslinking agent at about 170 ° C. A weight part, paraffin wax 0.05-0.1 weight part, a ultraviolet absorber 0.01-0.02 weight part are inserted, and cooling is stopped.

In the present invention, when the amount of isophthalic acid used is less than 15 parts by weight, the dye resistance is lowered. When the amount of isophthalic acid is more than 30 parts by weight, there is no problem in the dye resistance, but in terms of cost, commercial use as an unsaturated polyester resin for buttons is not only possible but also saturated polyols. Since the number of ester linkages increases, the property of hardening increases, and the value of the commodity decreases. Therefore, Preferably it is good to use in the range of 15-30 weight part.

In addition, the polyhydric alcohols used in the above-mentioned primary and secondary ester reactions can be used those that have been commonly used, specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like can be exemplified. Among these, propylene glycol is particularly preferable.

In addition, the unsaturated acid used in the above secondary ester reaction can be used that has been commonly used, specifically, maleic anhydride, fumaric acid and the like can be exemplified.

Examples of the polymerization inhibitor include hydroquinone, p- t-butyl catechol, and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and the like.

A styrene monomer is especially preferable as a crosslinking agent, In addition, acrylate etc. can be used.

The copper salt is preferably a divalent copper salt, and specific examples thereof include copper naphthenate, copper octoate, and the like. As a ultraviolet absorber, a benzotriazole type ultraviolet absorber is preferable, and a benzotriazole, benzophenone, ethyl salicylate, etc. are mentioned specifically ,.

The non-stainable unsaturated polyester resin composition produced by the above manufacturing method can be molded alone, but preferably, a button selectively or partially dyed can be obtained by appropriate blending with a general ortho-based unsaturated polyester resin composition { See FIG. 2 (A)}.

Dyeing is carried out by the post-dyeing method, which is formed by a rod mold or a centrifugal molding machine, and then immersed at a temperature of 60 to 95 ° C. in a dye bath to which a desired dye and a mordant for increasing the dyeing speed are added.

The range of use of the non-stainable unsaturated polyester resin composition of the present invention is not limited to buttons, but can be applied to any molded article molded using a conventional general ortho-based unsaturated polyester resin composition. In particular, when the molded article is intended for partial or selective dyeing, the intended purpose can be achieved by using in combination with a general ortho-based unsaturated polyester resin composition.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated more concretely based on an Example.

<Example 1 and Comparative Examples 1-2>

ingredient Content (parts by weight) Example 1 Comparative Example 1 Comparative Example 2 Propylene glycol 27.5 27.5 27.5 Isophthalic acid 20 5 - o -phthalic acid - 15 20 Fumaric acid 20 20 20 Hydroquinone 0.004 0.004 0.004 p -t-butylcatechol 0.005 0.005 0.005 Dibutyl phthalate 0.15 0.15 0.15 Naphthenic copper 0.001 0.001 0.001 Paraffin wax 0.08 0.08 0.08 Benzotriazole 0.01 0.01 0.01 Styrene 32.25 32.25 32.25

<Production method>

After 25 parts by weight of propylene glycol and 20 parts by weight of saturated acid (isophthalic acid or o -phthalic acid) were injected under nitrogen supply, the temperature was gradually raised to about 215 ° C over about 14 hours, and the acid value was measured at 215 ° C every hour to determine the acid value of 2 or less. It cooled to about 160 degreeC after becoming.

The remaining amount of propylene glycol (2.5 parts by weight) was inserted at 180 ° C, 20 parts by weight of fumaric acid was inserted at about 140 ° C, and the temperature was gradually raised to about 225 ° C over about 10 hours, and the resin solid solution / The mixture was diluted with toluene = 60/40 and cooled when the acid value 2 and viscosity UV reached.

Hydroquinone and p- t-butylcatechol were introduced at about 180 ° C., and copper salt, paraffin wax, and benzotriazole were inserted at about 60 ° C. while diluted with styrene at about 170 ° C., and cooling was stopped.

<Molding>

In the centrifugal molding machine, the resin composition prepared above was cured with cobalt accelerator 1% and methyl ethyl ketone peroxide 1% to form a sheet.

<Dyeing>

In the dyeing tank to which about 1 g of dye and about 0.2 g of mordant were added per 1 liter of water, the molded articles obtained on the sheet were left to stand for 10 minutes and dyed evenly.

After sufficient dyeing, taken out, washed with clean water, centrifuged and dried to measure the degree of dyeing.

<Result>

As a result, the button molded using the unsaturated polyester resin prepared in the composition of Example 1 was not dyed at all {see Figure 1}, while the unsaturated prepared in the composition of Comparative Examples 1 and 2 The buttons molded using the polyester resin were dyed evenly (see Figs. 1 and 2 (B)).

The unsaturated polyester resin composition provided by the present invention has the property that the molded article molded therefrom is not dyed. These properties can be used to make selective or partially dyed button moldings.

Claims (5)

In the unsaturated polyester resin composition for button production consisting of polyhydric alcohol, saturated acid, unsaturated acid, polymerization inhibitor, plasticizer, copper salt, paraffin wax, ultraviolet absorber and crosslinking agent, isophthalic acid is used as saturated acid with respect to 100 parts by weight of the composition. The non-staining unsaturated polyester resin composition characterized by containing ~ 30 parts by weight. The non-staining unsaturated polyester resin composition according to claim 1, which is composed of the following components (A) to (I) based on 100 parts by weight of the composition: (A) 22 to 33 parts by weight of polyhydric alcohol; (B) 15 to 30 parts by weight of isophthalic acid as saturated acid; (C) 17.829-25 weight part unsaturated acid; 0.01 to 0.02 parts by weight of (D) polymerization inhibitor; (E) 0.1 to 0.2 parts by weight of plasticizer; (F) 0.001 to 0.02 parts by weight of copper salt; (G) 0.05 to 0.1 parts by weight of paraffin wax; (H) 0.01 to 0.02 parts by weight of ultraviolet absorbent; And (I) 30-45 weight part of crosslinking agents. The non-staining unsaturated polyester resin composition according to claim 2, which is composed of the following components (A) to (I) based on 100 parts by weight of the composition: (A) 22 to 33 parts by weight of propylene glycol; (B) 15 to 30 parts by weight of isophthalic acid; (C) 17.829-25 weight part of fumaric acid or maleic anhydride; (D) 0.01 to 0.02 parts by weight of hydroquinone and p- t-butylcatechol; (E) 0.1 to 0.2 parts by weight of dibutyl phthalate; (F) 0.001 to 0.02 parts by weight of copper salt; (G) 0.05 to 0.1 parts by weight of paraffin wax; (H) 0.01 to 0.02 parts by weight of benzotriazole; And (I) 30-45 weight part of styrene monomers. Molded article molded using the non-staining unsaturated polyester resin composition of claim 1. The molded article according to claim 4, wherein the molded article is a button.