KR100390805B1 - Unsaturated Polyester Resin Composition Containing Thermochromic or Photochromic and Molded Product Made Therefrom - Google Patents

Abstract

The present invention provides an unsaturated polyester resin composition in which physical properties are not lowered even by the inclusion of a thermosensitive or photosensitive pigment material, molded articles such as buttons or accessories formed by curing the same, and a method of manufacturing the same. The unsaturated polyester resin composition of the present invention is an unsaturated polyester made of (A) an acid component and (b) a dihydric alcohol component consisting of (A) (a1) saturated dibasic acid component and (a2) unsaturated dibasic acid component. , (B) modified polyacrylate, (C) polysiloxane, (D) polymerizable monomer, and may further include (E) thermosensitive or photosensitive pigment material and / or (F) curing agent. In addition to the above components, the unsaturated polyester resin composition of the present invention may further include (G) ordinary pigments and / or (H) curing accelerators, and may further include various additives as required. The molded article of the present invention is produced by curing the above unsaturated polyester resin composition.

Description

Unsaturated Polyester Resin Composition Containing Thermochromic or Photochromic and Molded Product Made Therefrom

The present invention relates to an unsaturated polyester resin composition comprising a thermosensitive or photosensitive pigment material, a molded article produced therefrom and a method for producing the same.

Currently, unsaturated polyester resins are widely used as synthetic resins for buttons. Unsaturated polyester resins generally have a three-dimensional network structure by crosslinking a polymerizable monomer having a double bond with an unsaturated polyester, and have excellent physical properties in terms of workability, heat resistance, chemical resistance, impact resistance, and the like. It is suitable for buttons because of its small specific gravity and beautiful appearance after molding.

Buttons are attached to various clothes and basically lock, and in addition, they can be used as modern accessories. In order for a button to function as an accessory, it must be able to visually stimulate the human aesthetic in addition to the basic function of the button. Therefore, recently, buttons having various patterns have started to appear.

On the other hand, functional dyes, such as thermochromic or photochromic, are used not only in ink, recording paper, etc., but also in various fields. For example, they may be used in mugs to decorate mugs differently depending on the temperature, or they may be attached to beer bottles to serve as temperature indicators. The thermosensitive pigment material is a material that changes color reversibly or irreversibly in response to a temperature change, and is classified into a liquid crystal and a leucodye. Liquid crystals are used in thermometers, stress testers, etc., but are very sensitive to temperature, but have a disadvantage in that they are difficult to handle. Although leuco dyes are much less sensitive to temperature than liquid crystals, they are used in various fields in which temperature sensitivity is not so great that they are difficult to handle compared to liquid crystals. The photosensitive pigment material is a material that exhibits color reversibly or irreversibly when exposed to UV light (sunlight). These thermosensitive or photosensitive pigment materials can be combined with ordinary pigments (pigments, dyes, etc.) to produce a variety of colors depending on the temperature or exposure to sunlight, which can stimulate human vision as well as temperature indicators. For example, it is used for the surface design of mugs, the decoration of toys, etc.

However, there have been no examples in which the above-mentioned thermosensitive or photosensitive pigment material is used for buttons requiring a function as an accessory, and a brilliant button is not yet applied, and there are not many examples applied to other accessories.

It is an object of the present invention to provide an unsaturated polyester resin composition which can be used to prepare moldings such as buttons or accessories in which physical properties are not lowered even by the inclusion of a thermosensitive or photosensitive pigment material.

It is also an object of the present invention to provide a molded article such as a button or an accessory which is formed by curing the unsaturated polyester resin composition and whose physical properties are not degraded even by the inclusion of a thermosensitive or photosensitive pigment substance, and a method for producing the same.

In addition, an object of the present invention is to provide a button and a method of manufacturing a natural pattern is formed by mixing a variety of colors, as well as a button of a single color or a pure single color mixed with several colors.

In addition, an object of the present invention can be used as a raw material for producing a molded article such as a button or an accessory that does not lower the physical properties even by containing a thermosensitive or photosensitive pigment material, unsaturated with good compatibility with the above-mentioned thermosensitive or photosensitive pigment material It is providing a polyester resin composition. The unsaturated polyester resin composition of the present invention has good compatibility with not only the above-described thermosensitive or photosensitive pigment substance but also an organic aromatic component.

1 shows an apparatus for manufacturing a button having various colors by forming a pattern by mixing liquid materials of various colors, which are unsaturated polyester resin compositions, without mixing them completely, according to one embodiment of the present invention. .

FIG. 2 shows a plan and side cross-sectional view of the cylinder of FIG. 1. FIG.

Figure 3 shows an apparatus for manufacturing a button having a pattern by a variety of colors by mixing the liquid material of the various colors of the unsaturated polyester resin composition to form a pattern without mixing completely, according to another embodiment of the present invention .

Figure 4a shows the tools used to prepare the polyester resin composition of the present invention into sheets of multi-plates having various patterns by centrifugal molding.

Figure 4b shows an example of producing a button blank and a button by punching and processing a multi-patterned multi-sheet sheet formed from the polyester resin composition of the present invention by centrifugal molding method.

The above object is achieved by the unsaturated polyester resin composition of the present invention and a molded article such as buttons and accessories and a method for producing the same.

The unsaturated polyester resin composition of the present invention is an unsaturated polyester made of (A) an acid component and (b) a dihydric alcohol component consisting of (A) (a1) saturated dibasic acid component and (a2) unsaturated dibasic acid component. , (B) modified polyacrylate, (C) polysiloxane, and (D) polymerizable monomer. Moreover, the unsaturated polyester resin composition of this invention can contain the (E) thermosensitive or photosensitive pigment | dye substance, and / or (F) hardening | curing agent. In addition to the above components, the unsaturated polyester resin composition of the present invention may further include (G) a conventional pigment and / or (H) a curing accelerator, and may further include various additives as required.

Molded articles such as buttons or accessories of the present invention are prepared by curing the above unsaturated polyester resin composition. For example, the button of the present invention is injected into the above-mentioned unsaturated polyester resin composition, which is a liquid material, into a pipe suitable for the size of the button, and then cured at a predetermined temperature, taken out of the rod, and softened. And cut to form a button blank. This button blank is processed into a predetermined button shape and then subjected to a polishing process and a polishing process to complete a button as a final product. Also, instead of using rods in other ways, centrifugal molding can be used to vary the color of the buttons and to make the decoration more colorful.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In general, the unsaturated polyester resin refers to a cured resin obtained by dissolving unsaturated polyester in a vinyl monomer such as styrene and then polymerizing by adding a radical initiator. These unsaturated polyester resins are used to make fiber reinforced plastics (FRP) by making composite materials such as glass fibers.

The unsaturated polyester resin as described above can also be used as a raw material for the buttons. Prior to the present invention, the present inventors prepared a button by curing a specific composition of an unsaturated polyester resin composition not containing a thermosensitive or photosensitive pigment material, and furthermore, the unsaturated polyester resin composition of such a composition was applied to a thermosensitive or photosensitive pigment material. It was intended to produce a button by addition. However, when a button was manufactured by adding a thermosensitive or photosensitive pigment substance to an unsaturated polyester resin composition having such a composition, the button was obtained in a state in which physical properties were not satisfactory. In the following, first, the present invention will be described after the unsaturated polyester resin composition which does not contain a thermosensitive or photosensitive pigment | dye substance, and the problem at the time of making it contain this pigment | dye substance before this invention is described.

Prior to the present invention, the present inventors constructed an unsaturated polyester resin composition including an unsaturated polyester, a polymerizable monomer and a curing agent to produce a button.

Here, the polymerizable monomer in the unsaturated polyester resin composition is used in the range of 5 to 95% by weight based on the total weight of the polymerizable monomer and the unsaturated polyester.

The curing agent is used in an amount of about 0.3 to 3% by weight based on the total weight of the above-described polymerization components. In addition, in some cases, a curing retarder, a curing accelerator, a pigment, and the like may be included.

The unsaturated polyester used above is obtained by reacting a saturated dibasic acid component and an unsaturated dibasic acid component with a dihydric alcohol component.

At this time, phthalic anhydride or phthalic anhydride is used as the saturated dibasic acid component, and maleic anhydride (or maleic acid) or fumalic acid anhydride (or fumaric acid) as the unsaturated dibasic acid component. Etc. At this time, the saturated dibasic acid component does not have a double bond in itself or has only a non-reactive double bond (such as a benzene ring double bond) and thus does not provide a reactive double bond in the unsaturated polyester. Participate in the skeleton to provide the required physical properties. On the contrary, the unsaturated dibasic acid component itself has a reactive double bond to form a backbone of the unsaturated polyester, and to provide the unsaturated polyester with a reactive double bond capable of crosslinking with the polymerizable monomer. At this time, the ratio of the saturated dibasic acid component and the unsaturated dibasic acid component may be used in a molar ratio of about 1: 0.8 to 1.3.

In the above, ethylene glycol, diethylene glycol, and propylene glycol are used as the dihydric alcohol component. Here, ethylene and diethylene glycol are difficult to use alone because of poor compatibility with styrene, and is used in combination with propylene glycol. Ethylene glycol is used for improving mechanical strength and hardness, and diethylene glycol is used for mechanical strength and impact resistance. In addition, propylene glycol is used because of its excellent mechanical strength and hardness and its good compatibility with styrene. The ratio of these dihydric alcohol components depends on the desired physical properties, but for example, the ratio of ethylene glycol: diethylene glycol: propylene glycol may range from 1: 0.8 to 1.2: 0.8 to 1.2 in molar ratio. On the other hand, the ratio of the acid component and the dihydric alcohol component can be used in the range of about 1: 0.6 to 1.4 in molar ratio, preferably in the range of about 1: 1 to 1.1.

The unsaturated polyester resin composition described above was cured by a conventional method to produce a button. The button thus manufactured had suitable physical properties as a button.

However, in order to manufacture the button containing the dyeing material, when the button is prepared by adding the dyeing material to the unsaturated polyester resin composition, the hardness of the produced button is significantly lowered, and color is not uniformly expressed. Color separation occurs, and in particular, when a conventional pigment is added, color separation occurs between the pigment material and the conventional pigment, and cracks occur even in a soft state to obtain a button of satisfactory quality. Could not. In addition, there was a problem that bubbles are generated. The above phenomenon occurs because the pigment material acts as a plasticizer in the mixing with the unsaturated polyester resin to decrease the hardness, the color separation phenomenon of the pigment material itself due to the physical and chemical incompatibility with the unsaturated polyester resin And a color separation phenomenon between the pigment material and the usual pigment. Bubble generation is also considered to be due to the above reasons.

Thus, recognizing the fact that a button of satisfactory quality cannot be produced with an unsaturated polyester resin composition designed without considering the addition of the coloring matter material as described above, the present inventors have compatibility with the coloring matter material Efforts have been made to develop new unsaturated polyester resin compositions capable of retaining the physical properties as buttons, and as a result, the present invention has been completed.

Therefore, the present invention relates to an unsaturated polyester resin composition in which physical properties are not lowered even by containing the dye substance, a molded article such as a button formed by curing the same, and a manufacturing method thereof.

The unsaturated polyester resin composition of the present invention is an unsaturated polyester made of (A) an acid component and (b) a dihydric alcohol component comprising (A) (a1) saturated dibasic acid component and (a2) unsaturated dibasic acid component. , (B) modified polyacrylate, (C) polysiloxane, and (D) polymerizable monomer. Moreover, the unsaturated polyester resin composition of this invention may further contain the (E) thermosensitive or photosensitive pigment | dye substance, and / or (F) hardening | curing agent. Moreover, the unsaturated polyester resin composition of this invention can further contain the (G) normal pigment and / or (H) hardening accelerator in addition to the above.

The (a1) saturated dibasic acid component used as a structural component of (A) unsaturated polyester in the unsaturated polyester resin composition of this invention forms a frame | skeleton of unsaturated polyester. As such a saturated dibasic acid component, phthalic anhydride (or phthalic acid), isophthalic acid, terephthalic acid, 4-hydrogen phthalic anhydride, adipic acid, hepatic anhydride, etc. are mentioned. Among these, it is preferable to contain isophthalic acid or terephthalic acid. As a more preferable form, phthalic anhydride (or phthalic acid) is used in combination with isophthalic acid or terephthalic acid. At this time, as mentioned above, phthalic anhydride contributes to physical properties such as mechanical strength of unsaturated polyester as a component that forms a skeleton of unsaturated polyester, and is cured when used in combination with maleic anhydride as an unsaturated dibasic acid component. It serves to balance the resin's physical properties. On the other hand, isophthalic acid or terephthalic acid, like phthalic anhydride, is a component that forms the backbone of unsaturated polyester, which not only contributes to water resistance, but also contributes to improving compatibility of the unsaturated polyester with the pigment material. The ratio of phthalic anhydride and isophthalic acid or terephthalic acid used in the present invention may be in the range of 1: 0.5 to 1.5 in molar ratio.

On the other hand, the (a2) unsaturated dibasic acid component not only forms the backbone of the unsaturated polyester, but also provides the unsaturated polyester with a reactive double bond capable of causing crosslinking reaction with the polymerizable monomer. As such unsaturated dibasic acid component, maleic anhydride (or maleic acid), fumaric acid, or the like, which are commonly used, may be used.

In the present invention, the ratio of the unsaturated dibasic acid component and the saturated dibasic acid component used to form the unsaturated polyester may be in a range of about 1: 0.5 to 1.5 in molar ratio depending on the required physical properties.

On the other hand, as the (b) dihydric alcohol component used to form the unsaturated polyester of the present invention, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, propylene oxide addition bisphenol A etc. can be mentioned. It is preferable that the unsaturated polyester of this invention contains neopentyl glycol, hydrogenated bisphenol A, or propylene oxide addition bisphenol A. Especially preferably, it consists of ethylene glycol, propylene glycol, dipropylene glycol, and neopentyl glycol. Here, ethylene glycol and propylene glycol are used to provide the basic properties. In particular, ethylene glycol is less compatible with vinyl monomers such as styrene, and therefore uses less and uses more propylene glycol. Dipropylene glycol is used in a small amount to impart plasticity, neopentyl glycol is a component added to solve or alleviate the problems caused by the mixing of the pigment material. In the present invention, based on the total weight of the dihydric alcohol component, 7 to 15% by weight of ethylene glycol, 35 to 45% by weight of propylene glycol, 5 to 10% by weight of dipropylene glycol and 36 to 53% by weight of neopentyl glycol. Can be configured.

The unsaturated polyester (A) used in the present invention is 3 to 7% by weight of ethylene glycol, 15 to 21% by weight of propylene glycol, 2 to 5% by weight of dipropylene glycol, based on the total weight of the components for preparing unsaturated polyester. It is preferred to be prepared by the reaction components consisting of 15 to 25% by weight of neopentyl glycol, 15 to 25% by weight of phthalic anhydride, 15 to 25% by weight of maleic anhydride and 15 to 25% by weight of terephthalic acid. In the above, phthalic anhydride may be used instead of phthalic anhydride as equivalent to phthalic acid, and the weight of phthalic acid added may be calculated in terms of the weight of phthalic anhydride. The same applies to maleic anhydride.

The modified polyacrylate (B) used in the present invention is used to prevent the color separation of the pigment material and the color separation between the pigment material and the conventional pigment in the production of moldings such as buttons and accessories. It is a component to be added. Such modified polyacrylates are blended with unsaturated polyesters in unsaturated polyester resin compositions and also improve the compatibility of the unsaturated polyesters with the pigment material added, thereby resulting in color separation resulting from the addition of the pigment material in the moldings. The phenomenon can be prevented. Such modified polyacrylates should be added in an amount sufficient to prevent color separation, but if added too much, they may damage the inherent properties of the unsaturated polyester resin composition. It is preferable to add in the quantity of the range which does not largely affect the physical property of an ester resin composition. The amount of such modified polyacrylate is preferably in the range of 1 to 30% based on the weight of the unsaturated polyester to be formed.

The polysiloxane (C) used in the present invention is a component added to prevent bubbles from being generated by the pigment material in the production of moldings such as buttons and accessories. Such polysiloxane should be added in an amount sufficient to prevent bubbles from forming due to the addition of the pigment material in the molding, but if added too much, it may damage the inherent properties of the unsaturated polyester resin composition. It is preferable to add in the quantity of the range which does not affect the physical property of an unsaturated polyester resin composition largely, preventing generation | occurrence | production. The amount of such polysiloxane is preferably in the range of 1 to 30% by weight of the unsaturated polyester to be formed.

The (A) unsaturated polyester contained in the unsaturated polyester resin composition of the present invention crosslinks with (D) the polymerizable monomer in the presence or absence of the (F) curing agent to form a three-dimensional network structure. In this case, in addition to the (A) unsaturated polyester and (D) polymerizable monomer, the unsaturated polyester resin composition is added to improve physical properties of the unsaturated polyester and to improve compatibility with the coloring matter material (B). Modified polyacrylates and (C) polysiloxanes. In addition, (F) the curing agent and / or (E) the pigment material may be further included, and in some cases, (G) conventional pigments and / or (H) curing accelerator may be further included. In addition, when curing an unsaturated polyester resin composition, it is preferable to add a hardening | curing agent, and a small amount of a curing retarder or an inhibitor may be added in order not to naturally harden the unsaturated polyester resin composition which does not contain a hardening | curing agent. .

As the polymerizable monomer (D) contained in such an unsaturated polyester resin composition, styrene, chlorostyrene, α-methylstyrene, vinyltoluene, vinyl acetate, acrylate ester, diacrylphthalate, etc. may be used, and in particular, styrene is mainly used. do. These polymerizable monomers may be used alone, or two or more kinds of mixtures may be used. The polymerizable monomer may be used in an amount of 5 to 95% by weight, preferably 10 to 70% by weight, particularly preferably 25 to 55% by weight, based on the total weight of the unsaturated polyester and the polymerizable monomer. . These polymerizable monomers undergo radical reactions with the unsaturated polyesters by radical initiation of the curing agent or by heat to crosslink the unsaturated polyesters.

As the (F) curing agent used in the unsaturated polyester resin composition of the present invention, a radical polymerization initiator generally used may be used as it is. For example, methyl ethyl ketone peroxide, benzoyl peroxide, dibenzoyl peroxide, tert-butyl peroxy benzoate, azobisisobutylonitrile, t-butyl cumyl peroxide, cumene hydroperoxide, etc. can be used. . As the (H) accelerator, for example, organometallic salts such as cobalt octate and cobalt natate, organic amines such as dimethylaniline and diethylaniline, mercaptans such as dodecyl mercaptan and the like can be used. . The amount of curing agent used may vary depending on the rate and conditions of curing and ranges from 0.3 to 3% by weight relative to the total weight of unsaturated polyesters and polymerizable monomers. In addition, the quantity of the hardening accelerator used is 0.3-3 weight% of range.

As the (G) common pigment used in the unsaturated polyester resin composition of the present invention, a conventional pigment having no sensitivity to temperature or light can be used. For example, zinc oxide, titanium dioxide, lithopone, basic carbonate, etc. as a white pigment, iron oxide black, carbon black, etc. as a black pigment, lead chromate as a yellow pigment, yellow iron oxide, cadmium yellow, titanium yellow, etc. Chrome pigments such as chromium orange, molybdate orange, red pigments such as red iron oxide, lead trioxide, cadmium red, etc., purple pigments such as manganese violet, blue pigments such as blue pigment, ultramarine blue, cobalt blue, etc. And inorganic pigments such as emerald green and viridane, and include aluminum powder and bronze powder as metallic gloss, zinc sulfide as fluorescent pigment, and basic lead carbonate, bismuth oxychloride, mica titanium and arsenic acid as pearlescent pigments. Special pigments, such as a solder, are mentioned. Moreover, an azo pigment, a phthalocyanine pigment, etc. can be used as an organic pigment. The amount of the pigment used varies depending on the kind of pigment and the desired color concentration, but is in the range of 0.001 to 5% by weight based on the total weight of the unsaturated polyester and the polymerizable monomer.

The (E) thermosensitive pigment substance used in the unsaturated polyester resin composition of the present invention is preferably a reversible substance. The thermosensitive or photosensitive pigment material is preferably used at 5 to 15% by weight based on the total weight of the unsaturated polyester and the polymerizable monomer. As mentioned above, the thermosensitive pigment material is generally classified into a liquid crystal and a leuco dye, and the liquid crystal is very sensitive to temperature change and reacts very accurately. Thus, the liquid crystal is applied to the field that can accurately represent the temperature change, such as a thermometer. However, since leuco dye is relatively insensitive to temperature change compared to liquid crystal, it is difficult to use it in the field which can represent temperature change accurately, such as a thermometer. Usually, in leuco dyes, the temperature (coloring temperature or color development temperature) when changing from a colored state to a bleached state or from a bleached state shows a difference of about 3 to 6 ° C. However, it can be used in a wide range of applications where it is not necessary to accurately reflect temperature changes. This is because the leuco dye is easier to handle than the liquid crystal. Typically, thermochromic materials are mixtures of electron donating materials and electron accepting materials that are uniformly mixed, and these materials combine to form a color-expressing state below a certain temperature. . Conversely, above that particular temperature, the bonds between the two materials disappear and each material becomes independent and loses color. Typically, leuco dyes are electron donating materials. Although leuco dyes are colorless on their own, they have their own unique color when combined with electron accepting materials. In general, since the leuco dye does not have high light fastness, deformation or decomposition occurs due to continuous exposure to light, and thus the thermosensitive pigment material loses its function. In order to improve such light stability, an antioxidant, a light stabilizer, etc. may be added to the thermosensitive pigment material to increase light resistance. In addition, it may include a regulator for controlling the color development temperature (coloring temperature) of the thermosensitive pigment material. In addition, a reaction medium may be used to promote the reaction between the electron donating material and the electron accepting material. In addition, other materials may be added as needed. It does not specifically limit as a thermosensitive pigment | dye material which can be used by this invention, Examples of such a thermosensitive pigment | dye material are disclosed by US 5,879,438 and 5,919,404. In addition, as an example of the thermosensitive pigment material used in the present invention, TBL-30 Blue (as a pigment, 1-diazo-2,5-dibutoxy-4-morpholino), manufactured by Nissei Chemicals, Inc. Benzene chloride, bisphenol A epoxyacrylate as developer resin, diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide as homeostatic agent, and dimethyl silicone as silicone modifier, TR -30 Red (3,3-bis (1-butyl-2-methyl-1H-indol-3-yl) -1- (3H) -isobenzofuranone as a pigment, other coloring agents, antioxidants, silicone modifiers Same as above), TY-30 Yellow (2-hydroxy-3-naphthoic morpholinopropylamine as pigment, other coloring agents, antioxidants, silicone modifiers same as above), TB-31 Black ( 2,3-dihydroxynaphthalene-6-sulfonic acid, other coloring agents, antioxidants, and silicone modifiers are the same as the pigments).

In addition, the photochromic material used in the present invention is a material that exhibits color by changing the structure of the compound by irradiation of ultraviolet light (sunlight). It does not specifically limit as such a photosensitive pigment | dye material. An example of the structural change caused by the photosensitive pigment material and UV irradiation can be seen in the figure below.

The unsaturated polyester resin composition of the present invention basically contains (A) unsaturated polyester, (B) modified polyacrylate, (C) polysiloxane and (D) polymerizable monomer. The unsaturated polyester resin composition is a modified and improved unsaturated polyester resin composition previously used by the present inventors in order to improve compatibility with the thermosensitive or photosensitive pigment material used in the present invention. That is, (A) unsaturated polyesters were prepared using the raw materials and composition ratios as described above for compatibility with the thermosensitive or photosensitive pigment material. In addition, the physical properties of the composition were further improved by including (B) modified polyacrylate and (C) polysiloxane that were not previously included in the composition. The composition ratio of the above components may be appropriately selected within the above-mentioned range in consideration of the basic physical properties required by the molding of the unsaturated polyester resin composition and compatibility with the coloring matter. The resin composition may solve the problem caused by the non-compatibility when adding a material having a non-compatibility with an unsaturated polyester such as a thermosensitive or photosensitive pigment material to prepare a functional molding such as a functional button. have. Materials having non-compatibility with unsaturated polyesters include the aromatic components disclosed in the specification of Korean Patent Application No. 1999-38968 already filed by the present inventors as well as the thermosensitive or photosensitive pigment material used in the present invention. In addition, a general organic dye, such as an electrochromic dye (Electrochromic), which is a functional dye may also be applicable. Inorganic pigments are not mixed or dissolved with other components in the unsaturated polyester resin composition, but are dispersed, whereas the materials are mixed or dissolved with other components and become uneven when the compatibility is not good.

In addition, when the inorganic pigment is added to the unsaturated polyester resin composition as well as the pigment material, the aggregation of the inorganic pigment may occur due to the increase of plasticity and increase of non-compatibility due to the addition of the pigment material. In the present invention, such a problem can be solved.

In addition to the above components, the unsaturated polyester resin composition of the present invention may further include the above-described pigment substance, and may further include a conventional pigment. When the pigment material used in the present invention is used alone, the molded product formed by the unsaturated polyester resin composition of the present invention exhibits color due to the pigment material below the color development temperature when cooled, and is heated. When the color disappears above the bleaching temperature. On the other hand, in the case where the pigment material is used in combination with a conventional pigment, the molded product formed by the unsaturated polyester resin composition of the present invention when the color is expressed by the pigment material below the color development temperature when cooled, the usual pigment It is mixed with the color of to show its intermediate color. For example, if the pigment material expresses blue and the normal pigment which is not affected by the temperature is red, the intermediate index purple is displayed below the color temperature when cooled. When the molded product is heated, the color of the pigment material disappears above the discoloration temperature, so that the molded product exhibits a color of a conventional pigment, for example, red color. In the design for the change of color with temperature, only a single said pigment | dye material, the combination of a single said pigment | dye material and a single conventional pigment, or the combination of a plurality of said pigment | dye materials, and a plurality of conventional pigments, etc. Can be used.

Now, a method for producing a button as an example of a molded article with the unsaturated polyester resin composition containing the pigment material of the present invention will be described.

First, the liquid material, which is the unsaturated polyester resin composition of the present invention described above, is poured into a pipe suitable for a button size. Under the present circumstances, the rod is sealed below by rubber | gum or another means, For example, the thing of diameter 10mm-50mm and length 1m can be used. Then, the unsaturated polyester resin composition injected into the rod is cured. At this time, the curing temperature is preferably a temperature of 50 to 120 ° C. Injecting the unsaturated polyester resin composition into the rod may be performed by a simple method, but the liquid materials may be injected into the rod to form a natural pattern by mixing them with each other without completely mixing the liquid materials of various colors. It may be. (This will be described later). Next, the unsaturated polyester resin molding cured and molded into the shape of a rod is cooled to room temperature and taken out of the rod. Subsequently, the solution is immersed in hot water, softened, and then cut to form a button blank. At this time, the temperature of the water for softening may be in the range of usually 90 ~ 100 ℃. The thickness of the button blank is usually about 2 to 15 mm. The button blank thus produced is processed into a predetermined button shape. At this time, the button blanks are automatically fed one by one to the button processing machine (automatic duplex machine), and the cranks in the machine transfer the blanks to the bite position. The conveyed button blanks are machined into various shapes by the rotating bite. Next, the button thus processed is subjected to a polishing and polishing process. In the polishing process, the processed buttons are mixed with water, rubble and diatomaceous earth, put into a polishing container, and then polished for about 8 to 12 hours at about 60 rpm. The polished button is then put into a polishing process. In the polishing process, the polished button is mixed with bamboo and light medicine and rotated at about 60 rpm for about 4 to 12 hours to obtain an excellent glossy button.

On the other hand, as described above, the method of injecting the unsaturated polyester resin composition of the present invention into the rod can be carried out as follows. That is, it is possible to inject materials of different colors, but not to mix them completely to give a single color, but to inject various colors to form a natural pattern.

1 and 3 show an apparatus for producing buttons having patterns in various colors by mixing the liquid materials of various colors which are unsaturated polyester resin compositions to form a pattern without mixing them completely. 2 shows a plan view and a side cross-sectional view of the cylinder of FIG. 1. First, referring to FIGS. 1 and 2, a rod 10 sealed by a lower rubber stopper 11 is placed, and a funnel 20 is installed on an upper portion of the rod to facilitate injection of a liquid material. The upper part of this funnel is provided with the cylinder 30 in which the two partitions 31 and 32 are formed at predetermined intervals centering on an origin. The cylinder is divided into three zones A, B and C by two partitions 31 and 32. The lower part of the cylinder is in the form of a block, and the lower part of the cylinder is evenly drilled with small holes 33 at positions corresponding to the three divided zones A, B and C. While rotating the cylinder installed in this way, when three liquid materials of different colors are injected into the zones A, B, and C of the cylinder 30, the materials of different colors are drilled into the bottom of the cylinder. Through the force of gravity. Thus, materials of different colors are mixed with each other and are injected into the rods without being completely mixed in the funnel 20. Thus, materials of different colors mixed with each other form a natural pattern. In the above, a cylinder divided into partitions by means of partitions is used as a means for mixing a plurality of liquid materials to form a pattern. The most suitable means as such means is a cylinder as described above, but a polygonal cylinder can be used in addition to the cylinder.

Alternatively, referring to FIG. 3, a rod 10 whose lower portion is sealed with a rubber stopper 11 is placed, and a pentagonal plate 40 is installed vertically on the upper portion thereof. The plate has a shape in which four points form a rectangle and an isosceles are formed by the fifth point 41. The fifth point 41 is installed directly on the rod 10. The jaw 42 is formed on the isosceles formed by the fifth point 41. The upper surface of the plate is provided with hoses A, B and C for supplying liquid materials of different colors. And, just below these hoses, the pin 51 which can be moved to the left and right in contact with the surface of the plate 40 is supported by the long base 50 installed horizontally. This elongate stand 50 is connected to the rotating body 60. Thus, when the rotating body 60 rotates to the left and right, the long table 50 is moved horizontally by receiving the rotational force. That is, the rotational movement of the rotating body 60 is changed to the horizontal movement of the long table 50. Since the mechanism for converting the rotational motion of the rotating body into a linear motion is known in the art, the specific structure is omitted in the drawings. When the long table 50 is moved horizontally from side to side, the pin 51 supported by it is also in close contact with the plate surface to perform horizontal movement from side to side. At this time, if the liquid material of different colors is supplied through the hoses (A, B and C), the supplied liquid material flows down by the action of gravity, and completely by the horizontal movement of the pin 51 It can be mixed with each other to form a pattern without being mixed. The mixed liquid materials continue to flow along the plate 40 by the action of gravity, and the liquid materials flowing down to the edge 42 of the plate 40 are guided by the jaw 42 installed at the edge of the plate. It is led to the lowest point 41 of the plate and injected into the rod 10 there. Some of the liquid materials mixed by the horizontal motion of the pins 51 are guided to the lowest point 41 of the plate while flowing by gravity, in particular under the guidance of the jaw 42 installed at the edge of the plate. More perfectly mixed together to form a nice pattern. In the above description, the pentagonal plate may be installed completely vertically, but may be inclined so that the liquid material may flow down by gravity along the plate surface. Instead of the pentagonal plate, the triangular plate or the It is also possible to use an outer polygonal plate.

It will be appreciated that the method of forming a pattern by various colors as described above can be used not only for the button including the pigment material of the present invention but also for the manufacture of a general button. In addition, the unsaturated polyester resin composition of the present invention described above can be usefully used to produce not only buttons but also accessories such as bracelets and rings, and other moldings.

On the other hand, the example which manufactures a button by the centrifugal molding method using the polyester resin composition of this invention is demonstrated. The centrifugal molding method is a method in which a resin composition containing a curing agent is poured into a rotating drum to be molded. After the resin composition is cured and becomes a gel, the still flexible sheet is taken out of the drum and the sheet of Showa hardness 50-75 is punched out within 30 minutes to 2 hours. That is, a button blank of a desired size can be obtained by attaching and punching necessary stamps for each size to a punching machine. Inside the stamp is a punching knife, which is usually 8 to 10 to 50 mm in size. Blanks punched in this way are usually processed side by side because the side condition is not good and may be punched out. For example, if the desired size is 11.5 mm, punch it with a stamp with a 12 mm blade, and when processing, clean the side so that it is 11.5 mm. Since the heat generation state may be different according to the blank thickness, for example, different colors may occur because a large amount of heat is generated at a portion having a thicker thickness and less heat is generated at a portion having a smaller thickness. Therefore, the button blanks are evenly spread evenly on the plate, and then post-cured at a dryer temperature of 30 to 50 ° C. for about 7 to 10 minutes. After removal from the dryer, it is cooled to room temperature and the defective blanks are screened for subsequent processing.

The centrifugal molding method is characterized by excellent pearl dispersibility in the operation of forming a sheet for button blanks and no stickiness by adding wax. When working with pearls, it is easy to produce pearl-colored and glossy buttons with excellent color, and buttons can be produced with smooth stripes (wood grain). Therefore, it is suitable for producing a multi-sheet sheet in which a pearl button having a feeling of natural mother-of-pearl pattern and calm stripes are formed.

In the centrifugal molding method, sheets are usually formed of single plate, double plate, triple plate, etc., and multi-sheet sheet is put into the drum once, and once in gel state, two times in gel state and three times in gel state. Can be prepared. When forming a multi-plate, for example, the tools of FIG. 4A can be used to form various patterns. That is, the tool A can be used to inject the material once to form a first plate having a pattern by two colors. Here, the areas a and b of the tool A are partitioned off by an interlayer, each of which is filled with different colored materials. In addition, the bottom surface of each region is bored with a suitable size, and when inserted into a rotating drum, the material is dropped into the bottom of the drum by a hole formed in the bottom to form a natural pattern of two colors. Next, when the material is injected twice, tool B of FIG. 4A can be used to form stripes. In addition, when the material is added three times, a material of another color may be added to prepare a sheet of the triple plate. In the case where the pearlescent pigment is used in combination with the above pigment material by the centrifugal molding method, in order to exhibit the pearl effect by the pearlescent pigment, it is preferable to lower the temperature of the drum and to use more curing agent and curing accelerator. Therefore, when manufacturing a button by the centrifugal molding method, it is preferable that the conditions of a manufacturing process are as follows.

Speed of Drum: 60-180 rpm

Drum temperature: 10-40 ℃

Curing agent: 0.5%-3%, preferably 1-3%

Curing accelerator: 0.5%-3%, preferably 1-3%

Demold time: 20 minutes-1 hour 30 minutes

On the other hand, when forming a button blank by processing a sheet formed of a triple plate, it is possible to form a button blank by punching in a direction perpendicular to the plate surface, or by punching in a diagonal direction on the plate surface and then processing. 4B illustrates a plan view of a button formed by punching a triple sheet sheet in a direction perpendicular to the plate surface and then processing, and a side view showing a processing state thereof, and FIG. 4B illustrates a diagonal view of the triple sheet sheet on a plate surface The top view of the button blank formed by punching, and then processing is shown and the side view which shows the processing state thereof is shown.

In the above, the manufacturing method for the button has been described as an example, but in addition to the button, accessories such as bracelets, rings, and the like can also be manufactured using the centrifugal molding method described above.

Hereinafter, an Example demonstrates this invention. However, the following examples merely illustrate one example for specifically practicing the present invention and should not be understood as limiting the scope of the present invention.

Example

An unsaturated polyester was prepared from 36 g of ethylene glycol, 128 g of propylene glycol, 25 g of dipropylene glycol, 136 g of neopentyl glycol, 138 g of phthalic anhydride, 127 g of maleic anhydride, and 113 g of terephthalic acid, followed by 297 g of styrene monomer, 100 g of modified polyacrylate, and polysiloxane. 100 g, 5 g of cumene hydroperoxide as a curing agent, TBL-30 Blue (1-diazo-2,5-dibutoxy-4-morpholi) as a pigment from Nissei Chemicals, Inc. Nobenzene chloride, bisphenol A epoxyacrylate as developer resin, diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide as homeostatic agent, and dimethyl silicone as silicone modifier, TR-30 Red (3,3-bis (1-butyl-2-methyl-1H-indol-3-yl) -1- (3H) -isobenzofuranone, other coloring agents, antioxidants, silicone modifiers as pigments Is the same as above), TY -30 Yellow (2-hydroxy-3-naphthoic morpholinopropylamine as pigment, other colorants, antioxidants, silicone modifiers are the same as above), TB-31 Black (2,3-di as pigment) Hydroxynaphthalene-6-sulfonic acid, other coloring agents, antioxidants, and silicone modifiers are the same as above) 20 g of a pigment material, 3 g of naphthenic acid cobalt as a promoter, and 2 to 10 g of ordinary pigments of various colors are mixed. Liquid unsaturated polyester resin compositions of four colors were prepared. These materials were injected into a rod 1 m long and 30 mm in diameter using the apparatus of FIG. 1 and then cured at a temperature of 80 ° C. The cured moldings were cooled to room temperature and then removed from the rods and cut to obtain button blanks. The button blanks were processed into button shapes using a button processing machine, and then 1.5Kg of buttons, 0.4L of water, 3Kg of rubble and 50g of diatomaceous earth (CaCO2) were placed in a grinding bucket and polished for about 10 hours at about 60 rpm. . Subsequently, 1.5 Kg of buttons, 10 g of light, and 2 Kg of bamboo were mixed and rotated at about 60 rpm for about 6 hours to obtain an excellent glossy button.

Comparative Example 1

After preparing an unsaturated polyester with 75 g of ethylene glycol, 102 g of diethylene glycol, 80 g of propylene glycol, 316 g of phthalic anhydride, and 96 g of maleic anhydride, there were 33.1 g of styrene monomer, 3 g of t-butylperoxybenzoate as a curing agent, and naph as an accelerator. An unsaturated polyester resin composition was prepared by mixing 1 g of cobalt stannate and 2 g of a normal pigment of a suitable color. After injecting it into the rod according to a conventional method, a button was manufactured by hardening, demolding, cutting, processing, polishing and polishing.

Comparative Example 2

After preparing an unsaturated polyester with 75 g of ethylene glycol, 102 g of diethylene glycol, 80 g of propylene glycol, 316 g of phthalic anhydride, and 96 g of maleic anhydride, there were 33.1 g of styrene monomer, 3 g of t-butylperoxybenzoate as a curing agent, and naph as an accelerator. An unsaturated polyester resin composition was prepared by mixing 1 g of cobalt acid, 2 g of a pigment of a suitable color, and 20 g of the pigment material of Example 1 above. After injecting it into the rod according to a conventional method, a button was manufactured by hardening, demolding, cutting, processing, polishing and polishing.

In Comparative Example 1, a button was manufactured by preparing an unsaturated polyester resin composition not containing the dye material and curing the same, and there was no particular problem in the physical properties of the button. However, Comparative Example 2 was prepared by the addition of the color tone material to the composition of Comparative Example 1 to prepare an unsaturated polyester resin composition, and cured to produce a button, the produced button is a color in which the color appears partially Separation was observed with the naked eye, and there was a problem with the hardness such as cracks on the surface.

On the other hand, the embodiment is improved by the components constituting the unsaturated polyester resin composition and its component ratio to be suitable for the addition of the color tone material, the phenomenon appearing in the button produced by Comparative Example 2 button produced by the embodiment Did not appear.

The polyester resin composition of the present invention does not cause problems due to the incompatibility of the polyester and the pigment material generated by the mixing of the thermosensitive or photosensitive pigment material. Accordingly, the present invention provides an unsaturated polyester resin composition, a molded article such as a button or an accessory formed by the same, and the method of producing the same, in which physical properties are not lowered even by the addition of the coloring matter.

Claims (20)

(A) an unsaturated polyester made of (a) an acid component and (b) a dihydric alcohol component consisting of (a1) a saturated dibasic acid component and (a2) an unsaturated dibasic acid component; (B) modified polyacrylates; (C) polysiloxanes; And (D) a polymerizable monomer; Unsaturated polyester resin composition for producing buttons or accessories comprising a. The method of claim 1, (E) unsaturated polyester resin composition further comprising a thermochromic or photochromic and / or (F) curing agent. The method of claim 1, Based on the total weight of the unsaturated polyester and the polymerizable monomer, The polymerizable monomer is 30 to 70% by weight, the modified polyacrylate is 0.3 to 21% by weight, the polysiloxane is 0.3 to 21% by weight unsaturated polyester resin composition, characterized in that. The method of claim 2, The thermosensitive or photosensitive pigment material is an unsaturated polyester resin composition, characterized in that 0.001 to 15% by weight relative to the total weight of the unsaturated polyester and the polymerizable monomer, 0.3 to 3% by weight of the curing agent. The method of claim 4, wherein (G) 0.001 to 5% by weight and / or (H) 0.3 to 3% by weight of a curing accelerator, based on the total weight of the unsaturated polyester and the polymerizable monomer. The method according to claim 3 or 4, The saturated dibasic acid component is composed of phthalic anhydride (or phthalic acid) and isophthalic acid or terephthalic acid, the unsaturated dibasic acid component is composed of maleic anhydride (or maleic acid), the dihydric alcohol component is ethylene glycol, diethylene An unsaturated polyester resin composition comprising glycol, propylene glycol, dipropylene glycol and neopentyl glycol. The method according to claim 3 or 4, The unsaturated polyester may be 3 to 7% by weight of ethylene glycol, 15 to 21% by weight of propylene glycol, 2 to 5% by weight of dipropylene glycol, and neopentyl glycol 15 to 25, based on the total weight of the components for preparing the unsaturated polyester. Unsaturated polyester resin composition, characterized in that produced by the reaction components consisting of 15% by weight, 15-25% by weight phthalic anhydride, 15-25% by weight maleic anhydride, 15-25% by weight terephthalic acid. (A) an unsaturated polyester made of (a) an acid component and (b) a dihydric alcohol component consisting of (a1) a saturated dibasic acid component and (a2) an unsaturated dibasic acid component, (B) a modified polyacrylate, The molded article manufactured by hardening of the unsaturated polyester resin composition containing (C) polysiloxane and (D) polymerizable monomer. The method of claim 8, The unsaturated polyester resin composition further comprises (E) a thermosensitive or photosensitive pigment substance and (F) a curing agent. The method of claim 8, Based on the total weight of the unsaturated polyester and the polymerizable monomer, The polymerizable monomer is 30 to 70% by weight, the modified polyacrylate is 0.3 to 21% by weight, the molded article, characterized in that the polysiloxane is 0.3 to 21% by weight. The method of claim 9, The thermosensitive or photosensitive pigment material is 5 to 15% by weight relative to the total weight of the unsaturated polyester and the polymerizable monomer, the molding material, characterized in that 0.3 to 3% by weight. The method of claim 11, The unsaturated polyester resin composition further comprises 0.001 to 5% by weight of (G) pigment and 0.3 to 3% by weight of (H) curing accelerator based on the total weight of the unsaturated polyester and the polymerizable monomer. Molding. The method according to claim 11 or 12, wherein The saturated dibasic acid component is composed of phthalic anhydride (or phthalic acid) and isophthalic acid or terephthalic acid, the unsaturated dibasic acid component is composed of maleic anhydride (or maleic acid), the dihydric alcohol component is ethylene glycol, diethylene Molding, characterized in that consisting of glycol, propylene glycol, dipropylene glycol and neopentyl glycol. The method according to claim 11 or 12, wherein The unsaturated polyester may be 3 to 7% by weight of ethylene glycol, 15 to 21% by weight of propylene glycol, 2 to 5% by weight of dipropylene glycol, and neopentyl glycol 15 to 25, based on the total weight of the components for preparing the unsaturated polyester. Molding, characterized in that produced by the reaction components consisting of 15% by weight, 15-25% by weight phthalic anhydride, 15-25% by weight maleic anhydride, 15-25% by weight terephthalic acid. Unsaturated polyesters, polymerizable monomers, thermosensitive or photosensitive pigments, modified polyacrylates, and polysiloxanes are pipes suitable for button sizes in liquid materials, which are unsaturated polyester resin compositions optionally comprising conventional pigments, curing accelerators, and curing agents. Injecting into the flow, Curing the unsaturated polyester resin composition at a temperature of 50 to 120 ° C., Cooling the molded cured product to room temperature and taking it out of the rod; Immersing the molded cured product in high temperature water to soften it; Cutting the molded cured product into a button blank, Injecting the liquid material flowing into the rod is a step of injecting the liquid material flowing into the rod while allowing a plurality of colors to be mixed to form a pattern without mixing the plurality of the liquid material completely mixed in the button Manufacturing method. The method of claim 15, Processing the button blank into a predetermined button shape, Mixing the processed button with water, scum, diatomaceous earth into a keg and rotating the keg to polish the button, and Mixing the polished button with the bamboo and the light medicine into the keg and rotating the keg to polish the button Method of manufacturing a button further comprising. The method of claim 15, The step of pouring the liquid material of the unsaturated polyester resin composition into a pipe suitable for the button size, Preparing a cylinder or polygonal cylinder with a partition formed at predetermined intervals with respect to the origin and the bottom of which is clogged, the bottom of the cylinder or polygonal cylinder evenly drilled, Installing a funnel on top of the rod, and installing the cylindrical or polygonal cylinder on top of the funnel, and By injecting the liquid materials of different colors into the sections of the rotating cylinder or polygonal cylinder, the injected liquid materials flow down through the holes and the funnel formed in the bottom of the cylindrical or polygonal cylinder to form a pattern in the rod. Injecting the liquid materials into the rod to form Method of manufacturing a button comprising a. The method of claim 15, The step of pouring the liquid material of the unsaturated polyester resin composition into a pipe suitable for the button size, Installing a polygonal plate vertically on top of the rod or at an incline such that the liquid material can flow down by gravity, at which point one vertex of the plate is placed as the lowest point of the plate on top of the rod , The two corners that meet at this vertex have a jaw-, Installing hoses for supplying the plurality of liquid materials having different colors to contact the upper surface of the plate surface; Installing a pin that can move horizontally in contact with the plate surface of the lower portion of the hoses, a horizontally installed long rod supporting the pin, and a rotating body connected to the rod; Rotating the rotating body to the left and right to transmit the rotational force of the rotating body to the stage to reciprocate the left and right and the pin supported by the stage and in contact with the plate to reciprocate left and right , And While operating the rotating body, the liquid materials supplied by supplying the plurality of liquid materials having different colors through the hoses flow down along the plate surface by gravity and form a pattern by the left and right reciprocating motion of the pins. After mixing so as to have a guide that is guided by the jaw installed on the edge of the plate flows to the vertex at the top of the rod is further mixed to be injected while forming a pattern into the rod from the vertex Method of manufacturing a button comprising a. Unsaturated polyester resin compositions comprising unsaturated polyesters, polymerizable monomers, thermosensitive or photosensitive pigments, modified polyacrylates, polysiloxanes, and curing agents, and optionally conventional pigments, curing accelerators, may be subjected to centrifugal molding of single or multiple plates. Forming a sheet, The process conditions of the centrifugal molding method is the rotational speed of the drum 60-180 rpm, the temperature of the drum 10-40 ℃, the curing agent 0.5%-3%, the curing accelerator 0.5-3%, the demolding time 20 minutes-1 hour 30 minutes The manufacturing method of the molding to be used. The method of claim 19, The said conventional pigment is a manufacturing method of the molded object characterized by the pearlescent pigment.