JPH05500987A - Polyvinyl chloride articles whose surface has been modified and stabilized against ultraviolet light. - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] This application was filed on December 23, 1986 by the same inventor and assigned to the same assignee. This is a continuation-in-part of U.S. Patent Application No. 945.595, filed on the day of. These outputs The entire disclosure of the application is incorporated herein by reference.

The present invention relates to U, V, stabilized polyvinyl chloride articles, more particularly U, V. Concerning pigment-colored polyvinyl chloride articles whose surface has been effectively modified with stabilizers. do. More specifically, it is characterized by being substantially free of titanium dioxide. Regarding the above-mentioned article.

2. Description of conventional technology The white pigment titanium dioxide exhibits a dual function in polyvinyl chloride articles. No. The action of 1 is to absorb the incident U, V energy, reflect it, disperse it, or Stabilizes PVC against the harmful effects of U, V, and radiation by scattering become The second action of titanium dioxide is to make the article opaque and, if desired, to to make a colored article by incorporating a sufficient amount of colored pigment to overcome the white titanium dioxide be able to.

Unfortunately, the amount of available U, V, and titanium dioxide required for stabilization is approximately 12 phr. prevents the article from being heavily colored.

In fact, only pastel colored articles are obtained. For example, brown Intense blue and maroon colorations cannot be obtained as such. Therefore, substantially Polyvinyl chloride stabilized against U, V, characterized by not containing tan It is profitable to provide such goods.

Of course, the absence of titanium dioxide results in a loss of stabilizing effect on U, V, accompany. Therefore, such articles are classified as U.

■It is necessary to take other stabilization measures. Since titanium dioxide is a cheap raw material, , effective but expensive U, V, stabilizers such as benzophenone or benzo ) It is not economical to use IJ azole in place of titanium dioxide. moreover , containing this organic U, V, stabilizer in the bulk means that the stabilizer is substantially in the article. It exists internally to prevent deterioration caused by light, which is known as a surface phenomenon. I can't do it.

For these reasons, surface treatment of polyvinyl chloride containing titanium dioxide, An effective and economical U, V, stabilization of polyvinyl chloride resin was proposed. these Conventional surface treatments are based on the effect of various organic solvents on resin swelling. A solution of UV stabilizer is sprayed onto the surface area of the article to be protected. but However, none of these surface treatments were very industrially advantageous.

For example, Jochanan, Israel Patent No. 39037, November 1975. Published on March 10th, “Made of organic plastics, U, V, and resistant to oxidation” products and products that contain titanium dioxide on the surface of plastic sheets containing titanium dioxide. U, V.

Various methods of dissolving or suspending the absorbent are described. To this Jochanan The disclosed method therefore involves immersing the resin sheet in a solution of stabilizer or By spraying, brushing, roll printing or curtain coating the solution on the sheet. Apply. However, such methods require large amounts of stabilizers and solvents to be applied to the surface of the article. Because it remains on the surface, the modified surface may have linear marks or a hazy appearance. It becomes linear or pock-like.

Other attempts aimed at effective surface modification of polyvinyl chloride include Katz et al.'s “Pr oceedings of the A-C0S, Div, of Org, Co atings3, No. 043.709; No. 3.297.462: No. 3519.4 No. 62: No. 3.783.011; No. 3.892.889; No. 4.146.6 No. 58: No. 4.323.597: and Belgian Patent No. 612.206. It is listed. However, these disclosed methods are particularly effective against sun exposure, e.g. residential buildings that require effective protection from the elements and an appearance and surface integrity that is acceptable to the public. Opaque polyvinyl chloride stabilized against U and V by surface modification on the side. None provided a useful surface for resinous materials.

Therefore, the object of the present invention is to stabilize U, V, by surface modification. A polyvinyl chloride resin article, characterized in that it does not substantially contain titanium dioxide. The goal is to provide goods that meet the needs of the public.

Another object of the invention is that the article can be colored with pigments that make it translucent or opaque. The goal is to provide such products that can be used.

Yet another object of the present invention is to provide such U, V The object of the present invention is to provide an article that is stabilized against.

Another object of the invention is that the modified surface is substantially free of stabilizer and solvent substances. , the modified surface has a surface appearance and surface integrity that are not adversely affected by the modification and that such a resin sheet article that is substantially the same as the unmodified side of the sheet. It is to provide.

Yet another object of the invention is that the amount of stabilizer in the modified surface area of the sheet is at least 0.3 g/m2 of area, most preferably from 0.5 to 10.7 g/r n” and the surface area extends to a depth of about 200 μm from the surface, and the stabilizer such that at least 70% of the amount is present within the first 100 μm from the surface area. The purpose of the present invention is to provide a resin article that is of excellent quality.

Yet another object of the present invention is to We provide a method for manufacturing such polyvinyl chloride articles that protects vinyl sheets from the atmosphere. Is Rukoto.

These and other objects, nature and advantages of the present invention will be apparent from the following with reference to the accompanying drawings: It will become clear from the detailed explanation.

Brief description of the drawing FIG. 1 shows an article of the invention stabilized against U, V.

Figure 2 shows that an article stabilized for U and V in Figure 1 is produced by a continuous method. 1 is a schematic diagram of a device suitable for

Summary of the invention Those described here contain colored pigments stabilized by surface modification. A polyvinyl chloride article characterized by being substantially free of titanium dioxide It is an article that The modified surface is made up of stabilizers and solvents used with them. No qualitative residue remains and its appearance and surface integrity are substantially adversely affected by modification. Items that are unaffected and thus appear similar to the unaltered sides of the sheet. be.

The presence of colored pigments to make the article translucent or opaque; also white or pearlescent It can also be.

The surface area of the sheet extends to a depth of 200 μm from the surface, and this area is exposed to ultraviolet light. The stabilizer is sufficiently modified in-situ that the amount of stabilization is at least the surface area of the sheet. 0.3 g/m'', preferably about 0.5 to 10.7 g/m'.

At least 70% of this stabilizing amount is present within the first 100 μm of the surface area .

This U-, V-stabilized resin material can be used to stabilize polyvinyl chloride materials in a suitable solution. immerse the object in a suitable organic solvent and pass this liquid over the surface of the immersed object. The modified surface is contacted with a UV light stabilizer solution to remove residual stabilizer and solvent. removed in situ from the atmosphere, which is brought into contact with the external atmosphere i.e. non-volatile climate Remove without any problem.

Detailed description of the invention The product of the present invention is produced by first mixing an appropriate amount of color pigment and polyvinyl chloride resin. Manufactured by. The resulting mixture can be shaped into shaped bodies, such as sheets or other useful materials. Process it into a structure. For illustrative purposes, the following description refers to sheet products do. These sheet products include films, strips, ribbons, bars, rods, etc. It is understood that other products, which would be obvious to those skilled in the art, can also be made with the present invention, including molded articles. It should be.

The amount of colored pigment suitable for mixing with the PVC resin will make the product translucent or opaque. This is the amount to make it transparent.

As explained below, the surface-modified products of the present invention are substantially free of titanium dioxide. Provides effective UV stability under conditions of use.

Indeed, it is unexpected that a certain level of modification by UV stabilizers in the surface area of the product The effectiveness of such UV stability is actually increased in the absence of titanium dioxide in the product. be strengthened.

Figure 1 shows a UV stabilized product of the invention. The product may contain resin bodies, such as polyvinyl chloride. or other polymeric resin sheets or other molded structures. Products , side faces S and S', both sides of which are exposed to the atmosphere. each exposed The side surfaces have respective surfaces SUR and SUR'.

The side surface S has a surface area extending from the surface S into the sheet to a depth of about 200 μm. have The surface region SR has been modified with a stabilizing amount of UV stabilizing material, which amount in an amount of at least 0.3 g/m2 of surface, preferably 0.3 g/m2 of surface. 5-1 0.7g, with more than 70% of the stabilizer found within the first 100μm of the surface area. Served. Stabilizers are substantially not present within or in the bulk of the sheet and are The surface SUR is also substantially free of residual stabilizer.

The uniformity, appearance and extent of the surface finish of the modified surface SUR depends on the surface modification process. It is therefore unaffected and is also substantially the same as that of the unaltered surface SUR'. table The surface finish is tack-free and streak-free, which also remains intact after modification with stabilizers. Retains shape and hardness.

The molded resin bodies themselves are obtained by common processing techniques known to those skilled in the art. This way Examples of such mechanical operations are compression, injection, shedding, transfer molding, and vacuum forming. , extrusion, etc.

Such molded bodies range from flexible sheets to rigid structural members. but, The present invention is particularly designed to avoid adverse effects due to outdoor exposure and UV decay, especially with PVC residential sidewalls. Design a product that will resonate.

Therefore, polyvinyl chloride is the preferred resin for the products of this invention. but, Other resins that allow for incorporation with U, V, stabilizers are also suitable. Figure 2 shows the book 1 schematically depicts an apparatus useful for producing inventive UV-stabilized resin products.

Generally, methods using such devices involve immersing a resin sheet in a suitable liquid medium. , the surface of the immersed sheet to be modified in the liquid is exposed to U, V, light in a suitable organic solvent. contact with a solution of stabilizer and then remove residual stabilizer and solvent from the treated surface. Including on-the-spot substitutions. Suitable solvents are those that effectively swell the resin; Furthermore, it is immiscible with organic solvents and non-agglomerating with resins.

The preferred in-situ manufacturing method for the UV products of the present invention is a continuous process; The resin sheet is impregnated with an aqueous liquid, such as water, and then dissolved in a resin-swelling organic solvent. U, ■, the surface of the sheet to be modified by spraying a light stabilizer solution and passing it through water. During this contact, the sheet is immersed in water, and then the contact surface is thoroughly soaked. The swelling and stabilization side solution is sufficiently penetrated into the surface area of the sheet, and then the residual stabilization is carried out. The curing agent and solvent can be removed from the modified surface in situ using the aqueous liquid. It includes.

After contacting the surface of the sheet, excess stabilizing solution is allowed to drip off the surface thus treated. put down or washed. The individual methods depend on the tightness of each liquid and organic solvent used. Depends on the degree. water or an aqueous solution thereof as well as water being larger than such a solution Preferably, a liquid such as an organic solvent having a density is used.

Therefore, the preferred arrangement of liquids and solutions is a two-layer system, where water is The top layer is the solution of the stabilizer dissolved in the organic solvent is the bottom layer.

The organic solvent is selected from solvents that are immiscible with the liquid medium.

Otherwise, the solvent would not reach the resin surface and would simply dissolve there. . Other considerations in choosing a solvent are empirical considerations, i.e. V. I want to impregnate a resin product with a stabilizer. This characteristic is found in many factors, particularly the ability of the solvent to effectively swell the resin surface.

The device shown in Figure 2 is a two-layer system in which the liquid layer is the upper layer and the stabilizer solution is the lower layer. It is a system. The resin sheet is arranged in an impregnated state in the upper layer. Such a two-layer method In continuous operation, the stabilizer solution is pumped from the lower layer and then It is applied onto the sheet from the bottom of the layer. Excess stabilizer solution is then removed from the sheet by gravity. Fall back to the lower level. The organic solvent in the stabilizer solution forms a liquid blanket above it. is blocked from evaporating into the atmosphere by the This is advantageous because of the formation of a modified surface with integrity and for environmental reasons.

The apparatus of Figure 2 includes as an upper layer a tank 1 filled with approximately 374 water 2. Ru. A stabilizer solution of the UV absorber in an organic solvent, e.g. methylene chloride, is added to the tank. It exists as a lower layer within. For example, a continuous resin strip of extruded PVC The roll 4 is fed out from below the roller 5 through the upper layer at a predetermined speed. The roller 5 is a roller located below the water surface 6.

Further in front of the roller 5, what we refer to in this specification as the “application zone” In the area designated "A" a series of applicator nozzles 7 have their orifices It is arranged below the water surface level 6, with the strip 4 facing one side.

This applicator nozzle continuously allows the flow of stabilizer solution 3 to move the resin (S) + J-tube 4 is directed onto the upper surface 8 thereof. Stabilized in this way The solution remains on the surface of the strip, where the surface area is effectively modified by the stabilizer. be done.

Downstream of the application zone is the “exclusion zone” B, where residual stability The agent solution is then removed from the treated strip surface in situ. term" “In-situ” means that this removal process is also carried out without exposing the treated surface to the surrounding atmosphere: Rather, it means that the treated surface remains under the water where no solvent evaporation is possible. Kaka Solvent evaporation is particularly undesirable as it will leave streaks of solid stabilizer material on it. Not.

In the exclusion zone, remove sufficient stabilizer solution from the strip treatment surface. The jet element 9 directs a spray of reject liquid, preferably water 2, at a pressure of . The jet element 9 is a hollow body, i.e. a hollow rod terminating in a slit 11. The strip 4 passes through this slit 11 into the exclusion zone. transported to.

The stabilizer solution is deposited on the sheet surface during its passage from the application zone to the exclusion zone. The time during which the liquid resides is referred to herein as the "contact time" of the method.

The 20th roller 12 is located in front of the exclusion zone and below the water level; After the treated resin strip leaves the exclusion zone, Accept the input.

Variable speed to move the strip at a predetermined speed in and outside the tank. Place a nip roller fuller (not shown) on the outside of the tank and the strip Can be stored in suitable take-off rolls.

The apparatus and operation described above may be performed using an organic solvent having a density of less than 1, such as ethyl acetate, It is also applicable to 2-pentanone, 3-pentanone, etc. In the case of such organic solvents The stabilizer solution would be the top layer and the water would be the bottom layer. that time In this case, the stabilizer solution rises in the water and contacts the resin sheet from the bottom and then moves upwards. It will pass.

The present invention will be explained with reference to the following examples, in which the present invention Ming's UV stabilizer products were manufactured using the equipment and system shown in Figure 1.

The protection of this product against UV degradation under these method parameters is , changes in yellowness index (YI), or graphed as ΔYI values.

This YI value is measured by accelerated ultraviolet exposure test according to ASTM G-53-84. did. The change from initial to final YI was defined as YI. Zero (or negative) YI Values indicate minimal or no yellowing; positive YI values indicate that UV exposure This proves that yellowness increased due to the cause.

Cyasorb 5411 UV-stabilizer in methylene chloride Registration of American Cya-namid Co. A 310% by weight solution containing 1-2 phr of colored pigment was placed on a horizontal support. It was applied to the upper surface of a moving polyvinyl chloride resin l-IJ tube. This strip (This PVC strip is made of vinyl chloride homopolymer (vinyl chloride homopolymer). B.

F. Geon 103 from Goodrich EPF-76; Int, Visc, = 0. according to ASTM D 1243. 9 A mixture of 2) and 5. 0 phr reinforcing agent, 1,0 phr processing aid, 2. 0 phr calcium stearate lubricant and 1. 5 phr mercaptide (a kneaded and pressed sample made from a tin stabilizer).

Insert the applicator nozzle vertically from below the water surface toward the top of this sheet. Toward. The stabilizer is therefore absorbed into the upper surface area of this sheet and excess solvent The liquid fell to the bottom of the tank. The contact time was 24 seconds. This applicator - downstream of the zone to remove any residual stabilizer and solvent still on the treated surface. A jet of water was applied to the treated surface in order to This U, V, stabilized article as follows It was then taken up from the tank and wound onto a take-up roll.

The U, ■, stabilized article produced in Example 1 has a It has a surface area that extends to a total depth of up to about 200 μm from the surface. U, V, The amount of stabilizer present is at least 0.3 g/m'' of the surface area of the sheet; The amount of stabilizer is usually about 0.5 to 10.7 g/m2, and the amount of this stabilizer is small. At least 70% is present within the first 100 μm of this surface area. This Inside the sheet or in the bulk, that is, within 200 to 1300 μm (thickness of this sheet) There is substantially no stabilizer present. Furthermore, the modified table of this sheet There is substantially no residual stabilizer and solvent (less than 1% each) on the surface. Made of obtained If the article is uniform and tack-free, this surface has no traces of solid material on it; and maintains its horizontal smoothness and hardness.

Example 3 Following the steps of Example 1, test samples were prepared and weathered. The following conclusion Therefore, all data are presented as 10-week QUV unless otherwise stated. .

Table 1 QUV weathering test on all samples Sample color g/m” E (YI) ★1 Aodate 1.5 13.2 2 Blue 0 > 60.0 3 Green Tae★ 1.5 15.0 4 Green 0 26.6 (6 weeks) QUV) 5 Brown ＊＊＊＊ 3 5.4 6 Brown 0 21.2 ? White (pearl color) 3 17 8 White (pearl color) 0 & 2 9 White (pearl color) 3 1.8 10 White (pearl color) 021.4 11 Brick red color 6 35.6 12 Brick red 0 23.9 (6 weeks UV) outdoor weather resistant sample New Jersey) Sample Color g/m2 E (21 months) 13 Blue 1.0 19.9 14 Blue 1.5 51.5 ★Changes in tone level after weathering test account for E1, i.e. color intensity Therefore, it is shown as an energy value commonly used in color engineering.

Samples 1, 12, 13 and 14 are extruded strips of PVC. surface modification stabilizer Comparison of colored pigment samples with and without It was shown that the performance was significantly improved.

Mosquito Fu, o (F e r r o) F-8233 Myo★Ciba Geigi (Cib a-Gieg! /), Argalite green ) 44 L N P** Ferro V-9186 Iron Free Chest Nut Brown (Iron Free Chestnut Brown) EM-ke Michal (Chemicals), Rutile Fine Silver WR Bahrressen Tobigment 9111 (RutilePine 5ilver WRPear lessent Pigment 9111) 10+ Morbay Corp-), Kindred.

Red) R-6713 As mentioned above, the preferred liquid medium in the methods utilized herein is water or are aqueous solutions or emulsions thereof. However, other liquids also They can be used as long as they are not "incompatible" with organic solvents. "Incompatibility '' in an organic solvent at ambient temperature and pressure is greater than about 15% by weight. Defined herein to mean a liquid that has no solubility. liquid like this Includes alkanols and other water-miscible liquids.

Similarly, the solvent in the stabilizer solution should be a "liquid-immiscible solvent". , which also has a solubility in the liquid of greater than about 15% by volume at ambient temperature and pressure. Defined as not having.

Accordingly, suitable organic solvents for use herein include water-immiscible organic solvents. solvents, such as halogenated hydrocarbons having up to 6 carbon atoms in the molecular chain, preferably Contains up to 3; keroloform, 1,2-dichloroethane, 2chloro-2-methylene Includes propane and similar chlorinated hydrocarbons. A typical ketone is 2-penta non, 3-pentanone, 2-hexanone, 2,4-pentanedione, and the like. suitable Examples of suitable ethers include diethyl ether, diethyl ether, dimethoxyethane, and fluoride. Includes oran, tetrahydropyran, etc. Mixtures of mutually compatible organic solvents may also be used. Can be used. Preferred organic solvents are methylene chloride, 1,2-dichloroethane, ethyl acetate. 2-pentanone and 3-pentanone and mixtures of these solvents.

Suitable U, V, stabilizers include the following commercially available materials: Cyaso rb) U, V, 9: 2-hydroxy-4-methoxybenzophenone (American Cancyanamide registered trademark), Cyasorb U, V, 531: 2-Hydroxy-4-n-octoxybenzopheno (registered trademark of American Cyanamid), Sheasorb U, V, 5411:2 ( 2'-Hydroxy-5'-t-octylphenyl)-benz(triaso-) (registered trademark of Shiku American Cyanamid), Tinuvin P: 2 (2' hydroxy-5'-methylphenylphenyl) Benzotriazole (registered trademark of Ciba Geigy) Tinuvin 326: 0-(3'-t-butyl-2'-hydroxy- 5'-methylphenyl)-5-chlorobenzotriazole (Civer-Geigy) trademark) Sanduvor VSLI: 2-ethyl-2-ethoxyanilide (Sanduvor company trademark) Tinuvin 144 and 770: hindered amine light stabilizer (for HALS) Irgastab 2002 (Trademark of Civer-Geigy) Kel (trademark of Civer-Geigy) Listed below are those and other benzophylamides that are suitable U-L stabilizers for use in the present invention. Partial list of enones and triazoles, salicylates, formamide Gins, oxanilides, benzoates, etc. can also be used.

2.2'-dihydroxybenzophenone 2.2,4.4'--rtrahydrox Cybenzophenone 2.2'-dihydroxy-4,4'-dimethoxybenzophene 2 ．． 2'-dihydroxy-4,4'-diethoxybenzophe 2,2'-dihydroxy C-4,47-dipropoxybenzophenone 2.2'-dihydroxy-4,4'-dibutoxybenzophene 2,27-cyhydro xy-4-methoxy-4'-ethoxybenzphenone 2.2'-dihydroxy-4-methoxy-4'-propoxybenzophenone 2-hydroxy-4,4',5'-4rimethoxybenzophenone 2-Hydroxy-4-ethoxy-4'-methylbenzophenone 2-Hydroxy-4-ethoxy-4'-ethylbenzophenone 2-Hydroxy-4-ethoxy-4'-propylbenzophenone 2-Hydroxy-4-ethoxy-4'-methoxybenzophenone 2-Hydroxy-4,4'-jethoxybenzophenone 2-hydroxy-4-ethyl Toxi-4'-propoxybenzophenone 2-Hydroxy-4-ethoxy-4'-butoxybenzophenone 2-Hydroxy-4-ethoxy-4'-chlorobenzophenone 2-Hydroxy-4-ethoxy-4'-bromobenzophenone 2-(2'-hydroxy-57-methylphenyl)benzotriazole 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole 2-(2'-hydroxy-3'-methyl-5'-t-butylphenyl)benzo triazole 2-(2'-hydroxy-57-cyclohexylphenyl)benzotriazo rule 2-(2'-hydroxy-3',5'-cylomethylphenyl)benzotria sol 2-(2'-hydroxy-5'-t-butylphenyl)-5=chlorobenzo triazole 1-(2'-hydroxy-3'-di-t-butylphenyl)benzotriazo le 2.2'-dihydroxy-4-methoxy-4'-butoxybenzophenone 2.2'-dihydroxy-4-ethoxy-4'-propoxybenzophenone 2.3'-dihydroxy-4,4'-dimethoxybenzophenone 2.3'-dihydroxy-4-methoxy-47-butoxybenzophenone 2.3'-dihydroxy-4,4,5'-)rimethoxybenzophenone 2-Hydroxy-4,4,5'-)rimethoxybenzophenone 2-Hydroxy-4,4,6'-)ributoxybenzophenone 2-Hydroxy-4-ethoxy-2,4'-dibutylbenzophenone 2-Hydroxy-4-propoxy-4',6'-dichlorobenzophenone 2-Hydroxy-4-propoxy-4',6'-dibromobenzophenone 2.4-dihydroxybenzophenone 2-Hydroxy-4-methoxybenzophenone 2-hydroxy-4-ethoxybene Benzophenone 2-hydroxy-4-propoxybenzophenone 2-hydroxy- 4-Butoxybenzophenone 2-hydroxy-4-methoxy-4'-methylben Zophenone 2-Hydroxy-4-methoxy-47-propylbenzophenone 2-Hydroxy-4-methoxy-4'-butylbenzophenone 2-Hydroxy-4-methoxy-4'-t-butylbenzophenone 2-Hydroxy-4-methoxy-4'-chlorobenzophenone 2-Hydroxy-4-methoxy-27-chlorobenzophenone 2-Hydroxy-4-methoxy-4'-bromobenzophenone 2-hydroxy-4,4'-dimethoxybenzophenone 2-hydroxy-4,4 '-dimethoxy-3-methylbenzophenone 2-Hydroxy-4,4'-dimethoxy-3-methylbenzophenone 2-hydroxy-4,4'-2'-ethylbenzophenone 2-hydroxy- Acetophenone.

The preferred temperature for manufacturing the U, V, stabilized articles of the present invention is ambient temperature.

However, if desired, use a working temperature below or above ambient temperature. You may. For example, the water solubility of certain useful solvents, such as ethyl acetate, is decreases as the degree increases. Therefore, such solvents must be used at temperatures above ambient. It may be advantageous to use lower working temperatures. Similarly, modest at room temperature Organic solvents that only swell certain resins can cause the resin to swell by increasing the processing temperature. It can be very effective in impregnating the surface area with the required amount of stabilizer.

A preferred embodiment of the stabilizer article of the present invention is that only one side of the article is modified with stabilizer. but, if desired, by directing a jet of stabilizer solution onto both sides of the resin sheet. It is understood that both sides can be modified.

The present invention is also applicable to resin articles impregnated with additives other than U, V, and stabilizers. be. For example, additives such as antistatic agents, antioxidants, antiblocking agents, dyes, and slip agents, etc. Additives can be impregnated into the resin.

Although the present invention has been described in some detail in a preferred form, this disclosure is provided by way of example only. For illustrative purposes only, many modifications may be made without departing from the spirit and scope of the invention. You will understand what is possible.

Engraving (no changes to the content) FIG. 1 Engraving (no changes to the content) Summary book Translucent or opaque PVC with surface modification and stabilization against ultraviolet light. Describes a resin article and its manufacturing method. This article contains colored pigments and contains nitrogen dioxide. Characterized by the substantial absence of tan. Modified surface has no residual stabilizer and is substantially free of solvents and whose appearance and surface integrity are modified by this article. It is homogeneously identical to the side that does not exist. The method of the present invention allows polyvinyl chloride articles to be immersed in a liquid medium and contacted with an ultraviolet light stabilizer solution in a suitable organic solvent and left - Removal of stabilizers and solvents in a non-volatile environment, i.e. without contact with air.

Procedural amendment (formality) February 17, 1992

Claims (27)

[Claims] 1. It has a resin sheet that contains color pigments and is substantially free of titanium dioxide. is exposed to air on both sides and the surface area on one side is exposed to a stabilizing amount of ultraviolet light beam. The exposed surface is substantially free of stabilizers and has been modified with a stabilizer. On the other hand, uniformity, appearance and surface integrity are not substantially adversely affected by this modification. Articles stabilized against ultraviolet light that have not been exposed. 2. 2. The article of claim 1, wherein the pigment renders the article translucent or opaque. 3. has a pearl color The article according to claim 1. 4. The amount of stabilization is at least 0.3 g/m2 of the surface area of the sheet, and this surface the region extends to a depth of 200 μm from the surface and at least 70% of the stabilizer is at the surface. Exists within 100 μm from the surface of the area The article according to claim 1. 5. The stabilization amount is 0.5 to 10.7 g/m2 of the surface area of the sheet. The article according to claim 1. 6. Surface integrity is the uniformity, non-stickiness, and non-striation of a surface, including its initial shape and characterized by substantially retaining its hardness and hardness. The article according to claim 1. 7. The resin sheet is a flexible or semi-rigid polyvinyl chloride article The article according to claim 1. 8. The article of claim 1, wherein the resin is a rigid polyvinyl chloride article. 9. 2. The article of claim 1, wherein the surface area is modified at ambient temperature. 10. The stabilizing amount is about 0.5 to 10.7 g/m2 of the top sheet. The article according to claim 1. 11. Stabilizers include benzotriazoles, benzophenones, benzoates, salicylate rate, formamidine, hindered amine, or oxyanilide organic compound The article according to claim 1. 12. A solvent is applied to the surface of a resin article that contains color pigments and is substantially free of titanium oxide. Apply the UV light stabilizer solution in the solution and remove the resin stabilizer and solvent from the thus treated surface. Surface-modified resin articles that remove the solvent and carry out these two steps in an environment that does not vaporize the solvent. manufacturing method. 13. The method according to claim 12, wherein the two steps are carried out without contact with the atmosphere. 14. The stabilizer has a stabilizing amount of at least 0.3 g/m2 of the surface. The manufacturing method according to claim 12. 15. 13. The method of claim 12, wherein the stabilizing amount is about 0.5 to 10.7 g/m2. 16. The resin is polyvinyl chloride The manufacturing method according to claim 12. 17. 13. The manufacturing method according to claim 12, wherein the process is carried out in a continuous manner or in a moving resin sheet manner. 18. The solvent is a volatile organic solvent 13. The method according to claim 12. 19. Solvent is methylene chloride 13. The method according to claim 12. 20. 13. The method of claim 12, wherein the removal step is performed by jetting water onto the treated surface. 21. Made from polymers with colored pigments that are substantially free of titanium dioxide A method of impregnating an article with at least one component, the article comprising: immersing the article in a liquid; The immersed article is then brought into contact with a solution of the components in a solvent so that the liquid does not attack the article. The method is a liquid that does not mix with solvents and does not mix with solvents. 22. The polymer is polyvinyl chloride and the article contains colored pigments to make it translucent or opaque 22. The method according to claim 21. 23. the liquid contains an aqueous medium 22. The method according to claim 21. 24. The aqueous medium is water or water and a water-miscible solvent 24. The method according to claim 23. 25. Solvent is methylene chloride 22. The method according to claim 21. 26. at least one ultraviolet light stabilizer, including a colored pigment, in which titanium dioxide is present; A method of introducing polyvinyl chloride into the surface area of opaque articles made from non-containing polyvinyl chloride. (a) passing the article through an aqueous medium; (b) contacting substantially only one surface of the article with a stabilizer solution in an organic solvent; The article is moved through an aqueous medium that does not attack the article and is compatible with the solvent. It is an immiscible medium, (c) displace the solvent leaving substantially no solution on the surfaces it contacts; I won't let you escape A method that involves a process. 27. Made from polyvinyl chloride and contains colored pigments, but substantially no titanium dioxide. At least one ultraviolet light stabilizer on the surface area of the translucent or opaque sheet that does not contain The agent is introduced into the surface area and this surface area extends to a depth of approximately 200 μm. the amount of stabilizer applied is at least 0.3 g/m2 of the surface area; In this method, 70% of the surface area is enriched in the upper 100 μm of the surface area, and (a ) the sheet is moved substantially horizontally through the upper water layer and below this water layer, in the presence of a methylene chloride solution containing 1-60% wt/vol of stabilizer; (b) flowing the solution from the lower layer through the upper water layer onto substantially one surface of the sheet; At this time, the sheet is moved through the water layer and the solution is applied to the surface for about 2 seconds to about 2 minutes. (c) spray water onto the contacted surface of the sheet; A method comprising the step of retaining the layer and thereby removing the remaining solution on the surface.