WO1998017713A1 - Process for making a mineral filled acrylic sheet having a matte finish with improved stain resistance - Google Patents

Process for making a mineral filled acrylic sheet having a matte finish with improved stain resistance Download PDF

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Publication number
WO1998017713A1
WO1998017713A1 PCT/US1997/006200 US9706200W WO9817713A1 WO 1998017713 A1 WO1998017713 A1 WO 1998017713A1 US 9706200 W US9706200 W US 9706200W WO 9817713 A1 WO9817713 A1 WO 9817713A1
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WO
WIPO (PCT)
Prior art keywords
film
sheet
mineral
syrup
sheets
Prior art date
Application number
PCT/US1997/006200
Other languages
French (fr)
Inventor
Ettore Minghetti
Gary C. Layne
Original Assignee
Aristech Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aristech Chemical Corporation filed Critical Aristech Chemical Corporation
Priority to CA002232358A priority Critical patent/CA2232358A1/en
Priority to JP10519323A priority patent/JP2000502403A/en
Publication of WO1998017713A1 publication Critical patent/WO1998017713A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/148—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0024—Matt surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • This invention relates to the manufacturing of slab or sheets of poly (methyl methacrylate) (PMMA) which contain mineral fillers and which can be thermoformed into such articles as vanity tops or sinks.
  • PMMA poly (methyl methacrylate)
  • this invention describes how to produce sheets or slabs with a matte finish surface and appearance that does not require additional finishing steps and provides good stain resistance, as measured by existing industry standards.
  • Sheets and slabs of synthetic mineral appearing material are now commonly used as kitchen counter tops and interior and exterior decorative coverings of all kinds for buildings such as banks, air terminals, stores, and the like. Such applications frequently require that the material be fabricated to fit custom designed areas.
  • U. S. Patent No. 4,041,120 discloses an abrasion resistant surface layer for synthetic resin articles. However, that layer is firmly adherent to the base resin.
  • Toyooka et al. U. S. Patent No. 4,254,074 discloses synthetic resin sheets having a film, possibly bearing printing, adhering thereto.
  • Daff et al. in U. S. Patent No. 5,308,425 discloses a protective film placed on acrylic sheet.
  • the present differs in that the film here is non-compatible with a mineral filled acrylic sheet. The non-compatibility must be to a degree such that the surface characteristics of the mineral filled sheet are not substantially changed. Additionally, the resulting sheet will have a matte finish. Neither of these characteristics are present in Daff et al.
  • mineral filler particles such as alumina trihydrate (ATH) will be dispersed throughout the acrylic matrix. Some of these particles will be very near the surface of the sheet. These particles near the surface will have a very thin film of acrylic covering them. When the surface of the sheet is subsequently sanded this thin film of acrylic is unintentionally removed. The filler particles near the surface are then exposed and some of them will have been cut in half (or more-or-less) by the sanding.
  • ATH alumina trihydrate
  • acrylic sheets One of the qualities possessed by acrylic sheets is stain resistance.
  • the acrylic surface resists absorption of foreign materials commonly associated with the above-mentioned uses for mineral appearing products.
  • staining substances will more easily penetrate the surface, by being absorbed directly by the ATH or by penetrating at the interface of the ATH particles with the polymer matrix. This results in a poor aesthetic quality in the product.
  • the present invention overcomes this drawback in the prior art.
  • the mineral appearing sheets and products thermoformed therefrom of the present invention have a matte appearance. There is no need for subsequent sanding procedures.
  • the mineral filler particles near the surface are, for the most part, not exposed. Most, if not all, retain the acrylic film separating the particles from the outside environment.
  • the products of the present invention also have improved stain resistance when compared to typical matte surfaces in the prior art.
  • Acrylic sheets such as those described in U.S. Patent No. 5,521,243 can be produced with different surface finishes which will change after thermoforming and the appearance being unacceptable.
  • the hot sheet is stretched into a mold, there is a significant loss of gloss, which is variable and proportional to amount of stretching of any given unit of surface. If, for example, a bathroom vanity top is thermoformed from a sheet with a smooth finish, the resulting part will show:
  • the amount of mineral filler may be more than an order of magnitude (30-50% by weight) and the loss of gloss problem is unavoidable and very noticeable.
  • Sanding the surface of these sheets before or after the thermoforming step could provide a solution to the problem of loss of gloss, since the sanded finish does not change, or more exactly, the eye of an observer does not appreciate a visible change of the surface finish among the different areas of the finished part.
  • the sanding process cuts grooves into the surface, and this allows a staining agent to penetrate more easily below the surface.
  • These stains may be resistant to a rinsing liquid, such as a soapy solution or similar cleansing products.
  • This performance is measured, for example, by the ANSI Z.124.3: American National Standard for Plastic Lavatories.
  • staining agents are used to create stains which are then cleaned with specific procedures.
  • An overall rating of the stain resistance of the surface is obtained and a rating of 50 is required to pass the test.
  • the geometry of the surface of the sheet will have the same thin and uniform film of plastic matrix, but it is not flat and it has peaks and valleys which provide a matte look.
  • the stain resistance will remain about the same as that of a smooth finish.
  • the male type mold is also preferable for achieving a more uniform and thicker wall in the finished part.
  • the thermoformed sheet significantly decrease in thickness in some areas.
  • the thickness in the drain area may drop to 1/3 or 1/4 of its original value. If the same shape is produced in a male mold, the thickness in the drain area may be only 10-20% less than the original thickness. Consequently, if the original thickness is high enough, the thermoformed part from a male mold may be strong enough to be used as such, without the need of any type of back side reinforcement, such as polyester-fiberglass.
  • the present invention is not limited to any one particular sheet manufacturing process (e.g. continuous cast, injection molding, cell cast, end the like), in the preferred embodiment of the invention the continuous casting process, such as is described in U.S. Patent No. 3,376,371 by Opel et al., and Hellsund's U. S. Patent No. 52,271,383 are followed using an alumina trihydrate filled acrylic composition such as those described in U. S. Patent No. 5,521,243.
  • a roll of the selected material was mounted on an air brake support and tracking system, to provide some tension to eliminate wrinkles. The film would then go over a curved Mt. Hope type roller, also useful to eliminate wrinkles. The leading edge of the film or paper was taped across the bottom belt, which would then pull the film from the feed roll.
  • the polymerizing composition was dropped onto the film which covered the bottom belt.
  • the film or paper in question could be covering the top belt (or both belts) depending on operational choices and the available equipment configuration.
  • the film or paper can be left on the sheet until the thermoforming operation is initiated.
  • the film may have to be removed if it does restrain or negatively affects the surface quality of the finished part.
  • Melinex 377 1 mil thick, a polyethylene terephtalate film sold by ICI Corporation.
  • M-1000 2.5 mil, a polyvinyl alcohol film sold by Chris Craft Industrial Products.
  • Stipkote Papers 5 mil, paper base with clays and surface treatment coatings sold by S.D.
  • Sanded used 60 micron sandpaper.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A process for making acrylic sheets which contain mineral fillers and which can be thermoformed into integral top vanity tops or sinks. The sheets and thermoformed products thereof have a matte finish surface and appearance that does not require additional finishing steps such as sanding to create a uniform appearance. The sheets and thermoformed products possess good stain resistance, as measured by existing industry standards.

Description

PROCESS FOR MAKING A MINERAL FILLED ACRYLIC SHEET HAVING A MATTE FINISH WITH IMPROVED STAIN RESISTANCE
Technical Field
This invention relates to the manufacturing of slab or sheets of poly (methyl methacrylate) (PMMA) which contain mineral fillers and which can be thermoformed into such articles as vanity tops or sinks. In particular, this invention describes how to produce sheets or slabs with a matte finish surface and appearance that does not require additional finishing steps and provides good stain resistance, as measured by existing industry standards.
Background of the Invention
Sheets and slabs of synthetic mineral appearing material are now commonly used as kitchen counter tops and interior and exterior decorative coverings of all kinds for buildings such as banks, air terminals, stores, and the like. Such applications frequently require that the material be fabricated to fit custom designed areas.
The fabrication process requires extensive time and specially trained craftsmen to be completed successfully, since special tools and procedures are necessary. Until recently, if a shaped, one piece part of continuous monolithic material is desired, such a part could only be produced by casting it in a closed mold cavity under special conditions, the silicone forms a release layer.
In Oshima et al., U. S. Patent No. 4,041,120 discloses an abrasion resistant surface layer for synthetic resin articles. However, that layer is firmly adherent to the base resin. Similarly, Toyooka et al., U. S. Patent No. 4,254,074 discloses synthetic resin sheets having a film, possibly bearing printing, adhering thereto. Daff et al., in U. S. Patent No. 5,308,425 discloses a protective film placed on acrylic sheet. However, the present differs in that the film here is non-compatible with a mineral filled acrylic sheet. The non-compatibility must be to a degree such that the surface characteristics of the mineral filled sheet are not substantially changed. Additionally, the resulting sheet will have a matte finish. Neither of these characteristics are present in Daff et al.
In U.S. Patent No. 5,521,243 Minghetti et al., disclose the composition of a mineral appearing material which may be cast or otherwise formed into the shape of a sheet. These sheets are capable of being thermoformed into a vanity top or sink. As with prior art mineral appearing sheets, the post-polymerized sheet will have a glossy appearance. However, this glossy appearance becomes matte in areas of deep draw upon thermoforming. Thus, the final product will have a non-uniform appearance.
The same problem is experienced with non-thermoformed acrylic compositions such as those described by Ross et al., in U. S. Patent Nos. 4,961,995 and 5,032,625. In addition to the high costs associated with installation of the acrylic parts (placing the sheets into place, fitting, glueing, and the like) the intersection of adjacent sheets will necessarily be sanded to give a smooth fit. This sanding process will similarly remove the glossy appearance in that area, giving a non-uniform appearance.
To combat the difficulties listed above, mineral appearing sheets are often sanded in their entirety. This gives a uniform matte finish before and after the above applications are accomplished. However, the uniform sanding process has its own distinct drawbacks.
Visualizing the contents of a mineral appearing acrylic sheet, mineral filler particles such as alumina trihydrate (ATH) will be dispersed throughout the acrylic matrix. Some of these particles will be very near the surface of the sheet. These particles near the surface will have a very thin film of acrylic covering them. When the surface of the sheet is subsequently sanded this thin film of acrylic is unintentionally removed. The filler particles near the surface are then exposed and some of them will have been cut in half (or more-or-less) by the sanding.
One of the qualities possessed by acrylic sheets is stain resistance. The acrylic surface resists absorption of foreign materials commonly associated with the above-mentioned uses for mineral appearing products. When the mineral filler material such as ATH is exposed by sanding, staining substances will more easily penetrate the surface, by being absorbed directly by the ATH or by penetrating at the interface of the ATH particles with the polymer matrix. This results in a poor aesthetic quality in the product.
The present invention overcomes this drawback in the prior art. The mineral appearing sheets and products thermoformed therefrom of the present invention have a matte appearance. There is no need for subsequent sanding procedures. The mineral filler particles near the surface are, for the most part, not exposed. Most, if not all, retain the acrylic film separating the particles from the outside environment. The products of the present invention also have improved stain resistance when compared to typical matte surfaces in the prior art.
Summary of the Invention
Acrylic sheets such as those described in U.S. Patent No. 5,521,243 can be produced with different surface finishes which will change after thermoforming and the appearance being unacceptable. When the hot sheet is stretched into a mold, there is a significant loss of gloss, which is variable and proportional to amount of stretching of any given unit of surface. If, for example, a bathroom vanity top is thermoformed from a sheet with a smooth finish, the resulting part will show:
- a minor change in gloss (slight decrease) in the flat area surround the bowl area,
- a more noticeable change of gloss (moderate decrease) in the rim area around the bowl, - a very noticeable change of gloss (significant decrease to a dull finish) in the bottom or drain area of the bowl.
All this occurs because the polymer matrix stretches out and away from the solid particles of the mineral filler. This is a well known phenomenon in the mermoforrning of high gloss sheets where, at times, a small amount of pigments or solid powders (1-2% by weight) may be sufficient to cause the problem. In compositions contemplated by the present invention, the amount of mineral filler may be more than an order of magnitude (30-50% by weight) and the loss of gloss problem is unavoidable and very noticeable.
Sanding the surface of these sheets before or after the thermoforming step could provide a solution to the problem of loss of gloss, since the sanded finish does not change, or more exactly, the eye of an observer does not appreciate a visible change of the surface finish among the different areas of the finished part. However, the sanding process cuts grooves into the surface, and this allows a staining agent to penetrate more easily below the surface. These stains may be resistant to a rinsing liquid, such as a soapy solution or similar cleansing products.
This performance is measured, for example, by the ANSI Z.124.3: American National Standard for Plastic Lavatories. In it, staining agents are used to create stains which are then cleaned with specific procedures. An overall rating of the stain resistance of the surface is obtained and a rating of 50 is required to pass the test.
When the solid surface sheet is produced against an appropriate matte finish, like a plastic film or paper, the geometry of the surface of the sheet will have the same thin and uniform film of plastic matrix, but it is not flat and it has peaks and valleys which provide a matte look. The stain resistance will remain about the same as that of a smooth finish.
Another important factor affects the performance of the finished part, and that is the type of mold used. Our work has shown that the stain resistance decreases after the sheet is formed into a female mold, while it may increase or stay the same if a male mold is used. In a female mold forming, the finished surface is stretched, and it is reasonable to assume that the pores at its surface will grow larger and/or new ones may be formed, thus favoring the penetration of staining agents. In a male mold configuration, the finished surface is not stretched to any significant degree and it is pressed against the mold surface.
The male type mold is also preferable for achieving a more uniform and thicker wall in the finished part. In a female mold, the thermoformed sheet significantly decrease in thickness in some areas. In an average vanity top bowl, the thickness in the drain area may drop to 1/3 or 1/4 of its original value. If the same shape is produced in a male mold, the thickness in the drain area may be only 10-20% less than the original thickness. Consequently, if the original thickness is high enough, the thermoformed part from a male mold may be strong enough to be used as such, without the need of any type of back side reinforcement, such as polyester-fiberglass.
Detailed Description of the Invention
Several types of film were tested. They are listed in Table 1. These films or papers were used to cover a casting surface, so that the liquid composition would contact them and polymerize against them.
Cell casting experiments were performed in which the film or paper covered the surface of one of the two cell cast plates. The space between them was then filled with the liquid composition of choice, which would then be polymerized in a water bath and/or oven, following the known art methods.
Although the present invention is not limited to any one particular sheet manufacturing process (e.g. continuous cast, injection molding, cell cast, end the like), in the preferred embodiment of the invention the continuous casting process, such as is described in U.S. Patent No. 3,376,371 by Opel et al., and Hellsund's U. S. Patent No. 52,271,383 are followed using an alumina trihydrate filled acrylic composition such as those described in U. S. Patent No. 5,521,243. A roll of the selected material was mounted on an air brake support and tracking system, to provide some tension to eliminate wrinkles. The film would then go over a curved Mt. Hope type roller, also useful to eliminate wrinkles. The leading edge of the film or paper was taped across the bottom belt, which would then pull the film from the feed roll.
The polymerizing composition was dropped onto the film which covered the bottom belt. The film or paper in question could be covering the top belt (or both belts) depending on operational choices and the available equipment configuration.
If the sheet is made from a thermoformable composition, the film or paper can be left on the sheet until the thermoforming operation is initiated. The film may have to be removed if it does restrain or negatively affects the surface quality of the finished part.
Examples
The types of film used for mineral filled thermoformable acrylic sheets and thermoformed bowls therefrom are given in Table 1. The sheets were prepared as is set forth in U. S. Patent 5,521,243 (in turn referencing '371 and '383 patents). The evaluations of the Stain Resistance per ANSI Z.124.3 are given in Table. 2.
TABLE 1
Melinex 377: 1 mil thick, a polyethylene terephtalate film sold by ICI Corporation.
M-1000: 2.5 mil, a polyvinyl alcohol film sold by Chris Craft Industrial Products.
Stipkote Papers: 5 mil, paper base with clays and surface treatment coatings sold by S.D.
Warren Company.
Type of Stripkote Tested Results
TK-ETL- Velvet Good release - good appearance
SK-ETL-Matte Good release - good appearance
TABLE 2
(Stain Resistance ratings per ANSI Z.124.3 - 1986)
Flat Surface Thermoformed Bowl
Film or Paper Sample ID As Is Sanded Flat Surface Bowl
Melinex 377 85-2484 52 54 44 61(F)
Melinex 377 85-2485 57 54 59 68(F)
Melinex 377 85-6548 48 25(M)
M-1000 85-3341 33 34 39(F)
85-4480 39 56 28(M)
Stripkote 85-6236 57
TK-ETL
Stripkote Cell cast 39
SK-ETL
Notes:
Sanded: used 60 micron sandpaper.
Thermoformed bowl: "bowl" results were obtained in the drain area of the bowl. (F) and (M) = F denotes a female mold configuration; M denotes a male mold configuration; both molds produced a part with the same dimensions.
The best stain resistance ratings were obtained with M-1000 film, 33 and 39 for the surface "as is." The same film provided the best results when using a female mold (39). With Melinex 377, the performance of the surface "as is" was borderline acceptable (52, 57, 48), and it became unacceptable after meimoforming in a female mold (61). However, the use of a male mold significantly improved the stain resistance (25).

Claims

Claims
1. A process for making a mineral filled acrylic sheet having a matte finish comprising the steps of:
(a) making a prepolymerized syrup comprising methyl methacrylate and having mineral particles dispersed therein;
(b) polymerizing said syrup between at least two surfaces, said surfaces defining a space in the shape of a sheet, and wherein at least one of said surfaces is contacted by a film, said film being non-compatible with said syrup, and said film having a plurality of pores causing said sheet to have a matte finish after said syrup is polymerized, and wherein said film is removable from said sheet, wherein said removal does not cause significant exposure of said mineral particles to an outside environment; and
(c) removing said polymerized syrup from said surfaces.
2. A method according to claim 1 wherein said film comprises a polyvinyl alcohol film.
3. A method according to claim 1 wherein said film comprises a polyethylene terephtalate film.
4. A mineral appearing acrylic sheet having a matte appearance made by the method of claim 1.
5. A mineral appearing acrylic sheet according to claim 4 wherein said prepolymerized syrup comprises a thermoformable composition.
6. A thermoformed article made by thermoforming the sheet of claim 4.
PCT/US1997/006200 1996-10-21 1997-04-14 Process for making a mineral filled acrylic sheet having a matte finish with improved stain resistance WO1998017713A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002232358A CA2232358A1 (en) 1996-10-21 1997-04-14 Process for making a mineral filled acrylic sheet having a matte finish with improved stain resistance
JP10519323A JP2000502403A (en) 1996-10-21 1997-04-14 Method for producing an inorganic-filled acrylic sheet having improved stain resistance and a matte finish

Applications Claiming Priority (2)

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US73431796A 1996-10-21 1996-10-21
US08/734,317 1996-10-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022146984A1 (en) * 2020-12-30 2022-07-07 Aristech Surfaces Llc Methods for producing highly thermoformable acrylic solid surface
WO2023034893A1 (en) * 2021-09-01 2023-03-09 Trinseo Europe Gmbh Articles of manufacture produced from highly thermoformable acrylic solid surface with matte surface

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8858850B2 (en) * 2009-07-02 2014-10-14 E I Du Pont De Nemours And Company Process for preparing decorative surface appearance in acrylic material employing anisotropic particles

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB998802A (en) * 1961-01-13 1965-07-21 British Cellophane Ltd Improvements in or relating to moulding resin sheets
US3371383A (en) * 1965-09-28 1968-03-05 Swedlow Inc Continuous casting apparatus
US3376371A (en) * 1965-09-28 1968-04-02 Swedlow Inc Continuous casting process
EP0154108A2 (en) * 1983-12-02 1985-09-11 VCF Packaging Films Inc. Solvent cast acrylic film
JPH04364907A (en) * 1991-06-12 1992-12-17 Kurisuron:Kk Manufacture of artificial marble or the like
JPH0753750A (en) * 1993-08-13 1995-02-28 Teijin Ltd Mold release film
US5521243A (en) * 1993-11-26 1996-05-28 Aristech Chemical Corporation Acrylic sheet having uniform distribution of coloring and mineral filler before and after thermoforming

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB998802A (en) * 1961-01-13 1965-07-21 British Cellophane Ltd Improvements in or relating to moulding resin sheets
US3371383A (en) * 1965-09-28 1968-03-05 Swedlow Inc Continuous casting apparatus
US3376371A (en) * 1965-09-28 1968-04-02 Swedlow Inc Continuous casting process
EP0154108A2 (en) * 1983-12-02 1985-09-11 VCF Packaging Films Inc. Solvent cast acrylic film
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WO2023034893A1 (en) * 2021-09-01 2023-03-09 Trinseo Europe Gmbh Articles of manufacture produced from highly thermoformable acrylic solid surface with matte surface

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