JPS6132346B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides surface altering agents.
Thermoplastic polymers containing thermoplastic agents.
Surface modification refers to changing the surface properties of a thermoplastic polymer. Achieving surface modification of thermoplastic polymers has previously been accomplished by incorporating inorganic matting agents such as calcium silicates, magnesium silicates, amorphous silica gels, and the like. The use of such inorganic granulating materials has the disadvantage of causing deleterious effects on the physical properties of the thermoplastic. That is, loss of impact strength, toughness, clarity, processability, and similar properties. Inorganic matting agents or often have poor dispersion. Other prior methods of achieving surface modification of thermoplastics are by calendering, but such mechanical systems suffer from the disadvantages of lack of homogeneity and inability to be used in extrusion processes, limiting their use. A further disadvantage of mechanical matting or surface modification is that the calendering roll must be refinished from time to time, which is an expense and an inconvenience. Also, calendering is not a flexible method in that the reduction in gloss that occurs cannot be easily changed; the only way to change this is to change the calendering roll. A different way of altering the surface of the substrate is, of course, through the application of coating compositions, which are generally synthetic resin latexes or film-forming dispersions of polymers or solutions of binders in solvents.
Matte coatings are non-crosslinked in the coating composition,
Although suggested to be accomplished by mixing immiscible polymer particles, such coating systems are not useful for modifying the surface of thermoplastic polymers to be subjected to post-processing such as molding, thermoforming, or extrusion. It is an object of the present invention to provide a simple method for uniformizing the surface of thermoplastic polymers.
Furthermore, it is an objective to obtain thermoplastic polymers whose surface is modified without affecting other physical properties. Furthermore, it is an object of the present invention to obtain a thermoplastic polymer that is uniform, flexible, and easy to use, and further to obtain a thermoplastic polymer that has reduced surface gloss. Furthermore, the object is to obtain a matting agent that can withstand high temperatures for use in extrusion and molding of thermoplastics. These and other objects that will become apparent are achieved by the present invention, which in one embodiment comprises an extrudable, moldable, or thermoformable thermoplastic polymer having an average size of 1 to 30 microns. The surface-altering agent is comprised of cross-linked polymer particles having a surface-altering agent. Another embodiment of the present invention comprises a method of modifying the surface of a thermoplastic polymer by blending with the thermoplastic polymer a controlled amount of a surface modifying agent comprising crosslinked polymer particles as described above. The amount of surface-altering agent contained in the formulation is usually from about 0.1 to 50 parts by weight per 100 parts by weight of the formulation, preferably from about 1 to 10 parts by weight per 100 parts by weight of the formulation. The exact amount will depend on other factors such as the particular surface properties desired and the particular surface modification used as well as the particular thermoplastic polymer being modified. Suitable thermoplastic polymers whose surfaces can be modified according to the present invention include vinyl chloride polymers, which contain at least 50% vinyl chloride, more preferably 70 or 80% vinyl chloride.
% or more of vinyl chloride and propylene, vinyl acetate,
means a polymer made from a monomer system containing ethylene and a balance of other monomers such as the like; acrylonitrile-butadiene-styrene (ABS) copolymer, methyl methacrylate-butadiene-styrene (MBS), nylon, polyethylene terephthalate, Included are polyethylene, polypropylene, polycarbonate, polyalkyl methacrylate, polyurethane, polystyrene, other thermoplastic polymers and blends of two or more thermoplastic polymers. The term thermoplastic polymer is meant to exclude coating systems, ie binder/solvent systems, and thermoplastic polymers whose surfaces are to be modified are unsuitable for use in coating technology. The surface-altering agent can be prepared by any suitable method that yields crosslinked polymer particles having an average size of 1 to 30 microns. A preferred method is by an endopolymerization method, in which the monomers that ultimately form the particulate polymeric surface modifier are dissolved in the monomers mentioned above and phase separation occurs early during the polymerization process. The preformed polymer is polymerized in the presence of a soluble preformed polymer selected as follows. When phase separation occurs, the soluble preformed polymer becomes the continuous phase and the polymerized monomer becomes the discontinuous phase, i.e., as distinct spherical particles dispersed within the soluble preformed polymer phase, and the granulated polymer Form a surface-altering agent. The granulated surface-altering agent polymer is insoluble in so-called "soluble" polymers, the latter being the carrier polymer in the present technology. That is, the original preformed polymer dissolved in the monomer system remains intact, and as the monomer system polymerizes into the granulated polymer surface-altering agent, the granulated particles with an average particle size of 1 to 30 microns dispersed therein. It becomes a continuous phase with polymer. Suitable miscible preformed carrier polymers (soluble polymers) include polymethyl methacrylate or copolymers of methyl methacrylate with up to 20% lower alkyl acrylate as the preferred polymer. Optionally, other comonomers can be used in small amounts, such as styrene, vinyl acetate, vinyl chloride or acrylonitrile. Suitable molecular weights for preformed miscible carrier polymers are from about 10,000 to about 300,000. Approximately 86-99.95 for monomers suitable for surface-altering agents.
%, preferably about 98-99.5% of at least one monoethylenically unsaturated monomer, about 0.05 to 4
%, preferably from 0.5 to 2.0% of at least one polyunsaturated crosslinking monomer and optionally about
Contains up to 10% polar monomer (all by weight). Suitable monoethylenically unsaturated monomers are preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl, vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearates and styrenes, including styrene and ring-substituted styrenes. be. Preferred systems contain a major portion of styrenes and a minor portion of ( _C4 - _C8 ) alkyl acrylate, more preferably styrenes and _C4
- the ratio of _C8 acrylate is at least 1.5; Although it is widely possible to contain about 0.05 to 4% polyunsaturated crosslinking monomer, it is more desirable to use about 0.5 to 2%, based on the total weight of the monomer system. Although the exact amount of crosslinking monomer will vary with different monomer combinations,
It has been found that the surface modification properties of a particular system can vary greatly with small changes in the amount of crosslinking monomer, so it is important to carefully determine the exact amount of crosslinking agent to be used. Typical crosslinking monomers are those formed by the reaction of acrylic or methacrylic acid with ethylene, propylene, butylene or hexamethylene glycol. Also divinylbenzene; divinyl or diallyl compounds such as the divinyl ethers of the glycols mentioned above; diallyl phthalate; triallyl cyanurate; and other similar monomers having one or more polymerizable groups. Furthermore, polyethylenically unsaturated compounds include divinylpyridine, divinyltoluene, divinylnaphthalene, 1,3-divinylxylene, divinylethylbenzene, divinylsulfone, mono- or dithio derivatives of glycol, glycerol, pentaerystol, glycols, etc. and polyvinyl or polyallyl ether of resorcinol, divinyl ketone, divinyl sulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl seba cate, divinyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, allyl methacrylate, triallyl citrate, triallyl phosphate, N・N'-
Includes methylene diacrylamide, N.N'-ethylene diacrylamide, 1,2-di(α-methylmethylenesulfonamido)-ethylene, trivinylbenzene, trivinylnaphthalene, and polyvinylanthracene. Substantially any monomer having one or more addition polymerizable olefin groups is useful. A desirable crosslinking agent has the following formula: has. Here, R ₁ is H or CH ₃ -, and R is an ethylenically unsaturated group. Wherever such compounds are substituted, the chain length of such substitution is not critical, but is usually about 1 to 20, preferably 1 to 4 carbon atoms. In some cases, the polymer particles can be made infusible by secondary or latent crosslinking by containing up to about 10% by weight of polar monomers.
Generally, secondary or latent crosslinking will occur during processes such as hot roll milling, Banbury mixing or extrusion of the polymer mass. Polar monomers suitable for this function include those that are acrylic residues and are well exemplified by: acrylic acid; methacrylic acid, acrylamide, methacrylamide; epoxyallylic acrylates or methacrylates such as cricidyl methacrylate; Monoacrylic esters of glycols; hydroxyalkyl acrylates or methacrylates, isocyanatoalkyl acrylates and aminoalkyl acrylates or methacrylates, as well as other compounds described below. Possible through the use of heat and/or catalysts2
Examples of secondary or latent crosslinking reactions are as follows. Addition polymerizable unsaturated monomers containing such groups are well known in the art and include isocyanates such as isocyanatoethyl methacrylate, aminoalkyl compounds such as glycidyl methacrylate, and t-butylaminoethyl methacrylate, methacrylamide. Amides such as 4
-guanamines such as pentenoguanamine, hydroxyalkyl esters such as hydroxypropyl methacrylate and hydroxyethyl methacrylate, nitrites such as methacrylonitrile, N- such as methoxymethylmethacrylamide
Alkoxyalkylamides, hydroxyalkylamides such as N-methylolmethacrylamide, analogs of the above methacrylic acid derivatives with other unsaturated acids such as acrylic acid and itaconic acid, these acids themselves, dicarboxylic acids such as maleic acid. and half esters and amides thereof, vinyl esters of glycols such as ethylene glycol, and the like. As can be seen, the potentially crosslinkable addition-polymerizable unsaturated group monomers are −OH, 〓NH,

[Formula]-N=C=O, 〓CHCN,- COOH, and

It has a reactive polar group selected from those containing the formula: Although it is usually not necessary to provide such secondary crosslinking, in systems where it is necessary or desirable, the secondary crosslinking monomer may be 0.05 to 10%, preferably 0.1 to 10%, based on the total monomers forming the particulate polymer. Present in an amount of 3% by weight. When such monomers are used and contain alkyl groups, the groups usually contain about 1 to 20, preferably about 1 to 4 carbon atoms. A preferred secondary crosslinking comonomer is methacrylic acid, usually used in amounts up to 2% by weight. An alternative to this endopolymerization method of making surface-altering agents involves introducing the monomer into water containing the suspending agent under conditions that form suspended monomer globules having an average size of about 1 to 30 microns. , followed by polymerization and separation by conventional methods. Whether the particles are prepared by the endopolymerization method or the modified suspension method, polymerization is conveniently driven off by conventional free radical polymerization catalysts such as redox catalysts and peroxy compounds, heat or irradiation. Generally, these catalysts are present in an amount of about 0.02 to 1.0, preferably about 0.2 to 0.5 weight percent, based on the total monomers forming the surface-altering agent granulated polymer. If it is desired that the secondary or post-polymerization crosslinking described above be enhanced, the catalyst can be a combination of both high temperature and low temperature components. Typical catalysts include benzoyl peroxide, acetyl peroxide, t-butyl peracetate, dicumyl peroxide, azoisobutyronitrile (AIBN),
Includes t-butyl hydroperoxide and t-butyl peroxypivalate. Additionally, heat or irradiation or single compound catalysts in combination with heat and/or irradiation may be used. Furthermore, it should be noted that when radiation catalysis is used, metal promoters are often useful, for example with the use of ultraviolet light. Thermal or irradiation effects can be used in combination with other free radical generating substances. If the surface-altering agent polymer particles have an average size of 1 micron or less, the surface of the thermoplastic polymer,
That is, it does not have the desired effect on gloss reduction or anti-glossy. When the average particle size is greater than about 30 microns, the surface texture of the extruded or molded thermoplastic polymer becomes undesirably rough, making it unattractive for many applications, although it may be useful for certain applications. The particle size distribution can be narrow or wide, and different surface effects can be obtained by appropriate selection of the particle size range and distribution. for example,
A narrow distribution is desirable for printability, while a broader distribution is desirable for gloss reduction. If the surface-altering agent is produced by an endopolymerization process, it is a solid material at room temperature in the form of a solid composite of surface-altering particles in a continuous phase carrier polymer matrix. The solid composite is desirably granulated and then incorporated with the desired amount of thermoplastic polymer prior to or during processing of the thermoplastic. It is possible to provide the desired refractive index by appropriate selection of the monomers that form the surface-altering agent polymer particles. For applications requiring transparency of the thermoplastic polymer, it is desirable to select monomers such that the crosslinked particles have a refractive index within about 0.005 units of the refractive index of the thermoplastic/carrier polymer blend. In systems where transparency is not needed or desired, the refractive index of the surface-altering agent polymer particles is not important. Surface modification properties that can be achieved with the present invention include matting of thermoplastics, anti-blocking, improved printability, scuff resistance, or concealment of surface imperfections. By varying the amount of surface-altering agent, anti-blocking can be achieved without unavoidably dulling the thermoplastic itself. Blends of the invention are useful as monolayer sheets or laminates or in other shaped, cast, extruded or thermoformed articles. The formulations may further contain dyes, colorants, stabilizers, plasticizers, fillers, and other conventional additives. The formulation can be thermoformed without affecting surface modification. When the surface-modifying agent is prepared by endopolymerization, the soluble carrier polymer, ie, the preformed polymer, should be miscible with the thermoplastic polymer to be modified. For example, when it is desired to produce a matte PVC sheet, one desirable surface modifying agent/carrier combination is methyl methacrylate/ethyl acrylate (91/9) as the surface modifying agent in the carrier polymer. Ethyl acrylate/allyl methacrylate (61/34/3.5/
1.5). Although the following examples illustrate certain embodiments of the invention, it is to be understood that the invention is in no way limited to the illustrative embodiments. Example 1 This example demonstrates the production of a preformed polymeric surface modification agent. 26.79 pounds of preformed ethyl acrylate/methyl methacrylate copolymer (9/91 weight) polymer is dissolved at 50 DEG C. in a monomer system consisting of 44.17 pounds of styrene monomer, 24.62 pounds of n-butyl acrylate, and 2.90 pounds of ethyl acrylate. 2
After stirring for a period of time, the preformed polymer completely dissolves in the monomer system. After the solution was cooled to 30°C, the next ingredients were then added with appropriate stirring to ensure that each was thoroughly mixed before addition. : 1.085 lb. allyl methacrylate as a crosslinking agent for surface modifiers, 0.0009 lb. oxalic acid, 0.0725 lb. tert-dodecyl mercaptan, 0.1449 lb. t-butyl peroxypivalate, 0.0725 lb. 25% acetyl peroxide solution in dimethyl phthalate.
lb., and 0.1449 lb. of dicumyl peroxide. The mixture is then heated at 66 °C in an air circulating oven.
Polymerization is carried out for 16 hours, 2 hours at 80°C, and then 6 hours at 120°C. The resulting 1/2" slab of polymer is broken and further granulated into particles that can pass through a 5/16" mesh sieve. The endopolymer surface-altering agent is characterized by a particle size range of about 1 to 35 microns in diameter by electron microscopy measurements, with an average particle size of about 1.5 microns. As an indicator of the degree of crosslinking, the acetone extractable content is 41% by weight;
The swelling ratio as an indicator of crosslink density is 7.0. Example 2 This example illustrates the formulation of a surface-altering agent with a thermoplastic polymer. Surface modifier/carrier polymer composition in granular form prepared in Example 1 with 2 parts by weight and K value of 69, 50 parts of di(2-ethylhexyl) phthalate (DOP) as plasticizer, dibutyltin mercaptoacetate stabilized. Polyvinyl chloride containing 2 parts by weight of lubricant and 0.25 parts by weight of stearic acid lubricant.
100 parts by weight were mixed and milled on a roll mill at 325° C. for 5 minutes at a speed difference of 20/20 RPM to form a 15 mil thick film. The surface of the film in contact with the roll was painted black to eliminate reflections from the second surface, and the specular gloss was measured at an angle of incidence of 60°.
For comparison, 15 containing 2 parts by weight of an inorganic surface modifying agent (amorphous silica) manufactured under similar processing conditions.
Mil Thick Films and 15 mil thick films containing no surface modifying agents, polymeric or inorganic, were prepared and measured. The results are shown in Table 1.

[Table] Example 3 This example uses a surface modification agent and hard (non-plastic) PVC.
The formulation of 5 parts by weight of the granular Example 1 surface modifier composition and 12 parts by weight of MBS having a K value of 61.
mold impact modifier (Acryloid KM611), 3 parts by weight acrylic processing aid (Acryloid K120N),
2 parts by weight of dibutyltin mercaptoacetate,
0.75 parts by weight of glycerol monostearate and
100 parts by weight of polyvinyl chloride containing 0.75 parts by weight of partially saponified ester were mixed and rolled for 4 minutes at 350° with a speed difference of 20/20 RPM. A 35 mil sample was removed from the roll mill, the back side was painted black to eliminate reflections from the second surface, and the specular gloss was measured at a 60° angle of incidence. The remainder of the raw material is kneaded for an additional 3 minutes at 350° and then formed into 0.100 ¹¹ sheets at 350° using a 3 minute preheat/2 minute press/3 minute cool cycle at 70 tons pressure. The molded sheet was tested for V-Nottsu Izotsu impact strength and was further tested for inorganic surface altering agent (amorphous silica gel) manufactured under similar processing conditions.
Measurements of optical clarity are made in comparison to molded sheets containing 5 parts and molded sheets containing no polymer or inorganic surface-altering agent. The results are shown in Table 2.

[Table] Lycagel undeformed vs. 0 13.9 22.5 73.0 11.1
As can be seen from the table above, the surface modifying agents of the present invention provide superior gloss reduction, impact strength and clarity over amorphous silica gel. Example 4 The procedure and composition disclosed in Example 1 was carried out except that the amounts of styrene monomer and n-butyl acrylate monomer were 61.50 pounds and 7.29 pounds, respectively, and the procedure used in Example 1, Table 1. Gloss reduction was tested by. The result is 60
゜Gloss (%) is 18.5. Example 5 The amount of styrene monomer was 41.17 lbs.
The composition and procedure disclosed in Example 1 was carried out, except that butyl acrylate was replaced with 27.62 pounds of 2-ethylhexyl acrylate, and gloss reduction was tested by the procedure used in Example 1, Table 1. It was done. The result is 60° gloss (%) 11.0
It is. Example 6 This example illustrates a suspension polymerization method for the preparation of a surface-altering agent of the invention in a carrier polymer (endopolymer). The mixing procedure disclosed in Example 1 is carried out using 266.2 g of a copolymer of about 10% ethyl acrylate copolymerized with about 90% methyl methacrylate as the preformed polymer. The monomer system in which the preformed polymer is dissolved consists of 430.2 g of styrene monomer, 240.6 g of n-butyl acrylate and 27.62 g of ethyl acrylate. Next ingredient: Allyl methacrylate 21.70
g, 7.202 g of t-butyl peroxypivalate and 7.202 g of lauryl peroxide are added to the syrup. Add deionized water to a suitable reaction vessel.
986.4g, Amberlite W-1 suspension agent (Rohm
and Haas Co.) 7.864g, sodium nitrate 1.380
g, and 1.380 g of potassium chloride. The monomer/polymer solution is then pumped into a container containing the aqueous solution. The mixture is stirred intermittently to form a stable suspension. The suspension is stirred at 300 rpm and polymerized for 1 hour at 70°C, 1 hour at 80°C, and 1 hour at 90°C. The endopolymer is characterized by granular polymer spheres with an average size of 6, ranging from 1 to 33 microns in diameter. The prepared surface-altering agents are tested for gloss reduction by the procedure used in Example 1, Table 1. The result is 60° gloss (%) 12.0. Example 7 This example illustrates a suspension method for producing surface-altering agent particles without the use of a carrier polymer. In the appropriate reaction volume, 760 g of deionized water, 30.0 g of an 8% aqueous solution of hydroxyethyl cellulose, Acrysol
A mixture of 4.00 g of GS suspension agent (sodium polyacrylate from Rohm and Haas), 0.300 g of Pharmagel (gelatin), and 4.00 g of sodium chloride is stirred until all ingredients are dissolved. Especially n-
Butyl acrylate 266g, styrene 478g, ethyl acrylate 32.0g, allyl methacrylate
A mixture of 24.0 g, benzoyl peroxide, 8.00 g, and lauryl peroxide, 8.00 g is prepared. The monomer mixture is added to the aqueous solution and a stirring impeller is placed at the interface between the aqueous and organic phases. The mixture is stirred intermittently to form a stable suspension. The suspension is stirred at 300 rpm and heated to 75°C for over 40 minutes. Polymerization is completed with the next time/temperature cycle. : 11/4 hours at 75°C, 1 hour at 83°C, 1 hour at 91°C and 1 hour at 97°C. The resulting suspension is cooled and separated in a manner known in the art. The resulting polymer particles have an average size of 12 microns and range in diameter from 1 to 30 microns. The prepared surface-altering agent is tested for gloss reduction by the procedure used in Example 1. The result is 60° gloss (%) 17.0. Example 8 The mixing procedure disclosed in Example 1 was carried out by dissolving 888 g of the same carrier polymer in a monomer system consisting of 1464 g styrene monomer, 816 g n-butyl acrylate, and 96 g ethyl acrylate, and then the following components were cooled. Added to syrup:
1,3-butylene glycol dimethacrylate
11.9g, tert-dodecyl mercaptan 2.4g, tert
-Dodecyl mercaptan 2.4g, oxalic acid 2.8% aqueous solution
0.86g, t-butyl peroxypivalate 4.3
g, 2.4 g of a 25% acetyl peroxide solution in dimethyl naphthalate, and 4.8 g of digmyl peroxide. The resulting mixture is placed in a bag container and bulk polymerized in an air circulation oven at 66°C for 16 hours, at 80°C for 2 hours, and then at 120°C for 6 hours. After the bags were removed from the resulting opaque 1/2" slab of polymer, the slab was broken and further granulated into particles that could pass through a 5/16" mesh sieve and polished using the procedure of Example 1. The reduction is tested. The result is 60° gloss (%) 16.0. Example 9 1,3-butylene glycol diacrylate
Example 8 except that 5.9 g is used instead of 1,3-dibutylene glycol dimethacrylate
The procedures and compositions disclosed in Table 1 are carried out and gloss reduction is tested by the procedure used in Example 1, Table 1. The result is 60° gloss (%) 16.0. Example 10 Trimethylpropane trimethacrylate instead of 1,3-butylene glycol dimethacrylate
The procedure and composition disclosed in Example 8 is carried out, except that 11.9 g is used, and the gloss reduction is tested by the procedure used in Example 1, Table 1. The result is 60° gloss (%) 14.0. Example 11 The procedure and composition disclosed in Example 8 was carried out using 2.4 g of divinylbenzene in place of 1,3-butylene glycol dimethacrylate, and gloss reduction was achieved by the procedure used in Example 1, Table 1. will be tested. The result is 60° gloss (%) 20.0. Example 12 (Comparative) This example demonstrates the importance of selecting the appropriate amount of crosslinking monomer and its relationship to the resulting properties. A The procedure of Example 1 was carried out, changing only the amount of crosslinker, allyl methacrylate, and the following table shows the results of the acetone extractables test, swelling ratio, 60° gloss and dispersion.

Table B The surface modification agent was prepared by the carrier polymer technique of Example 1, but with styrene and divinylbenzene as the only monomers and mixed into PVC in a similar manner. Different results were obtained by varying the ratio of styrene to crosslinking monomer. 0 to 0.1% in monomer mixture
With crosslinking agent, the surface modification agent is well dispersed in PVC and the 60° gloss is 91
The crosslinkers from 0, 0.05 and 0.1% decreased to 84, 76 and 58, respectively. At 0.5 to 1% crosslinker, the dispersibility is poor to very poor; at 3 and 5% crosslinker, the surface altering agent cannot be dispersed at all and the test sheet has large visible particles, which results in uneven gloss. The results showed a lack of "surface modification" as defined in the present invention. Example 13 This example demonstrates the preparation of a surface modification agent containing styrene, butyl acrylate, ethyl acrylate, and allyl methacrylate in a preformed ABS polymer. 28.27 pounds of styrene, butyl acrylate
40.60 pounds and 2.90 pounds of ethyl acrylate are mixed together. 26.88 pounds of ABS polymer (eg, Lastran A-31 from Monsanto Chemical Company) are slowly added to the above mixture with good stirring. It is then heated to 50-55°C for about 2 hours until all the ABS polymer is well melted. This solution is at 30℃
Once cooled, 0.90 lb. of allyl methacrylate and 0.001 lb. of oxalic acid are added, ensuring that each component is well stirred and mixed before adding the next. Similarly tertiary lead decyl mercaptan
0.0727 lbs. t-butyl peroxypivalate
0.1454 lbs., 0.727 lbs. of a 25% acetyl peroxide solution in dimethyl phthalate, and 0.1454 lbs. dicumyl peroxide are added with stirring. This mixture is polymerized in an air circulation oven at 66°C for 16 hours, at 80°C for 2 hours and then at 120°C for 6 hours. After cooling, the product is cooled with dry ice (solid carbon dioxide gas) and then granulated into particles that can pass through a 5/16" mesh sieve. Empopolymer's surface-altering agent has a particle size that is approximately 100% in diameter, as determined by electron microscopy. It is characterized by a range of 1 to 35 microns, with an average particle size of approximately 1.4 microns.Extractable dimethyl formaldehyde, as an indicator of the degree of crosslinking, is 33.1% and the swelling ratio, as an indicator of crosslinking density, is 8.2. Example 14 This example illustrates the formulation of a surface-altering agent with a thermoplastic polymer. 3 parts by weight of the surface-altering agent/carrier polymer composition in particulate form prepared in Example 1 and
100 parts by weight of ABS polymer was mixed and used in a two-roll mill to form a film with a thickness of 15 mil.
The mixture was kneaded for 5 minutes at a speed difference of 23/20 rpm. The surface of the film in contact with the roll was painted black, and the reflective gloss at an incident angle of 60° was measured. For comparison, a 15 mil thick film containing 3 parts by weight of an inorganic surface modifying agent (amorphous silica) and a 15 mil film containing no surface modifying agent were prepared under similar processing conditions.
A film of thickness was manufactured and measured. The results are shown in Table 3. Table 3 Additives 60° Gloss (%) Invention product 15 Amorphous silica 53 Unmodified control 91

Claims (1)

[Claims] 1 0.1 per 100 parts of thermoplastic polymer and total blend
An extrudable, moldable, or thermoformable surface-modifying formulation characterized in that it consists of ~50 parts of a surface-modifying agent of the polymer as described below, provided that the surface-modifying agent comprises styrene or ring-substituted styrene and C ₄ -C ₈ alkyl acrylate of at least 1.5 and further between about 0.5 and 2% based on the total weight of the monomer system. (where R ₁ is H or CH ₃ and R is a C ₂ to _{C 6} ethylenically unsaturated group), and the surface modification agent has an average particle size of 1 to 1. 30
It is micron. 2 0.1 per 100 parts of thermoplastic polymer and total formulation
An extrudable, moldable, or thermoformable surface-modifying formulation characterized in that it consists of ~50 parts of a surface-modifying agent of the polymer as described below, provided that the surface-modifying agent comprises styrene or ring-substituted styrene and C ₄ -C ₈ alkyl acrylate of at least 1.5 and further between about 0.5 and 2% based on the total weight of the monomer system. (wherein R ₁ is H or CH ₃ and R is a C ₂ to _{C 6} ethylenically unsaturated group), the crosslinked polymer has an average particle size of 1 to 30 microns, and the monomer The crosslinked polymer is supported on a carrier polymer made of polymethyl methacrylate or a copolymer of lower alkyl acrylate and methyl methacrylate that is soluble in the system.