JPH0134463B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL FIELD OF APPLICATION The present invention relates to colored thermoplastic resins. More particularly, the present invention provides a method in which a multi-stage polymer is incorporated therein to provide improved depth of color as well as impact resistance and to provide a substantially non-uniform color tone when the colored polymer formulation is molded into an article. do not have,
It relates to colored polyester and/or polycarbonate resins. BACKGROUND OF THE INVENTION The impact resistance of polyesters and/or polycarbonates is improved by incorporating impact modifiers. However, when the colored polyester or polycarbonate formulations described above are molded into articles, the improvement in impact strength is achieved at the cost of non-uniform color appearance. This is often manifested in the form of a whitening or washed-out appearance of the matrix with a nacreous appearance, especially near the gate of the product or mold. Furthermore, the visual appearance of the color intensity of the molded product itself is impaired, making the molded product less appealing to consumers. US Pat. No. 3,971,835 teaches impact modified vinyl halide formulations. The impact modifier comprises a hard first stage polymer consisting of a styrenic monomer and up to 50 weight percent of a monovinylidene monomer copolymerizable therewith.
It is a graft polymer made in three steps sequentially.
Additionally, a crosslinking agent may also be present in the first stage. The second stage is a rubbery polymer such as a crosslinked alkyl acrylate such as butyl acrylate. The final step is a hard thermoplastic polymer such as methyl methacrylate. US Pat. No. 3,971,835 also teaches that pigments can be incorporated into modified vinyl halogenated polymer systems. This patent does not mention the problem of non-uniform color appearance such as pearlescent luster in molded products, or the problem of color intensity. This patent concerns the problem of improving impact strength;
It concerns the transparency of vinyl halogenated polymers. US Pat. No. 3,793,402 concerns the issue of the degree of haze in methacrylate polymers. The impact modifier of this patent has a crosslinked styrene core with an elastomer stage and a final hard stage. The elastomer stage is a material such as a cross-linked alkyl acrylate and the outer stage is an alkyl methacrylate such as methyl methacrylate. This patent teaches that colorants are used as part of the formulation. This patent does not address the issue of pearlescent or color intensity of colored polyester and/or polycarbonate resins. US Pat. No. 3,162,695 is concerned with the flow properties of polycarbonate resins. This patent teaches a two-stage graft polymer with a butadiene and styrene core and a methyl methacrylate shell. This patent does not mention the use of pigments or colorants with polycarbonate. Moreover, since butadiene is an essential constituent of this polymer mixture, its presence in the core adversely affects the weatherability of the polycarbonate. US Pat. No. 3,864,428 describes a polyester/polycarbonate mixture in which there is a graft copolymer of a butadiene polymer and a vinyl monomer. The vinyl monomer is styrene and the butadiene-styrene copolymer is not crosslinked. Colorants may also be included in the formulation. The subject matter of this patent are issues relating to formability as well as impact strength, resistance to thermal deformation and chemical resistance. This patent does not address issues of pearlescent luster or color intensity. US Pat. No. 3,891,719 relates to molded article formulations of polycarbonate and graft copolymers of styrene and acrylonitrile or acrylic ester polymers. This patent addresses issues of tensile strength, elongation, and resistance to light and weather. This patent teaches that polymers containing small amounts of butadiene lead to discoloration under the influence of intense light and/or heat. This patent teaches pigments that can be used in thermoplastic molding formulations. The graft polymers used in this patent are all soft core containing materials such as butyl acrylate. This patent does not give any attention to or address issues of pearlescent luster or color intensity. US Pat. No. 4,026,970 describes unpigmented polymers mixed with multi-stage polymers that serve as reinforcing agents for thermoplastics such as polyesters and polycarbonates. The core of the multi-stage polymer of this patent contains mostly acrylonitrile and vinylidene monomers and a graft binder. Vinylidene monomers are styrene or styrenic materials. The formulation of this patent is an unpigmented formulation in which the multi-stage polymer contains less than 50 percent styrenic monomer in its core. Among the graft binders mentioned in this patent are:
Divinylbenzene is one of the crosslinking agents used in the present invention. This patent is also unaware of or does not address the issue of nacre or color intensity. None of the above-mentioned patents recognizes or addresses the issue of nacre or color intensity of colored polyester and/or polycarbonate resins. Problems to be Solved by the Invention Therefore, it is an object of the present invention to incorporate an impact-resistant modifier that has good color strength and does not produce pearlescent luster when molding a product. To provide a colored polyester and/or polycarbonate resin. Other objects and advantages will become apparent from the description below. SUMMARY OF THE INVENTION Broadly speaking, the present invention comprises from about 60 to 99.9 parts by weight of a colored thermoplastic resin selected from the class consisting of polyester, polycarbonate, and mixtures thereof and about 0.1 part by weight. up to about 40 parts by weight of sequentially polymerized multi-stage polymers. The multi-stage polymer comprises: (a) a polymer core of at least about 10 parts based on the weight of the multi-stage polymer; the core is polymerized from a styrenic monomer or a mixture of a styrenic monomer and a second monomer; in which the styrenic monomer in the core is at least about 50 weight percent and is crosslinked; (b) a second stage consisting of a polymerized soft stage; and (c) a hard thermoplastic outer layer. step. Compounding a polyester and/or polycarbonate resin with at least three stages of a multi-stage polymer having a predominately cross-linked styrenic core followed by a soft stage and a final or outer stage being a hard stage. It is surprising to find that it is thereby possible to substantially eliminate pearlescent luster and also to improve the intensity of the color. All parts and percentages herein are by weight unless otherwise specified. The core of the multistage polymer is at least 10 parts by weight of the multistage polymer, preferably from 10 parts to 40 parts by weight. The core consists of a styrenic monomer or a styrenic monomer and a second monomer, of which at least 50%
Made by polymerization, in which the weight percent is styrenic monomer. Desirably, the styrenic monomer used to prepare the core is from about 50% to about 99.9% of the core. More preferably, the styrene monomer content is about 75%.
to 99.9%. The preferred monomer for preparing the core is styrene, but other styrenic monomers may also be used in combination with styrene or with each other. Other styrenic monomers used in this case include alphamethylstyrene, monochlorostyrene, tertiary-butylstyrene, vinyl toluene, p-isopropylstyrene, 3,
There are 4-dimethyl styrene, p-bromo styrene, 3,4-dichlorostyrene, and others. If desired, the core may contain a non-styrenic monovinylidene comonomer (second monomer) of about
It can also be prepared using up to 49%. Additionally, if a comonomer is used, it is preferably from about 1% to about 20%. Non-styrenic monovinylidene monomers used as comonomers with styrenic materials to prepare this core include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and others; acrylonitrile , vinyl esters such as methacrylonitrile and others; acrylic acid, methacrylic acid and others. If an alkyl methacrylate is used in preparing the core, such alkyl methacrylate is an alkyl methacrylate having from 1 to about 8 carbon atoms in the alkyl portion thereof. Additionally, alkyl acrylates having from 1 to about 8 carbon atoms in the alkyl portion can also be used. Such alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, and others. The crosslinking agent for the styrenic core is a polyethylenically unsaturated monomer having a plurality of reactive groups capable of addition polymerization with substantially the same reaction rate. The amount of crosslinker used is approximately 0.1 based on the weight of the core.
from about 10% by weight, preferably from about 0.1 to about 5% by weight. Polyethylenically unsaturated monomers used as crosslinkers for the core include polyvinylbenzene, 2
or divinyl esters of tribasic acids, dialkyl esters of polyfunctional acids, diallyl esters of polyfunctional acids, divinyl esters of polyhydric alcohols, esters of di- or trimethacrylic acid of polyhydric alcohols, and mixtures thereof. The crosslinker used for the core is divinyl
Adipate, dialkyl phthalates such as diethyl phthalate, diallyl maleate, diallyl fumarate, divinyl ether of ethylene glycol, dimethacrylate of ethylene glycol, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate , ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, divinylbenzene, trivinylbenzene and others. Once the core polymerization is complete, ie, the monomers of the core polymerization mixture have been substantially consumed, a soft stage is polymerized on the surface of the core phase. The soft stage comprises about 40 to about 80 parts of the multistage polymer, preferably about 60 parts.
Approximately 80 copies. The soft stage is made from monomers such as alkyl acrylates having from 1 to about 8 carbon atoms in the alkyl portion. The monomer used to create the soft stage is ethyl acrylate, n-
Butyl acrylate, 2-ethyl hexyl
Acrylate, isobutyl acrylate and others. Soft stages can also be created by the use of single monomer systems or comonomer systems. If comonomers are used, such comonomers can be used in amounts up to 50% of the soft stage. The comonomers that may be present include uncrosslinked vinylidene monomers such as acrylonitrile, alkyl methacrylates having from about 1 to about 8 carbon atoms in the alkyl moiety, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, styrenic materials such as styrene or cores. Any of the styrenic materials mentioned in connection with the styrenic materials used in the preparation of isobornyl methacrylate, isoprene, chloroprene and others. The comonomer used to create the soft stage can constitute up to about 50% of the soft stage, but preferably up to about 25%. Soft stages can also be prepared using crosslinkers and graft binders. The grafting agent used is a polyethylenic compound having a plurality of addition-polymerizable reactive groups where at least one reactive group polymerizes at a substantially different rate of polymerization than at least one other reactive group. It is an unsaturated monomer. The grafting monomers used in the present invention are:
Allyl methacrylate, allyl acrylate, acrylic acid, methacrylic acid, maleic acid (mono and di-esters), fumaric acid (mono and di-esters) and itaconic acid (mono and di-esters).
allyl, methallyl and crotyl esters of esters; allyl, methallyl and crotyl vinyl
thioether; N-allyl, methallyl or crotyl maleamide; vinyl ester of 3-butene and 4-pentenoic acid, triallyl cyanurate; o-allyl, methallyl or crotyl o-alkyl, allyl, alkaryl or aralkyl, p
-vinyl, aryl or methallyl phosphonates, triallyl, trimethallyl or tricrotyl phosphonates; o-vinyl, o,o-diallyl, dimethallyl or dioctyl phosphonates; acrylic acid, methacrylic acid, maleic acid (mono- and di-esters), fumaric acid Acids (mono and di-
esters), itaconic acid (mono- and di-esters)
Cycloalkenyl esters such as 2,3
or 4-cyclohexenol acrylate, acrylic acid, methacrylic acid, maleic acid (mono- and di-esters), fumaric acid (mono- and di-esters)
and bicyclo(2,2,1)hept-5-en-2-yl esters of itaconic acid (mono- and di-esters); vinyl cyclohex-4-
En-1-yl ether, bicyclo(2,
2,1) Vinyl ethers and vinyl thioethers of cycloalkanols and cycloalkenenethiols, such as the vinyl ether of hept-5-en-2-ol, cycloalkenecarboxylic acids or vinyl bicyclo(2,2,1)hept-5ene -2-carboxylate vinyl esters, diallyl maleate and others. Soft stage crosslinkers include divinyl esters of di- or tribasic acids such as trimethylolpropane triacrylate, divinyl adipate; dialkyl esters of polyfunctional acids such as dialkyl phthalate, diallyl maleate or diallyl fumarate. Di- or trimethacrylates of polyhydric alcohols and esters of acrylic acid, such as trimethylol propane triacrylate and trimethacrylate, ethylene glycol dimethacrylate. ,
propylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol diacrylate, 1,
2- or 1,3-propylene glycol diacrylate and 1,3- or 1,4-butylene
Contains glycol diacrylates and others. The crosslinker and graft binder may be present individually in an amount of about 0.1 to about 10% based on the weight of the soft stage. Desirably about 0.1 to about 5
%. The outer stage is polymerized in the presence of the core and soft stage. The soft stage is polymerized in the presence of the core.
Although stages can be added to the core and soft stages before the final outside is created, the outside and optional intermediate stages that are added in succession to the soft stage constitute the remainder of the multistage polymer. The hard outer stage uses monomers that are polymerized to form the hard outer stage. The monomers used include from 1 to about 8 on the alkyl portion thereof.
alkyl methacrylate having carbon atoms of
Styrene, substituted styrenes, acrylonitrile, methacrylonitrile and mixtures thereof are used. Monomers forming the final stage are in particular methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, acrylonitrile, isobornyl methacrylate and others. Grafting agents or crosslinking agents can also be added to the outer stages if desired. If used, such graft binders or crosslinkers are the same as those used in making the soft stage. As previously stated, the weight of the intermediate stage (if present) and the outer stages will make up the remainder of the multistage polymer. One or more intermediate stages may be added, such intermediate stages being soft stages or hard stages or a combination thereof. If an intermediate step is present, it is preferred that the intermediate step be polymerized from a styrenic material. This styrenic material is the same as the styrenic material cited in connection with the styrenic material used in the polymerization when forming the core. If there is a styrenic intermediate stage, such styrenic intermediate stage is crosslinked in the same manner as in making the styrenic core. The amount of crosslinking agent used in this case is also the same as that used to make the styrenic core. If there is a styrenic intermediate stage, the core should be about 10 to about 30% by weight based on the weight of the multistage polymer.
parts by weight, and preferably up to 20 parts by weight of the styrenic intermediate stage based on the weight of the multistage polymer. Other monomers can also be used to form intermediate stages. These are such as are used to form an intermediate soft stage or an intermediate hard stage. Such monomers will be obvious to those skilled in the art and include the monomers used to form the soft or hard stages described in this invention. The amount of pigment used in this formulation is from about 0.1 parts to about 30 parts by weight per 100 parts by weight of resin (polyester and/or polycarbonate). The amount of pigment generally used is from about 2 to about 15 parts by weight per 100 parts of resin. Any pigment that is compatible with polyester and/or polycarbonate can be used. Pigments that can be used include red and brown iron oxides, cadmium and mercury sulphides, chromates, molybdates,
organic pigments such as aluminates and titanates, carbon black, benzenoid pigments, etc. Other pigments are known to those skilled in the art. The pigment is added to the multi-stage polymer after it is formed and then blended with the polycarbonate and/or polyester resin. Or, conversely, the polyester and/or polycarbonate resin can be loaded with pigments, ie before being blended with the multi-stage polymer. Furthermore, the resin, pigment and multi-stage polymer can be blended simultaneously. The colored polycarbonate and/or polyester resin generally comprises from about 60 parts to about 99.9 parts, preferably about 75 parts by weight of the total composition.
It is 98 copies from the item. Any thermoplastic polycarbonate resin can be used in the present invention. Such polycarbonates generally include polycarbonates derived from bisphenol A and in particular polycarbonates of 2,2-(4,4'-dihydroxy-diphenyl)propane, (4,4'-dihydroxy-diphenyl)-methane. polycarbonates of di-(monohydroxyphenyl)-substituted aromatic hydrocarbons, in which a hydroxy-phenyl group is attached to the same carbon atom of the hydrocarbon; i.e., 1,1-(4,4'- dihydroxy-diphenyl)-cyclohexane;
2,2-(4,4'-dihydroxy-diphenyl)butane;2,2-(4,4'-dihydroxy-
diphenyl)-pentane;2,2-(4,4'-dihydroxy-diphenyl)-hexane; and 2,2-(4,4'-dihydroxy-diphenyl)
- Contains heptane polycarbonates. Other polycarbonates used are those made with reactive dihydric phenols such as resorcinol, hydroquinone, or dihydroxydiphenylene. Especially bis-(4-hydroxyphenyl)-
Polycarbonates made from bis(hydroxyphenyl)-alkanes such as 2,2-propane (bisphenol A) or bis-(4,hydroxy-3,5-dimethyl phenyl)-2,2-propane. . Furthermore, polycarbonates that can be used include:
Alpha alpha'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene;halogenated-bis-(hydroxyphenyl)-alkane; bis-(hydroxyphenyl)-cycloalkane, sulfones, -sulfoxides,
ethers or sulfides, optionally in mixtures with glycols; derivatives of trinuclear bisphenols and carbonic acid, such as their diesters, dihalides, and optionally not insignificant amounts of dicarboxylic acids suitable for ester formation; These are polycarbonates derived from derivatives. Other polycarbonates are well known to those skilled in the art. The polyester used in the formulation of the present invention is a polyester having chain units having an aromatic ring in the main chain of the polymer. This aromatic ring may be a substituted aromatic ring. Examples of substituents on aromatic rings are chlorine, halogen atoms such as brome, methyl, ethyl, butyl,
A _C1 - _C8 alkyl group such as 2-ethyl hexyl or a tertiary isobutyl group. The polyesters are obtained in known manner by reaction of aromatic dicarboxylic acids or ester-forming derivatives thereof with glycols. Such reactions are generally known as direct esterification or transesterification. The acid component of polyester is naphthalene-2,6
Acids such as dicarboxylic acids and terephthalic acids, which have substituents such as lower alkyl esters as described above, similar to their ester-forming derivatives. Glycols include 1,4-butanediol and 1,
Polymethylene glycols having 2 to 8 carbon atoms, such as 6-heptane diol.
The acid and/or glycol components can also be replaced with other acids or other ester-forming derivatives. For example, other acid components include isophthalic acid other than naphthalene 2,6 dicarboxylic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid, and ester-forming derivatives thereof. Examples of other glycol ingredients used include:
1,4-cyclohexanediol, bisphenol A and its ester-forming derivatives. If the acid and/or glycol components are replaced with other acids or ester-forming derivatives thereof, such substitutions are desirably in amounts up to about 30 mole percent. Examples of polyesters particularly used in this invention are polyethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene 2,6-naphthalate, polytetramethylene 2,6-naphthalate, polyhexamethylene 2,6-naphthalate. , poly(C ₁ to about C ₈ ) alkylene terephthalates such as polypropylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, and polyethylhexyl terephthalate. A particularly desirable resin formulation is a mixture of equal weights of polycarbonate resin and polyester resin. The multi-stage polymers of this invention can be made by any known method. This manufacturing method is well known to those familiar with the industry. Simply put, multi-stage polymers that undergo sequential product polymerization are
It is made by emulsion polymerization of the monomers used to make the core or by emulsion polymerization of a soft stage and subsequent stages in the presence of a previously formed polymerized core. Polymerizations are carried out in the presence of catalysts, and such polymerizations can also contain polymerization control agents that act as chain transfer agents. The emulsifier used controls the particle size during the subsequent stages of core polymerization. The soap used in emulsion polymerization is desirably used in the minimum amount necessary to achieve the desired result.
The resulting multi-stage polymer is separated by coagulation or spray drying. The sequentially produced multi-step polymerization is completed at temperatures from about 0°C to about 125°C. Desirably the temperature is about 30°C to about 95°C. Chain transfer agents are added during polymerization to control the molecular weight at each step. The final particle size of the polymer produced in the sequential polymerization reaction is between about 150 and about 500 nanometers. Preferably about 200 to about 450
Between nanometers. Other ingredients such as light stabilizers or antioxidants can also be added to the formulation after polymerization. The other ingredients are also known and obvious to those in the field of this art. Mixing the multi-stage polymer with the polyester and/or polycarbonate can be done by any known method. The multi-stage polymer and polyester and/or polycarbonate are compounded into a well-dispersed mixture in an extruder, roll mill or similar equipment to make the mold formulation. In particularly desirable kneading methods, polycarbonate and/or polyester
It is dried for 12 to 20 hours at a temperature of 105°C to 120°C. The polyester and/or polycarbonate is then mixed with the pigment. Then, multi-stage polymers
Mixed with pigmented polyester and/or polycarbonate resin. For example, in a 1-inch single-screw extruder, the internal temperature of the extruder is approximately 430°C.
The mixture is kneaded at a rotation speed of 40 to 80 times per minute. The blended pellets are redried using drying conditions as described above. The dried pellets may be formed by injection molding or molding, or by other methods well known in the art. The multistage polymers used in the examples described below were made by sequential emulsion polymerization as described above. General Procedures for Examples The materials used in the formulation as ingredients were Merlon M-50 polycarbonate, a product of Mobay Chemical Corporation, with an intrinsic viscosity of 1.5; Celanex 2002-2;
2002-2) Poly(butylene terephthalate) with an intrinsic viscosity of 1.0, a product of Celanese Corporation; Carodel PET5-822C,
Intrinsic viscosity 0.8, a product of Rohm and Haas
poly(ethylene terephthalate) and red pigment C-PES-589 (obtained from Reed Plastics, 71.2% by weight polymeric carrier, 3.4% organic red pigment)
(a mixture of 2.5% inorganic dispersant and 22.9% inorganic red pigment). The pigment and the polyester and/or polycarbonate were mixed in the manner described below.
Prior to mixing the polycarbonate and/or polyester with the red pigment, the resin is dried at 110°C for about 16 hours. The dried pellets are combined and mixed with the red pigment and multi-stage polymer (if present as part of the composition). Kneading was carried out using a 1-inch Chiron single-screw extruder, at a temperature of 450〓 to 480〓, and at a screw rotation speed of 1 min.
Finished with rotation. The blended pellets are re-dried under the conditions described above. Compounding is the same with or without a multi-stage polymer, and with or without polycarbonate or polyester alone. In the tests in the examples, the kneaded resin formulations were injection molded using an Egan automatic molding machine at a temperature of 525°, a screw rotation speed of 50 revolutions per minute, an extrusion time of 8 seconds, an injection pressure of 800 psi, and a mold temperature of 144° to 197°. was used. Injection molded specimens were molded with two point gates to a size of 6 x 4 inches and 1/8 inch thick. In the following examples, notched Izo impact tests were performed on 1/8 inch thick specimens at 0°C and 10°C.
and 23°C. This test is ASTM D-
It was carried out according to the method of 256. Instrumental vertical height impact testing (VHIT) was performed on a General Research Corporation Dynatap testing machine. This test measures the energy required to cause at least one crack in a 1/8 inch thick sample. This test involves dropping a hemispherical dart at a rate of 10 feet per second onto a sample suspended between two clamps. The color intensity and presence or absence of pearlescent luster of the samples were determined visually. The following examples are provided to better illustrate the nature and manner of carrying out the invention. Examples Abbreviations used in the examples represent the following. PC = polycarbonate PBT = poly(butylene terephthalate) PET = poly(ethylene terephthalate) RP = red pigment (red pigment) BA = n-butyl acrylate TMPTA = trimethylol propane triacrylate DALM = diallyl maleate MMA = methyl methacrylate S = styrene DVB =Divinylbenzene A slash is used to distinguish components of a single stage, and two slashes represent the beginning of a different stage after it. In the examples presented below, it will be seen that formulations of the invention exhibit substantially the same impact strength relative to comparative formulations. It will also be apparent that the color intensity and lack of nacre are significantly improved over the comparative formulations.

【table】

【table】

【table】

[Table] Examples 1-4 50 parts of polycarbonate (Marlon M-50) plus each of Examples 1-4 and the control composition plus poly(butylene terephthalate) (Seranex 200-2) and 2.0 parts of red Pigment (C-PES-
589) were mixed in a 1 inch Chiron single screw extruder as described in the General Procedures section above and injection molded as described above. Impact tests were conducted on each molded sample and the color characteristics of each sample were observed. The results are shown in Table 1.

【table】
Ru.
Control E 6 7.9 2.9 2.5
570 Both samples, pearlescent light at both gates

It shows a swamp and the melt bond line is obvious.
12 15.7 8.6 3.4
600

The color is also not uniform and not strong.
The table shows the improvement of the formulation according to the invention in terms of uniformity of color, depth of color and substantial absence of nacreous luster. The data in the table shows that non-impact blends of polycarbonate and polyester have poor impact resistance but good color properties. In the table, Controls A and C contain no pigment, and Controls B and D contain the pigment specified in this example.

【table】
As a result, the color cannot be observed.
Control C None 0.97 0.70 0.65
660
Control B None 1.5 1.2 1.1
Controls B and D are pearls at the entrance gate.

No foil luster was observed, melt bonding line contrast D None 0.95 0.80 0.55
610

Hardly visible, uniform color and strong

There are times.
Examples 5-7 In Examples 5 to 7, 100 parts of polycarbonate or poly(butylene terephthalate) was used as the resin.
The effect of the formulation of the present invention when using 100 parts or poly(ethylene terephthalate). The procedure used in Examples 1 to 4 was repeated with the exception of the resin used. Pigments are used and the amounts are the same as in Examples 1-4. The test results are shown in the table.

【table】
It is hard to see, the color is uniform and strong.

There are times.

【table】
Lower color intensity compared to Example 7

It's coming down.
Examples 8-13 Examples 8-13 demonstrate the effectiveness of the present invention when using different levels of styrene in the core of a multi-stage polymer. The procedure used in Examples 1-4 was repeated here. Examples 8-13 used the polycarbonate and poly(butylene terephthalate) and amounts thereof used in Examples 1-4, as well as the pigments and amounts thereof. Mixing was completed similar to that done in Examples 1-4. The test results are shown in the table.

【table】
strong.
Examples 14-16 Examples 14-16 demonstrate the effectiveness of the present invention when using different levels of crosslinker in the styrene core. The procedure of Examples 8-13 was repeated in this case. The results are shown in the table.

【table】
Stronger than you can put it on.
16 12 12.8 4.5 3.1
560 Very slight pearl foil on the sample gate

Gloss and melt bond lines are not noticeable.

The color is strong and uniform.
Examples 17-18 Example 17 shows the case where a non-styrene copolymer was used in the core portion. Example 18 shows a formulation according to the invention. The test results are shown in the table.

【table】
I can't see it at all. The color is strong and uniform

Ru.
Control L 12.0 15.7 8.6 3.4
600 Mother of pearl on both entrance gates.

Melt bond lines are noticeable. color is uneven

First, it's not very strong.
Examples 19-22 Example 19 describes a multi-stage polymer in which the non-core stages of the multi-stage polymer contain styrene, but no styrene is present in the core. The advantages according to the invention are not obtained in this case. Example 20 describes a multi-stage polymer that includes a crosslinker in the non-core stages of the multi-stage polymer, but not in the core stage. Example 21 shows that the advantages of the present invention are not obtained when the multistage polymer core is composed of non-crosslinked styrene. Example 22 shows that although additional non-core styrene stages are present, the benefits of the present invention are not obtained when uncrosslinked styrene constitutes the core of the multi-stage polymer. The procedure used in Examples 8-13 was repeated here. The results are shown in the table.

【table】
lower than what was obtained.
Examples 23-24 Example 23 (Control Q) illustrates a multi-stage polymer when the core of the multi-stage polymer was polymerized from a methyl methacrylate hard polymer. The advantages of the invention have not been achieved. Example 24 (Control R) shows that the advantages of the invention are not obtained when the core is made of cross-linked methyl methacrylate. The approach taken in Examples 8-13 was repeated here. The results are shown in the table.

Table: The subsequently produced multi-stage polymers that are part of this invention demonstrate the impact resistance, processability,
Used to modify properties such as thermal stability and weather resistance. The amount of multi-stage polymer used in conjunction with such other polymers and polymer mixtures can vary widely. Thus, the amounts used in connection with polyesters, polycarbonates and mixtures thereof mentioned herein may also be used, less than or more than those used. Polymers or polymer mixtures used with the multi-stage polymers are as mentioned herein: polyesters, polycarbonates and mixtures thereof; polyphenylenes, polyphenylene oxides and mixtures thereof; acrylonitrile-styrene-butadiene copolymers. alone or in mixtures with polycarbonates and/or polyvinyl chloride homopolymers or copolymers, as well as mixtures thereof and with polycarbonates; acrylic polymers, such as methacrylic acid, alkyl acrylates (especially those containing 1 to 12 carbon atoms in the alkyl moiety); polybutadiene and its copolymers as well as mixtures thereof, especially with alkyl acrylates; polyvinyl One of the well-known modifiers for halogenated polyvinyls such as chlorides and their copolymers, as well as methacrylate-butadiene-styrene copolymers with or without acrylonitrile as a component of the copolymer. or higher modified halogenated polyvinyl, chlorinated polyethylene, styrene, acrylate-styrene copolymers; polypropylene, polypropylene copolymers, mixtures of propylene with polymers from ethylene propylene diene monomers, and homopolymers from ethylene propylene diene monomers. Polymers; polyvinylidene chloride and/or fluoride, polytetrafluoroethylene; polyether imides and mixtures thereof; polyethylene homopolymers and cobolymers alone or in mixtures with polycarbonates or other polymers; styrene-maleic anhydride copolymers alone or halogenated Polyvinyl, a mixture with polyvinyl chloride, or with polycarbonate, or with both; polyamides, such as nylon 6 or 66 or 11 or 12, and mixtures thereof, as well as mixtures of nylon with polymers from ethylene propylene diene monomers. ; polyacetyl homopolymers and copolymers and mixtures thereof;
styrene-acrylonitrile copolymers; polyester mixtures such as the polyester mixtures described in this invention; and others. Although the invention has been described in some preferred embodiments and illustrated by specific embodiments, the scope of the invention as claimed herein is not limited thereby.

Claims (1)

Claims: 1. from about 60 parts by weight to about 99.9 parts by weight of a colored thermoplastic resin selected from the group consisting of polyester, polycarbonate, and mixtures thereof, and from about 0.1 parts by weight to about 0.1 parts by weight to about 90 parts by weight of a multi-stage polymer sequentially formed. 40 parts by weight of the multistage polymer, wherein the multistage polymer comprises (a) at least about 10 parts of a polymer core per 100 parts by weight of the multistage polymer, provided that the core comprises a styrenic monomer or a styrenic monomer and a styrenic monomer; 2
(b) an alkyl acrylate having from 1 to 8 carbon atoms in the alkyl portion; a second stage consisting of a soft stage polymerized from a monomer or said alkyl acrylate monomer and a crosslinking agent and/or a graft binder, or said alkyl acrylate monomer and a comonomer; and (c) an alkyl moiety having from 1 to 8 carbon atoms. a hard thermoplastic outer stage polymerized from a methacrylate monomer, or with the addition of at least one intermediate stage polymerized from a styrenic monomer or a styrenic monomer and a crosslinker between the soft and hard stages; A mixture of polymers. 2 The core has a weight of approximately 0.1 based on the weight of the core.
The polymer mixture of claim 1 which is crosslinked with a crosslinking agent in an amount of from about 10 percent to about 10 percent. 3 The core crosslinking agent is polyvinylbenzene, divinyl esters of di- or tribasic acids, dialkyl esters of polyfunctional acids, diallyl esters of polyfunctional acids, divinyl esters of polyhydric alcohols,
3. The polymer mixture according to claim 2, which is selected from the group consisting of ditrimethacrylic acid esters of polyhydric alcohols, di- or triacrylic acid esters of polyhydric alcohols, and mixtures thereof. 4 The soft stage crosslinking agent is trimethylolpropane triacrylate, divinyl adipate, dialkyl phthalate, diallyl maleate, diallyl fumarate, divinyl ether of ethylene glycol, ethylene glycol dimethacrylate, propylene glycol dimethacrylate,
1,3-Butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-
Butylene glycol diacrylate, 1,4-
A polymer mixture according to claim 1, which is selected from the group consisting of butylene glycol diacrylate, divinylbenzene, trivinylbenzene and mixtures thereof. 5 The styrenic monomer is styrene, α-
selected from the group consisting of methylstyrene, monochlorostyrene, t-butylstyrene, vinyltoluene, p-isopropylstyrene, 3,4-dimethylstyrene, p-bromustyrene, 3,4-dichlorostyrene and mixtures thereof A polymer mixture according to claim 1. 6. Polymer mixture according to claim 1, in which at least one intermediate stage is added between the soft stage and the outer stage. 7. The polymer mixture of claim 6, wherein said additional intermediate step is polymerized from a styrenic monomer. 8. The polymer mixture of claim 6, wherein said additional intermediate step is polymerized from a styrenic monomer and a crosslinking agent. 9. The polymer mixture according to claim 1, wherein the second monomer is a non-styrenic, non-crosslinkable monovinylidene monomer. 10. The polymer mixture of claim 1, wherein the second monomer is an alkyl methacrylate. 11. The polymer mixture according to claim 1, wherein the second monomer is a vinyl ester. 12. The polymer mixture according to claim 1, wherein the second monomer is acrylonitrile. 13. The polymer mixture according to claim 1, wherein the second monomer is methacrylic acid. 14. The polymer mixture of claim 1, wherein the second monomer is acrylic acid. 15. The polymer mixture of claim 1, wherein said second monomer is an alkyl methacrylate having from 1 to about 8 carbon atoms in the alkyl portion. 16. The polymer mixture according to claim 15, wherein the alkyl methacrylate is methyl methacrylate. 17. The polymer mixture of claim 1, wherein said second monomer is an alkyl acrylate having from 1 to about 8 carbon atoms in the alkyl portion. 18. The polymer mixture of claim 17, wherein said alkyl acrylate is selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and mixtures thereof. 19 The second monomer is about 1% to about 20
Polymer mixture according to claim 1, present in a percentage amount. 20 The crosslinking agent is approximately
3. The polymer mixture of claim 2, wherein the polymer mixture is present in an amount of 0.1 percent to about 5 percent. 21. The polymer mixture of claim 1, wherein the core is from about 10 to about 40 parts by weight based on the weight of the multi-stage polymer. 22. The core of claim 1, wherein the core is from about 10 to about 30 parts by weight based on the weight of the multi-stage polymer, and there is an additional intermediate styrenic stage between the soft stage and the outer stage. polymer mixture. 23. The polymer mixture of claim 1, wherein the soft stage is from about 40 to about 80 parts by weight based on the weight of the multistage polymer. 24. The polymer mixture of claim 1, wherein the soft stage is from about 60 to about 80 parts by weight based on the weight of the multistage polymer. 25 The soft stage includes 1 to about 8 on the alkyl moiety.
2. A polymer mixture according to claim 1, which is polymerized from an alkyl acrylate having 5 carbon atoms. 26. The polymer mixture of claim 25, wherein the alkyl acrylate is selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and isobutyl acrylate. 27 The crosslinking agent is approximately
26. The polymer mixture of claim 25, wherein the polymer mixture is present in an amount of 0.1 to about 10 percent. 28. The polymer mixture of claim 25, wherein the graft binder is present in an amount of about 0.1 to about 10 percent based on the weight of the soft stage. 29 The soft stage comprises from about 0.1 to about 10 percent crosslinking agent and about 0.1 percent, based on the weight of the soft stage.
The polymer mixture of claim 1 containing from about 10 percent graft binder. 30. the soft stage is polymerized from an alkyl acrylate monomer and a comonomer;
The polymer mixture of claim 1, wherein said comonomer is less than about 50 percent by weight of the soft stage. 31. The polymer mixture according to claim 30, wherein the comonomer is a non-crosslinkable vinylidene monomer. 32. Claim 3, wherein said comonomer is selected from the group consisting of acrylonitrile, alkyl methacrylates having from 1 to about 8 carbon atoms in the alkyl moiety, styrenic monomers, isoprene, chloroprene, and mixtures thereof.
Polymer mixture according to item 0. 33. The polymer mixture of claim 1, wherein the outer stage is polymerized from a _C1 to about _C8 alkyl methacrylate. 34 said outer stage comprises methyl methacrylate;
A polymer mixture according to claim 1, which is selected from the group consisting of ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, acrylonitrile, isobornyl methacrylate and mixtures thereof. 35. The polymer mixture of claim 1, wherein the outer stage is from about 10 to about 35 parts by weight based on the weight of the multistage polymer. 36. The polymer mixture of claim 1, wherein the polyester is poly( _C1 - _C8 ) alkylene terephthalate. 37. The polymer mixture of claim 1, wherein the polyester is poly(butylene terephthalate). 38. The polymer mixture according to claim 1, wherein the polycarbonate is an aromatic polycarbonate. 39 Claim 1, wherein the polycarbonate is derived from bisphenol A.
Polymer mixtures as described in Section. 40. The polymer mixture of claim 1, wherein the colored thermoplastic resin is a mixture of polyester and polycarbonate and a pigment. 41. The polymer mixture of claim 1, wherein the colored resin is a mixture of aromatic polycarbonate and poly(butylene terephthalate) and a pigment. 42. The polymer mixture of claim 41 containing approximately equal weights of said aromatic polycarbonate and said poly(butylene terephthalate). 43. The polymer mixture of claim 1, wherein said pigment is present in an amount of about 0.1 to about 15 parts by weight based on 100 parts by weight of thermoplastic resin. 44. The polymer mixture of claim 1, wherein said pigment is present in an amount of about 2 to about 5 parts by weight based on 100 parts by weight of thermoplastic resin. 45. The polymer mixture of claim 1 containing from about 25 to about 75 percent said polycarbonate and from about 75 to about 25 percent said polyester, based on the total weight of unpigmented thermoplastic resin.