JPH06500812A - Flame retardant brominated styrene based latex - Google Patents

Abstract

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

Description

[Detailed description of the invention] Background of the invention of flame-retardant brominated styrene-based latex field of invention The present invention relates to a polymer latex composition and a method for producing the same, and in particular, to a polymer latex composition and a method for producing the same. Generated ethylenically unsaturated aromatic monomer and at least one other type of monomer - It relates to latex containing.

Description of prior art Acrylic, styrene-acrylic and vinyl-acrylic latexes are It is used commercially for various surface coatings. Latte used in many paint applications It is desirable that the box has flame retardant properties. This is especially true when latex Woven fabrics, carpets, paints, transparent paints, adhesives, sealants, caulking, non-woven fabrics, Applicable when used as a fabric binder, etc.

The usual way to impart flame retardancy to latex is by incorporating flame retardant additives. be. Many of these flame retardant additives contain bromine, such as brominated diphenyl or or diphenyl oxide compound together with antimony trioxide. but, The problem with these flame retardant additives is that their use results in an extremely white coloration. and the occurrence of sedimentation effects, as well as the development of toxicity due to the presence of antimony trioxide. It has the major drawback of being raw.

Common approaches to impart flame retardancy have traditionally been solid organic and inorganic The compound was added to latex. US Patent No. 3477. 974, an aqueous dispersion of a halogenated organic compound and a metal oxide is bonded to a polymer. It is described that it is added to a bonding agent. This approach has traditionally been Although it has been suggested that it imparts flammability, it also introduces a number of undesirable properties. Ru. No matter what dispersion technique is used, solids end up as latex emulsions. Separate from. Dispersions tend to have high viscosity, which hinders latex application.

The presence of solids makes latex films difficult to handle and prevents melting of the latex. It interferes with facultative ability or "hand." Also, solid supports It tends to have a coloring effect that masks or changes the color of the material.

Liquid compounds have also traditionally been added to latex. US Patent No. 3, 766°189 adds liquid chlorination to the latex to achieve flame retardancy. teaches the use of paraffin. The disadvantage of using liquids is that over time The latex moves to the surface from the rimmer and separates from the liquid latex emulsion. It has an adverse effect on adhesion, plasticization, and swelling, and also has poor water resistance.

Salts and other water-soluble solids solve the problem of settling solids, but In addition to creating other problems, it is generally detrimental to the stability of latex emulsions. affect.

Chemically incorporating monomers into Ftex polymers to impart flame retardancy has traditionally had limited success. PVC-based latex is easily flammable. It is barely better than its flame-retardant analogs. In vinylidene chloride form Further addition of chlorine has been very limited due to high cost.

base catalyst and polymerized halogen-containing vinylidene monomers and other vinylidene monomers. A curable resin composition containing an aqueous solution of Nomer was manufactured by Mitsui Toatsu Chemical Co., Ltd. in September 1981. Disclosed in Japanese Patent No. 56120754-12 issued on May 22nd. Ru. According to Mitsui's patent, water-based suspensions or emulsions of vinyl polymers are , water resistance, crack resistance and dirt resistance (stain resistance) are weak, and proposed by Mitsui. Compositions have been reported to overcome these drawbacks. The above patent applies to bromination discloses a variety of halogenated vinyl monomers, including seven monomers. However, the use of polybrominated heptamers is not disclosed.

Additionally, Mitsui's patents are limited to water, crack and stain treatments. Mitsui's The patent describes the production of flame-retardant latex using brominated vinyl monomers. There is no recognition that the patent is There is no disclosure whatsoever as to what percentage of rivers will be used. The above patent is , proposes that the halogen-containing monomers contain up to 15% by weight of the copolymer. This corresponds to a maximum of about 6% of the bromine content in the resin. Mitsui patent furthermore contains a low percentage of halogen-containing monomers, up to 10 ! It is shown that it is preferable to correspond to a bromine content of 1%, that is, a maximum of 4%. ing. These percentages are insufficient to impart the desired flame retardancy . Mitsui's patent is far from the present invention in that it states that the lower the bromine content, the better. It teaches that.

Bromine-containing plastics were introduced as 5 Lasicarbo on December 15, 1979. No. 13,052-M filed on July 9, 1980 by B.V. Described in European Patent Application No. 79200761.4 published as -1 has been done. SLa Hoicarbom's application is for polyolefins, polystyrene and copolymers of styrene and butadiene, and styrene and acrylonitrile. The aim is to manufacture plastic materials such as , ABS, etc. Sji Otori 1cs rbon application plastics require high levels of bromine, 20 to 44 wt. % bromine.

There remains a need for polymer latexes that have desirable flame retardant properties. moreover , its polymer latex can be easily mixed with other latexes as flame retardants. Both are important. The polymer latex of the present invention satisfies these requirements and is useful. Flame-retardant heavy-duty backside coatings, paints, paints, adhesives, sealants, caulking agents , is useful in applications such as nonwoven fabric binders.

Summary of the invention According to the present invention, ring halogenated I; Copolymers with alkyl acrylate and/or methacrylate monomers, Additionally, polymer latexes optionally containing at least one other monomer are provided. Served. In one embodiment, the halogenated aromatic polymer is present in an amount providing 7 to 20% by weight of bromine in a typical latex composition. . In another embodiment, the halogenated aromatic monomer is polybrominated. and especially an average of at least about 1.5 monomers per monomer unit. A 7-mer with bromine can be used.

Compositions of the invention are exemplified by three categories of latex compositions.

In a fourth embodiment, the latex is a ring-membered aromatic superunit. , alkyl acrylate monomer unit, alkyl methacrylate monomer - unit, or a second monomer unit consisting of a combination thereof. including. In a second embodiment, the latex is of these first two types. In addition, it contains unsaturated esters of saturated carboxylic acids, halogens, etc. a third selected from aromatic monomers or unsaturated carboxylic acid monomers; Including seven units. In a third embodiment, the latex comprises four types of seven - unit, i.e., a ring member-substituted aromatic monomer unit, an alkyl alkyl rylate and/or alkyl methacrylate monomer units, unsaturated carbon Contains a high-temperature unit, as well as a halogen storage and release monomer.

It is an object of the present invention to provide a flame retardant polymer latex with desired physical properties. Is Rukoto.

A further object of the invention is that it can be used in a wide variety of applications, such as textile backing coatings, coatings, Flame retardant useful in paints, adhesives, sealants, caulks, binders for non-woven fabrics, etc. The purpose of the present invention is to provide a polymer latex with high properties.

Further objects and advantages of the invention are described below.

Description of preferred embodiments To facilitate an understanding of the principles of the invention, embodiments are set forth below by way of reference. . However, this is not intended to limit the scope of the invention; Further modifications and applications of the principles of the invention described herein are contemplated by the invention. It is reasonable that a person skilled in the technical field related to the invention can easily conceive of this. It will be understood.

The present invention has superior physical properties, is useful in a wide variety of applications, and is superior to prior art compositions. A polymer latex composition having improved flame retardant properties is provided. Traditionally Efforts have not been able to provide compositions of the type described above, but polymers Incorporating a ring-membered aromatic upper unit into a latex can improve compositions. Compositions with improved flame retardancy without compromising physical properties other than flame retardancy It turns out that it is possible to obtain I;.

Brominated aromatic monomers are commonly included in various latex compositions, It also includes those known to be useful as aromatic mortuary materials. , but is not limited to this. The brominated tops are part of the funerary materials. or used in place of all. In the present invention, the above-mentioned ring-membered aromatic Using aromatic monomers, a wide range of customizations are being made using aromatic monomers. New technology provides improved flame retardancy without compromising the physical properties of latex. Obtainable.

Reacting one or more hexamers with, for example, brominated styrene Then, the copolymer latex of the present invention is obtained. Brominated aromatic Proper selection of the 7-mers used together creates a flame-retardant latte useful in a wide range of applications. can manufacture boxes. Such uses include, for example, indoor decoration and textile back coatings for clothing, carpet linings, non-woven filter media binders, paint There are adhesives, caulking materials, sealants, etc.

The latex of the present invention is a ring member-substituted t; an aromatic monomer and at least one Contains other monomers. The compositions of the present invention can be applied to three categories of latex. exemplified by the gas composition. In a first embodiment, the latex (cyclobromine Infused aromatic monomer units and alkyl acrylate monomers alkyl methacrylate monomer unit or a combination thereof The first contains two types of monomer units: Unsaturated carboxylic acid, unsaturated carboxylic acid, 7 halogens and aromatic acid a third monomer unit selected from Force 1; Third embodiment 6 1. Latex (length, 4 types of monomer units, i.e., ring-membered aromatic Aromatic mono-v-units, alkyl acrylates and/or alkyl methacrylates rylate monomer unit, unsaturated carboxylic monomer unit, and ) Includes Gen 7 Riichi Aromatic Upper Waist Tsuma.

The present invention is based on the formula (1) In formula c, X-1 to 4, R, are -H or -CHs, and R, l, -H or 1 It is an alkyl group having 1 to 4 carbon atoms. ] on the ring-brominated aromatic Use a tsumar unit. Typical ring halogenated aromatic polymers are t6 styrene with bromine substitution (mohedi)tri and tetra) on the phenyl nucleus, methylstyrene Styrene, 1-methylstyrene, α-methylmethylstyrene A mixture of or a mixture of isomers may be used. To explain in more detail, A preferred ring member-substituted aromatic compound is polybrominated styrene, Dipromostyrene is most preferred. A preferred dipromostyrene material is Ind+ a++a, Wesl LafBeHe's Grest Lakes Chemi This material is obtained from Cal Corporation++++. Usually about 15% by weight monobromostyrene and 3% by weight tribromostyrene. Contains.

In one embodiment of the present invention, the ring-substituted aromatic polymer is a latex compound. It is present in an amount sufficient to achieve the desired flame retardancy, based on the total weight of the composition. This point In this case, the ring-membered monomer contributes 7 to 20% bromine by weight of the total composition. Contains a certain amount. More preferably, the ring member primed heptamer is 9- to 18-fold. Contained in an amount to give % bromine.

In another aspect of the invention, the ring-substituted aromatic compound in polybrominated form It has been found that it is preferable to utilize aromatic monomers. This applies to the entire composition. The number of ring members required to achieve a given weight percent of bromine is Minimize the number of knits. A low percentage of ring-membered seven-mer units The use of Minimize negative effects. Therefore, the ring-substituted aromatic upper unit is Contains a polybrominated unit, and a ring-membered seven-mer unit is a unit. It is an embodiment of the invention that the composition contains an average of at least about 1.5 bromine per sample. Ru. A monobrominated ring member containing a monobrominated aromatic unit in the form I; As for Tex, less than 20% of the ring-membered Hosha Koshigami Tsumar units are Preferably, it is monobrominated.

At the same time, it is desirable that latex compositions be easily prepared. highly odor Hydrogenated ethylene saturated aromatic additives, e.g. pure tetrabromostylene Lenses are not liquid at room temperature, and these prevent easy latex preparation. did Therefore, monobrominated heptamer units and polybrominated heptamers in latex The ratio to the monomer units obtained corresponds to that of unsaturated, ring-membered, aromatic monomer units. Preferably, the mixture is liquid at room temperature. For example, the production of the latex of the present invention The preferred material used for construction is the Grtxt Lakes Ckemi described above. exl Dipromostile as manufactured by Corporatrom The composition is liquid at room temperature and contains 15% monobromostyrene, Contains a mixture of 82% lomostyrene and 3% tribromostyrene. liquid at room temperature Other monobrominated and polybrominated t; aromatic monomer mixtures are likewise preferably used in the production of the present latex composition. Mixture at room temperature Contain as high an overall bromine percentage as possible while remaining liquid. preferable.

In a first embodiment of the invention, the polymer latex comprises ring members of formula (I) further contains alkyl = (meth) of formula (If). ) containing acrylates, [In the formula, R1 is -H or -CH, and R3 has 1 to 20 carbon atoms] ].

Representative alkyl acrylates useful according to the invention include methyl acrylate, ethyl acrylate, acrylate, n-propyl acrylate, isopropyl acrylate, n- Butyl acrylate, inbutyl acrylate, n-amyl acrylate, n- Hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate rate, n-hebutyl acrylate, isohebutyl acrylate, 1-methyl- hebutyl acrylate, n-ofthiol acrylate, e.g. 6-methyl-hep inophthioacrylates such as tylacrylate, n-nonyl acrylate isononyl such as 3,5,5-trimethylhexyl acrylate Acrylates, n-decyl acrylate, lauryl acrylate and corresponding methacrylates, and other primary, secondary and tertiary higher alkyl alkyl acrylates and methacrylates, and the alkyl group has 1 to 20 carbon atoms. Those in the range of can be used, preferably those having 2 to 10 carbon atoms. be. Preferred seven polymers include ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and methyl methacrylate. Also, hydroxyl acrylic acid or methacrylic acid Rukyl esters are useful in the present invention.

In one of the first embodiments of the invention, the latex composition is Aromatic extraction unit and alkyl acrylate and/or alkyl methane Contains tacrylate monomer units. As mentioned above, ring-membered aromatic The monomer units preferably contain 7 to 20% bromine, based on the weight of the total composition. More preferably, the amount of bromine is 9 to 18%.

In addition, the ring member-substituted aromatic extractor unit preferably has a Contains on average at least about 1.5 bromine. This @1 of latex of the present invention In other embodiments, the composition comprises a ring-membered aroma extractor unit. and an alkyl acrylate/methacrylate monomer unit. do.

In a second embodiment of the invention, the polymer latex comprises a ring-membered aromatic Nukijo Tsumar unit (1) and alkyl acrylate/methacrylate unit (■) and further contains an unsaturated upper unit (III) of a saturated carboxylic acid. , aromatic mercury unit (IV) or carboxylic acid monomer unit Contains the third monomer unit of (V).

The acid ester monomer unit has the formula (Iff) [wherein R4 is 1 to 3 carbon atoms] It is an alkyl group having . ]. Typical acid ester monomer units Examples include vinyl acetate, vinyl propionate and vinyl butyrate. vinyl acetate is preferred.

The non-brominated aromatic monomer unit has the formula (rV), where R1 and R7 are As defined in ]. The standard halogen-free aromatic waistband is , styrene, α-methylstyrene, methylstyrene, σ-methylmethylstyrene , ethylstyrene, and α-methylethylstyrene stomach.

The carboxylic acid monomer unit has the formula (v) [wherein R1 is -H or -CH] It is 3. ]. Typical ethylenically unsaturated carboxylic acid monomers are These are lylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. preferred Acrylic acids are acrylic acid and methacrylic acid.

Ring member-substituted aromatic extraction unit and alkyl acrylate/methacrylate Selection of the rate monomer unit is as described above. Related features of the invention l :8, the latex contains a ring-substituted aromatic monomer unit (■), an alkali Kill acrylate/methacrylate monomer unit (■) and acid nyste Lumo/Ma! Nino l- (III), funerary implements materialized aromatic upper waist unit (IV ) and a third unit selected from the group consisting of carboxylic acid monomer unit (V). From knitting becomes essential.

In the third embodiment of the present invention, a ring member-substituted aroma extractor unit (■ ), alkyl acrylate/methacrylate monomer unit (II), funeral implements Chemicalized aromatic upper unit (rV) and carboxylic acid monomer unit (v) A muphorimar latex containing the following is provided. Related Features I:8 Latex is a ring member-substituted aromatic upper unit (1), alkyl acrylate/metallic Tacrylate monomer unit (■), funerary materialized aromatic waist unit (rV ) and a carboxylic acid monomer unit (V).

Advantageously, the latex according to the invention can be manufactured according to conventional methods. can be done. For example, latex is produced by an emulsion system (water, emulsifier, initiators and chain transfer agents), total monomers in the desired ratio in the polymer. It is produced by polymerizing in small quantities. The technology for producing latex is solution Also included are polymerizations, bulk polymerizations, and suspension polymerizations. Suitable initiators include radicals Initiators used for polymerization, e.g. organic peroxides, hydrogen peroxide, azo or Examples include diazo compounds, persulfates, redox systems, and the like. suitable emulsifier and Examples include anionic, cationic, nonionic or amphoteric emulsifiers. . Useful chain transfer agents include aliphatic, aryl mercaptans and disulfide CCI CBr. %CH1.8 and CHCI3. These utensils Of these, mercaptans are preferred.

Polymerization may be carried out in the presence of air. -30~110℃ in the absence of oxygen Faster reactions are observed in the temperature range, preferably from about 0 to about 80°C. It will be done.

The polymer latex according to the present invention can be used as a flame-retardant textile lining paint, paint, paint, etc. The resulting products include adhesives, adhesives, adhesives, caulking agents, and nonwoven fabric binders. Nanatsuma - The choice of - depends on the end use of the latex. As a criterion, the desired Glass transition temperature (Tg), physical properties and chemical resistance.

The flame retardant latex used in the present invention can be used in combination with other latex compositions, e.g. Non! ! Latex and paints with improved properties when added to flammable latex You can also get In particular, the flame retardant latex according to the present invention and other latexes The combination with gas produces a coating with improved flame retardant properties. latte of the invention odor to the desired level of the combined latex and paint. to achieve the desired level of flame retardancy, as described above. Adhesion, fi Improvements in properties have also been achieved in terms of lume-forming properties, chemical resistance and flexibility. It will be done.

The following examples are intended to illustrate the invention and are not intended to limit the invention in any way. It's not a matter of nature. Unless otherwise noted, percentages are by weight. Examples 1 to 5 Production of DBS/2-EHA copolymer latex Dipromostyrene (DBS)/ An 8 oz. I went with the bottle. Ingredients (122.5 or 180 parts by weight of deionized water, dodecyl 3 parts of sodium sulfate, 3 parts of potassium persulfate, 0.0 parts of t-dodecyl mercaptan. 2 parts and 100 parts of all 7mers in the desired ratio in the polymer) into an 8 oz. Loaded, flushed thoroughly with nitrogen, then reacted at 50°C for 15 hours. It was about 45.8 or 3685% solids. Cool the entire bottle to room temperature and de-ignite. 3 parts of hot water and 20.18 parts of 50% H2O were added followed by stirring for 20 minutes.

The results of these preparations are shown in Table I. Latex is well suited for a variety of coating applications. , exhibiting improved flame retardancy.

Table■ Preparation example of DBS/2-EHA copolymer latex Loading and reaction time Solids Conversion rate Dis/2-EHA kr % % + 34:66 is 45.1 100! 30 Near G 15 45.1 1 003 HalG 15 45.1 100+ +5:ls Is 36.5 1005 H:81 Is 364 100 The foregoing method can be used, for example, with ethyl acrylate, n-propyl acrylate and n-propyl acrylate. - By repeating with butyl acrylate, an equally excellent latex composition is obtained. A product is obtained.

Examples 6 to 11 DBS/2-EHA/VAc Terpolymer Latex Preparation Examples 1-5 General By repeating the same operating procedure, dipromostyrene (DBS) 0-30% by weight, 2- Ethylhexyl acrylate (2-EHA) is ~80% by weight OJ:! /ff [Preparation of terpolymer latex containing 10-85% by weight of vinyl (VAc)] did. As shown in Table 1, the reaction was carried out at 50°C for 15 to 16.25 hours, with a conversion rate of 9. 5-100%, solids reached 34.7-36.5%. 2-ethylhexylac The rylate is ethyl acrylate, n-propyl acrylate, n-butyl acrylate. vinyl acetate and vinyl globionate. By repeating the above preparation but substituting vinyl and vinyl butyrad, Similarly, good latex compositions are obtained. Latex is suitable for various coating applications. and exhibit improved flame retardant properties.

table" DBS/! - Preparation example of EHA/VAc terpolymer latex Loaded monomer - Reaction time Solids Conversion rate DBS/ToEHA/VAc kr % %6 3 0:32:3! +5 35.7 917! 0:60:! OIs 34.7 151 10:40:40 Is 317 H920:20760 +5 35 ．． 7 1810 10:10:10 1! , H3L5 100II O215: 85 +a, ts 35. ! H Example 12-17 DBS/2-EHA/S Terpolymer Latex Preparation Examples 1-5 General Repeat the operating procedure to add 0-20% by weight of dipromostyrene (DBS), 2-ethyl 10-60% by weight of hexyl acrylate (2-EHA) and styrene (S) Terpolymer latexes containing 20-90% by weight were prepared. Nanatsuma is As shown in Table ■, the conversion rate was 91-100% at 50°C for 15-18.25 hours. Polymerized to 33.2-36.5% solids. 2-ethylhexyl acrylate tylacrylate, n-propyl acrylate, n-butyl acrylate and Replace styrene with methyl methacrylate, methyl styrene, α-methyl styrene. Ren, a-methylmethylstyrene, ethylstyrene and σ-methylethylstyrene Ren l! Alternatively, a similarly good latte can be obtained by repeating the above preparation. A sugar composition is obtained. Latex is well suited and improved for a variety of coating applications. Shows flame retardancy.

Table■ Preparation example of DBS/1-EHA/S terpolymer latex Loaded monomer Reaction time Solids Conversion rate DBS/2-EIiA/S hr % % + 2 20 :60:20 +s, o 33.2 9+H20:40:10 +s, ss 3 6.5 100+4 20+20+60 15 35.5 97+5 15:i o:45 18.25 36.1 99+6 10:10:50 u, o 36 ．． +9917 0:10:90 11.25:16. + 99 Examples 18 ~24 Manufacture of DBS/EA or BA/MAA terpolymer latex Ren (DBS)/ethyl acrylate (EA) or butyl acrylate (B A)/methacrylic acid (MAA) emulsion polymerization was carried out in an 8 oz bottle. Honnari 103.67 parts by weight of deionized water, 3 parts of sodium dodecyl sulfate, and potassium persulfate. 0.3 parts of sodium sulfite, 0.3 M of sodium sulfite, and 0.3 parts of t-dodecylmercaptan. 2 parts or 0 parts, 20 to 30 parts of DBS, 80 parts of EA or BAO, and ~8 parts of MAAO into an 8 oz. The mixture was reacted at 50° C. for 7 hours to obtain about 50% solids. Cool the entire jar to room temperature. The mixture was cooled and neutralized to 1% NaOH't' pH 7. Table the results of these preparations. Shown in ■. Ethyl acrylate or butyl acrylate is replaced with n-propyl acrylate. lylate and 2-ethylhexyl acrylate, replacing methacrylic acid with arylate and 2-ethylhexyl acrylate. An equally good latex can be obtained by repeating the above preparation, substituting acrylic acid. A gas composition is obtained. Latex is well suited for a variety of coating applications and has improved Indicates flammability.

Table■ DBS/EA or HA/M Mum Terpolymer Latex Preparation Example Loading Upper Zummer reaction time Solids Conversion rate DBS/EA/BA/MAA hr % % 1g 20+78:O:2 7 50 100+9 20:H:0:0 7S otG.

20 30:O:67:3 7 50 10021 20:O Near 7:3 7 5G 10022 20: O Near 6:4 7 50. 10023 20: fl Near 4:6 1 50 106HH:O Near 2:8 γ 50 to.

Examples 25-28 Example of preparation of DBS/2-EHA or EA/MAA terpolymer latex Repeat the general operating steps 18-24 to prepare dipromostyrene (DBS) 20 ~25% by weight, 2-ethylhexyl acrylate (2-EHA) or ethyl Acrylate (EA) 0-65% by weight, and methyl methacrylate (MAA) A terpolymer latex containing 15-23% by weight was prepared. The reactions are shown in Table V As shown in Figure 3, 50% solids and 100% conversion were achieved at 50°C for 9 hours. 2 -EHA or EA to n-propyl acrylate and butyl acrylate Replaced MMA with ethyl methacrylate, isopropyl methacrylate and The same preparation was made by repeating the above preparation, substituting t-butyl methacrylate. A similarly good latex composition can be obtained. Latex is well suited for a variety of coating applications. together, exhibiting improved flame retardancy.

Table V Preparation of DBS/2-EHA or EA/&IMA terpolymer latex Example Loading time Reaction time Solids Conversion rate DBS/2-ERA/EM/MAA h r % % 25 20:65:O:15 9 50 100H20+57 :0:23 9 5G 10027 2S:O:57:IS 9 So tG.

H20:O:51:23 9 511 1o.

Examples 29-30 Production of DBS/EA/MMA/MAA tetrapolymer latex Alkyl aryl Triton X-207 (TriLon X-407) 17. 561) Ewo Zenmo/? -Dissolved in 100 parts (NH.) ! S, 0.0.1 2 parts, N a H S O s O, 1 6 parts and Examples 1-5 except that they were loaded into bottles containing 113.51 parts deionized water. Dipromostyrene (DBS) 0-20%, ethylene Acrylate (EA) 65%, Methyl methacrylate (MMA) 13-33% Preparation of tetrapolymer latex with 2% methacrylic acid (MMA) and 8 oz. I went with a bottle of water. The reaction was carried out at 65°C for 2.5 to 4.5 hours as shown in Table 1. , 45.3-46.3% solids, conversion of 93-95% was reached. Product at 30℃ Cool, filter, and adjust pH to 9.5 with 2-amino-2-methyl-1-propanol. Adjusted to. Ethyl acrylate, 2-ethylhexyl acrylate, n-pro Replaced with pyracrylate and n-butyl acrylate, and replaced with methyl methacrylate. ethyl methacrylate, isopropyl methacrylate and t-butyl methacrylate and acrylic acid for methacrylic acid. By repeating the process, similarly good latex compositions can be obtained. latex It is well suited for a variety of coating applications and has a modified oxygen index of 25. Shows improved flame retardancy.

Table■ Preparation example of DBS/EA/MMA/MAA terpolymer latex Loading mono mer reaction time solids conversion rate oxygen index DIIS/EA/MMA/MAA hr%%Examples 31-34 A DBS/BA/S/MAA tetrapolymer latex was prepared. 30% of the product Cool to °C, filter and pH with 2-amino-2-methyl-1-propatol. was adjusted to 9.5. Butyl acrylate to ethyl acrylate table ■ Dis/IA/S/MA^ Preparation example of tetrapolymer latex Loading knob - Reaction time Solids Conversion rate Oxygen index DBS/BA/S/MAA hr % %H 311:6 F:0:31 If 44.0! ? 2432 20:' 11:0:22 3.67 434 97 -33 H:SS:43:2 19 ．． 15 4G. ! D H34 G:55:43:2 14 45. $54 01, using 5 parts of a block copolymer of propylene oxide and ethylene oxide (F108, manufactured by 7 bus companies) 2. Octylphenoxy polyethoxyethanol 7.59 parts used (Triton - 1 6 5, manufactured by Rohm and Haas) Example 35 Production of related copolymer latex The preparation of related latex copolymers as described above also provides equally advantageous products. generate. For example, instead of dipromostyrene, various ethylenically unsaturated, Ring-brominated aromatic additives, e.g. methylstyrene, σ-methylstyrene , α-methylmethylstyrene, ethylstyrene and a-methylethylstyrene (mono-, di-, tri- and tetra-bromine substitutions on the benzene ring) are used. especially , polybrominated units, especially those that are liquid at room temperature and have an average per unit Brominated aromatic monomers containing mixtures having at least 1.5 bromine in The latex according to this patent can be easily prepared and has improved flame retardancy and good physical properties. It has the following characteristics. As previously described herein, using separate monomers, Similarly excellent flame retardant latex compositions were obtained by preparation according to the examples described above. It will be done. The selection of the seven-pointer depends primarily on the desired physical properties of the latex produced. dependence on the resulting paint due to the presence of ring-brominated aromatic monomer units. Provides advanced flame retardancy.

Although the present invention has been described in detail in the above description and specific examples thereof, this does not mean that the present invention This is for illustrative purposes only and is not intended to limit the characteristics of the invention. favorable fruit Only the embodiments have been described. However, any and all modifications and variations consistent with the spirit of the invention are contemplated. Furthermore, it is included in the scope of protection.

Submission of translation of written amendment (Article 184-8 of the Patent Law) March 8, 1993・ SaS

Claims (39)

[Claims] 1. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer knit, and formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ Monomer unit, [wherein X=1 to 4, R1 is -H or -CH3, R2 is -H or an alkyl group having 1 to 4 carbon atoms, and R3 is a carbon It is an alkyl group having 1 to 20 atoms. ] A flame-retardant polymer latex composition comprising the ring-brominated aromatic monomer. A composition in which the mer unit is present in an amount providing 7 to 20% bromine by weight of the total composition. . 2. the ring brominated monomer unit provides 9 to 18% by weight of bromine; A composition according to claim 1, wherein the composition is present in 3. The ring brominated aromatic monomer units are on average less than 2. The composition of claim 1, wherein the composition contains about 1.5% bromine. 4. A ring-brominated aromatic monomer unit forms a monobrominated unit and a polybrominated monomer unit. an aromatic monomer unit in which the monobrominated unit is ring-brominated. 4. The composition of claim 3, wherein the composition is less than 20% of the total amount. 5. The ratio of monobrominated units to polybrominated units is A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. The composition according to claim 3. 6. The amount of the ring-brominated monomer unibut provides 9 to 18% by weight of bromine. 4. A composition according to claim 3, wherein the composition is present in 7. The composition comprises essentially ring-brominated aromatic monomer units and alkyl ( The composition according to claim 1, comprising a meth)acrylate monomer unit. 8. the ring brominated monomer unit provides 9 to 18% by weight of bromine; 8. A composition according to claim 7, wherein the composition is present in 9. The ring brominated aromatic monomer units are on average small per unit. 8. The composition of claim 7, comprising at least about 1.5 bromine. 10. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer knit, and formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ Monomer unit, [wherein X=1 to 4, R1 is -H or -CH3, R2 is -H or an alkyl group having 1 to 4 carbon atoms, and R3 is a carbon It is an alkyl group having 1 to 20 atoms. ] A flame-retardant polymer latex composition comprising the ring-brominated aromatic monomer. compositions in which the mer units contain an average of at least about 1.5 bromine per unit; . 11. The ring brominated monomer unit provides 9-18% by weight of bromine. 11. The composition of claim 10, wherein the composition is present in an amount. 12. The ratio of monobrominated units to polybrominated units corresponds to A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. 11. The composition of claim 10, wherein the ratio is 13. The composition comprises essentially ring-brominated aromatic monomer units and alkyl (meth)acrylate monomer unit. The composition according to claim 10. 14. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer knit, and formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ A third monomer selected from those containing a monomer unit and having the following formula: mer unit, (2) formula (III) (III): ▲Acid ester monomer unit with mathematical formulas, chemical formulas, tables, etc. , (b) Formula (IV) (IV): ▲Non-brominated aromatic monomer unit with mathematical formulas, chemical formulas, tables, etc. and (c) formula (V) (V): ▲ Carboxylic acid monomer unit with mathematical formulas, chemical formulas, tables, etc. [In the formula, X=1 to 4, R1 is -H or -CH3, and R2 is -H or is an alkyl group having 1 to 4 carbon atoms, and R3 is an alkyl group having 1 to 20 carbon atoms. R4 is an alkyl group having 1 to 3 carbon atoms. ] a flame-retardant polymer latex composition comprising said ring-brominated aromatic monomer; -units are present in an amount to provide 7 to 20% bromine by weight of the total composition. 15. The ring brominated monomer unit provides 9-18% by weight of bromine. 15. The composition of claim 14, wherein the composition is present in an amount of 16. The ring-brominated aromatic monomer units are on average small per unit. 15. The composition of claim 14, comprising at least about 1.5 bromine. 17. A ring-brominated aromatic monomer unit has a monobrominated unit and a poly-brominated unit. a monobrominated unit, and the monobrominated unit is a ring-brominated aromatic monomer. 17. The composition of claim 16, wherein the composition is less than 20% of the knits. 18. The ratio of monobrominated units to polybrominated units corresponds to A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. 17. The composition of claim 16, wherein the composition is a ratio of 19. The ring brominated monomer unit provides 9-18% by weight of bromine. 19. The composition of claim 18, wherein the composition is present in an amount. 20. Ring-brominated aromatic monomer unit, alkyl (meth)acrylate monomer unit, and (2) acid ester monomer unit, (b) non-bromine (c) a group consisting of an aromatic monomer unit and (c) a carboxylic acid monomer unit 15. The composition of claim 14 consisting essentially of a third monomer unit selected from thing. 21. The ring brominated monomer unit provides 9-18% by weight of bromine. 21. The composition of claim 20, wherein the composition is present in an amount. 22. The ring-brominated aromatic monomer units are on average small per unit. 21. The composition of claim 20, comprising at least about 1.5 bromine. 23. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer knit, and formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ A third monomer selected from those containing a monomer unit and having the following formula: mer unit, (a) formula (III) (III): ▲Acid ester monomer, unit with mathematical formulas, chemical formulas, tables, etc. , (b) Formula (IV) (IV): ▲Non-brominated aromatic monomer unit with mathematical formulas, chemical formulas, tables, etc. and (c) formula (V) (V): ▲ Carboxylic acid monomer unit with mathematical formulas, chemical formulas, tables, etc. [In the formula, X=1 to 4, R1 is -H or -CH3, and R2 is -H or is an alkyl group having 1 to 4 carbon atoms, and R3 is an alkyl group having 1 to 20 carbon atoms. R4 is an alkyl group having 1 to 3 carbon atoms. ] A flame-retardant polymer latex composition comprising the ring-brominated aromatic monomer. compositions in which the mer units contain an average of at least about 1.5 bromine per unit; . 24. The ring brominated monomer unit provides 9-18% by weight of bromine. 24. The composition of claim 23, wherein the composition is present in an amount of 25. The ratio of monobrominated units to polybrominated units corresponds to A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. 24. The composition of claim 23, wherein the composition is a ratio of 26. Ring-brominated aromatic monomer unit, alkyl (meth)acrylate monomer unit, and (a) acid ester monomer unit, (b) non-bromine (c) a group consisting of an aromatic monomer unit and (c) a carboxylic acid monomer unit 24. The composition of claim 23 consisting essentially of a third monomer unit selected from thing. 27. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer Knit, formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ Monomer unit, formula (IV) (IV): ▲Non-brominated aromatic monomer unit with mathematical formulas, chemical formulas, tables, etc. and formula (V) (V): ▲ Carboxylic acid monomer unit with mathematical formulas, chemical formulas, tables, etc. [In the formula, X=1 to 4, R1 is -H or -CH3, and R2 is -H or is an alkyl group having 1 to 4 carbon atoms, and R3 is an alkyl group having 1 to 20 carbon atoms. It is an alkyl group. ] A flame-retardant polymer latex composition comprising the ring-brominated aromatic monomer. A composition in which the mer unit is present in an amount providing 7 to 20% bromine by weight of the total composition. . 28. The ring brominated monomer unit provides 9-18% by weight of bromine. 28. The composition of claim 27, wherein the composition is present in an amount. 29. The ring-brominated aromatic monomer units are on average small per unit. 28. The composition of claim 27, comprising at least about 1.5 bromine. 30. A ring-brominated aromatic monomer unit has a monobrominated unit and a poly-brominated unit. a monobrominated unit, and the monobrominated unit is a ring-brominated aromatic monomer. 30. The fabric of claim 29, which is less than 20% of the knit. 31. The ratio of monobrominated units to polybrominated units corresponds to A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. 30. The composition of claim 29, wherein the composition is a ratio of 32. The ring brominated monomer unit provides 9-18% by weight of bromine. 30. The composition of claim 29, wherein the composition is present in an amount. 33. The composition comprises essentially ring-brominated aromatic monomer units, alkyl (meth)acrylate monomer units, non-brominated aromatic monomer units, and a carboxylic acid monomer unit. 34. The ring brominated monomer unit provides 9-18% by weight of bromine. 34. The composition of claim 33, wherein the composition is present in an amount of 35. The ring brominated aromatic monomer unit is on average small per unit. 34. The composition of claim 33, comprising at least about 1.5 bromine. 36. Formula (I) (I): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Ring-brominated aromatic monomer Knit, formula (II) (II): ▲Alkyl (meth)acrylate with mathematical formulas, chemical formulas, tables, etc.▼ Monomer unit, formula (IV) (IV): ▲Non-brominated aromatic monomer unit with mathematical formulas, chemical formulas, tables, etc. and formula (V) (V): ▲ Carboxylic acid monomer unit with mathematical formulas, chemical formulas, tables, etc. [In the formula, X=1 to 4, R1 is -H or -CH2, and R2 is -H or an alkyl group having 1 to 4 carbon atoms, and R2 has 1 to 20 carbon atoms; It is an alkyl group. ] A flame-retardant polymer latex composition comprising the ring-brominated aromatic monomer. compositions in which the mer units contain an average of at least about 1.5 bromine per unit; . 37. The ring brominated monomer unit provides 9-18% by weight of bromine. 37. The composition of claim 36, wherein the composition is present in an amount of 38. The ratio of monobrominated units to polybrominated units corresponds to A mixture of unsaturated ring-brominated aromatic monomers is liquid at room temperature. 37. The composition of claim 36, wherein the composition is a ratio of 39. The composition comprises essentially ring-brominated aromatic monomer units, alkyl (meth)acrylate monomer units, non-brominated aromatic monomer units, and a carboxylic acid monomer unit.